JP6874376B2 - A quinophthalone compound, a pigment dispersant using the quinophthalone compound, a coloring composition for a color filter, and a color filter. - Google Patents

Description

In order to increase the contrast and brightness of the color filter, it is required to disperse the finely divided pigment in a finer state (good dispersibility). However, since the finely divided 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 increased. There is a problem that it deteriorates remarkably. It is often difficult to achieve both dispersibility and contrast at a high level.

Various dye derivatives have been developed to solve such problems. 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 coloring composition satisfying all of lightness, contrast, dispersibility, and heat resistance when dispersing the finely divided pigment, and a new coloring composition cannot be obtained. The development of quinophthalone compounds has been desired. Further, Patent Documents 8 to 9 describe quinophthalone compounds having a phthalimide group substituted with a sulfonic acid as an intermediate of Examples, but the usefulness in color filter applications is not described in the specification. ..

Japanese Unexamined Patent Publication No. 2003-167112 JP-A-2002-179979 Japanese Unexamined Patent Publication No. 2002-121456 Japanese Unexamined Patent Publication No. 2004-067715 Japanese Unexamined Patent Publication No. 2004-307854 JP-A-2007-156395 Japanese Unexamined Patent Publication No. 2014-199308 Japanese Unexamined Patent Publication No. 2008-050420 Japanese Unexamined Patent Publication No. 2008-081566

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

［一般式（１）中、Ｘ_１は、−Ｏ−又は−ＮＨ−を表し、Ｒ_１は、無置換のアルキレン基を表し、Ｍは、水素原子又は酸性基の１価〜３価の金属カチオン；アルキルアンモニウムカチオンを表す。Ｒ_２〜Ｒ_１０は、それぞれ独立に、水素原子、ハロゲン原子、ニトロ基、アルコキシ基、置換もしくは無置換のアルキル基、置換もしくは無置換のアリール基又は−ＣＯＯＰを表し、隣接する置換基が結合して置換もしくは無置換の芳香環を形成してもよい。Pは、置換もしくは無置換のアルキル基を表す。］
That is, the present invention relates to the quinophthalone compound (A) represented by the following general formula (1).
General formula (1)

[In the general formula (1), X ₁ represents -O- or -NH-, R ₁ represents an unsubstituted alkylene group , and M is a monovalent to trivalent metal of a hydrogen atom or an acidic group. Cation: Represents an alkylammonium cation. R _{2 to} R ₁₀ independently represent a hydrogen atom, a halogen atom, a nitro group, an alkoxy group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group or −COOP, and adjacent substituents are bonded to each other. May form a substituted or unsubstituted aromatic ring. P represents a substituted or unsubstituted alkyl group. ]

_{The present invention also relates to the quinophthalone compound (A), wherein R 1} in the general formula (1) is a divalent linking group containing an unsubstituted alkylene group having 1 to 8 carbon atoms.

The present invention also relates to the above quinophthalone compound (A) in which M in the general formula (1) is a monovalent to trivalent metal cation of a hydrogen atom or an acidic group.

［一般式（２）中、Ｘ_２は、−Ｏ−又は−ＮＨ−を表し、Ｒ_１１は、炭素数１〜５の無置換のアルキレン基を表し、Ｍは、水素原子又は酸性基の１価〜３価の金属カチオン；アルキルアンモニウムカチオンを表す。Ｒ_１２〜Ｒ_１６は、それぞれ独立に、水素原子、ハロゲン原子、ニトロ基又はアルコキシ基を表す。］ The present invention also relates to the above quinophthalone compound (A') represented by the following general formula (2).
General formula (2)

[In the general formula (2), X ₂ represents -O- or -NH-, R ₁₁ represents an unsubstituted alkylene group having 1 to 5 carbon atoms, and M is 1 of a hydrogen atom or an acidic group. Valuable to trivalent metal cation; represents an alkylammonium cation. R _{12 to} R ₁₆ independently represent a hydrogen atom, a halogen atom, a nitro group or an alkoxy group. ]

The present invention also relates to a pigment dispersant containing the above quinophthalone compound.

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

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

Further, in the present invention, in a color filter including at least one red filter segment, at least one green filter segment and at least one blue filter segment, at least one green filter segment is formed from the coloring composition for a color filter. Regarding color filters.

By using the quinophthalone compound (A) represented by the general formula (1) of the present invention in combination with a colorant, a coloring composition for a low-viscosity color filter having good brightness, contrast, heat resistance and few foreign substances is provided. can do.

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

［一般式（１）中、Ｘ_１は、−Ｏ−又は−ＮＨ−を表し、Ｒ_１は、無置換のアルキレン基を表し、Ｍは、水素原子又は酸性基の１価〜３価の金属カチオン；アルキルアンモニウムカチオンを表す。
Ｒ_２〜Ｒ_１０は、それぞれ独立に、水素原子、ハロゲン原子、ニトロ基、アルコキシ基、置換もしくは無置換のアルキル基、置換もしくは無置換のアリール基又は−ＣＯＯＰを表し、隣接する置換基が結合して置換もしくは無置換の芳香環を形成してもよい。Pは、置換もしくは無置換のアルキル基を表す。］
<Kinophthalone compound (A)>
The quinophthalone compound (A) of the present invention is represented by the following general formula (1).
General formula (1)

[In the general formula (1), X ₁ represents -O- or -NH-, R ₁ represents an unsubstituted alkylene group , and M is a monovalent to trivalent metal of a hydrogen atom or an acidic group. Cation: Represents an alkylammonium cation.
R _{2 to} R ₁₀ independently represent a hydrogen atom, a halogen atom, a nitro group, an alkoxy group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group or −COOP, and adjacent substituents are bonded to each other. May form a substituted or unsubstituted aromatic ring. P represents a substituted or unsubstituted alkyl group. ]

Each group in the general formula (1) will be described.
Examples of the halogen atom in R _{2 to} R ₁₀ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

The alkyl group in R ₂ to R ₁₀ and P, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, octadecyl group, tri Fluoromethyl group, isopropyl group, isobutyl group, isopentyl group, 2-ethylhexyl group, 2-hexyldodecyl group, sec-butyl group, tert-butyl group, sec-pentyl group, tert-pentyl group, tert-octyl group, neopentyl group Groups, cyclopropyl groups, cyclobutyl groups, cyclopentyl groups, cyclohexyl groups, adamantyl groups, norbornyl groups, boronyl groups, 4-decylcyclohexyl groups and the like can be mentioned, but are not limited thereto.

The alkoxy group in R _{2 to} R ₁₀ is a group in which an oxygen atom is bonded to the above-mentioned alkyl group.

As the aryl group in R ₂ to R _10, a phenyl group, biphenylyl group, terphenylyl group, quarter phenylene Lil group, an indenyl group, a naphthyl group, a binaphthalenyl group, ternaphthalenyl group, a quaternaphthalenyl group, azulenyl group, heptalenyl Group, biphenylenyl group, indacenyl group, fluoranthenyl group, acephenanthrylenyl group, aceanthryleneyl group, phenylenyl group, fluorenyl group, anthryl group, biantrasenyl group, taranthrasenyl group, quarter anthrasenyl group, anthracinolyl Group, phenanthryl group, triphenylenyl group, pyrenyl group, chrysenyl group, naphthalsenyl group, pryadenyl group, pisenyl group, perylenel group, pentaphenyl group, pentasenyl group, tetraphenylenyl group, hexaphenyl group, hexasenyl group, rubisenyl group, Examples thereof include, but are not limited to, a coronenyl group, a trinaphthylenyl group, a heptaphenyl group, a heptasenyl group, a pyrantrenyl group, and an ovalenyl group.

In R _{7 to} R ₁₀ , adjacent substituents are preferably bonded to form a substituted or unsubstituted aromatic ring, and R ₈ and R ₉ are more preferably bonded to form an aromatic ring.

The unsubstituted alkylene group in _{R 1} may be a divalent linking group containing an alkylene group obtained by removing one hydrogen atom from the above-mentioned alkyl group , and the alkylene groups may be linked to each other.

The unsubstituted alkylene group in _{R 1} preferably has 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, further preferably 1 to 5 carbon atoms, and most preferably 1 to 3 carbon atoms.

The hydrogen atoms of the alkyl group, alkoxy group, aryl group, alkylene group and arylene group in the general formula (1) may be further substituted with other substituents, and such substituents include a halogen atom and an alkyl group. , Alkyl group substituted with halogen atom, aryl group, nitro group, hydroxyl group, alkoxy group, carboxyl group, sulfo group and the like. Among these, halogen atom, alkyl group, aryl group and alkoxy group are described above. Is synonymous with.

In the general formula (1), X ₁ represents −O− or −NH−, preferably −O−.

Examples of the monovalent to trivalent metal cations of the acidic group in M of the general formula (1) include sodium, potassium, magnesium, calcium, iron, cobalt, nickel, copper, zinc, aluminum and the like, and aluminum is more preferable. ..

Examples of the alkylammonium cation of the acidic group in M of the general formula (1) include ammonium of long-chain monoalkylamines such as octylamine, laurylamine and stearylamine, palmityltrimethylammonium, dilauryldimethylammonium and distearyldimethylammonium. Quaternary alkylammonium cations are mentioned, with laurylamine being more preferred.

M in the general formula (1) is preferably a hydrogen atom or a monovalent to trivalent metal cation of an acidic group.

［一般式（２）中、Ｘ_２は、−Ｏ−又は−ＮＨ−を表し、Ｒ_１１は、炭素数１〜５の無置換のアルキレン基を表し、Ｍは、水素原子又は酸性基の１価〜３価の金属カチオン；アルキルアンモニウムカチオンを表す。Ｒ_１２〜Ｒ_１６は、それぞれ独立に、水素原子、ハロゲン原子、ニトロ基又はアルコキシ基を表す。］ As the quinophthalone compound (A) represented by the general formula (1), the quinophthalone compound (A') represented by the following general formula (2) is preferable.
General formula (2)

[In the general formula (2), X ₂ represents -O- or -NH-, R ₁₁ represents an unsubstituted alkylene group having 1 to 5 carbon atoms, and M is 1 of a hydrogen atom or an acidic group. Valuable to trivalent metal cation; represents an alkylammonium cation. R _{12 to} R ₁₆ independently represent a hydrogen atom, a halogen atom, a nitro group or an alkoxy group. ]

The substituent in the general formula (2) is synonymous with the substituent in the general formula (1).

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 a coloring material. The quinophthalone compound (A) of the present invention is preferably used in combination with at least one pigment selected from the yellow pigment (C) and the phthalocyanine pigment (D).
Hereinafter, typical pigments and dyes that can be used in the present invention are listed.

Examples of the yellow pigment (C) 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 the quinophthalone pigments described in 192, 193, 194, 196, 198, 199, 213, 214 and Japanese Patent No. 4993026 can be used. In particular, from the viewpoint of heat resistance, light resistance, and lightness of the filter segment, the yellow dye is C.I. I. Pigment Yellow is preferably at least one selected from the group consisting of 138, 139, 150 and 185.

Yellow dyes include azo dyes, azo metal complex salt dyes, anthraquinone dyes, indigo dyes, thioindigo dyes, phthalocyanine dyes, diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, thiazine dyes, cationic dyes, cyanine dyes, nitro dyes, and quinoline dyes. , Naftquinone dyes, oxazine dyes and the like.

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 and 192, 199 and the like can be mentioned.

In addition, 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 and the like can also be mentioned.

In addition, 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, Examples include 105 and 106.

In addition, 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 can also be mentioned.

In addition, 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.

The 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, 270, 272, 273, 274, 276, 277, 278, 279, 280, 281, 282, 283, Examples thereof include, but are not limited to, 284, 285, 286, 287, or the diketopyrrolopyrrole pigment described in JP-A-2011-523433. 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, and 338.

The 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 (D) that can be used in the present invention is, for example, C.I. I. Pigment Green 7, 10, 36, 37, 58, 62, 63, Japanese Patent Application Laid-Open No. 2008-19383, Japanese Patent Application Laid-Open No. 2007-320986, Japanese Patent Application Laid-Open No. 2004-070342, etc. However, it is not particularly limited to these.

The 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, but the present invention is not particularly limited thereto.

When the yellow pigment (C) 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 (C). More preferably, it is 5% by mass or more and 40% by mass or less. If the ratio of the quinophthalone compound (A) is too small with respect to the colorant, the effects of improving brightness, contrast, heat resistance, foreign matter suppression, initial viscosity, and storage stability tend 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 relation to the color characteristics of the quinophthalone compound (A).

As the phthalocyanine pigment (C), a copper halide phthalocyanine pigment, a zinc halide phthalocyanine pigment, an aluminum phthalocyanine pigment, or a halogenated aluminum phthalocyanine pigment is preferable. More preferably, C.I. I. Pigment Green 58, 62 or 63.

When a green dye is used in combination with a yellow dye containing the quinophthalone compound (A) represented by the general formula (1), the green dye / quinophthalone compound represented by the general formula (1) is used from the viewpoint of lightness and hue. The mass ratio of the yellow dye containing (A) is preferably in the range of 10/90 to 80/20.

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

Salt milling treatment is a process of heating a mixture of a colorant, a water-soluble inorganic salt, and a water-soluble organic solvent using a kneader such as a kneader, a 2-roll mill, a 3-roll mill, a ball mill, an attritor, or a sand mill. After mechanically kneading, the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water. 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 salt milling 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 and the like can be used, but sodium chloride (salt) is preferably used from the viewpoint of price. 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, 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 having a boiling point of 120 ° C. or higher is preferable from the viewpoint of safety. Such examples include, for example, 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, most preferably 50 to 500% by mass, based on the total mass of the colorant (100% by mass).

When the colorant is subjected to salt milling treatment, a resin may be added if 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, water-insoluble, 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% by mass based on the total mass of the colorant (100% by mass). Further, when the colorant is subjected to 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 is a resin that disperses a colorant such as a pigment or a pigment and a quinophthalone compound (A) 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 preferably 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-developable colored resist material, it is preferable to use an alkali-soluble vinyl-based resin in which an acidic group-containing ethylenically unsaturated monomer is copolymerized. Further, an active energy ray-curable resin having an ethylenically unsaturated double bond can also be used for the purpose of further improving the light sensitivity and the solvent resistance.

In particular, by using an active energy ray-curable resin having an ethylenically unsaturated double bond in the side chain for the alkali-developed resist for color filters, foreign matter in the coating film is not generated after the colorant is applied, and the resist material is contained. The stability of the colorant is improved, which is preferable. When a linear resin that does not have an ethylenically unsaturated double bond is used for the side chain, the colorant is less likely to be trapped by the resin in a liquid in which the resin and the colorant are mixed, and the resin has a degree of freedom. However, by using an active energy ray-curable resin having an ethylenically unsaturated double bond in the side chain, the colorant becomes a resin in a liquid in which the resin and the colorant are mixed. Since it is easily trapped, the dye is difficult to elute in the solvent resistance test, the colorant component is difficult to aggregate and 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, and even if the solvent is removed in the subsequent development step, the colorant components are less likely to aggregate and precipitate.

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

When the binder resin is used as a photosensitive coloring composition for a color filter, it acts as a colorant adsorbing group and an alkali-soluble group during development from the viewpoints of pigment dispersibility, permeability, developability, and heat resistance. The balance of aliphatic and aromatic groups that act as carboxyl groups, colorant carriers and affinity groups for solvents is important for pigment dispersibility, permeability, developability and durability, with an acid value of 20-300 mgKOH. It is preferable to use a resin of / g. If 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 remains.

Since the binder resin has good film-forming properties and various resistances, it is preferable to use the binder resin in an amount of 30 parts by mass or more with respect to 100 parts by mass of the total mass of the colorant, 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, and polyvinyl acetate. , Polyurethane resin, polyester resin, vinyl resin, alkyd resin, polystyrene resin, polyamide resin, rubber resin, cyclized rubber resin, celluloses, polyethylene (HDPE, LDPE), polybutadiene, polyimide resin and the like. .. Above all, it is preferable to use an acrylic resin.

Examples of the vinyl-based alkali-soluble resin obtained by copolymerizing an acidic group-containing ethylenically unsaturated monomer include a resin having an acidic group such as a carboxyl group and a sulfone group. Specifically, the alkali-soluble resin includes an acrylic resin having an acidic group, an α-olefin / (maleic anhydride) maleic anhydride copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth) acrylic acid copolymer, or Isobutylene / (maleic anhydride) maleic anhydride copolymer and the like can be mentioned. Among them, an acrylic resin having an acidic group and at least one resin selected from a styrene / styrene sulfonic acid copolymer, particularly an acrylic resin having an acidic group, is preferably used because of its high heat resistance and transparency.

Examples of the active energy ray-curable resin having an ethylenically unsaturated double bond include a resin in which an unsaturated ethylenically double bond is introduced by the methods (a) and (b) shown below.

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

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

Examples of unsaturated monobasic acids include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-position haloalkyl of (meth) acrylic acid, alkoxyls, halogens, nitros, and cyano substituents. Examples thereof include monocarboxylic acids, which may be used alone or in combination of two or more.

Examples of the polybasic acid anhydride include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride and the like, and these may be used alone or in combination of two or more. It doesn't matter. If necessary, such as by increasing the number of carboxyl groups, a tricarboxylic dianhydride such as trimellitic dianhydride may be used, or a tetracarboxylic dianhydride such as pyromellitic dianhydride may be used to obtain the remaining anhydride. The group can also be hydrolyzed. Further, when etrahydrophthalic anhydride or maleic anhydride having an unsaturated ethylenically double bond is used as the polybasic acid anhydride, the unsaturated ethylenically 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 with one or more other monomers. There is a method of introducing an unsaturated ethylenically double bond and a carboxyl group by adding an unsaturated ethylenic monomer having an epoxy group to a part of the carboxyl groups.

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

Examples of the unsaturated ethylenic monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxybutyl (meth) acrylate, and glycerol. Examples thereof include hydroxyalkyl (meth) acrylates such as (meth) acrylate and cyclohexanedimethanol mono (meth) acrylate, and these may be used alone or in combination of two or more. Further, a polyether mono (meth) acrylate obtained by addition-polymerizing the above hydroxyalkyl (meth) acrylate with ethylene oxide, propylene oxide, and / or butylene oxide, (poly) γ-valerolactone, and (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. 2-Hydroxyethyl (meth) acrylate or glycerol (meth) acrylate is preferable from the viewpoint of suppressing foreign matter in the coating film.

Examples of the unsaturated ethylenic monomer having an isocyanate group include 2- (meth) acryloyloxyethyl isocyanate and 1,1-bis [(meth) acryloyloxy] ethyl isocyanate, but the present invention is limited to these. However, two or more types can be used together.

(Thermosetting resin)
Examples of the thermosetting resin used for 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 a low molecular weight 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 crosslink density of the coating film is increased, the heat resistance is improved, and the pigment aggregation during the firing of the filter segment is suppressed. Be done.
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 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-cyclohexene-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3- Methyl-1,3-butanol, 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 monotersial 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 Diethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethylate , 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 Cyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, dibasic acid ester and the like can be mentioned. These organic solvents may be used alone or in admixture of two or more.

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

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

<Manufacturing method of coloring composition>
In the coloring composition of the present invention, a dispersant containing the quinophthalone compound (A) represented by the general formula (1), the coloring agent, and the binder resin are contained in a coloring agent carrier composed of a solvent, if necessary. , Preferably, together with a dispersion aid such as a dye derivative, can be produced by finely dispersing using various dispersion 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) is highly soluble, specifically, if it is highly soluble in the organic solvent used, dissolved by stirring, and no foreign matter is confirmed, the above-mentioned It is not necessary to disperse and manufacture in such a fine manner.

Further, the coloring composition of the present invention may be produced by mixing a pigment, a quinophthalone compound (A) represented by the general formula (1), another coloring agent and the like separately dispersed in a coloring agent 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 appropriately used. Since the dispersion aid is excellent in dispersing the colorant and has a great effect of preventing the reaggregation of the colorant after dispersion, a coloring composition obtained by dispersing the colorant in the colorant carrier using the dispersion aid is used. When used, a color filter having high spectral transmittance can be obtained.

Examples of the dye derivative include compounds in which an organic pigment, anthraquinone, acridone or triazine is introduced with a basic substituent, an acidic substituent, or a phthalimidemethyl group which may have a substituent. Those described in Japanese Patent Publication No. 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, and these can be used. It can be used alone or in combination of two or more.

The blending amount of the dye derivative is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and most preferably 3 parts by mass or more with respect to 100 parts by mass of the colorant from the viewpoint of improving dispersibility. Further, from the viewpoint of heat resistance and light resistance, it is preferably 40 parts by mass or less, and most preferably 35 parts by mass or less with respect to 100 parts by mass of the colorant.

The resin-type dispersant has a pigment-affinitive moiety having a property of adsorbing to the colorant and a moiety compatible with the colorant carrier, and adsorbs to the colorant to stabilize the dispersion on the colorant carrier. It works. Specifically, as the resin type dispersant, 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. , Polysiloxane, long-chain polyaminoamide phosphate, hydroxyl group-containing polycarboxylic acid ester, modified products of these, amides and salts thereof formed by the reaction of poly (lower alkyleneimine) with polyester having a free carboxyl group. Oil-based dispersants such as, (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, water-soluble such as polyvinylpyrrolidone Resins, water-soluble polymer compounds, polyester-based, modified polyacrylate-based, ethylene oxide / propylene oxide-added compounds, phosphoric acid ester-based, etc. are used, and these can be used alone or in admixture of two or more. It is not necessarily limited to these.

Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 170 manufactured by Big Chemie Japan. , 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 Bykuman, etc., SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000 , 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc., BASF EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451 and 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc. And so on.

Examples of the surfactant include sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkylnaphthalin sulfonate, sodium alkyldiphenyl ether disulfonate. , Monoethanolamine lauryl sulfate, Triethanolamine lauryl sulfate, Ammonium lauryl sulfate, Monoethanolamine stearate, Monoethanolamine styrene-acrylic acid copolymer, Anionic surfactants such as polyoxyethylene alkyl ether phosphate; 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 their ethylene oxide adducts; alkyl betaines such as alkyldimethylaminoacetic acid betaine and amphoteric surfactants such as alkylimidazoline, which may be used alone or in combination of two or more. They can be mixed and used, but are not necessarily limited to these.

When a resin-type dispersant or a surfactant is added, it is preferably 0.1 to 55 parts by mass, more preferably 0.1 to 45 parts by mass with respect to 100 parts by mass of the colorant from the viewpoint of the effect on dispersion. 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. Further, 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 can contain a photopolymerization initiator. When the photopolymerization initiator is used, the blending amount is preferably 5 to 400 parts by mass based on the total mass of the colorant (100 parts by mass), and is 10 to 300 parts by mass from the viewpoint of photocurability. More preferably.

As the photopolymerization initiator, a conventionally known polymerization initiator can be used. Specifically, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzylmethyl ketal, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone. , 1-Hydroxycyclohexylphenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-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] 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- Phenyl phosphines such as phosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide; other examples include phenylglycoxymethyl ester. More specifically, Irgacure 651, Irgacure 184, Darocure 1173, Irgacure 500, Irgacure 1000, Irgacure 2959, Irgacure 907, Irgacure 369, Irgacure 379, Irgacure 1700, Irgacure 149, Irgacure. Cure 1800, Irgacure 1850, Irgacure 819, Irgacure 784, Irgacure 261, Irgacure OXE-01, Irgacure OXE-02 (BASF), Adecaoptomer N1717, Adecaoptomer N1919, Adeca Acluls NCI- 831 (ADEKA), Esacure1001M (Lamberti), JP-A-59-1281, JP-A-61-9621, Triazine derivatives described in JP-A-60-60104, JP-A-59-1504, and JP-A-59-1504. Organic peroxides described in JP-A-61-243807, Japanese Patent Publication No. 43-23684, Japanese Patent Publication No. 44-6413, Japanese Patent Application Laid-Open No. 47-1604, and USP No. 3567453. , USP No. 2848328, USP No. 2852379 and USP No. 2940853, Organic Azide Compounds, Japanese Patent Publication No. 36-22062, Japanese Patent Publication No. 37-13109, Japanese Patent Publication No. 38-18015. Ortho-quinone diazodes described in Japanese Patent Publication No. 45-9610, Japanese Patent Application Laid-Open No. 55-39162, Japanese Patent Application Laid-Open No. 59-140203 and "MACROMOLECULES", Vol. 10, p. 1307 ( Various onium compounds including the iodonium compound described in 1977), the azo compound described in JP-A-59-142205, JP-A-1-54440, European Patent No. 109851, European Patent No. 126712. Book, "Journal of Imaging Science (J.IMAG.SCI.)", Vol. 30, p. 174 (1986), Metal Allen Complex, Titanosens, JP-A-61-151197, Contains transition metals such as ruthenium described in "COORDINATION CHEMISTRY REVIEW", Vol. 84, pp. 85-277 (1988) and JP-A-2-182701. Transition metal complexes to be used, aluminate complexes described in JP-A-3-209477, borate compounds described in JP-A-2-157760, JP-A-55-127550 and JP-A-60-202437. 2,4,5-Triarylimidazole dimer, carbon tetrabromide, organic halogen compounds described in JP-A-59-107344, sulfonium complexes or oxosulfonium complexes described in JP-A-5-255347, Kaisho 54-99185, JP-A-63-264560 and Aminoketone compounds described in JP-A-10-299777, JP-A-2001-264530, JP-A-2001-261716, JP-A-2000-80068. , JP-A-2001-233842, JP-A-2004-534977, JP-A-2006-342166, JP-A-2008-09470, JP-A-2009-40762, JP-A-2010-15025, JP-A-2010-189279, JP-A-2010 -1892880, Japanese Patent Application Laid-Open No. 2010-526846, Japanese Patent Application Laid-Open No. 2010-527338, Japanese Patent Application Laid-Open No. 2010-527339, USP3558309 (1971), USP4202697 (1980), and JP-A-61-24558. Examples include oxime ester compounds.

These photopolymerization initiators can be used alone or in admixture of two or more at any ratio, if necessary.

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

Examples of monomers and oligomers that are cured by ultraviolet rays or heat to produce a transparent resin include polyethylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and 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 (Meta) Acrylate, Trimethylol Propanetri (Meta) Acrylate, Tris (Acryloxyethyl) Isocyanurate, Tris (Methyloxyethyl) Isocyanurate, Dipentaerythritol Penta (Meta) Acrylate, Dipentaerythritol Hexa (Meta) ) Acrylate, various acrylic acid esters such as caprolactone-modified dipentaerythritol hexaacrylate, ditrimethylolpropanetetra (meth) acrylate, epoxy acrylate, pentaerythritol tetra (meth) acrylate, and methacrylic acid ester, (meth) acrylic acid, styrene, acetic acid. Vinyl, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinylformamide, acrylonitrile and the like can be mentioned, but the effects of the present invention are limited thereto. It is not something that is done.

Moreover, the photopolymerizable monomer may contain an acid group. For example, esterified products of free hydroxyl group-containing poly (meth) acrylates of polyhydric alcohol and (meth) acrylic acid and dicarboxylic acids; esterified products of polyvalent carboxylic acid and monohydroxyalkyl (meth) acrylates, etc. Can be mentioned. Specific examples include monohydroxyoligoacrylates such as trimethylolpropane diacrylate, trimethylolpropanedimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentamethacrylate, or monohydroxyoligomethacrylates. Free carboxyl group-containing monoesteride with dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, and terephthalic acid; propane-1,2,3-tricarboxylic acid (tricarbaryl 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 thereof include monohydroxymonoacrylates such as hydroxyethyl methacrylate, 2-hydroxypropyl acrylate and 2-hydroxypropyl methacrylate, and oligoesterides containing a free carboxyl group with monohydroxymonomethacrylates, but the effects of the present invention are limited thereto. It is not something that is done.

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

<Sensitizer>
Further, the coloring composition of the present invention may contain a sensitizer.
Examples of the sensitizer include benzophenone derivatives, unsaturated ketone derivatives such as chalcone derivatives and dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, and naphthoquinone derivatives. Polymethine dyes such as anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonoal derivatives, acrydin 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 thereof include porphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrilium derivatives, tetraphyllin derivatives, anurene derivatives, spiropirane derivatives, spiroxazine derivatives, thiospiropirane derivatives, metal arene complexes, and organic ruthenium complexes. , 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), Chuzaburo Ikemori et al., "Special". Examples of dyes and sensitizers described in "Functional Materials" (1986, CMC) are not limited to these, and other dyes and sensitizers that absorb light from the ultraviolet to the near infrared region. Sensitive agents may be mentioned, and two or more of these may be used in any ratio as required. Among the above sensitizers, the thioxanthone derivatives include 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, and 1-chloro-4-propoxythioxanthone. Examples of benzophenones include benzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, 4,4'-dimethylbenzophenone, 4,4'-dimethoxybenzophenone, and 4,4'-bis. Examples of coumarins include (diethylamino) benzophenone, and examples of coumarins include coumarin 1, coumarin 338, and coumarin 102. Examples of ketocoumarins include 3,3'-carbonylbis (7-diethylaminocoumarin) and the like. However, it is not limited to these.

Two or more sensitizers may be used at an arbitrary ratio, if necessary. When the sensitizer is used, the blending amount 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 is photocured. From the viewpoint of sex, it is more preferably 5 to 50 parts by mass.

<Multifunctional thiol>
The coloring composition of the present invention can contain a polyfunctional thiol that acts as a chain transfer agent.
The polyfunctional thiol may be a compound having two or more thiol groups, for example, hexanedithiol, decandithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene. Glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropanthioglycolate, trimethylolpropanthiotripropionate, trimethylolpropanthris (5-mercaptobutyrate), pentaerythritol tetraxthioglycolate, Pentaerythritol tetraxthiopropionate, tris (2-hydroxyethyl) trimercaptopropionate, isocyanurate, 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 alone or in admixture of two or more at any ratio as required.

The content of the polyfunctional thiol is preferably 0.1 to 30% by mass, more preferably 1 to 20% by mass, based on the mass of the total solid content of the coloring composition (100% by mass). 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 lowered.

<Amine compounds>
Further, 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, and 2-dimethylaminobenzoate. Examples thereof include ethyl, 2-ethylhexyl 4-dimethylaminobenzoate, and N, N-dimethylparatoluidine.

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

A particularly preferable leveling agent is a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, which has a hydrophilic group but has low solubility in water, and when added to a coloring composition, the same. It is useful to have a feature of low surface tension lowering ability and good wettability to the glass plate despite low surface tension lowering ability, and the amount of addition does not cause defects in the coating film due to foaming. Those capable of sufficiently suppressing chargeability can be preferably used. As a leveling agent having such preferable properties, dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used. The polyalkylene oxide unit includes a polyethylene oxide unit and a polypropylene oxide unit, and dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

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 polyalkylene oxide unit is bonded to the terminal of dimethylpolysiloxane, and dimethylpolysiloxane. It may be any of the linear block copolymer types that are alternately and repeatedly bonded. Didimethylpolysiloxane 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. 2207, but is not limited to these.

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

Anionic surfactants to be added as an auxiliary to the leveling agent include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkylnaphthalin sulfonate, and alkyldiphenyl ether disulfonic 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 include ester.

Examples of the chaotic surfactant added as a supplement to the leveling agent include alkyl quaternary ammonium salts and ethylene oxide adducts thereof. Nonionic surfactants to be added as a supplement to the leveling agent include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate, and polyoxyethylene sorbitan monostearate. , Polyethylene glycol monolaurate and the like; alkyl betaines such as alkyldimethylaminoacetic acid betaine, amphoteric surfactants such as 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, or the like, if necessary, in order to assist the curing of the thermosetting resin. Phenolic resins, amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds and the like are effective as the curing agent, but the curing agent is not particularly limited to these, and is a thermosetting resin. Any curing agent may be used as long as it can react with. Further, among these, a compound having two or more phenolic hydroxyl groups in one molecule and an amine-based curing agent are preferably mentioned. Examples of the curing accelerator include amine compounds (for example, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl). -N, N-dimethylbenzylamine, etc.), quaternary ammonium salt compounds (eg, triethylbenzylammonium chloride, etc.), blocked isocyanate compounds (eg, dimethylamine, etc.), imidazole derivative bicyclic amidin compounds and salts thereof (eg, 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, etc.) -Methacryloxyethyl-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, etc.) 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 ingredients>
The coloring 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 can be contained in order to improve the adhesion with the transparent substrate.

Examples of the storage stabilizer include quaternary ammonium chloride 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 with respect to 100 parts by mass of the total amount of the colorant.

Adhesion improvers include vinylsilanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane and vinyltrimethoxysilane, (meth) acrylic silanes such as γ-methacryloxypropyltrimethoxysilane, and β- (5, 4-Epylcyclohexyl) ethyltrimethoxysilane, β- (5,4-epylcyclohexyl) methyltrimethoxysilane, β- (5,4-epylcyclohexyl) ethyltriethoxysilane, β- (5,4-epylcyclohexyl) Epoxysilanes such as methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (amino) Ethyl) γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysisilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-amino Examples thereof include aminosilanes such as propyltrimethoxysilane and N-phenyl-γ-aminopropyltriethoxysilane, and silane coupling agents such as 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 colorant in the coloring composition.

<Removal of coarse particles>
The coloring composition of the present invention was mixed with coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, and more preferably 0.5 μm or more of coarse particles by means of centrifugation, sintering filter, 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 having a size of 0.5 μm or more. More preferably, it is 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 filter segment.

As the base material such as the transparent substrate constituting the color filter, glass plates such as soda-lime glass, low-alkali borosilicate glass, and non-alkali aluminoborosilicate glass, and resin plates such as polycarbonate, polymethylmethacrylate, and polyethylene terephthalate are used. Used. Further, 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 the panelization.

<Manufacturing method of color filter>
The color filter of the present invention can be manufactured by a printing method or a photolithography method.
The formation of filter segments by the printing method can be patterned simply by repeating printing and drying of the coloring composition prepared as the printing ink, so that the color filter manufacturing method is low cost and excellent in mass productivity. There is. Further, with the development of printing technology, it is possible to print a fine pattern having high dimensional accuracy and smoothness. In order to perform printing, it is preferable that the composition is such that the ink does not dry or solidify on the printing plate or on the blanket. It is also important to control the fluidity of the ink on the printing machine, and the viscosity of the ink can be adjusted by using a dispersant or an extender pigment.

When the filter segment is formed by the photolithography method, the coloring composition prepared as the solvent-developing type or alkali-developing type colored resist material is applied onto a transparent substrate by spray coating, spin coating, slit coating, roll coating or the like. By the method, the coating is applied so that the dry film thickness is 0.2 to 5 μm. If necessary, the dried film is exposed to ultraviolet rays through a mask having a predetermined pattern provided in contact with or without contact with the film. Then, after immersing in a solvent or an alkaline developer or spraying the 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 manufacture a color filter. be able to. Further, in order to promote the polymerization of the colored resist material, heating can be applied as needed. According to the photolithography method, a color filter having higher accuracy than the above printing method can be manufactured.

At the time of development, an aqueous solution of sodium carbonate, sodium hydroxide or the like is used as the alkaline developer, 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, the colored resist material is applied and dried, and then a water-soluble or alkaline water-soluble resin such as polyvinyl alcohol or a 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 methods, and the coloring composition of the present invention can be used in any of the methods. The electrodeposition method is a method of manufacturing a color filter by electrodepositing each color filter segment on the transparent conductive film by electrophoresis of colloidal particles using the transparent conductive film formed on the substrate. .. Further, 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 each color filter segment is formed on the transparent substrate or the reflective substrate. As the black matrix, a multilayer film of chromium or chromium / chromium oxide, 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 form a thin film transistor (TFT) on the transparent substrate or the reflective substrate in advance, and then form each color filter segment. Further, an overcoat film, a transparent conductive film, or the like is formed on the color filter of the present invention, if necessary.

The color filter is bonded to the opposite substrate using a sealing agent, liquid crystal is injected from the injection port provided in the sealing portion, the injection port is sealed, and a polarizing film or a retardation film is placed on the outside of the substrate as necessary. A liquid crystal display panel is manufactured by laminating.

Such liquid crystal display panels include twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), vertical alignment (VA), and optical convencend bend (OCB). It can be used in the 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 the example, "parts" and "%" represent "parts by mass" and "% by mass", respectively. Further, "PGMAC" means propylene glycol monomethyl ether acetate.

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

(Acid value of resin)
80 ml of acetone and 10 ml of water are added to 0.5 to 1.0 part of the resin solution, stirred and uniformly dissolved, and a 0.1 mol / L KOH aqueous solution is used as a titrator, and an automatic titrator (“COM-555”” is used. The acid value of the resin solution was measured by titration using (manufactured by Hiranuma Sangyo). 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 substitutions in pigment)
The number of halogen substitutions in the pigment is determined by analyzing the liquid obtained by burning the pigment by the oxygen combustion flask method and absorbing the combusted product in water by ion chromatography (ICS-2000 ion chromatography, manufactured by DIONEX). 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). The halogen content is the signal intensity of the molecular ion peaks corresponding to each component (each peak value) and the integrated value of each peak value (total peak value) in the mass spectrum obtained by mass spectrometry of the pigment powder. Was calculated and calculated from the ratio of each peak value to all peak values. 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 the total peak value was 1% or more.

<Manufacturing method of binder resin>
(Adjustment 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 4-neck flask, the temperature was raised to 80 ° C., the inside of the reaction vessel was replaced with nitrogen, and then a dropping tube was used. 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, 7.4 parts of paracumylphenol ethylene oxide-modified acrylate (“Aronix M110” manufactured by Toa Synthetic Co., Ltd.), A mixture of 0.4 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropping, 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 is sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content. Propylene glycol monoethyl is prepared so that the non-volatile content is 20% by mass in the previously synthesized resin solution. Acrylic resin solution 1 was prepared by adding ether acetate.

(Preparation of acrylic resin solution 2)
207 parts of cyclohexanone was placed in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube and a stirrer in a separable 4-neck flask, the temperature was raised to 80 ° C., the inside of the reaction vessel 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 Toa Synthetic 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 completion of the dropping, the reaction was continued for another 3 hours to obtain a copolymer resin solution. Next, for the entire amount of the obtained copolymer solution, nitrogen gas was stopped, dry air was injected for 1 hour, and the mixture was stirred, cooled to room temperature, and then 2-methacryloyloxyethyl isocyanate (Karens manufactured by Showa Denko Co., Ltd.). A mixture of 6.5 parts of MOI), 0.08 parts of dibutyltin laurate and 26 parts of cyclohexanone was added dropwise at 70 ° C. over 3 hours. After completion of the dropping, the reaction was continued for another 1 hour to obtain a solution of acrylic resin. After cooling to room temperature, about 2 parts of the resin solution was sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content, and cyclohexanone was added to the previously synthesized resin solution so that the non-volatile content was 20% by weight. 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 solution 1)
A flask equipped with a cooling tube and a stirrer was charged with 1.0 part by mass of AIBN (2,2'-azobisisobutyronitrile) and 186 parts by mass of propylene glycol monomethyl ether acetate, followed by 27 parts by mass of methyl methacrylate and butyl methacrylate. 27 parts by mass, 21 parts by mass of 2-ethylhexyl methacrylate, 18 parts by mass of benzyl methacrylate and 3.6 parts by mass of cumyldithiobenzoate were charged and replaced with nitrogen for 30 minutes. Then, the reaction solution was gently stirred to raise the temperature of the reaction solution to 60 ° C., and this temperature was maintained for 24 hours for living radical polymerization. Next, a solution prepared by dissolving 1.0 part by mass of AIBN and 35 parts by mass of dimethylaminoethyl methacrylate in 70 parts by mass of propylene glycol monomethyl ether acetate and substituting nitrogen for 30 minutes was added to this reaction solution, and living radical polymerization was carried out at 60 ° C. for 24 hours. A solution of the block copolymer was obtained. To the obtained block copolymer solution, 25 parts by mass of benzyl chloride and 50 parts by mass of propylene glycol monomethyl ether were added, and the reaction was carried out at 80 ° C. for 2 hours to adjust the solid content concentration to 40%. Dispersant solution 1 was obtained. The resin type dispersant 1 has an A block having a repeating unit derived from methacryloyloxyethylbenzyldimethylammonium chloride and dimethylaminoethylmethacrylate and a B block having a repeating unit derived from methylmethacrylate, butylmethacrylate, 2-ethylhexylmethacrylate and benzylmethacrylate. It is a block copolymer composed of. As a result of proton NMR measurement, the copolymerization ratio of each repeating unit was methacryloxyethyl benzyldimethylammonium chloride / dimethylaminoethyl methacrylate / methyl methacrylate / butyl methacrylate / 2-ethylhexyl methacrylate / benzyl methacrylate = 34/4/18/18 /. It was 14/12 (mass ratio).

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

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

(Method for identifying quinophthalone compounds)
The identification of the quinophthalone compound of the present invention is a mass spectrum molecule obtained from Waters ACQUITY UPLS H-Class (column used: ACQUITY UPLC BEH C18 Volume 130 Å, 1.7 μm, 2.1 mm × 50 mm) / Ms TAP XEVO TQD. The obtained compound was identified based on the agreement between the ion peak and the mass number obtained by calculation.

[Example 1] (Production of quinophthalone compound A-1)
60 parts of methyl benzoate, 60 parts of benzoic acid, 20 parts of 8-hydroxyquinaldine and 22.3 parts of phthalic anhydride 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. After the precipitated crystals were separated by filtration, the crystals were further washed with methanol and dried under reduced pressure to obtain 32.0 parts (yield 88%) of Intermediate 1.
132 parts of the intermediate, 320 parts of N, N-dimethylacetamide (DMAc), 18.5 parts of diazabicycloundecene (DBU), and 22.6 parts of 1,4-butanesulton were added, and the mixture was heated and stirred at 120 ° C. .. After 5 hours, after cooling to 25 ° C., 500 parts of water was added to this reaction solution. After stirring for 30 minutes, the precipitated solid was separated by filtration, further washed with 1000 parts of water, and dried under reduced pressure to obtain 21.1 parts (yield 45%) of compound A-1.

[Example 2] (Production of quinophthalone compound A-2)
132 parts of the intermediate, 320 parts of DMAc, 18.5 parts of DBU, and 22.6 parts of 1,4-butansulton were added, and the mixture was heated and stirred at 120 ° C. After 5 hours, the mixture was cooled to 25 ° C., 160 parts of water was added to the reaction solution, and the mixture was stirred for 30 minutes. Next, 105.7 parts of 8% liquid aluminum sulfate was added, and the mixture was stirred for 30 minutes. Then, the precipitated solid was filtered off, washed with 500 parts of water, and dried under reduced pressure to add 41 to compound A-2. .2 parts (yield 86%) were obtained.

[Example 3] (Production of quinophthalone compound A-3)
132 parts of the intermediate, 320 parts of DMAc, 18.5 parts of DBU, and 22.6 parts of 4-butane sulton were added, and the mixture was heated and stirred at 120 ° C. After 5 hours, the mixture was cooled to 25 ° C., 160 parts of water was added to the reaction solution, and the mixture was stirred for 30 minutes. Next, 22.6 parts of laurylamine was added, and after stirring for 30 minutes, the precipitated solid was filtered off, further washed with 500 parts of water, dried under reduced pressure, and 53.4 parts of compound A-3 was added. (Yield 79%) was obtained.

[Example 4] (Production of quinophthalone compound A-4)
In the synthetic reaction of Intermediate 1, the reaction was carried out in the same manner except that 22.3 parts of phthalic anhydride was changed to 33.2 parts of tetrafluorophthalic anhydride, and 40.8 parts of Intermediate 2 (yield 90%) was added. )Obtained.
In the synthetic reaction of compound A-1, 32 parts of the intermediate was 240.8 parts of the intermediate, 320 parts of DMAc was 410 parts, 18.5 parts of DBU was 18.9 parts, and 22.6 parts of 1,4-butane sultone was 1 part. , 3-Propane sultone was changed to 20.7 parts, and the reaction was carried out in the same manner to obtain 30.1 parts (yield 54%) of compound A-4.

[Example 5] (Production of quinophthalone compound A-5)
In the synthetic reaction of compound A-3, 32 parts of the intermediate was 240.8 parts of the intermediate, 320 parts of DMAc was 410 parts, 18.5 parts of DBU was 18.9 parts, and 22.6 parts of 1,4-butansulton was 1 part. , 3-Propane sulton (20.7 parts) and laurylamine (22.6 parts) were changed to 28.8 parts, and the same reaction was carried out to obtain 70.7 parts (yield 75%) of Compound A-5.

[Example 6] (Production of quinophthalone compound A-6)
In the synthetic reaction of Intermediate 1, the reaction was carried out in the same manner except that 22.3 parts of phthalic anhydride was changed to 43.1 parts of tetrachlorophthalic anhydride, and 48.8 parts of Intermediate 3 (yield 91%). )Obtained.
In the synthetic reaction of compound A-1, 32 parts of intermediate was 348.8 parts of intermediate, 320 parts of DMAc was 490 parts, 18.5 parts of DBU was 19.2 parts, and 22.6 parts of 1,4-butansulton was 23 parts. The reaction was carried out in the same manner except that the content was changed to .4 parts, and 37.3 parts (yield 58%) of compound A-6 was obtained.

[Example 7] (Production of quinophthalone compound A-7)
In the synthetic reaction of compound A-2, 32 parts of intermediate was 348.8 parts of intermediate, 320 parts of DMAc was 490 parts, 18.5 parts of DBU was 19.2 parts, and 22.6 parts of 1,4-butanesulfon was 23 parts. The reaction was carried out in the same manner except that 105.7 parts of .4 parts and 8% liquid aluminum sulfate were changed to 109.2 parts, and 57.3 parts (yield 89%) of Compound A-7 was obtained.

[Example 8] (Production of quinophthalone compound A-8)
In the synthetic reaction of Intermediate 1, the reaction was carried out in the same manner except that 22.3 parts of phthalic anhydride was changed to 29.9 parts of 2,3-naphthalenedicarboxylic acid anhydride, and 37.5 parts of Intermediate 4 (yield) was obtained. The rate was 88%).
In the synthetic reaction of compound A-1, the reaction was carried out in the same manner except that 32 parts of intermediate was changed to 437.5 parts of intermediate and 320 parts of DMAc was changed to 380 parts, and 36.8 parts of compound A-8 (yield). Rate 70%) Obtained.

[Example 9] (Production of quinophthalone compound A-9)
In the synthetic reaction of compound A-2, the reaction was carried out in the same manner except that 32 parts of intermediate was changed to 437.5 parts of intermediate and 320 parts of DMAc was changed to 380 parts, and 46.8 parts of compound A-9 (yield). Rate 89%) Obtained.

[Example 10] (Production of quinophthalone compound A-10)
In the synthetic reaction of Intermediate 1, the same reaction was carried out except that 20 parts of 8-hydroxyquinaldine was changed to 20 parts of 6-bromo-8-hydroxyquinaldine and 22.3 parts of phthalic anhydride were changed to 14.9 parts. , 27.2 parts (yield 88%) of Intermediate 5 was obtained.
In the synthetic reaction of compound A-1, 32 parts of intermediate was 527.2 parts of intermediate, 320 parts of DMAc was 270 parts, 18.5 parts of DBU was 12.4 parts, and 22.6 parts of 1,4-butansulton was 15 parts. The reaction was carried out in the same manner except that it was changed to 1 part, and the reaction was carried out in the same manner except that it was changed to 1. 23.8 parts (yield 64%) of Compound A-10 was obtained.

[Example 11] (Production of quinophthalone compound A-11)
In the synthetic reaction of Intermediate 1, the reaction was carried out in the same manner except that 22.3 parts of phthalic anhydride was changed to 46.1 parts of 2,3-dibromophthalic anhydride, and 50 parts of Intermediate 6 (yield 89). %)Obtained.
In the synthetic reaction of compound A-1, 32 parts of intermediate was 650 parts of intermediate, 320 parts of DMAc was 500 parts, 18.5 parts of DBU was 18.7 parts, and 22.6 parts of 1,4-butansultone was 1,3 parts. The reaction was carried out in the same manner except that the amount was changed to 20.5 parts of −propane sultone to obtain 34.4 parts (yield 54%) of Compound A-11.

[Example 12] (Production of quinophthalone compound A-12)
In the synthetic reaction of Intermediate 1, 20 parts of 8-hydroxyquinaldine was changed to 20 parts of 5-nitro-8-hydroxyquinaldine, and 22.3 parts of phthalic anhydride was changed to 33.6 parts of tetrachlorophthalic anhydride. Reacted in the same manner to obtain 40.7 parts (yield 88%) of Intermediate 7.
In the synthetic reaction of compound A-1, 32 parts of the intermediate was 740.7 parts of the intermediate, 320 parts of DMAc was 410 parts, 18.5 parts of DBU was 14.5 parts, and 22.6 parts of 1,4-butansulton was 17 parts. The reaction was carried out in the same manner except that the content was changed to .6 parts, and 33.6 parts (yield 64%) of Compound A-12 was obtained.

[Example 13] (Production of quinophthalone compound A-13)
In the synthesis reaction of Intermediate 1, 20 parts of 8-hydroxyquinaldine was changed to 20 parts of 4-methoxy-8-hydroxyquinaldine, and 22.3 parts of phthalic anhydride was changed to 22.6 parts of 4-methoxyphthalic anhydride. The reaction was carried out in the same manner except for the above, and 31.4 parts (yield 85%) of Intermediate 8 was obtained.
In the synthetic reaction of compound A-1, 32 parts of the intermediate was 8 31.4 parts of the intermediate, 320 parts of DMAc was 310 parts, 18.5 parts of DBU was 15.1 parts, and 22.6 parts of 1,4-butane sultone was 1 part. , 3-Propane sultone was changed to 16.5 parts, and the reaction was carried out in the same manner to obtain 19.1 parts (yield 45%) of compound A-13.

[ Reference Example 14 ] (Production of quinophthalone compound A-14)
440 parts of the intermediate, 400 parts of DMAc, 5.6 parts of sodium hydroxide and 17.7 parts of 2-bromoethanol were added, and the mixture was heated and stirred at 120 ° C. After 5 hours, after cooling to 25 ° C., 400 parts of methanol was added to this reaction solution. After stirring for 30 minutes, the precipitated solid was filtered off, washed with 500 parts of water, and dried under reduced pressure to obtain 39.8 parts (yield 88%) of Intermediate 9.
In the synthetic reaction of compound A-1, 32 parts of intermediate was 9 39.8 parts of intermediate, 320 parts of DMAc was 400 parts, 18.5 parts of DBU was 17.4 parts, and 22.6 parts of 1,4-butane sultone was 1 part. , 3-Propane sultone was changed to 19 parts, and the reaction was carried out in the same manner to obtain 34.6 parts (yield 66%) of compound A-14.

[Example 15] (Production of quinophthalone compound A-15)
In the synthetic reaction of Intermediate 1, the reaction was carried out in the same manner except that 22.3 parts of phthalic anhydride was changed to 30.8 parts of 4-tert-butylphthalic anhydride, and 37.3 parts of Intermediate 10 (yield). 86%) obtained.
In the synthetic reaction of compound A-1, 32 parts of the intermediate was 10 37.3 parts of the intermediate, 320 parts of DMAc was 380 parts, 18.5 parts of DBU was 18.1 parts, and 22.6 parts of 1,4-butane sultone was 1 part. , 3-Propane sultone was changed to 19.8 parts, and the reaction was carried out in the same manner to obtain 29.3 parts (yield 58%) of compound A-15.

[Example 16] (Production of quinophthalone compound A-16)
In the synthetic reaction of Intermediate 1, the reaction was carried out in the same manner except that 22.3 parts of phthalic anhydride was changed to 29 parts of 4-trimellitic anhydride, and 39.4 parts of Intermediate 11 (yield 94%). Obtained.
In the synthetic reaction of compound A-2, 32 parts of intermediate 11 39.4 parts, 320 parts of DMAc 400 parts, 18.5 parts of DBU 39.6 parts, and 22.6 parts of 1,4-butanesulfon 40 parts. The reaction was carried out in the same manner except that 2 parts and 105.7 parts of 8% liquid aluminum sulfate were changed to 226 parts, and 50.8 parts (yield 71%) of Compound A-16 was obtained.

[Example 17] (Production of quinophthalone compound A-17)
In the synthetic reaction of Intermediate 1, the reaction was carried out in the same manner except that 22.3 parts of phthalic anhydride was changed to 24.5 parts of 4-methylphthalic anhydride, and 33.2 parts of Intermediate 12 (yield 87%). )Obtained.
In the synthetic reaction of compound A-1, 32 parts of the intermediate was 12 33.2 parts of the intermediate, 320 parts of the DMAc was 330 parts, 18.5 parts of the DBU was 18.3 parts, and 22.6 parts of 1,4-butansulton was 22 parts. The reaction was carried out in the same manner except that the content was changed to 3 parts, and 28.3 parts (yield 59%) of compound A-17 was obtained.

[ Reference Example 18 ] (Production of quinophthalone compound A-18)
440 parts of the intermediate, 400 parts of DMAc, 6.1 parts of sodium hydroxide, and 30.5 parts of 4-hydroxyphenacyl bromide were added, and the mixture was heated and stirred at 120 ° C. After 5 hours, after cooling to 25 ° C., 400 parts of methanol was added to this reaction solution. After stirring for 30 minutes, the precipitated solid was filtered off, washed with 500 parts of water, and dried under reduced pressure to obtain 28.0 parts (yield 56%) of Intermediate 13.
In the synthetic reaction of compound A-1, 32 parts of the intermediate 13 28.0 parts, 320 parts of DMAc 280 parts, 11 parts of DBU 18.5 parts, and 1,3 parts of 1,4-butane sultone 22.6 parts. The reaction was carried out in the same manner except that the mixture was changed to 12.1 parts of propane sultone to obtain 19.8 parts (yield 55%) of Compound A-18.

[Example 19] (Production of quinophthalone compound A-19)
In the synthesis reaction of Intermediate 1, 20 parts of 8-hydroxyquinaldine was converted to 20 parts of 3-methoxy-8-hydroxyquinaldine, and 22.3 parts of phthalic anhydride were converted to 25.2 parts of 2,3-naphthalenedicarboxylic acid anhydride. The reaction was carried out in the same manner except for the modification, and 34.0 parts (yield 87%) of Intermediate 14 was obtained.
In the synthetic reaction of compound A-1, 32 parts of the intermediate was 14 34.0 parts of the intermediate, 320 parts of DMAc was 340 parts, 18.5 parts of DBU was 15.4 parts, and 22.6 parts of 1,4-butane sultone was 1 part. , 3-Propane sultone was changed to 16.9 parts, and the reaction was carried out in the same manner to obtain 26.7 parts (yield 59%) of compound A-19.

[Example 20] (Production of quinophthalone compound A-20)
In the synthesis reaction of Intermediate 1, 20 parts of 8-hydroxyquinaldine was converted to 20 parts of 7-bromo-8-hydroxyquinaldine and 22.3 parts of phthalic anhydride were converted to 20.0 parts of 2,3-naphthalenedicarboxylic acid anhydride. The reaction was carried out in the same manner except for the modification, and 28.8 parts (yield 82%) of Intermediate 15 was obtained.
In the synthetic reaction of compound A-1, 32 parts of the intermediate was 15 28.8 parts of the intermediate, 320 parts of DMAc was 290 parts, 11.5 parts of DBU was 11.5 parts, and 22.6 parts of 1,4-butansulton was 14 parts. The reaction was carried out in the same manner except that the content was changed to 1 part, and 24.8 parts (yield 65%) of Compound A-20 was obtained.

[Example 21] (Production of quinophthalone compound A-21)
Add 60 parts of methyl benzoate, 60 parts of benzoic acid, 20 parts of 8-aminoquinaldine, and 22.5 parts of 2,3-naphthalenedicarboxylic acid anhydride, heat to 180 ° C., and stir for 6 hours while distilling off water. went. 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 further washed with methanol to obtain a cake. Subsequently, 200 parts of isobutanol and 28.5 parts of dimethylpropylamine were added to the cake, heated to 100 ° C., and stirred for 6 hours while distilling off methanol. After cooling to room temperature, the reaction mixture was added to 500 parts of methanol and stirred at room temperature for 1 hour. After the precipitated crystals were separated by filtration, the crystals were further washed with methanol and dried under reduced pressure to obtain 39.8 parts (yield 93%) of Intermediate 16.
In the synthetic reaction of compound A-1, 32 parts of the intermediate was 16 39.8 parts of the intermediate, 320 parts of DMAc was 400 parts, 18.5 parts of DBU was 0.9 parts, and 22.6 parts of 1,4-butansulton was 24 parts. The reaction was carried out in the same manner except that the parts were changed to parts, and 24.6 parts (yield 41%) of compound A-21 was obtained.

[Example 22] (Production of quinophthalone compound A-22)
In the synthetic reaction of compound A-2, 32 parts of the intermediate was 16 39.8 parts of the intermediate, 320 parts of the DMAc was 400 parts, 18.5 parts of the DBU was 0.9 parts, and 22.6 parts of 1,4-butan sulton was 24 parts. The reaction was carried out in the same manner except that 105.7 parts of 8% liquid aluminum sulfate was changed to 112.4 parts, and 38.5 parts (yield 69%) of Compound A-22 was obtained.

[Example 23] (Production of quinophthalone compound A-23)
In the synthetic reaction of compound A-3, 32 parts of the intermediate was 16 39.8 parts of the intermediate, 320 parts of DMAc was 400 parts, 18.5 parts of DBU was 0.9 parts, and 22.6 parts of 1,4-butansulton was 24 parts. The reaction was carried out in the same manner except that 22.6 parts of laurylamine was changed to 24 parts, and 41.9 parts (yield 54%) of Compound A-23 was obtained.

[Example 24] (Production of quinophthalone compound A-24)
In the synthesis reaction of Intermediate 16, the reaction was carried out in the same manner except that 22.5 parts of 2,3-naphthalenedicarboxylic acid anhydride was changed to 25.2 parts of 3-fluorophthalic anhydride, and 32. 5 parts (yield 84%) were obtained.
In the synthetic reaction of compound A-1, 32 parts of the intermediate was 17 32.5 parts of the intermediate, 320 parts of DMAc was 330 parts, 18.5 parts of DBU was 0.8 parts, and 22.6 parts of 1,4-butansulton was 1 part. , 3-Propane sulton was changed to 19.5 parts, and the reaction was carried out in the same manner to obtain 20.6 parts (yield 38%) of compound A-24.

[Example 25] (Production of quinophthalone compound A-25)
In the synthetic reaction of Intermediate 16, the reaction was carried out in the same manner except that 22.5 parts of 2,3-naphthalenedicarboxylic acid anhydride was changed to 29.3 parts of 3-nitrophthalic acid anhydride, and Intermediate 18 was changed to 37.1. Part (yield 88%) was obtained.
In the synthetic reaction of compound A-1, 32 parts of the intermediate was 18 37.1 parts of the intermediate, 320 parts of DMAc was 370 parts, 18.5 parts of DBU was 0.8 parts, and 22.6 parts of 1,4-butansulton was 22 parts. The reaction was carried out in the same manner except that the content was changed to .7 parts, and 25.5 parts (yield 43%) of Compound A-25 was obtained.

[Example 26] (Production of quinophthalone compound A-26)
In the synthetic reaction of compound A-1, 32 parts of intermediate was 431.2 parts of intermediate, 320 parts of DMAc was 320 parts, 18.5 parts of DBU was 15.4 parts, and 22.6 parts of 1,4-butanesulton was 2 parts. The reaction was carried out in the same manner except that the content was changed to 29.1 parts of sodium bromoethanesulfonate to obtain 16.1 parts (yield 39%) of compound A-26.

[Example 27] (Production of quinophthalone compound A-27)
In the synthetic reaction of compound A-1, 32 parts of the intermediate was 440.0 parts of the intermediate, 320 parts of DMAc was 400 parts, 18.5 parts of DBU was 19.8 parts, and 22.6 parts of 1,4-butanesulton was 6 parts. The reaction was carried out in the same manner except that the mixture was changed to 25.1 parts of sodium bromohexyl sulfonate to obtain 12.5 parts (yield 21%) of compound A-27.

(Production of quinophthalone compound A-28)
In the synthetic reaction of compound A-1, 32 parts of the intermediate was 440.0 parts of the intermediate, 320 parts of DMAc was 400 parts, 18.5 parts of DBU was 19.8 parts, and 22.6 parts of 1,4-butanesulton was 8 parts. The reaction was carried out in the same manner except that the content was changed to 27.1 parts of sodium bromooctylsulfonate to obtain 15.1 parts (yield 24%) of compound A-28.

<Production method of comparative quinophthalone pigment>
In the reference example of the present invention, in addition to the quinophthalone compounds produced in Examples 1 to 27, the quinophthalone compounds produced by the following production methods were used as comparative examples.

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

Kinoftalone compound (B-1)

(Production of quinophthalone compound B-2)
A quinophthalone compound (B-2) was obtained according to the synthesis method described in JP-A-2014-199308.

Kinoftalone compound (B-2)

(Production of quinophthalone compound B-3)
In the synthetic reaction of Intermediate 1, the same reaction was carried out except that 20 parts of 8-hydroxyquinaldine was changed to 20 parts of 6-hydroxyquinaldine, and 30.9 parts (yield 85%) of Intermediate 20 was obtained. ..
In the synthetic reaction of compound A-1, 32 parts of the intermediate was 20 30.9 parts of the intermediate, 320 parts of DMAc was 310 parts, 19.5 parts of DBU was 17.9 parts, and 22.6 parts of 1,4-butansulton was 21 parts. The reaction was carried out in the same manner except that the content was changed to 8 parts, and 20 parts (yield 44%) of compound B-3 was obtained.

(Production of quinophthalone compound B-4)
In the synthetic reaction of compound A-2, 132 parts of the intermediate was 20 30.9 parts of the intermediate, 320 parts of DMAc was 310 parts, 19.5 parts of DBU was 17.9 parts, and 22.6 parts of 1,4-butanesulfon was 21 parts. The reaction was carried out in the same manner except that 6 parts and 105.7 parts of 8% liquid aluminum sulfate were changed to 102.1 parts, and 39.8 parts (yield 86%) of compound B-4 was obtained.

(Production of quinophthalone compound B-5)
In the synthetic reaction of compound A-3, 132 parts of the intermediate was 20 30.9 parts of the intermediate, 320 parts of DMAc was 310 parts, 19.5 parts of DBU was 17.9 parts, and 22.6 parts of 1,4-butan sulton was 21 parts. The reaction was carried out in the same manner except that 6 parts and 22.6 parts of laurylamine were changed to 29.7 parts, and 52.8 parts (yield 81%) of Compound B-5 was obtained.

(Production of quinophthalone compound B-6)
In the synthetic reaction of Intermediate 1, 20 parts of 8-hydroxyquinaldine was changed to 20 parts of 2-methyl-4-quinolinol, and 22.3 parts of phthalic anhydride was changed to 29.9 parts of 2,3-naphthalenedicarboxylic acid anhydride. The reaction was carried out in the same manner except for the above, and 35 parts (yield 85%) of Intermediate 21 was obtained.
In the synthetic reaction of compound A-1, 32 parts of intermediate was 21 35 parts of intermediate, 320 parts of DMAc was 350 parts, 18.5 parts of DBU was 17.3 parts, and 22.6 parts of 1,4-butane sultone was 1,3 parts. The reaction was carried out in the same manner except that the amount was changed to 18.9 parts of −propane sultone to obtain 31.8 parts (yield 65%) of compound B-6.

(Production of quinophthalone compound B-7)
In the synthetic reaction of compound A-3, 132 parts of the intermediate was 21 35 parts of the intermediate, 320 parts of DMAc was 350 parts, 18.5 parts of DBU was 17.3 parts, and 22.6 parts of 1,4-butanesulton was 1,3 parts. -The reaction was carried out in the same manner except that 18.9 parts of propane sulton and 105.7 parts of 8% liquid aluminum sulfate were changed to 98.6 parts, and 43.1 parts (yield 88%) of compound B-7 was obtained. ..

<Manufacturing method of yellow pigment [C]>
(Manufacturing of refined yellow pigment (C-1))
Kinoftalone yellow pigment C.I. I. Pigment Yellow 138 (BASF's "Pariotor Yellow L 0962HD"), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, this kneaded product was put into 8 liters 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. for 24 hours. , A finely divided yellow pigment (C-1) was obtained.

(Manufacturing of refined yellow pigment (C-2))
Isoindoline yellow pigment C.I. I. Pigment Yellow 139 (BASF's "Pariotor Yellow L 2146HD"), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, this kneaded product was put into 8 liters 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. for 24 hours. , A finely divided yellow pigment (C-2) was obtained.

(Manufacturing of refined yellow pigment (C-3))
According to the synthesis method described in Japanese Patent No. 5267696, a quinophthalone compound represented by the following formula (1) was obtained. C.I. used in the colorant (C-1). I. A finely divided yellow pigment (C-3) was obtained in the same manner as the yellow pigment (C-1) except that Pigment Yellow 138 was changed to the quinophthalone compound of the following formula (1).

Equation (1)

<Manufacturing method of phthalocyanine pigment [D]>
(Manufacture of refined phthalocyanine pigment (D-1))
Phthalocyanine-based green pigment C.I. I. Pigment Green 58 (“FASTOGEN GREEN A110” manufactured by DIC Corporation), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, this kneaded product was put 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. for 24 hours. , A finely divided phthalocyanine pigment (D-1) was obtained.

(Manufacture of refined phthalocyanine pigment (D-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, stirred, and reacted at 20 ° C. for 6 hours. .. Then, the reaction mixture was poured into 5000 parts of ice water at 3 ° C., and the precipitated solid was collected by filtration and washed with water. To a beaker, 500 parts of a 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 a phthalocyanine pigment (P-2) (yield 40%, number of halogen atom substitutions 10.1, halogen distribution width 9).
To a three-necked flask, 500 parts of N-methylpyrrolidone, 50 parts of phthalocyanine pigment (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, 500 parts of water was added, the product was filtered, washed with methanol, and dried to add 51.6 parts (yield 88%, halogen atom) of the phthalocyanine pigment (D-2). The number of substitutions was 10.1 and the halogen distribution width was 9).

<Other / Manufacturing method of finely divided pigment>
(Manufacturing of refined red pigment (PR254-1))
Diketopyrrolopyrrole pigment C.I. I. Pigment Red 254 (BASF's "B-CF"), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, this kneaded product was put 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. for 24 hours. , 190 parts of a finely divided diketopyrrolopyrrole pigment (PR254-1) was obtained.

(Manufacturing of refined red pigment (PR177-1))
Anthraquinone red pigment C.I. I. Pigment Red 177 (BASF's "Chromophthalred A2B"), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, this kneaded product was put 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. for 24 hours. , Anthraquinone-based refined red pigment (PR177-1) was obtained.

(Manufacturing of refined blue pigment (PB15: 6-1))
Phthalocyanine blue pigment C.I. I. Pigment Blue 15: 6 (“LIONOL BLUE ES” manufactured by Toyo Color Co., Ltd., 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). It was kneaded at 80 ° C. for 6 hours. Next, this kneaded product was put 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. for 24 hours. , A finely divided blue pigment (PB15: 6-1) was obtained.

(Manufacturing of refined purple pigment (PV23-1))
Dioxazine-based purple pigment C.I. I. Pigment Violet 23 (“LIONOGEN VIOLET RL” manufactured by Toyo Color Co., Ltd.), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, this kneaded product was put 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. for 24 hours. , Purple finely divided purple pigment (PV23-1) was obtained.

<Manufacturing method of other pigment dispersion>
(Parthalocyanine / pigment dispersion (FP-1))
The following mixture is stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini model M-250 MKII” manufactured by Eiger Japan Co., Ltd.) using zirconia beads having a diameter of 0.5 mm for 3 hours, and then the pore diameter is 5. The mixture was filtered through a 0 μm filter to prepare a pigment dispersion (FP-1) having a non-volatile component of 20% by mass.
Phthalocyanine pigment (D-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

(Parthalocyanine / pigment dispersion (FP-2))
A pigment dispersion (FP-2) was prepared in the same manner as in FP-1, except that the phthalocyanine pigment (D-1) was changed to (D-2).

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

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

(PB15: 6, Pigment Dispersion (BP-1))
A PB15: 6 pigment dispersion (BP-1) was prepared in the same manner as in FP-1, except that the phthalocyanine pigment (D-1) was changed to PB15: 6-1.

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

<Manufacturing of yellow pigment dispersion (coloring composition)>
[Example 28]
(Pigment dispersion (YP-1))
The following mixture is stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini model M-250 MKII” manufactured by Eiger Japan Co., Ltd.) using zirconia beads having a diameter of 0.5 mm for 3 hours, and then the pore diameter is 5. The mixture was filtered through a 0 μm filter to prepare a pigment dispersion (YP-1) having a non-volatile component of 20% by mass.
Kinoftalone compound (A-1): 1.8 parts Micronized yellow pigment (C-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 29 to 65, Comparative Examples 1 to 10]
(Pigment dispersion (YP-2-48))
Pigment dispersions (YP-2 to 48) were prepared in the same manner as in Example 28, except that the quinophthalone compound and the yellow pigment were changed to the types shown in Table 1.
However, Examples 41 and 45 are reference examples.

<Evaluation of yellow pigment dispersion (coloring composition)>
The obtained pigment dispersion was evaluated as follows. The results are shown in Table 1.
(Evaluation of contrast (CR))
The light emitted from the backlight unit for a liquid crystal display passes through a polarizing plate, is polarized, passes through a coating film of a coloring composition coated on a glass substrate, and reaches the other polarizing plate. At this time, if the polarizing plate and the polarizing planes of the polarizing plate are parallel, light passes through the polarizing plate, but if the polarizing planes are orthogonal to each other, 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 or the like occurs due to the colorant particles, and if a part of the polarizing surface is displaced, the light is transmitted when the polarizing plates are parallel. When the amount of light emitted is reduced and the polarizing plates are orthogonal, part of the light is transmitted. This transmitted light was measured as the brightness on the polarizing plate, and the ratio of the brightness when the polarizing plates were parallel to 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 reduced and the brightness when orthogonal is increased, so that the contrast ratio is lowered.

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. The measurement was carried out through a black mask having a 1 cm square hole in the measurement portion.

A coated substrate was obtained in which the pigment dispersion (YP-1 to 48) was placed on a glass substrate having a thickness of 100 mm × 100 mm and a thickness of 1.1 mm using a spin coater so that x = 0.420 in a C light source. The drying conditions were 60 ° C. for 20 minutes and 230 ° C. for 60 minutes after application. The contrast ratio was determined according to the following criteria.
S: 9000 or more: extremely good A: 6000 or more to less than 9000: good B: 3000 or more to less than 6000: practically possible C: less than 3000: defective

(Evaluation of heat resistance)
The pigment dispersion (YP-1 to 48) was applied onto a 100 mm × 100 mm, 1.1 mm thick glass substrate using a spin coater, then dried at 60 ° C. for 20 minutes, and then dried at 230 ° C. for 30 minutes. A coated substrate was produced by heating and allowing to cool. The produced coated substrate was adjusted to a film thickness of 1.5 μm after heat treatment at 230 ° C. Use a microspectrophotometer (“OSP-SP100” manufactured by Olympus Optical Co., Ltd.) to measure the chromaticity ([L * (1), a * (1), b * (1)]) of the obtained coating film at the C light source. Measured using. After that, as a heat resistance test, the mixture was heated at 230 ° C. for 60 minutes, the chromaticity ([L * (2), a * (2), b * (2)]) with a C light source was measured, and the following formula was used. , The color difference ΔEab * was calculated.
ΔEab * = √ ((L * (2) -L * (1)) ² + (a * (2) -a * (1)) ² + (b * (2) -b * (1)) ² )
S: ΔEab * is less than 3.0: extremely 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 * If it is 6.0 or more: Defective

(Evaluation of initial viscosity)
The viscosity of the pigment dispersion was measured at an initial viscosity at 25 ° C. 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: 20 mPa · s or more: Defective

(Evaluation of storage stability)
The obtained pigment dispersion is stored in a thermostat at 40 ° C. for 1 week to accelerate with time, then the viscosity of the coloring composition after aging is measured by the same method as the 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 viscosity change rate is less than ± 10% and no sediment is formed: Very good A: When the viscosity change rate is ± 10% or more and less than 15% and no sediment is formed: Good B: Viscosity change When the rate is ± 15% or more and less than 20% and no sediment is generated: Practical C: When the viscosity change rate exceeds ± 20%, or even if the viscosity change rate is within ± 20%, the sediment is formed. If so: Bad

As shown in Table 1, the pigment dispersion YP-1 to 38 using the quinophthalone compounds A-1 to 28 of the present invention has high CR, high heat resistance, low viscosity and storage stability regardless of the type of yellow pigment to be combined. The evaluation result was excellent. Among them, the quinophthalone compounds A-8, 9 and 14 were particularly good. On the other hand, A-27 and 28, which have long alkyl groups, are slightly inferior in CR, initial viscosity, and storage stability to the above-mentioned quinophthalone compounds A-1 to 26. Therefore, the alkylene group of R1 is preferably 1 to 5 carbon atoms. became. The pigment dispersions YP-39, 40, 46, 47 of the following quinophthalone compounds B-1 and B-2 resulted in significantly inferior results in CR, heat resistance, initial viscosity and storage stability as compared with the examples of the present invention. It was. Further, the pigment dispersions YP-41 to 45 of the quinophthalone compounds B-3 to 7 having different positions of the substituents of the quinophthalone compound (A) of the present invention have good CR and heat resistance, but have good initial viscosity and storage stability. The result is significantly inferior, indicating that the position of the substituent is important.

<Preparation of green pigment dispersion (coloring composition)>
A green coloring composition was prepared using the yellow pigment dispersion (YP-1 to 48) and the phthalocyanine / pigment dispersion (FP-1, 2).

[Example 66]
(Green pigment dispersion (GP-1))
A pigment dispersion (GP-1) was prepared by stirring and mixing the mixture having the following composition so as to be uniform.
Phthalocyanine / pigment dispersion (FP-2): 22.2 parts Yellow pigment dispersion (YP-1): 27.8 parts

[Examples 67 to 114, Comparative Examples 11 to 27]
(Green pigment dispersion (GP-2 to 66))
Green pigment dispersions (GP-2 to 66) were obtained in the same manner as in Example 66, except that the breakdown of 50 parts in total of the pigment dispersion was changed to the types and mass parts shown in Table 2. ..
However, Examples 79 and 83 are reference examples.

<Evaluation of green pigment dispersion (coloring composition)>
The obtained green pigment dispersion was evaluated as follows. Further, the heat resistance, the initial viscosity and the storage stability were evaluated by preparing a coating film in the same manner as the yellow pigment dispersion and using the same evaluation criteria. The results are shown in Table 2.

(Evaluation of contrast)
The pigment dispersion (GP-1 to 66) is placed on a glass substrate having a thickness of 100 mm × 100 mm and 1.1 mm using a spin coater so that x = 0.297 and y = 0.570 in a C light source. A coated substrate was obtained. The drying conditions were 60 ° C. for 20 minutes and 230 ° C. for 60 minutes after application. The contrast ratio was determined according to the following criteria.
S: 9000 or more: extremely good A: 6000 or more to less than 9000: good B: 3000 or more to less than 6000: practically possible C: less than 3000: defective

(Foreign matter evaluation)
The pigment dispersion (GP-1 to 66) is applied onto a 100 mm × 100 mm, 1.1 mm thick glass substrate using a spin coater, then dried at 60 ° C. for 20 minutes and heated at 230 ° C. for 60 minutes. Further, the coating film substrate was prepared by further heating at 250 ° C. for 60 minutes and allowing it to cool. The produced coated substrate was adjusted to a film thickness of 1.5 μm after heat treatment at 250 ° C. The number of foreign substances in the coating film of the obtained coating film substrate was measured. The evaluation was carried out by observing the surface using a metallurgical microscope "BX60" manufactured by Olympus System Corporation. The magnification was set to 500 times, and the number of foreign substances observable in any five fields of view was measured by transmission.
S: Number of foreign substances is less than 3: Extremely good A: Number of foreign substances is 3 or more and less than 20: Good B: Number of foreign substances is 21 or more and less than 100: Practical C: Number of foreign substances is 100 More than one: defective

As shown in Table 2, the results were equivalent to those in Table 1.

<Manufacturing of photosensitive coloring composition>
[Example 115]
(Green Photosensitive Coloring Composition (GR-1))
The mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through 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 Toa Synthetic Co., Ltd.): 2.0 parts Dipentaerythritol hexa Acrylate photopolymerization initiator (BASF "Irgacure 907"): 1.2 parts Sensitizer (Hodoya Chemical Industry Co., Ltd. "EAB-F"): 0.3 parts Cyclohexanone: 39.0 parts

[Examples 116 to 163, Comparative Examples 28 to 44]
Green photosensitive coloring compositions (GR-2 to 66) were obtained in the same manner as in Example 115, except that the pigment dispersion GP-1 was changed to GP-2 to GP-66.

<Evaluation of photosensitive coloring composition>
The obtained green pigment photosensitive coloring composition was evaluated as follows. The results are shown in Table 3.

(Evaluation of lightness)
The pigment dispersion (GR-1 to 66) is placed on a glass substrate having a thickness of 100 mm × 100 mm and 1.1 mm using a spin coater so that x = 0.297 and y = 0.570 in a C light source. A coated substrate was obtained. The drying conditions were 60 ° C. for 20 minutes and 230 ° C. for 60 minutes after application. The brightness (Y) of the obtained substrate was measured with a microspectrophotometer (“OSP-SP200” manufactured by Olympus Optical Co., Ltd.).

(Evaluation of foreign matter)
The number of foreign substances in the coating film of the coating film substrate used for the brightness measurement was measured. The evaluation was carried out by observing the surface using a metallurgical microscope "BX60" manufactured by Olympus System Corporation. The magnification was set to 500 times, and the number of foreign substances observable in any five fields of view was measured by transmission.
S: Number of foreign substances is less than 3: Extremely good A: Number of foreign substances is 3 or more and less than 20: Good B: Number of foreign substances is 21 or more and less than 100: Practical C: Number of foreign substances is 100 More than one: defective

(Evaluation of solvent resistance)
The green photosensitive coloring composition (GR-1 to 66) was applied to a glass substrate on which a black matrix was previously formed by a spin coating method, and then dried in a clean oven at 70 ° C. for 20 minutes. Then, after cooling this substrate to room temperature, ultraviolet light was exposed through a photomask using an ultra-high pressure mercury lamp. Then, this substrate was spray-developed with a 0.2 mass% sodium carbonate aqueous solution at 23 ° C. for 30 seconds, 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 striped colored pixel layer on the substrate. The obtained striped green pixels were 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 for heat resistance.

As shown in Table 3, the coloring composition using the quinophthalone compound (A) represented by the general formula (1) of the present invention gave good results in terms of brightness, foreign matter and solvent resistance. On the other hand, the coloring compositions using the conventional quinophthalone compounds B-1 and 2 were clearly inferior to the compounds of this example in terms of foreign matter and resistance. Further, the coloring composition using the quinophthalone compounds B-3 to 7 having different positions of the substituents of the quinophthalone compound (A) of the present invention results in significantly inferior brightness, foreign matter and solvent resistance, and the position of the substituents is important. It can be seen that it is

<Making color filters>
(Red Photosensitive Coloring Composition (RR-1))
The mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through 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 Toa Synthetic Co., Ltd.): 2.0 parts Photopolymerization initiator ("Irgacure 907" manufactured by BASF): 1.2 parts Sensitizer ("Hodoya Chemical Industry Co., Ltd." EAB-F "): 0.3 parts 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 through 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 (Toa synthesis) "Aronix M-402" manufactured by Aronix M-402): 2.0 parts Photopolymerization initiator (BASF "Irgacure 907"): 1.2 parts Sensitizer ("EAB-F" manufactured by Hodoya Chemical Industry Co., Ltd.): 0.3 part cyclohexanone: 39.0 parts

The red photosensitive coloring composition (RR-1) was applied to a glass substrate on which a black matrix was formed in advance by a spin coating method, and then dried in a clean oven at 70 ° C. for 20 minutes. Then, after cooling this substrate to room temperature, ultraviolet rays were exposed through a photomask using an ultra-high pressure mercury lamp. Then, this substrate was spray-developed with a 0.2 mass% sodium carbonate aqueous solution at 23 ° C. for 30 seconds, 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 striped colored pixel layer on the substrate. Next, using the green photosensitive coloring composition (GR-2) of the present invention, a green colored pixel layer is formed in the same manner as the red colored pixel layer, and further, a blue photosensitive coloring composition (BR-1) is obtained. It was used to form a blue colored pixel layer to obtain a color filter (CF-1). The 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 high brightness and an excellent contrast ratio, demonstrating the effect of the present invention.

Claims (7)

The quinophthalone compound (A) represented by the following general formula (1).
General formula (1)

[In the general formula (1), X ₁ represents -O- or -NH-, R ₁ represents an unsubstituted alkylene group , and M is a monovalent to trivalent metal of a hydrogen atom or an acidic group. Cation: Represents an alkylammonium cation. R _{2 to} R ₁₀ independently represent a hydrogen atom, a halogen atom, a nitro group, an alkoxy group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group or −COOP, and adjacent substituents are bonded to each other. May form a substituted or unsubstituted aromatic ring. P represents a substituted or unsubstituted alkyl group. ] The quinophthalone compound (A) according to claim 1 , wherein M in the general formula (1) is a monovalent to trivalent metal cation of a hydrogen atom or an acidic group. The quinophthalone compound (A') according to claim 1 , which is represented by the following general formula (2).
General formula (2)

[In the general formula (2), X ₂ represents -O- or -NH-, R ₁₁ represents an unsubstituted alkylene group having 1 to 5 carbon atoms, and M is 1 of a hydrogen atom or an acidic group. Valuable to trivalent metal cation; represents an alkylammonium cation. R _{12 to} R ₁₆ independently represent a hydrogen atom, a halogen atom, a nitro group or an alkoxy group. ] A pigment dispersant containing the quinophthalone compound according to any one of claims 1 to 3. A coloring composition for a color filter containing the pigment dispersant, the coloring agent, the organic solvent and the binder resin according to claim 4. The coloring composition for a color filter according to claim 5 , further comprising at least one selected from a photopolymerizable monomer and a photopolymerization initiator. In a color filter comprising at least one red filter segment, at least one green filter segment and at least one blue filter segment, at least one green filter segment is formed from the color filter coloring composition according to claim 5 or 6. Color filter to be done.