JP2021105175A - Halogenated phthalocyanine coloring material, coloring material solution, colored curable composition, color filter, and display device - Google Patents

Abstract

To provide a halogenated phthalocyanine coloring material improved in color purity.SOLUTION: The halogenated phthalocyanine coloring material is represented by the general formula (1) in the figure. (Each symbol in general formulas (1) and (2) are as described in the specification.)SELECTED DRAWING: None

Description

The present invention relates to a halogenated phthalocyanine colorant, a colorant solution, a color curable composition, a color filter, and a display device.

In recent years, with the development of personal computers, especially portable personal computers, the demand for liquid crystal displays has been increasing. The penetration rate of mobile displays (mobile phones, smartphones, tablet PCs) is also increasing, and the market for liquid crystal displays is expanding more and more. Recently, organic light emitting display devices such as organic EL displays having high visibility due to self-luminous light have also attracted attention as next-generation image display devices. In terms of the performance of these image display devices, further improvement in image quality and reduction in power consumption such as improvement in contrast and color reproducibility are strongly desired.

Color filters are used in these liquid crystal display devices and organic light emission display devices. For example, in the formation of a color image of a liquid crystal display device, the light that has passed through the color filter is colored as it is in the color of each pixel constituting the color filter, and the light of those colors is combined to form a color image. As the light source at that time, in addition to the conventional cold cathode fluorescent lamp, an organic light emitting element that emits white light or an inorganic light emitting element that emits white light may be used. Further, in the organic light emitting display device, a color filter is used for color adjustment and the like.
Therefore, in color filters, there are increasing demands for higher brightness, higher contrast, and improved color reproducibility.

Here, the color filter is generally formed on a transparent substrate, a colored layer formed on the transparent substrate and composed of colored patterns of the three primary colors of red, green, and blue, and on the transparent substrate so as to partition each colored pattern. It has a formed light-shielding portion.

As a method for forming pixels in a color filter, a pigment dispersion method having excellent characteristics on average is most widely adopted from the viewpoints of spectral characteristics, durability, pattern shape, accuracy, and the like.
In a color filter having pixels formed by using the pigment dispersion method, there are problems that the light transmittance of the color filter becomes small and the contrast becomes low due to the pigment particles.
Therefore, attempts have been made to achieve a color filter having improved brightness and contrast by using a coloring composition using a dye that does not form particles.

Patent Document 1 contains a colorant containing a halogenated phthalocyanine dye, a thermosetting compound, and a solvent that at least dissolves the halogenated phthalocyanine dye and the thermosetting compound, and the total content of the colorants is the total solid content. A color curable composition, which is 60 to 90% by mass, is disclosed.
However, the halogenated phthalocyanine dye disclosed in Patent Document 1 has a problem of poor color purity.

Japanese Unexamined Patent Publication No. 2014-43556

The present invention has been made in view of the above circumstances, and a halogenated phthalocyanine color material having improved color purity, a color material liquid having improved color purity and brightness, and color curability using the halogenated phthalocyanine color material. It is an object of the present invention to provide a composition, a color filter using the color curable composition, and a display device using the color filter.

The halogenated phthalocyanine coloring material according to the present invention is a halogenated phthalocyanine coloring material represented by the following general formula (1).

［一般式（１）中、Ｘ^１〜Ｘ^１６は、それぞれ独立に水素原子、ハロゲン原子、ヒドロキシ基、又は炭化水素含有基を表し、Ｘ^１〜Ｘ^１６の少なくとも１つは、塩素原子、又は臭素原子であり、且つ、Ｘ^１〜Ｘ^１６の少なくとも１つは、下記一般式（２）で表される１価の基であり、Ｍは、Ｃｕ、Ｚｎ、Ｃｏ、Ｍｏ及びＡｌからなる群から選択される１種の金属を表す。

[In the general formula (1), X ^{1 to} X ¹⁶ independently represent a hydrogen atom, a halogen atom, a hydroxy group, or a hydrocarbon-containing group, and ^{at least one of X 1 to} X ¹⁶ is a chlorine atom or a chlorine atom, or It is a bromine atom, and ^{at least one of X 1 to} X ¹⁶ is a monovalent group represented by the following general formula (2), and M is a group consisting of Cu, Zn, Co, Mo and Al. Represents one type of metal selected from.

（一般式（２）中、Ｙ^１は、−Ｏ−、−Ｓ−、−ＮＲ^Ｙ−、又は−Ｎ^＋（・Ａ^ａ−）Ｒ^Ｙ１Ｒ^Ｙ２−（ここで、Ｒ^Ｙ、Ｒ^Ｙ１、及びＲ^Ｙ２はそれぞれ独立に、水素原子または炭素数１〜６のアルキル基を表し、Ａ^ａ−は、ａ価のアニオンを表し、ａは１以上の整数である。）を表し、Ｚ^１、Ｚ^２、及びＺ^３はそれぞれ独立に、ハロゲン原子、置換もしくは非置換のアルキル基、置換もしくは非置換のアルコキシ基、置換もしくは非置換のアリール基、及び、置換もしくは非置換のアリールオキシ基からなる群から選択される少なくとも１種を表し、ｎは０〜３の整数であり、複数のＺ^３は同一であっても異なっていても良く、＊は、フタロシアニン骨格との結合位置を示す。）］

(In the general formula ^{(2), Y} 1 is, -O -, - S -, - NR Y -, or ^{-N + (· A a-) R} Y1 R Y2 - ( ^{wherein, R Y,} R ^Y1, and ^{R Y2} each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon ^{atoms, a a-} represents a valence of the anion, a is 1 or more is an ^{integer.), Z} 1, Z ² and Z ³ each independently consist of a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted aryloxy group. represents at least one selected from the group, n is an integer of 0 to 3, the plurality of Z ³ may be the same or different and * indicates the bonding position to the phthalocyanine skeleton.) ]

The color material liquid according to the present invention contains the halogenated phthalocyanine color material according to the present invention and a solvent.

The coloring curable composition according to the present invention contains a coloring material, a polymer, a polymerizable compound, an initiator, and a solvent, and the coloring material contains the halogenated phthalocyanine coloring material according to the present invention. ..

The color filter according to the present invention is a color filter including at least a transparent substrate and a colored layer provided on the transparent substrate, and at least one of the colored layers is a colored curable composition according to the present invention. It is characterized by being a colored layer which is a cured product of.

The present invention provides a display device comprising the color filter according to the present invention.

According to the present invention, a halogenated phthalocyanine color material having improved color purity, a color material liquid having improved color purity and brightness, a color curable composition using the halogenated phthalocyanine color material, and the color curable composition can be obtained. It is possible to provide a color filter used and a display device using the color filter.

FIG. 1 is a schematic view showing an example of the color filter of the present invention. FIG. 2 is a schematic view showing an example of the display device of the present invention. FIG. 3 is a schematic view showing another example of the display device of the present invention.

Hereinafter, the halogenated phthalocyanine coloring material, the coloring material liquid, the coloring curable composition, the color filter, and the display device according to the present invention will be described in detail in order.
In the present invention, light includes electromagnetic waves having wavelengths in the visible and invisible regions, and radiation, and radiation includes, for example, microwaves and electron beams. Specifically, it refers to an electromagnetic wave having a wavelength of 5 μm or less and an electron beam.
In the present invention, (meth) acrylic represents each of acrylic and methacrylic, and (meth) acrylate represents each of acrylate and methacrylate.
Further, in the present specification, "~" indicating a numerical range is used to mean that the numerical values described before and after the numerical range are included as the lower limit value and the upper limit value.

[Halogenated phthalocyanine coloring material]
The halogenated phthalocyanine coloring material according to the present invention is a halogenated phthalocyanine coloring material represented by the following general formula (1).

［一般式（１）中、Ｘ^１〜Ｘ^１６は、それぞれ独立に水素原子、ハロゲン原子、ヒドロキシ基、又は炭化水素含有基を表し、Ｘ^１〜Ｘ^１６の少なくとも１つは、塩素原子、又は臭素原子であり、且つ、Ｘ^１〜Ｘ^１６の少なくとも１つは、下記一般式（２）で表される１価の基であり、Ｍは、Ｃｕ、Ｚｎ、Ｃｏ、Ｍｏ及びＡｌからなる群から選択される１種の金属を表す。

[In the general formula (1), X ^{1 to} X ¹⁶ independently represent a hydrogen atom, a halogen atom, a hydroxy group, or a hydrocarbon-containing group, and ^{at least one of X 1 to} X ¹⁶ is a chlorine atom or a chlorine atom, or It is a bromine atom, and ^{at least one of X 1 to} X ¹⁶ is a monovalent group represented by the following general formula (2), and M is a group consisting of Cu, Zn, Co, Mo and Al. Represents one type of metal selected from.

（一般式（２）中、Ｙ^１は、−Ｏ−、−Ｓ−、−ＮＲ^Ｙ−、又は−Ｎ^＋（・Ａ^ａ−）Ｒ^Ｙ１Ｒ^Ｙ２−（ここで、Ｒ^Ｙ、Ｒ^Ｙ１、及びＲ^Ｙ２はそれぞれ独立に、水素原子または炭素数１〜６のアルキル基を表し、Ａ^ａ−は、ａ価のアニオンを表し、ａは１以上の整数である。）を表し、Ｚ^１、Ｚ^２、及びＺ^３はそれぞれ独立に、ハロゲン原子、置換もしくは非置換のアルキル基、置換もしくは非置換のアルコキシ基、置換もしくは非置換のアリール基、及び、置換もしくは非置換のアリールオキシ基からなる群から選択される少なくとも１種を表し、ｎは０〜３の整数であり、複数のＺ^３は同一であっても異なっていても良く、＊は、フタロシアニン骨格との結合位置を示す。）］

(In the general formula ^{(2), Y} 1 is, -O -, - S -, - NR Y -, or ^{-N + (· A a-) R} Y1 R Y2 - ( ^{wherein, R Y,} R ^Y1, and ^{R Y2} each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon ^{atoms, a a-} represents a valence of the anion, a is 1 or more is an ^{integer.), Z} 1, Z ² and Z ³ each independently consist of a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted aryloxy group. represents at least one selected from the group, n is an integer of 0 to 3, the plurality of Z ³ may be the same or different and * indicates the bonding position to the phthalocyanine skeleton.) ]

In the phthalocyanine coloring material, it is difficult to control the purity of the reaction product, and it is difficult to control the color purity.
On the other hand, in the halogenated phthalocyanine coloring material represented by the general formula (1) of the present invention, ^{at least one of X 1 to} X ¹⁶ is a chlorine atom or a bromine atom, and X ^{1 to X. At} least one of 16 is a monovalent group represented by the general formula (2). Since ^{at least one of X 1 to} X ¹⁶ is a chlorine atom or a bromine atom, the color derived from the phthalocyanine skeleton, which is the hue in the blue region, is shifted by a long wavelength by the electron attracting effect, and the color is colored green for a color filter. The color will be suitable for the layer. Moreover, the monovalent group represented by the general formula (2), to the linking group Y ¹ that binds to a phthalocyanine skeleton two ortho positions to the (2,6 position), at least said specific substituent .. Therefore, having a monovalent group represented by the general formula (2) improves the purity of the intermediate during production, and it is easy to suppress the mixing of structures having different numbers of substitutions that affect the color. As a result, the purity of the target reaction product is improved, so that the half width of the maximum absorption wavelength to the minimum transmission wavelength within the wavelength range of 420 nm to 600 nm of the coloring material is narrowed, and the color purity is improved. As a result, the color material liquid using the halogenated phthalocyanine color material represented by the general formula (1) and the color curable composition have a controlled transmission spectrum shape, and the color purity is improved. The brightness is improved by mixing with a yellow color material and adjusting the color to green.
Further, the halogenated phthalocyanine coloring material represented by the general formula (1) of the present invention tends to have good solvent solubility and resin solubility, and a colored layer formed by using the coloring curable composition of the present invention. Has good contrast.

In the general formula (1), X ^{1 to} X ¹⁶ independently represent a hydrogen atom, a halogen atom, a hydroxy group, or a hydrocarbon-containing group, respectively.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like. Among them, a chlorine atom or a bromine atom is preferable from the viewpoint of color, and at least one of ^{X 1 to} X ^{16 is used.} Is a chlorine atom or a bromine atom.
Among them, from the viewpoint of color and maximum absorption wavelength range, ^{4 to 12 out of X 1 to} X ¹⁶ and 8 to 12 among them are one or more selected from the group consisting of chlorine atoms and bromine atoms. preferable.
Further, from the viewpoint of color and maximum absorption wavelength range, ^{it is preferable that 4 to 12 of X 1 to} X ¹⁶ and 8 to 12 of them are chlorine atoms.

X ^{1 to} X ¹⁶ may be hydrogen atoms. The number of hydrogen atoms in X ^{1 to} X ¹⁶ may be appropriately selected by adjusting the color, but may be 0 to 8 or 0 to 4.
X ^{1 to} X ¹⁶ may be a hydroxy group. The number of hydroxy groups among X ^{1 to} X ¹⁶ may be appropriately selected from the viewpoint of color and maximum absorption wavelength range, but may be 0 to 4, and may be 0 to 2. ..

The hydrocarbon-containing group means a substituent containing a hydrocarbon, and the hydrocarbon-containing group may contain a heteroatom. Examples of the hetero atom include an oxygen atom, a sulfur atom, a nitrogen atom, a silicon atom and the like, and an oxygen atom, a sulfur atom and a nitrogen atom are preferably mentioned. In the hydrocarbon-containing group, the hetero atom may be contained in the carbon chain, may be contained at the end on the binding site side, or may be contained as a substituent.
Examples of the hydrocarbon-containing group include a substituted or unsubstituted hydrocarbon group, a substituted or unsubstituted heterocyclic group, a group represented by the following general formula (C1), and a group represented by the following general formula (C2). , And a group represented by the following general formula (C3).
General formula (C1): -L ^1- R ¹
General formula (C2): -L ^1- (R ^{2- L 2} ) _n1- R ³
General formula (C3):-(R ^1- L ² ) _n2- R ³
(Formula (C1), in (C2), and (C3), ^{L 1} and ^{L 2} each independently represents a linking group containing a hetero ^atom, R 1, ^{R 2,} and ^{R 3} are each independently, Represents a substituted or unsubstituted hydrocarbon group, and n1 and n2 independently represent an integer of 1 to 4).

The ^{linking groups containing heteroatoms in L 1} and L ² include -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, and -SO. _{-, - SO 2 -, -} O-SO 2 -, - O-CO-O -, - CO-NR L -, - O-CO-NR L -, - NR L -CO -, - SO 2 -NR ^{L -, - SO-NR L} -, - S-NR L -, - NR L -S -, - NR L -SO -, - NR L -SO 2 -, - NR L -, - N + (· A ^a- ) R ^L1 R ^L2- (Here, ^RL , ^RL1 , and ^RL2 independently represent a hydrogen atom, a hydrocarbon group, -COR ⁴ , or -SO ₂ R ⁴ , and R ⁴ is carbonized. A hydrogen group and ^Aa- represent an a-valent anion, and a is an integer of 1 or more.)
^{The hydrocarbon groups in RL} , ^RL1 and ^RL2 may be the same as the hydrocarbon groups described later, but are preferably alkyl groups having 1 to 10 carbon atoms, and alkyl groups having 1 to 6 carbon atoms. More preferably it is a group.
A-valent anion represented by A ^a- may be the same as a number of anions in the general formula (2) described later.

Examples of the hydrocarbon group include an aliphatic hydrocarbon group and an aromatic hydrocarbon group (aryl group), and the aliphatic hydrocarbon group is unsaturated even if it is a saturated aliphatic hydrocarbon group (alkyl group). It may be an aliphatic hydrocarbon group (alkenyl group, alkynyl group). The aliphatic hydrocarbon group may be linear, branched or cyclic, and the alkyl group includes a cycloalkyl group.

The alkyl group preferably includes a linear, branched or cyclic alkyl group having 1 to 24 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group and a tert-butyl group. , Pentyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, dodecyl group, hexadecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, 1-norbornyl group, 1-adamantyl group and the like.
The alkenyl group preferably includes an alkenyl group having 2 to 18 carbon atoms, and examples thereof include a vinyl group, an allyl group, an isopropenyl group, a 3-butene-1-yl group and the like.
The aryl group preferably includes an aryl group having 6 to 24 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, a biphenyl group and a terphenyl group.

As used herein, "substituted or unsubstituted" means that it may have a substituent. For example, a "substituted or unsubstituted alkyl group" includes an alkyl group having a substituent and an alkyl group having no substituent.
Substituents of aliphatic hydrocarbon groups include halogen atoms, substituted or unsubstituted alkoxy groups, substituted or unsubstituted aryl groups, substituted or unsubstituted aryloxy groups, substituted or unsubstituted alkoxycarbonyl groups, substituted or Examples thereof include an unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, an amino group, a hydroxyl group and the like, among which a halogen atom, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted aryl group. It may be one or more selected from the group consisting of an aryloxy group, and may be one or more selected from the group consisting of a halogen atom, an alkoxy group, an aryl group, and an aryloxy group.
Substituents of aromatic hydrocarbon groups include halogen atoms, substituted or unsubstituted alkyl groups, substituted or unsubstituted alkoxy groups, substituted or unsubstituted aryloxy groups, substituted or unsubstituted alkoxycarbonyl groups, substituted or Examples thereof include an unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, an amino group, a hydroxyl group and the like, among which a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, and a substituted or unsubstituted alkoxy group. It may be one or more selected from the group consisting of an aryloxy group, and may be one or more selected from the group consisting of a halogen atom, an alkyl group, an alkoxy group, and an aryloxy group.
The substituent of the alkoxy group, the alkoxycarbonyl group and the alkylthio group may be the same as the substituent of the aliphatic hydrocarbon group, and the substituent of the aryloxy group and the arylthio group may be the substituent of the aromatic hydrocarbon group. It may be similar.
The alkoxycarbonyl group having the substituent may have, for example, a structure in which a glycidyl (meth) acrylate is reacted with a carboxy group, and -COO-CH ₂ CH (OH) CH _2- OCO-CH = CH ₂ Or, -COO-CH ₂ CH (OH) CH _2- OCO-C (CH ₃ ) = CH ₂ .

Examples of the aliphatic hydrocarbon group having a substituent include a phenoxyethyl group, a benzyl group, a phenylethyl group, an N-butylaminosulfonylpropyl group, an N-butylaminocarbonylmethyl group and an N, N-dibutylaminosulfonylpropyl group. , Ethoxyethyl group, 2-chloroethyl group and the like.

Examples of the aromatic hydrocarbon group (substituted aryl group) having a substituent include a 2-chlorophenyl group, a 2-methoxyphenyl group, a 4-butoxycarbonylphenyl group, a 4-N, N-dibutylaminocarbonylphenyl group, and 4 Examples thereof include -N-butylaminosulfonylphenyl group, 4-N, N-dibutylaminosulfonylphenyl group, 2-chloronaphthyl group, 2-methoxynaphthyl group, 4-butoxycarbonylnaphthyl group and the like.

In the halogenated phthalocyanine coloring material of the present invention, ^{at least one of X 1 to} X ¹⁶ contains a monovalent group represented by the following general formula (2) as one of the hydrocarbon-containing groups.

（一般式（２）中、Ｙ^１は、−Ｏ−、−Ｓ−、−ＮＲ^Ｙ−、又は−Ｎ^＋（・Ａ^ａ−）Ｒ^Ｙ１Ｒ^Ｙ２−（ここで、Ｒ^Ｙ、Ｒ^Ｙ１、及びＲ^Ｙ２はそれぞれ独立に、水素原子または炭素数１〜６のアルキル基を表し、Ａ^ａ−は、ａ価のアニオンを表し、ａは１以上の整数である。）を表し、Ｚ^１、Ｚ^２、及びＺ^３はそれぞれ独立に、ハロゲン原子、置換もしくは非置換のアルキル基、置換もしくは非置換のアルコキシ基、置換もしくは非置換のアリール基、及び、置換もしくは非置換のアリールオキシ基からなる群から選択される少なくとも１種を表し、ｎは０〜３の整数であり、複数のＺ^３は同一であっても異なっていても良く、＊は、フタロシアニン骨格との結合位置を示す。）］

(In the general formula ^{(2), Y} 1 is, -O -, - S -, - NR Y -, or ^{-N + (· A a-) R} Y1 R Y2 - ( ^{wherein, R Y,} R ^Y1, and ^{R Y2} each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon ^{atoms, a a-} represents a valence of the anion, a is 1 or more is an ^{integer.), Z} 1, Z ² and Z ³ each independently consist of a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted aryloxy group. represents at least one selected from the group, n is an integer of 0 to 3, the plurality of Z ³ may be the same or different and * indicates the bonding position to the phthalocyanine skeleton.) ]

Z ^{1, Z 2,} and the halogen atom in Z ^3, substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted aryloxy group, respectively , The same as above may be used.
The halogen atom in Z ^{1, Z 2,} and Z ^3, is preferably Among them, a resin soluble chlorine atom in terms of or bromine atom, preferably a chlorine atom.
Z ^{1, Z 2,} and the substituted or unsubstituted alkyl group in ^{Z 3,} among them having 1 to 20 carbon atoms, straight-chain, branched chain or preferably a cyclic alkyl group, and among them straight from 1 to 10 carbon atoms, Chain or branched alkyl groups are preferred, with methyl, ethyl, propyl, isopropyl, n-butyl and tert-butyl groups being preferred.
Substituted or unsubstituted alkoxy groups in Z ¹ , Z ² , and Z ³ include linear, branched, or cyclic alkoxy groups having 1 to 20 carbon atoms, such as methoxy group, ethoxy group, and the like. Linear alkoxy groups such as propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group; isopropoxy group, isobutoxy group, s-butoxy group, t-butoxy group. Examples thereof include branched alkoxy groups such as groups and isooctyloxy groups, cyclic alkoxy groups such as cyclopentyloxy groups, cyclohexyloxy groups, norbornyloxy groups and adamantyloxy groups, and among them, linear or linear alkoxy groups having 1 to 15 carbon atoms. Branched chain alkoxy groups are preferable, and among them, methoxy group, ethoxy group, propoxy group, isopropoxy group and the like are preferable.
As the ^{substituted or unsubstituted aryl group in Z 1} , Z ² , and Z ³ , a substituted or unsubstituted phenyl group or a naphthyl group is preferable, a substituted or unsubstituted phenyl group is more preferable, and a phenyl group, among others, is preferable. Chlorophenyl group, bromophenyl group, fluorophenyl group, methylphenyl group, ethylphenyl group, propylphenyl group, isopropylphenyl group, butylphenyl group, tert-butylphenyl group, pentylphenyl group, hexylphenyl group, heptylphenyl group, octyl Phenyl group, nonylphenyl group, decanylphenyl group, chloronaphthyl group, bromonaphthyl group, fluoronaphthyl group, methylnaphthyl group, ethylnaphthyl group, propylnaphthyl group, isopropylnaphthyl group, butylnaphthyl group, tert-butylnaphthyl group, Penyl naphthyl group, hexyl naphthyl group, heptyl naphthyl group, octyl naphthyl group, nonyl naphthyl group, decanyl naphthyl group and the like are preferable.
As the ^{substituted or unsubstituted aryloxy group in Z 1} , Z ² and Z ³ , a substituted or unsubstituted phenoxy group or a naphthoxy group is preferable, a substituted or unsubstituted phenoxy group is more preferable, and a phenoxy group is particularly preferable. , Chlorophenoxy group, bromophenoxy group, fluorophenoxy group, methylphenoxy group, ethylphenoxy group, propylphenoxy group, isopropylphenoxy group, butylphenoxy group, tert-butylphenoxy group, pentylphenoxy group, hexylphenoxy group, heptylphenoxy group. , Octylphenoxy group, nonylphenoxy group, decanylphenoxy group, chloronaphthoxy group, bromonaphthoxy group, fluoronaphthoxy group, methylnaphthoxy group, ethylnaphthoxy group, propylnaphthoxy group, isopropylnaphthoxy group, butylnaphthoxy group, tert-butylnaphthoxy group , Pentylnaphthoxy group, hexylnaphthoxy group, heptylnaphthoxy group, octylnaphthoxy group, nonylnaphthoxy group, decanylnaphthoxy group and the like are preferable.

In terms of solvent solubility ^{, at least one of Z 1} , Z ² , and Z ³ contains one selected from the group consisting of substituted or unsubstituted alkyl groups and substituted or unsubstituted alkoxy groups. It is more preferable to contain one selected from the group consisting of substituted or unsubstituted alkyl groups, among which linear, branched or cyclic alkyl groups or halogens having 1 to 20 carbon atoms are preferable. Alkyl carbonate groups are preferable, and straight-chain or branched alkyl groups having 1 to 10 carbon atoms or alkyl halides are preferable, and among them, it is more preferable to contain a methyl group, an ethyl group, a chloromethyl group, a chloroethyl group and the like. preferable.

From the viewpoint of resin solubility, it is preferable that at least one of ^{Z 1} , Z ² , and Z ^{3 contains a halogen atom, and at least one of Z 1} , Z ² , and Z ³ is a halogen atom or halogenated. It preferably contains an alkyl group, more preferably a halogen atom, and more preferably a chlorine atom.

From the viewpoint of resin solubility ^{, at least one of Z 1} , Z ² , and Z ³ is selected from the group consisting of a substituted or unsubstituted aryl group and a substituted or unsubstituted aryloxy group. It is preferably contained, and among them, a substituted or unsubstituted phenyl group or naphthyl group, a substituted or unsubstituted phenoxy group or naphthoxy group is preferable.

From the viewpoint of solvent solubility and resin solubility, substituted or unsubstituted alkyl groups and substituted or unsubstituted alkyl groups as at least one of ^{Z 1} , Z ² , and Z ^{3 in one molecule of the halogenated phthalocyanine coloring material} It is more preferable to contain a halogen atom in combination with one selected from the group consisting of the alkoxy groups of.

N, which is the number of substitutions of Z ³ , is an integer of 0 to 3, and is preferably an integer of 0 to 2 and preferably an integer of 0 to 1 from the viewpoint of solvent solubility and resin solubility. .. n is 0, i.e. the substituents Z ³ may not have.

From ^{the viewpoint of reaction selectivity, Y 1} is preferably −O− or −S−, and more preferably −O−.
Further, Y ¹ is preferably −S− from the viewpoint of reaction rate.
Further, Y ^{1 is preferably −NR Y} − (where ^RY is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), and is preferably −NH −, from the viewpoint of imparting heat resistance. preferable.

Further, ^{Y 1,} from the viewpoint of improvement of the various resistance such as heat ^{resistance, -N + (· A a-)} R Y1 R Y2 - ( ^wherein, R ^{Y, R Y1,} and ^{R Y2} are each independently , A hydrogen atom or an alkyl group having 1 to 6 carbon atoms, A a ⁻ represents an a-valent anion, and a is an integer of 1 or more).
−N ⁺ ( ^{.A a−} ) ^{RY1 RY2} − indicates that the quaternary ammonium cation forms a salt with an a-valent anion.
a is an integer of 1 or more, and the a-valent anion may be a divalent or higher anion.
When A ^a- is a divalent or higher anion, the divalent or higher anion further forms a salt with a cation different from the quaternary ammonium cation represented by ^{−N + RY1 RY2 −.} It may form a salt with, for example, another quaternary ammonium cation present in the molecule of the phthalocyanine halide colorant, a quaternary ammonium cation of another molecule of the phthalocyanine halide colorant, or yet another cation. You may.
When the a-valent anion is a divalent or higher anion, the halogenated phthalocyanine coloring material facilitates the formation of a molecular aggregate in which a plurality of molecules are associated via continuous ionic bonds, resulting in an apparent molecular weight. It is preferable because it becomes large and various resistances such as heat resistance are improved.

The a-valent anion may be an organic anion or an inorganic anion. Here, the organic anion represents an anion containing at least one carbon atom. The inorganic anion represents an anion that does not contain a carbon atom.

When it is an organic anion, its structure is not particularly limited. Of these, an organic group having an anionic substituent is preferable.
Examples of the anionic substituent, for ^{_{example, -SO 2 N - SO 2 CH}} 3, -SO 2 N - COCH 3, -SO 2 N - SO 2 CF 3, -SO 2 N - COCF 3, -CF 2 SO 2 ^{_{N - SO 2 CH 3, -CF}} 2 SO 2 N - COCH 3, -CF 2 SO 2 N - SO 2 CF 3, -CF 2 SO 2 N - COCF 3 or imidate group such as, -SO ₃ ^-, Substituents such as −CF ₂ SO ₃ ⁻ , −COO ⁻ , and −CF ₂ COO ⁻ can be mentioned.
Among them, ease and manufacturing cost of raw materials available, from the viewpoint high effect of maintaining the color-developed state is stabilized cations by high acidity, and imidate ^{_{groups, -SO 3 -, -CF 2 SO}} 3 - are preferred, further is preferably (a sulfonato group) ^- -SO _3.
When it is a divalent or higher anion and a plurality of anionic substituents are substituted, the same substituent may be used, or different substituents may be used.

The organic group in which one or more anionic substituents are substituted is not particularly limited. Examples of the organic group include linear, branched, or cyclic saturated or unsaturated hydrocarbon groups, monocyclic or polycyclic aromatic groups, and groups in which these are combined, and these are O, in the carbon chain. Heterogeneous atoms such as S and N may be contained, a carbonyl group, a carboxy group, an oxycarbonyl group and an amide group may be contained, and a hydrogen atom may be substituted. It may be a dye which is an organic compound or an organometallic compound.
Examples of the organic group in which the anionic substituent is substituted include the organic groups described in paragraphs 0056 to 0058 of International Publication No. 2018/003708.

In the case of a monovalent inorganic anion, for example, a halide ion such as a fluoride ion, a chloride ion, a bromide ion, or an iodide ion, a nitrate ion (NO ⁻ ), a perchlorate ion (ClO ₄ ⁻ ), or the like can be used. Can be mentioned.

Above all, the a-valent anion is preferably a divalent or higher inorganic anion from the viewpoint of improving the heat resistance of the halogenated phthalocyanine coloring material.
Examples of the divalent or higher inorganic anion include an inorganic oxo acid and a dehydration condensate thereof. For example, a divalent or higher oxo acid anion (phosphate ion, sulfate ion, chromic acid ion, tungstate ion (WO _4). ^2), molybdate ions (MoO 4 ^_2-), etc.) and can be more oxo acids and inorganic anions and mixtures thereof polyacid ions condensed.

Examples of the polyacid, isopolyacid ion _{(M m} O ^{n) c-} and a even heteropoly acid ion _{(X l} M _m O ⁿ⁾ may be a ^c-. In the above ionic formula, M represents a poly atom, X represents a hetero atom, m represents a composition ratio of a poly atom, and n represents a composition ratio of an oxygen atom. Examples of the poly atom M include Mo, W, V, Ti, Nb and the like. Examples of the heteroatom X include Si, P, As, S, Fe, and Co. Further, a counter cation such as ^{Na +} or H ^{+ may be partially contained.}
Among them, a polyacid having one or more elements selected from tungsten (W) and molybdenum (Mo) is preferable from the viewpoint of excellent heat resistance.
Examples of such polyacids include isopolic acid, tungstate ion [W ₁₀ O ₃₂ ] ^4- , molybdenum acid ion [Mo ₆ O ₁₉ ] ^2- , and heteropolyacid, phosphotung acid ion [ PW ₁₂ O ₄₀ ] ^3- , [P ₂ W ₁₈ O ₆₂ ] ^6- , Heterometalate ion [SiW ₁₂ O ₄₀ ] ^4- , Phosphormolybdenum _{acid ion [PMo 12} O ₄₀ ] ^3- , Heteropolymetalate ion [ SiMo ₁₂ O ₄₀ ] ^4- , Lintangst molybdenate ion [PW _12-x Mo _x O ₄₀ ] ^3- (x is an integer of 1 to 11), [P ₂ W _18-y Mo _y O ₆₂ ] ^6- ( y is an integer of 1 to 17), kaitungsto molybdenate ion [SiW _12-x Mo _x O ₄₀ ] ^4- (x is an integer of 1 to 11), and the like. The polyacid containing at least one of tungsten (W) and molybdenum (Mo) is preferably a heteropolyacid among the above, from the viewpoint of heat resistance and easy availability of raw materials, and further phosphorus (P). ) Is more preferable.
Furthermore, it is heat resistant to be one of lintangsto molybdate ion [PW ₁₀ Mo ₂ O ₄₀ ] ^3- , [PW ₁₁ Mo ₁ O ₄₀ ] ^3- , and phosphotungstate ion [PW ₁₂ O ₄₀ ] ^3-. It is more preferable from the viewpoint of sex.
The a-valent anion can be used alone or in combination of two or more in one molecule.
A coloring material in which a quaternary ammonium cation forms a salt with an a-valent anion can be produced by forming a salt by a conventionally known production method.

Examples of the monovalent group represented by the general formula (2) include structures of the monovalent group represented by the following general formula (2') having a combination shown in Table 1 below. , Not limited to these.

In the halogenated phthalocyanine colorant of the present invention, from the viewpoint easily improved Of these color purity, one of the ^X 1 to X ^4, any one of the ^X 5 to X ^8, wherein ^X 9 to X ^{It is preferable that any one of 12} and any one of X ^{13 to} X ¹⁶ have a total of four monovalent groups represented by the general formula (2), and further, X ² or It is more preferable that X ³ , X ⁶ or X ⁷ , X ¹⁰ or X ¹¹ , and X ¹⁴ or X ¹⁵ have a total of four monovalent groups represented by the general formula (2).

In the halogenated phthalocyanine colorant of the present invention improves the color purity, and from the viewpoint of improving the solvent solubility, one of the X ¹ to X ^4, any of the X ⁵ to X ⁸ One, any one of the above X ^{9 to} X ¹² , and any one of the above X ^{13 to} X ¹⁶ has a total of four monovalent groups represented by the general formula (2). In addition, in the monovalent group represented by the general formula (2), ^{as at least one of Z 1} , Z ² , and Z ³ , a substituted or unsubstituted alkyl group and a substituted or unsubstituted alkoxy. One molecule selected from the group consisting of groups is preferably contained in an amount of 1 or more, further 4 or more, preferably 8 or less, and further 6 or less.
Further, in this case, from the viewpoint of improving the chroma and color purity, the remaining three of ^X 1 to X ^4, the remaining three of the ^X 5 to X ^8, the remaining of the ^X 9 ^{to X 12} 3, and, the remaining three of the X ¹³ to X ^16, which is preferably selected from the group consisting of halogen atoms and hydrogen atoms, more preferably selected from the group consisting of halogen atom, a chlorine atom And more preferably selected from the group consisting of bromine atoms.

In the halogenated phthalocyanine colorant of the present invention improves the color purity, and from the viewpoint of improving the solvent solubility and resin solubility, one of the X ¹ to X ^4, wherein X ⁵ ~ one of X ^8, one of the ^X 9 ^{to X 12,} and, in one of the ^X 13 ^{to X 16,} a monovalent group represented by the general formula (2) A total of four, substituted or unsubstituted alkyl groups, and substituted or unsubstituted alkoxy groups as at least one of ^{Z 1} , Z ² , and Z ³ in one molecule of the halogenated phthalocyanine coloring material. It is preferable to contain a halogen atom in combination with one selected from the group consisting of, and in this case, at least one of ^{Z 1} , Z ² , and Z ^{3 is contained in one molecule of the halogenated phthalocyanine coloring material.} As such, it is preferable that one molecule selected from the group consisting of substituted or unsubstituted alkyl groups and substituted or unsubstituted alkoxy groups is contained in one molecule at least one, and further at least two or at least three or more. , 7 or less, more preferably 6 or less, 5 or less, and 4 may be contained. Further, it is preferable that one molecule selected from the group consisting of halogen atoms contains 1 or more, further 2 or more, 3 or more, and further contains 7 or less, further 6 or less, and 5 or less. It is preferable, and 4 pieces may be contained.
Further, in this case, from the viewpoint of improving the chroma and color purity, the remaining three of ^X 1 to X ^4, the remaining three of the ^X 5 to X ^8, the remaining of the ^X 9 ^{to X 12} 3, and, the remaining three of the X ¹³ to X ^16, which is preferably selected from the group consisting of halogen atoms and hydrogen atoms, more preferably selected from the group consisting of halogen atom, a chlorine atom And more preferably selected from the group consisting of bromine atoms.

Examples of the hydrocarbon-containing group different from the above-mentioned substituted or unsubstituted hydrocarbon group and the monovalent group represented by the general formula (2) include a heterocyclic group (preferably having 1 to 18 carbon atoms). Heterocyclic groups such as 2-thienyl group, 4-pyridyl group, 2-furyl group, 2-pyrimidinyl group, 1-pyridyl group, 2-benzothiazolyl group, 1-imidazolyl group, 1-pyrazolyl group, benzotriazole- 1-yl group), silyl group (preferably a silyl group having 3 to 18 carbon atoms, for example, trimethylsilyl group, triethylsilyl group, tributylsilyl group, tert-butyldimethylsilyl group, tert-hexyldimethylsilyl group), alkoxy Group (preferably an alkoxy group having 1 to 24 carbon atoms, for example, a methoxy group, an ethoxy group, a 1-butoxy group, a 2-butoxy group, an isopropoxy group, a tert-butoxy group, a dodecyloxy group, a cyclopentyloxy group, a cyclohexyl. Oxy group), aryloxy group (preferably aryloxy group having 6 to 24 carbon atoms, for example, phenoxy group, 1-naphthoxy group), heterocyclic oxy group (preferably heterocyclic oxy group having 1 to 18 carbon atoms). , For example, 1-phenyltetrazole-5-oxy group, 2-tetrahydropyranyloxy group), silyloxy group (preferably a silyloxy group having 1 to 18 carbon atoms, for example, trimethylsilyloxy group, tert-butyldimethylsilyloxy group. , Diphenylmethylsilyloxy group), acyloxy group (preferably an acyloxy group having 2 to 24 carbon atoms, for example, acetoxy group, pivaloyloxy group, benzoyloxy group, dodecanoyloxy group), alkoxycarbonyloxy group (preferably having 2 to 24 carbon atoms). 2 to 24 alkoxycarbonyloxy groups, for example, an ethoxycarbonyloxy group, a tert-butoxycarbonyloxy group, and if it is a cycloalkyloxycarbonyloxy group, for example, a cyclohexyloxycarbonyloxy group), an aryloxycarbonyloxy group. (Preferably an aryloxycarbonyloxy group having 7 to 24 carbon atoms, for example, a phenoxycarbonyloxy group) and the like.

Further, as the hydrocarbon-containing group, for example, a carbamoyloxy group (preferably a carbamoyloxy group having 1 to 24 carbon atoms, for example, an N, N-dimethylcarbamoyloxy group, an N-butylcarbamoyloxy group, N- Phenylcarbamoyloxy group, N-ethyl-N-phenylcarbamoyloxy group), sulfamoyloxy group (preferably sulfamoyloxy group having 1 to 24 carbon atoms, for example, N, N-diethylsulfamoyloxy group. , N-propylsulfamoyloxy group), alkylsulfonyloxy group (preferably alkylsulfonyloxy group having 1 to 24 carbon atoms, for example, methylsulfonyloxy group, hexadecylsulfonyloxy group, cyclohexylsulfonyloxy group), aryl A sulfonyloxy group (preferably an arylsulfonyloxy group having 6 to 24 carbon atoms, for example, a phenylsulfonyloxy group), an acyl group (preferably an acyl group having 2 to 24 carbon atoms, for example, an acetyl group, a pivaloyl group, a benzoyl group). , Tetradecanoyl group, cyclohexanoyl group), alkoxycarbonyl group (preferably alkoxycarbonyl group having 2 to 24 carbon atoms, for example, methoxycarbonyl group, ethoxycarbonyl group, octadecyloxycarbonyl group, cyclohexyloxycarbonyl group, 2 , 6-di-tert-butyl-4-methylcyclohexyloxycarbonyl group), aryloxycarbonyl group (preferably aryloxycarbonyl group having 7 to 24 carbon atoms, for example, phenoxycarbonyl group), carbamoyl group (preferably carbon) Numbers 2 to 24 carbamoyl groups, such as N, N-diethylcarbamoyl group, N-ethyl-N-octylcarbamoyl group, N, N-dibutylcarbamoyl group, N-propylcarbamoyl group, N-phenylcarbamoyl group, N -Methyl N-phenylcarbamoyl group, N, N-dicyclohexylcarbamoyl group), amino group (preferably an amino group having 1 to 24 carbon atoms, for example, methylamino group, N, N-dibutylamino group, tetradecyl Amino group, 2-ethylhexylamino group, cyclohexylamino group), anilino group (preferably 6 to 24 anilino groups, for example, anilino group, N-methylanilino group), heterocyclic amino group (preferably 1 to 18). Heterocyclic amino groups, such as 4-pyridylamino groups, carboxylic amide groups (preferably 2 to 24 carboxylic amide groups, for example. , Acetamide group, benzamide group, tetradecaneamide group, pivaloylamide group, cyclohexaneamide group), ureido group (preferably a ureido group having 2 to 24 carbon atoms, for example, N, N-dimethylureido group, N-phenylureido group). , An imide group (preferably an imide group having 3 to 24 carbon atoms, for example, an N-succinimide group, an N-phthalimide group), an alkoxycarbonylamino group (preferably an alkoxycarbonylamino group having 2 to 24 carbon atoms, for example, for example. A methoxycarbonylamino group, an ethoxycarbonylamino group, a tert-butoxycarbonylamino group, an octadecyloxycarbonylamino group, a cyclohexyloxycarbonylamino group), an aryloxycarbonylamino group (preferably an aryloxycarbonylamino group having 7 to 24 carbon atoms). , For example, a phenoxycarbonylamino group), a sulfonyl group (preferably a sulfonamide group having 1 to 24 carbon atoms, such as a methanesulfonamide group, a butanesulfonamide group, a benzenesulfonamide group, a hexadecanesulfonamide group, a cyclohexanesulfone. Amid group), sulfamoylamino group (preferably sulfamoylamino group having 1 to 24 carbon atoms, for example, N, N-dipropylsulfamoylamino group, N-ethyl-N-dodecylsulfamoylamino group. ), Azo group (preferably an azo group having 1 to 24 carbon atoms, for example, a phenylazo group, a 3-pyrazolylazo group), an alkylthio group (preferably an alkylthio group having 1 to 24 carbon atoms, for example, a methylthio group, an ethylthio group). A group, an octylthio group, a cyclohexylthio group), an arylthio group (preferably an arylthio group having 6 to 24 carbon atoms, for example, a phenylthio group), a heterocyclic thio group (preferably a heterocyclic thiogroup having 1 to 18 carbon atoms). For example, 2-benzothiazolylthio group, 2-pyridylthio group, 1-phenyltetrazolylthio group), alkylsulfinyl group (preferably an alkylsulfinyl group having 1 to 24 carbon atoms, for example, dodecanesulfinyl group), arylsulfinyl. A group (preferably an arylsulfinyl group having 6 to 24 carbon atoms, for example, a phenylsulfinyl group), an alkylsulfonyl group (preferably an alkylsulfonyl group having 1 to 24 carbon atoms, for example, a methylsulfonyl group, an ethylsulfonyl group, propyl). Sulfonyl group, butylsulfonyl group, isopropylsulfonyl group, 2-ethylhexylus Luhonic group, hexadecylsulfonyl group, octylsulfonyl group, cyclohexylsulfonyl group), arylsulfonyl group (preferably arylsulfonyl group having 6 to 24 carbon atoms, for example, phenylsulfonyl group, 1-naphthylsulfonyl group), sulfamoyl group (sulfamoyl group). A sulfamoyl group having 24 or less carbon atoms is preferable, and for example, a sulfamoyl group, an N, N-dipropyl sulfamoyl group, an N-ethyl-N-dodecyl sulfamoyl group, an N-ethyl-N-phenyl sulfamoyl group, N-cyclohexylsulfamoyl group), phosphonyl group (preferably a phosphonyl group having 1 to 24 carbon atoms, for example, phenoxyphosphonyl group, octyloxyphosphonyl group, phenylphosphonyl group), phosphinoylamino group (preferably Is a phosphinoylamino group having 1 to 24 carbon atoms, and examples thereof include a diethoxyphosphinoylamino group and a dioctyloxyphosphinoylamino group.

Solvent solubility, from the viewpoint of resin solubility, in the X ¹ to X ^16, wherein said hydrocarbon-containing group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, In addition, it is preferably at least one selected from the group consisting of monovalent groups represented by the following general formula (3), and further, the monovalent group represented by the following general formula (3). Is preferable.

（一般式（３）中、Ｙ^２は、−Ｏ−、−Ｓ−、−ＮＲ^Ｙ−、又は−Ｎ^＋（・Ａ^ａ−）Ｒ^Ｙ１Ｒ^Ｙ２−（ここで、Ｒ^Ｙ、Ｒ^Ｙ１、及びＲ^Ｙ２はそれぞれ独立に、水素原子または炭素数１〜６のアルキル基を表し、Ａ^ａ−は、ａ価のアニオンを表し、ａは１以上の整数である。）を表し、Ａｒは、置換もしくは非置換のアリール基を表し、＊は、フタロシアニン骨格との結合位置を示す。）

(In the general formula ^{(3), Y} 2 is, -O -, - S -, - NR Y -, or ^{-N + (· A a-) R} Y1 R Y2 - ( ^{wherein, R Y,} R ^Y1, And ^RY2 independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, A ^a- represents an a-valent anion, and a is an integer of 1 or more). It represents a substituted or unsubstituted aryl group, and * indicates the bonding position with the phthalocyanine skeleton.)

In the general formula (3), Ar represents a substituted or unsubstituted aryl group, and may be the same as the above-mentioned substituted or unsubstituted aryl group.
The monovalent group represented by the general formula (3), which is different from the monovalent group represented by the general formula (2), is, for example, the following formula (from the viewpoint of solvent solubility and resin solubility). Substituents represented by s-1) to (s-3) can be mentioned, but the present invention is not limited thereto.

In the general formula (1), M represents one kind of metal selected from the group consisting of Cu (copper), Zn (zinc), Co (cobalt), Mo (molybdenum) and Al (aluminum). From the viewpoint of good electrical reliability and high permeability, it is preferably one kind of metal selected from the group consisting of Cu, Zn, and Al, more preferably Cu or Zn, and more preferably Zn. More preferred.
In the halogenated phthalocyanine coloring material, M may be contained alone or in combination of two or more, but it is preferably one kind from the viewpoint of color purity.

Examples of the halogenated phthalocyanine coloring material of the present invention are given below, but the present invention is not limited thereto.
The table below shows the substituents represented by the following general formula and their numbers. In addition, Sub in the following general formula represents another substituent. In the table, (s-1) to (s-3) represent the above-mentioned substituents. Further, (Sub et al. 1) represents −O− (CH ₂ ) _n −CH ₃ n = 22, and (Sub et al. 2) represents −O− (CH ₂ CH ₂ O) _n −CH ₃ n = 5. ..

The halogenated phthalocyanine coloring material may be a multimer of halogenated phthalocyanine. Examples of the multimer include a dimer, a trimer, and a tetramer linked by a divalent to tetravalent linking group as described in paragraphs 0076 to 0105 of JP2014-43556A. Examples include a body and a polymer-type multimer having a linking group formed by polymerization.

As a method for producing the halogenated phthalocyanine coloring material, a conventionally known production method can be appropriately selected and used. For example, a production method in which a phthalonitrile compound and a metal salt are cyclized in a molten state or in an organic solvent can be preferably used, and for example, it can be produced with reference to Japanese Patent Application Laid-Open No. 2014-43556. As for the phthalonitrile compound used as a starting material, a conventionally known production method can be appropriately selected and synthesized, and a commercially available product may be used.

[Color material liquid]
The coloring material liquid according to the present invention contains the halogenated phthalocyanine coloring material according to the present invention and a solvent.
The color material liquid of the present invention may contain the halogenated phthalocyanine color material of the present invention, a yellow color material, and a solvent.
Further, the color material liquid of the present invention may contain the halogenated phthalocyanine color material of the present invention, a green color material different from the halogenated phthalocyanine color material, and a solvent.
Since the colorant liquid of the present invention contains the halogenated phthalocyanine colorant of the present invention as the colorant, it is possible to form a colored layer having excellent color purity and brightness.
The color material liquid of the present invention may contain the halogenated phthalocyanine color material of the present invention, a yellow color material, a green color material different from the halogenated phthalocyanine color material, and a solvent.
Further, the color material liquid of the present invention may further contain other color materials or may further contain other components as long as the effects of the present invention are not impaired.
The "color material liquid" of the present invention includes a "color material solution" in which the color material is dissolved in a solvent and a "color material dispersion" in which particles of the color material are dispersed in the solvent. "Liquid" is included.
Hereinafter, each component of the coloring material liquid of the present invention will be described in detail in order.
The halogenated phthalocyanine coloring material of the present invention contained in the coloring material may be the same as described above, and thus the description thereof will be omitted here.

<Color material>
In the present invention, the coloring material may be any one capable of developing a desired color, and is not particularly limited, and various organic pigments, inorganic pigments, dyes, salt-forming compounds of dyes, and the like may be mixed alone or in combination of two or more. Can be used. Among them, organic pigments are preferably used because they have high color development and high heat resistance. Examples of the organic pigment include compounds classified as Pigments in the color index (CI; published by The Society of Dyers and Colorists), specifically, the following color index (CI). .) Numbered ones can be mentioned.

Examples of the yellow color material include C.I. I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 55, 60, 61, 65, 71, 73, 74, 81, 83, 93, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116, 117, 119, 120, 126, 127, 128, 129, 138, 139, 150, 151, 152, 153, 154, 155, Yellow pigments such as 156, 166, 168, 175, 185, 231 and their derivative pigments, coumarin dyes, cyanine dyes, merocyanine dyes, azo dyes, methine dyes, azomethine dyes, quinophthalone dyes, etc. Yellow dye and the like.

As the yellow color material, a quinophthalone-based color material is preferable because it has good heat resistance and light resistance and high transmittance. The quinophthalone-based coloring material is also preferable in that it has a hue suitable for color filter applications.
The quinophthalone-based coloring material refers to a coloring material synthesized by condensing a quinoline derivative such as quinaldine with a phthalic anhydride derivative or a phthalic anhydride derivative, and may be any of pigments, dyes, and salt-forming compounds of dyes. good.
Among the quinophthalone-based colorants, examples of the quinophthalone pigment include C.I. I. Pigment Yellow 138 and the like.
Examples of the quinophthalone dye include C.I. I. Dispersius Yellow 54, 64, 67, 134, 149, 160, C.I. I. Solvent Yellow 114, 157 and the like can be mentioned, among which C.I. I. Disperse Yellow 54 is preferred.

On the other hand, as a green color material different from the halogenated phthalocyanine color material of the present invention, C.I. I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, 58, 59, 62, 63, etc. Examples thereof include green pigments such as squalylium, triarylmethane, anthraquinone, coumarin, cyanine, and green dyes such as azo dyes.
From the viewpoint of easiness of adjusting the chromaticity, the phthalocyanine green pigment is preferable as the green color material different from the halogenated phthalocyanine color material.
Examples of the phthalocyanine green pigment include C.I. I. Pigment Green 7, 36, 58, 59, 62, 63 and the like. From the viewpoint of ease of adjusting the brightness, the phthalocyanine green pigment is C.I. I. Pigment Green 7, 58, 59, 62, or 63, preferably C.I. I. Pigment Green 58, 59, 62, or 63 is preferred. I. Pigment Green 59 is more preferred.

Examples of other coloring materials include blue coloring materials and orange coloring materials.
As an orange color material, C.I. I. Pigment Orange 1, 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 61, 63, 64, 71, 73;
As a blue color material, C.I. I. Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60.

In the color material liquid of the present invention, the yellow color material is appropriately selected and used alone or in combination of two or more.
In the color material liquid containing the halogenated phthalocyanine color material of the present invention, the yellow color material, and the solvent, the content ratio of the halogenated phthalocyanine color material of the present invention to the entire color material is adjusted to a desired chromaticity. It may be adjusted as appropriate, and is not particularly limited. Above all, from the viewpoint of desired chromaticity adjustment, it is preferable that the halogenated phthalocyanine color material of the present invention is contained in an amount of 30 to 95% by mass with respect to the entire color material containing the halogenated phthalocyanine color material of the present invention. It is more preferably contained in an amount of 40 to 85% by mass, and even more preferably contained in an amount of 50 to 80% by mass.

In the color material liquid of the present invention, the content ratio of the yellow color material to the halogenated phthalocyanine color material of the present invention may be appropriately adjusted according to a desired chromaticity, and is not particularly limited. Above all, from the viewpoint of desired chromaticity adjustment, it is preferable to contain 5 to 233 parts by mass of the yellow color material with respect to 100 parts by mass of the halogenated phthalocyanine color material of the present invention, and 18 to 150 parts by mass of the yellow color material. More preferably, it is more preferably contained in an amount of 25 to 100 parts by mass.

In the color material liquid of the present invention, a green color material different from the halogenated phthalocyanine color material is appropriately selected and used alone or in combination of two or more.
In a coloring material liquid containing the halogenated phthalocyanine coloring material of the present invention, a green coloring material different from the halogenated phthalocyanine coloring material, and a solvent, the inclusion of the halogenated phthalocyanine coloring material of the present invention in the entire coloring material. The ratio may be appropriately adjusted according to the desired chromaticity, and is not particularly limited. Above all, from the viewpoint of desired chromaticity adjustment and brightness adjustment, the halogenated phthalocyanine color material of the present invention is contained in an amount of 10 to 95% by mass with respect to the entire color material containing the halogenated phthalocyanine color material of the present invention. It is more preferable to contain 15 to 85% by mass, and even more preferably 20 to 80% by mass.

In the color material liquid of the present invention, the content ratio of the green color material different from the halogenated phthalocyanine color material to the halogenated phthalocyanine color material of the present invention may be appropriately adjusted according to the desired chromaticity. There is no particular limitation. Among them, from the viewpoint of desired chromaticity adjustment and brightness adjustment, the halogenated phthalocyanine color material of the present invention contains 5 to 900 parts by mass of a green color material different from the halogenated phthalocyanine color material with respect to 100 parts by mass. It is more preferable to contain 18 to 567 parts by mass, and even more preferably 25 to 400 parts by mass.

Further, in the color material liquid of the present invention, the content ratio when the halogenated phthalocyanine color material, the yellow color material, and other color materials of the present invention are used, the halogenated phthalocyanine color material of the present invention, and the halogenation. When a green color material different from the phthalocyanine color material and other color materials are used, the content ratio is preferably the same as that of the color curable composition described later. However, since two or more kinds of coloring material liquids can be appropriately mixed and used to produce a coloring curable composition described later, it is preferable that the content ratio is not the same as that of the coloring curable composition described later. Used.

The average primary particle size when the coloring material used in the present invention is dispersed is not particularly limited as long as it can develop a desired color when the coloring layer of the color filter is used, and the coloring material used is not particularly limited. Although it varies depending on the type of the above, it is preferably in the range of 10 to 100 nm, and more preferably 15 to 60 nm. When the average primary particle size of the color material is within the above range, the display device provided with the color filter manufactured by using the color material liquid of the present invention can have high contrast and high quality.

The average primary particle size when the coloring material in the present invention is dispersed represents the “volume distribution median diameter (D50)”. The average primary particle size of the coloring material is the scanning transmission electron by attaching a dedicated bright-field STEM sample table and optional detector to the electric field radiation scanning electron microscope (S-4800) manufactured by Hitachi High-Technologies Co., Ltd. It can be used as a microscope (hereinafter abbreviated as "STEM"), take a STEM photograph of 200,000 times, import it into the software below, select 100 coloring materials arbitrarily on the photograph, and each diameter (passing length). S) is measured, and it is obtained as a 50% cumulative particle diameter by volume from the volume-based distribution.
The measurement sample to be used for STEM is prepared by mixing a coloring material and toluene and dropping the mixture onto a collodion film-attached mesh. Further, when obtaining the volume-based particle size distribution and the volume distribution median diameter (D50) from the STEM photograph, the image analysis type particle size distribution measurement software "Mac-View Ver.4" manufactured by Mountech Co., Ltd. is used.

The average dispersed particle size when the coloring material in the coloring material liquid is dispersed varies depending on the type of coloring material used, but is preferably in the range of 10 to 100 nm, and in the range of 15 to 60 nm. More preferably.
The average dispersed particle size of the colored material in the colored material liquid is at least the dispersed particle size of the colored material particles dispersed in the dispersion medium containing a solvent, and is measured by a laser light scattering particle size distribution meter. be. To measure the particle size with a laser light scattering particle size distribution meter, the color material solution is appropriately diluted with a solvent used in the color material solution to a concentration that can be measured by the laser light scattering particle size distribution meter (for example, 1000 times). Then, it can be measured at 23 ° C. by a dynamic light scattering method using a laser light scattering particle size distribution meter (for example, Nanotrack particle size distribution measuring device UPA-EX150 manufactured by Nikkiso Co., Ltd.). The average distributed particle size here is the volume average particle size.

In the coloring material liquid of the present invention, the content of the coloring material is not particularly limited. When dissolved in a solvent, the content of the coloring material may be 50 to 100 parts by mass and 70 to 100 parts by mass with respect to 100 parts by mass of the total solid content in the coloring material liquid from the viewpoint of storage stability. It may be a department.
When dispersing in a solvent, it is preferable to use a dispersant, and from the viewpoint of dispersibility, the content of the coloring material is 10 to 80 parts by mass, based on 100 parts by mass of the total solid content in the coloring material liquid. It is preferably blended in a proportion of 20 to 70 parts by mass.

<Solvent>
The solvent used in the present invention is not particularly limited as long as it is an organic solvent that does not react with each component in the coloring material liquid and can dissolve or disperse them. The solvent can be used alone or in combination of two or more.
Specific examples of the solvent include alcohol solvents such as methyl alcohol, ethyl alcohol, i-propyl alcohol and methoxy alcohol; carbitol solvents such as methoxyethoxyethanol and ethoxyethoxyethanol; ethyl acetate, butyl acetate and methoxypropion. Ester solvents such as methyl acid, ethyl methoxypropionate, ethyl ethoxypropionate, ethyl lactate, methyl hydroxypropionate, ethyl hydroxypropionate, n-butyl acetate, isobutyl acetate, n-butyl butyrate, clohexanol acetate; acetone, Ketone solvents such as methyl ethyl ketone, cyclohexanone, 2-heptanone; glycol ether acetate such as methoxyethyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-1-butyl acetate, 3-methoxybutyl acetate, ethoxyethyl acetate Solvents: Carbitol acetate solvents such as methoxyethoxyethyl acetate, ethoxyethoxyethyl acetate and butyl carbitol acetate (BCA); Diacetates such as propylene glycol diacetate and 1,3-butylene glycol diacetate; ethylene glycol monomethyl Glycol ether solvents such as ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, dipropylene glycol dimethyl ether; N, N-dimethyl Aprotonic amide solvents such as formamide, N, N-dimethylacetamide, N-methylpyrrolidone; lactone solvents such as γ-butyrolactone; cyclic ether solvents such as tetrahydrofuran; unsaturated carbides such as benzene, toluene, xylene and naphthalene. Hydrogen-based solvents; saturated hydrocarbon-based solvents such as N-heptane, N-hexane, and N-octane; organic solvents such as aromatic hydrocarbons such as toluene and xylene can be mentioned. Among these solvents, glycol ether acetate-based solvent, carbitol acetate-based solvent, glycol ether-based solvent, and ester-based solvent are preferably used in terms of solubility of other components. Among them, the solvents used in the present invention include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 2-methoxyethyl acetate, propylene glycol monomethyl ether, diethylene glycol ethyl methyl ether, butyl carbitol acetate (BCA), and 3-methoxy. Solubility and application of other components must be at least one selected from the group consisting of -3-methyl-1-butyl acetate, ethyl lactate, methyl 2-hydroxypropionate, and 3-methoxybutyl acetate. It is preferable from the viewpoint of aptitude.

Further, from the viewpoint of developability, solvent resolubility and the like, a mixed solvent containing two or more kinds of solvents may be used.
The color material liquid of the present invention preferably contains the above solvent in a range of 55 to 95% by mass, particularly 65 to 90% by mass, based on the total amount of the color material liquid containing the solvent. It is preferably in the range, more preferably in the range of 70 to 88% by mass. If the amount of solvent is too small, the viscosity tends to increase. Further, if the amount of the solvent is too large, the density of the coloring material decreases, and it may be difficult to achieve the target chromaticity coordinates.

<Dispersant>
When the color material is dispersed in the color material liquid of the present invention, a dispersant may be further contained from the viewpoint of color material dispersibility and color material dispersion stability.
In the present invention, the dispersant can be appropriately selected and used from conventionally known dispersants. As the dispersant, for example, cationic, anionic, nonionic, amphoteric, silicone-based, and fluorine-based surfactants can be used. Among the surfactants, the polymer dispersant is preferable because it can be dispersed uniformly and finely.

Examples of the polymer dispersant include (co) polymers of unsaturated carboxylic acid esters such as polyacrylic acid esters; (partial) amine salts of (co) polymers of unsaturated carboxylic acids such as polyacrylic acid. (Partial) ammonium salts and (partial) alkylamine salts; (co) polymers of hydroxyl group-containing unsaturated carboxylic acid esters such as hydroxyl group-containing polyacrylic acid esters and their modifications; polyurethanes; unsaturated polyamides; polysiloxane Classes; long-chain polyaminoamide phosphates; polyethyleneimine derivatives (amides obtained by the reaction of poly (lower alkyleneimine) with free carboxy group-containing polyesters and their bases); polyallylamine derivatives (polyallylamine and free carboxy) (Reaction product obtained by reacting one or more compounds selected from three kinds of compounds of polyester, polyamide or ester and amide cocondensate (polyester amide) having a group) and the like can be mentioned.

The polymer dispersant may be, for example, a polymer dispersant containing a nitrogen atom in the main chain or side chain and having an amine value, and among them, a polymer containing a repeating unit having a tertiary amine. It may be a polymer dispersant. Among them, since the main chain skeleton is hard to be thermally decomposed and has high heat resistance, for example, a polymer having a structural unit represented by the following general formula (I) as described in JP-A-2016-224447, or a polymer having a structural unit represented by the following general formula (I). Even if a dispersant which is at least one of a block copolymer having a structural unit represented by the following general formula (I) and a salt-type block copolymer as described in WO2016 / 104493 is used. good.

（一般式（Ｉ）中、Ｒ^１は水素原子又はメチル基、Ａは、２価の連結基、Ｒ^２及びＲ^３は、それぞれ独立して、水素原子、又はヘテロ原子を含んでもよい炭化水素基を表し、Ｒ^２及びＲ^３が互いに結合して環構造を形成してもよい。）
前記符号の説明は、特開２０１６−２２４４４７号を参照することができる。

(In the general formula (I), R ¹ is a hydrogen atom or a methyl group, A is a divalent linking group, and R ² and R ³ are hydrocarbons which may independently contain a hydrogen atom or a hetero atom. Representing a group, R ² and R ³ may be bonded to each other to form a ring structure.)
For the description of the reference numerals, Japanese Patent Application Laid-Open No. 2016-224447 can be referred to.

Further, the polymer dispersant may be, for example, a polymer dispersant containing an acidic group in the main chain or the side chain and having an acid value. Among them, the structural unit represented by the following general formula (I') and the following general formula (for example, as described in Japanese Patent Application Laid-Open No. 2015-107471) and the following general formula ( It is a graft copolymer having at least one selected from the structural units represented by I ") and the structural unit represented by the following general formula (II), or is represented by the following general formula (I'). A block copolymer having a block portion containing at least one selected from the structural unit represented by the following general formula (I ”) and a block portion containing the structural unit represented by the following general formula (III). A non-aqueous dispersant may be used.

（一般式（Ｉ’）及び一般式（Ｉ”）中、Ｌ^１は、直接結合又は２価の連結基、Ｒ^１は、水素原子又はメチル基、Ｒ^２は、炭化水素基、−［ＣＨ（Ｒ^６）−ＣＨ（Ｒ^７）−Ｏ］_ｘ１−Ｒ^８、又は−［（ＣＨ_２）_ｙ１−Ｏ］_ｚ１−Ｒ^８で示される１価の基、Ｒ^６及びＲ^７は、それぞれ独立に水素原子又はメチル基、Ｒ^８は、水素原子、炭化水素基、−ＣＨＯ、−ＣＨ_２ＣＨＯ、−ＣＯ−ＣＨ＝ＣＨ_２、−ＣＯ−Ｃ（ＣＨ_３）＝ＣＨ_２又は−ＣＨ_２ＣＯＯＲ^９で示される１価の基であり、Ｒ^９は水素原子又は炭素数１〜５のアルキル基であり、前記炭化水素基は置換基を有していてもよい。ｘ１は１〜１８の整数、ｙ１は１〜５の整数、ｚ１は１〜１８の整数を表す。
一般式（Ｉ’）中、Ｘ^＋は有機カチオンを表す。
一般式（ＩＩ）中、Ｌ^２は、直接結合又は２価の連結基、Ｒ^３は、水素原子又はメチル基、Ｐｏｌｙｍｅｒは、下記一般式（ＩＶ）で表される構成単位及び一般式（Ｖ）で表される構成単位から選ばれる１種以上を有するポリマー鎖を表す。
一般式（ＩＩＩ）中、Ｒ^４は、水素原子又はメチル基、Ｒ^５は、炭化水素基、−［ＣＨ（Ｒ^１０）−ＣＨ（Ｒ^１１）−Ｏ］_ｘ２−Ｒ^１２、−［（ＣＨ_２）_ｙ２−Ｏ］_ｚ２−Ｒ^１２、−［ＣＯ−（ＣＨ_２）_ｙ２−Ｏ］_ｚ２−Ｒ^１２、−ＣＯ−Ｏ−Ｒ^１２’又は−Ｏ−ＣＯ−Ｒ^１２”で示される１価の基、Ｒ^１０及びＲ^１１は、それぞれ独立に水素原子又はメチル基、Ｒ^１２は、水素原子、炭化水素基、−ＣＨＯ、−ＣＨ_２ＣＨＯ又は−ＣＨ_２ＣＯＯＲ^１３で示される１価の基であり、Ｒ^１２’は、炭化水素基、−［ＣＨ（Ｒ^１０）−ＣＨ（Ｒ^１１）−Ｏ］_ｘ２’−Ｒ^１２、−［（ＣＨ_２）_ｙ２’−Ｏ］_ｚ２’−Ｒ^１２、−［ＣＯ−（ＣＨ_２）_ｙ２’−Ｏ］_ｚ２’−Ｒ^１２で示される１価の基であり、Ｒ^１２”は炭素数１〜１８のアルキル基、Ｒ^１３は水素原子又は炭素数１〜５のアルキル基であり、前記炭化水素基は、置換基を有していてもよい。ｘ２及びｘ２’は１〜１８の整数、ｙ２及びｙ２’は１〜５の整数、ｚ２及びｚ２’は１〜１８の整数を示す。））

(In the general formula (I') and the general formula (I "), L ¹ is a direct bond or a divalent linking group, R ¹ is a hydrogen atom or a methyl group, R ² is a hydrocarbon group,-[CH (R ⁶ ) -CH (R ⁷ ) -O] _x1- R ⁸ or-[(CH ₂ ) _y1- O] The monovalent groups represented by _z1- R ^{8 , R 6} and R ⁷ , are independent of each other. Hydrogen atom or methyl group, R ⁸ is hydrogen atom, hydrocarbon group, -CHO, -CH ₂ CHO, -CO-CH = CH ₂ , -CO-C (CH ₃ ) = CH ₂ or -CH ₂ COOR a monovalent group represented by ^9, R ⁹ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, the hydrocarbon groups are .x1 which may have a substituent 1 to 18 integer , Y1 represents an integer of 1 to 5, and z1 represents an integer of 1 to 18.
In the general formula (I'), X ⁺ represents an organic cation.
In the general formula (II), L ² is a direct bond or a divalent linking group, R ³ is a hydrogen atom or a methyl group, and Polymer is a structural unit represented by the following general formula (IV) and the general formula (V). ) Represents a polymer chain having one or more selected from the structural units represented by).
In the general formula (III), R ⁴ is a hydrogen atom or a methyl group, R ⁵ is a hydrocarbon group,-[CH (R ¹⁰ ) -CH (R ¹¹ ) -O] _x2- R ¹² ,-[(CH). ^{_{2) y2 -O] z2 -R 12}} , - [CO- (CH 2) y2 -O] z2 -R 12, -CO-O-R 12 ' or ^{-O-CO-R 12} 1 monovalent labeled ^" Groups, R ¹⁰ and R ¹¹ , are independent hydrogen atoms or methyl groups, and R ¹² is a hydrogen atom, hydrocarbon group, -CHO, -CH ₂ CHO or -CH ₂ COOR ¹³ monovalent group. R ^12'is a hydrocarbon group,-[CH (R ¹⁰ ) -CH (R ¹¹ ) -O] _x2'- R ¹² ,-[(CH ₂ ) _y2'- O] _z2'- R ¹² ,-[CO- (CH ₂ ) _y2'- O] _z2'- R ¹² is a monovalent group, R ^{12 "} is an alkyl group having 1 to 18 carbon atoms, and R ¹³ is a hydrogen atom or carbon number. It is an alkyl group of 1 to 5, and the hydrocarbon group may have a substituent. x2 and x2'are integers of 1 to 18, y2 and y2'are integers of 1 to 5, and z2 and z2'are integers of 1 to 18. )))

（一般式（ＩＶ）及び一般式（Ｖ）中、Ｒ^１４は水素原子又はメチル基であり、Ｒ^１５は炭化水素基、−［ＣＨ（Ｒ^１６）−ＣＨ（Ｒ^１７）−Ｏ］_ｘ３−Ｒ^１８、−［（ＣＨ_２）_ｙ３−Ｏ］_ｚ３−Ｒ^１８、−［ＣＯ−（ＣＨ_２）_ｙ３−Ｏ］_ｚ３−Ｒ^１８、−ＣＯ−Ｏ−Ｒ^１９又は−Ｏ−ＣＯ−Ｒ^２０で示される１価の基、Ｒ^１６及びＲ^１７は、それぞれ独立に水素原子又はメチル基、Ｒ^１８は、水素原子、炭化水素基、−ＣＨＯ、−ＣＨ_２ＣＨＯ又は−ＣＨ_２ＣＯＯＲ^２１で示される１価の基、Ｒ^１９は、炭化水素基、−［ＣＨ（Ｒ^１６）−ＣＨ（Ｒ^１７）−Ｏ］_ｘ４−Ｒ^１８、−［（ＣＨ_２）_ｙ４−Ｏ］_ｚ４−Ｒ^１８、−［ＣＯ−（ＣＨ_２）_ｙ４−Ｏ］_ｚ４−Ｒ^１８で示される１価の基、Ｒ^２０は炭素数１〜１８のアルキル基、Ｒ^２１は水素原子又は炭素数１〜５のアルキル基であり、前記炭化水素基は、置換基を有していてもよい。
ｍは１〜５の整数、ｎ及びｎ’は５〜２００の整数を示す。ｘ３及びｘ４は１〜１８の整数、ｙ３及びｙ４は１〜５の整数、ｚ３及びｚ４は１〜１８の整数を示す。）
前記符号の説明は、特開２０１５−１０７４７１号を参照することができる。

(In the general formula (IV) and the general formula (V), R ¹⁴ is a hydrogen atom or a methyl group, R ¹⁵ is a hydrocarbon group,-[CH (R ¹⁶ ) -CH (R ¹⁷ ) -O] _x3- R ¹⁸ ,-[(CH ₂ ) _y3- O] _z3- R ¹⁸ ,-[CO- (CH ₂ ) _y3- O] _z3- R ¹⁸ , -CO-O-R ¹⁹ or -O-CO-R ²⁰ The monovalent groups represented by, R ¹⁶ and R ¹⁷ , are independently represented by a hydrogen atom or a methyl group, and R ¹⁸ is represented by a hydrogen atom, a hydrocarbon group, -CHO, -CH ₂ CHO or -CH ₂ COOR ²¹ . The monovalent group, R ^19, is a hydrocarbon group, − [CH (R ¹⁶ ) −CH (R ¹⁷ ) −O] _x4- R ¹⁸ , − [(CH ₂ ) _y4 −O] _z4- R ¹⁸ , -[CO- (CH ₂ ) _y4- O] _z4- R ¹⁸ is a monovalent group, R ²⁰ is an alkyl group having 1 to 18 carbon atoms, and R ²¹ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. The hydrocarbon group may have a substituent.
m is an integer of 1 to 5, and n and n'are integers of 5 to 200. x3 and x4 are integers of 1 to 18, y3 and y4 are integers of 1 to 5, and z3 and z4 are integers of 1 to 18. )
For the description of the reference numerals, Japanese Patent Application Laid-Open No. 2015-107471 can be referred to.

In the colorant liquid of the present invention, the content of the dispersant is appropriately selected according to the type of the colorant to be used, the solid content concentration in the color curable composition described later, and the like.
The content of the dispersant is 3 to 45 parts by mass, more preferably 5 to 35 parts by mass with respect to 100 parts by mass of the total solid content in the coloring material liquid from the viewpoint of dispersibility and dispersion stability. It is preferable to do so.
In the present invention, the solid content is all other than the above-mentioned solvent, and includes monomers dissolved in the solvent and the like.

(Other ingredients)
The color material liquid of the present invention may further contain a dispersion auxiliary resin and other components, if necessary, as long as the effects of the present invention are not impaired.
Examples of the dispersion auxiliary resin include alkali-soluble resins exemplified in the color curable composition described later. The steric hindrance of the alkali-soluble resin makes it difficult for the colorant particles to come into contact with each other, which may have the effect of stabilizing the dispersion and reducing the amount of the dispersant due to the effect of stabilizing the dispersion.
Other components include, for example, a surfactant for improving wettability, a silane coupling agent for improving adhesion, a defoaming agent, an anti-repellent agent, an antioxidant, an antioxidant, and an ultraviolet absorber. And so on.

The colorant solution of the present invention is used as a preliminary preparation for preparing a color curable composition described later. That is, the color material liquid is (mass of color material component in composition) / (mass of solid content other than color material component in composition) that is preliminarily prepared in the stage before preparing the color curable composition described later. ) It is a coloring material liquid with a high ratio. Specifically, the ratio (mass of color material component in composition) / (mass of solid content other than color material component in composition) is usually 1.0 or more. By mixing the color material liquid with each component described later, a color curable composition having excellent plate-making characteristics or color material dispersibility can be prepared.

<Manufacturing method of color material liquid>
In the present invention, in the method for producing a color material liquid, either a color material liquid in which the color material is dissolved in a solvent can be obtained, or a color material liquid in which the color material is dispersed in a solvent by the dispersant can be obtained. The method is not particularly limited as long as it can be obtained.
For example, the method for producing a colorant liquid according to the present invention includes a step of dissolving the colorant in a solvent. Two or more kinds of coloring materials may be dissolved in the solvent, or two or more kinds of coloring materials may be mixed after dissolving one or more kinds of coloring materials to obtain the coloring material liquid of the present invention. good.
Further, for example, the method for producing a colorant liquid according to the present invention includes a step of preparing the dispersant and a step of dispersing the colorant in a solvent in the presence of the dispersant. Two or more kinds of coloring materials may be co-dispersed in the solvent in the presence of the dispersant, or one or more kinds of coloring materials may be dispersed or co-dispersed, and then two or more kinds of coloring material liquids are mixed. Thereby, the coloring material liquid of the present invention may be obtained.

When the coloring material is dispersed, it can be dispersed using a conventionally known disperser.
Specific examples of the disperser include a roll mill such as a two-roll and three-roll mill, a ball mill, a ball mill such as a vibrating ball mill, a paint conditioner, a continuous disc type bead mill, and a bead mill such as a continuous annular type bead mill. As a preferable dispersion condition of the bead mill, the bead diameter used is preferably 0.03 to 3.0 mm, more preferably 0.05 to 2.0 mm.
Specifically, pre-dispersion is performed with 2.0 mm zirconia beads having a relatively large bead diameter, and main dispersion is performed with 0.1 mm zirconia beads having a relatively small bead diameter. Further, after dispersion, it is preferable to filter with a filter of 0.5 to 2 μm.

The color material dispersion liquid and the color material according to the present invention are used in various applications in which good color purity is required, and are also used in inkjet inks, printing inks, writing instruments, cosmetics, and the like.

[Color curable composition]
The color curable composition according to the present invention contains a coloring material, a polymer, a polymerizable compound, an initiator, and a solvent, and the coloring material contains the halogenated phthalocyanine coloring material of the present invention. ..
The color curable composition according to the present invention may contain the color material liquid according to the present invention, a polymerizable compound, and an initiator.
Since the coloring curable composition of the present invention contains the halogenated phthalocyanine coloring material of the present invention, it is possible to form a colored layer having excellent color purity and brightness.

The color curable composition of the present invention contains at least a coloring material, a polymer, a polymerizable compound, an initiator, and a solvent, and further other components as long as the effects of the present invention are not impaired. May be contained. Hereinafter, each component contained in the coloring curable composition of the present invention will be described, but the coloring material, the solvent, and the dispersant that may be contained are the same as those described in the coloring material liquid of the present invention. Therefore, the description here will be omitted as appropriate.

<Color material>
The color material in the color curable composition of the present invention may be the same as the color material described in the color material liquid.
In the color curable composition of the present invention, the content ratio of the halogenated phthalocyanine color material of the present invention to the entire color material may be appropriately adjusted according to a desired chromaticity, and is not particularly limited. Above all, from the viewpoint of desired chromaticity adjustment, the content ratio of the halogenated phthalocyanine coloring material of the present invention to the entire coloring material is preferably 30 to 95% by mass, more preferably 40 to 85% by mass. It is preferably contained in an amount of 50 to 80% by mass, even more preferably.

In the color curable composition of the present invention, the yellow color material is appropriately selected and used alone or in combination of two or more.
In the color curable composition of the present invention, the content ratio of the yellow color material to the halogenated phthalocyanine color material of the present invention may be appropriately adjusted according to a desired chromaticity, and is not particularly limited. Above all, from the viewpoint of desired chromaticity adjustment, it is preferable to contain 5 to 233 parts by mass of the yellow color material with respect to 100 parts by mass of the halogenated phthalocyanine color material of the present invention, and 18 to 150 parts by mass of the yellow color material. More preferably, it is more preferably contained in an amount of 25 to 100 parts by mass.

In the color curable composition of the present invention, the content ratio of the green color material different from the halogenated phthalocyanine color material to the halogenated phthalocyanine color material of the present invention may be appropriately adjusted to a desired chromaticity. There is no particular limitation. Among them, from the viewpoint of desired chromaticity adjustment and brightness adjustment, the halogenated phthalocyanine color material of the present invention contains 5 to 900 parts by mass of a green color material different from the halogenated phthalocyanine color material with respect to 100 parts by mass. It is more preferable to contain 18 to 567 parts by mass, and even more preferably 25 to 400 parts by mass.

Further, when the color curable composition of the present invention further contains a green color material other than the halogenated phthalocyanine color material of the present invention, the green color material containing the halogenated phthalocyanine color material of the present invention with respect to the entire color material. The content ratio of the above may be appropriately adjusted according to the desired chromaticity, and is not particularly limited. Above all, from the viewpoint of desired chromaticity adjustment and brightness adjustment, it is preferable to contain 30 to 95% by mass of the green color material containing the halogenated phthalocyanine color material of the present invention with respect to the entire color material, and 50 to 80%. It is more preferable to contain by mass%.
Further, the content ratio of the yellow color material to the green color material including the halogenated phthalocyanine color material of the present invention may be appropriately adjusted according to a desired chromaticity, and is not particularly limited. Above all, from the viewpoint of desired chromaticity adjustment and brightness adjustment, it is preferable to contain 5 to 70 parts by mass of the yellow color material with respect to 100 parts by mass of the green color material containing the halogenated phthalocyanine color material of the present invention. It is more preferable to contain 20 to 50 parts by mass.

Further, in the color curable composition of the present invention, other color materials other than the green color material and the yellow color material may be further contained in the color material as long as the effect of the present invention is not impaired. The total content of the green color material containing the halogenated phthalocyanine color material of the present invention and the yellow color material is preferably 70 to 100% by mass, particularly 80 to 100% by mass, based on the entire color material. More preferably.

[Binder component]
The polymer, the polymerizable compound, and the polymerization initiator contained in the color-curable composition according to the present invention impart film-forming property and adhesion to the surface to be coated as a binder component of the color-curable composition.
As the binder component, a conventionally known binder component used for forming a colored layer can be appropriately used, and is not particularly limited, but can be polymerized and cured by, for example, visible light, ultraviolet rays, electron beams, or the like. Examples thereof include a photosensitive binder component and a thermosetting binder component that can be polymerized and cured by heating, and a mixture thereof can also be used.
As the thermosetting binder component, a polymer which may have a thermopolymerizable functional group as a polymer, a compound having a thermopolymerizable functional group in the molecule as a polymerizable compound, and the thermal polymerization as a polymerization initiator. Examples thereof include a system containing at least a thermal polymerization initiator including a curing agent that reacts with a sex functional group. Examples of the thermopolymerizable functional group include an epoxy group, an isocyanate group, a carboxy group, an amino group, a hydroxyl group and the like.

When a photolithography step is used when forming a colored layer using the colored curable composition according to the present invention, a photosensitive binder component having alkali developability is preferably used. A thermosetting binder component may be further used as the photosensitive binder component.
Examples of the photosensitive binder component include a positive type photosensitive binder component and a negative type photosensitive binder component. Examples of the positive photosensitive binder component include an alkali-soluble resin as a polymer, a compound having a bond cleaved by an acid in the molecule and an ethylenically unsaturated group as a polymerizable compound, and thermal radical polymerization as a polymerization initiator. Examples thereof include a system containing an initiator and a photoacid generator.
As the negative photosensitive binder component, a system containing at least an alkali-soluble resin as a polymer, a compound having an ethylenically unsaturated group in the molecule as a polymerizable compound, and a photopolymerization initiator as a polymerization initiator is preferable. Used.
As the binder component contained in the coloring curable composition according to the present invention, the negative photosensitive binder component is preferable because a pattern can be easily formed by using an existing process by a photolithography method.

<Polymer>
As the polymer, when a photolithography step is used to form the colored layer, an alkali-soluble resin soluble in an alkali developer is preferably used.
The alkali-soluble resin has an acidic group, and can be appropriately selected and used as long as it acts as a binder resin and is soluble in the alkali developer used for pattern formation.
In the present invention, the alkali-soluble resin can be referred to as having an acid value of 30 mgKOH / g or more as a guide.

Examples of the acidic group contained in the alkali-soluble resin include a carboxy group. Examples of the alkali-soluble resin having a carboxy group include a carboxy group-containing copolymer having a carboxy group and an epoxy (meth) acrylate resin having a carboxy group. Examples of the carboxy group-containing copolymer include an acrylic copolymer having a carboxy group and an acrylic copolymer such as a styrene-acrylic copolymer having a carboxy group.
Further, these acrylic copolymers, acrylic copolymers such as styrene-acrylic copolymers having a carboxy group, and epoxy acrylate resins may be mixed and used in combination of two or more.

Acrylic copolymers such as an acrylic copolymer having a carboxy group and a styrene-acrylic copolymer having a carboxy group can be copolymerized with, for example, a carboxy group-containing ethylenically unsaturated monomer and, if necessary, a copolymer. It is a (co) polymer obtained by (co) polymerizing other monomers by a known method.

Examples of the carboxy group-containing ethylenically unsaturated monomer include (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, and acrylic acid dimer. Be done. Further, an addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and a cyclic anhydride such as maleic anhydride, phthalic anhydride or cyclohexanedicarboxylic acid anhydride, ω-carboxy-polycaprolactone mono (ω-carboxy-polycaprolactone mono ( Meta) acrylate and the like can also be used. Further, an anhydride-containing monomer such as maleic anhydride, itaconic anhydride, or citraconic anhydride may be used as the precursor of the carboxyl group. Of these, (meth) acrylic acid is particularly preferable from the viewpoints of copolymerizability, cost, solubility, glass transition temperature, and the like.

The alkali-soluble resin preferably has a hydrocarbon ring from the viewpoint of excellent adhesion to the substrate. By having the hydrocarbon ring which is a bulky group in the alkali-soluble resin, shrinkage during curing is suppressed, peeling from the substrate is alleviated, and substrate adhesion is improved. Further, it is also preferable to use an alkali-soluble resin having a hydrocarbon ring which is a bulky group in that the solvent resistance of the obtained colored layer is improved and the swelling of the colored layer is suppressed.
Examples of such a hydrocarbon ring include a cyclic aliphatic hydrocarbon ring which may have a substituent, an aromatic ring which may have a substituent, and a combination thereof. May have a substituent such as a carbonyl group, a carboxyl group, an oxycarbonyl group, or an amide group.

Specific examples of hydrocarbon rings include aliphatic hydrocarbons such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, norbornane, tricyclo [5.2.1.0 (2,6)] decane (dicyclopentane), and adamantan. Rings: Aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, phenanthrene, and fluorene; chain polycycles such as biphenyl, terphenyl, diphenylmethane, triphenylmethane, and stilben, and cardo structures (9,9-diarylfluorene), etc. Can be mentioned.

Above all, when the hydrocarbon ring contains an aliphatic hydrocarbon ring, it is preferable because the heat resistance and adhesion of the colored layer are improved and the brightness of the obtained colored layer is improved.
Further, when the fluorene skeleton contains a structure in which two benzene rings are bonded (cardo structure), the curability of the colored layer is improved, the solvent resistance is improved, and swelling with respect to NMP is particularly suppressed. preferable.
The hydrocarbon ring may be contained as a monovalent group or may be contained as a divalent or higher valent group.

In the alkali-soluble resin used in the present invention, it is easier to adjust the amount of each structural unit by using an acrylic copolymer having a structural unit having a hydrocarbon ring in addition to the structural unit having a carboxy group. It is preferable because it is easy to improve the function of the structural unit by increasing the amount of the structural unit having a hydrocarbon ring.
The acrylic copolymer having a structural unit having a carboxy group and the above-mentioned hydrocarbon ring is prepared by using an ethylenically unsaturated monomer having a hydrocarbon ring as the above-mentioned "other copolymerizable monomer". be able to.

The ethylenically unsaturated monomer having a hydrocarbon ring used for the alkali-soluble resin having a hydrocarbon ring is, for example, cyclohexyl (e) in terms of the combination with the compound (E) having a fluorocarbon group and a crosslinked cyclic aliphatic group. Preferably, meth) acrylate, dicyclopentanyl (meth) acrylate, adamantyl (meth) acrylate, isobornyl (meth) acrylate, phenoxyethyl (meth) acrylate, styrene, a monomer having the cardo structure and an ethylenically unsaturated group, and the like are preferable. Cyclohexyl (meth) acrylate and di, among others, can be used and have a large effect of suppressing the precipitation of a compound derived from a coloring material even after heat treatment (hereinafter, may be referred to as “precipitation suppressing effect”). Cyclopentanyl (meth) acrylate, adamantyl (meth) acrylate, benzyl (meth) acrylate, styrene, and a monomer having the cardo structure and an ethylenically unsaturated group are preferable.

The alkali-soluble resin used in the present invention also preferably has an ethylenically unsaturated bond in the side chain. When it has an ethylenically unsaturated bond, the alkali-soluble resins or the alkali-soluble resin and the polyfunctional monomer may form a cross-linking bond in the curing step of the resin composition during the production of the color filter. The film strength of the cured film is further improved to improve the development resistance, and the heat shrinkage of the cured film is suppressed to improve the adhesion to the substrate.
The ethylenically unsaturated group means a group containing a radically polymerizable carbon-carbon double bond, and examples thereof include a (meth) acryloyl group, a vinyl group, and an allyl group.
The method for introducing an ethylenically unsaturated bond into the alkali-soluble resin may be appropriately selected from conventionally known methods. For example, a method of adding a compound having an epoxy group and an ethylenically unsaturated bond in the molecule to the carboxyl group of the alkali-soluble resin, for example, glycidyl (meth) acrylate, and introducing an ethylenically unsaturated bond into the side chain. Alternatively, a method in which a structural unit having a hydroxyl group is introduced into a copolymer, a compound having an isocyanate group and an ethylenically unsaturated bond is added to the molecule, and an ethylenically unsaturated bond is introduced into a side chain. And so on.

The alkali-soluble resin used in the present invention may further contain other structural units such as methyl (meth) acrylate and ethyl (meth) acrylate, which are structural units having an ester group. The structural unit having an ester group not only functions as a component that suppresses alkali solubility of the color curable composition, but also functions as a component that improves solubility in a solvent and further improves solvent resolubility.

The alkali-soluble resin used in the present invention may be an acrylic resin such as an acrylic copolymer and a styrene-acrylic copolymer having a structural unit having a carboxyl group and a structural unit having a hydrocarbon ring. Preferably, it is an acrylic resin such as an acrylic copolymer and a styrene-acrylic copolymer having a structural unit having a carboxyl group, a structural unit having a hydrocarbon ring, and a structural unit having an ethylenically unsaturated bond. More preferably.

The alkali-soluble resin used in the present invention can have desired performance by appropriately adjusting the amount of the monomer for inducing each structural unit.

The copolymerization ratio of the carboxy group-containing ethylenically unsaturated monomer in the carboxy group-containing copolymer is usually 5% by mass or more and 50% by mass or less, preferably 10% by mass or more and 40% by mass or less. In this case, when the copolymerization ratio of the carboxy group-containing ethylenically unsaturated monomer is 5% by mass or more, the decrease in solubility of the obtained coating film in an alkaline developer can be suppressed, and pattern formation becomes easy. Further, when the copolymerization ratio is 50% by mass or less, chipping of the pattern and roughening of the film on the pattern surface during development with an alkaline developer are unlikely to occur. The copolymerization ratio is a value calculated from the amount of each monomer charged.

Further, in an acrylic resin such as an acrylic copolymer having a structural unit having an ethylenically unsaturated bond and a styrene-acrylic copolymer, which are more preferably used as an alkali-soluble resin, an epoxy group and an ethylenically unsaturated bond are formed. The amount of the monomer charged in combination with the above is preferably 10% by mass or more and 95% by mass or less, preferably 15% by mass or more and 90% by mass or less, based on 100% by mass of the amount of the carboxyl group-containing ethylenically unsaturated monomer charged. More preferably.

The preferable weight average molecular weight (Mw) of the carboxy group-containing copolymer is preferably in the range of 1,000 or more and 50,000 or less, and more preferably 3,000 or more and 20,000 or less. When the weight average molecular weight of the carboxy group-containing copolymer is 1,000 or more, sufficient curability of the coating film can be obtained, and when it is 50,000 or less, pattern formation becomes easy during development with an alkaline developer.
The weight average molecular weight (Mw) in the present invention is determined by gel permeation chromatography (GPC) as a standard polystyrene-equivalent value.

Specific examples of the acrylic copolymer having a carboxy group include those described in JP2013-029832A.

The epoxy (meth) acrylate resin having a carboxy group is not particularly limited, and for example, an epoxy (meth) obtained by reacting a reaction product of an epoxy compound with an unsaturated group-containing monocarboxylic acid with an acid anhydride. ) An acrylate compound is suitable. The epoxy compound, unsaturated group-containing monocarboxylic acid, and acid anhydride can be appropriately selected from known ones and used.
Among the epoxy (meth) acrylate resins having a carboxy group, those containing the cardo structure in the molecule improve the effect of suppressing display defects, improve the curability of the colored layer, and leave the colored layer. It is preferable because the film ratio is high.

The alkali-soluble resin preferably has an acid value of 30 mgKOH / g or more, and more preferably 40 mgKOH / g or more, from the viewpoint of developability (solubility) in the alkaline aqueous solution used in the developing solution. The carboxy group-containing copolymer has an acid value of 50 mgKOH / g or more and 300 mgKOH / g or less in terms of developability (solubility) in an alkaline aqueous solution used for a developing solution and adhesion to a substrate. More preferably, it is 60 mgKOH / g or more and 280 mgKOH / g or less, and even more preferably 70 mgKOH / g or more and 250 mgKOH / g or less.
In the present invention, the acid value can be measured according to JIS K 0070.

The ethylenically unsaturated bond equivalent when the side chain of the alkali-soluble resin has an ethylenically unsaturated group is 100 or more and 2000 or less from the viewpoint that the film strength of the cured film is improved and the precipitation of the coloring material can be further suppressed. The range is preferably in the range of 140 or more and 1500 or less. When the ethylenically unsaturated bond equivalent is 100 or more, the development resistance and adhesion are excellent. Further, if it is 2000 or less, the ratio of the structural unit having a carboxyl group and other structural units such as a structural unit having a hydrocarbon ring can be relatively increased, so that the developability and heat resistance are excellent. There is. Here, the ethylenically unsaturated bond equivalent is the weight average molecular weight per mole of the ethylenically unsaturated bond in the alkali-soluble resin, and is represented by the following mathematical formula (1).

Formula (1) Ethylene unsaturated bond equivalent (g / mol) = W (g) / M (mol)
(In the formula (1), W represents the mass (g) of the alkali-soluble resin, and M represents the number of moles (mol) of the ethylenic double bond contained in the alkali-soluble resin W (g).)

The ethylenically unsaturated bond equivalent is measured, for example, by measuring the number of ethylenically unsaturated bonds contained in 1 g of an alkali-soluble resin in accordance with a test method for raw materials as described in JIS K 0070: 1992. It may be calculated.

The content of the alkali-soluble resin used in the color-curable composition is not particularly limited, but is preferably 5 parts by mass or more and 60 parts by mass or less with respect to 100 parts by mass of the total solid content of the color-curable composition. More preferably, it is in the range of 10 parts by mass or more and 40 parts by mass or less. When the content of the alkali-soluble resin is at least the above lower limit value, sufficient alkali developability can be easily obtained, and when the content of the alkali-soluble resin is at least the above upper limit value, the film is roughened or the pattern is chipped during development. Is easy to suppress.
In the present invention, the solid content is all other than the solvent, and includes the monomer dissolved in the solvent and the like.

The content of the polymer having an ethylenically unsaturated group in the color-curable composition is preferably 5 parts by mass or more and 60 parts by mass or less with respect to 100 parts by mass of the total solid content of the color-curable composition. Yes, more preferably 10 parts by mass or more and 45 parts by mass or less. When the content of the polymer having an ethylenically unsaturated group is at least the above lower limit value, sufficient curing can be obtained, and peeling of the coating film of the patterned color curable composition can be suppressed. Further, when the content of the polymer having an ethylenically unsaturated group is not more than the above upper limit value, peeling due to curing shrinkage can be suppressed.

Further, the color curable composition according to the present invention contains, as the polymer, for example, phenol resin, urea resin, diallyl phthalate resin, melamine resin, guanamine resin, unsaturated polyester resin, polyurethane resin, epoxy resin, aminoalkyd resin, and the like. It may contain a thermosetting polymer such as a melamine-urea cocondensate resin, a silicon resin, or a polysiloxane resin.

The polymer may be used alone or in combination of two or more.
The content of the polymer in the color-curable composition is not particularly limited, but is preferably 5 parts by mass or more and 60 parts by mass or less with respect to 100 parts by mass of the total solid content of the color-curable composition. It is more preferable that the amount is 50 parts by mass or more. When the polymer content is at least the above lower limit value, the decrease in film strength can be suppressed, and when the polymer content is at least the above upper limit value, components other than the polymer can be sufficiently contained. ..

<Polymerizable compound>
The polymerizable compound is not particularly limited as long as it can be polymerized by an initiator described later, and for example, a photopolymerizable compound or a thermopolymerizable compound can be used. As the thermopolymerizable compound, a compound having a thermopolymerizable functional group such as a carboxyl group, an amino group, an epoxy group, a hydroxyl group, a glycidyl group, an isocyanate group, and an alkoxyl group can be used in the molecule. Further, by using a compound having an ethylenically unsaturated group in combination with a thermal radical polymerization initiator, it can also be used as a thermally polymerizable compound. As the polymerizable compound, a photopolymerizable compound that can be polymerized with a photoinitiator, which will be described later, is preferable because a pattern can be easily formed by a photolithography method using an existing process.

The photopolymerizable compound used in the color-curable composition may be any compound as long as it can be polymerized by a photoinitiator described later, and is not particularly limited, and usually, a compound having two or more ethylenically unsaturated double bonds is used. It is used, and is particularly preferably a polyfunctional (meth) acrylate having two or more acryloyl groups or methacryloyl groups.
As such a polyfunctional (meth) acrylate, it may be appropriately selected and used from conventionally known ones. Specific examples include those described in Japanese Patent Application Laid-Open No. 2013-029832.

One of these photopolymerizable compounds may be used alone, or two or more thereof may be used in combination. Further, when the color curable composition of the present invention is required to have excellent photocurability (high sensitivity), the photopolymerizable compound has three or more polymerizable double bonds (trifunctional). Is preferable, and poly (meth) acrylates of trivalent or higher polyhydric alcohols and their dicarboxylic acid-modified products are preferable. Specifically, trimethylpropantri (meth) acrylate and pentaerythritol tri (meth) are preferable. Acrylate, succinic acid-modified product of pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol penta (meth) acrylate A succinic acid modified product, dipentaerythritol hexa (meth) acrylate and the like are preferable.

The content of the polymerizable compound in the color-curable composition is preferably 5 parts by mass or more and 60 parts by mass or less with respect to 100 parts by mass of the total solid content of the color-curable composition, and is 10 parts by mass or more and 50 parts by mass. It is more preferably 20 parts by mass or more and 40 parts by mass or less. When the content of the polymerizable compound is at least the above lower limit value, curing failure can be suppressed, so that the exposed portion can be suppressed from being eluted during development, and the content of the polymerizable compound is at least the above upper limit value. Since development defects can be suppressed and heat shrinkage can be suppressed, minute wrinkles are less likely to occur on the entire surface of the colored layer.

<Initiator>
The initiator used in the color-curable composition of the present invention is not particularly limited, and one or a combination of two or more of the various conventionally known initiators can be used. Examples of the initiator include polymerization initiators such as thermal polymerization initiators and photopolymerization initiators, and specific examples thereof include those described in JP2013-029832A.

Examples of the photoinitiator include aromatic ketones, benzoin ethers, halomethyloxadiazole compounds, α-aminoketones, biimidazoles, N, N-dimethylaminobenzophenone, halomethyl-S-triazine compounds, thioxanthone and the like. be able to. Specific examples of the photoinitiator include aromatic ketones such as benzophenone, 4,4'-bisdiethylaminobenzophenone and 4-methoxy-4'-dimethylaminobenzophenone, benzoin ethers such as benzoin methyl ether, and ethyl benzoin. Benzoyls, biimidazoles such as 2- (o-chlorophenyl) -4,5-phenylimidazole dimer, 2-trichloromethyl-5- (p-methoxystyryl) -1,3,4-oxadiazol and the like. Halomethyloxaziazole compounds, halomethyl-S-triazine compounds such as 2- (4-butoxy-naphtho-1-yl) -4,6-bis-trichloromethyl-S-triazine, 2,2-dimethoxy-1 , 2-Diphenylethane-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone, 1,2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) ) -Butanone- ,, 1-Hydroxy-cyclohexyl-phenylketone, benzyl, benzoyl benzoic acid, methyl benzoyl benzoate, 4-benzoyl-4'-methyldiphenyl sulfide, benzyl methyl ketal, dimethylaminobenzoate, p-dimethylamino benzoate Isoamyl acid, 2-n-butoxyethyl-4-dimethylaminobenzoate, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 4-benzoyl-methyldiphenylsulfide, 1-hydroxy- Cyclohexyl-phenylketone, 2-benzyl-2- (dimethylamino) -1- [4- (4-morpholinyl) phenyl] -1-butanone, 2- (dimethylamino) -2-[(4-methylphenyl) methyl ] -1- [4- (4-morpholinyl) phenyl] -1-butanone, α-dimethoxy-α-phenylacetophenone, phenylbis (2,4,6-trimethylbenzoyl) phosphine oxide, 2-methyl-1- [4- (Methylthio) phenyl] -2- (4-morpholinyl) -1-propanol, 1- (9,9-dibutyl-9H-fluoren-2-yl) -2-methyl-2- (4-morpholinyl) -1-Propanon and the like can be mentioned.
Among them, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2-benzyl-2- (dimethylamino) -1- (4-morpholinophenyl) -1- Butanone, 4,4'-bis (diethylamino) benzophenone, and diethylthioxanthone are preferably used. Furthermore, it is sensitive to combine an α-aminoacetophenone-based initiator such as 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one with a thioxanthone-based initiator such as diethylthioxanthone. It is preferable because it suppresses adjustment and water stains and improves development resistance.
When the α-aminoacetophenone-based initiator and the thioxanthone-based initiator are used, the total content thereof is preferably 5% by mass to 15% by mass with respect to the total solid content of the color-curable composition. When the amount of the initiator is 15% by mass or less, the sublimated product in the manufacturing process is reduced, which is preferable. When the amount of the initiator is 5% by mass or more, development resistance such as water stain is improved.

In the present invention, the photoinitiator preferably contains an oxime ester-based photoinitiator because the sensitivity can be improved. Further, by using the oxime ester-based photoinitiator, it is easy to suppress the variation in the line width in the plane when forming the fine line pattern. Further, by using the oxime ester-based photoinitiator, the residual film ratio tends to be improved and the effect of suppressing the occurrence of water stains tends to be enhanced.
The oxime ester-based photoinitiator preferably has an aromatic ring, and has a condensed ring containing an aromatic ring, from the viewpoint of reducing contamination of the colored curable composition by decomposition products and contamination of the apparatus. It is more preferable to have a fused ring containing a benzene ring and a hetero ring.
Examples of the oxime ester-based photoinitiator include 1,2-octadion-1- [4- (phenylthio)-, 2- (o-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methyl). Benzoyl) -9H-carbazole-3-yl]-, 1- (o-acetyloxime), JP-A-2000-80068, JP-A-2001-233842, JP-A-2010-527339, JP-A-2010-527338, It can be appropriately selected from the oxime ester-based photoinitiators described in JP-A-2013-041153 and the like. Commercially available products include Irgacure OXE-01 having a diphenylsulfide skeleton, Adeka Arkuru's NCI-930, TR-PBG-345, TR-PBG-304 having a carbazole skeleton, Irgacure OXE-02 having a fluorene skeleton, and Adeka Arkuru's NCI. −831, TR-PBG-365, TR-PBG-3057 having a diphenylsulfide skeleton (all manufactured by Joshu Strong Electronics New Materials Co., Ltd.) and the like may be used. In particular, it is preferable to use an oxime ester-based photoinitiator having a diphenylsulfide skeleton or a fluorene skeleton from the viewpoint of brightness. Further, it is preferable to use an oxime ester-based photoinitiator having a carbazole skeleton from the viewpoint of high sensitivity.

Further, it is preferable to use an oxime ester-based photoinitiator in combination with a photoinitiator having a tertiary amine structure from the viewpoint of suppressing water stains and improving sensitivity. Since the photoinitiator having a tertiary amine structure has a tertiary amine structure which is an oxygen quencher in the molecule, the radicals generated from the initiator are not easily deactivated by oxygen, and the sensitivity can be improved. be. Examples of commercially available photoinitiators having a tertiary amine structure include 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one (for example, Irgacure 907, manufactured by BASF). 2-Benzyl-2- (dimethylamino) -1- (4-morpholinophenyl) -1-butanone (eg, Irgacure 369, manufactured by BASF), 4,4'-bis (diethylamino) benzophenone (eg, Hycure ABP, etc.) (Made by Kawaguchi Yakuhin).
Further, it is preferable to combine the oxime ester-based photoinitiator with the thioxanthone-based initiator from the viewpoints of adjusting the sensitivity, suppressing water stains, and improving the development resistance. It is preferable to combine an initiator in that the brightness and the residual film ratio are improved, the sensitivity can be easily adjusted, the effect of suppressing the occurrence of water stains is high, and the development resistance is improved.

The content of the initiator in the color-curable composition is preferably 0.1 part by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the total solid content of the color-curable composition, and is preferably 1 part by mass or more and 10 parts by mass. It is more preferably less than or equal to parts by mass. When the content of the initiator is at least the above lower limit value, curing proceeds sufficiently, and when the content of the initiator is at least the above upper limit value, side reactions can be suppressed and stability over time can be maintained. ..

The total content of the binder components (polymer, polymerizable compound, initiator) used in the color-curable composition of the present invention is 35% by mass or more and 97% by mass with respect to the total solid content of the color-curable composition. % Or less is preferable, and it is more preferable to blend in a ratio of 40% by mass or more and 96% by mass or less. When it is at least the above lower limit value, a colored layer having excellent hardness and adhesion to the substrate can be obtained. Further, when it is not more than the above upper limit value, the developability is excellent and the generation of minute wrinkles due to heat shrinkage is suppressed.

<Arbitrary additive component>
The color-curable composition may contain various additives, if necessary.
Additives include, for example, antioxidants, chain transfer agents such as mercapto compounds, leveling agents, polymerization inhibitors, plasticizers, surfactants, defoamers, silane coupling agents, UV absorbers, adhesion promoters and the like. And so on.

It is preferable that the color-curable composition of the present invention further contains an antioxidant from the viewpoint of heat resistance. The antioxidant may be appropriately selected from conventionally known ones. Specific examples of the antioxidant include hindered phenol-based antioxidants, amine-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, hydrazine-based antioxidants, and the like, and have heat resistance. From this point of view, it is preferable to use a hindered phenolic antioxidant.

Specific examples of the surfactant and the plasticizer include those described in JP2013-029832A.

<Mixing ratio of each component in the color curable composition>
The total content of the coloring material is preferably 3 to 65% by mass, more preferably 4 to 60% by mass, based on the total solid content of the color curable composition. When it is at least the above lower limit value, the colored layer when the coloring curable composition is applied to a predetermined film thickness (usually 1.0 to 5.0 μm) has a sufficient color density. Further, if it is not more than the above upper limit value, it is possible to obtain a colored layer having excellent storage stability, sufficient hardness, and adhesion to a substrate. In particular, when forming a coloring layer having a high concentration of coloring material, the content of the coloring material is 15 to 65% by mass, more preferably 25 to 60% by mass, based on the total solid content of the coloring curable composition. It is preferable to mix in a ratio.
Further, the content when the dispersant is contained is not particularly limited as long as the coloring material can be uniformly dispersed, but for example, with respect to the total solid content of the color curable composition. Can be used in an amount of 1 to 40% by mass. Further, it is preferably blended in a proportion of 2 to 30% by mass with respect to the total solid content of the color curable composition, and particularly preferably in a proportion of 3 to 25% by mass. When it is at least the above lower limit value, the dispersibility and dispersion stability of the coloring material are excellent, and the storage stability of the color curable composition is excellent. Further, when it is not more than the above upper limit value, the developability is good. In particular, when forming a colored layer having a high colorant concentration, the content of the dispersant is 2 to 25% by mass, more preferably 3 to 20% by mass, based on the total solid content of the color curable composition. It is preferable to mix in a ratio. In the case of a salt-type block copolymer, the mass of the dispersant is one or more compounds selected from the block copolymer before salt formation and the group consisting of the general formulas (1) to (3). Is the total mass of and.
Further, the content of the solvent may be appropriately set within a range in which the colored layer can be formed with high accuracy. It is usually preferably in the range of 55 to 95% by mass, and more preferably in the range of 65 to 88% by mass with respect to the total amount of the color curable composition containing the solvent. When the content of the solvent is within the above range, the coating property can be made excellent.

In the color curable composition of the present invention, the P / V ratio ((mass of color material component in composition) / (mass of solid content other than color material component in composition) ratio) is degassing or heat shrinkage. From this point of view, it is preferably 0.1 or more, more preferably 0.2 or more, and on the other hand, it is excellent in display failure and manufacturing convenience, that is, solvent resolubility, development residue, development adhesion, and the like. From the viewpoint of excellent development resistance, water stain generation suppressing effect, etc., it is preferably 0.6 or less, and more preferably 0.5 or less.

<Curing film of colored curable composition>
The color curable composition has chromaticity coordinates in the XYZ color system of JIS Z8701 measured using a C light source in the range of x = 0.180 to 0.330 and y = 0.5000 to 0.750. It is preferable that the cured film in the above can be formed.
Above all, from the viewpoint of improving color reproducibility, the chromaticity coordinates in the XYZ color system of JIS Z8701 measured using a C light source are x = 0.188 to 0.324 and y = 0.550 to 0. It is preferable that a cured film in the range of .750 can be formed, and further, it is possible to form a cured film in the range of x = 0.200 to 0.324 and y = 0.570 to 0.750. It is more preferable that a cured film in the range of x = 0.205 to 0.324 and y = 0.580 to 0.750 can be formed.

Above all, in the chromaticity coordinates in the XYZ color system of JIS Z8701 whose film thickness is 2.8 μm or less and the color is measured by a C light source with a single pixel, x = 0.200 to 0.300, y = 0. It is preferable to be able to display a color space in the range of .500 to 0.700 and a stimulus value Y of 61 ≦ Y, and further, x = 0.200 to 0.300, y = 0.5000 to 0.700 and a stimulus value Y. Is more preferable to be able to display a color space in the range of 61.5 ≦ Y.
As a good blending ratio or combination for displaying the color space in the range of 61.5 ≤ Y, the total content of the colorants is 20-75% by mass based on the total solid content of the color curable composition. As a combination in the coloring materials, the content ratio (G: Y) of the entire green coloring material (G) containing the halogenated phthalocyanine coloring material of the present invention and the yellow coloring material (Y) is 80:20 to 30:70. Is preferable. In the above, the content ratio of the halogenated phthalocyanine coloring material to the entire green coloring material (G) is preferably 30% by mass or more.

<Manufacturing method of color curable composition>
The method for producing the color curable composition of the present invention is not particularly limited, and for example, a polymer, a polymerizable compound, an initiator, and other components are added to the color material liquid of the present invention, if necessary. , Can be obtained by mixing using a known mixing means. Alternatively, a color material solution containing only the halogenated phthalocyanine color material of the present invention, a color material solution of a yellow color material, and, if necessary, a color material solution of another color material are prepared, and these colors are prepared. It can be obtained by mixing the material liquid, the polymer, the polymerizable compound, the initiator, and if necessary, other components by using a known mixing means.

Since the colored curable composition according to the present invention can form a colored layer having improved color purity, it can be particularly preferably used for color filter applications.
The color-curable composition according to the present invention is used in various applications in which good color purity is required, and is also used in inkjet inks and printing inks.

[Color filter]
The color filter according to the present invention is a color filter including at least a transparent substrate and a colored layer provided on the transparent substrate, and at least one of the colored layers is the colored curable composition according to the present invention. It has a colored layer which is a cured product of.

Such a color filter according to the present invention will be described with reference to the drawings. FIG. 1 is a schematic cross-sectional view showing an example of the color filter of the present invention. According to FIG. 1, the color filter 10 of the present invention has a transparent substrate 1, a light-shielding portion 2, and a colored layer 3.

(Colored layer)
At least one of the colored layers used in the color filter of the present invention is a colored layer formed by curing the color-curable composition according to the present invention.
The colored layer is usually formed in the opening of a light-shielding portion on a transparent substrate, which will be described later, and is usually composed of a colored pattern of three or more colors.
The arrangement of the colored layers is not particularly limited, and may be, for example, a general arrangement such as a stripe type, a mosaic type, a triangle type, or a 4-pixel arrangement type. Further, the width, area and the like of the colored layer can be arbitrarily set.
The thickness of the colored layer is appropriately controlled by adjusting the coating method, the solid content concentration and the viscosity of the colored curable composition, etc., but is usually preferably in the range of 1 to 5 μm.

The colored layer can be formed, for example, by the following method.
First, the above-mentioned color-curable composition of the present invention is applied onto a transparent substrate described later by using a coating means such as a spray coating method, a dip coating method, a bar coating method, a roll coating method, a spin coating method, or a die coating method. Then, a wet coating film is formed. Of these, the spin coating method and the die coating method can be preferably used.
Next, the wet coating film is dried using a hot plate or an oven, exposed to it through a mask having a predetermined pattern, and cured by photopolymerizing an alkali-soluble resin, a polyfunctional monomer, or the like. Use as a coating film. Examples of the light source used for exposure include ultraviolet rays such as a low-pressure mercury lamp, a high-pressure mercury lamp, and a metal halide lamp, and an electron beam. The exposure amount is appropriately adjusted depending on the light source used, the thickness of the coating film, and the like.
In addition, heat treatment may be performed in order to accelerate the polymerization reaction after exposure. The heating conditions are appropriately selected depending on the blending ratio of each component in the color curable composition to be used, the thickness of the coating film, and the like.

Next, a coating film is formed in a desired pattern by developing with a developing solution to dissolve and remove the unexposed portion. As the developing solution, a solution in which an alkali is usually dissolved in water or a water-soluble solvent is used. An appropriate amount of a surfactant or the like may be added to this alkaline solution. Moreover, a general method can be adopted as a developing method.
After the development treatment, the developing solution is usually washed and the cured coating film of the coloring curable composition is dried to form a colored layer. After the development treatment, a heat treatment may be performed to sufficiently cure the coating film. The heating conditions are not particularly limited and are appropriately selected depending on the intended use of the coating film.

(Shading part)
The light-shielding portion in the color filter of the present invention is formed in a pattern on a transparent substrate described later, and can be the same as that used as a light-shielding portion in a general color filter.
The pattern shape of the light-shielding portion is not particularly limited, and examples thereof include a striped shape and a matrix shape. The light-shielding portion may be a metal thin film such as chromium obtained by a sputtering method, a vacuum vapor deposition method, or the like. Alternatively, the light-shielding portion may be a resin layer in which light-shielding particles such as carbon fine particles, metal oxides, inorganic pigments, and organic pigments are contained in the resin binder. In the case of a resin layer containing light-shielding particles, a method of patterning by development using a photosensitive resist, a method of patterning using an inkjet ink containing light-shielding particles, a method of thermal transfer of a photosensitive resist, etc. be.

The film thickness of the light-shielding portion is set to about 0.2 to 0.4 μm in the case of a metal thin film, and is set to about 0.5 to 2 μm in the case of a black pigment dispersed or dissolved in a binder resin. Will be done.

(substrate)
As the substrate, a transparent substrate, a silicon substrate, which will be described later, and a transparent substrate or a silicon substrate on which an aluminum, silver, silver / copper / palladium alloy thin film, or the like is formed are used. Another color filter layer, a resin layer, a transistor such as a TFT, a circuit, or the like may be formed on these substrates.
The transparent substrate in the color filter of the present invention may be a substrate that is transparent to visible light, and is not particularly limited, and a transparent substrate used in a general color filter can be used. Specifically, a transparent rigid material having no flexibility such as quartz glass, non-alkali glass, or synthetic quartz plate, or a transparent flexible material having flexibility such as a transparent resin film, an optical resin plate, or a flexible glass. The material is mentioned.
The thickness of the transparent substrate is not particularly limited, but one of about 100 μm to 1 mm can be used depending on the use of the color filter of the present invention.
In addition to the substrate, the light-shielding portion, and the colored layer, the color filter of the present invention may have, for example, an overcoat layer, a transparent electrode layer, an alignment film, a columnar spacer, or the like.

[Display device]
The display device according to the present invention is characterized by having the color filter according to the present invention. In the present invention, the configuration of the display device is not particularly limited, and can be appropriately selected from conventionally known display devices, and examples thereof include a liquid crystal display device and an organic light emitting display device. In the present invention, even in a horizontal electric field type liquid crystal display device, various display defects such as liquid crystal orientation disorder due to the electrical characteristics of green pixels and a burn-in phenomenon due to switching threshold deviation are suppressed. The device is preferably selected.

<Liquid crystal display device>
The liquid crystal display device of the present invention is characterized by having the above-mentioned color filter according to the present invention, an opposing substrate, and a liquid crystal layer formed between the color filter and the opposing substrate.
Such a liquid crystal display device of the present invention will be described with reference to the drawings. FIG. 2 is a schematic view showing an example of the display device of the present invention, and is a schematic view showing an example of the liquid crystal display device. As illustrated in FIG. 2, the liquid crystal display device 40 of the present invention has a liquid crystal layer formed between a color filter 10, a counter substrate 20 having a TFT array substrate and the like, and the color filter 10 and the counter substrate 20. It has 30 and.
The liquid crystal display device of the present invention is not limited to the configuration shown in FIG. 2, and can be generally known as a liquid crystal display device using a color filter.

The drive method of the liquid crystal display device of the present invention is not particularly limited, and a drive method generally used for a liquid crystal display device can be adopted. Examples of such a drive system include a TN system, an IPS system, an OCB system, an MVA system, and the like. In the present invention, any of these methods can be preferably used.
Further, as the facing substrate, it can be appropriately selected and used according to the driving method of the liquid crystal display device of the present invention and the like.
Further, as the liquid crystal constituting the liquid crystal layer, various liquid crystals having different dielectric anisotropy and a mixture thereof can be used depending on the driving method of the liquid crystal display device of the present invention.

As a method for forming the liquid crystal layer, a method generally used as a method for producing a liquid crystal cell can be used, and examples thereof include a vacuum injection method and a liquid crystal dropping method.
In the vacuum injection method, for example, a liquid crystal cell is prepared in advance using a color filter and an opposing substrate, the liquid crystal is heated to form an isotropic liquid, and the liquid crystal is made into the liquid crystal cell by using the capillary effect. The liquid crystal layer can be formed by injecting in the state of the above and sealing with an adhesive. After that, the enclosed liquid crystal can be oriented by slowly cooling the liquid crystal cell to room temperature.
In the liquid crystal dropping method, for example, a sealant is applied to the periphery of the color filter, the color filter is heated to a temperature at which the liquid crystal becomes isotropic, and the liquid crystal is dropped in an isotropic liquid state using a dispenser or the like. Then, the liquid crystal layer can be formed by superimposing the color filter and the opposing substrate under reduced pressure and adhering them with the sealant. After that, the enclosed liquid crystal can be oriented by slowly cooling the liquid crystal cell to room temperature.

<Organic light emission display device>
The organic light emitting display device according to the present invention is characterized by having the above-mentioned color filter according to the present invention and an organic light emitting body.
Such an organic light emitting display device of the present invention will be described with reference to the drawings. FIG. 3 is a schematic view showing another example of the display device of the present invention, and is a schematic view showing an example of the organic light emitting display device. As illustrated in FIG. 3, the organic light emitting display device 100 of the present invention includes a color filter 10 and an organic light emitting body 80. An organic protective layer 50 or an inorganic oxide film 60 may be provided between the color filter 10 and the organic light emitter 80.

As a method of laminating the organic light emitting body 80, for example, a transparent anode 71, a hole injection layer 72, a hole transport layer 73, a light emitting layer 74, an electron injection layer 75, and a cathode 76 are sequentially formed on the upper surface of the color filter. Examples thereof include a method and a method in which the organic light emitting body 80 formed on another substrate is bonded onto the inorganic oxide film 60. As the transparent anode 71, the hole injection layer 72, the hole transport layer 73, the light emitting layer 74, the electron injection layer 75, the cathode 76, and other configurations of the organic light emitter 80, known ones can be appropriately used. The organic light emitting display device 100 produced in this manner can be applied to, for example, both a passive drive type organic EL display and an active drive type organic EL display.
The organic light emitting display device of the present invention is not limited to the configuration shown in FIG. 3, and can be generally known as an organic light emitting display device using a color filter.

Hereinafter, the present invention will be specifically described with reference to examples. These descriptions do not limit the present invention.

(Synthesis Example 3: Synthesis of Alkali Soluble Resin A Solution)
A mixed solution of 40 parts by mass of BzMA, 15 parts by mass of MMA, 25 parts by mass of MAA, and 3 parts by mass of AIBN was added dropwise to a polymerization tank containing 150 parts by mass of PGMEA at 100 ° C. for 3 hours. did. After completion of the dropping, the mixture was further heated at 100 ° C. for 3 hours to obtain a polymer solution. The weight average molecular weight of this polymer solution was 7,000.
Next, 20 parts by mass of GMA, 0.2 parts by mass of triethylamine, and 0.05 parts by mass of p-methoxyphenol were added to the obtained polymer solution, and the mixture was heated at 110 ° C. for 10 hours to obtain main chain methacrylic acid. The reaction between the carboxylic acid group of the acid and the epoxy group of glycidyl methacrylate was carried out. During the reaction, air was bubbled into the reaction solution to prevent polymerization of glycidyl methacrylate. The reaction was followed by measuring the acid value of the solution. The obtained alkali-soluble resin A is a resin in which a side chain having an ethylenic double bond is introduced into a main chain formed by copolymerization of BzMA, MMA, and MAA using GMA, and has an acid value of 74 mgKOH / g. The weight average molecular weight was 12000. The alkali-soluble resin A solution had a solid content of 40% by mass.

(Example 1)
(1) Production of Halogenated Phthalocyanine Coloring Material 1 10.0 g (37.61 mmol) of tetrachlorophthalonitrile and 50 ml of acetone were placed in a 100 ml flask, and the mixture was refluxed at 40 ° C. until it was dissolved. Next, 4.60 g (37.65 mmol) of 2,6 dimethylphenol was added, and the mixture was heated under reflux at 40 ° C. until it was dissolved. Then, 7.80 g (56.44 mmol) of potassium carbonate was added and reacted for 3 hours. After completion of the reaction, potassium carbonate was removed by filtration, the solvent was distilled off from the obtained reaction solution by drying under reduced pressure, the obtained solid was dissolved in chloroform, and the solution was separated with pure water. The organic layer after liquid separation was purified by a silica gel column to obtain Intermediate 1. Intermediate 1 had the following structure when analyzed by LC-MS (manufactured by Agilent Technologies, quadrupole LC / MS, Agent1260 Infinity). Further, a typical chemical structural formula of Intermediate 1 is shown below.

8.437 g (24.0 mmol) of Intermediate 1 and 50 ml of 1-pentanol were placed in a 100 ml flask, and the mixture was refluxed at 90 ° C. until it was dissolved. Then, in the same manner, 1.10 g (6.00 mmol) of zinc acetate (anhydrous) and 4.567 g (30.0 mmol) of diazabicycloundecene (DBU) were added, the temperature was raised to 130 ° C., and the reaction was carried out for 3 hours. .. After completion of the reaction, a mixed solvent of pure water and methanol was added, and the precipitated product was filtered and recovered.
The recovered product was dissolved in dichloromethane and separated with pure water. The organic layer after liquid separation was purified by a silica gel column to obtain a halogenated phthalocyanine coloring material 1 having the following structure. Further, a typical chemical structural formula of the halogenated phthalocyanine coloring material 1 is shown below.

(2) Production of Color Material Liquid G1 13 parts by mass of halogenated phthalocyanine color material 1 and 87 parts of PGMEA were placed in a sample bottle, and stirrer stirring was performed to dissolve the color material in PGMEA to obtain a color material liquid G1. ..

(3) Production of Color Curable Composition G1 43.76 parts by mass of the coloring material liquid G1 obtained in (2) above, 9.09 parts by mass of the alkali-soluble resin A solution obtained in Synthesis Example 3, and many. 8.97 parts by mass of functional monomer (trade name: Aronix M-403, manufactured by Toa Synthetic Co., Ltd.), 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one (photostart) Agent: 0.25 parts by mass of trade name Irgacure 907, manufactured by BASF Co., Ltd., 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (photoinitiator: trade name Irgacure) 369, manufactured by BASF), 0.25 parts by mass, ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl]-, 1- (O-acetyloxime) (light) Initiator: 0.76 parts by mass of Adeca Arckles NCI-831 (manufactured by ADEKA), 0.04 parts by mass of fluorine-based surfactant (trade name Megafuck F559, manufactured by DIC Co., Ltd.), PGMEA 36.88 parts by mass was added to obtain a coloring curable composition G1.

(4) Formation of Colored Layer The color-curable composition G1 obtained in (3) above is placed on a glass substrate (“NA35” manufactured by NH Technoglass Co., Ltd.) having a thickness of 0.7 mm and a thickness of 100 mm × 100 mm. After applying with a spin coater, dry at 80 ° C. for 3 minutes using a hot plate ^{, irradiate with ultraviolet rays of 60 mJ / cm 2} using an ultra-high pressure mercury lamp, and post-bake in a clean oven at 230 ° C. for 30 minutes. By doing so, the film thickness was adjusted so that the chromaticity was y = 0.400 with the C light source to form the colored layer G1.

(Example 2)
(1) Production of Halogenated Phthalocyanine Coloring Material 2 In the synthesis of Intermediate 1 of Example 1, instead of 4.60 g (37.65 mmol) of 2,6 dimethylphenol, 6.13 g (37.) of 2,6 dichlorophenol. Intermediate 2 was obtained in the same manner as Intermediate 1 except that 61 mmol) was used. Intermediate 2 had the following structure when analyzed by LC-MS in the same manner as Intermediate 1. Further, a typical chemical structural formula of Intermediate 2 is shown below.

In Example 1, instead of using 8.437 g (24.0 mmol) of Intermediate 1, 4.71 g (12.0 mmol) of Intermediate 2 and 4.22 g (12.0 mmol) of Intermediate 1 were used. A halogenated phthalocyanine coloring material 2 having the following structure was obtained in the same manner as in Example 1 except that it was used.
Further, a typical chemical structural formula of the halogenated phthalocyanine coloring material 2 is shown below.

(2) Production of Coloring Material Liquid G2 Example 1 except that the halogenated phthalocyanine coloring material 2 obtained above was used in an equimolar amount instead of the halogenated phthalocyanine coloring material 1. The coloring material liquid G2 was obtained in the same manner as in (2) of 1.
(3) Production of Coloring Curable Composition G2 Coloring is performed in the same manner as in (3) of Example 1 except that the coloring material liquid G2 is used instead of the coloring material liquid G1 in (3) of Example 1. A curable composition G2 was obtained.
(4) Formation of Colored Layer In the same manner as in (4) of Example 1 except that the above-mentioned color-curable composition G2 was used instead of the color-curable composition G1 in (4) of Example 1. , A colored layer G2 was obtained.

(Comparative Example 1)
(1) Production of Comparative Halogenated Phthalocyanine Coloring Material 1)
Intermediate 1 except that 4.60 g (37.65 mmol) of 3,4 dimethylphenol was used instead of 4.60 g (37.65 mmol) of 2,6 dimethylphenol in the synthesis of Intermediate 1 of Example 1. In the same manner as above, Comparative Intermediate 1 was obtained. When the comparative intermediate 1 was analyzed by LC-MS in the same manner as the intermediate 1, it was a mixture of the comparative intermediate 1-1 having the following structure and the comparative intermediate 1-2. Representative chemical structural formulas of Comparative Intermediate 1-1 and Comparative Intermediate 1-2 are shown below.

(2) Synthesis of Comparative Halogenated Phthalocyanine Coloring Material 1 In Example 1, instead of using 8.437 g (24.0 mmol) of Intermediate 1, Intermediate 3 (Intermediate 3-1 + 3-2) was used. A comparative halogenated phthalocyanine coloring material 1 having the following structure was obtained in the same manner as in Example 1 except that 40 g (24.0 mmol) was used.
In the following formula, the comparative partial structure a and the comparative partial structure 2 2: 2 (mol ratio) in the structure of the four phenylene groups represent the mol ratio of the average value of the entire coloring material, and the comparison is made in one molecule. Partial structure a: Comparative partial structure b = 0: 4 to 4: 0 compounds are presumed to be mixed.
Further, a typical chemical structural formula of the comparative halogenated phthalocyanine coloring material 1 is shown below.

(2) Production of Comparative Color Material Liquid CG1 Except that in (2) of Example 1, an equal molar amount of the comparative halogenated phthalocyanine color material 1 obtained above was used instead of the halogenated phthalocyanine color material 1. A comparative color material liquid CG1 was obtained in the same manner as in (2) of Example 1.
(3) Production of Comparative Color Curable Composition CG1 The same as in (3) of Example 1 except that the comparative color material liquid CG1 was used instead of the color material liquid G1 in (3) of Example 1. , A comparative color curable composition CG1 was obtained.
(4) Formation of Colored Layer The same as in (4) of Example 1 except that the comparative color-curable composition CG1 was used instead of the color-curable composition G1 in (4) of Example 1. The colored layer CG1 was obtained.

[evaluation]
<Half-value width of spectrum of halogenated phthalocyanine color material>
For each of the colored layers obtained in Examples and Comparative Examples, the spectrum half-value width when y = 0.400 was calculated in the transmittance measured using the Olympus microspectrophotometric measuring device OSP-SP200. The spectrum half-value width was determined by the difference (nm) between the long wavelength and the short wavelength at the 50% transmittance position at the peak top of the spectrum.
(Spectrum half width evaluation standard)
〇: Spectral half width is less than 95 nm ×: Spectral half width is 95 nm or more

<Optical performance, contrast>
For each of the colored layers obtained in Examples and Comparative Examples, the contrast, chromaticity (x, y), and brightness (Y) were measured by using the Tsubosaka Electric contrast measuring device CT-1B and the Olympus microspectroscopy measuring device OSP-SP200. Measured using.
(Contrast evaluation standard)
A: Green exceeds 7000 B: Green is 6300-7000
C: Green is less than 6300 (color purity (color degree 1) evaluation standard)
As the target chromaticity, the chromaticity of x was evaluated when y = 0.400 was fixed with the C light source.
A: Within 0.183 ± 0.01 B: Exceeds 0.183 ± 0.01 Within 0.02 C: Exceeds 0.183 ± 0.02 Within 0.04 D: Exceeds 0.183 ± 0.04

<Resin solubility of coloring material>
After applying the color-curable compositions of Examples and Comparative Examples on a glass substrate (manufactured by NH Techno Glass Co., Ltd., “NA35”) having a thickness of 0.7 mm and 100 mm × 100 mm, respectively, using a spin coater. A dry coating film was obtained by drying at 80 ° C. for 3 minutes using a hot plate.
After post-baking the applied dry coating film in a clean oven at 230 ° C. for 30 minutes, the resin solubility was evaluated by the presence or absence of precipitation of the coloring material.
(Resin solubility evaluation criteria)
A: Whether the dry coating film is post-baked in a clean oven at 230 ° C. for 30 minutes, or the coating film is additionally post-baked in a clean oven at 230 ° C. for 30 minutes after baking, the optical microscope reflects 200 times. No deposits are observed in the 1 mm square region in the optical observation.
B: Even if the dry coating film is post-baked in a clean oven at 230 ° C. for 30 minutes, no precipitate is observed in a 1 mm square region in the observation of 200 times reflected light with an optical microscope, but in addition, 30 in a clean oven at 230 ° C. After min post-baking, less than 10 precipitates are observed in a 1 mm square region.
C: Even if the dry coating film is post-baked in a clean oven at 230 ° C. for 30 minutes, no precipitate is observed in a 1 mm square region in the observation of 200 times reflected light with an optical microscope, but in addition, 30 in a clean oven at 230 ° C. After post-baking for 1 minute, 10 or more precipitates are observed in a 1 mm square region.
D: When the dry coating film is post-baked in a clean oven at 230 ° C. for 30 minutes, precipitates are observed in a 1 mm square region in 200 times reflected light observation with an optical microscope.

<Solvent solubility of coloring materials>
A color material liquid having a color material concentration of 1% by mass, which is a mixture of 99 parts by mass of PGMEA and 1 part by mass of a color material, and a color having a color material concentration of 5% by mass, which is a mixture of 95 parts by mass of PGMEA and 5 parts by mass of a color material. A material solution was prepared, and the presence or absence of precipitation of the coloring material was observed.
A: The color material does not precipitate even after the color material liquid having a color material concentration of 5% by mass is left for one week.
B: The color material liquid having a color material concentration of 5% by mass does not precipitate after being left for 1 day, but the color material precipitates after being left for 1 week.
C: In the color material solution having a color material concentration of 5% by mass, the color material is dissolved immediately after mixing, but the color material precipitates after being left for one day.
D: In the color material solution having a color material concentration of 1% by mass, the color material is dissolved immediately after mixing, but the color material precipitates after being left for one day.

<Heat resistance>
The color-curable compositions of Examples and Comparative Examples were placed on a glass substrate (manufactured by NH Techno Glass Co., Ltd., "NA35") having a thickness of 0.7 mm, respectively, and the chromaticity after post-baking was y = 0.400. It was applied using a spin coater so as to become. Then, it was heated and dried on a hot plate at 80 ° C. for 3 minutes. A cured film was obtained by irradiating ultraviolet rays of ^{60 mJ / cm 2} using an ultra-high pressure mercury lamp without using a photomask. The obtained film was post-baked in a clean oven at 230 ° C. for 25 minutes, and the brightness was measured using a "microspectroscopy measuring device OSP-SP200" manufactured by Olympus Corporation.
Then, the obtained film is post-baked in a clean oven at 240 ° C. for 25 minutes, the chromaticity (L ₀ , a ₀ , b ₀ ) of the colored film is measured, and then in a clean oven at 240 ° C. After post-baking for 50 minutes, the chromaticity (L ₁ , a ₁ , b ₁ ) of the obtained colored film was measured again.
The change in chromaticity of the colored film from 25 minutes to 75 minutes at 240 ° C. was evaluated by the following formula. The results are shown in the table.
ΔEab = {(L _{1 −} L ₀ ) ² + (a _{1 −} a ₀ ) ² + (b ₁ − b ₀ ) ² } ^1/2
It is evaluated that the smaller the value of ΔEab, the better the heat resistance. If ΔEab is 3.0 or less, it is judged that there is no practical problem.
(Heat resistance evaluation standard)
A: ΔEab is 2.0 or less B: ΔEab is over 2.0 3.0 or less C: ΔEab is over 3.0

<Developability: Evaluation of development residue>
The color-curable compositions obtained in Examples and Comparative Examples were placed on a glass substrate (“NA35” manufactured by NH Techno Glass Co., Ltd.) having a thickness of 0.7 mm and a thickness of 100 mm × 100 mm, respectively, using a spin coater. After coating, a colored layer having a thickness of 2.5 μm was formed by drying at 80 ° C. for 3 minutes using a hot plate. The glass plate on which the colored layer was formed was shower-developed for 60 seconds using a 0.05 mass% potassium hydroxide aqueous solution as an alkaline developer. After visually observing the unexposed portion (50 mm × 50 mm) of the glass substrate after the formation of the colored layer, wipe it off sufficiently with a lens cleaner (manufactured by Toray Industries, Inc., trade name Toraysee MK Clean Cloth) soaked in ethanol. The degree of coloring of the lens cleaner was visually observed.
(Development residue evaluation criteria)
A: No development residue was visually confirmed and the lens cleaner was not colored at all. B: No development residue was visually confirmed and the lens cleaner was slightly colored. C: The development residue was slightly confirmed visually. D: The development residue was slightly confirmed by visual inspection, and the coloring of the lens cleaner was confirmed. E: The development residue was visually confirmed and the coloring of the lens cleaner was confirmed. If the development residue evaluation standard is A, B or C, it can be practically used.

The evaluation results of Examples 1 and 2 and Comparative Example 1 are shown in Table 5.

(Example 3)
(1) Production of color material liquid G3
As the dispersant, a dispersant b (salt block copolymer) solution was prepared in the same manner as in the production of the dispersant b of Synthesis Example II-2 described in paragraph 0302 of International Publication No. 2016/1049493.
The dispersant b solution was 6.18 parts by mass as the dispersant, the halogenated phthalocyanine color material 1 was 9.1 parts by mass as the color material, and the yellow color material C.I. I. Pigment Yellow 138 (PY138, trade name: Chromofine Yellow 6206EC, manufactured by Dainichi Seika Kogyo Co., Ltd.) in 3.9 parts by mass, the alkali-soluble resin A solution obtained in Synthesis Example 3 in 14.63 parts by mass, and PGMEA. 66.19 parts by mass, particle size 2.0 mm 100 parts by mass of zirconia beads are placed in a mayonnaise bottle and shaken with a paint shaker (manufactured by Asada Iron Works Co., Ltd.) for 1 hour as preliminary crushing, and then the particle size is 2.0 mm. The zirconia beads were taken out, 200 parts by mass of zirconia beads having a particle size of 0.1 mm were added, and the zirconia beads were similarly dispersed for 4 hours with a paint shaker as the main crushing to obtain a coloring material liquid G3.

(2) Production of Color Curable Composition G3 In the production of the color curable composition G1 of Example 1, except that the color material liquid G3 obtained in (1) above was used instead of the color material liquid G1. , A color curable composition G3 was obtained in the same manner as in Example 1.

(3) Formation of Colored Layer The color-curable composition G3 obtained in (2) above is placed on a glass substrate (“NA35” manufactured by NH Technoglass Co., Ltd.) having a thickness of 0.7 mm and a thickness of 100 mm × 100 mm. After applying with a spin coater, dry at 80 ° C. for 3 minutes using a hot plate ^{, irradiate with ultraviolet rays of 60 mJ / cm 2} using an ultra-high pressure mercury lamp, and post-bake in a clean oven at 230 ° C. for 30 minutes. By doing so, the film thickness was adjusted so that the chromaticity was y = 0.300 with the C light source, and the colored layer G3 was formed.

(Example 4, Comparative Example 2)
(1) Production of Color Material Liquids G4 and CG2 As shown in Table 6, in (1) of Example 3, the halogenated phthalocyanine color material 1 (“1” in Table 6) was used as the halogenated phthalocyanine color material. In the same manner as in Example 3, the color was changed to the halogenated phthalocyanine color material 2 (“2” in Table 6) or the comparative halogenated phthalocyanine 1 (“Comparison 1” in Table 6). Material solutions G4 and CG2 were obtained.

(2) Production of Color Curable Compositions G4 and CG2 In the production of the color curable composition G3 of Example 3, instead of using the color material liquid G3, the color material liquid G4 or CG2 obtained in (1) above is used. Color curable compositions G4 and CG2 were obtained in the same manner as in Example 3 except that

(3) Formation of Colored Layer In the production of the colored layer G3 of Example 3, instead of using the colored curable composition G3, the colored curable composition G4 or CG2 obtained in (2) above was used, respectively. Obtained colored layers G4 and CG2 in the same manner as in Example 3.

Contrast, color purity, heat resistance, and development residue were evaluated for Examples 3 to 4 and Comparative Example 2 in the same manner as in Example 1. The evaluation results are shown in Table 6.
The following indexes were used for the contrast and color purity evaluation of the color material liquid and the color curable composition when mixed with the yellow color material.
<Optical performance, contrast>
For each of the colored layers obtained in Examples 3 to 4 and Comparative Example 2, the contrast, chromaticity (x, y), and brightness (Y) were measured by Tsubosaka Electric's contrast measuring device CT-1B and Olympus's microspectroscopy measuring device. Measured using OSP-SP200.
(Contrast evaluation standard)
A: Green exceeds 7000 B: Green is 6300-7000
C: Green is less than 6300 (color purity (luminance Y value) evaluation standard)
The brightness (Y) when fixed at y = 0.600 and x = 0.300 with the light source YAG is
AA: 62.5 or more A: 62.0 or more and less than 62.5 B: 61.5 or more and less than 62.0 C: 61.0 or more and less than 61.5 D: less than 61.0

(Example 9)
(1) Manufacture of color material liquid G9
In Example 3, as the coloring material, the halogenated phthalocyanine coloring material 1 was added to 9.1 parts by mass and C.I. I. Instead of using 3.9 parts by mass of Pigment Yellow 138, 9.1 parts by mass of the halogenated phthalocyanine color material 1 was used as a green color material different from the halogenated phthalocyanine color material. I. Pigment Green 36 (trade name: FASTOGEN GREEN 2YK-50, manufactured by DIC Corporation) was used in the same manner as in Example 3 except that 3.9 parts by mass was used to obtain a coloring material liquid G9.

(2) Production of Color Curable Composition G9 In the production of the color curable composition G1 of Example 1, instead of using the color material liquid G1, the color material liquid G9 obtained in (1) above was used. Obtained a color curable composition G9 in the same manner as in Example 1.

(3) Formation of Colored Layer The color-curable composition G9 obtained in (2) above is placed on a glass substrate (“NA35” manufactured by NH Technoglass Co., Ltd.) having a thickness of 0.7 mm and a thickness of 100 mm × 100 mm. After applying with a spin coater, dry at 80 ° C. for 3 minutes using a hot plate ^{, irradiate with ultraviolet rays of 60 mJ / cm 2} using an ultra-high pressure mercury lamp, and post-bake in a clean oven at 230 ° C. for 30 minutes. By doing so, the film thickness was adjusted so that the chromaticity was y = 0.400 with the C light source, and the colored layer G9 was formed.

(Example 10, Comparative Example 5)
(1) Production of Color Material Liquids G10 and CG5 As shown in Table 7, in (1) of Example 9, the halogenated phthalocyanine color material 1 (“1” in Table 7) was used as the halogenated phthalocyanine color material. In the same manner as in Example 9, the color was changed to the halogenated phthalocyanine color material 2 (“2” in Table 7) or the comparative halogenated phthalocyanine 1 (“Comparison 1” in Table 7). Material solutions G10 and CG5 were obtained.

(2) Production of Color Curable Compositions G10 and CG5 In the production of the color curable composition G9 of Example 9, instead of using the color material liquid G9, the color material liquids G10 and CG5 obtained in (1) above were used. Color curable compositions G10 and CG5 were obtained in the same manner as in Example 9 except that

(3) Formation of Colored Layer In the production of the colored layer G9 of Example 9, instead of using the colored curable composition G9, the colored curable composition G10 or CG5 obtained in (2) above was used, respectively. Obtained colored layers G10 and CG5 in the same manner as in Example 9.

(Example 11)
(1) Manufacture of color material liquid G11
In Example 3, as the coloring material, the halogenated phthalocyanine coloring material 1 was added to 9.1 parts by mass and C.I. I. Instead of using 3.9 parts by mass of Pigment Yellow 138, 9.1 parts by mass of the halogenated phthalocyanine color material 1 was used as a green color material different from the halogenated phthalocyanine color material. I. Pigment Green 7 (trade name: Chromofine Green 6428EC, manufactured by Dainichiseika Kogyo Co., Ltd.) was used in the same manner as in Example 3 except that 3.9 parts by mass was used to obtain a coloring material liquid G11.

(2) Production of Color Curable Composition G11 In the production of the color curable composition G9 of Example 9, instead of using the color material liquid G9, the color material liquid G11 obtained in (1) above was used. Obtained a color curable composition G11 in the same manner as in Example 9.

(3) Formation of Colored Layer In the production of the colored layer G9 of Example 9, the color-curable composition G11 obtained in (2) above was used instead of the color-curable composition G9. A colored layer G11 was obtained in the same manner as in Example 9.

(Example 12, Comparative Example 6)
(1) Production of Color Material Liquids G12 and CG6 As shown in Table 7, in (1) of Example 11, the halogenated phthalocyanine color material 1 (“1” in Table 7) was used as the halogenated phthalocyanine color material. In the same manner as in Example 11, the color was changed to the halogenated phthalocyanine color material 2 (“2” in Table 7) or the comparative halogenated phthalocyanine 1 (“Comparison 1” in Table 7). Material solutions G12 and CG6 were obtained.

(2) Production of Color Curable Compositions G12 and CG6 In the production of the color curable composition G11 of Example 11, instead of using the color material liquid G11, the color material liquid G12 or CG6 obtained in (1) above is used. Color curable compositions G12 and CG6 were obtained in the same manner as in Example 11 except that

(3) Formation of Colored Layer In the production of the colored layer G11 of Example 11, instead of using the colored curable composition G11, the colored curable compositions G12 and CG6 obtained in (2) above were used, respectively. Obtained colored layers G12 and CG6 in the same manner as in Example 11.

(Example 13)
(1) Manufacture of color material liquid G13
In Example 3, as the coloring material, the halogenated phthalocyanine coloring material 1 was added to 9.1 parts by mass and C.I. I. Instead of using 3.9 parts by mass of Pigment Yellow 138, 9.1 parts by mass of the halogenated phthalocyanine color material 1 was used as a green color material different from the halogenated phthalocyanine color material. I. Pigment Green 59 (PG59, trade name: FASTOGEN GREEN C100 DIC Corporation) was used in the same manner as in Example 3 except that 3.9 parts by mass was used to obtain a coloring material liquid G13.

(2) Production of Color Curable Composition G13 In the production of the color curable composition G9 of Example 1, instead of using the color material liquid G9, the color material liquid G13 obtained in (1) above was used. Obtained a color curable composition G13 in the same manner as in Example 9.

(3) Formation of Colored Layer In the production of the colored layer G9 of Example 9, the color-curable composition G13 obtained in (2) above was used instead of the color-curable composition G9. A colored layer G13 was obtained in the same manner as in Example 9.

(Example 14, Comparative Example 7)
(1) Production of Color Material Liquids G14 and CG7 As shown in Table 7, in (1) of Example 13, the halogenated phthalocyanine color material 1 (“1” in Table 7) was used as the halogenated phthalocyanine color material. In the same manner as in Example 13, the color was changed to the halogenated phthalocyanine coloring material 2 (“2” in Table 7) or the comparative halogenated phthalocyanine 1 (“Comparison 1” in Table 7). Material solutions G14 and CG7 were obtained.

(2) Production of Color Curable Compositions G14 and CG7 In the production of the color curable composition G13 of Example 13, instead of using the color material liquid G13, the color material liquid G14 or CG7 obtained in (1) above is used. Color curable compositions G14 and CG7 were obtained in the same manner as in Example 13 except that

(3) Formation of Colored Layer In the production of the colored layer G13 of Example 13, instead of using the colored curable composition G13, the colored curable composition G14 or CG7 obtained in (2) above was used, respectively. Obtained colored layers G14 and CG7 in the same manner as in Example 13.

Contrast, color purity (chromaticity 1), heat resistance, and development residue were evaluated for Examples 9 to 14 and Comparative Examples 5 to 7 in the same manner as in Example 1. The evaluation results are shown in Table 7.

[Summary of results]
The halogenated phthalocyanine color material of Comparative Example 1, which corresponds to the conventional halogenated phthalocyanine color material, had a wide spectrum half-value width of the color material and poor color purity. Further, the halogenated phthalocyanine coloring material of Comparative Example 1 was inferior in resin solubility.
On the other hand, the halogenated phthalocyanine colorants of Examples 1 and 2, which are the halogenated phthalocyanine colorants of the present invention, not only have good contrast, but also have a narrow spectral half-value width of the colorant and good color purity. Met. The halogenated phthalocyanine coloring materials of Examples 1 and 2 had good resin solubility and solvent solubility, and Example 2 was particularly excellent in resin solubility.
In Examples 3 to 4 in which the halogenated phthalocyanine color material of Examples 1 and 2 which is the halogenated phthalocyanine color material of the present invention is further combined with the yellow color material, not only the contrast is good but also the contrast is good. Since the color purity was better than that of the comparative example using the halogenated phthalocyanine coloring material of Comparative Example 1, the brightness was also good.
Examples 9 to 14 in which the halogenated phthalocyanine color material of Examples 1 and 2 which is the halogenated phthalocyanine color material of the present invention is further combined with a green color material different from the halogenated phthalocyanine color material of the present invention. In each case, not only the contrast was good, but also the color purity was better than that of the comparative example using the halogenated phthalocyanine coloring material of Comparative Example 1.
Further, in the color curable composition using the halogenated phthalocyanine color material of Examples 1 and 2, the development residue is suppressed as compared with the color curable composition using the halogenated phthalocyanine color material of Comparative Example 1. Was excellent. In Comparative Example 1, since a disubstituted dimethylphenoxy group is generated during the synthesis of the intermediate, the number of terminal methyl groups (hydrophobic components) is increased as compared with Examples 1 and 2, so that the solubility in a developing solution is increased. Is presumed to have decreased.

1 Transparent substrate 2 Light-shielding part 3 Colored layer 10 Color filter 20 Opposing substrate 30 Liquid crystal layer 40 Liquid crystal display device 50 Organic protective layer 60 Inorganic oxide film 71 Transparent anode 72 Hole injection layer 73 Hole transport layer 74 Light emitting layer 75 Electron injection layer 76 Cathode 80 Organic light emitter 100 Organic light emission display device

Claims (17)

A halogenated phthalocyanine coloring material represented by the following general formula (1).

[In the general formula (1), X ^{1 to} X ¹⁶ independently represent a hydrogen atom, a halogen atom, a hydroxy group, or a hydrocarbon-containing group, and ^{at least one of X 1 to} X ¹⁶ is a chlorine atom or a chlorine atom, or It is a bromine atom, and ^{at least one of X 1 to} X ¹⁶ is a monovalent group represented by the following general formula (2), and M is a group consisting of Cu, Zn, Co, Mo and Al. Represents one type of metal selected from.

(In the general formula ^{(2), Y} 1 is, -O -, - S -, - NR Y -, or ^{-N + (· A a-) R} Y1 R Y2 - ( ^{wherein, R Y,} R ^Y1, and ^{R Y2} each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon ^{atoms, a a-} represents a valence of the anion, a is 1 or more is an ^{integer.), Z} 1, Z ² and Z ³ each independently consist of a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted aryloxy group. represents at least one selected from the group, n is an integer of 0 to 3, the plurality of Z ³ may be the same or different and * indicates the bonding position to the phthalocyanine skeleton.) ] In the X ¹ to X ^16, wherein said hydrocarbon-containing group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, and is represented by the following general formula (3) The halogenated phthalocyanine coloring material according to claim 1, which is at least one selected from the group consisting of monovalent groups.

(In the general formula ^{(3), Y} 2 is, -O -, - S -, - NR Y -, or ^{-N + (· A a-) R} Y1 R Y2 - ( ^{wherein, R Y,} R ^Y1, And ^RY2 independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, A ^a- represents an a-valent anion, and a is an integer of 1 or more). It represents a substituted or unsubstituted aryl group, and * indicates the bonding position with the phthalocyanine skeleton.) To ^{any one of X 1 to} X ⁴ , any one of X ^{5 to} X ⁸ , any one of X ^{9 to} X ¹² , and any one of X ^{13 to} X ^16. The halogenated phthalocyanine coloring material according to claim 1 or 2, which has a total of four monovalent groups represented by the general formula (2). A color material liquid containing the halogenated phthalocyanine color material according to any one of claims 1 to 3 and a solvent. The coloring material liquid according to claim 4, further containing a yellow coloring material. The color material liquid according to claim 5, wherein the yellow color material is a quinophthalone-based color material. The color material liquid according to claim 4, further containing a green color material different from the halogenated phthalocyanine color material. The color material liquid according to claim 7, wherein the green color material different from the halogenated phthalocyanine color material is a phthalocyanine green pigment. A green color material different from the halogenated phthalocyanine color material is C.I. I. The color material solution according to claim 7 or 8, which is at least one selected from the group consisting of pigment greens 58, 59, 62, and 63. A color curable composition containing the halogenated phthalocyanine coloring material according to any one of claims 1 to 3, a polymer, a polymerizable compound, an initiator, and a solvent. The color-curable composition according to claim 10, further comprising a yellow colorant. The color-curable composition according to claim 11, wherein the yellow color material is a quinophthalone-based color material. The color curable composition according to claim 10, further containing a green color material different from the halogenated phthalocyanine color material. The color-curable composition according to claim 13, wherein the green color material different from the halogenated phthalocyanine color material is a phthalocyanine green pigment. A green color material different from the halogenated phthalocyanine color material is C.I. I. The color-curable composition according to claim 13 or 14, which is at least one selected from the group consisting of pigment greens 58, 59, 62, and 63. A color filter comprising a substrate and a colored layer provided on the substrate, wherein at least one of the colored layers is a cured product of the colored curable composition according to any one of claims 10 to 15. Is a color filter. A display device having the color filter according to claim 16.

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