CN117677675A

CN117677675A - Halogenated phthalocyanine color material, colored curable composition, color filter, and display device

Info

Publication number: CN117677675A
Application number: CN202280049999.1A
Authority: CN
Inventors: 塚本力飞; 井上渚
Original assignee: DNP Fine Chemicals Co Ltd
Current assignee: DNP Fine Chemicals Co Ltd
Priority date: 2021-07-20
Filing date: 2022-07-11
Publication date: 2024-03-08
Also published as: WO2023002875A1; TW202321377A; JPWO2023002875A1

Abstract

The present invention provides a landing device capable of suppressing the precipitation of foreign matters and improving the contrastHalogenated phthalocyanine color materials of the color layer. The halogenated phthalocyanine color material of the present invention is represented by the following general formula (1). [ chemical formula 1 ]]

Description

Halogenated phthalocyanine color material, colored curable composition, color filter, and display device

Technical Field

The invention relates to a halogenated phthalocyanine material, a colored curable composition, a color filter and a display device.

Background

In recent years, with the development of personal computers, particularly personal computers for portable use, the demand for liquid crystal displays has been increasing. The popularity of mobile displays (cellular phones, smart phones, tablet PCs (Personal Computer, personal computers)) is also increasing, and the market for liquid crystal displays is expanding. In addition, recently, an organic light emitting display device such as an organic EL (Electroluminescence) display which has high visibility due to self-luminescence has also been attracting attention as a next-generation image display device. In terms of performance of these image display devices, improvement of contrast and color reproducibility, that is, further improvement of image quality and reduction of power consumption have been strongly desired.

Color filters are used in these liquid crystal display devices and organic light emitting display devices. For example, in the formation of a color image in a liquid crystal display device, light having passed through a color filter is directly colored into the color of each pixel constituting the color filter, and the light of these colors is synthesized to form the color image. As the light source in this case, in addition to the conventional cold cathode tube, a white-emitting organic light-emitting element or a white-emitting inorganic light-emitting element may be used. In addition, in the organic light emitting display device, a color filter is used to perform color adjustment or the like.

Therefore, in the color filter, there is an increasing demand for improving the color reproducibility by increasing the brightness and contrast.

Here, the color filter generally has: a transparent substrate; a coloring layer formed on the transparent substrate and including coloring patterns of three primary colors of red, green and blue; and a light shielding portion formed on the transparent substrate so as to divide each of the coloring patterns.

Among them, a pigment dispersion method having an average excellent characteristic is most widely used as a method for forming pixels in a color filter from the viewpoints of spectroscopic characteristics, durability, pattern shape, accuracy, and the like.

In a color filter having pixels formed by a pigment dispersion method, there is a problem that the light transmittance of the color filter becomes low or the contrast becomes low due to pigment particles.

Accordingly, attempts have been made to use a coloring composition using a dye that does not form particles, thereby achieving a color filter with improved brightness and contrast.

However, dyes generally have problems of poor heat resistance and solvent resistance, and low solubility in solvents, and thus, they are difficult to put into practical use. For the green colored layer, studies have been made on using a predetermined phthalocyanine-based dye as a dye (for example, see patent documents 1 to 3).

Prior art literature

Patent literature

Patent document 1: japanese patent laid-open No. 2009-051896

Patent document 2: japanese patent laid-open publication No. 2014-125460

Patent document 3: japanese patent 2020-42263

Disclosure of Invention

Problems to be solved by the invention

However, it has been found that aggregates derived from a color material (hereinafter, referred to as foreign matters) are precipitated in the obtained colored layer in the colored resin compositions described in the above patent documents 1 to 3. Patent document 3 describes that a colored resin composition capable of forming a pattern having sufficient brightness to be practical and suppressing the generation of foreign matter is provided. However, this technique of coloring a resin composition also has a problem that foreign matter is likely to be deposited after heat treatment (after post baking step) and the contrast is poor, as shown in the following comparative example.

The present invention has been made in view of the above-described circumstances, and an object thereof is to provide: a halogenated phthalocyanine colorant capable of forming a colored layer in which precipitation of foreign matters is suppressed and contrast is improved; a colored curable composition. In addition, the present invention aims to provide: a color filter and a display device using the color curable composition.

Means for solving the problems

The halogenated phthalocyanine color material of the present invention is a halogenated phthalocyanine color material represented by the following general formula (1).

[ chemical formula 1]

[ in the general formula (1), X ¹ ～X ¹⁶ Each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, a substituted or unsubstituted hydrocarbon group having 1 to 6 carbon atoms, or a monovalent group represented by the following general formula (2),

X ¹ ～X ¹⁶ at least one of (A) is a fluorine atom, X ¹ ～X ¹⁶ At least one of them is a monovalent group represented by the following general formulae (2-1) to (2-5), X ¹ ～X ¹⁶ At least one of them is a monovalent group represented by the following general formula (2-6).

General formula (2): * -O-R ^P

General formula (2-1): * -O-R ^L1 -R ^a

General formula (2-2): * -O- (R) ^L2 -O) _n -R ^b

General formula (2-3): * -O-R ^L2 -COO-R ^b

General formula (2-4): * -O-R ^L2 -OCO-R ^b

General formula (2-5): * -O-R ^c

General formula (2-6): * -O-R ^a

(in the general formulae (2) and (2-1) to (2-6),

R ^P represents a substituted or unsubstituted straight-chain or branched aliphatic hydrocarbon group having 1 to 6 carbon atoms, a substituted or unsubstituted alicyclic hydrocarbon group having 5 to 14 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 14 carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 14 ring-forming atoms, -R ^L1 -R ^a 、-(R ^L2 -O) _n -R ^b 、-R ^L2 -COO-R ^b or-R ^L2 -OCO-R ^b ，R ^L1 Represents an aliphatic hydrocarbon group having 1 to 6 carbon atoms or a-CO-group, R ^L2 Each independently represents an aliphatic hydrocarbon group having 1 to 6 carbon atoms, R ^a Represents a substituted or unsubstituted aromatic hydrocarbon group having 6 to 14 carbon atoms, R ^b Represents a hydrogen atom, a substituted or unsubstituted straight-chain or branched aliphatic hydrocarbon group having 1 to 6 carbon atoms, a substituted or unsubstituted alicyclic hydrocarbon group having 5 to 14 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 14 carbon atoms, or a substituted or unsubstituted heterocyclic group having 5 to 14 ring-forming atoms, R ^c Represents a substituted or unsubstituted alicyclic hydrocarbon group having 5 to 14 carbon atoms. n represents an integer of 1 to 5. * Represents a bonding position to the phthalocyanine skeleton. )]

The colored curable composition of the present invention contains a color material, a polymer, a polymerizable compound, an initiator, and a solvent, and the color material contains the halogenated phthalocyanine color material of the present invention.

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

The present invention provides a display device including the color filter of the present invention.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, there can be provided: a halogenated phthalocyanine colorant capable of forming a colored layer in which precipitation of foreign matters is suppressed and contrast is improved; a colored curable composition which can form a colored layer having improved contrast using the halogenated phthalocyanine colorant; a color filter using the colored curable composition; and a display device using the color filter.

Drawings

Fig. 1 is a schematic diagram showing an example of a color filter according to the present invention.

Fig. 2 is a schematic diagram 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.

Detailed Description

The halogenated phthalocyanine color material, the colored curable composition, the color filter and the display device of 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 also includes radiation including, for example, microwaves and electron beams. Specifically, electromagnetic waves having a wavelength of 5 μm or less and electron beams.

In the present invention, (meth) acrylic acid means any one of acrylic acid and methacrylic acid, (meth) acrylic acid ester means any one of acrylic acid ester and methacrylic acid ester, and (meth) acryl means any one of acryl group and methacryl group.

In the present specification, "to" representing a numerical range is used in a meaning including numerical values described before and after the numerical value as a lower limit value and an upper limit value.

In this specification, "substituted or unsubstituted" means that a substituent may be present. For example, "substituted or unsubstituted alkyl" includes alkyl groups having substituents and alkyl groups having no substituents.

I. Halogenated phthalocyanine color material

[ chemical formula 2]

X ¹ ～X ¹⁶ at least one of (A) is a fluorine atom, X ¹ ～X ¹⁶ At least one of them is a monovalent group represented by the following general formulae (2-1) to (2-5), X ¹ ～X ¹⁶ At least one of them is a monovalent represented by the following general formula (2-6)A group.

General formula (2): * -O-R ^P

General formula (2-1): * -O-R ^L1 -R ^a

General formula (2-2): * -O- (R) ^L2 -O) _n -R ^b

General formula (2-3): * -O-R ^L2 -COO-R ^b

General formula (2-4): * -O-R ^L2 -OCO-R ^b

General formula (2-5): * -O-R ^c

General formula (2-6): * -O-R ^a

(in the general formulae (2) and (2-1) to (2-6),

The phthalocyanine color material has a planar structure of a phthalocyanine ring, and is easily formed into a laminated structure by pi-pi interaction, and has high crystallinity. Therefore, the colored layer containing the phthalocyanine color material has the following problems: after the heat treatment (post baking step), foreign matter is easily deposited due to crystal growth and aggregation of the phthalocyanine color material, and contrast is deteriorated.

In contrast, in the halogenated phthalocyanine color material represented by the general formula (1) of the present invention, X ¹ ～X ¹⁶ At least one of (A) is a fluorine atom, X ¹ ～X ¹⁶ At least one of them is a monovalent group represented by the above general formulae (2-1) to (2-5), X ¹ ～X ¹⁶ At least one of them is a monovalent group represented by the above general formula (2-6).

Due to X ¹ ～X ¹⁶ Since at least one of them is a fluorine atom, the color derived from the phthalocyanine skeleton, which is the hue (Japanese: hue) of the blue region, is shifted in long wavelength by the electron withdrawing effect, and a color suitable for a green colored layer for a color filter is obtained. The monovalent groups represented by the general formulae (2-1) to (2-6) are each a group which is bonded to the phthalocyanine skeleton via an ether bond and is movable, and therefore crystallinity can be reduced. In the phthalocyanine color material of the present invention, 1 molecule contains the monovalent groups represented by the general formulae (2-1) to (2-5) and the monovalent groups represented by the general formulae (2-6) in a mixed manner, and therefore, compared with, for example, a compound containing only the monovalent groups represented by the general formulae (2-6), the regularity of the compound is reduced, and therefore, the crystallinity is reduced. Result estimation: after the heat treatment (post baking step) of the colored layer, the colored curable composition using the halogenated phthalocyanine colorant represented by the general formula (1) can form a colored layer in which the deposition of foreign matters is suppressed and the contrast is improved, by suppressing the crystal growth and aggregation of the phthalocyanine colorant.

In the general formula (1), X is ¹ ～X ¹⁶ Examples of the halogen atom in (b) may include: fluorine atom, chlorine atom, bromine atom, iodine atom, etc., among them, fluorine atom, X are preferable from the viewpoint of color tone (Japanese: color smell) ¹ ～X ¹⁶ At least one of which is a fluorine atom.

Among them, X is preferable from the viewpoints of color tone and maximum absorption wavelength region ¹ ～X ¹⁶ 6 to 10, especially 7 to 9, of the groups are fluorine atoms.

X ¹ ～X ¹⁶ Or may be a hydrogen atom. X is X ¹ ～X ¹⁶ The number of hydrogen atoms in (a) may be appropriately selected according to the adjustment of the color tone, and may be 0 to 8, 0 to 4, or 0 to 2.

X ¹ ～X ¹⁶ Or may be a hydroxyl group. X from the aspect of hue and maximum absorption wavelength region ¹ ～X ¹⁶ The number of hydroxyl groups in (a) may be appropriately selected, and may be 0 to 4, and may be 0 to 2.

In the general formula (1), X is ¹ ～X ¹⁶ Examples of the hydrocarbon group among the above-mentioned substituted or unsubstituted hydrocarbon groups having 1 to 6 carbon atoms include: straight-chain, branched aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups. The aliphatic hydrocarbon group may be a saturated aliphatic hydrocarbon group (alkyl group) or an unsaturated aliphatic hydrocarbon group (alkenyl group, alkynyl group).

Examples of the aliphatic hydrocarbon group having 1 to 6 carbon atoms include a straight-chain or branched-chain hydrocarbon group: examples of the alicyclic hydrocarbon group include methyl, ethyl, linear or branched propyl, linear or branched butyl, linear or branched pentyl, linear or branched hexyl, vinyl, propenyl, 1-butenyl, and the like: cyclopentyl, cyclohexyl, and the like. Examples of the aromatic hydrocarbon group include phenyl groups.

In the case where the hydrocarbon group has a substituent, examples of the substituent include: halogen atom, -OR ^s1 、-COR ^s1 、-COOR ^s1 (here, R ^s1 A substituted or unsubstituted hydrocarbon group having 1 to 14 carbon atoms, or a substituted or unsubstituted heterocyclic group having 5 to 14 ring-forming atoms), and the like, specifically, examples thereof include: halogen atoms, hydroxyl groups, aldehyde groups, carboxyl groups, alkoxy groups, aryloxy groups, heteroaryloxy groups, acyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, heteroaryloxycarbonyl groups, and the like. With respect to R ^s1 The hydrocarbon group having 1 to 14 carbon atoms may be the same as the alicyclic hydrocarbon group and the aromatic hydrocarbon group described below, except for the hydrocarbon group having 1 to 6 carbon atoms. The heterocyclic group having 5 to 14 ring members may be the same as the heterocyclic group having 5 to 14 ring members described below. R is R ^s1 The hydrocarbon group may be a hydrocarbon group having 1 to 6 carbon atoms, and the heterocyclic group may be a heterocyclic group having 5 to 6 ring-forming atoms.R ^s1 The hydrocarbon group may have 1 to 6 carbon atoms, the hydrocarbon group may have 1 to 4 carbon atoms, or the methyl group, the ethyl group, the linear or branched propyl group.

In addition, as R ^s1 The substituent of the hydrocarbon group or heterocyclic group in (a) may be an alkoxy group having 1 to 5 carbon atoms.

In the general formula (1), X ¹ ～X ¹⁶ Can be a monovalent group represented by the following general formula (2), X ¹ ～X ¹⁶ At least one of them is a monovalent group represented by the following general formulae (2-1) to (2-5), X ¹ ～X ¹⁶ At least one of them is a monovalent group represented by the following general formula (2-6).

General formula (2): * -O-R ^P

General formula (2-1): * -O-R ^L1 -R ^a

General formula (2-2): * -O- (R) ^L2 -O) _n -R ^b

General formula (2-3): * -O-R ^L2 -COO-R ^b

General formula (2-4): * -O-R ^L2 -OCO-R ^b

General formula (2-5): * -O-R ^c

General formula (2-6): * -O-R ^a

(in the general formulae (2) and (2-1) to (2-6),

R ^P represents a substituted or unsubstituted straight-chain or branched aliphatic hydrocarbon group having 1 to 6 carbon atoms, a substituted or unsubstituted alicyclic hydrocarbon group having 5 to 14 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 14 carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 14 ring-forming atoms, -R ^L1 -R ^a 、-(R ^L2 -O) _n -R ^b 、-R ^L2 -COO-R ^b or-R ^L2 -OCO-R ^b ，R ^L1 Represents an aliphatic hydrocarbon group having 1 to 6 carbon atoms or a-CO-group, R ^L2 Each independently represents an aliphatic hydrocarbon group having 1 to 6 carbon atoms, R ^a Represents a substituted or unsubstituted aromatic hydrocarbon group having 6 to 14 carbon atoms, R ^b Represents a hydrogen atom, a substituted or unsubstituted C1-6 linear or branched aliphatic hydrocarbon group, or a substituted or unsubstituted C1-6 aliphatic hydrocarbon groupA substituted or unsubstituted alicyclic hydrocarbon group having 5 to 14 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 14 carbon atoms, or a substituted or unsubstituted heterocyclic group having 5 to 14 ring-forming atoms, R ^c Represents a substituted or unsubstituted alicyclic hydrocarbon group having 5 to 14 carbon atoms. n represents an integer of 1 to 5. * Represents the bonding position with the phthalocyanine skeleton)

R in the general formula (2) ^P The substituted or unsubstituted straight-chain or branched aliphatic hydrocarbon group having 1 to 6 carbon atoms may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group.

Examples of the straight-chain or branched aliphatic hydrocarbon group having 1 to 6 carbon atoms include: methyl, ethyl, straight or branched propyl, straight or branched butyl, straight or branched pentyl, straight or branched hexyl, ethenyl, propenyl, 1-butenyl, and the like. The linear or branched aliphatic hydrocarbon group having 1 to 6 carbon atoms may be a linear or branched aliphatic hydrocarbon group having 1 to 4 carbon atoms, or may be a linear or branched aliphatic hydrocarbon group having 1 to 3 carbon atoms.

R in the general formula (2) ^P Among the substituted or unsubstituted alicyclic hydrocarbon groups having 5 to 14 carbon atoms, examples of the alicyclic hydrocarbon group having 5 to 14 carbon atoms include: cyclopentyl, cyclohexyl, norbornyl, adamantyl, and the like. The alicyclic hydrocarbon group may be an alicyclic hydrocarbon group having 5 to 10 carbon atoms, or an alicyclic hydrocarbon group having 5 to 6 carbon atoms.

R in the general formula (2) ^P Among the substituted or unsubstituted aromatic hydrocarbon groups having 6 to 14 carbon atoms, examples of the aromatic hydrocarbon group having 6 to 14 carbon atoms include: phenyl, naphthyl, biphenyl, fluorenyl, anthracyl, and the like. The aromatic hydrocarbon group may be an aromatic hydrocarbon group having 6 to 10 carbon atoms, and may be a phenyl group.

R in the general formula (2) ^P In (a) a heterocyclic group having 5 to 14 ring atoms which is substituted or unsubstituted, examples of the heterocyclic group having 5 to 14 ring atoms include: furan ring, thiophene ring, pyrrole ring, 2H-pyran ring, 4H-thiopyran ring, pyridine ring having 1 free valence (Japanese: through atom )And a group such as a pyridine ring, a 1, 3-oxazole ring, an isoxazole ring, a 1, 3-thiazole ring, an isothiazole ring, an imidazole ring, a pyrazole ring, a furazan ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, a carbazole ring, and an acridine ring. The heterocyclic group may be a heterocyclic group having 5 to 6 ring members.

At R ^P In the case where the straight-chain OR branched aliphatic hydrocarbon group having 1 to 6 carbon atoms has a substituent, examples of the substituent include a halogen atom and-OR ^s1 、-COR ^s1 、-COOR ^s1 (here, R ^s1 A hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 14 carbon atoms or a substituted or unsubstituted heterocyclic group having 5 to 14 ring-forming atoms), etc., and may be a halogen atom, a hydroxyl group, an aldehyde group, a carboxyl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heteroaryloxycarbonyl group, etc.

At R ^P In the case where the alicyclic hydrocarbon group, aromatic hydrocarbon group and heterocyclic group in (a) have a substituent(s), examples of the substituent(s) include a halogen atom, a substituted OR unsubstituted straight-chain OR branched aliphatic hydrocarbon group having 1 to 6 carbon atoms, -OR ^s1 、-COR ^s1 、-COOR ^s1 (here, R ^s1 A hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 14 carbon atoms or a substituted or unsubstituted heterocyclic group having 5 to 14 ring-forming atoms), etc., and may be a halogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a hydroxyl group, an aldehyde group, a carboxyl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heteroaryloxycarbonyl group, etc.

With respect to R as described above ^s1 The hydrocarbon group having 1 to 14 carbon atoms except for the above X ¹ ～X ¹⁶ In the above, the hydrocarbon group having 1 to 6 carbon atoms may be other than the above-mentioned R ^P The alicyclic hydrocarbon group and the aromatic hydrocarbon group are the same. In addition, the heterocyclic group having 5 to 14 ring-forming atoms may be the same as R ^P The heterocyclic groups having 5 to 14 ring members are the same.

From the aspect of solvent solubility, R ^s1 The hydrocarbon group may be C1-6 hydrocarbon group, C1-4 linear or branched aliphatic hydrocarbon group, or hetero-hydrocarbon groupThe cyclic group may be a heterocyclic group having 5 to 6 ring members. R is R ^s1 The hydrocarbon group may have 1 to 6 carbon atoms, the hydrocarbon group may have 1 to 4 carbon atoms, and the hydrocarbon group may be a methyl group, an ethyl group, a linear or branched propyl group.

In addition, regarding R ^P The alicyclic hydrocarbon group, aromatic hydrocarbon group, heterocyclic group may be a linear or branched aliphatic hydrocarbon group having 1 to 6 carbon atoms which is substituted with the above-mentioned linear or branched aliphatic hydrocarbon group having 1 to 6 carbon atoms, and may be a linear or branched aliphatic hydrocarbon group having 1 to 4 carbon atoms.

In the general formulae (2) and (2-1) to (2-4), R ^L1 Represents an aliphatic hydrocarbon group having 1 to 6 carbon atoms or a-CO-group, and R ^L2 Each independently represents an aliphatic hydrocarbon group having 1 to 6 carbon atoms.

R ^L1 R is R ^L2 The aliphatic hydrocarbon group having 1 to 6 carbon atoms in (b) is a divalent aliphatic hydrocarbon group, and examples thereof include: the divalent straight-chain, branched-chain, saturated or unsaturated aliphatic hydrocarbon group or alicyclic hydrocarbon group may be a divalent straight-chain or branched-chain aliphatic hydrocarbon group or may be a saturated aliphatic hydrocarbon group.

Examples of the aliphatic hydrocarbon group having a straight chain or branched chain include: methylene, ethylene, linear or branched propylene, linear or branched butylene, linear or branched pentylene, linear or branched hexylene, and the like.

R ^L1 R is R ^L2 The aliphatic hydrocarbon group having 1 to 6 carbon atoms may be an aliphatic hydrocarbon group having 1 to 3 carbon atoms.

R of the formula (2-2) ^L2 The aliphatic hydrocarbon group having 1 to 6 carbon atoms in (a) may be an ethylene group or a branched propylene group.

N in the general formula (2-2) represents an integer of 1 to 5 and may be 1 to 3.

In the general formulae (2), (2-1) and (2-6), R ^a Represents a substituted or unsubstituted aromatic hydrocarbon group having 6 to 14 carbon atoms. As R ^a The substituted or unsubstituted aromatic hydrocarbon group having 6 to 14 carbon atoms in (C) may be the same as R ^P The same applies.

In the general formulae (2) and (2-2) to (2-4), R ^b Represents a hydrogen atom, a substituted or unsubstituted straight-chain or branched aliphatic hydrocarbon group having 1 to 6 carbon atoms, a substituted or unsubstituted alicyclic hydrocarbon group having 5 to 14 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 14 carbon atoms, or a substituted or unsubstituted heterocyclic group having 5 to 14 ring-forming atoms.

R ^b The substituted or unsubstituted aliphatic hydrocarbon group having 1 to 6 carbon atoms, the substituted or unsubstituted alicyclic hydrocarbon group having 5 to 14 carbon atoms, the substituted or unsubstituted aromatic hydrocarbon group having 6 to 14 carbon atoms, or the substituted or unsubstituted heterocyclic group having 5 to 14 ring-forming atoms may be the same as the above R ^P The same applies.

R is from the viewpoint of easily reducing crystallinity of the color material ^b Can be a substituted or unsubstituted alicyclic hydrocarbon group having 5 to 14 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 14 carbon atoms, or a substituted or unsubstituted heterocyclic group having 5 to 14 ring-forming atoms. From the aspect of solvent solubility, R ^b The aromatic hydrocarbon group may be a substituted or unsubstituted alicyclic hydrocarbon group having 5 to 14 carbon atoms, or a substituted or unsubstituted aromatic hydrocarbon group having 6 to 14 carbon atoms, may be a substituted or unsubstituted alicyclic hydrocarbon group having 5 to 10 carbon atoms, or a substituted or unsubstituted aromatic hydrocarbon group having 6 to 10 carbon atoms, and may be a substituted or unsubstituted cyclopentyl group, a substituted or unsubstituted cyclohexyl group, or a substituted or unsubstituted phenyl group.

In addition, R is from the aspect of solvent solubility ^b Can be an unsubstituted aliphatic hydrocarbon group having 1 to 3 carbon atoms.

In addition, R is from the aspect of good solubility in high polarity solvents ^b May be a hydrogen atom.

In the general formula (2-5), R ^c Represents a substituted or unsubstituted alicyclic hydrocarbon group having 5 to 14 carbon atoms. As R ^c The alicyclic hydrocarbon group having 5 to 14 carbon atoms may be substituted or unsubstituted With R as above ^P The same applies.

Wherein R of the general formula (2) is from the aspect of a coloring layer which is easy to form foreign matters and is inhibited from precipitating and has improved contrast ^p 、R ^a 、R ^b The aromatic hydrocarbon group in (b) may be a monovalent group represented by the following general formula (3).

[ chemical formula 3]

(in the general formula (3), -W-is a single bond or-O-, R ^s1 Is a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 14 carbon atoms or a substituted or unsubstituted heterocyclic group having 5 to 14 ring-forming atoms. R is R ^s2 Is a halogen atom, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. p is an integer of 1 to 3, and q is an integer of 0 to 2. Wherein, in the case that p is 2 or 3, a plurality of W, R ^s1 Each of which may be the same or different, wherein in the case where q is 2, a plurality of R ^s2 The two may be the same or different. * Indicating the bonding location. )

In the above general formula (3), R ^s1 May be the same as described above.

From the aspect of solvent solubility, R is taken as ^s1 The aliphatic hydrocarbon group may be a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 6 carbon atoms, and the alkyl group may be a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms. The alkyl group is preferably an alkyl group having 1 to 5 carbon atoms, more preferably a linear alkyl group having 1 to 5 carbon atoms. At R ^s1 In the case of a substituted alkyl group, the substituted alkyl group may be a group having an alkoxy group having 1 to 5 carbon atoms as a substituent.

p may be 1 or 2 and may be 1. In the case of p=1, -CO-W-R ^s1 the-O-moiety bonded to the monovalent group represented by the general formula (3) may be bonded to the 3-position or the 4-position, or may be bonded to the 4-position. In the case of p=2, 2-CO-W-R ^s1 the-O-moiety bonded to the monovalent group represented by the general formula (3) may be bonded to the 3, 5-position or the 2, 4-position, or may be bonded to the 3, 5-position.

q may be 0 or 1, and may be 0.

Wherein,r of the general formula (2) is from the aspect of a coloring layer which is easy to form foreign matters and is inhibited from precipitating and has improved contrast ^p 、R ^b 、R ^c The alicyclic hydrocarbon group in (a) may be a monovalent group represented by the following general formula (4).

[ chemical formula 4]

(in the general formula (4), -W-is a single bond or-O-, R ^s1 Is a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 14 carbon atoms or a substituted or unsubstituted heterocyclic group having 5 to 14 ring-forming atoms. R is R ^s2 Is a halogen atom, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. p is an integer of 1 to 3, and q is an integer of 0 to 2. Wherein, in the case that p is 2 or 3, a plurality of W, R ^s1 Each of which may be the same or different, wherein in the case where q is 2, a plurality of R ^s2 The two may be the same or different. * Indicating the bonding location. )

In the above general formula (4), R ^s1 May be the same as described above.

From the aspect of solvent solubility, R is taken as ^s1 The aliphatic hydrocarbon group may be a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 6 carbon atoms, and the alkyl group may be a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms. The alkyl group is preferably an alkyl group having 1 to 5 carbon atoms, more preferably a linear alkyl group having 1 to 5 carbon atoms. At R ^s1 In the case of a substituted alkyl group, a group having an alkoxy group having 1 to 5 carbon atoms as a substituent is preferable.

p may be 1 or 2 and may be 1. In the case of p=1, -CO-W-R ^s1 the-O-moiety bonded to the monovalent group represented by the general formula (4) may be bonded to the 3-position or the 4-position, or may be bonded to the 4-position. In the case of p=2, 2-CO-W-R ^s1 the-O-moiety bonded to the monovalent group represented by the general formula (4) may be bonded to the 3, 5-position or the 2, 4-position, or may be bonded to the 3, 5-position.

q may be 0 or 1, and may be 0.

Of the monovalent groups represented by the above general formulae (2-1) to (2-5), the above general formula (2-1) is represented byThe bulky terminal is more bulky and the bulky terminal is more easily moved, and is preferable in view of easy inhibition of crystal growth by steric hindrance. Wherein R of the above general formula (2-1) ^a In the case where the aromatic hydrocarbon group is a monovalent group represented by the above general formula (3), it is preferable in view of the easiness of formation of a colored layer in which precipitation of foreign matters is suppressed and the contrast is improved.

Among the monovalent groups represented by the above general formulae (2-1) to (2-5), the above general formula (2-5) is preferable in that the terminal is bulky and crystal growth is easily inhibited by steric hindrance. Wherein R of the above general formula (2-5) ^c In the case where the aliphatic hydrocarbon group in (a) is a monovalent group represented by the above general formula (4), a colored layer in which precipitation of foreign matters is suppressed and the contrast is improved is preferable.

Among the monovalent groups represented by the general formulae (2-1) to (2-5), the general formula (2-2), the general formula (2-3) and the general formula (2-4) are preferable in that the affinity with the polymer and the polymerizable compound is easily improved by the alkylene oxide chain or the ester moiety, and the aggregation of the color material is easily suppressed.

R at the terminal in the above general formula (2-2), the above general formula (2-3) and the above general formula (2-4) ^b In the case of a substituted or unsubstituted alicyclic hydrocarbon group having 5 to 14 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 14 carbon atoms, or a substituted or unsubstituted heterocyclic group having 5 to 14 ring-forming atoms, it is preferable in view of easiness in improving affinity with a polymer or a polymerizable compound, easiness in suppressing aggregation of a color material, large terminal volume, and easiness in suppressing crystal growth by steric hindrance. Wherein R at the end ^b In the case of the monovalent group represented by the general formula (3) or the monovalent group represented by the general formula (4), it is preferable in view of suppressing the deposition of foreign matters and improving the contrast of the colored layer.

In the halogenated phthalocyanine color material of the present invention, the deposition of foreign matters which are easily formed is suppressed, the contrast is improved, and the color is formed by color mixingX is preferred in terms of a colored layer exhibiting color characteristics excellent in brightness and tinting strength at the time of various color standards ¹ ～X ¹⁶ 6 to 10, particularly 7 to 9 of the monovalent groups represented by the above general formula (2).

In the halogenated phthalocyanine color material of the present invention, X is preferable in terms of suppressing the deposition of foreign matters and improving the contrast of the colored layer ¹ ～X ¹⁶ 3 to 5, on average 3.5 to 4.5, in particular 4, of the monovalent groups represented by the general formulae (2-1) to (2-5).

In the halogenated phthalocyanine color material of the present invention, X is preferable in terms of suppressing the deposition of foreign matters and enhancing the contrast of the colored layer ¹ ～X ¹⁶ 3 to 5, on average 3.5 to 4.5, in particular 4, of the monovalent groups represented by the above general formula (2 to 6).

In the halogenated phthalocyanine color material of the present invention, it is preferable that X is the above from the viewpoint of suppressing the deposition of foreign matters and improving the contrast ¹ ～X ⁴ Any of the above X ⁵ ～X ⁸ Any of the above X ⁹ ～X ¹² Any of the above, X ¹³ ～X ¹⁶ Any one of the above has a total of 4 monovalent groups represented by the above general formulae (2-1) to (2-5), and X is ¹ ～X ⁴ Any of the above X ⁵ ～X ⁸ Any of the above X ⁹ ～X ¹² Any of the above, X ¹³ ～X ¹⁶ Any of the above has a total of 4 monovalent groups represented by the above general formulae (2-6), and more preferably X ² Or X ³ 、X ⁶ Or X ⁷ 、X ¹⁰ Or X ¹¹ And X ¹⁴ Or X ¹⁵ The total of 4 monovalent groups represented by the general formulae (2-1) to (2-5) are each represented by the general formulae (2-6), and the total of 4 monovalent groups are each represented by the general formulae (2-6).

Further, in this case, from the aspect of chromaticity improvement, it is preferable that the above X ¹ ～X ⁴ The remaining two of the above X ⁵ ～X ⁸ The remaining two of the above X ⁹ ～X ¹² The remaining two of (A) and X ¹³ ～X ¹⁶ At least one of the remaining two groups (a) contains a fluorine atom, and the remaining groups (b) are preferably selected from the group consisting of halogen atoms and hydrogen atoms, more preferably from the group consisting of halogen atoms, and even more preferably all fluorine atoms.

The method for producing the halogenated phthalocyanine material may be appropriately selected from conventionally known methods. For example, it is possible to suitably use: the method for producing the cyclized reaction between the phthalonitrile compound and the metal salt in a molten state or in an organic solvent can be, for example, produced by referring to Japanese patent application laid-open No. 2014-43556 or Japanese patent application laid-open No. 2020-42263. The phthalonitrile compound used as the starting material can be synthesized by appropriately selecting a conventionally known production method, and commercially available products can be used.

Colored curable composition

The colored curable composition of the present invention contains the halogenated phthalocyanine colorant of the present invention, and therefore, a colored layer in which precipitation of foreign matters is suppressed and contrast is improved can be formed.

The colored curable composition of the present invention contains at least a color material, a polymer, a polymerizable compound, an initiator, and a solvent, and may further contain other components within a range that does not impair the effects of the present invention.

< color Material >

In the present invention, the color material may contain other color materials in addition to the halogenated phthalocyanine color material represented by the above general formula (1).

The other color materials are not particularly limited as long as the desired color development can be achieved, and various organic pigments, inorganic pigments, dyes, salt-forming compounds of dyes, and the like may be used alone or in combination of 2 or more. 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 (Pigment) in color index (c.i.; issued by The Society of Dyers and Colourists company), and specifically, the Pigment index (c.i.) is given as the following.

As the color material, a yellow color material may be further contained.

The color material may further contain a green color material different from the halogenated phthalocyanine color material represented by the general formula (1).

Examples of the yellow color material include: c.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, 156, 166, 168, 175, 185, 231, derivative pigments of these, and the like; coumarin dyes, cyanine dyes, merocyanine dyes, azo dyes, methine dyes, azomethine dyes, quinophthalone dyes, and other yellow dyes.

Among them, quinophthalone-based color materials are preferable in terms of good heat resistance and light resistance and high transmittance. Further, quinophthalone-based color materials are also preferable in terms of having a hue suitable for color filter applications.

The quinophthalone-based color material is synthesized by condensing quinoline derivatives such as quinaldine with phthalic anhydride derivatives or naphthalic anhydride derivatives, and may be any of pigments, dyes, and salt-forming compounds of dyes.

Examples of the quinophthalone-based color material include c.i. pigment yellow 138 as a quinophthalone pigment.

Examples of quinophthalone dyes include: c.i. disperse yellow 54, 64, 67, 134, 149, 160; c.i. solvent yellow 114, 157, etc., of which c.i. disperse yellow 54 is preferred.

On the other hand, examples of the green color material different from the halogenated phthalocyanine color material of the present invention include: green pigments such as c.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; squarylium (Japanese), triarylmethane, anthraquinone, coumarin, cyanine, azo dye, or other green dye.

From the viewpoint of easy adjustment of chromaticity, phthalocyanine green pigment is preferable as a green color material different from the halogenated phthalocyanine color material.

Examples of the phthalocyanine green pigment include: c.i. pigment green 7, 36, 58, 59, 62, 63, etc. From the viewpoint of easy adjustment of brightness, the phthalocyanine green pigment is preferably c.i. pigment green 7, 58, 59, 62 or 63, preferably c.i. pigment green 58, 59, 62 or 63, more preferably c.i. pigment green 59.

Examples of the other color materials include: blue color material, orange color material, and the like.

Examples of the orange color material include: c.i. pigment orange 1, 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 61, 63, 64, 71, 73;

examples of the blue color material include: c.i. pigment blue 15, 15: 3. 15: 4. 15: 6. 60.

In the colored curable composition of the present invention, the content ratio of the halogenated phthalocyanine color material of the present invention to the entire color material is not particularly limited, and may be appropriately adjusted according to the desired chromaticity. The content of the halogenated phthalocyanine color material of the present invention to the entire color material is preferably 30 to 95% by mass, more preferably 40 to 85% by mass, and even more preferably 50 to 80% by mass, from the viewpoint of adjusting the color to a desired color.

In the colored curable composition of the present invention, when a yellow color material is contained, the yellow color material may be appropriately selected, and 1 or 2 or more kinds thereof may be used singly or in combination.

In the colored curable composition of the present invention, the content ratio of the yellow color material to the halogenated phthalocyanine color material of the present invention is not particularly limited, and may be appropriately adjusted according to the desired chromaticity. Among them, the yellow color material is preferably contained in an amount of 5 to 233 parts by mass, more preferably 18 to 150 parts by mass, even more preferably 25 to 100 parts by mass, based on 100 parts by mass of the halogenated phthalocyanine color material of the present invention, from the viewpoint of adjusting the color to a desired color.

In the colored curable composition of the present invention, when a green color material different from the halogenated phthalocyanine color material is contained, 1 or 2 or more kinds of green color materials different from the halogenated phthalocyanine color material can be appropriately selected and used singly or in combination.

In the colored 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 is not particularly limited, and may be appropriately adjusted to a desired chromaticity. Among them, the green color material different from the halogenated phthalocyanine color material of the present invention is preferably 5 to 900 parts by mass, more preferably 18 to 567 parts by mass, and even more preferably 25 to 400 parts by mass, based on 100 parts by mass of the halogenated phthalocyanine color material of the present invention, from the viewpoints of adjustment to a desired chromaticity and adjustment of brightness.

In addition, in the case where the colored curable composition of the present invention further contains a green color material other than the halogenated phthalocyanine color material of the present invention, the content ratio of the green color material containing the halogenated phthalocyanine color material of the present invention to the entire color material is not particularly limited, and may be appropriately adjusted according to the desired chromaticity. Among them, the green color material containing the halogenated phthalocyanine color material of the present invention is preferably 30 to 95% by mass, more preferably 50 to 80% by mass, based on the entire color material, from the viewpoints of adjustment to a desired chromaticity and adjustment of brightness.

The content ratio of the yellow color material to the green color material including the halogenated phthalocyanine color material of the present invention is not particularly limited, and may be appropriately adjusted according to the desired chromaticity. Among them, the yellow color material is preferably contained in an amount of 5 to 70 parts by mass, more preferably 20 to 50 parts by mass, relative to 100 parts by mass of the green color material containing the halogenated phthalocyanine color material of the present invention, from the viewpoints of adjustment to a desired chromaticity and adjustment of brightness.

The color curable composition of the present invention may further contain, in addition to the green color material and the yellow color material, other color materials than the green color material and the yellow color material in such a range that the effect of the present invention is not impaired, and the total content of the green color material and the yellow color material containing the halogenated phthalocyanine color material of the present invention is preferably 70 to 100% by mass, and more preferably 80 to 100% by mass, based on the entire color material.

The total content of the coloring materials is, for example, preferably 3 to 65 mass%, more preferably 4 to 60 mass%, based on the total solid content of the colored curable composition. When the lower limit is not less than the above, the colored layer has a sufficient color density when the colored curable composition is applied to a predetermined film thickness (usually 1.0 to 5.0 μm). In addition, when the upper limit value is less than or equal to the above, the storage stability is excellent, and a colored layer having sufficient hardness and adhesion to a substrate can be obtained. In particular, when a colored layer having a high color material concentration is formed, the content of the color material is preferably in the range of 15 to 65 mass%, more preferably 25 to 60 mass%, relative to the total solid content of the colored curable composition.

In the present invention, the solid component is all components except the above-mentioned solvent, and includes a monomer dissolved in the solvent and the like.

[ Binder component ]

The polymer, the polymerizable compound and the initiator contained in the colored curable composition of the present invention are used as binder components of the colored curable composition to impart film forming properties and adhesion to the surface to be coated.

The binder component used for forming a conventionally known colored layer can be used appropriately, and is not particularly limited, and examples thereof include: a photosensitive binder component which is polymerized and cured by visible light, ultraviolet light, electron beam, or the like; the thermosetting binder component which can be polymerized and cured by heating, and mixtures of these can also be used.

The thermosetting binder component may be, for example, a system comprising at least: a polymer which may have a thermally polymerizable functional group as a polymer, a compound having a thermally polymerizable functional group in a molecule as a polymerizable compound, a thermal polymerization initiator containing a curing agent which reacts with the thermally polymerizable functional group as an initiator, and the like. Examples of the thermally polymerizable functional group include: epoxy, isocyanate, carboxyl, amino, hydroxyl, and the like.

When a photolithography step is used in forming a colored layer using the colored curable composition of the present invention, a photosensitive binder component having alkali developability is suitably used. The photosensitive binder component may also be a thermosetting binder component.

Examples of the photosensitive binder component include: positive photosensitive binder component and negative photosensitive binder component. Examples of the positive photosensitive binder component include a system comprising: an alkali-soluble resin as a polymer; a compound having an acid-cleavable bond and an ethylenically unsaturated group in the molecule as a polymerizable compound; a thermal radical polymerization initiator as an initiator; 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 a molecule as a polymerizable compound, and a photopolymerization initiator as an initiator.

The binder component contained in the colored curable composition of the present invention is preferably the negative photosensitive binder component described above, since a pattern can be easily formed by photolithography using a conventional process.

< Polymer >)

When a photolithography step is used for forming the colored layer, an alkali-soluble resin soluble in an alkali developer is preferably used as the polymer.

The alkali-soluble resin has an acidic group, and may be appropriately selected and used as long as it functions as a binder resin and is soluble in an alkali developer used in forming a pattern.

In the present invention, the alkali-soluble resin may have an acid value of 30mgKOH/g or more as a standard.

Examples of the acidic group of the alkali-soluble resin include a carboxyl group. Examples of the alkali-soluble resin having a carboxyl group include: carboxyl group-containing copolymers having carboxyl groups, epoxy (meth) acrylate resins having carboxyl groups, and the like. Examples of the carboxyl group-containing copolymer include: and (meth) acrylic copolymers such as (meth) acrylic copolymers having a carboxyl group and styrene- (meth) acrylic copolymers having a carboxyl group.

Further, these (meth) acrylic copolymers, a (meth) acrylic copolymer such as a styrene- (meth) acrylic copolymer having a carboxyl group, and an epoxy (meth) acrylate resin may be used in a mixture of 2 or more kinds.

The (meth) acrylic copolymer having a carboxyl group, and the (meth) acrylic copolymer such as a styrene- (meth) acrylic copolymer having a carboxyl group are, for example: (Co) polymers obtained by (co) polymerizing carboxyl group-containing ethylenically unsaturated monomers and, if necessary, other copolymerizable monomers by known methods.

Examples of the carboxyl group-containing ethylenically unsaturated monomer include: (meth) acrylic acid, vinylbenzoic acid, maleic acid, monoalkyl maleate, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, (meth) acrylic acid dimer, and the like. In addition, it is also possible to use: addition reaction products of monomers having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and cyclic anhydrides such as maleic anhydride, phthalic anhydride and cyclohexanedicarboxylic anhydride; omega-carboxy-polycaprolactone mono (meth) acrylates, and the like. In addition, anhydride-containing monomers such as maleic anhydride, itaconic anhydride, and citraconic anhydride may be used as the precursor of the carboxyl group. Among them, (meth) acrylic acid is particularly preferred in terms of copolymerizability, cost, solubility, glass transition temperature, and the like.

The alkali-soluble resin preferably further has a hydrocarbon ring in view of excellent adhesion to the substrate. By providing the alkali-soluble resin with a hydrocarbon ring as a bulky group, shrinkage during curing is suppressed, peeling from the substrate is eased, and substrate adhesion is improved. In addition, by using an alkali-soluble resin having a hydrocarbon ring as a bulky group, the solvent resistance of the obtained colored layer is improved, and in particular, it is also preferable in terms of suppressing swelling of the colored layer.

Examples of such hydrocarbon rings include: a cyclic aliphatic hydrocarbon ring which may have a substituent, an aromatic ring which may have a substituent, and a combination of these, and the hydrocarbon ring may have a substituent such as a carbonyl group, a carboxyl group, an oxycarbonyl group, an amide group, or the like.

Specific examples of the hydrocarbon ring include: an aliphatic hydrocarbon ring such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, norbornane, tricyclo [5.2.1.0 (2, 6) ] decane (dicyclopentane), adamantane, an aromatic hydrocarbon ring such as benzene, naphthalene, anthracene, phenanthrene, fluorene, a chain-like polycyclic such as biphenyl, terphenyl, diphenylmethane, triphenylmethane, stilbene, cardo structure (9, 9-diaryl fluorene), and the like.

Among them, when an aliphatic hydrocarbon ring is contained as the hydrocarbon ring, the heat resistance and adhesion of the colored layer are improved, and the brightness of the obtained colored layer is preferably improved.

In addition, in the case of a structure (Cardo structure) in which two benzene rings are bonded to a fluorene skeleton, it is particularly preferable in view of improving the curability of the colored layer and improving the solvent resistance, especially in view of suppressing the swelling of NMP.

The hydrocarbon ring may be contained in the form of a monovalent group or may be contained in the form of a group having a valence of two or more.

In the alkali-soluble resin used in the present invention, a (meth) acrylic copolymer containing a structural unit having the hydrocarbon ring in addition to a structural unit having a carboxyl group is preferably used in view of easy adjustment of the amount of each structural unit and easy improvement of the function of the structural unit by increasing the amount of the structural unit having the hydrocarbon ring.

The (meth) acrylic copolymer containing a structural unit having a carboxyl group and the hydrocarbon ring described above can be produced by using an ethylenically unsaturated monomer having a hydrocarbon ring as the "copolymerizable other monomer" described above.

As the ethylenically unsaturated monomer having a hydrocarbon ring used for the alkali-soluble resin having a hydrocarbon ring, for example, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, adamantyl (meth) acrylate, isobornyl (meth) acrylate, phenoxyethyl (meth) acrylate, styrene, a monomer having the aforementioned Cardo structure and ethylenically unsaturated group, and the like can be preferably used, and among them, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, adamantyl (meth) acrylate, benzyl (meth) acrylate, styrene, a monomer having the aforementioned Cardo structure and ethylenically unsaturated group are preferable from the viewpoint of a large effect of suppressing precipitation of foreign matters derived from the color material even after the heat treatment.

The alkali-soluble resin used in the present invention preferably has an ethylenically unsaturated bond in a side chain. In the case of having an ethylenically unsaturated bond, the alkali-soluble resins may form a cross-linking bond with each other or with a polyfunctional monomer or the like in the curing step of the resin composition at the time of manufacturing the color filter. The cured film has further improved film strength and development resistance, and the cured film is suppressed in heat shrinkage and has excellent adhesion to a substrate.

The ethylenically unsaturated group means a group containing a carbon-carbon double bond which can undergo radical polymerization, and examples thereof include: (meth) acryl, vinyl, allyl, and the like.

The method of introducing an ethylenically unsaturated bond into the alkali-soluble resin may be appropriately selected from conventionally known methods. Examples thereof include: a method of introducing an ethylenically unsaturated bond into a side chain of a compound having both an epoxy group and an ethylenically unsaturated bond in a carboxyl group-containing molecule of an alkali-soluble resin, for example, glycidyl (meth) acrylate; a method in which a structural unit having a hydroxyl group is introduced into a copolymer in advance, a compound having an isocyanate group and an ethylenic unsaturated bond in the molecule is added, and an ethylenic unsaturated bond is introduced into a side chain; etc.

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

The alkali-soluble resin used in the present invention is preferably a (meth) acrylic resin such as a (meth) acrylic copolymer and a styrene- (meth) acrylic copolymer containing a structural unit having a carboxyl group and a structural unit having a hydrocarbon ring, more preferably a (meth) acrylic resin such as a (meth) acrylic copolymer and a styrene- (meth) acrylic copolymer containing a structural unit having a carboxyl group, a structural unit having a hydrocarbon ring and a structural unit having an ethylenically unsaturated bond.

The alkali-soluble resin used in the present invention can obtain desired properties by appropriately adjusting the addition amount of the monomer derived from each structural unit.

The copolymerization ratio of the carboxyl group-containing ethylenically unsaturated monomer in the carboxyl 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, if the copolymerization ratio of the carboxyl group-containing ethylenically unsaturated monomer is 5 mass% or more, the resulting coating film can be inhibited from decreasing in solubility in an alkaline developer, and patterning is facilitated. If the copolymerization ratio is 50 mass% or less, defects in the pattern or roughness of the film on the surface of the pattern are less likely to occur when the film is developed with an alkaline developer. The copolymerization ratio is a value calculated from the addition amount of each monomer.

In addition, in the (meth) acrylic resin such as the (meth) acrylic copolymer and the styrene- (meth) acrylic copolymer containing a structural unit having an ethylenically unsaturated bond, which are more preferably used as the alkali-soluble resin, the amount of the monomer having both an epoxy group and an ethylenically unsaturated bond is preferably 10% by mass or more and 95% by mass or less, and more preferably 15% by mass or more and 90% by mass or less, relative to 100% by mass of the amount of the carboxyl group-containing ethylenically unsaturated monomer.

The weight average molecular weight (Mw) of the carboxyl group-containing copolymer is preferably in the range of 1,000 to 50,000, more preferably 3,000 to 20,000. When the weight average molecular weight of the carboxyl group-containing copolymer is 1,000 or more, the curability of the coating film can be sufficiently obtained, and when 50,000 or less, the coating film is easily patterned when developed with an alkaline developer.

The weight average molecular weight (Mw) in the present invention is determined as a standard polystyrene equivalent by Gel Permeation Chromatography (GPC).

Specific examples of the (meth) acrylic copolymer having a carboxyl group include those described in JP-A2013-029832.

The epoxy (meth) acrylate resin having a carboxyl group is not particularly limited, and examples thereof include: an epoxy (meth) acrylate compound obtained by reacting an epoxy compound with an unsaturated group-containing monocarboxylic acid reactant and an acid anhydride. The epoxy compound, unsaturated group-containing monocarboxylic acid, and acid anhydride may be appropriately selected from known ones and used.

Among them, epoxy (meth) acrylate resins having carboxyl groups are preferable to contain the Cardo structure in the molecule, since they have an improved effect of suppressing defects and an improved curability of the colored layer, and the residual film rate of the colored layer is high.

The acid value of the alkali-soluble resin is preferably 30mgKOH/g or more, more preferably 40mgKOH/g or more, from the viewpoint of developability (solubility) with respect to an alkaline aqueous solution used in the developer. The acid value of the carboxyl group-containing copolymer is preferably 50mgKOH/g or more and 300mgKOH/g or less, more preferably 60mgKOH/g or more and 280mgKOH/g or less, still more preferably 70mgKOH/g or more and 250mgKOH/g or less, from the viewpoint of developability (solubility) with respect to an aqueous alkali solution used in the developer and from the viewpoint of adhesion to a substrate.

In the present invention, the acid value can be measured in accordance with JIS K0070.

In terms of improving the film strength of the cured film and further suppressing precipitation of the color material, the ethylenically unsaturated bond equivalent in the case where the side chain of the alkali-soluble resin has an ethylenically unsaturated group is preferably in the range of 100 to 2000, particularly preferably in the range of 140 to 1500. When the equivalent of the ethylenic unsaturated bond is 2000 or less, the development resistance and the adhesion are excellent. When the ratio is 100 or more, the ratio of the structural unit having a carboxyl group to other structural units such as the structural unit having a hydrocarbon ring can be relatively increased, and therefore, the developability and heat resistance are excellent. Here, the ethylenically unsaturated bond equivalent is a weight average molecular weight per 1 mol of the ethylenically unsaturated bonds in the above alkali-soluble resin, and is represented by the following formula (1).

The ethylenically unsaturated bond equivalent (g/mol) =w (g)/M (mol) of the formula (1)

(in the formula (1), W represents the mass (g) of the alkali-soluble resin, M represents the mole number (mol) of the ethylenic unsaturated bonds contained in the alkali-soluble resin W (g))

The above-mentioned ethylenically unsaturated bond equivalent can be calculated, for example, by the following means: according to JIS K0070: the iodine value test method described in 1992 measures the number of ethylenically unsaturated bonds contained in 1g of the alkali-soluble resin.

The content of the alkali-soluble resin used in the color-curable composition is not particularly limited, but is preferably in the range of, for example, 5 to 60 mass%, more preferably 10 to 40 mass%, with respect to the total solid content of the color-curable composition. When the content of the alkali-soluble resin is not less than the above-mentioned lower limit, sufficient alkali developability is easily obtained, and when the content of the alkali-soluble resin is not more than the above-mentioned upper limit, film roughness and pattern defects at the time of development are easily suppressed.

The content of the polymer having an ethylenically unsaturated group in the colored curable composition is, for example, preferably 5 to 60 parts by mass, and more preferably 10 to 45 parts by mass, based on the total amount of the solid components of the colored curable composition. When the content of the polymer having an ethylenically unsaturated group is not less than the above lower limit, sufficient curing can be obtained, and peeling of the coating film of the patterned colored curable composition can be suppressed. In addition, when the content of the polymer having an ethylenically unsaturated group is not more than the above upper limit, peeling due to curing shrinkage can be suppressed.

The colored curable composition of the present invention may contain, for example, a thermosetting polymer such as a phenol resin, a urea resin, a diallyl phthalate resin, a melamine resin, a guanamine resin, an unsaturated polyester resin, a polyurethane resin, an epoxy resin, an amino alkyd resin, a melamine-urea cocondensation resin, a silicone resin, or a polysiloxane resin as the polymer.

The polymer may be used alone or in combination of 1 or more than 2 kinds.

The content of the polymer in the photocurable composition is not particularly limited, but is preferably 5 to 60% by mass, more preferably 10 to 50% by mass, based on the total solid content of the photocurable composition. If the polymer content is not less than the above-mentioned lower limit, the decrease in film strength can be suppressed, and if the polymer content is not more than the above-mentioned upper limit, the 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 the following initiator, and for example, a photopolymerizable compound or a thermally polymerizable compound can be used. As the thermally polymerizable compound, a compound having thermally polymerizable functional groups such as carboxyl groups, amino groups, epoxy groups, hydroxyl groups, glycidyl groups, isocyanate groups, and alkoxy groups in the molecule can be used. Further, a compound having an ethylenically unsaturated group is used in combination with a thermal radical polymerization initiator, and can also be used as a thermally polymerizable compound. Among them, a photopolymerizable compound which can be polymerized by the following photoinitiator is preferable, since a pattern can be easily formed by photolithography using a conventional process.

The photopolymerizable compound used in the colored curable composition is not particularly limited as long as it can be polymerized by the following photoinitiator, and a compound having 2 or more ethylenically unsaturated bonds is usually used, and a polyfunctional (meth) acrylate having 2 or more acryl groups or methacryl groups is particularly preferable.

Such a polyfunctional (meth) acrylate may be appropriately selected from conventionally known ones and used. Specific examples thereof include multifunctional (meth) acrylates described in JP-A2013-029832.

These photopolymerizable compounds may be used alone or in combination of 1 or more than 2. In the case where excellent photocurability (high sensitivity) is required for the colored curable composition of the present invention, the photopolymerizable compound is preferably a poly (meth) acrylate having 3 or more (trifunctional) polymerizable ethylenic unsaturated bonds, preferably a tri-or higher polyhydric alcohol, and a dicarboxylic acid modified product of these, specifically, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, succinic acid modified product of pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, succinic acid modified product of dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, or the like.

The content of the polymerizable compound in the colored curable composition is, for example, preferably 5 to 60% by mass, more preferably 10 to 50% by mass, and even more preferably 20 to 40% by mass, based on the total solid content of the colored curable composition. If the content of the polymerizable compound is not less than the above-mentioned lower limit, curing failure can be suppressed, and therefore dissolution of the exposed portion during development can be suppressed, and if the content of the polymerizable compound is not more than the above-mentioned upper limit, developing failure can be suppressed, and heat shrinkage can be suppressed, and therefore micro wrinkles are less likely to occur on the entire surface of the colored layer.

< initiator >

The initiator used in the colored curable composition of the present invention is not particularly limited, and 1 or 2 or more initiators may be used in combination from among various conventionally known initiators. Examples of the initiator include a polymerization initiator such as a thermal polymerization initiator and a photopolymerization initiator, and specifically, examples thereof include those described in JP-A2013-029832.

Examples of the photoinitiator include: aromatic ketones, benzoin ethers, halomethyl oxadiazole compounds, α -aminoketones, bisimidazoles, N-dimethylaminobenzophenone, halomethyl-s-triazine compounds, thioxanthones, and the like. Specific examples of the photoinitiator include: aromatic ketones such as benzophenone and 4,4' -bis-diethylaminobenzophenone, 4-methoxy-4 ' -dimethylaminobenzophenone, benzoin ethers such as benzoin methyl ether, benzoins such as ethylbenzoin, bisimidazoles such as 2- (o-chlorophenyl) -4, 5-phenylimidazole dimer, halomethyl oxadiazole compounds such as 2-trichloromethyl-5- (p-methoxystyryl) -1,3, 4-oxadiazole, halomethyl-s-triazine compounds such as 2- (4-butoxy-naphthalen-1-yl) -4, 6-bis-trichloromethyl-s-triazine, halomethyl-s-triazine compounds such as 2- (4-butoxy-naphthalen-1-yl) -4, 2-dimethoxy-1, 2-diphenylethane-1-ketone, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinophenone, 1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -single, 1-hydroxycyclohexyl phenyl ketone, benzoyl benzoic acid methyl ester, 4-benzoyl-4 ' -methylbenzoyl-diphenyl ketone, dimethyl-4-benzoyl ketone, dimethyl-thioketone, dimethyl thioketone, 2-thioxanthone, 2-dimethyl thioxanthone, 1-hydroxy-cyclohexyl-phenyl ketone, 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-propanone, 1- (9, 9-dibutyl-9H-fluoren-2-yl) -2-methyl-2- (4-morpholinyl) -1-propanone, and the like.

Among them, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropan-1-one, 2-benzyl-2- (dimethylamino) -1- (4-morpholinophenyl) -1-butanone, 4' -bis (diethylamino) benzophenone, and diethylthioxanthone are preferably used. From the viewpoints of sensitivity adjustment, water spotting inhibition, and development resistance improvement, it is further preferable to combine an α -aminoacetophenone initiator such as 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropane-1-one with a thioxanthone initiator such as diethylthioxanthone.

The total content of the α -aminoacetophenone initiator and the thioxanthone initiator in the case of using them is preferably, for example, 5 to 15% by mass relative to the total solid content of the color curable composition. If the ratio is not more than the upper limit value, sublimates in the production process are reduced, which is preferable. When the lower limit is not less than the above-mentioned limit, development resistance such as water spotting is improved.

In the present invention, among them, the photoinitiator preferably contains an oxime ester-based photoinitiator from the viewpoint of improving sensitivity. In addition, by using an oxime ester photoinitiator, it is easy to suppress the difference in-plane linewidth when forming a fine line pattern. In addition, by using an oxime ester photoinitiator, the residual film rate is increased, and the inhibition effect of water spot generation tends to be high.

Among these, the oxime ester photoinitiator is preferably an oxime ester photoinitiator having an aromatic ring, more preferably an oxime ester photoinitiator having a condensed ring including an aromatic ring, and even more preferably an oxime ester photoinitiator having a condensed ring including a benzene ring and a heterocyclic ring, from the viewpoint of reducing contamination of a colored curable composition and contamination of an apparatus due to decomposition products.

The oxime ester photoinitiator may be appropriately selected from oxime ester photoinitiators described in 1, 2-octanedione-1- [4- (phenylthio) -,2- (o-benzoyl oxime) ], ethanone, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -,1- (o-acetyl oxime), japanese patent application laid-open No. 2000-80068, japanese patent application laid-open No. 2001-233836, japanese patent application laid-open No. 2010-527339, japanese patent application laid-open No. 2010-527338, and Japanese patent application laid-open No. 2013-04153. As commercial products, irgacure OXE-01 having a diphenyl sulfide skeleton, adeka Arkls NCI-930, TR-PBG-3057, irgacure OXE-02 having a carbazole skeleton, adeka Arkls NCI-831, TR-PBG-304, TR-PBG-345, TR-PBG-365 having a fluorene skeleton, etc. can be used (Irgacure series is manufactured by BASF corporation, adeka Arkls series is manufactured by ADEKA corporation, TR series is manufactured by Hemsl powerful electronic new materials corporation). From the viewpoint of brightness, it is particularly preferable to use an oxime ester photoinitiator having a diphenyl sulfide skeleton or a fluorene skeleton. In addition, from the viewpoint of high sensitivity, an oxime ester photoinitiator having a carbazole skeleton is preferably used. From the viewpoints of sensitivity and brightness, it is preferable to use an oxime ester photoinitiator having a diphenyl sulfide skeleton in combination with an oxime ester photoinitiator having a fluorene skeleton. In addition, from the viewpoints of sensitivity and brightness, it is preferable to use an oxime ester photoinitiator having a diphenyl sulfide skeleton and an oxime ester photoinitiator having a carbazole skeleton in combination.

In addition, a photoinitiator having a tertiary amine structure may be used in combination with the oxime ester-based photoinitiator in order to suppress water spotting and to improve sensitivity. The reason for this is that the photoinitiator having a tertiary amine structure has a tertiary amine structure as an oxygen quencher in the molecule, and therefore, the radical generated by the initiator is less likely to be deactivated by oxygen, and the sensitivity can be improved. Examples of the commercially available photoinitiator having a tertiary amine structure include: 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (e.g., irgacure 907, manufactured by BASF), 2-benzyl-2- (dimethylamino) -1- (4-morpholinophenyl) -1-butanone (e.g., irgacure 369, manufactured by BASF), 4' -bis (diethylamino) benzophenone (e.g., hicure ABP, manufactured by Sichuan medicine), and the like.

In addition, the thioxanthone-based initiator may be combined with the oxime ester-based photoinitiator from the viewpoint of adjusting sensitivity, suppressing water spotting, and improving development resistance, and from the viewpoint of improving brightness and film residue ratio, the sensitivity is easily adjusted, the water spotting suppressing effect is high, and the development resistance is improved, 2 or more oxime ester-based photoinitiators may be combined with the thioxanthone-based initiator.

The content of the initiator in the colored curable composition is, for example, preferably 0.1 to 15 mass%, and more preferably 1 to 10 mass%, relative to the total solid content of the colored curable composition. If the content of the initiator is not less than the above-mentioned lower limit, curing proceeds sufficiently, and if the content of the initiator is not more than the above-mentioned upper limit, side reactions can be suppressed, and stability with time can be maintained.

< sensitizer >)

In the present invention, since the dye diffused in the system easily absorbs the light to be exposed and the generation of the radical from the initiator is easily lost, it is preferable to include a sensitizer in combination with the photoinitiator in order to compensate for this. Among them, a thiol sensitizer is preferably contained in view of good reactivity of the (meth) acrylic acid polymerization system, and more preferably, a thiol sensitizer is contained in combination with the oxime ester initiator.

Examples of the thiol sensitizer include: monofunctional thiol compounds having 1 thiol group and polyfunctional thiol compounds having 2 or more thiol groups.

Examples of the monofunctional thiol compound include: 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-5-methoxybenzothiazole, 2-mercapto-5-methoxybenzimidazole, 3-mercaptopropionic acid, methyl 3-mercaptopropionate, ethyl 3-mercaptopropionate, octyl 3-mercaptopropionate, and the like.

Examples of the polyfunctional thiol compound include: 1, 4-bis (3-mercaptobutyryloxy) butane, 1,3, 5-tris (3-mercaptobutoxyethyl) -1,3, 5-triazine-2, 4,6 (1H, 3H, 5H) -trione, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexa (3-mercaptopropionate), tetraethyleneglycol bis (3-mercaptopropionate), and the like.

In the colored curable composition of the present invention, the content of the sensitizer is, for example, 0.5 to 10% by mass based on the total solid content of the colored curable composition, from the viewpoint of the effect of improving curability. The content of the sensitizer is more preferably 1 to 6 mass%, and still more preferably 2 to 5 mass%, based on the total solid content of the colored curable composition.

The binder component (polymer, polymerizable compound, initiator, sensitizer if necessary) used in the colored curable composition of the present invention is preferably contained in a total amount of 35 to 97 mass%, more preferably 40 to 96 mass%, relative to the total amount of the solid components of the colored curable composition. When the lower limit is not less than the above, a colored layer excellent in hardness and adhesion to a substrate can be obtained. In addition, when the amount is equal to or less than the upper limit value, the developing property is excellent, and generation of micro wrinkles due to heat shrinkage is suppressed.

< 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 the components in the colored curable composition and can dissolve or disperse these components. The solvent may be used alone or in combination of 2 or more.

Specific examples of the solvent include: alcohol solvents such as methanol, ethanol, isopropanol, and methoxy alcohol; carbitol solvents such as methoxyethoxyethanol and ethoxyethoxyethanol; ester solvents such as ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, ethyl lactate, methyl hydroxypropionate, ethyl hydroxypropionate, n-butyl acetate, isobutyl acetate, n-butyl butyrate, and cyclohexyl acetate; ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone, and 2-heptanone; glycol ether acetate solvents such as methoxyethyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-1-butyl acetate, 3-methoxybutyl acetate, and ethoxyethyl acetate; carbitol acetate solvents such as methoxyethoxyethyl acetate, ethoxyethoxyethyl acetate, butyl Carbitol Acetate (BCA); diacetates such as propylene glycol diacetate and 1, 3-butanediol diacetate; glycol ether solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, dipropylene glycol dimethyl ether, and the like; aprotic amide solvents such as N, N-dimethylformamide, N-dimethylacetamide, and N-methylpyrrolidone; lactone solvents such as gamma-butyrolactone; cyclic ether solvents such as tetrahydrofuran; unsaturated hydrocarbon solvents such as benzene, toluene, xylene, and naphthalene; saturated hydrocarbon solvents such as N-heptane, N-hexane, and N-octane; organic solvents such as aromatic hydrocarbons including toluene and xylene. Among these solvents, glycol ether acetate solvents, carbitol acetate solvents, glycol ether solvents, and ester solvents are suitably used in terms of the solubility of other components. Among them, the solvent used in the present invention is preferably 1 or more selected from 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), 3-methoxy-3-methyl-1-butyl acetate, ethyl lactate, methyl 2-hydroxypropionate and 3-methoxybutyl acetate, from the viewpoints of solubility of other components and coating suitability.

In addition, from the viewpoints of developability, solvent resolubility, and the like, a mixed solvent containing 2 or more solvents may be used.

The solvent content may be appropriately set within a range where the colored layer can be formed with good precision. The amount of the solvent is preferably 55 to 95% by mass, and more preferably 65 to 88% by mass, based on the total amount of the colored curable composition containing the solvent. When the content of the solvent is within the above range, the coatability can be improved.

< dispersant >)

In the colored curable composition of the present invention, when the color material is dispersed, a dispersant may be further contained in terms of the color material dispersibility and the color material dispersion stability.

In the present invention, the dispersant may be appropriately selected from conventionally known dispersants and used. As the dispersant, for example, surfactants such as cationic, anionic, nonionic, amphoteric, silicone, and fluorine surfactants can be used. Among the surfactants, polymeric dispersants are preferred in terms of being uniformly and finely dispersible.

Examples of the polymer dispersant include: (co) polymers of unsaturated carboxylic acid esters such as polyacrylates; (partial) amine salts, (partial) ammonium salts, (partial) alkylamine salts of (co) polymers of unsaturated carboxylic acids such as polyacrylic acid; (co) polymers of hydroxyl group-containing unsaturated carboxylic acid esters such as hydroxyl group-containing polyacrylates, and modified products of these; polyurethanes; unsaturated polyamides; polysiloxanes; long chain polyaminoamide phosphates; polyethyleneimine derivatives (amides obtained by reaction of poly (lower alkylene imine) with polyesters containing free carboxyl groups, bases of these); polyallylamine derivatives (reaction products obtained by reacting polyallylamine with 1 or more compounds selected from 3 compounds including polyesters having free carboxyl groups, polyamides, or cocondensates of esters and amides (polyesteramides)), and the like.

The polymer dispersant may be, for example, a polymer dispersant having a nitrogen atom in the main chain or a side chain and an amine value, and may be a polymer dispersant containing a polymer having a repeating unit having a tertiary amine. Among them, a dispersant having at least 1 of a polymer having a structural unit represented by the following general formula (I) as described in japanese patent application laid-open publication No. 2016-224447, a block copolymer having a structural unit represented by the following general formula (I) as described in international publication No. 2016/104493, and a salt-type block copolymer can be used in view of the fact that the main chain skeleton is not easily thermally decomposed and has high heat resistance.

[ chemical formula 5]

(in the general formula (I), R ¹ Represents a hydrogen atom or a methyl group, A represents a divalent linking group, R ² R is R ³ Each independently represents a hydrogen atom, or a hydrocarbon group which may contain a hetero atom, R ² R is R ³ Can be bonded to each other to form a ring structure. )

The above symbols are described with reference to Japanese patent application laid-open No. 2016-224447.

The polymer dispersant may be, for example, one having an acid value and containing an acidic group in the main chain or side chain. Among them, for example, a nonaqueous dispersant which is a graft copolymer having at least one structural unit selected from the group consisting of structural units represented by the following general formula (I ') and structural units represented by the following general formula (I'), and a block portion having structural units represented by the following general formula (III) as described in japanese patent application laid-open No. 2015-107471 can be used because the main chain skeleton is not easily thermally decomposed and has high heat resistance.

[ chemical formula 6]

(in the general formula (I ') and the general formula (I'), L ¹ R is a direct bond or a divalent linking group ¹ Is a hydrogen atom or methyl group, R ² Is a hydrocarbon group, - [ CH (R) ⁶ )-CH(R ⁷ )-O] _x1 -R ⁸ Or- [ (CH) ₂ ) _y1 -O] _z1 -R ⁸ Represented monovalent radicals, R ⁶ R is R ⁷ Each independently is a hydrogen atom or a methyl group, R ⁸ Is hydrogen atom, alkyl, -CHO, -CH ₂ CHO、-CO-CH＝CH ₂ 、-CO-C(CH ₃ )＝CH ₂ or-CH ₂ COOR ⁹ Represented monovalent radicals, R ⁹ The hydrocarbon group may have a substituent, and is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. x1 represents an integer of 1 to 18, y1 represents an integer of 1 to 5, and z1 represents an integer of 1 to 18.

In the general formula (I'), X ⁺ Representing an organic cation.

In the general formula (II), L ² Represents a direct bond or a divalent linking group, R ³ The Polymer represents a Polymer chain having 1 or more kinds selected from the structural units represented by the following general formula (IV) and the structural units represented by the general formula (V).

In the general formula (III), R ⁴ Is a hydrogen atom or 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 "monovalent group represented by R ¹⁰ R is R ¹¹ Each independently is a hydrogen atom or a methyl group, R ¹² Is hydrogen atom, alkyl, -CHO, -CH ₂ CHO or-CH ₂ COOR ¹³ Represented monovalent radicals, R ¹² ' is a hydrocarbyl 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 Represented monovalent radicals, R ¹² "is C1-18 alkyl, R ¹³ The hydrocarbon group may have a substituent, and is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. x2 and x2' represent integers from 1 to 18, y2 and y2' represent integers from 1 to 5, and z2' represent integers from 1 to 18. ))

[ chemical formula 7]

(in the general formula (IV) and the general formula (V), R ¹⁴ Is a hydrogen atom or 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 Represented monovalent radicals, R ¹⁶ R is R ¹⁷ Each independently is a hydrogen atom or a methyl group, R ¹⁸ Is hydrogen atom, alkyl, -CHO, -CH ₂ CHO or-CH ₂ COOR ²¹ Represented monovalent radicals, 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 Represented monovalent radicals, R ²⁰ Is C1-18 alkyl, R ²¹ Is a hydrogen atom or an alkyl group having 1 to 5 carbon atomsThe hydrocarbon group may have a substituent.

m represents an integer of 1 to 5, and n' represent integers of 5 to 200. x3 and x4 represent integers of 1 to 18, y3 and y4 represent integers of 1 to 5, and z3 and z4 represent integers of 1 to 18. )

The above symbols are described with reference to Japanese patent application laid-open No. 2015-107471.

In the photocurable composition of the present invention, the content of the dispersant is appropriately selected depending on the type of the colorant to be used and further depending on the solid content concentration and the like in the photocurable composition described below.

The content of the dispersing agent in the photocurable composition of the present invention is not particularly limited as long as the colorant can be uniformly dispersed, and is preferably in the range of, for example, 1 to 40% by mass, more preferably 2 to 30% by mass, and even more preferably 3 to 25% by mass, relative to the total solid content of the photocurable composition. When the lower limit is not less than the above, the dispersibility and dispersion stability of the color material are excellent, and the storage stability of the color curable composition is further excellent. In addition, if the upper limit value is less than or equal to the above, the developability is good. In particular, in the case of forming a colored layer having a high color material concentration, the content of the dispersant is preferably in the range of, for example, 2 to 25 mass%, more preferably 3 to 20 mass%, relative to the total solid content of the colored curable composition. In the case of a salt-type block copolymer, the mass of the dispersant is the total mass of the block copolymer before salifying and 1 or more compounds selected from the general formulae (1) to (3).

< optional additive component >

Various additives may be contained in the colored curable composition as required.

Examples of the additive include: antioxidants, leveling agents, polymerization terminators, plasticizers, surfactants, defoamers, silane coupling agents, ultraviolet absorbers, adhesion promoters, and the like.

From the viewpoint of heat resistance, the colored curable composition of the present invention preferably further contains an antioxidant. The antioxidant may be appropriately selected from conventionally known antioxidants. Specific examples of the antioxidant include: hindered phenol antioxidants, amine antioxidants, phosphorus antioxidants, sulfur antioxidants, hydrazine antioxidants, and the like are preferably used from the viewpoint of heat resistance.

Further, specific examples of the surfactant and the plasticizer include those described in JP-A2013-029832.

In the colored curable composition of the present invention, the P/V ratio ((mass of the color material component in the composition)/(mass of the solid component other than the color material component in the composition)) is preferably 0.1 or more, more preferably 0.2 or more, and on the other hand, is preferably 0.6 or less, more preferably 0.5 or less, from the viewpoint of excellent display failure and manufacturing convenience, that is, excellent solvent resolubility, development residue, development adhesion, development resistance, water spot generation inhibiting effect, and the like.

Process for producing colored curable composition

The method for producing the colored curable composition of the present invention is not particularly limited, and it can be produced, for example, by mixing a color material, a polymer, a polymerizable compound, an initiator, a solvent, and various optional additives by a known mixing method.

In the case where the colored curable composition of the present invention contains a color material, a polymer, a polymerizable compound, an initiator, a dispersant, a solvent, and various optional additives, examples of the method for producing the resin composition include: (1) A method of preparing a color material dispersion by adding a color material and a dispersant to a solvent, and mixing a polymer, a polymerizable compound, an initiator, and various additive components as needed; (2) A method of simultaneously adding a color material, a dispersant, a polymer, a polymerizable compound, an initiator, and various optional additives to a solvent and mixing them; (3) A method in which a dispersant, a polymer, a polymerizable compound, an initiator, and various optional additives are added to a solvent, mixed, and then a color material is added to disperse the mixture; (4) A method of preparing a color material dispersion by adding a color material, a dispersant and a polymer to a solvent, and further adding a polymer, a solvent, a polymerizable compound, an initiator and various optional additives to the dispersion, and mixing the mixture; etc.

Among these methods, the methods (1) and (4) are preferable in that aggregation and uniform dispersion of the color material can be effectively prevented.

The method for preparing the color material dispersion liquid can be appropriately selected from conventionally known dispersion methods and used.

For example, the method for producing the color material dispersion liquid includes: preparing the dispersant; and dispersing the color material in a solvent in the presence of the dispersing agent. Co-dispersing more than 2 color materials in a solvent in the presence of the dispersing agent; after dispersing or co-dispersing 1 or more kinds of color materials, 2 or more kinds of color material dispersions may be mixed to obtain a color material dispersion.

In the case of dispersing the color material, the dispersion can be performed using a conventionally known dispersing machine.

Specific examples of the dispersing machine include: roller mills such as a double-roller mill, a three-roller mill and the like; ball mills such as ball mills and vibration ball mills, paint conditioners, continuous disk type bead mills, continuous ring type bead mills, and the like. Regarding preferable dispersion conditions of the bead mill, the bead diameter used is preferably 0.03 to 3.0mm, more preferably 0.05 to 2.0mm.

Specifically, examples thereof include: the pre-dispersion was performed by 2.0mm zirconia beads having a relatively large bead diameter, and the final dispersion was further performed by 0.1mm zirconia beads having a relatively small bead diameter. It is preferable that the dispersion is followed by filtration through a 0.5 to 2 μm filter.

In the case of using only a color material dissolved in the color curable composition as a color material other than the halogenated phthalocyanine color material of the present invention, a color material solution in which a color material is dissolved in a solvent may be used instead of the color material dispersion liquid containing the dispersant. The pattern including a "color material solution" in which a color material is dissolved in a solvent and a "color material dispersion" in which particles of a color material are dispersed in a solvent is sometimes referred to as "color material solution" in the present invention.

The colored curable composition of the present invention can form a colored layer in which precipitation of foreign matters is suppressed and contrast is improved, and can form a colored layer excellent in brightness by containing the halogenated phthalocyanine colorant of the present invention, and therefore is particularly suitable for color filter applications.

The colored curable composition of the present invention can be used for various applications requiring good contrast while suppressing precipitation of foreign matters, and can also be used for inkjet inks or printing inks.

III color filter

The color filter of the present invention comprises at least a transparent substrate and a colored layer provided on the transparent substrate, and at least one of the colored layers has a colored layer which is a cured product of the colored curable composition of the present invention.

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

< coloring 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 above-mentioned colored curable composition of the present invention.

The colored layer is usually formed in an opening of a light shielding portion on a transparent substrate described below, and is usually composed of a colored pattern of 3 colors or more.

The arrangement of the coloring layers is not particularly limited, and general arrangements such as stripe type, mosaic type, delta type, four-pixel arrangement type (japanese: 4-pixel arrangement type) and the like can be used. The width, area, etc. of the colored layer can be arbitrarily set.

The thickness of the colored layer is suitably controlled by adjusting the coating method, the solid content concentration, viscosity, etc. of the colored curable composition, and is preferably in the range of 1 to 5 μm in general.

The colored layer can be formed, for example, by the following method.

First, the colored curable composition of the present invention is applied to a transparent substrate described below by using a coating method 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, to form a wet coating film. Among them, spin coating and die coating are preferable.

Next, the wet coating film is dried using a heating plate, an oven, or the like, and then exposed to light through a mask having a predetermined pattern, whereby an alkali-soluble resin, a polyfunctional monomer, or the like is subjected to photopolymerization to produce a cured coating film. Examples of the light source used for exposure include: ultraviolet rays, electron beams, etc. of low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, etc. The exposure amount is appropriately adjusted according to the light source used, the thickness of the coating film, and the like.

In addition, a heat treatment may be performed after the exposure to promote the polymerization reaction. The heating conditions are appropriately selected depending on the blending ratio of the components in the colored curable composition to be used, the thickness of the coating film, and the like.

Then, a developing treatment is performed using a developer, and the unexposed portions are dissolved and removed, whereby a coating film is formed in a desired pattern. As the developer, a solution obtained by dissolving an alkali in water or a water-soluble solvent is generally used. A surfactant or the like may be added to the alkali solution in an appropriate amount. In addition, the development method may employ a general method.

After the development treatment, the developer is generally washed, and the cured coating film of the colored 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 according to the application of the coating film.

< shading part >)

The light shielding portions in the color filter of the present invention are formed in a pattern on a transparent substrate described below, and can be the same as those used as the light shielding portions in a general color filter.

The pattern shape of the light shielding portion is not particularly limited, and may be, for example, a stripe shape, a matrix shape, or the like. The light shielding portion may be a metal thin film of chromium or the like formed by a sputtering method, a vacuum 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 the resin layer containing light-shielding particles, there are a method of patterning by development using a photosensitive resist, a method of patterning by using an inkjet ink containing light-shielding particles, a method of thermally transferring a photosensitive resist, and the like.

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

< substrate >

As the substrate, a transparent substrate, a silicon substrate, a substrate having aluminum, silver/copper/palladium alloy thin films formed on a transparent substrate or a silicon substrate, or the like is used. On these substrates, a further color filter layer, a resin layer, transistors such as TFTs, circuits, and the like may be formed.

The transparent substrate used in the color filter of the present invention is not particularly limited as long as it is a base material transparent to visible light, and a transparent substrate used in a general color filter can be used. Specifically, examples thereof include: transparent rigid materials having no flexibility such as quartz glass, alkali-free glass, and synthetic quartz plates; or a transparent flexible material having flexibility such as a transparent resin film, an optical resin sheet, or a flexible glass.

The thickness of the transparent substrate is not particularly limited, and a transparent substrate of the order of 100 μm to 1mm, for example, can be used according to the application 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 be formed with, for example, a cover (i.e., a cover コ in japanese), a transparent electrode layer, an alignment film, a columnar spacer, and the like.

IV display device

The display device of the present invention is characterized by having the color filter of the present invention. In the present invention, the configuration of the display device is not particularly limited, and may 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, a liquid crystal display device is preferably selected in view of suppressing various display defects such as disorder of liquid crystal alignment due to electric characteristics of green pixels and afterimage phenomenon due to threshold variation of switches in a lateral electric field liquid crystal display device.

< liquid Crystal display device >)

The liquid crystal display device of the present invention is characterized by comprising the color filter of the present invention, an opposite substrate, and a liquid crystal layer formed between the color filter and the opposite substrate.

A liquid crystal display device according to the present invention will be described with reference to the drawings. Fig. 2 is a schematic diagram showing an example of the display device of the present invention, and is a schematic diagram showing an example of the liquid crystal display device. As illustrated in fig. 2, the liquid crystal display device 40 of the present invention includes a color filter 10, an opposite substrate 20 including a TFT array substrate and the like, and a liquid crystal layer 30 formed between the color filter 10 and the opposite substrate 20.

The liquid crystal display device of the present invention is not limited to the configuration shown in fig. 2, and a known configuration can be adopted as a liquid crystal display device in which a color filter is generally used.

The driving method of the liquid crystal display device of the present invention is not particularly limited, and a driving method commonly used for a liquid crystal display device can be employed. Examples of such a driving method include: TN system, IPS system, OCB system, MVA system, and the like. Any of these ways may be suitably used in the present invention.

The counter substrate may be appropriately selected and used according to the driving method of the liquid crystal display device of the present invention.

Further, as the liquid crystal constituting the liquid crystal layer, various liquid crystals having different dielectric anisotropies, and mixtures of these can be used according to the driving method or the like of the liquid crystal display device of the present invention.

As a method for forming the liquid crystal layer, a method commonly used as a method for manufacturing a liquid crystal cell can be used, and examples thereof include a vacuum injection method and a liquid crystal dropping method.

In the case of the vacuum injection method, for example, the liquid crystal layer can be formed as follows: a liquid crystal cell is previously manufactured using a color filter and a counter substrate, and is heated to form an isotropic liquid, and the liquid crystal is injected into the liquid crystal cell in a state of the isotropic liquid by capillary effect, and is sealed with an adhesive, thereby forming a liquid crystal layer. Thereafter, the liquid crystal cell is cooled slowly to room temperature, whereby the enclosed liquid crystal can be aligned.

In addition, in the liquid crystal dropping method, for example, the liquid crystal layer can be formed as follows: the liquid crystal layer is formed by applying a sealant to the peripheral edge of the color filter, heating the color filter to a temperature at which the liquid crystal becomes isotropic phase, dropping the liquid crystal in an isotropic liquid state using a dispenser or the like, and laminating the color filter and the counter substrate under reduced pressure and bonding them with the sealant. Thereafter, the liquid crystal cell is cooled slowly to room temperature, whereby the enclosed liquid crystal can be aligned.

< organic light emitting display device >)

The organic light-emitting display device of the present invention is characterized by comprising the color filter of 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 diagram showing another example of the display device of the present invention, and is a schematic diagram showing an example of an organic light emitting display device. As illustrated in fig. 3, the organic light emitting display device 100 of the present invention has a color filter 10 and an organic light emitter 80. An organic protective layer 50, an inorganic oxide film 60 may be provided between the color filter 10 and the organic light emitter 80.

Examples of the method for stacking the organic light-emitting body 80 include: a method of sequentially forming 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 on the upper surface of the color filter; and a method of bonding the organic light-emitting element 80 formed on the other substrate to the inorganic oxide film 60. 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 structures in the organic light-emitting body 80 can be suitably used as known ones. The organic light-emitting display device 100 thus manufactured can be applied to, for example, a passive drive type organic EL display or 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 a known configuration can be adopted as an organic light-emitting display device in which a color filter is generally used.

Examples

Hereinafter, the present invention will be specifically described with reference to examples. The present invention is not limited by these descriptions.

The halogenated phthalocyanine color material intermediate was analyzed by LC-MS (Agilent technology, quadrupolar LC/MS, agilent1260 Infinity).

Synthesis example 1 Synthesis of alkali-soluble resin A solution

A mixed solution of 40 parts by mass of benzyl methacrylate (BzMA), 15 parts by mass of Methyl Methacrylate (MMA), 25 parts by mass of methacrylic acid (MAA) and 3 parts by mass of Azobisisobutyronitrile (AIBN) was dropped into a polymerization vessel to which 150 parts by mass of Propylene Glycol Monomethyl Ether Acetate (PGMEA) was added at 100℃over 3 hours under a nitrogen stream. After completion of the dripping, the mixture was heated at 100℃for 3 hours to obtain a polymer solution. The weight average molecular weight of the polymer solution was 7000.

Next, 20 parts by mass of Glycidyl Methacrylate (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 ℃ for 10 hours, whereby the reaction of the carboxylic acid groups of the main chain methacrylic acid with the epoxy groups of the glycidyl methacrylate was performed. In the reaction, in order to prevent polymerization of glycidyl methacrylate, air was bubbled into the reaction solution. The reaction was traced by measuring the acid value of the solution. The alkali-soluble resin A obtained was obtained by introducing a side chain having an ethylenically unsaturated bond into a main chain formed by copolymerization of BzMA, MMA and MAA using GMA, and had an acid value of 74mgKOH/g and a weight average molecular weight of 12000. The solid content of the alkali-soluble resin a solution was 40 mass%.

Example 1

(1) Production of halogenated phthalocyanine color Material 1

5.0g (25.0 mmol) of tetrachlorophthalonitrile and 25ml of N, N-dimethylformamide were put into a 100ml flask and stirred at 40℃until dissolved. Next, 4.15g (25.0 mmol) of methyl 4- (hydroxymethyl) benzoate was charged, and stirred at 40℃until it was dissolved. Next, 5.18g (37.5 mmol) of potassium carbonate was charged, and the mixture was reacted at 100℃for 6 hours. After the completion of the reaction, potassium carbonate was removed by filtration, and the obtained reaction solution was distilled off from the solvent by an evaporator to dissolve the obtained solid in chloroform, followed by liquid separation treatment with pure water.

The separated organic layer was subjected to recrystallization in acetone to obtain intermediate 1-1.

Intermediate 1-1 was analyzed by LC-MS. The representative chemical formula of intermediate 1-1 is shown below.

[ chemical formula 8]

Intermediate 1-1

Into a 50ml flask, 15.97ml of acetone and 1 to 1.5.19 g (15.0 mmol) of intermediate were charged, and the mixture was stirred at 0 ℃. Then, 3.11g (22.5 mmol) of potassium carbonate was charged, and then, 2.49g (15.0 mmol) of ethyl 4-hydroxybenzoate was dissolved in 10g of acetone and was dropped over 2 hours while stirring at 0 ℃. Further, stirring was additionally carried out for 1 hour to terminate the reaction. After the completion of the reaction, potassium carbonate was removed by filtration, and the obtained reaction solution was distilled off from the solvent by an evaporator to dissolve the obtained solid in chloroform, followed by liquid separation treatment with pure water.

The separated organic layer was subjected to recrystallization in acetone to obtain intermediate 1-2.

Intermediate 1-2 was analyzed by LC-MS. Representative chemical formulas of intermediates 1-2 are shown below.

[ chemical formula 9]

Intermediate 1-2

A50 ml flask was charged with 1-2.94 g (8.00 mmol) of the intermediate and 19.70g of benzonitrile, followed by 0.64g (2.00 mmol) of zinc iodide, and the mixture was reacted at 150℃for 16 hours with stirring. After the reaction solution was cooled to room temperature, 20ml of a mixed solvent of water and methanol (3:7) was added thereto, and the resulting precipitate was recovered through a filter paper, and stirring in a beaker and filtration and washing were repeated a plurality of times with isopropyl alcohol.

The obtained product was dried to obtain a halogenated phthalocyanine color material 1. Representative chemical formulas are shown below.

[ chemical formula 10]

Color material 1

(2) Production of color material liquid G1

As a dispersant, a dispersant b (salt-type block copolymer) solution was prepared in the same manner as in the production of dispersant b of Synthesis example II-2 described in paragraph 0302 of International publication No. 2016/104493.

8.13 parts by mass of the above-mentioned dispersant b solution as a dispersant, 1.8 parts by mass of a halogenated phthalocyanine coloring material as a coloring material, 5.2 parts by mass of C.I. pigment yellow 138 (PY 138, trade name: chromofine Yellow 6206EC, manufactured by Dai Kagaku Co., ltd.) as a yellow coloring material, 14.63 parts by mass of the alkali-soluble resin A solution obtained in Synthesis example 1, 64.25 parts by mass of PGMEA, and 100 parts by mass of zirconia beads having a particle diameter of 2.0mm were put into a mayonnaise bottle, and were oscillated as a pre-break by a paint shaker (manufactured by light Tian Tiegong Co., ltd.) for 1 hour, next zirconia beads having a particle diameter of 2.0mm were taken out, 200 parts by mass of zirconia beads having a particle diameter of 0.1mm were added, and similarly as a main break, dispersed by a paint shaker for 4 hours, to obtain a coloring material liquid G1.

(3) Production of colored curable composition G1

The color material liquid G1.43 parts by mass obtained in the above (2), the alkali-soluble resin A solution obtained in Synthesis example 1 4.23 parts by mass, the polyfunctional monomer (trade name ARONIX M-403, manufactured by Toyama Synthesis Co., ltd.), 3.95 parts by mass, the photoinitiator (trade name TR-PBG-3057, manufactured by Hemsw powerful electronic New Material Co., ltd.) 0.50 parts by mass, the photoinitiator (trade name Adeka Arkls NCI-831, manufactured by ADEKA Co., ltd.) 0.50 parts by mass, the sensitizer (pentaerythritol tetrakis (3-mercaptobutyrate), trade name Karenz MT-PE1, manufactured by Showa electric Co., ltd.) 0.13 parts by mass, the fluorine-based surfactant (trade name MEGAFAC F559, manufactured by DIC Co., ltd.) 0.34 parts by mass, the silane coupling agent (trade name KBM503, manufactured by Shin-Etsu Silicone Co., ltd.) 0.34 parts by mass, the PGMEA26.24 parts by mass, and the Propylene Glycol Monomethyl Ether (PGME) 20.65 parts by mass were added to obtain the color curable composition G1.

(4) Formation of colored layer

The colored curable composition G1 obtained in the above (3) was applied onto a GLASS substrate of 100mm X100 mm (manufactured by NH TECHNO GLASS, inc., "NA 35") at a thickness of 0.7mm using a spin coater, and then dried at 80℃for 3 minutes using a heating plate, and irradiated with an ultra-high pressure mercury lamp at 60mJ/cm ² Further, the film was post-baked in a clean oven at 230℃for 30 minutes to adjust the film thickness to 2.5. Mu.m, thereby forming a colored layer G1.

Example 2

(1) Production of halogenated phthalocyanine color Material 2

5.0g (25.0 mmol) of tetrachlorophthalonitrile and 25ml of N, N-dimethylformamide were put into a 100ml flask and stirred at 40℃until dissolved. Next, 3.35g (25.0 mmol) of diethylene glycol monoethyl ether was charged, and stirred at 40℃until it was dissolved. Next, 5.18g (37.5 mmol) of potassium carbonate was charged, and the mixture was reacted at 100℃for 6 hours. After the completion of the reaction, potassium carbonate was removed by filtration, and the obtained reaction solution was distilled off from the solvent by an evaporator to dissolve the obtained solid in chloroform, followed by liquid separation treatment with pure water.

And purifying the separated organic layer through a silica gel column to obtain an intermediate 2-1.

Intermediate 2-1 was analyzed by LC-MS. The representative chemical formula of intermediate 2-1 is shown below.

[ chemical formula 11]

Intermediate 2-1

Into a 50ml flask, 2-1.29 g (20.0 mmol) of the intermediate and 17.0ml of acetone were charged, and stirring was performed at 0 ℃. Then, 4.15g (30.0 mmol) of potassium carbonate was charged, and then, 3.32g (20.0 mmol) of ethyl 4-hydroxybenzoate was dissolved in 10g of acetone and was dropped over 2 hours while stirring at 0 ℃. Further, stirring was additionally carried out for 1 hour to terminate the reaction. After the completion of the reaction, potassium carbonate was removed by filtration, and the obtained reaction solution was distilled off from the solvent by an evaporator to dissolve the obtained solid in chloroform, followed by liquid separation treatment with pure water.

The separated organic layer was subjected to recrystallization in acetone to obtain intermediate 2-2.

Intermediate 2-2 was analyzed by LC-MS. The representative chemical formula of intermediate 2-2 is shown below.

[ chemical formula 12]

Intermediate 2-2

A50 ml flask was charged with 2-2.68 g (8.00 mmol) of the intermediate and 16.66g of benzonitrile, followed by 0.64g (2.00 mmol) of zinc iodide, and the mixture was reacted at 150℃for 16 hours with stirring. After the reaction solution was cooled to room temperature, 20ml of a mixed solvent of water and methanol (3:7) was added thereto, and the resulting precipitate was recovered through a filter paper, and stirring in a beaker and filtration and washing were repeated a plurality of times with isopropyl alcohol.

The obtained product was dried to obtain a halogenated phthalocyanine color material 2. Representative chemical formulas are shown below.

[ chemical formula 13]

Color material 2

(2) Production of color material liquid G2

A color material liquid G2 was obtained in the same manner as in (2) of example 1, except that the halogenated phthalocyanine color material 2 obtained above was used in an equimolar amount instead of the halogenated phthalocyanine color material 1 in (2) of example 1.

(3) Production of colored curable composition G2

A color curable composition G2 was obtained in the same manner as in (3) of example 1 except that the above-described color material liquid G2 was used instead of the color material liquid G1 in (3) of example 1.

(4) Formation of colored layer

A colored layer G2 was obtained in the same manner as in (4) of example 1, except that the colored curable composition G2 was used instead of the colored curable composition G1 in (4) of example 1.

Example 3

(1) Production of halogenated phthalocyanine color material 3

5.0g (25.0 mmol) of tetrachlorophthalonitrile and 25ml of N, N-dimethylformamide were put into a 100ml flask and stirred at 40℃until dissolved. Next, 2.60g (25.0 mmol) of ethyl glycolate was charged, and stirred at 40℃until it was dissolved. Next, 5.18g (37.5 mmol) of potassium carbonate was charged, and the mixture was reacted at 100℃for 6 hours. After the completion of the reaction, potassium carbonate was removed by filtration, and the obtained reaction solution was distilled off from the solvent by an evaporator to dissolve the obtained solid in chloroform, followed by liquid separation treatment with pure water.

The separated organic layer was purified by a silica gel column to obtain intermediate 3-1.

Intermediate 3-1 was analyzed by LC-MS. The representative chemical formula of intermediate 3-1 is shown below.

[ chemical formula 14]

Intermediate 3-1

Into a 50ml flask, 3-1.68 g (20.0 mmol) of the intermediate and 18.4ml of acetone were charged, and stirring was performed at 0 ℃. Then, 4.15g (30.0 mmol) of potassium carbonate was charged, and then, 3.32g (20.0 mmol) of ethyl 4-hydroxybenzoate was dissolved in 10g of acetone and was dropped over 2 hours while stirring at 0 ℃. Further, stirring was additionally carried out for 1 hour to terminate the reaction. After the completion of the reaction, potassium carbonate was removed by filtration, and the obtained reaction solution was distilled off from the solvent by an evaporator to dissolve the obtained solid in chloroform, followed by liquid separation treatment with pure water.

The separated organic layer was subjected to recrystallization in acetone to obtain intermediate 3-2.

Intermediate 3-2 was analyzed by LC-MS. The representative chemical formula of intermediate 3-2 is shown below.

[ chemical formula 15]

Intermediate 3-2

A50 ml flask was charged with 3-2.44 g (8.00 mmol) of the intermediate and 17.2g of benzonitrile, followed by 0.64g (2.00 mmol) of zinc iodide, and the mixture was reacted at 150℃for 16 hours with stirring. After the reaction solution was cooled to room temperature, 20ml of a mixed solvent of water and methanol (3:7) was added thereto, and the resulting precipitate was recovered through a filter paper, and stirring in a beaker and filtration and washing were repeated a plurality of times with isopropyl alcohol.

The obtained product was dried to obtain a halogenated phthalocyanine color material 3. Representative chemical formulas are shown below.

[ chemical formula 16]

Color material 3

(2) Production of color material liquid G3

A color material liquid G3 was obtained in the same manner as in (2) of example 1, except that the halogenated phthalocyanine color material 3 obtained above was used in an equimolar amount in place of the halogenated phthalocyanine color material 1 in (2) of example 1.

(3) Production of colored curable composition G3

A color curable composition G3 was obtained in the same manner as in (3) of example 1 except that the above-described color material liquid G3 was used instead of the color material liquid G1 in (3) of example 1.

(4) Formation of colored layer

A colored layer G3 was obtained in the same manner as in (4) of example 1, except that the colored curable composition G3 was used instead of the colored curable composition G1 in (4) of example 1.

Example 4

(1) Production of halogenated phthalocyanine color Material 4

5.0g (25.0 mmol) of tetrachlorophthalonitrile and 25ml of N, N-dimethylformamide were put into a 100ml flask and stirred at 40℃until dissolved. Next, 4.31g (25.0 mmol) of ethyl trans-4-hydroxycyclobenzoate was charged, and stirred at 40℃until it was dissolved. Next, 5.18g (37.5 mmol) of potassium carbonate was charged, and the mixture was reacted at 100℃for 6 hours. After the completion of the reaction, potassium carbonate was removed by filtration, and the obtained reaction solution was distilled off from the solvent by an evaporator to dissolve the obtained solid in chloroform, followed by liquid separation treatment with pure water.

The separated organic layer was purified by a silica gel column to obtain intermediate 4-1.

Intermediate 4-1 was analyzed by LC-MS. The representative chemical formula of intermediate 4-1 is shown below.

[ chemical formula 17]

Intermediate 4-1

Into a 50ml flask, 25.1ml of acetone and 4-1.03 g (20.0 mmol) of the intermediate were charged, and the mixture was stirred at 0 ℃. Then, 4.15g (30.0 mmol) of potassium carbonate was charged, and then, 3.32g (20.0 mmol) of ethyl 4-hydroxybenzoate was dissolved in 10g of acetone and was dropped over 2 hours while stirring at 0 ℃. Further, stirring was additionally carried out for 1 hour to terminate the reaction. After the completion of the reaction, potassium carbonate was removed by filtration, and the obtained reaction solution was distilled off from the solvent by an evaporator to dissolve the obtained solid in chloroform, followed by liquid separation treatment with pure water.

The separated organic layer was subjected to recrystallization in acetone to obtain intermediate 4-2.

Intermediate 4-2 was analyzed by LC-MS. The representative chemical formula of intermediate 4-2 is shown below.

[ chemical formula 18]

Intermediate 4-2

A50 ml flask was charged with 4-2.99 g (8.00 mmol) of the intermediate and 19.9g of benzonitrile, followed by 0.64g (2.00 mmol) of zinc iodide, and the mixture was reacted at 150℃for 16 hours with stirring. After the reaction solution was cooled to room temperature, 20ml of a mixed solvent of water and methanol (3:7) was added thereto, and the resulting precipitate was recovered through a filter paper, and stirring in a beaker and filtration and washing were repeated a plurality of times with isopropyl alcohol.

The obtained product was dried to obtain a halogenated phthalocyanine color material 4. Representative chemical formulas are shown below.

[ chemical formula 19]

Color material 4

(2) Production of color Material liquid G4

A color material liquid G4 was obtained in the same manner as in (2) of example 1, except that the halogenated phthalocyanine color material 4 obtained above was used in an equimolar amount in place of the halogenated phthalocyanine color material 1 in (2) of example 1.

(3) Production of colored curable composition G4

A color curable composition G4 was obtained in the same manner as in (3) of example 1 except that the above-described color material liquid G4 was used instead of the color material liquid G1 in (3) of example 1.

(4) Formation of colored layer

A colored layer G4 was obtained in the same manner as in (4) of example 1, except that the colored curable composition G4 was used instead of the colored curable composition G1 in (4) of example 1.

Comparative example 1

(1) Production of comparative halogenated phthalocyanine color Material 1

5.0g (25.0 mmol) of tetrachlorophthalonitrile and 25ml of N, N-dimethylformamide were put into a 100ml flask and stirred at 40℃until dissolved. Next, 8.31g (50.0 mmol) of ethyl 4-hydroxybenzoate was charged, and stirred at 40℃until it was dissolved. Next, 5.18g (37.5 mmol) of potassium carbonate was charged, and the mixture was reacted at 0℃for 3 hours. After the completion of the reaction, potassium carbonate was removed by filtration, and the obtained reaction solution was distilled off from the solvent by an evaporator to dissolve the obtained solid in chloroform, followed by liquid separation treatment with pure water.

The organic layer after the separation was recrystallized in acetone to obtain comparative intermediate 1.

Comparative intermediate 1 was analyzed by LC-MS. Representative chemical formulas of comparative intermediate 1 are shown below.

[ chemical formula 20]

Comparative intermediate 1

A50 ml flask was charged with 3.94g (8.00 mmol) of the comparative intermediate and 19.7g of benzonitrile, followed by 0.64g (2.00 mmol) of zinc iodide, and the reaction was carried out at 150℃for 16 hours with stirring. After the reaction solution was cooled to room temperature, 20ml of a mixed solvent of water and methanol (3:7) was added thereto, and the resulting precipitate was recovered through a filter paper, and stirring in a beaker and filtration and washing were repeated a plurality of times with isopropyl alcohol.

The obtained product was dried to obtain a comparative halogenated phthalocyanine color material 1.

Representative chemical formulas of the comparative halogenated phthalocyanine color material 1 are shown below.

[ chemical formula 21]

(2) Production of comparative color material liquid CG1

A comparative color material liquid CG1 was obtained in the same manner as in (2) of example 1, except that the comparative halogenated phthalocyanine color material 1 obtained above was used in an equimolar amount instead of the halogenated phthalocyanine color material 1 in (2) of example 1.

(3) Comparative production of colored curable composition CG1

Comparative color curable composition CG1 was obtained in the same manner as in (3) of example 1 except that the above comparative color material liquid CG1 was used instead of color material liquid G1 in (3) of example 1.

(4) Formation of colored layer

A colored layer CG1 was obtained in the same manner as in (4) of example 1, except that the comparative colored curable composition CG1 was used instead of the colored curable composition G1 in (4) of example 1.

Comparative example 2

(1) Production of comparative halogenated phthalocyanine color Material 2

5.0g (25.0 mmol) of tetrachlorophthalonitrile and 25ml of N, N-dimethylformamide were put into a 100ml flask and stirred at 40℃until dissolved. Next, 4.40g (50.0 mmol) of 1-pentanol was charged, and stirring was performed at 40℃until it was dissolved. Next, 5.18g (37.5 mmol) of potassium carbonate was charged, and the mixture was reacted at 100℃for 15 hours. After the completion of the reaction, potassium carbonate was removed by filtration, and the obtained reaction solution was distilled off from the solvent by an evaporator to dissolve the obtained solid in chloroform, followed by liquid separation treatment with pure water.

The separated organic layer was purified by a silica gel column to obtain comparative intermediate 2.

Comparative intermediate 2 was analyzed by LC-MS. Representative chemical formulas of comparative intermediate 2 are shown below.

[ chemical formula 22]

Comparative intermediate 2

A50 ml flask was charged with 2.66 g (10.0 mmol) of the comparative intermediate and 18.3g of benzonitrile, followed by 0.80g (2.50 mmol) of zinc iodide, and the mixture was reacted at 150℃for 16 hours with stirring. After the reaction solution was cooled to room temperature, 20ml of a mixed solvent of water and methanol (3:7) was added thereto, and the resulting precipitate was recovered through a filter paper, and stirring in a beaker and filtration and washing were repeated a plurality of times with isopropyl alcohol.

The obtained product was dried to obtain a comparative halogenated phthalocyanine color material 2.

Representative chemical formulas of the comparative halogenated phthalocyanine color material 2 are shown below.

[ chemical formula 23]

(2) Production of comparative color material liquid CG2

A comparative color material liquid CG2 was obtained in the same manner as in (2) of example 1, except that the comparative halogenated phthalocyanine color material 2 obtained above was used in an equimolar amount instead of the halogenated phthalocyanine color material 1 in (2) of example 1.

(3) Comparative production of colored curable composition CG2

Comparative color curable composition CG2 was obtained in the same manner as in (3) of example 1 except that the above comparative color material liquid CG2 was used instead of color material liquid G1 in (3) of example 1.

(4) Formation of colored layer

A colored layer CG2 was obtained in the same manner as in (4) of example 1, except that the comparative colored curable composition CG2 was used instead of the colored curable composition G1 in (4) of example 1.

Comparative example 3

(1) Production of comparative halogenated phthalocyanine color material 3

Into a 50ml flask, 2.40g (12.0 mmol) of tetrafluoro-phthalonitrile and 12.0g of benzonitrile were charged, and then 0.96g (3.00 mmol) of zinc iodide was charged, followed by reaction for 16 hours at 150℃with stirring. After the reaction solution was cooled to room temperature, 20ml of a mixed solvent of water and methanol (3:7) was added thereto, and the resulting precipitate was recovered through a filter paper, and stirring in a beaker and filtration and washing were repeated a plurality of times with isopropyl alcohol.

The obtained product was dried to obtain a comparative halogenated phthalocyanine color material 3. Representative chemical formulas of the comparative halogenated phthalocyanine color material 3 are shown below.

[ chemical formula 24]

(2) Production of comparative color material liquid CG3

A comparative color material liquid CG3 was obtained in the same manner as in (2) of example 1, except that the comparative halogenated phthalocyanine color material 3 obtained above was used in an equimolar amount instead of the halogenated phthalocyanine color material 1 in (2) of example 1.

(3) Comparative production of colored curable composition CG3

Comparative color curable composition CG3 was obtained in the same manner as in (3) of example 1 except that the above comparative color material liquid CG3 was used instead of color material liquid G1 in (3) of example 1.

(4) Formation of colored layer

A colored layer CG3 was obtained in the same manner as in (4) of example 1, except that the comparative colored curable composition CG3 was used instead of the colored curable composition G1 in (4) of example 1.

Comparative example 4

(1) Production of comparative halogenated phthalocyanine color Material 4

5.0g (25.0 mmol) of tetrachlorophthalonitrile and 25ml of N, N-dimethylformamide were put into a 100ml flask and stirred at 40℃until dissolved. Next, 8.31g (50.0 mmol) of methyl 4- (hydroxymethyl) benzoate was charged, and stirred at 40℃until it was dissolved. Next, 5.18g (37.5 mmol) of potassium carbonate was charged, and the mixture was reacted at 100℃for 15 hours. After the completion of the reaction, potassium carbonate was removed by filtration, and the obtained reaction solution was distilled off from the solvent by an evaporator to dissolve the obtained solid in chloroform, followed by liquid separation treatment with pure water.

The separated organic layer was purified by a silica gel column to obtain comparative intermediate 4.

Comparative intermediate 4 was analyzed by LC-MS. Representative chemical formulas of comparative intermediate 4 are shown below.

[ chemical formula 25]

Comparative intermediate 4

The obtained product was dried to obtain a comparative halogenated phthalocyanine color material 4.

Representative chemical formulas of the comparative halogenated phthalocyanine color material 4 are shown below.

[ chemical formula 26]

(2) Production of comparative color Material liquid CG4

A comparative color material liquid CG4 was obtained in the same manner as in (2) of example 1, except that the comparative halogenated phthalocyanine color material 4 obtained above was used in an equimolar amount instead of the halogenated phthalocyanine color material 1 in (2) of example 1.

(3) Comparative production of colored curable composition CG4

Comparative color curable composition CG4 was obtained in the same manner as in (3) of example 1 except that the above comparative color material liquid CG4 was used instead of color material liquid G1 in (3) of example 1.

(4) Formation of colored layer

A colored layer CG4 was obtained in the same manner as in (4) of example 1, except that the comparative colored curable composition CG4 was used instead of the colored curable composition G1 in (4) of example 1.

Comparative example 5

(1) Production of comparative halogenated phthalocyanine color Material 5

Into a 100ml flask, 6.0g (30.0 mmol) of tetrachlorophthalonitrile and 30ml of N, N-dimethylformamide were charged, and stirred at 40℃until dissolved. Next, 8.05g (60.0 mmol) of diethylene glycol monoethyl ether was charged, and stirred at 40℃until it was dissolved. Next, 6.22g (45.0 mmol) of potassium carbonate was charged, and the mixture was reacted at 100℃for 15 hours. After the completion of the reaction, potassium carbonate was removed by filtration, and the obtained reaction solution was distilled off from the solvent by an evaporator to dissolve the obtained solid in chloroform, followed by liquid separation treatment with pure water.

The separated organic layer was purified by a silica gel column to obtain comparative intermediate 5.

Comparative intermediate 5 was analyzed by LC-MS. Representative chemical formulas of the comparative intermediates are shown below.

[ chemical formula 27]

Comparative intermediate 5

A50 ml flask was charged with 5.28 g (10.00 mmol) of the comparative intermediate and 17.0g of benzonitrile, followed by 0.80g (2.50 mmol) of zinc iodide, and the mixture was reacted at 150℃for 16 hours with stirring. After the reaction solution was cooled to room temperature, 20ml of a mixed solvent of water and methanol (3:7) was added thereto, and the resulting precipitate was recovered through a filter paper, and stirring in a beaker and filtration and washing were repeated a plurality of times with isopropyl alcohol.

The obtained product was dried to obtain a comparative halogenated phthalocyanine color material 5.

Representative chemical formulas of the comparative halogenated phthalocyanine color material 5 are shown below.

[ chemical formula 28]

(2) Production of comparative color Material liquid CG5

A comparative color material liquid CG5 was obtained in the same manner as in (2) of example 1, except that the comparative halogenated phthalocyanine color material 5 obtained above was used in an equimolar amount instead of the halogenated phthalocyanine color material 1 in (2) of example 1.

(3) Comparative production of colored curable composition CG5

Comparative color curable composition CG5 was obtained in the same manner as in (3) of example 1 except that the above comparative color material liquid CG5 was used instead of color material liquid G1 in (3) of example 1.

(4) Formation of colored layer

A colored layer CG5 was obtained in the same manner as in (4) of example 1, except that the comparative colored curable composition CG5 was used instead of the colored curable composition G1 in (4) of example 1.

Comparative example 6

(1) Production of comparative halogenated phthalocyanine color Material 6

5.0g (25.0 mmol) of tetrachlorophthalonitrile and 25ml of N, N-dimethylformamide were put into a 100ml flask and stirred at 40℃until dissolved. Next, 5.21g (50.0 mmol) of ethyl glycolate was charged, and stirred at 40℃until it was dissolved. Next, 5.18g (37.5 mmol) of potassium carbonate was charged, and the mixture was reacted at 100℃for 15 hours. After the completion of the reaction, potassium carbonate was removed by filtration, and the obtained reaction solution was distilled off from the solvent by an evaporator to dissolve the obtained solid in chloroform, followed by liquid separation treatment with pure water.

The separated organic layer was purified by a silica gel column to obtain comparative intermediate 6.

Comparative intermediate 6 was analyzed by LC-MS. Representative chemical formulas of comparative intermediate 6 are shown below.

[ chemical formula 29]

Comparative intermediate 6

A50 ml flask was charged with 3.68g (10.00 mmol) of the comparative intermediate and 18.4g of benzonitrile, followed by 0.80g (2.50 mmol) of zinc iodide, and the mixture was reacted at 150℃for 16 hours with stirring. After the reaction solution was cooled to room temperature, 20ml of a mixed solvent of water and methanol (3:7) was added thereto, and the resulting precipitate was recovered through a filter paper, and stirring in a beaker and filtration and washing were repeated a plurality of times with isopropyl alcohol.

The obtained product was dried to obtain a comparative halogenated phthalocyanine color material 6.

Representative chemical formulas of the comparative halogenated phthalocyanine color material 6 are shown below.

[ chemical formula 30]

(2) Production of comparative color Material liquid CG6

A comparative color material liquid CG6 was obtained in the same manner as in (2) of example 1, except that the comparative halogenated phthalocyanine color material 6 obtained above was used in an equimolar amount instead of the halogenated phthalocyanine color material 1 in (2) of example 1.

(3) Comparative production of colored curable composition CG6

Comparative color curable composition CG6 was obtained in the same manner as in (3) of example 1 except that the above comparative color material liquid CG6 was used instead of color material liquid G1 in (3) of example 1.

(4) Formation of colored layer

A colored layer CG6 was obtained in the same manner as in (4) of example 1, except that the comparative colored curable composition CG6 was used instead of the colored curable composition G1 in (4) of example 1.

Comparative example 7

(1) Production of comparative halogenated phthalocyanine color Material 7

5.0g (25.0 mmol) of tetrachlorophthalonitrile and 25ml of N, N-dimethylformamide were put into a 100ml flask and stirred at 40℃until dissolved. Next, 8.61g (50.0 mmol) of methyl trans-4-hydroxycyclohexacarboxylate was charged, and stirred at 40℃until it was dissolved. Next, 5.18g (37.5 mmol) of potassium carbonate was charged, and the mixture was reacted at 100℃for 15 hours. After the completion of the reaction, potassium carbonate was removed by filtration, and the obtained reaction solution was distilled off from the solvent by an evaporator to dissolve the obtained solid in chloroform, followed by liquid separation treatment with pure water.

The separated organic layer was purified by a silica gel column to obtain comparative intermediate 7.

Comparative intermediate 7 was analyzed by LC-MS. Representative chemical formulas of comparative intermediate 7 are shown below.

[ chemical formula 31]

Comparative intermediate 7

A50 ml flask was charged with 7.68 g (10.00 mmol) of the comparative intermediate and 18.4g of benzonitrile, followed by 0.80g (2.50 mmol) of zinc iodide, and the mixture was reacted at 150℃for 16 hours with stirring. After the reaction solution was cooled to room temperature, 20ml of a mixed solvent of water and methanol (3:7) was added thereto, and the resulting precipitate was recovered through a filter paper, and stirring in a beaker and filtration and washing were repeated a plurality of times with isopropyl alcohol.

The obtained product was dried to obtain a comparative halogenated phthalocyanine color material 7.

Representative chemical formulas of the comparative halogenated phthalocyanine color material 7 are shown below.

[ chemical formula 32]

(2) Production of comparative color Material liquid CG7

A comparative color material liquid CG7 was obtained in the same manner as in (2) of example 1, except that the comparative halogenated phthalocyanine color material 7 obtained above was used in an equimolar amount instead of the halogenated phthalocyanine color material 1 in (2) of example 1.

(3) Comparative production of colored curable composition CG7

Comparative color curable composition CG7 was obtained in the same manner as in (3) of example 1 except that the above comparative color material liquid CG7 was used instead of color material liquid G1 in (3) of example 1.

(4) Formation of colored layer

A colored layer CG7 was obtained in the same manner as in (4) of example 1, except that the comparative colored curable composition CG7 was used instead of the colored curable composition G1 in (4) of example 1.

[ evaluation method ]

(1) Evaluation of solubility of colored curable composition

Immediately after the preparation of the colored curable composition and after the preparation, the composition was allowed to stand at 25℃and 50% humidity for 2 weeks, and then the presence or absence of insoluble matters was visually observed.

(evaluation criterion)

And (2) the following steps: without insoluble matter

X: has insoluble matter

(2) Evaluation of colored layer

The colored layer was dried during formation, the post-exposure cured film (pre-heating cured film) and the colored layer (post-heating cured film) were subjected to deposition of foreign matters and evaluation of contrast, respectively.

< precipitation of foreign matter >

The colored layer was dried and the post-exposure cured film (pre-heating cured film) and the colored layer (post-heating cured film) were observed by light microscopy at 200 x reflection, and evaluated according to the following evaluation criteria.

(evaluation criterion for precipitation of foreign substance)

A: no precipitate was observed in the 200-fold reflected light observation with an optical microscope.

B: in the observation with an optical microscope under 200-fold reflected light, 10 or less fine precipitates smaller than 1 μm were observed per 1mm square region.

C: in the optical microscope 200-fold reflection light observation, more than 10 fine precipitates smaller than 1 μm were observed per 1mm square region, and/or 10 or less precipitates of 1 μm or more were observed per 1mm square region.

D: in the observation with an optical microscope under 200-fold reflected light, more than 10 precipitates of 1 μm or more were observed per 1mm square region.

Contrast ratio

For each colored layer (cured film before and after the heating step), contrast was measured using a contrast measuring device CT-1B manufactured by osaka electric and a microscopic spectroscopic measuring device OSP-SP200 manufactured by olynbas, with a blank sample set at 18000.

(contrast evaluation reference)

A: contrast exceeds 10000

B: contrast is 8000-10000

C: contrast is less than 8000

D: cannot be measured (data is unreliable due to many foreign matters)

TABLE 1

Results summarization

With respect to the halogenated phthalocyanine color materials of comparative examples 1 to 3, which correspond to the conventional halogenated phthalocyanine color materials, foreign matters were deposited on the cured film after the heating step, and the contrast was poor. Regarding the halogenated phthalocyanine color materials of comparative examples 2 and 3, the dissolution stability of the composition was also poor because foreign matter was precipitated from the cured film after drying and exposure.

In the halogenated phthalocyanine color materials of comparative examples 4 to 7, foreign matters were deposited on the cured film after the heating step, and the contrast was poor. Regarding the halogenated phthalocyanine color materials of comparative examples 5 and 6, foreign matters were precipitated from the cured film after drying and exposure.

In contrast, in the halogenated phthalocyanine color materials of examples 1 to 4, which are the halogenated phthalocyanine color materials of the present invention, no foreign matter was deposited in the cured film after the heating step, and the contrast was good.

Description of the reference numerals

1 transparent substrate

2 shading part

3 coloring layer

10 color filter

20 opposite 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 luminescent layer

75 electron injection layer

76 cathode

80 organic light-emitting body

100 organic light emitting display device

Claims

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

general formula (VI)(1) Wherein X is ¹ ～X ¹⁶ Each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, a substituted or unsubstituted hydrocarbon group having 1 to 6 carbon atoms, or a monovalent group represented by the following general formula (2),

X ¹ ～X ¹⁶ at least one of (A) is a fluorine atom, X ¹ ～X ¹⁶ At least one of them is a monovalent group represented by the following general formulae (2-1) to (2-5), X ¹ ～X ¹⁶ At least one of them is a monovalent group represented by the following general formula (2-6);

general formula (2): * -O-R ^P

General formula (2-1): * -O-R ^L1 -R ^a

General formula (2-2): * -O- (R) ^L2 -O) _n -R ^b

General formula (2-3): * -O-R ^L2 -COO-R ^b

General formula (2-4): * -O-R ^L2 -OCO-R ^b

General formula (2-5): * -O-R ^c

General formula (2-6): * -O-R ^a

In the general formulae (2) and (2-1) to (2-6),

R ^P represents a substituted or unsubstituted straight-chain or branched aliphatic hydrocarbon group having 1 to 6 carbon atoms, a substituted or unsubstituted alicyclic hydrocarbon group having 5 to 14 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 14 carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 14 ring-forming atoms, -R ^L1 -R ^a 、-(R ^L2 -O) _n -R ^b 、-R ^L2 -COO-R ^b or-R ^L2 -OCO-R ^b ，R ^L1 Represents an aliphatic hydrocarbon group having 1 to 6 carbon atoms or a-CO-group, R ^L2 Each independently represents an aliphatic hydrocarbon group having 1 to 6 carbon atoms, R ^a Represents a substituted or unsubstituted aromatic hydrocarbon group having 6 to 14 carbon atoms, R ^b Represents a hydrogen atom, a substituted or unsubstituted straight-chain or branched aliphatic hydrocarbon group having 1 to 6 carbon atoms, a substituted or unsubstituted alicyclic hydrocarbon group having 5 to 14 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 14 carbon atoms, orA heterocyclic group having 5 to 14 ring members and R ^c Represents a substituted or unsubstituted alicyclic hydrocarbon group having 5 to 14 carbon atoms; n represents an integer of 1 to 5; * Represents a bonding position to the phthalocyanine skeleton.

2. A colored curable composition comprising a color material, a polymer, a polymerizable compound, an initiator, and a solvent, wherein the color material comprises the halogenated phthalocyanine color material according to claim 1.

3. The colored curable composition according to claim 2, further comprising a sensitizer.

4. A colored curable composition according to claim 2 or 3, wherein the initiator comprises an oxime ester-based photoinitiator.

5. The colored curable composition according to any one of claims 2 to 4, further comprising a yellow color material.

6. A color filter comprising at least 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 2 to 5.

7. A display device having the color filter of claim 6.