JP6720675B2 - Quinophthalone compound, pigment dispersant using the quinophthalone compound, coloring composition for color filter and color filter - Google Patents

Description

In order to increase the contrast and brightness of the color filter, it is required to disperse the finely treated pigment in a finer state (good dispersibility). However, since the finely treated pigment has a large surface area, the cohesive force between the pigment particles becomes strong, and when the dispersibility of the pigment is insufficient, the dispersion becomes highly viscous and the contrast of the color filter Is significantly deteriorated. It is often difficult to achieve both high level dispersibility and contrast.

In order to solve such problems, various dye derivatives have been developed. For example, Patent Documents 1 to 7 propose coloring compositions using a quinophthalone compound as a dye derivative. With the quinophthalone compounds proposed in these patent documents, it is not possible to obtain a colored composition that satisfies all of the brightness, contrast, dispersibility, and heat resistance when dispersing the finely treated pigment, and a new Development of quinophthalone compounds has been desired. Further, in Patent Documents 8 to 9, quinophthalone compounds having a phthalimide group substituted with sulfonic acid are described as intermediates of Examples, but the utility in color filter applications is not described in the specification. ..

JP, 2003-167112, A JP-A-2002-179979 JP-A-2002-121456 JP, 2004-067715, A JP, 2004-307854, A JP, 2007-156395, A JP, 2014-199308, A JP, 2008-050420, A JP, 2008-081566, A

An object of the present invention is to provide a coloring composition for a color filter which is excellent in brightness, contrast, dispersibility and heat resistance.

That is, the present invention relates to a quinophthalone compound (A) represented by the following general formula (1).

General formula (1)

[In the general formula (1), R _{1 to} R ₉ each independently have a hydrogen atom, a halogen atom, a nitro group, an optionally substituted alkyl group having 20 or less carbon atoms, and a substituent. Represents an alkoxy group having 20 or less carbon atoms or an aryl group having 20 or less carbon atoms which may have a substituent, and adjacent substituents are bonded to each other to form an aliphatic saturated hydrocarbon-based or aromatic-based You may form a cyclic structure.
Q1 represents a divalent linking group.
A1 and B1 are each independently represented by a hydroxyl group, a chlorine atom, the following general formula (2) or the following general formula (3), and at least one is a group represented by the following general formula (2). ..

Formula (2) _{-X 1} -Z 1
(In the general formula (2), X ₁ represents —NH— or —O—. Z ₁ may have a substituent having 20 or less carbon atoms, or may have a substituent. Represents a good alkyl group having 20 or less carbon atoms, and X ₁ and Z ₁ represent an arylene group having 20 or less carbon atoms which may have a substituent, and a heteroari having 20 or less carbon atoms which may have a substituent. lane group, a substituted alkylene group having 20 or less carbon atoms which may _{have, -NHSO 2 -, - NHCO -} , - OSO 2 -, - OCO -, - S -, - selected from NH- and -O- May be linked by at least one divalent linking group.
However, Z ₁ has at least one substituent selected from —COOH, —SO ₃ H, and —OSO ₃ H. )

Formula (3) _{-X 2} -Z 2
(In the general formula (3), X ₂ represents —NH— or O—. Z ₂ is a carbon that may have a substituent (in the general formula (3), X ₂ is —NH— or Represents —O— Z ₂ may have an alkyl group having 20 or less carbon atoms which may have a substituent, an alkenyl group having 20 or less carbon atoms which may have a substituent, and a substituent. It represents an aryl group having 20 or less carbon atoms or a heteroaryl group having 20 or less carbon atoms which may have a substituent, and X ₂ and Z ₂ are arylene having 20 or less carbon atoms which may have a substituent. Group, a heteroarylene group having 20 or less carbon atoms which may have a substituent, an alkylene group having 20 or less carbon atoms which may have a substituent, -NHSO ₂ -, -NHCO-, -OSO ₂ -, They may be linked by at least one divalent linking group selected from -OCO-, -S-, -NH- and -O-.
However, _{Z 2} has no -COOH, -SO ₃ H at or OSO ₃ H as a substituent. )]

The present invention also relates to the above-mentioned quinophthalone compound (A), in which Q ₁ in the general formula (1) is represented by the following general formula (4).

Formula _{(4) - (X 3)} n - (Z 3) m -X 4 - *
[In the general formula (4), _{X 3 is, -NHSO 2 -, - NHCO -} , - OSO 2 -, - OCO -, - NH- or an -O-.
Z ₃ is an arylene group having 20 or less carbon atoms which may have a substituent, a heteroarylene group having 20 or less carbon atoms which may have a substituent, or a carbon number 20 which may have a substituent. The following alkylene groups are represented, and when m is 2 or more, a plurality of Z _3's may be the same or different, and a plurality of Z _3's are —NHSO ₂ —, —NHCO—, —OSO ₂ —, —. They may be linked by at least one divalent linking group selected from OCO-, -S-, -NH- and -O-.
X ₄ represents -NH- or -O-.
n represents an integer of 0 or 1, and m represents an integer of 0 to 5.
* Is a linking hand with the triazine ring. ]

The present invention also relates to the above quinophthalone compound (A) in which n is 1 and m is 1 in the general formula (4).

The present invention also relates to a pigment dispersant containing the quinophthalone compound (A).

The present invention also relates to a coloring composition for a color filter containing the above pigment dispersant, a coloring agent, an organic solvent and a binder resin.

The present invention also relates to the above coloring composition for a color filter, which further contains at least one selected from a photopolymerizable monomer and a photopolymerization initiator.

Furthermore, the present invention provides a color filter comprising at least one red filter segment, at least one green filter segment and at least one blue filter segment, wherein at least one green filter segment is formed from the above color filter coloring composition. Color filters.

By using the quinophthalone compound represented by the general formula (1) of the present invention in combination with a coloring agent, it is possible to provide a low-viscosity colored composition for color filters, which has good lightness, contrast, heat resistance, and little foreign matter. it can.

Hereinafter, the present invention will be described in detail. In addition, "CI" in this specification means a color index (CI).

<Quinophthalone compound (A) represented by the general formula (1)>
The quinophthalone compound (A) represented by the following general formula (1) of the present invention will be described.

General formula (1)

[In the general formula (1), R _{1 to} R ₉ each independently have a hydrogen atom, a halogen atom, a nitro group, an optionally substituted alkyl group having 20 or less carbon atoms, and a substituent. Represents an alkoxy group having 20 or less carbon atoms or an aryl group having 20 or less carbon atoms which may have a substituent, and adjacent substituents are bonded to each other to form an aliphatic saturated hydrocarbon-based or aromatic-based You may form a cyclic structure.
Q1 represents a divalent linking group.
A1 and B1 are each independently represented by a hydroxyl group, a chlorine atom, the following general formula (2) or the following general formula (3), and at least one is a group represented by the following general formula (2). ..

Formula (2) _{-X 1} -Z 1
(In the general formula (2), X ₁ represents —NH— or —O—. Z ₁ may have a substituent having 20 or less carbon atoms, or may have a substituent. Represents a good alkyl group having 20 or less carbon atoms, and X ₁ and Z ₁ represent an arylene group having 20 or less carbon atoms which may have a substituent, and a heteroari having 20 or less carbon atoms which may have a substituent. lane group, a substituted alkylene group having 20 or less carbon atoms which may _{have, -NHSO 2 -, - NHCO -} , - OSO 2 -, - OCO -, - S -, - selected from NH- and -O- May be linked by at least one divalent linking group.
However, Z ₁ has at least one substituent selected from —COOH, —SO ₃ H, and —OSO ₃ H. )

Formula (3) _{-X 2} -Z 2
(In the general formula (3), X ₂ represents —NH— or —O—. Z ₂ may have a substituent having 20 or less carbon atoms, or may have a substituent. It represents an alkenyl group having 20 or less carbon atoms, an aryl group having 20 or less carbon atoms that may have a substituent, or a heteroaryl group having 20 or less carbon atoms that may have a substituent, and X ₂ and Z ₂ Is an arylene group having 20 or less carbon atoms, which may have a substituent, a heteroarylene group having 20 or less carbon atoms, which may have a substituent, and an alkylene having 20 or less carbon atoms, which may have a substituent. _{group, -NHSO 2 -, - NHCO -} , - OSO 2 -, - OCO -, - S -, - selected from NH- and -O- may be linked by at least one divalent linking group ..
However, _{Z 2} has no -COOH, -SO ₃ H at or OSO ₃ H as a substituent. )]

Q1 in the general formula (1) is preferably a linking group represented by the following general formula (4).

Formula _{(4) - (X 3)} n - (Z 3) m -X 4 - *
[In the general formula (4), _{X 3 is, -NHSO 2 -, - NHCO -} , - OSO 2 -, - OCO -, - NH- or an -O-.
Z ₃ is an arylene group having 20 or less carbon atoms which may have a substituent, a heteroarylene group having 20 or less carbon atoms which may have a substituent, or a carbon number 20 which may have a substituent. The following alkylene groups are represented, and when m is 2 or more, a plurality of Z _3's may be the same or different, and a plurality of Z _3's are —NHSO ₂ —, —NHCO—, —OSO ₂ —, —. They may be linked by at least one divalent linking group selected from OCO-, -S-, -NH- and -O-.
X ₄ represents -NH- or -O-.
n represents an integer of 0 or 1, and m represents an integer of 0 to 5.
* Is a linking hand with the triazine ring. ]

Each group in the general formulas (1) to (4) will be described.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

As the alkyl group, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, octadecyl group, trifluoromethyl group, isopropyl group, isobutyl Group, isopentyl group, 2-ethylhexyl group, 2-hexyldecyl group, sec-butyl group, tert-butyl group, sec-pentyl group, tert-pentyl group, tert-octyl group, neopentyl group, cyclopropyl group, cyclobutyl group Examples thereof include, but are not limited to, a cyclopentyl group, a cyclohexyl group, an adamantyl group, a norbornyl group, a boronyl group and a 4-decylcyclohexyl group.

The alkoxy group is a group in which an oxygen atom is bonded to the above alkyl group.

Examples of the alkenyl group include a linear, branched, monocyclic or condensed polycyclic alkenyl group. They may have multiple carbon-carbon double bonds in the structure. As specific examples, vinyl group, 1-propenyl group, allyl group, 2-butenyl group, 3-butenyl group, isopropenyl group, isobutenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4- Pentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, cyclopentenyl group, cyclohexenyl group, 1,3-butadienyl group, cyclohexadienyl group, cyclopenta group Examples thereof include, but are not limited to, a dienyl group and the like.

Examples of the aryl group include a phenyl group, a biphenylyl group, a terphenylyl group, a quarterphenylyl group, a pentalenyl group, an indenyl group, a naphthyl group, a binaphthalenyl group, a tarnaphthalenyl group, a quarternaphthalenyl group, an azulenyl group, a heptenyl group, a biphenylenyl group, and an indacenyl group. Group, fluoranthenyl group, acephenanthrylenyl group, aceanthrylenyl group, phenalenyl group, fluorenyl group, anthryl group, bianthracenyl group, teranthracenyl group, quarter anthracenyl group, anthraquinolyl group, phenanthryl group, triphenylenyl group Group, pyrenyl group, chrysenyl group, naphthacenyl group, preadenyl group, picenyl group, perylenyl group, pentaphenyl group, pentacenyl group, tetraphenylenyl group, hexaphenyl group, hexacenyl group, rubicenyl group, coronenyl group, trinaphthylenyl group, Examples thereof include, but are not limited to, a heptaphenyl group, a heptacenyl group, a pyrantrenyl group, an ovalenyl group, and the like.

Heteroaryl groups include pyrrole, pyrazole, imidazole, oxazole, triazole, oxadiazole, triazole, thiadiazole, pyran, pyridine, pyridiazine, pyrimidine, triazine, benzofuran, benzothiophene, indole, benzimidazole, benzothiazole, quinoline, isoquinoline. , Quinoxaline, carbazole, and the like, but are not limited thereto.

The arylene group, heteroarylene group, and alkylene group represent a divalent linking group obtained by removing one hydrogen atom from the above aryl group, heteroaryl group, and alkyl group.

The hydrogen atom of an alkyl group, an alkoxy group, an alkenyl group, an aryl group, a heteroaryl group, an arylene group, a heteroarylene group, or an alkylene group may be further substituted with another substituent.

Examples of such a substituent include a halogen atom, an alkyl group, an alkyl group substituted with a halogen atom, an aryl group, a nitro group, a hydroxyl group, an alkoxy group, a carboxyl group, a sulfo group, and the like. The atom, alkyl group, aryl group, and alkoxy group have the same meanings as described above.

In the general formula (1), R _{1 to} R ₉ are preferably each independently a hydrogen atom, a halogen atom, a nitro group, or an alkoxy group having 20 or less carbon atoms which may have a substituent, More preferably, each independently a hydrogen atom or a halogen atom. Adjacent substituents may combine with each other to form an aliphatic saturated hydrocarbon-based or aromatic-based cyclic structure. Among them, it is particularly preferable that R _{6 to} R ₉ are halogen atoms, R ₇ and R ₈ are halogen atoms, or that R ₇ and R ₈ together form an aromatic ring.

In the general formula (2), X ₁ is preferably NH, Z ₁ is preferably an aryl group having 20 or less carbon atoms which may have a substituent, and the aryl group is a phenyl group. Or a naphthyl group is more preferable. As the substituent that may have, a hydroxy group is preferable. Z ₁ has at least one substituent selected from —COOH, —SO ₃ H and —OSO ₃ H. Examples of Z ₁ include an aromatic sulfonic acid which may have a substituent and an aromatic carboxylic acid which may have a substituent, and the like, and preferably hydroxybenzoic acid.

Z ₂ in the general formula (3) is preferably an aryl group having a carbon number of 20 or less, which may have a substituent, and the aryl group is preferably a phenyl group. Further, the substituent which may be closed in _{Z 2,} -COOH, does not include -SO ₃ H and -OSO ₃ H.

In the general formula (4), n and m are preferably 1, X ₃ is preferably —NHSO ₂ — or —OSO ₂ —, and Z ₃ is an arylene group having 20 or less carbon atoms or 20 carbon atoms. The following alkylene group is preferable, an arylene group having 20 or less carbon atoms is more preferable, and a phenylene group is particularly preferable. X ₄ is preferably -NH-.

Specific examples of the quinophthalone compound (A) of the general formula (1) are shown below, but the present invention is not limited thereto.

<Colorant>
In addition to the quinophthalone compound (A) represented by the general formula (1), various conventionally known pigments and dyes can be arbitrarily selected and contained as colorants. The quinophthalone compound (A) of the present invention is preferably used in combination with at least one pigment selected from the yellow pigment (B) and the phthalocyanine pigment (C).
Typical pigments and dyes that can be used in the present invention are listed below.

Examples of the yellow pigment (B) that can be used in the present invention include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, Yellow pigments such as quinophthalone pigments described in 192, 193, 194, 196, 198, 199, 213, 214 and Japanese Patent No. 4993026 can be used. Particularly, from the viewpoints of heat resistance, light resistance, and brightness of the filter segment, examples of the yellow dye include C.I. I. Pigment Yellow 138, 139, 150 and 185 is preferable.

As the yellow dye, azo dye, azo metal complex salt dye, anthraquinone dye, indigo dye, thioindigo dye, phthalocyanine dye, diphenylmethane dye, triphenylmethane dye, xanthene dye, thiazine dye, cationic dye, cyanine dye, nitro dye, quinoline dye. , Naphthoquinone dyes and oxazine dyes.

Specific examples of the yellow dye include C.I. I. Acid Yellow 2,3,4,5,6,7,8,9,9:1,10,11,11:1,12,13,14,15,16,17,17:1,18,20, 21, 22, 23, 25, 26, 27, 29, 30, 31, 33, 34, 36, 38, 39, 40, 40:1, 41, 42, 42:1, 43, 44, 46, 48, 51, 53, 55, 56, 60, 63, 65, 66, 67, 68, 69, 72, 76, 82, 83, 84, 86, 87, 90, 94, 105, 115, 117, 122, 127, 131, 132, 136, 141, 142, 143, 144, 145, 146, 149, 153, 159, 166, 168, 169, 172, 174, 175, 178, 180, 183, 187, 188, 189, 190, 191, 192, 199 and the like.

Also, C.I. I. Direct Yellow 1, 2, 4, 5, 12, 13, 15, 20, 24, 25, 26, 32, 33, 34, 35, 41, 42, 44, 44:1, 45, 46, 48, 49, 50, 51, 61, 66, 67, 69, 70, 71, 72, 73, 74, 81, 84, 86, 90, 91, 92, 95, 107, 110, 117, 118, 119, 120, 121, 126, 127, 129, 132, 133, 134 etc. are also mentioned.

Also, C.I. I. Basic Yellow 1, 2, 5, 11, 13, 14, 15, 19, 21, 24, 25, 28, 29, 37, 40, 45, 49, 51, 57, 79, 87, 90, 96, 103, 105, 106 and the like.

Also, C.I. I. Solvent Yellow 2, 3, 4, 7, 8, 10, 11, 12, 13, 14, 15, 16, 18, 19, 21, 22, 25, 27, 28, 29, 30, 32, 33, 34, 40, 42, 43, 44, 45, 47, 48, 56, 62, 64, 68, 69, 71, 72, 73, 77, 79, 81, 82, 83, 85, 88, 89, 90, 93, 94, 98, 104, 107, 114, 116, 117, 124, 130, 131, 133, 135, 138, 141, 143, 145, 146, 147, 157, 160, 162, 163, 167, 172, 174, 175, 176, 177, 179, 181, 182, 183, 184, 185, 186, 187, 188, 190, 191, 192, 194, 195 and the like are also included.

Also, C.I. I. Disperse Yellow 1, 2, 3, 5, 7, 8, 10, 11, 13, 13, 23, 27, 33, 34, 42, 45, 48, 51, 54, 56, 59, 60, 63, 64 , 67, 70, 77, 79, 82, 85, 88, 93, 99, 114, 118, 119, 122, 123, 124, 126, 163, 184, 184:1, 202, 211, 229, 231, 232. 233, 241, 245, 246, 247, 248, 249, 250, 251 and the like.

Red pigments that can be used in the present invention include, for example, C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48:1, 48:2, 48:3, 48: 4, 49, 49:1, 49:2, 57:1, 81, 81:1, 81:2, 81:3, 81:4, 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 221, 224, 226, 242, 246, 254, 255, 264, 269, 270, 272, 273, 274, 276, 277, 278, 279, 280, 281, 282, 283, 284, 285, 286, 287, or the diketopyrrolopyrrole pigment described in JP-A No. 2011-523433, but the invention is not particularly limited thereto. Further, red dyes such as xanthene-based, azo-based, disazo-based, and anthraquinone-based dyes can also be used. Specifically, C.I. I. Examples thereof include salt-forming compounds of xanthene-based acid dyes such as Acid Red 52, 87, 92, 289, 338.

Orange pigments that can be used in the present invention include, for example, C.I. I. Pigment Orange 38, 43, 71, 73 and the like, but are not particularly limited thereto.

The green pigment (C) that can be used in the present invention is, for example, C.I. I. Pigment Green 7, 10, 36, 37, 58, 59, JP 2008-19383A, JP 2007-320986A, JP 2004-70342A, and the like, and the zinc phthalocyanine pigments and the like are listed, It is not particularly limited to these.

Blue pigments that can be used in the present invention include, for example, C.I. I. Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22, 60, 64, JP-A-2004-333817, Examples thereof include aluminum phthalocyanine pigments described in Japanese Patent No. 4893859 and the like, but are not particularly limited thereto.

When the yellow pigment (B) is contained, the quinophthalone compound (A) represented by the general formula (1) is preferably 5% by mass or more and 60% by mass or less with respect to the yellow pigment (B). It is more preferably 10% by mass or more and 50% by mass or less. If the ratio of the quinophthalone compound (A) is too small with respect to the colorant, the effect of improving the brightness, contrast, heat resistance, foreign matter suppression, initial viscosity and storage stability tends to be small.

Further, among the colorants, it is preferable to use any one of the phthalocyanine pigments (C) alone or in combination of two or more in view of the color characteristics of the quinophthalone compound (A).

The phthalocyanine pigment (C) is preferably a halogenated copper phthalocyanine pigment, a halogenated zinc phthalocyanine pigment, an aluminum phthalocyanine pigment, or a halogenated aluminum phthalocyanine pigment. More preferably, C.I. I. Pigment Green 58 or a halogenated aluminum phthalocyanine compound represented by the general formula (8).

General formula (8)

[In general formula (8), E represents a halogen atom, and n represents an integer of 4 to 16. However, the average value of the substitution number of the halogen atom represented by E is 6 to 15, and the halogen distribution width is 4 or more.
G represents -OP (= O) R101R102, -OC (= O) R103, -OS (= O) 2 R104. R101 and R102 each independently represent a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxyl group which may have a substituent or a substituent. It represents an aryloxy group which may have.
R103 is a hydrogen atom, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an aryl group which may have a substituent, or a heterocycle which may have a substituent. Represents a group.
R104 represents a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a heterocyclic group which may have a substituent. ]

Examples of the halogen atom in the general formula (8) include fluorine, bromine, chlorine and iodine, with bromine and chlorine being preferred.

In the halogenated aluminum phthalocyanine compound represented by the general formula (8), the average number of substitutions of the halogen atom represented by E is 6 to 15, and 8 to 15 is preferable from the viewpoint of hue and fastness. Alternatively, the width of the distribution of the logogen is 4 or more, preferably 4 to 9. When the halogen distribution width is 4 or more, the association between the phthalocyanine molecules is apt to be significantly suppressed, and it is clear that the particle size is increased due to the association between the molecules and, as a result, the reduction of the contrast is greatly suppressed. became. Here, the "halogen distribution width" is a distribution of the number of halogens substituted in the phthalocyanine pigment represented by the general formula (8). The halogen distribution width, in the mass spectrum obtained by mass spectrometry, the signal intensity (each peak value) of the molecular ion peak corresponding to each component, and the value obtained by integrating each peak value (total peak value), The number of peaks in which the ratio of each peak value to the total peak value was 1% or more was counted and used as the halogen distribution width.

Examples of the alkyl group in the general formula (8) include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, neopentyl group, n-hexyl group, n-octyl group, stearyl group. , A linear or branched alkyl group such as a 2-ethylhexyl group, and an alkyl group having 1 to 6 carbon atoms is preferable.
Examples of the substituent of the alkyl group having a substituent include a halogen atom such as chlorine, fluorine and bromine, an alkoxyl group such as a methoxy group, an aryl group such as a phenyl group and a tolyl group, and a nitro group. Further, there may be a plurality of substituents. Therefore, examples of the alkyl group having a substituent include a trichloromethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a 2,2-dibromoethyl group, a 2-ethoxyethyl group, and a 2-butoxy group. Ethyl group, 2-nitropropyl group, benzyl group, 4-methyl benzyl group, 4-tert-butyl benzyl group, 4-methoxy benzyl group, 4-nitro benzyl group, 2,4-dichloro benzyl group. Groups and the like.

Examples of the aryl group in the general formula (8) include a monocyclic aromatic hydrocarbon group such as a phenyl group and a p-tolyl group, and a condensed aromatic hydrocarbon group such as a naphthyl group and an anthryl group. Hydrocarbon groups are preferred. Further, an aryl group having 6 to 12 carbon atoms is preferable.
Examples of the substituent of the aryl group having a substituent include a halogen atom such as chlorine, fluorine and bromine, an alkoxyl group, an amino group and a nitro group. Further, there may be a plurality of substituents. Therefore, examples of the aryl group having a substituent include a p-bromophenyl group, a p-nitrophenyl group, a p-methoxyphenyl group, a 2,4-dichlorophenyl group, a pentafluorophenyl group, a 2-dimethylaminophenyl group, Examples thereof include a 2-methyl-4-chlorophenyl group, a 4-methoxy-1-naphthyl group, a 6-methyl-2-naphthyl group, a 4,5,8-trichloro-2-naphthyl group and an anthraquinonyl group.

Examples of the alkoxyl group in the general formula (8) include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a tert-butoxy group, a neopentyloxy group, and 2,3-dimethyl-3-. Examples thereof include linear or branched alkoxyl groups such as a pentyloxy group, an n-hexyloxy group, an n-octyloxy group, a stearyloxy group, and a 2-ethylhexyloxy group, and an alkoxyl group having 1 to 6 carbon atoms is preferable.
Examples of the substituent of the alkoxyl group having a substituent include a halogen atom such as chlorine, fluorine and bromine, an alkoxyl group, an aryl group such as a phenyl group and a tolyl group, and a nitro group. Further, there may be a plurality of substituents. Therefore, examples of the alkoxyl group having a substituent include a trichloromethoxy group, a trifluoromethoxy group, a 2,2,2-trifluoroethoxy group, a 2,2,3,3-tetrafluoropropoxy group, and a 2,2- Examples thereof include a ditrifluoromethylpropoxy group, a 2-ethoxyethoxy group, a 2-butoxyethoxy group, a 2-nitropropoxy group and a benzyloxy group.

The aryloxy group in the general formula (8) is an aryloxy group composed of a monocyclic aromatic hydrocarbon group such as a phenoxy group or a p-methylphenoxy group, or a condensed aromatic hydrocarbon such as a naphthaloxy group or an anthryloxy group. The aryloxy group consisting of a group is mentioned, and the aryloxy group consisting of a monocyclic aromatic hydrocarbon group is preferable. Further, an aryloxy group having 6 to 12 carbon atoms is preferable.
Examples of the substituent of the aryloxy group having a substituent include a halogen atom such as chlorine, fluorine and bromine, an alkyl group, an alkoxyl group, an amino group and a nitro group. Further, there may be a plurality of substituents. Therefore, examples of the aryloxy group having a substituent include a p-nitrophenoxy group, a p-methoxyphenoxy group, a 2,4-dichlorophenoxy group, a pentafluorophenoxy group, and a 2-methyl-4-chlorophenoxy group. Can be mentioned.

Examples of the cycloalkyl group in the general formula (8) include a monocyclic aliphatic hydrocarbon group such as a cyclopentyl group, a cyclohexyl group, a 2,5-dimethylcyclopentyl group, and a 4-tert-putylcyclohexyl group, a bornyl group, and an adamantyl group. And condensed aliphatic hydrocarbon groups such as groups. Moreover, a C5-C12 cycloalkyl group is preferable.
Examples of the substituent of the cycloalkyl group having a substituent include a halogen atom such as chlorine, fluorine and bromine, an alkyl group, an alkoxyl group, a hydroxyl group, an amino group and a nitro group. Further, there may be a plurality of substituents. Examples of the cycloalkyl group having a substituent include a 2,5-dichlorocyclopentyl group and a 4-hydroxycyclohexyl group.

Examples of the heterocyclic group in the general formula (8) include an aliphatic heterocyclic group such as a pyridyl group, a pyrazyl group, a piperidino group, a pyranyl group, a morpholino group and an acridinyl group, and an aromatic heterocyclic group. Further, a heterocyclic group having 4 to 12 carbon atoms is preferable, and a heterocyclic group having 5 to 13 ring members is preferable.
Examples of the substituent of the heterocyclic group having a substituent include a halogen atom such as chlorine, fluorine and bromine, an alkyl group, an alkoxyl group, a hydroxyl group, an amino group and a nitro group. Further, there may be a plurality of substituents. Examples of the heterocyclic group having a substituent include a 3-methylpyridyl group, an N-methylpiperidyl group, an N-methylpyrrolyl group and the like.

As the halogenated aluminum phthalocyanine compound represented by the general formula (8), from the viewpoint of dispersibility and color characteristics, at least one of R101 and R102 is an aryl group or a substituent which may have a substituent. It is preferably an aryloxy group which may have, more preferably both R101 and R102 are an aryl group or an aryloxy group, and it is further preferable that both R101 and R102 are a phenyl group or a phenoxy group. preferable. In addition, R103 and R104 are preferably an aryl group which may have a substituent or a heterocyclic group which may have a substituent.

When a yellow dye containing the quinophthalone compound (A) represented by the general formula (1) is used in combination with a green dye, from the viewpoint of lightness and hue, green dye/quinophthalone compound represented by the general formula (1). The mass ratio of the yellow dye containing (A) is preferably in the range of 10/90 to 70/30.

(Fine colorant miniaturization)
The colorant used in the coloring composition of the present invention is suitable as a colorant for a color filter by subjecting the colorant particles to miniaturization by salt milling treatment or the like, if necessary, in order to obtain high brightness and high contrast. Can be used for The volume average primary particle diameter of the colorant is preferably 10 nm or more in order to enhance dispersibility in the colorant carrier. Further, in order to obtain a filter segment with high contrast, it is preferably 80 nm or less. A particularly preferable range is 20 to 60 nm.

The salt milling treatment is performed by heating a mixture of a colorant, a water-soluble inorganic salt and a water-soluble organic solvent with a kneader such as a kneader, a two-roll mill, a three-roll mill, a ball mill, an attritor or a sand mill. This is a treatment for removing the water-soluble inorganic salt and the water-soluble organic solvent by washing with water after mechanically kneading. The water-soluble inorganic salt acts as a crushing aid, and the colorant is crushed by utilizing the high hardness of the inorganic salt during salt milling. By optimizing the conditions for the salt milling treatment of the colorant, it is possible to obtain a colorant having a very fine volume average primary particle size, a narrow distribution width, and a sharp particle size distribution. ..

As the water-soluble inorganic salt, sodium chloride, barium chloride, potassium chloride, sodium sulfate or the like can be used, but it is preferable to use sodium chloride (salt) from the viewpoint of cost. From the viewpoint of both treatment efficiency and production efficiency, the water-soluble inorganic salt is preferably used in an amount of 50 to 2000% by mass, and most preferably 300 to 1000% by mass, based on the total mass of the pigment (100% by mass).

The water-soluble organic solvent has a function of wetting the colorant and the water-soluble inorganic salt, and is not particularly limited as long as it dissolves (mixes) in water and does not substantially dissolve the inorganic salt used. However, since the temperature rises during salt milling and the solvent easily evaporates, a high boiling point of 120° C. or higher is preferable from the viewpoint of safety. Examples thereof include 2-methoxyethanol, 2-butoxyethanol, 2-(isopentyloxy)ethanol, 2-(hexyloxy)ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol. , Triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol, etc. Is used. These water-soluble organic solvents are preferably used in an amount of 5 to 1000% by mass, and most preferably 50 to 500% by mass, based on the total mass of the colorant (100% by mass).

When salt-milling the colorant, a resin may be added as necessary. Here, the type of resin used is not particularly limited, and a natural resin, a modified natural resin, a synthetic resin, a synthetic resin modified with a natural resin, or the like can be used. The resin used is preferably solid at room temperature and insoluble in water, and more preferably partially soluble in the water-soluble organic solvent. The amount of the resin used is preferably in the range of 2 to 200 mass% based on the total mass of the colorant (100 mass %).
Further, when the colorant is subjected to the salt milling treatment, the quinophthalone compound (A) represented by the general formula (1) may be added if necessary. The quinophthalone compound (A) acts as a pigment dispersant and has the effect of promoting miniaturization.

<Binder resin>
The binder resin disperses a colorant such as a pigment or a dye and a quinophthalone compound represented by the general formula (1), and examples thereof include a thermoplastic resin and a thermosetting resin.

The binder resin is preferably a resin having a spectral transmittance of 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region. When used in the form of an alkali development type colored resist material, it is preferable to use an alkali-soluble vinyl resin obtained by copolymerizing an acidic group-containing ethylenically unsaturated monomer. Further, an active energy ray-curable resin having an ethylenically unsaturated double bond can be used for the purpose of further improving photosensitivity and solvent resistance.

In particular, by using an active energy ray-curable resin having an ethylenically unsaturated double bond in the side chain for an alkali-developing resist for color filters, no foreign matter is generated in the coating film after applying the colorant, and This is preferable because the stability of the colorant is improved. When a straight-chain resin that does not have an ethylenically unsaturated double bond in the side chain is used, the colorant should be difficult to be trapped in the resin in a liquid containing the resin and the colorant, and it should have a degree of freedom. Although the colorant component easily aggregates and precipitates in, the use of an active energy ray-curable resin that has an ethylenically unsaturated double bond in the side chain allows the colorant to become a resin in a liquid in which the resin and the colorant are mixed. Since it is easily trapped, the dye is less likely to elute in the solvent resistance test, the colorant component is less likely to aggregate/precipitate, and the resin is three-dimensionally crosslinked when exposed to active energy rays to form a film. It is presumed that the colorant molecules are fixed in the above step and the colorant component is less likely to aggregate/precipitate even if the solvent is removed in the subsequent developing step.

The weight average molecular weight (Mw) of the binder resin is preferably in the range of 5,000 to 100,000, more preferably in the range of 5,000 to 80,000 in order to disperse the colorant preferably. The number average molecular weight (Mn) is preferably in the range of 2,500 to 50,000, and the value of Mw/Mn is preferably 10 or less.

When the binder resin is used as a photosensitive coloring composition for a color filter, it functions as a colorant adsorbing group and an alkali-soluble group at the time of development, from the viewpoint of pigment dispersibility, penetrability, developability, and heat resistance. The balance of the carboxyl group, the aliphatic group and the aromatic group that act as the affinity group for the colorant carrier and the solvent is important for the dispersibility, penetrability, developability and durability of the pigment, and the acid value is 20 to 300 mgKOH. It is preferable to use /g of resin. When the acid value is less than 20 mgKOH/g, the solubility in a developing solution is poor and it is difficult to form a fine pattern. If it exceeds 300 mgKOH/g, no fine pattern will remain.

The binder resin is preferably used in an amount of 30 parts by mass or more with respect to 100 parts by mass of the total amount of the colorant because the film forming property and various resistances are good, and the colorant concentration is high and good color characteristics are obtained. Since it can be expressed, it is preferably used in an amount of 500 parts by mass or less.

(Thermoplastic resin)
Examples of the thermoplastic resin used for the binder resin include acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate. , Polyurethane resins, polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resins. .. Above all, it is preferable to use an acrylic resin.

Examples of the vinyl-based alkali-soluble resin copolymerized with an acidic group-containing ethylenically unsaturated monomer include resins having an acidic group such as a carboxyl group and a sulfone group. Specific examples of the alkali-soluble resin include an acrylic resin having an acidic group, an α-olefin/(anhydrous) maleic acid copolymer, a styrene/styrene sulfonic acid copolymer, an ethylene/(meth)acrylic acid copolymer, or Examples thereof include isobutylene/(anhydrous) maleic acid copolymer. Above all, at least one resin selected from an acrylic resin having an acidic group and a styrene/styrene sulfonic acid copolymer, particularly an acrylic resin having an acidic group is preferably used because it has high heat resistance and transparency.

Examples of the active energy ray-curable resin having an ethylenically unsaturated double bond include resins having an unsaturated ethylenic double bond introduced by the following methods (a) and (b).

[Method (a)]
As the method (a), for example, a side chain epoxy group of a copolymer obtained by copolymerizing an unsaturated ethylenic monomer having an epoxy group and one or more other monomers , An unsaturated ethylenic double bond having a carboxyl group of an unsaturated monobasic acid is subjected to an addition reaction, and the generated hydroxyl group is reacted with a polybasic acid anhydride to form an unsaturated ethylenic double bond and a carboxyl group. There is a way to introduce.

Examples of the unsaturated ethylenic monomer having an epoxy group include glycidyl (meth)acrylate, methylglycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4 epoxybutyl (meth)acrylate, And 3,4 epoxycyclohexyl (meth)acrylate, which may be used alone or in combination of two or more kinds. From the viewpoint of reactivity with the unsaturated monobasic acid in the next step, glycidyl (meth)acrylate is preferable.

Examples of the unsaturated monobasic acid include (meth)acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-position haloalkyl of (meth)acrylic acid, alkoxyl, halogen, nitro, and cyano-substituted compounds. Examples thereof include monocarboxylic acid, and these may be used alone or in combination of two or more kinds.

Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, and the like. These may be used alone or in combination of two or more kinds. I don't care. If necessary, such as increasing the number of carboxyl groups, use a tricarboxylic acid anhydride such as trimellitic anhydride, or use a tetracarboxylic acid dianhydride such as pyromellitic dianhydride to leave the remaining anhydride. It is also possible to hydrolyze the group. Further, when etrahydrophthalic anhydride or maleic anhydride having an unsaturated ethylenic double bond is used as the polybasic acid anhydride, the unsaturated ethylenic double bond can be further increased.

As a method similar to the method (a), for example, a side chain of a copolymer obtained by copolymerizing an unsaturated ethylenic monomer having a carboxyl group and one or more other monomers There is a method of adding an unsaturated ethylenic monomer having an epoxy group to a part of the carboxyl group to introduce an unsaturated ethylenic double bond and a carboxyl group.

[Method (b)]
As the method (b), an unsaturated ethylenic monomer having a hydroxyl group is used, and a monomer of an unsaturated monobasic acid having another carboxyl group is copolymerized with another monomer. There is a method of reacting a side chain hydroxyl group of the obtained copolymer with an isocyanate group of an unsaturated ethylenic monomer having an isocyanate group.

As the unsaturated ethylenic monomer having a hydroxyl group, 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 2- or 3- or 4-hydroxybutyl (meth)acrylate, glycerol Examples thereof include (meth)acrylates and hydroxyalkyl (meth)acrylates such as cyclohexanedimethanol mono(meth)acrylate, and these may be used alone or in combination of two or more kinds. Further, a polyether mono(meth)acrylate obtained by addition-polymerizing ethylene oxide, propylene oxide, and/or butylene oxide, etc. to the hydroxyalkyl(meth)acrylate, (poly)γ-valerolactone, (poly)ε-caprolactone And/or (poly)ester mono(meth)acrylate to which (poly)12-hydroxystearic acid or the like is added can also be used. From the viewpoint of suppressing foreign matter in the coating film, 2-hydroxyethyl (meth)acrylate or glycerol (meth)acrylate is preferable.

Examples of the unsaturated ethylenic monomer having an isocyanate group include 2-(meth)acryloyloxyethylisocyanate, 1,1-bis[(meth)acryloyloxy]ethylisocyanate, and the like, but are not limited thereto. Alternatively, two or more types can be used together.

(Thermosetting resin)
Examples of the thermosetting resin used as the binder resin include epoxy resin, benzoguanamine resin, rosin-modified maleic acid resin, rosin-modified fumaric acid resin, melamine resin, urea resin, cardo resin, and phenol resin.

The thermosetting resin may be, for example, a low molecular compound such as an epoxy compound, a benzoguanamine compound, a rosin-modified maleic acid compound, a rosin-modified fumaric acid compound, a melamine compound, a urea compound, a cardo compound, and a phenol compound. It is not limited to this. By including such a thermosetting resin, the resin reacts when the filter segment is fired, the crosslinking density of the coating film is increased, the heat resistance is improved, and the effect of suppressing pigment aggregation during firing of the filter segment is obtained. To be
Among these, epoxy resin, cardo resin, or melamine resin is preferable.

<Organic solvent>
In the coloring composition of the present invention, a colorant is sufficiently dissolved in a monomer, a resin, etc., and is applied onto a substrate such as a glass substrate so that the dry film thickness is 0.2 to 5 μm to form a filter segment. An organic solvent is included to facilitate this.

Examples of the organic solvent include ethyl lactate, benzyl alcohol, 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate and 1,4-dioxane. , 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3- Methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N,N-dimethylacetamide, N,N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, o-xylene, o-chlorotoluene, o-diethylbenzene , O-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, Ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol Monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol Dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether Dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene Glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methyl Examples thereof include cyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate and dibasic acid ester. These organic solvents can be used alone or in combination of two or more.

Among them, dispersibility of the colorant, penetrability, and good coatability of the coloring composition, ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl It is preferable to use glycol acetates such as ether acetate, alcohols such as benzyl alcohol and diacetone alcohol, and ketones such as cyclohexanone.

In addition, since the organic solvent can adjust the coloring composition to an appropriate viscosity and can form a filter segment having a desired uniform film thickness, an amount of 500 to 4000 parts by mass relative to 100 parts by mass of the total amount of the colorant. It is preferable to use.

<Method for producing colored composition>
The coloring composition of the present invention comprises a dispersant containing the quinophthalone compound (A) represented by the general formula (1), the colorant, and the binder resin in a colorant carrier containing a solvent, if necessary. Preferably, it can be produced by finely dispersing it together with a dispersing aid such as a pigment derivative using various dispersing means such as a three-roll mill, a two-roll mill, a sand mill, a kneader, or an attritor. Further, when the phthalocyanine pigment represented by the general formula (1) has high solubility, specifically, when the phthalocyanine pigment has high solubility in an organic solvent to be used and is not dissolved by stirring, and foreign matter is not confirmed, It is not necessary to manufacture it by finely dispersing it.

Further, the coloring composition of the present invention may be produced by mixing a pigment, the quinophthalone compound (A) represented by the general formula (1), other colorants, and the like separately dispersed in a colorant carrier. it can.

[Dispersion aid]
When the colorant is dispersed in the colorant carrier, a dispersion aid such as a dye derivative, a resin type dispersant, or a surfactant can be used as appropriate. The dispersion aid is excellent in dispersing the colorant and has a large effect of preventing re-aggregation of the colorant after dispersion, so that a coloring composition obtained by dispersing the colorant in the colorant carrier using the dispersion aid is prepared. When used, a color filter having a high spectral transmittance can be obtained.

Examples of the dye derivative include organic pigments, anthraquinones, acridones, or triazines having a basic substituent, an acidic substituent, or a compound having a phthalimidomethyl group optionally having a substituent introduced therein. 63-305173, Japanese Patent Publication No. 57-15620, Japanese Patent Publication No. 59-40172, Japanese Patent Publication No. 63-17102, Japanese Patent Publication No. 5-9469, etc. can be used. A single type or a mixture of two or more types can be used.

From the viewpoint of improving dispersibility, the amount of the dye derivative is preferably 0.5 part by mass or more, more preferably 1 part by mass or more, and most preferably 3 parts by mass or more, relative to 100 parts by mass of the colorant. From the viewpoint of heat resistance and light resistance, the amount is preferably 40 parts by mass or less, and most preferably 35 parts by mass or less, relative to 100 parts by mass of the colorant.

The resin-type dispersant has a pigment-affinity part having a property of adsorbing to the colorant and a part compatible with the colorant carrier, and is adsorbed to the colorant to stabilize the dispersion in the colorant carrier. It works. Specific examples of the resin-type dispersant include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamine salts. , Polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, modified products thereof, amides formed by the reaction of poly(lower alkyleneimine) with polyester having a free carboxyl group, and salts thereof Water-soluble dispersants such as (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, polyvinylpyrrolidone, etc. Resins, water-soluble polymer compounds, polyester systems, modified polyacrylate systems, ethylene oxide/propylene oxide addition compounds, phosphoric acid ester systems and the like are used, and these can be used alone or in combination of two or more, It is not necessarily limited to these.

As a commercially available resin type dispersant, Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 170 manufactured by Big Chemie Japan Co., Ltd. , 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155, or Anti-Terra-U, 203, 204, or BYK. -P104, P104S, 220S, 6919, or Lactimon, Lactimon-WS or Bykumen, etc., SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000 manufactured by Lubrizol Japan. , 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, EFKA-46, 47, 48, manufactured by BASF. 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc., Azino PA111, PB711, PB821, PB822, PB824 manufactured by Ajinomoto Fine-Techno Co., Inc. Etc.

As the surfactant, sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkylnaphthalenesulfonate, sodium alkyldiphenyletherdisulfonate. Anionic surfactants such as lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, stearic acid monoethanolamine, styrene-acrylic acid copolymer monoethanolamine, and polyoxyethylene alkyl ether phosphate ester; Nonionic surfactants such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate; alkyl Chaotic surfactants such as quaternary ammonium salts and ethylene oxide adducts thereof; amphoteric surfactants such as alkylbetaine such as alkyldimethylaminoacetic acid betaine and alkylimidazoline; and these may be used alone or in combination of two or more. Although they can be used as a mixture, they are not necessarily limited thereto.

When a resin-type dispersant and a surfactant are added, from the viewpoint of the effect on dispersion, it is preferably 0.1 to 55 parts by mass, more preferably 0.1 to 45 parts by mass, relative to 100 parts by mass of the colorant. Is.

The coloring composition of the present invention can be used as a photosensitive coloring composition for a color filter by further adding a photopolymerizable monomer and/or a photopolymerization initiator. Furthermore, the coloring composition of the present invention may contain a sensitizer, a polyfunctional thiol, an amine compound, a leveling agent, a curing agent, a curing accelerator, and other additive components.

<Photopolymerization initiator>
The coloring composition of the present invention may contain a photopolymerization initiator. The amount of the photopolymerization initiator used is preferably 5 to 400 parts by mass, based on the total mass of the colorant (100 parts by mass), and 10 to 300 parts by mass from the viewpoint of photocurability. More preferably.

A conventionally known polymerization initiator can be used as the photopolymerization initiator. Specifically, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzylmethylketal, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone , 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butane , Oligo[2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone], 2-hydroxy-1-[4-[4-(2-hydroxy-2-methylpropionyl)benzyl ]Phenyl]-2-acetophenones such as 2-methylpropan-1-one; benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; 2,4,6-trimethylbenzoyl-diphenyl- Examples thereof include phosphines such as phosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide; and phenylglyoxylic methyl ester. More specifically, Irgacure 651, Irgacure 184, Darocur 1173, Irgacure 500, Irgacure 1000, Irgacure 2959, Irgacure 907, Irgacure 369, Irgacure 379, Irgacure 1700, Irgacure 149, Irgac Cure 1800, Irgacure 1850, Irgacure 819, Irgacure 784, Irgacure 261, Irgacure OXE-01, Irgacure OXE-02 (BASF), Adeka Optimer N1717, Adeka Optimer N1919, Adeka Arcules NCI-. 831 (ADEKA), Esacure 1001M (Lamberti), Japanese Patent Publication No. 59-1281, Japanese Patent Publication No. 61-9621 and Japanese Patent Publication No. 60-60104, and triazine derivatives described in Japanese Patent Publication No. 59-1504 and Organic peroxides described in JP-A-61-243807, JP-B-43-23684, JP-B-44-6413, JP-B-47-1604, and diazonium compound described in USP No. 3567453. , U.S. Pat. No. 2,848,328, U.S. Pat. No. 2,852,379, and U.S. Pat. No. 2,940,853, organic azide compounds, JP-B-36-22062, JP-B-37-13109, JP-B-38-18015. And ortho-quinone diazides described in JP-B-45-9610, JP-B-55-39162, JP-A-59-140203 and "MACROMOLECULES", Volume 10, p. 1307 ( (1977) various onium compounds including iodonium compounds, azo compounds described in JP-A-59-142205, JP-A-1-54440, EP-109851, EP-126712. , “Journal of Imaging Science (J.IMAG.SCI.)”, Volume 30, p. 174 (1986), metal allene complexes, and titanocenes described in JP-A-61-151197. Containing transition metals such as ruthenium described in "COORDINATION CHEMISTRY REVIEW", Vol. 84, pp. 85-277 (1988) and JP-A-2-182701. Transition metal complex, an aluminate complex described in JP-A-3-209477, a borate compound described in JP-A-2-157760, JP-A-55-127550 and JP-A-60-202437. 2,4,5-triarylimidazole dimer, carbon tetrabromide, an organic halogen compound described in JP-A-59-107344, a sulfonium complex or an oxosulfonium complex described in JP-A-5-255347, JP-A-54-99185, JP-A-63-264560 and JP-A-10-29977, aminoketone compounds, JP-A-2001-264530, JP-A-2001-261761 and JP-A-2000-80068. JP-A-2001-233842, JP-T-2004-534797, JP-A-2006-342166, JP-A-2008-094770, JP-A-2009-40762, JP-A-2010-15025, JP-A-2010-189279, JP-A-2010. -189280 publication, special table 2010-526846, special table 2010-527338, special table 2010-527339, USP3558309 specification (1971), USP4202697 specification (1980) and JP-A-61-255858. Examples include oxime ester compounds.

These photopolymerization initiators may be used alone or as a mixture of two or more kinds at an arbitrary ratio according to need.

<Photopolymerizable monomer>
The photopolymerizable monomer of the present invention includes a monomer or oligomer that is cured by ultraviolet rays or heat to produce a transparent resin, and these can be used alone or in combination of two or more.

Examples of the monomer or oligomer that is cured by ultraviolet rays or heat to form a transparent resin include polyethylene glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, epoxy (meth). Acrylate, EO-modified bisphenol A di(meth)acrylate, 1,4-butanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth) Acrylate, polyester (meth)acrylate, trimethylolpropane tri(meth)acrylate, tris(acryloxyethyl)isocyanurate, tris(methacryloxyethyl)isocyanurate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth) ) Acrylate, caprolactone-modified dipentaerythritol hexaacrylate, ditrimethylolpropane tetra(meth)acrylate, epoxy acrylate, pentaerythritol tetra(meth)acrylate, and various other acrylic acid esters and methacrylic acid esters, (meth)acrylic acid, styrene, acetic acid Examples thereof include vinyl, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N-hydroxymethyl(meth)acrylamide, N-vinylformamide, acrylonitrile, but the effect of the present invention is not limited to these. It is not something that will be done.

Further, the photopolymerizable monomer may contain an acid group. For example, esterification products of free hydroxyl group-containing poly(meth)acrylates of polyhydric alcohols and (meth)acrylic acid with dicarboxylic acids; esterification products of polyhydric carboxylic acids with monohydroxyalkyl (meth)acrylates, etc. Can be mentioned. Specific examples include trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, and other monohydroxyoligoacrylates or monohydroxyoligomethacrylates. And a free carboxyl group-containing monoester of dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, and terephthalic acid; propane-1,2,3-tricarboxylic acid (tricarballylic acid), butane-1,2,4 -Tricarboxylic acids such as tricarboxylic acid, benzene-1,2,3-tricarboxylic acid, benzene-1,3,4-tricarboxylic acid, benzene-1,3,5-tricarboxylic acid and 2-hydroxyethyl acrylate, 2- Examples include monohydroxy monoacrylates such as hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, and 2-hydroxypropyl methacrylate, and free carboxyl group-containing oligoesterification products with monohydroxy monomethacrylates, but the effect of the present invention is limited to these. It is not something that will be done.

The content of the photopolymerizable monomer is preferably 10 to 300 parts by mass, and further 10 to 200 parts by mass with respect to 100 parts by mass of the colorant from the viewpoint of photocurability and developability. It is preferable.

<Sensitizer>
Further, the coloring composition of the present invention may contain a sensitizer.
Examples of the sensitizer include benzophenone derivatives, chalcone derivatives, unsaturated ketone derivatives represented by dibenzalacetone, 1,2-diketone derivatives represented by benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives. , Anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonole derivatives, and other polymethine dyes, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, Indoline derivative, azulene derivative, azurenium derivative, squarylium derivative, porphyrin derivative, tetraphenylporphyrin derivative, triarylmethane derivative, tetrabenzoporphyrin derivative, tetrapyrazinoporphyrazine derivative, phthalocyanine derivative, tetraazaporphyrazine derivative, tetraquinoxalylo Examples include porphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphyllin derivatives, annulene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, and organic ruthenium complexes. However, the present invention is not limited to these.

More specific examples include Nobu Okawara et al., "Dye Handbook" (1986, Kodansha), Nobu Okawara et al., "Chemistry of Functional Dyes" (1981, CMC), Tadasaburo Ikemori et al., Special Functional materials" (1986, CMC), but are not limited to these, and other dyes and sensitizers that absorb light in the ultraviolet to near infrared region. Sensitizers may be mentioned, and two or more of them may be used in an arbitrary ratio as required. Among the above-mentioned sensitizers, thioxanthone derivatives include 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone and 1-chloro-4-propoxythioxanthone. And the like. Examples of benzophenones include benzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, 4,4′-dimethylbenzophenone, 4,4′-dimethoxybenzophenone, 4,4′-bis. Examples thereof include (diethylamino)benzophenone, coumarins such as coumarin 1, coumarin 338, and coumarin 102. Examples of ketocoumarins include 3,3′-carbonylbis(7-diethylaminocoumarin). However, the present invention is not limited to these.

Two or more kinds of sensitizers may be used in an arbitrary ratio, if necessary. The compounding amount of the sensitizer is preferably 3 to 60 parts by mass with respect to 100 parts by mass of the total mass of the photopolymerization initiator (E) contained in the colored photosensitive composition, and photocuring is performed. From the viewpoint of sex, it is more preferably 5 to 50 parts by mass.

<Multifunctional thiol>
The coloring composition of the present invention may contain a polyfunctional thiol that functions as a chain transfer agent.
The polyfunctional thiol may be a compound having two or more thiol groups, and examples thereof include hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, and ethylene. Glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris(5-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, Pentaerythritol tetrakisthiopropionate, tris(2-hydroxyethyl) isocyanurate trimercaptopropionate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2-(N,N- Dibutylamino)-4,6-dimercapto-s-triazine and the like can be mentioned.
These polyfunctional thiols can be used singly or as a mixture of two or more kinds at an arbitrary ratio according to need.

The content of the polyfunctional thiol is preferably 0.1 to 30% by mass, and more preferably 1 to 20% by mass, based on the mass (100% by mass) of the total solid content of the coloring composition. If the content of the polyfunctional thiol is less than 0.1% by mass, the effect of adding the polyfunctional thiol is insufficient, and if it exceeds 30% by mass, the sensitivity is too high and the resolution is decreased.

<Amine compound>
In addition, the coloring composition of the present invention may contain an amine compound having a function of reducing dissolved oxygen. Examples of such amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminobenzoate. Ethyl, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethylparatoluidine and the like can be mentioned.

<Leveling agent>
In order to improve the leveling property of the composition on the transparent substrate, it is preferable to add a leveling agent to the colored composition of the present invention. As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure in its main chain is preferable. Specific examples of dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Toray Dow Corning Co., and BYK-333 manufactured by BYK Chemie. Specific examples of dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by BYK Chemie. Dimethylsiloxane having a polyether structure in the main chain and dimethylsiloxane having a polyester structure in the main chain can be used together. The content of the leveling agent is usually preferably 0.003 to 0.5 mass% in the total 100 mass% of the coloring composition.

Particularly preferred as a leveling agent is a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, which has a small hydrophilicity even though having a hydrophilic group, when added to the coloring composition, It has the characteristic of low surface tension lowering ability, and it is useful that it has good wettability to the glass plate in spite of the low surface tension lowering ability. Those that can sufficiently suppress the charging property can be preferably used. As a leveling agent having such preferable properties, dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used. Polyalkylene oxide units include polyethylene oxide units and polypropylene oxide units, and dimethylpolysiloxane may have both polyethylene oxide units and polypropylene oxide units.

In addition, the bonding form of the polyalkylene oxide unit with dimethylpolysiloxane includes a pendant type in which the polyalkylene oxide unit is bonded in the repeating unit of dimethylpolysiloxane, a terminal modified type in which the end of dimethylpolysiloxane is bonded, and dimethylpolysiloxane. It may be of a linear block copolymer type in which alternately and repeatedly bonded. Dimethylpolysiloxane having a polyalkylene oxide unit is commercially available from Toray Dow Corning Co., Ltd., for example, FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, FZ. -207, but not limited thereto.

Anionic, cationic, nonionic or amphoteric surfactants can be supplementarily added to the leveling agent. Two or more kinds of surfactants may be mixed and used.

Examples of anionic surfactants that are supplementarily added to the leveling agent include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkylnaphthalenesulfonate, and alkyldiphenyletherdisulfonic acid. Sodium, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate Examples thereof include esters.

Examples of the chaotic surfactant that is supplementarily added to the leveling agent include alkyl quaternary ammonium salts and ethylene oxide adducts thereof. Nonionic surfactants that are supplementarily added to the leveling agent include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene sorbitan monostearate. Examples thereof include polyethylene glycol monolaurate and the like; amphoteric surfactants such as alkylbetaine such as alkyldimethylaminoacetic acid betaine and alkylimidazoline, and fluorine-based and silicone-based surfactants.

<Curing agent, curing accelerator>
Further, the coloring composition of the present invention may contain a curing agent, a curing accelerator, etc., if necessary, in order to assist the curing of the thermosetting resin. As the curing agent, phenolic resins, amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds, etc. are effective, but are not particularly limited to these, and thermosetting resins Any curing agent may be used as long as it can react with. Among these, compounds having two or more phenolic hydroxyl groups in one molecule and amine curing agents are preferable. Examples of the curing accelerator include amine compounds (eg, dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl). -N,N-dimethylbenzylamine etc.), quaternary ammonium salt compound (eg triethylbenzylammonium chloride etc.), blocked isocyanate compound (eg dimethylamine etc.), imidazole derivative bicyclic amidine compound and salts thereof (eg Imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2- Ethyl-4-methylimidazole etc.), phosphorus compounds (eg triphenylphosphine etc.), guanamine compounds (eg melamine, guanamine, acetoguanamine, benzoguanamine etc.), S-triazine derivatives (eg 2,4-diamino-6). -Methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine/isocyanuric acid adduct, 2,4-diamino-6- Methacryloyloxyethyl-S-triazine/isocyanuric acid adduct) and the like can be used. These may be used alone or in combination of two or more. The content of the curing accelerator is preferably 0.01 to 15 parts by mass with respect to 100 parts by mass of the thermosetting resin.

<Other additive components>
The colored composition of the present invention may contain a storage stabilizer in order to stabilize the viscosity of the composition over time. Further, an adhesion improver such as a silane coupling agent may be contained in order to improve the adhesion to the transparent substrate.

Examples of storage stabilizers include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and their methyl ethers, t-butylpyrocatechol, tetraethylphosphine, tetraphenylphosphine and the like. Examples thereof include organic phosphine and phosphite. The storage stabilizer can be used in an amount of 0.1 to 10 parts by mass based on 100 parts by mass of the total amount of the colorant.

Examples of the adhesion improver include vinyl silanes such as vinyltris(β-methoxyethoxy)silane, vinylethoxysilane, and vinyltrimethoxysilane, (meth)acrylsilanes such as γ-methacryloxypropyltrimethoxysilane, β-(5, 4-epoxycyclohexyl)ethyltrimethoxysilane, β-(5,4-epoxycyclohexyl)methyltrimethoxysilane, β-(5,4-epoxycyclohexyl)ethyltriethoxysilane, β-(5,4-epoxycyclohexyl) Epoxysilanes such as methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β(aminoethyl)γ-aminopropyltrimethoxysilane, N-β(amino Ethyl)γ-aminopropyltriethoxysilane, N-β(aminoethyl)γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-amino Examples of the silane coupling agent include aminosilanes such as propyltrimethoxysilane and N-phenyl-γ-aminopropyltriethoxysilane, and thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane. The adhesion improver can be used in an amount of 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, based on 100 parts by mass of the total amount of the coloring agent in the coloring composition.

<Removal of coarse particles>
The colored composition of the present invention is mixed with coarse particles of 5 μm or more, preferably 1 μm or more, more preferably 0.5 μm or more and coarse particles by means of centrifugation, a sintering filter, a membrane filter or the like. It is preferable to remove dust. As described above, it is preferable that the coloring composition does not substantially contain particles of 0.5 μm or more. It is more preferably 0.3 μm or less.

<Color filter>
Next, the color filter of the present invention will be described. The color filter of the present invention comprises at least one red filter segment, at least one green filter segment, and at least one blue filter segment.
Further, the color filter may further include a magenta color filter segment, a cyan color filter segment, and a yellow color filter segment.

As a substrate such as a transparent substrate that constitutes a color filter, a glass plate such as soda lime glass, low alkali borosilicate glass, or alkali-free aluminoborosilicate glass, or a resin plate such as polycarbonate, polymethylmethacrylate, or polyethylene terephthalate. Used. In addition, a transparent electrode made of indium oxide, tin oxide, or the like may be formed on the surface of the glass plate or the resin plate for driving the liquid crystal after paneling.

<Method of manufacturing color filter>
The color filter of the present invention can be manufactured by a printing method or a photolithography method.
Since the formation of the filter segment by the printing method can be patterned by simply printing and drying the coloring composition prepared as the printing ink, the manufacturing method of the color filter is low cost and excellent in mass productivity. There is. Furthermore, the development of printing technology enables printing of fine patterns having high dimensional accuracy and smoothness. For printing, it is preferable that the composition is such that the ink does not dry and solidify on the printing plate or on the blanket. Further, it is important to control the fluidity of the ink on the printing machine, and the ink viscosity can be adjusted by the dispersant and the extender pigment.

When the filter segment is formed by a photolithography method, the coloring composition prepared as the solvent-developing or alkali-developing colored resist material is applied on a transparent substrate by spray coating, spin coating, slit coating, roll coating, or the like. Depending on the method, it is applied so that the dry film thickness is 0.2 to 5 μm. If necessary, the dried film is exposed to ultraviolet light through a mask having a predetermined pattern, which is provided in contact or non-contact with the film. Then, after immersing in a solvent or an alkaline developer or spraying a developer with a spray or the like to remove the uncured portion to form a desired pattern, the same operation is repeated for other colors to produce a color filter. be able to. Furthermore, in order to accelerate the polymerization of the colored resist material, heating can be carried out if necessary. According to the photolithography method, it is possible to manufacture a color filter with higher accuracy than the above printing method.

Upon development, an aqueous solution of sodium carbonate, sodium hydroxide or the like is used as an alkali developing solution, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Further, an antifoaming agent or a surfactant can be added to the developing solution. In order to increase the UV exposure sensitivity, after coating and drying the above colored resist material, a water-soluble or alkaline water-soluble resin such as polyvinyl alcohol or water-soluble acrylic resin is applied and dried to form a film that prevents polymerization inhibition by oxygen. After that, ultraviolet exposure can be performed.

The color filter of the present invention can be produced by an electrodeposition method, a transfer method, an inkjet method or the like in addition to the above method, and the coloring composition of the present invention can be used in any method. The electrodeposition method is a method for producing a color filter by utilizing a transparent conductive film formed on a substrate to form each color filter segment on the transparent conductive film by electrophoretic deposition of colloidal particles. .. The transfer method is a method in which a filter segment is formed in advance on the surface of a peelable transfer base sheet and the filter segment is transferred to a desired substrate.

A black matrix can be formed in advance before forming each color filter segment on the transparent substrate or the reflective substrate. As the black matrix, chromium, a chromium/chromium oxide multilayer film, an inorganic film such as titanium nitride, or a resin film in which a light shielding agent is dispersed is used, but the black matrix is not limited thereto. It is also possible to previously form a thin film transistor (TFT) on the transparent substrate or the reflective substrate and then form each color filter segment. In addition, an overcoat film, a transparent conductive film, or the like is formed on the color filter of the present invention as needed.

The color filter is attached to the counter substrate using a sealant, liquid crystal is injected from the injection port provided in the sealing section, and then the injection port is sealed. If necessary, a polarizing film or a retardation film is placed on the outside of the substrate. A liquid crystal display panel is manufactured by pasting.

Such liquid crystal display panels include twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), vertical alignment (VA), and optically convenced bend (OCB). It can be used in a liquid crystal display mode in which colorization is performed using a color filter such as.

Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. In addition, in an example, "part" and "%" represent a "mass part" and "mass %", respectively. Further, “PGMAC” means propylene glycol monomethyl ether acetate.

(Polymerization average molecular weight (Mw))
The polymerization average molecular weight (Mw) of the resin is a polystyrene conversion measured by using TSKgel column (manufactured by Tosoh Corporation) and GPC equipped with an RI detector (manufactured by Tosoh Corporation, HLC-8120GPC) using THF as a developing solvent. It is a weight average molecular weight (Mw).

(Acid value of resin)
To 0.5 to 1.0 part of the resin solution, 80 ml of acetone and 10 ml of water were added and stirred to be uniformly dissolved, and a 0.1 mol/L KOH aqueous solution was used as a titration liquid to prepare an automatic titrator (“COM-555”). (Manufactured by Hiranuma Sangyo), and the acid value of the resin solution was measured. Then, the acid value per solid content of the resin was calculated from the acid value of the resin solution and the solid content concentration of the resin solution.

(Number of halogen substitution of pigment)
The number of halogen substitutions in the pigment was analyzed by ion chromatography (ICS-2000 ion chromatography, manufactured by DIONEX) of a liquid obtained by burning the pigment by an oxygen combustion flask method and absorbing the combustion product in water. It was obtained by quantifying the amount of halogen and converting it into the number of halogen substitutions.

(Halogen distribution width of pigment)
The halogen distribution width in the pigment was determined using a time-of-flight mass spectrometer (autoflex III (TOF-MS), manufactured by Bruker Daltonics). In the mass spectrum obtained by mass spectrometric analysis of the pigment powder, the halogen content is the signal intensity of each molecular ion peak corresponding to each component (each peak value) and the value obtained by integrating each peak value (all peak values). Was calculated and calculated from the ratio of each peak value to the total peak value. The halogen distribution width was defined as the halogen distribution width by counting the number of peaks in which the ratio of each peak value to all peak values was 1% or more.

<Method for producing binder resin>
(Preparation of acrylic resin solution 1)
70.0 parts of cyclohexanone was charged into a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirrer in a separable four-necked flask, the temperature was raised to 80° C., the inside of the reaction vessel was replaced with nitrogen, and then a dropping tube From n-butyl methacrylate 13.3 parts, 2-hydroxyethyl methacrylate 4.6 parts, methacrylic acid 4.3 parts, paracumylphenol ethylene oxide modified acrylate (Toagosei Co., Ltd. "Aronix M110") 7.4 parts, A mixture of 0.4 parts of 2,2′-azobisisobutyronitrile was added dropwise over 2 hours. After the dropping was completed, the reaction was continued for another 3 hours to obtain a solution of an acrylic resin having a weight average molecular weight (Mw) of 26000. After cooling to room temperature, about 2 g of the resin solution was sampled and dried by heating at 180° C. for 20 minutes to measure the non-volatile content, and the non-volatile content was adjusted to 20% by mass in the resin solution synthesized above. Acrylic resin solution 1 was prepared by adding ether acetate.

(Preparation of acrylic resin solution 2)
207 parts of cyclohexanone was charged into a reaction container equipped with a thermometer, a cooling pipe, a nitrogen gas introduction pipe, a dropping pipe and a stirring device in a separable 4-neck flask, heated to 80° C., and the inside of the reaction container was replaced with nitrogen, and then dropped. From the tube, 20 parts of methacrylic acid, 20 parts of paracumylphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 45 parts of methyl methacrylate, 8.5 parts of 2-hydroxyethyl methacrylate, and 2,2'-azobis. A mixture of 1.33 parts of isobutyronitrile was added dropwise over 2 hours. After the dropping was completed, the reaction was continued for another 3 hours to obtain a copolymer resin solution. Next, with respect to the total amount of the obtained copolymer solution, nitrogen gas was stopped, and after stirring while injecting dry air for 1 hour, the mixture was cooled to room temperature, and then 2-methacryloyloxyethyl isocyanate (Karenzu manufactured by Showa Denko KK) A mixture of 6.5 parts of MOI), 0.08 part of dibutyltin laurate, and 26 parts of cyclohexanone was added dropwise at 70° C. over 3 hours. After the dropping was completed, the reaction was continued for another hour to obtain a solution of acrylic resin. After cooling to room temperature, about 2 parts of the resin solution was sampled, dried by heating at 180° C. for 20 minutes to measure the nonvolatile content, and cyclohexanone was added to the resin solution synthesized above so that the nonvolatile content became 20% by weight. Then, an acrylic resin solution 2 was prepared. The weight average molecular weight (Mw) was 18,000.

<Adjustment of resin type dispersant>
(Preparation of resin type dispersant 1)
A commercially available resin type dispersant “BYK-21116” manufactured by BYK Chemie was used as the resin type dispersant 1.

(Preparation of resin type dispersant solution 2)
A commercially available resin-type dispersant, EFKA4300 manufactured by BASF Corp., and propylene glycol monomethyl ether acetate were mixed to prepare a solution having a nonvolatile content of 40% by mass to obtain a resin-type dispersant solution 2.

<Method for producing quinophthalone compound [A]>
Prior to the production of the quinophthalone compound, a method for identifying the quinophthalone compound used in the present invention will be described.

(Method for identifying quinophthalone compound)
The quinophthalone compound of the present invention was identified by ACQUITY UPLS H-Class (Water column: ACQUITY UPLC BEH C18 Column 130Å, 1.7 μm, 2.1 mm×50 mm)/Ms TAP XEVO TQD molecular mass spectrum. The obtained compound was identified based on the agreement between the ion peak and the mass number obtained by calculation. The theoretical value and measured value of each are summarized in Table 1.

[Example 1]
(Production of quinophthalone compound A-1)

Methyl benzoate (30 parts), benzoic acid (30 parts), 8-aminoquinaldine (10 parts) and phthalic anhydride (20.6 parts) were added, and the mixture was heated to 180° C. and stirred for 6 hours while distilling off water. After cooling to room temperature, the reaction mixture was added to 500 parts of methanol and stirred at room temperature for 1 hour. The precipitated crystals were separated by filtration and then washed with methanol to obtain a cake. Subsequently, 100 parts of isobutanol and 14.9 parts of dimethylpropylamine were added to the above cake, heated to 100° C., and stirred for 6 hours while distilling methanol off. After cooling to room temperature, the reaction mixture was added to 500 parts of methanol and stirred at room temperature for 1 hour. The precipitated crystals were separated by filtration, washed with methanol, and dried under reduced pressure to give Intermediate 1 (15.5 parts, yield 85%).
Cyanuric chloride (9.9 parts) and acetone (1000 parts) were added, and the mixture was stirred while cooling in an ice bath. Thereto, 15.5 parts of Intermediate 1 was dissolved in 1000 parts of N-methylpyrrolidone and added dropwise to a solution of cyanuric chloride over 1 hour. After stirring for 3 hours between 5°C and 15°C, 20.5 parts of sulfanilic acid was added, and the mixture was heated to 85°C and stirred for 5 hours. After cooling to room temperature, the reaction mixture was poured into 3000 parts of water and stirred at room temperature for 1 hour. The precipitated crystals were separated by filtration, washed with water and methanol, and dried under reduced pressure to obtain 24.5 parts (yield 64%) of compound A-1.

[Example 2]
(Production of quinophthalone compound A-2)

In the synthesis reaction of Intermediate 1, the same reaction was performed except that 20.6 parts of phthalic anhydride was changed to 27.6 parts of 2,3-naphthalenedicarboxylic anhydride, and 19.5 parts of Intermediate 2 The rate was 91%).
10.6 parts of cyanuric chloride and 1000 parts of acetone were added, and the mixture was stirred while cooling in an ice bath. Thereto, 19.5 parts of Intermediate 2 was dissolved in 1000 parts of N-methylpyrrolidone and added dropwise to a solution of cyanuric chloride over 1 hour. After stirring for 3 hours between 5°C and 15°C, 10.0 parts of sulfanilic acid was added, heated to 50°C, and stirred for 3 hours. Next, 6.5 parts of aniline was added, heated to 85° C., and stirred for 2 hours. After cooling to room temperature, the reaction mixture was poured into 3000 parts of water and stirred at room temperature for 1 hour. The precipitated crystals were separated by filtration, washed with water and methanol, and dried under reduced pressure to obtain 26.3 parts (yield 67%) of compound A-2.

[Example 3]
(Production of quinophthalone compound A-3)

In the synthetic reaction of Intermediate 1, 10 parts of 8-aminoquinaldine was added to 10 parts of 6-bromo-8-aminoquinaldine, 13.7 parts of 20.6 parts of phthalic anhydride and 14.9 parts of dimethylpropylamine. The same reaction was performed except that the amount was changed to 9.9 parts to obtain 13.6 parts (yield 88%) of Intermediate 3.
In the synthetic reaction of compound A-2, 19.5 parts of Intermediate 2 was converted to 13.6 parts of Intermediate 3, 6.8 parts of 10.6 parts of cyanuric chloride, and 10.0 parts of sulfanilic acid were added to 4-(aminomethyl)benzoic acid. The same reaction was performed except that 5.6 parts of acid and 6.5 parts of aniline were changed to 7.1 parts of 8-hydroxyquinaldine to obtain 19.6 parts (yield 70%) of compound A-3.

[Example 4]
(Production of quinophthalone compound A-4)
In the synthetic reaction of the intermediate 1, 10 parts of 8-aminoquinaldine was added to 5 parts, 20.6 parts of phthalic anhydride was added to 13.7 parts of tetrabromophthalic anhydride, and 14.9 parts of dimethylpropylamine was added to 7.4 parts. The same reaction was performed except that the amount was changed to 1 part, and 16.0 parts (yield 84%) of intermediate 4 was obtained.
In the synthetic reaction of compound A-2, 19.5 parts of Intermediate 2 was converted to 16.0 parts of Intermediate 4, 10.6 parts of cyanuric chloride was 4.9 parts, and 10.0 parts of sulfanilic acid was added to 4-methylphenol.2. The same reaction was performed except that 9 parts and 6.5 parts of aniline were changed to 3.5 parts of 4-aminophenol to obtain 16.9 parts (yield 71%) of Intermediate 5.
Intermediate 5 (16.9 parts), sodium hydroxide (0.9 parts) and N-methylpyrrolidone (400 parts) were added, and the mixture was heated to 130° C., and 1,3-propanesultone (2.8 parts) was added, and the mixture was heated with stirring for 5 hours. After cooling to room temperature, the reaction mixture was added to 800 parts of methanol and stirred at room temperature for 1 hour. The precipitated crystals were separated by filtration, washed with methanol, and dried under reduced pressure to obtain 13.8 parts (yield 72%) of compound A-4.

[Example 5]
(Production of quinophthalone compound A-5)

Methyl benzoate (30 parts), benzoic acid (30 parts), 6-nitro-8-hydroxyquinaldine (10 parts) and phthalic anhydride (8.7 parts) were added, and the mixture was heated to 180°C and stirred for 6 hours while distilling water. .. After cooling to room temperature, the reaction mixture was added to 500 parts of methanol and stirred at room temperature for 1 hour. The precipitated crystals were separated by filtration, washed with methanol, and dried under reduced pressure to obtain 14.4 parts (yield 88%) of intermediate 6.
In the synthetic reaction of Compound A-1, 15.5 parts of Intermediate 1 was 14.4 parts of Intermediate 6, 8.0 parts of 9.9 parts of cyanuric chloride, and 20.5 parts of sulfanilic acid were added to 4-aminophthalic acid. The same reaction was performed except for changing to 2 parts to obtain 23.0 parts (yield 70%) of Compound A-5.

[Example 6]
(Production of quinophthalone compound A-6)

In the synthetic reaction of Intermediate 6, 10 parts of 6-nitro-8-hydroxyquinaldine was added to 10 parts of 8-hydroxyquinaldine, and 20.6 parts of phthalic anhydride was added to 16.4 parts of 4,5-dichlorophthalic anhydride. The same reaction was carried out except that the above was changed to 1 to obtain 19.1 parts (yield 85%) of intermediate 7.
In the synthetic reaction of compound A-2, 19.5 parts of Intermediate 2 was converted into 16.4 parts of Intermediate 7, 10.6 parts of cyanuric chloride was 9.9 parts, and 10.0 parts of sulfanilic acid was added to 4-aminophthalic acid. The same reaction was performed except that 7 parts and 6.5 parts of aniline were changed to 4.9 parts of 2-methoxyethanol to obtain 26.2 parts (yield 71%) of compound A-6.

[Example 7]
(Production of quinophthalone compound A-7)
8-Aminoquinaldine (10 parts), methanol (100 parts), sodium carbonate (5 parts) and 4-acetamidobenzenesulfonyl chloride (17.7 parts) were added, and the mixture was stirred at 25°C to 35°C for 4 hr. 70 parts of water and 20 parts of 35% hydrochloric acid were added there, and it heat-stirred at 80 degreeC for 2 hours. After cooling to room temperature, the reaction mixture was put into 200 parts of water and stirred at room temperature for 1 hour. The precipitated crystals were separated by filtration, washed with water, and dried under reduced pressure to obtain 18.6 parts (yield 94%) of intermediate 8.
In the synthesis reaction of Intermediate 1, 10 parts of 8-aminoquinaldine was added to 810 parts of Intermediate, 20.6 parts of phthalic anhydride was added to 20.1 parts of tetrachlorophthalic anhydride, and 14.9 parts of dimethylpropylamine. The same reaction was performed except that the amount was changed to 7.5 parts, and 16.5 parts (yield 89%) of intermediate 9 was obtained.
In the synthetic reaction of compound A-1, 15.5 parts of intermediate 1 was intermediate 16.5 parts, cyanuric chloride 9.9 parts was 5.2 parts, sulfanilic acid 20.5 parts was 5-aminosalicylic acid 9. The same reaction was performed except that the amount was changed to 6 parts to obtain 22.4 parts (yield: 82%) of compound A-7.

[Example 8]
(Production of quinophthalone compound A-8)
8-Aminoquinaldine (10 parts), methanol (100 parts), sodium carbonate (5 parts) and 4-hydroxybenzenesulfonyl chloride (14.6 parts) were added, and the mixture was stirred at 25°C to 35°C for 4 hr. The reaction mixture was poured into 200 parts of water and stirred at room temperature for 1 hour. The precipitated crystals were separated by filtration, washed with water, and dried under reduced pressure to give Intermediate 10 (18.9 parts, yield 95%).
In the synthesis reaction of intermediate 6, except that 10 parts of 6-nitro-8-hydroxyquinaldine was changed to 10 parts of intermediate 10 and 8.7 parts of phthalic anhydride was changed to 11.0 parts of tetrachlorophthalic anhydride. The same reaction was performed to obtain 16.9 parts (yield 91%) of Intermediate 11.
In the synthetic reaction of compound A-1, 15.5 parts of intermediate 1 was intermediated with 16.9 parts of intermediate 11, 5.3 parts of 9.9 parts of cyanuric chloride, and 20.5 parts of sulfanilic acid were added to 9 parts of 4-hydroxysalicylic acid. The same reaction was carried out except that the amount was changed to 8 parts to obtain 18.1 parts (yield 65%) of Compound A-7.

[Example 9]
(Production of quinophthalone compound A-9)

In the synthetic reaction of compound A-2, 19.5 parts of Intermediate 2 was converted to 15.0 parts of Intermediate 9, 10.6 parts of cyanuric chloride was 4.8 parts, 10.0 parts of sulfanilic acid was 4.5 parts and aniline. The same reaction was performed except that 6.5 parts was changed to 2.9 parts to obtain 19.5 parts (yield: 82%) of compound A-9.

[Example 10]
(Production of quinophthalone compound A-10)

In the synthetic reaction of compound A-2, 19.5 parts of Intermediate 2 was used as 15.0 parts of Intermediate 9, 10.6 parts of cyanuric chloride as 4.8 parts, and 10.0 parts of sulfanilic acid as 5-aminosalicylic acid. The same reaction was performed except that 0 parts and 6.5 parts of aniline were changed to 3.4 parts of 4-aminophenol to obtain 19.7 parts (yield 83%) of Compound A-10.

[Example 11]
(Production of quinophthalone compound A-11)
In the synthesis reaction of Intermediate 9, 10 parts of Intermediate 8 was changed to 15 parts, 20.1 parts of tetrachlorophthalic anhydride was changed to 15.6 parts of phthalic anhydride, and 7.5 parts of dimethylpropylamine was changed to 11.3 parts. Other than that, the same reaction was carried out to obtain 18.9 parts (yield 89%) of intermediate 12.
In the synthetic reaction of compound A-1, 15.5 parts of Intermediate 1 was converted into 15 parts of Intermediate 12, 6.2 parts of 9.9 parts of cyanuric chloride, 20.5 parts of sulfanilic acid and 10.3 of 4-hydroxybenzoic acid. The reaction was performed in the same manner except that the amount was changed to 1 part, and 17.5 parts (yield 65%) of compound A-11 was obtained.

[Example 12]
(Production of quinophthalone compound A-12)

In the synthetic reaction of compound A-2, 19.5 parts of Intermediate 2 was used as 15.0 parts of Intermediate 9, 10.6 parts of cyanuric chloride as 4.8 parts, and 10.0 parts of sulfanilic acid as 5-aminosalicylic acid. The same reaction was performed except that 0 part and 6.5 parts of aniline were changed to 30.0 parts of water to obtain 17.9 parts (yield 84%) of Compound A-12.

[Example 13]
(Production of quinophthalone compound A-13)
In the synthetic reaction of Intermediate 9, 10 parts of Intermediate 8, 11.0 parts of tetrachlorophthalic anhydride, 20.9 parts of 2,3-naphthalenedicarboxylic acid anhydride, and 7.5 parts of dimethylpropylamine were used. The same reaction was performed except that the amount was changed to 0.3 part to obtain 21.7 parts (yield 92%) of intermediate 13.
In the synthetic reaction of compound A-2, 19.5 parts of Intermediate 2 was added with 15.0 parts of Intermediate 13, 5.6 parts of 10.6 parts of cyanuric chloride, 10.0 parts of sulfanilic acid and 5-aminosalicylic acid. The same reaction was performed except that 7 parts and 6.5 parts of aniline were changed to 4.6 parts of taurine, to obtain 21.9 parts (yield 85%) of Compound A-13.

[Example 14]
(Production of quinophthalone compound A-14)
In the synthetic reaction of the intermediate 8, 10 parts of 8-aminoquinaldine, 10 parts of 1-amino-3-methylbenzoquinoline, 5.0 parts of sodium carbonate, 4.0 parts of 4-acetamidobenzenesulfonyl chloride 17 The same reaction was carried out except that 0.7 part was changed to 13.5 parts to obtain 16.1 parts (yield 92%) of intermediate 14.
In the synthetic reaction of Intermediate 9, 10 parts of Intermediate 8 were added, 15 parts of Intermediate 14 were added, 11.0 parts of tetrachlorophthalic anhydride were added with 13.5 parts of phthalic anhydride, and 7.5 parts of dimethylpropylamine were added with 9.7 parts. The same reaction was carried out except that the above was changed to 19.14 parts (yield 94%) of Intermediate 15.
In the synthetic reaction of compound A-2, 19.5 parts of Intermediate 2 was intermediated with 15.0 parts of Intermediate 15, 10.6 parts of cyanuric chloride was 5.6 parts, and 10.0 parts of sulfanilic acid was hydroquinone potassium monosulfate. The same reaction was performed except that 0 parts and 6.5 parts of aniline were changed to 6.2 parts of 4-phenylphenol to obtain 12.7 parts (yield 45%) of Compound A-14.

[Example 15]
(Production of quinophthalone compound A-15)

In the synthetic reaction of compound A-2, 19.5 parts of Intermediate 2 was used as 15.0 parts of Intermediate 9, 10.6 parts of cyanuric chloride as 4.8 parts, and 10.0 parts of sulfanilic acid as 5-aminosalicylic acid. 12.8 parts (yield 52%) of Compound A-15 was obtained by performing the same reaction except that 0 parts and 6.5 parts of aniline were changed to 4.4 parts of 2-aminoethyl hydrogen sulfate.

[Example 16]
(Production of quinophthalone compound A-16)
In the synthetic reaction of the intermediate 8, 10 parts of 8-aminoquinaldine was added to 10 parts of 6-methoxy-8-aminoquinaldine, 4.4 parts of 5 parts of sodium carbonate, and 14.6 parts of 4-hydroxybenzenesulfonyl chloride to 4 parts. -Acetamidobenzoyl chloride The same reaction was performed except that the content was changed to 13.3 parts to obtain 15.0 parts (yield 92%) of Intermediate 16.
In the synthesis reaction of Intermediate 1, 10 parts of 8-aminoquinaldine was added to 10 parts of Intermediate 16, 20.6 parts of phthalic anhydride was added to 21.9 parts of 4,5-dibromophthalic anhydride, and dimethylpropylamine was added to 14. The same reaction was performed except that 9 parts was changed to 7.7 parts, and 17.0 parts (yield 88%) of Intermediate 17 was obtained.
In the synthetic reaction of compound A-2, 19.5 parts of Intermediate 2 was converted into 17.0 parts of Intermediate 17, 5.3 parts of 10.6 parts of cyanuric chloride, 5.0 parts of 10.0 parts of sulfanilic acid and aniline. The same reaction was performed except that 6.5 parts was changed to 6 parts of 5-amino-2-methylbenzotrifluoride to obtain 22.5 parts (yield 77%) of compound A-16.

[Example 17]
(Production of quinophthalone compound A-17)
In the synthetic reaction of intermediate 16, 10 parts of 6-methoxy-8-aminoquinaldine, 10 parts of 6-nitro-8-aminoquinaldine, 4.1 parts of sodium carbonate 4.4 parts, 4-acetamidobenzoyl chloride 13 The same reaction was performed except that the amount of 1.3 parts was changed to 12.3 parts, and 11.9 parts (yield 75%) of intermediate 18 was obtained.
In the synthesis reaction of Intermediate 1, 10 parts of 8-aminoquinaldine was added to 10 parts of Intermediate 18, 20.6 parts of phthalic anhydride was added to 13.5 parts of 2,3-naphthalenedicarboxylic acid anhydride, and dimethylpropylamine was added to 14. The same reaction was performed except that 9 parts was changed to 7.3 parts, and 12.6 parts (yield 81%) of Intermediate 19 was obtained.
In the synthesis reaction of compound A-2, 19.5 parts of Intermediate 2 was 12.6 parts of A-19, 4.6 parts of 10.6 parts of cyanuric chloride, 4.4 parts of 10.0 parts of sulfanilic acid, and aniline. The same reaction was performed except that 6.5 parts was changed to 2.6 parts of 2-penten-1-ol to obtain 13.5 parts (yield 64%) of compound A-17.

[Example 18]
(Production of quinophthalone compound A-18)

In the synthetic reaction of Intermediate 6, except that 10 parts of 6-nitro-8-hydroxyquinaldine was changed to 5 parts of 8-hydroxyquinaldine and 8.7 parts of phthalic anhydride was changed to 10.8 parts of tetrachlorophthalic anhydride. Was subjected to the same reaction to obtain 12.8 parts (yield 95%) of Intermediate 20.
In the synthesis reaction of Intermediate 8, 10 parts of 8-aminoquinaldine was 12.8 parts of Intermediate 20, 100 parts of methanol was 640 parts of N-methylpyrrolidone, and 5 parts of sodium carbonate was 1,8-diazabicyclo[5,4,4]. 0]-7-undecene 5.5 parts, 4-acetamidobenzenesulfonyl chloride 18.7 parts 8.8 parts, water 70 parts 0 parts, 35% hydrochloric acid 20 parts 190 parts To give 16.1 parts (yield 85%) of intermediate 21.
In the synthetic reaction of Compound A-1, 15.5 parts of Intermediate 1 was 16.1 parts of Intermediate 21, 5.1 parts of 9.9 parts of cyanuric chloride, and 20.5 parts of sulfanilic acid were added to 9.15 of 5-aminosalicylic acid. The same reaction was performed except that the amount was changed to 3 parts to obtain 21.6 parts (yield 81%) of compound A-18.

[Example 19]
(Production of quinophthalone compound A-19)
In the synthetic reaction of Intermediate 6, 10 parts of 6-nitro-8-hydroxyquinaldine was added to 5 parts of 8-hydroxyquinaldine, and 8.7 parts of phthalic anhydride was added to 7.5 parts of 2,3-naphthalenedicarboxylic anhydride. The reaction was performed in the same manner except that the content was changed to obtain 9.7 parts (yield 91%) of Intermediate 22.
In the synthesis reaction of the intermediate 21, the same reaction was performed except that 12.8 parts of the intermediate 20 was changed to 9.7 parts of the intermediate 22 to obtain 14.2 parts (yield 88%) of the intermediate 23. ..
In the synthetic reaction of compound 2, 19.5 parts of Intermediate 2 was 14.2 parts of Intermediate 23, 10.6 parts of cyanuric chloride was 4.9 parts, and 10.0 parts of sulfanilic acid was sodium 4-hydroxybenzenesulfonate. 13.5 parts (yield 64%) of compound A-19 was obtained in the same manner as above except that 3.1 parts of phenol and 3.1 parts of aniline were changed to 3.1 parts.

[Example 20]
(Production of quinophthalone compound A-20)

In the synthesis reaction of intermediate 21, the same reaction was performed except that 12.8 parts of intermediate 20 was changed to 9.7 parts of intermediate 7 to obtain 14.2 parts of intermediate 24 (yield 88%). ..
In the synthetic reaction of compound A-2, 19.5 parts of Intermediate 2 was 14.2 parts of Intermediate 24, 4.9 parts of 10.6 parts of cyanuric chloride, and 10.0 parts of sulfanilic acid were added to 4-hydroxybenzenesulfonic acid. 13.5 parts (yield 64%) of compound A-20 was obtained by performing the same reaction except that 5.3 parts of sodium and 6.5 parts of aniline were changed to 3.1 parts of phenol.

[Example 21]
(Production of quinophthalone compound A-21)

5.6 parts of cyanuric chloride and 250 parts of acetone were added, and the mixture was stirred while cooling in an ice bath. Then, 15 parts of Intermediate 23 was dissolved in 1000 parts of N-methylpyrrolidone, and the solution was added dropwise to a solution of cyanuric chloride over 1 hour. After stirring for 3 hours between 5°C and 15°C, 7.3 parts of S acid was added, and the mixture was heated to 50°C and stirred for 3 hours. After cooling to room temperature, the reaction mixture was poured into 3000 parts of water and stirred at room temperature for 1 hour. The precipitated crystals were separated by filtration, washed with water and methanol, and dried under reduced pressure to give compound A-21 (21.3, yield 83%).

[Example 22]
(Production of quinophthalone compound A-22)

In the synthetic reaction of Intermediate 6, except that 10 parts of 6-nitro-8-hydroxyquinaldine was changed to 5 parts of 8-hydroxyquinaldine and 8.7 parts of phthalic anhydride was changed to 8.3 parts of tetrafluorophthalic anhydride. Was similarly reacted to obtain 11 parts of Intermediate 25 (yield 97%).
In the synthetic reaction of Intermediate 21, the same reaction was performed except that 12.8 parts of Intermediate 20 was changed to 11 parts of Intermediate 25, and 14.8 parts (Yield 91%) of Intermediate 26 was obtained.
In the synthetic reaction of compound A-2, 19.5 parts of Intermediate 2 was converted to 14.8 parts of Intermediate 26, 5.3 parts of 10.6 parts of cyanuric chloride, 10.0 parts of sulfanilic acid and 3 parts of 4-aminobenzoic acid. The same reaction was performed except that 2.9 parts and aniline 6.5 parts were changed to 2,4-dibromoaniline 8.6 parts to obtain 22.7 parts (yield 81%) of compound A-22.

[Example 23]
(Production of quinophthalone compound A-23)

In the synthetic reaction of compound A-2, 19.5 parts of Intermediate 2 was A-1 16.1 parts, 10.6 parts of cyanuric chloride was 5.1 parts, and 10.0 parts of sulfanilic acid was 2-aminoethyl hydrogen sulfate. The same reaction was carried out except that 3.9 parts and 6.5 parts of aniline were changed to 3.1 parts to obtain 21.0 parts (yield 85%) of Compound A-23.

[Example 24]
(Production of quinophthalone compound A-24)
In the synthesis reaction of Intermediate 21, 12.8 parts of Intermediate 20, 700 parts of 640 parts of N-methylpyrrolidone, and 5.5 parts of 1,8-diazabicyclo[5,4,0]-7-undecene were added. 5.4 parts, 4-acetamido benzene sulfonyl chloride 18.8 parts were changed to 4-acetamido benzoyl chloride 8.4 parts, and the same reaction was performed, and intermediate 27 was 16.4 parts (yield 84 %)Obtained.
Intermediate 2 19.5 parts of compound A-2, intermediate 27 16.4 parts, cyanuric chloride 10.6 parts 5.5 parts, sulfanilic acid 10.0 parts 5.1 parts, aniline 6.5 parts Was reacted in the same manner except that the allylamine was changed to 2.2 parts to obtain 17.1 parts (yield 68%) of Compound A-24.

[Example 25]
(Production of quinophthalone compound A-25)
In the synthetic reaction of Intermediate 27, 15 parts of Intermediate 20, 15 parts of Intermediate 25, 700 parts of N-methylpyrrolidone 640 parts, and 5 parts of sodium carbonate were added 1,8-diazabicyclo[5,4,0]-7- Undecene 5.4 parts was changed to 6.3 parts and 4-acetamidobenzoyl chloride 8.4 parts was changed to 9.9 parts, and the same reaction was carried out to obtain 15 parts of intermediate 28 (yield 74%). ..
In the synthesis reaction of compound A-2, 19.5 parts of Intermediate 2 was 15 parts of Intermediate 28, 10.6 parts of cyanuric chloride was 5.7 parts, and 10.0 parts of sulfanilic acid was aniline 4-propionate 5.6. And 6.5 parts of aniline were changed to 3.4 parts to carry out the same reaction to obtain 21.2 parts of compound A-25 (yield 83%).

[Example 26]
(Production of quinophthalone compound A-26)

In the synthesis reaction of Intermediate 1, the same reaction was performed except that 20.6 parts of phthalic anhydride was changed to 39.8 parts of tetrachlorophthalic anhydride, and 24.8 parts of Intermediate 29 (yield 92% )Obtained.
Intermediate 29 (24.8 parts), N-methylpyrrolidone (1860 parts) and 1,8-diazabicyclo[5,4,0]-7-undecene (9.7 parts) were added, and the mixture was heated with stirring at 120°C. 16.6 parts of 3-bromopropylamine hydrobromide was added thereto, and the mixture was heated and stirred for 4 hours. After cooling to room temperature, the reaction mixture was put into 4000 parts of methanol and stirred at room temperature for 1 hour. The precipitated crystals were separated by filtration, washed with methanol, and dried under reduced pressure to obtain 13.1 parts of Intermediate 30 (yield 43%).
In the synthetic reaction of compound A-1, 15.5 parts of Intermediate 1 was changed to 13.1 parts of Intermediate 30, 9.9 parts of cyanuric chloride was changed to 5.0 parts, and 20.5 parts of sulfanilic acid was changed to 10.4 parts. The same reaction was performed except that the above was performed to obtain 21.9 parts (yield 89%) of Compound A-26.

[Example 27]
(Production of quinophthalone compound A-27)
In the synthetic reaction of Intermediate 30, 24.8 parts of Intermediate 29, 2020 parts of Intermediate 17, 1500 parts of 1860 parts of N-methylpyrrolidone, 1,8-diazabicyclo[5,4,0]-7-undecene9. The reaction was performed in the same manner except that 7 parts were changed to 8.6 parts and 3-bromopropylamine hydrobromide 16.6 parts was changed to 7.6 parts of 4-chloro-1-butanol, and Intermediate 31 was converted to 20 parts. 0.6 part (yield 88%) was obtained.
Intermediate 31 20.6 parts, 4-aminocyclohexanecarboxylic acid 8.3 parts, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide 10.2 parts, 4-dimethylaminopyridine 1.2 parts, N- 2000 parts of methylpyrrolidone was added, and the mixture was stirred at 20 to 25°C for 8 hours. The reaction mixture was poured into 4000 parts of water and stirred at room temperature for 1 hour. The precipitated crystals were separated by filtration, washed with methanol, and dried under reduced pressure to obtain 16.7 parts (yield 65%) of intermediate 32.
In the synthetic reaction of compound A-2, 19.5 parts of Intermediate 2 was 16.7 parts of Intermediate 32, 10.6 parts of cyanuric chloride was 5.0 parts, 10.0 parts of sulfanilic acid was 4.6 parts, and aniline. The same reaction was performed except that 6.5 parts was changed to 3.0 parts to obtain 19.4 parts (yield 75%) of Compound A-27.

[Example 28]
(Production of quinophthalone compound A-28)
The same reaction was performed except that 16.6 parts of 3-bromopropylamine hydrobromide salt of Intermediate 30 was changed to 10.5 parts of 3-bromopronol, and 15.5 parts of Intermediate 33 (yield 55%).
In the synthesis reaction of the intermediate 32, 20.6 parts of the intermediate 31 was added to 15.5 parts of the intermediate 33, 8.3 parts of 4-aminocyclohexanecarboxylic acid was added to 5.2 parts of 6-aminopicolinic acid, and 1-(3- Dimethylaminopropyl)-3-ethylcarbodiimide 10.2 parts were changed to 6.6 parts and 4-dimethylaminopyridine 1.2 parts were changed to 0.8 parts, and the same reaction was performed, and intermediate 34 was added to 13. 3 parts (yield 70%) were obtained.
In the synthetic reaction of compound A-1, 15.5 parts of Intermediate 1 was changed to 13.3 parts of Intermediate 34, 9.9 parts of cyanuric chloride was changed to 4.1 parts, and 20.5 parts of sulfanilic acid was changed to 8.5 parts. The same reaction was performed except that the above was performed to obtain 15.1 parts (yield 67%) of Compound A-28.

Example 29
(Production of quinophthalone compound A-29)
The same reaction was performed except that 10 parts of 6-nitro-8-hydroxyquinaldine was changed to 10 parts of 8-hydroxyquinaldine and 8.7 parts of phthalic anhydride was changed to 11.2 parts in the synthesis reaction of Intermediate 6. Thus, 14.2 parts (yield 78%) of Intermediate 35 was obtained.
In the synthesis reaction of the intermediate 30, 24.8 parts of the intermediate 29, 14.2 parts of the intermediate 35, 1860 parts of 1860 parts of N-methylpyrrolidone, 1,8-diazabicyclo[5,4,0]-7-undecene. Intermediate 36 was reacted in the same manner except that 9.7 parts was changed to 9.0 parts and 3-bromopropylamine hydrobromide 16.6 parts was changed to 12.4 parts of triethylene glycol monochlorohydrin. 18.0 parts (yield 87%) were obtained.
Intermediate 2 of Compound A-2 19.5 parts, Intermediate 36 18.0 parts, cyanuric chloride 10.6 parts 7.9 parts, sulfanilic acid 10.0 parts 7.4 parts, aniline 6.5 parts. Was changed to 7.0 parts of 4-aminobenzoic acid, and the same reaction was performed to obtain 24.5 parts (yield 71%) of compound A-29.

[Example 30]
(Production of quinophthalone compound A-30)

In the synthetic reaction of the intermediate 21, 12.8 parts of the intermediate 20, 10 parts of the intermediate 17, 500 parts of 640 parts of N-methylpyrrolidone, 1,8-diazabicyclo[5,4,0]-7-undecene5. 5 parts to 4.3 parts, 4-acetamidobenzenesulfonyl chloride 17.7 parts to 2,5-dichloro-4-acetamidobenzenesulfonyl chloride 8.5 parts, 35% hydrochloric acid 190 parts to 150 parts The reaction was performed in the same manner as above, except that 13.7 parts (yield 90%) of Intermediate 37 was obtained.
In the synthetic reaction of compound A-1, 15.5 parts of Intermediate 1 was 13.7 parts of Intermediate 21, 9.9 parts of cyanuric chloride was 3.9 parts, and 20.5 parts of sulfanilic acid was 4-aminosalicylic acid. The same reaction was performed except that the amount was changed to 1 part, to obtain 18.3 parts (yield 83%) of compound A-30.

[Example 31]
(Production of quinophthalone compound A-31)
10 parts of Intermediate 17, 1000 parts of N-methylpyrrolidone, and 4.3 parts of 1,8-diazabicyclo[5,4,0]-7-undecene were added, and the mixture was heated and stirred at 120°C. 6.9 parts of methyl 5-bromovalerate was added thereto, and the mixture was heated and stirred for 4 hours. Next, 50 parts of 25% aqueous sodium hydroxide solution was added, and the mixture was heated and stirred. After cooling to room temperature for 1 hour, the reaction mixture was added to 100 parts of 35% hydrochloric acid aqueous solution and 4000 parts of methanol, and stirred at room temperature for 1 hour. The precipitated crystals were separated by filtration, washed with methanol, and dried under reduced pressure to obtain 10.9 parts (yield 88%) of intermediate 38.
In the synthetic reaction of the intermediate 32, 20.6 parts of the intermediate 31 was added to 10.9 parts of the intermediate 38, 8.3 parts of 4-aminocyclohexanecarboxylic acid was added to 3.2 parts of 2,5-dihydroxy-1,4-dithiane. , 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide 10.2 parts were changed to 4.0 parts and 4-dimethylaminopyridine was changed to 1.2 parts to 0.5 parts to carry out the same reaction, 7.7 parts (yield 56%) of intermediate 39 was obtained.
In the synthetic reaction of compound A-1, 15.5 parts of Intermediate 1 was added to 7.7 parts of Intermediate 39, 2.2 parts of 9.9 parts of cyanuric chloride, 20.5 parts of sulfanilic acid and 3 parts of 4-aminobenzoic acid. The same reaction was performed except that the amount was changed to 0.5 part to obtain 8.1 parts (yield 69%) of Compound A-31.

[Example 32]
(Production of quinophthalone compound A-32)
4-Hydroxy-4'-nitrobiphenyl 15 parts, ethanol 150 parts, and sodium hydroxide 3.1 parts were added, and it heated at 70 degreeC and stirred for 30 minutes. 15 parts of 1-bromo-2-chloroethane was added thereto, and the mixture was heated and stirred for 4 hours. Next, after cooling to room temperature for 1 hour, 20.5 parts of reduced iron and 150 parts of 1N hydrochloric acid were added to the reaction mixture, and the mixture was stirred at 20°C to 25°C for 10 hours. After the solid content was filtered off, 300 parts of water and 100 parts of ethyl acetate were added to the reaction mixture to extract the ethyl acetate layer. Next, 1-bromo-2-chloroethane and ethyl acetate were distilled off by evaporation to obtain 9.5 parts (yield 55%) of a mixture of intermediates 40 and 41.
In the synthetic reaction of Intermediate 30, 24.8 parts of Intermediate 29, 250 parts of Intermediate 225, 250 parts of 1860 parts of N-methylpyrrolidone, 1,8-diazabicyclo[5,4,0]-7-undecene9. The same reaction was carried out except that 7 parts were changed to 2.7 parts, and 3-bromopropylamine hydrobromide 16.6 parts was changed to 5.5 parts of a mixture of intermediates 40 and 41. 7.4 parts (yield 91%) were obtained.
Intermediate 2 19.5 parts of compound A-2, intermediate 42 7.4 parts, cyanuric chloride 10.6 parts 2.5 parts, sulfanilic acid 10.0 parts 2.4 parts, aniline 6.5 parts Was reacted in the same manner except that 10 parts of water was used to obtain 7.9 parts (yield 72%) of Compound A-32.

Table 1 shows the results of mass spectrometry of the quinophthalone compounds (A-1 to A-32). In addition, the theoretical value is −1 from the calculated mass number because H of the compound is desorbed due to the nature of measurement.

<Method for producing comparative quinophthalone compound>
In the reference example of the present invention, in addition to the quinophthalone compounds produced in Examples 1 to 32, a quinophthalone compound produced by the following production method was used as a comparative example.

(Production of quinophthalone compound (D-1))
A quinophthalone compound (D-1) was obtained according to the synthetic method described in Japanese Patent No. 4585781.

Quinophthalone compound (D-1)

(Production of quinophthalone compound (D-2))
A quinophthalone compound (D-2) was obtained according to the synthetic method described in Japanese Patent No. 4871634.

Quinophthalone compound (D-2)

(Production of quinophthalone compound (D-3))
A quinophthalone compound (D-3) was obtained according to the synthetic method described in JP-A-2014-199308.

Quinophthalone compound (D-3)

<Production method of yellow pigment [B]>
(Production of micronized yellow pigment (B-1))
Quinophthalone yellow pigment C.I. I. Pigment Yellow 138 (“Paliotol Yellow L 0962HD” manufactured by BASF), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80° C. for 6 hours. Next, this kneaded product was poured into 8 liters of warm water, stirred for 2 hours while heating to 80° C. to form a slurry, filtered, washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85° C. overnight. A fine yellow pigment (B-1) was obtained.

(Production of micronized yellow pigment (B-2))
Isoindoline yellow pigment C.I. I. Pigment Yellow 139 (“Palotoll Yellow L 2146HD” manufactured by BASF), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80° C. for 6 hours. Next, this kneaded product was poured into 8 liters of warm water, stirred for 2 hours while heating to 80° C. to form a slurry, filtered, washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85° C. overnight. A fine yellow pigment (B-2) was obtained.

(Production of micronized yellow pigment (B-3))
The following quinophthalone compound (Chemical Formula 53) was obtained according to the synthetic method described in Japanese Patent No. 5267696. The C.I. used in the colorant (A-1). I. Pigment Yellow 138 was changed to a quinophthalone-based pigment represented by the following formula (Formula 53) to obtain a colorant (B-3) in the same manner as in the yellow pigment (B-1).

<Method for producing phthalocyanine pigment [C]>
(Production of micronized phthalocyanine pigment (C-1))
Phthalocyanine green pigment C.I. I. Pigment Green 58 (“FASTOGEN GREEN A110” manufactured by DIC), 200 parts, sodium chloride 1400 parts, and diethylene glycol 360 parts were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80° C. for 6 hours. Next, this kneaded product was poured into 8000 parts of warm water, stirred for 2 hours while heating at 80° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85° C. overnight. A fine phthalocyanine pigment (C-1) was obtained.

(Production of micronized phthalocyanine pigment (C-2))
500 parts of 98% sulfuric acid, 50 parts of chloroaluminum phthalocyanine (P-1), 129.3 parts of 1,2-dibromo-5,5-dimethylhydantoin (DBDMH) were added and stirred, and reacted at 20° C. for 6 hours. .. Then, the above reaction mixture was poured into 5000 parts of 3° C. ice water, and the precipitated solid was collected by filtration and washed with water. To a beaker, 500 parts of 2.5% aqueous sodium hydroxide solution and the residue collected by filtration were added, and the mixture was stirred at 80° C. for 1 hour. Then, this mixture was collected by filtration, washed with water, and dried to obtain 57.3 parts of phthalocyanine pigment (P-2) (yield 40%, halogen atom substitution number 10.1, halogen distribution width 9).
To a three-necked flask, 500 parts of N-methylpyrrolidone, 50 parts of P-2 and 13.9 parts of diphenyl phosphate were added, heated to 90° C. and reacted for 8 hours. After cooling this to room temperature, the product was filtered, washed with methanol and dried to give 51.6 parts of phthalocyanine pigment (C-2) (yield 88%, halogen atom substitution number 10.1, halogen distribution). Width 9) obtained.

<Others/Method for producing finely divided pigment>
(Production of micronized red pigment (PR254-1))
Diketopyrrolopyrrole pigment C.I. I. Pigment Red 254 (“B-CF” manufactured by BASF) (200 parts), sodium chloride (1400 parts), and diethylene glycol (360 parts) were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80° C. for 6 hours. Next, this kneaded product was poured into 8000 parts of warm water, stirred for 2 hours while heating at 80° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85° C. overnight. , 190 parts of micronized diketopyrrolopyrrole pigment (PR254-1) was obtained.

(Production of micronized red pigment (PR177-1))
Anthraquinone red pigment C.I. I. Pigment Red 177 (“Pariogen Red L4039” manufactured by BASF), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80° C. for 6 hours. Next, this kneaded product was poured into 8000 parts of warm water, stirred for 2 hours while heating at 80° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85° C. overnight. , Anthraquinone-based micronized red pigment (PR177-1) was obtained.

(Production of micronized blue pigment (PB15:6-1))
Phthalocyanine-based blue pigment C.I. I. Pigment Blue 15:6 (TOYOCOLOR "LIONOL BLUE ES", specific surface area 60 m ² /g) 200 parts, sodium chloride 1400 parts, and diethylene glycol 360 parts were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho), Kneading was carried out at 80° C. for 6 hours. Next, this kneaded product was poured into 8000 parts of warm water, stirred for 2 hours while heating at 80° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85° C. overnight. Thus, a finely divided blue pigment (PB15:6-1) was obtained.

(Production of micronized purple pigment (PV23-1))
Dioxazine-based purple pigment C.I. I. Pigment Violet 23 (“LIONOGEN VIOLET RL” manufactured by Toyo Color Co., Ltd.) 200 parts, sodium chloride 1400 parts, and diethylene glycol 360 parts were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80° C. for 6 hours. Next, this kneaded product was poured into 8000 parts of warm water, stirred for 2 hours while heating at 80° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85° C. overnight. A purple finely divided purple pigment (PV23-1) was obtained.

<Other method for producing pigment dispersion>
(Phthalocyanine/pigment dispersion (FP-1))
After the following mixture was stirred and mixed so as to be uniform, it was dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan Co., Ltd.) for 3 hours using zirconia beads having a diameter of 0.5 mm, and then the pore size was 5. The mixture was filtered through a 0 μm filter to prepare a pigment dispersion (FP-1) having a nonvolatile content of 20% by mass.
Phthalocyanine pigment (C-1): 11.0 parts Acrylic resin solution 1: 17.5 parts Propylene glycol monomethyl ether acetate: 66.5 parts Resin type dispersant solution 2: 5.0 parts

(Phthalocyanine/pigment dispersion (FP-2))
A pigment dispersion (FP-2) was produced in the same manner as in FP-1, except that the phthalocyanine pigment (C-1) was changed to (C-2).

(PR254/Pigment dispersion (RP-1))
PR254/pigment dispersion (RP-1) was prepared in the same manner as FP-1, except that the phthalocyanine pigment (C-1) was changed to PR254-1.

(PR177/Pigment dispersion (RP-2))
A PR177/pigment dispersion (RP-2) was produced in the same manner as in FP-1, except that the phthalocyanine pigment (C-1) was changed to PR177-1.

(PB15:6 pigment dispersion (BP-1))
PB15:6.pigment dispersion (BP-1) was produced in the same manner as FP-1, except that the phthalocyanine pigment (C-1) was changed to PB15:6-1.

(PV23/pigment dispersion (VP-1))
PV23/pigment dispersion (VP-1) was produced in the same manner as in FP-1, except that the phthalocyanine pigment (C-1) was changed to PV23-1.

<Production of yellow pigment dispersion (coloring composition)>
[Example 33]
(Pigment dispersion (YP-1))
After the following mixture was stirred and mixed so as to be uniform, it was dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan Co., Ltd.) for 3 hours using zirconia beads having a diameter of 0.5 mm, and then the pore size was 5. The mixture was filtered through a 0 μm filter to prepare a pigment dispersion (YP-1) having a nonvolatile content of 20% by mass.
Quinophthalone compound (A-1): 1.8 parts Yellow pigment (B-1): 10.2 parts Acrylic resin solution 1: 10.5 parts Propylene glycol monomethyl ether acetate: 70.0 parts Resin type dispersant 1: 7 .5 copies

[Examples 34 to 72, Comparative Examples 1 to 5]
(Pigment dispersion (YP-2 to 45))
Pigment dispersions (YP-2 to 45) were produced in the same manner as in Example 33 except that the quinophthalone compound and the yellow pigment were changed to the types shown in Table 2.

<Evaluation of yellow pigment dispersion (coloring composition)>
The following evaluation was performed on the obtained pigment dispersion. The results are shown in Table 2.
(Evaluation of contrast (CR))
The light emitted from the backlight unit for liquid crystal display passes through the polarizing plate and is polarized, passes through the coating film of the coloring composition applied on the glass substrate, and reaches the other polarizing plate. At this time, if the polarizing plate and the polarizing plane of the polarizing plate are parallel to each other, light passes through the polarizing plate, but if the polarizing planes are orthogonal, the light is blocked by the polarizing plate. However, when the light polarized by the polarizing plate passes through the coating film of the coloring composition, scattering occurs due to the colorant particles and a part of the plane of polarization is displaced, and the light is transmitted when the polarizing plates are parallel. When the polarizing plate is orthogonal, a part of light is transmitted. The transmitted light was measured as the brightness on the polarizing plate, and the ratio between the brightness when the polarizing plates were parallel and the brightness when the polarizing plates were orthogonal was calculated as the contrast ratio.
(Contrast ratio) = (Brightness when parallel)/(Brightness when orthogonal)
Therefore, when scattering occurs due to the colorant in the coating film, the brightness when parallel is decreased and the brightness when orthogonal is increased, so that the contrast ratio is decreased.

A color luminance meter (“BM-5A” manufactured by Topcon Corporation) was used as the luminance meter, and a polarizing plate (“NPF-G1220DUN” manufactured by Nitto Denko Corporation) was used as the polarizing plate. At the time of measurement, the measurement was performed through a black mask having a 1 cm square hole formed in the measurement portion.

The pigment dispersion (YP-1 to 45) was applied onto a glass substrate having a thickness of 100 mm×100 mm and a thickness of 1.1 mm by using a spin coater to obtain a coated substrate such that x=0.420 at a C light source. Drying conditions were 60° C. for 20 minutes after coating, and 230° C. for 60 minutes. The contrast ratio was judged according to the following criteria.
S: 9000 or more: Very good A: 6000 or more and less than 9000: Good B: 3000 or more and less than 6000: Practical C: Less than 3000: Poor

(Evaluation of heat resistance)
The pigment dispersion (YP-1 to 45) was applied onto a glass substrate having a thickness of 100 mm×100 mm and a thickness of 1.1 mm by using a spin coater, followed by drying at 60° C. for 20 minutes and then at 230° C. for 30 minutes. A coating substrate was prepared by heating and cooling. The manufactured coated substrate was heat-treated at 230° C. so as to have a film thickness of 1.5 μm. The chromaticity ([L*(1), a*(1), b*(1)]) of the obtained coating film with a C light source was measured by a microspectrophotometer (“OSP-SP100” manufactured by Olympus Optical Co., Ltd.). It was measured using. After that, as a heat resistance test, it was heated at 230° C. for 60 minutes, and the chromaticity ([L*(2), a*(2), b*(2)]) with a C light source was measured and calculated by the following formula. , And the color difference ΔEab* was determined.
ΔEab* = √((L*(2)- L*(1)) ² + (a*(2)- a*(1)) ² +( b*(2)- b*(1)) ² )
S: ΔEab* is less than 3.0: Very good A: ΔEab* is 3.0 or more and less than 4.0: Good B: ΔEab* is 4.0 or more and less than 6.0: Practical C: ΔEab* is In case of 6.0 or more: bad

(Evaluation of initial viscosity)
Regarding the viscosity of the pigment dispersion, the initial viscosity at 25° C. was measured using an E-type viscometer (“ELD-type viscometer” manufactured by Toki Sangyo Co., Ltd.).
S: less than 10 mPa·s: extremely good A: 10 mPa·s or more, less than 15 mPa·s: good B: 15 mPa·s or more, less than 20 mPa·s: practical C: if 20 mPa·s or more: poor

(Evaluation of storage stability)
The obtained pigment dispersion was stored in a thermostat at 40° C. for 1 week to accelerate the aging, and then the viscosity of the coloring composition after aging was measured by the same method as the above-mentioned viscosity measurement, and stored at 40° C. for 1 week The rate of change in viscosity before and after was calculated, and evaluated in two stages according to the following criteria.
S: When the rate of change in viscosity is less than ±10% and no sediment is formed: Very good A: When the rate of change in viscosity is ±10% or more and less than 15% and no sediment is formed: Good B: Change in viscosity When the rate is ±15% or more and less than 20% and no sediment is formed: Practical C: When the rate of viscosity change exceeds ±20%, or when the rate of viscosity change is within ±20%, sediment is generated. If it has occurred: bad

As shown in Table 2, the pigment dispersions YP-1 to 40 using the quinophthalone compound (A) having a quinophthalone skeleton, a triazine ring and an acidic group of the present invention are good in CR, heat resistance, initial viscosity and storage stability. It was a good evaluation result. Preferably, the quinophthalone compound A-9, 11, 14, 19 to 23, 26, 30 was good. More preferably, the quinophthalone compound A-7,8,10,12,13,15,18,30 gave the best result. On the other hand, the pigment dispersions YP-41 to 45 of the conventional quinophthalone compounds D-1 to D3, which do not contain a triazine ring and an acidic group at the same time, are more excellent in CR, heat resistance, initial viscosity and storage stability than the examples of the present invention. The result was extremely inferior.

<Preparation of green pigment dispersion (coloring composition)>
A green coloring composition was prepared using the yellow pigment dispersions (YP-1 to 45) and the phthalocyanine/pigment dispersions (FP-1, 2).

Example 73
(Green pigment dispersion (GP-1))
A mixture having the following composition was stirred and mixed so as to be uniform to prepare a pigment dispersion (GP-1).
Phthalocyanine/pigment dispersion (FP-2): 22.2 parts Yellow pigment dispersion (YP-1): 27.8 parts

[Examples 74 to 124, Comparative Examples 6 to 15]
(Green pigment dispersion (GP-2 to 62))
Green pigment dispersions (GP-1 to 62) were obtained in the same manner as in Example 73, except that the content of 50 parts in total of the pigment dispersion was changed to the types and parts by mass shown in Table 3. ..

<Evaluation of green pigment dispersion (coloring composition)>
The following evaluation was performed on the obtained green pigment dispersion. Further, heat resistance, initial viscosity and storage stability were evaluated by the same evaluation criteria by preparing a coating film in the same manner as the yellow pigment dispersion. The results are shown in Table 3.

(Evaluation of contrast)
Pigment dispersions (GP-1 to 62) are applied on a glass substrate having a thickness of 100 mm×100 mm and a thickness of 1.1 mm using a spin coater such that x=0.297, y=0.570 in a C light source. A coated substrate was obtained. Drying conditions were 60° C. for 20 minutes after coating, and 230° C. for 60 minutes. The contrast ratio was judged according to the following criteria.
S: 9000 or more: Very good A: 6000 or more and less than 9000: Good B: 3000 or more and less than 6000: Practical C: Less than 3000: Poor

(Foreign material evaluation)
The pigment dispersion (GP-1 to 62) is applied onto a glass substrate having a thickness of 100 mm×100 mm and a thickness of 1.1 mm by using a spin coater, then dried at 60° C. for 20 minutes and heated at 230° C. for 60 minutes. Further, additional heating was performed at 250° C. for 60 minutes, and the mixture was allowed to cool to prepare a coated substrate. The produced coated substrate was subjected to heat treatment at 250° C. so as to have a thickness of 1.5 μm. The number of foreign matters in the coating film of the obtained coating film substrate was measured. For the evaluation, the surface was observed using a metal microscope "BX60" manufactured by Olympus System Co., Ltd.). The magnification was set to 500 times, and the number of foreign substances observable in arbitrary 5 fields of view was measured.
S: The number of foreign matter is less than 3: Very good A: The number of foreign matter is 3 or more and less than 20: Good B: The number of foreign matter is 21 or more, less than 100: Practical C: The number of foreign matter is 100 More than one: defective

As shown in Table 3, the pigment dispersions GP-1 to GP40 using the quinophthalone compound (A) having the quinophthalone skeleton, the triazine ring and the acidic group at the same time according to the present invention are CR, heat resistance, foreign matter, initial viscosity and storage stability. The evaluation result was good. The green pigment dispersion using the quinophthalone compounds A-9 to 13, 15, 19, and 26 was preferable. More preferably, the green pigment dispersion using the quinophthalone compound A-7, 8, 10, 18, 30 gave the best result. On the other hand, pigment dispersions GP53 to 62 using conventional quinophthalone compounds D-1 to 3 which do not contain a triazine ring and an acidic group at the same time are more excellent than the examples of the present invention in heat resistance, foreign matter, initial viscosity and storage stability. The result was extremely inferior.

<Production of photosensitive coloring composition>
[Example 125]
(Green photosensitive coloring composition (GR-1))
A mixture having the following composition was stirred and mixed so as to be uniform, and then filtered with a filter having a pore size of 1 μm to prepare a green photosensitive coloring composition (GR-1).
Green pigment dispersion (GP-1): 50.0 parts Acrylic resin solution 1: 7.5 parts Photopolymerizable monomer ("Aronix M-402" manufactured by Toagosei Co., Ltd.): 2.0 parts Dipentaerythritol hexa Acrylate Photopolymerization Initiator (“IRGACURE 907” manufactured by BASF): 1.2 parts Sensitizer (“EAB-F” manufactured by Hodogaya Chemical Co., Ltd.): 0.3 parts Cyclohexanone: 39.0 parts

[Examples 126 to 176, Comparative Examples 16 to 25]
Green photosensitive coloring compositions (GR-2 to 62) were obtained in the same manner as in Example 125, except that the pigment dispersion GP-1 was changed to GP-2 to GP-62.

<Evaluation of photosensitive coloring composition>
The following evaluation was performed about the obtained green pigment photosensitive coloring composition. The results are shown in Table 4.

(Evaluation of brightness)
Pigment dispersions (GR-1 to 62) are used on a glass substrate having a thickness of 100 mm×100 mm and a thickness of 1.1 mm by using a spin coater such that x=0.297, y=0.570 in a C light source. A coated substrate was obtained. Drying conditions were 60° C. for 20 minutes after coating, and 230° C. for 60 minutes. The brightness (Y) of the obtained substrate was measured with a microspectrophotometer (“OSP-SP200” manufactured by Olympus Optical Co., Ltd.).

(Evaluation of brightness)
The number of foreign matters in the coating film of the coating film substrate used for measuring the brightness was measured. For the evaluation, the surface was observed using a metal microscope "BX60" manufactured by Olympus System Co., Ltd.). The magnification was set to 500 times, and the number of foreign substances observable in arbitrary 5 fields of view was measured.
S: The number of foreign matter is less than 3: Very good A: The number of foreign matter is 3 or more and less than 20: Good B: The number of foreign matter is 21 or more, less than 100: Practical C: The number of foreign matter is 100 More than one: defective

(Evaluation of solvent resistance)
The green photosensitive coloring composition (GR-1 to 62) was applied to a glass substrate on which a black matrix had been formed in advance by spin coating, and then dried in a clean oven at 70°C for 20 minutes. Then, after cooling this substrate to room temperature, it was exposed to ultraviolet light through a photomask using an ultrahigh pressure mercury lamp. Thereafter, this substrate was spray-developed for 30 seconds with a 0.2% by mass sodium carbonate aqueous solution at 23° C., washed with ion-exchanged water, and dried. Further, heat treatment was performed at 230° C. for 30 minutes in a clean oven to form a stripe-shaped colored pixel layer on the substrate. The obtained striped green pixel was immersed in N-methyl-2-pyrrolidone (NMP) and methanol (MeOH) for 15 minutes, and the color difference of the green pixel portion before and after the immersion was measured. The color difference measurement method, calculation method, and evaluation criteria were the same as those for heat resistance.

As shown in Table 4, the coloring composition using the quinophthalone compound (A) represented by the general formula (1) of the present invention gave good results in lightness, foreign matter and solvent resistance. On the other hand, the coloring composition using the conventional quinophthalone compounds D-1 to 3 which did not contain a triazine ring and an acidic group at the same time was clearly inferior to the compound of this example in foreign matter and resistance.

<Production of color filter>
(Red photosensitive coloring composition (RR-1))
The mixture having the following composition was stirred and mixed so as to be uniform, and then filtered with a filter having a pore size of 1 μm to prepare a red photosensitive coloring composition (RR-1).
PR254/Pigment dispersion (RP-1)/Pigment dispersion: 30.0 parts PR177/Pigment dispersion (RP-2)/Pigment dispersion: 20.0 parts Acrylic resin solution 1: 7.5 parts Photopolymerizable Monomer (“Aronix M-402” manufactured by Toagosei Co., Ltd.): 2.0 parts Photopolymerization initiator (“Irgacure 907” manufactured by BASF): 1.2 parts Sensitizer (“Hodogaya Chemical Co., Ltd.” EAB-F"): 0.3 part Cyclohexanone: 39.0 parts

(Blue photosensitive coloring composition (BR-1))
The mixture having the following composition was stirred and mixed so as to be uniform, and then filtered with a filter having a pore size of 1 μm to prepare a blue photosensitive coloring composition (BR-1).
PB15:6/Pigment dispersion (BP-1): 45.0 parts PV23/Pigment dispersion (VP-1): 5.0 parts Acrylic resin solution 1: 7.5 parts Photopolymerizable monomer (Toagosei) "Aronix M-402" manufactured by the company): 2.0 parts Photopolymerization initiator ("Irgacure 907" manufactured by BASF): 1.2 parts Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.): 0.3 parts Cyclohexanone: 39.0 parts

The red photosensitive coloring composition (RR-1) was applied by a spin coating method to a glass substrate on which a black matrix was previously formed, and then dried at 70° C. for 20 minutes in a clean oven. Then, after cooling this substrate to room temperature, it was exposed to ultraviolet rays through a photomask using an ultra-high pressure mercury lamp. Thereafter, this substrate was spray-developed for 30 seconds with a 0.2% by mass sodium carbonate aqueous solution at 23° C., washed with ion-exchanged water, and dried. Further, heat treatment was performed at 230° C. for 30 minutes in a clean oven to form a stripe-shaped colored pixel layer on the substrate. Next, using the green photosensitive coloring composition (GR-2) of the present invention, a green coloring pixel layer was formed in the same manner as the red coloring pixel layer, and a blue photosensitive coloring composition (BR-1) was further formed. A blue-colored pixel layer was formed using it to obtain a color filter (CF-1). The formed film thickness of each colored pixel layer was 2.0 μm.

The color filter using the green coloring composition containing the quinophthalone compound of the present invention has the high brightness and the excellent contrast ratio, which proves the effect of the present invention.

Claims (6)

A quinophthalone compound (A) represented by the following general formula (1).
General formula (1)
[In the general formula (1), R _{1 to} R ₉ each independently have a hydrogen atom, a halogen atom, a nitro group, an optionally substituted alkyl group having 20 or less carbon atoms, and a substituent. Represents an alkoxy group having 20 or less carbon atoms or an aryl group having 20 or less carbon atoms which may have a substituent, and adjacent substituents are bonded to each other to form an aliphatic saturated hydrocarbon-based or aromatic-based You may form a cyclic structure.
Q ₁ is a group represented by the following general formula (4).

Formula _{(4) - (X 3)} n - (Z 3) m -X 4 - *
(In the general formula (4), _{X 3 is, -NHSO 2 -, - NHCO -} , - OSO 2 -, - OCO -, - NH- or an -O-.
Z ₃ is an arylene group having 20 or less carbon atoms which may have a substituent, a heteroarylene group having 20 or less carbon atoms which may have a substituent, or a carbon number 20 which may have a substituent. The following alkylene groups are represented, and when m is 2 or more, a plurality of Z _3's may be the same or different, and a plurality of Z _3's are —NHSO ₂ —, —NHCO—, —OSO ₂ —, —. They may be linked by at least one divalent linking group selected from OCO-, -S-, -NH- and -O-.
X ₄ represents -NH- or -O-.
n represents an integer of 0 or 1, and m represents an integer of 0 to 5.
* Is a linking hand with the triazine ring. )

A1 and B1 are each independently represented by a hydroxyl group, a chlorine atom, the following general formula (2) or the following general formula (3), and at least one is a group represented by the following general formula (2). ..

Formula (2) _{-X 1} -Z 1
(In the general formula (2), X ₁ represents —NH— or —O—. Z ₁ may have a substituent having 20 or less carbon atoms, or may have a substituent. Represents a good alkyl group having 20 or less carbon atoms, and X ₁ and Z ₁ represent an arylene group having 20 or less carbon atoms which may have a substituent, and a heteroari having 20 or less carbon atoms which may have a substituent. lane group, a substituted alkylene group having 20 or less carbon atoms which may _{have, -NHSO 2 -, - NHCO -} , - OSO 2 -, - OCO -, - S -, - selected from NH- and -O- May be linked by at least one divalent linking group.
However, Z ₁ has at least one substituent selected from —COOH, —SO ₃ H, and —OSO ₃ H. )

Formula (3) _{-X 2} -Z 2
(In the general formula (3), X ₂ represents —NH— or —O—. Z ₂ may have a substituent having 20 or less carbon atoms, or may have a substituent. It represents an alkenyl group having 20 or less carbon atoms, an aryl group having 20 or less carbon atoms that may have a substituent, or a heteroaryl group having 20 or less carbon atoms that may have a substituent, and X ₂ and Z ₂ Is an arylene group having 20 or less carbon atoms, which may have a substituent, a heteroarylene group having 20 or less carbon atoms, which may have a substituent, and an alkylene having 20 or less carbon atoms, which may have a substituent. _{group, -NHSO 2 -, - NHCO -} , - OSO 2 -, - OCO -, - S -, - selected from NH- and -O- may be linked by at least one divalent linking group ..
However, _{Z 2} has no -COOH, -SO ₃ H at or OSO ₃ H as a substituent. )] In formula (4), n is 1, quinophthalone compound of Claim 1 m is 1 (A). A pigment dispersant containing the quinophthalone compound (A) according to claim 1 . A coloring composition for a color filter, comprising the pigment dispersant according to claim 3 , a coloring agent, an organic solvent and a binder resin. The coloring composition for a color filter according to claim 4 , further containing at least one selected from a photopolymerizable monomer and a photopolymerization initiator. A color filter comprising at least one red filter segment, at least one green filter segment and at least one blue filter segment, wherein at least one green filter segment is formed from the color filter coloring composition according to claim 4 or 5. Color filter.