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

Abstract

The present application provides a halogenated phthalocyanine color material capable of forming a colored layer in which the deposition of foreign matter is inhibited and the contrast is improved. The halogenated phthalocyanine color material of the present application is represented by the following general formula (1). [Chemical Formula 1] (Each symbol of the general formula (1) is as described in the specification.)

Description

TECHNICAL FIELD

[0001] The present application relates to a halogenated phthalocyanine color material, a colored curable composition, a color filter, and a display device. BACKGROUND

[0002] In recent years, with the development of personal computers, particularly portable personal computers, the demand for liquid crystal displays is increasing. The popularity of mobile displays (portable telephones, smartphones, tablet PCs (Personal Computers)) is also increasing, and the market for liquid crystal displays is expanding. In addition, recently, organic light emitting display devices such as organic EL (Electroluminescence) displays, which have high visibility due to self-emission, are also attracting attention as next-generation image display devices. In terms of the performance of these image display devices, there is a strong desire to improve the contrast and color reproducibility, i.e., further high image quality and reduction in power consumption.

[0003] A color filter is used in these liquid crystal display devices or organic light emitting display devices. For example, with respect to the formation of a color image of a liquid crystal display device, light that has passed through the color filter is directly colored into the color of each pixel that constitutes the color filter, and the light of these colors is synthesized to form a color image. As a light source at this time, in addition to the conventional cold cathode tube, an organic light emitting element that emits white light, an inorganic light emitting element that emits white light are sometimes used. In addition, in an organic light emitting display device, a color filter is used to perform color adjustment and the like.

[0004] Therefore, in color filters, there is a growing demand for high luminance, high contrast, and improved color reproducibility.

[0005] Here, a color filter generally has a transparent substrate, a colored layer that is formed on the transparent substrate and includes a colored pattern of red, green, and blue three primary colors, and a light shielding portion that is formed on the transparent substrate in a manner of dividing each colored pattern.

[0006] As a method of forming pixels in a color filter, from the viewpoints of light splitting characteristics, durability, pattern shape, and precision, and the like, a pigment dispersion method that has excellent average characteristics is most widely used.

[0007] In a color filter having pixels formed using a pigment dispersion method, there is a problem that the light transmittance of the color filter becomes small or the contrast becomes low due to pigment particles.

[0008] Therefore, attempts have been made to use a colored composition that uses a dye that does not form particles to achieve a color filter in which the luminance and contrast are improved.

[0009] However, dyes generally have poor heat resistance, solvent resistance, and solubility in solvents, and are difficult to put into practical use. For green colored layers, research has been conducted on using a specific phthalocyanine-based dye as a dye (see, for example, Patent Documents 1 to 3).

[0010] Prior Art Documents

[0011] Patent Documents

[0012] Patent Document 1: Japanese Patent Application Publication No. 2009-051896

[0013] Patent Document 2: Japanese Patent Application Publication No. 2014-125460

[0014] Patent Document 3: Japanese Patent No. 2020-42263 SUMMARY

[0015] PROBLEMS TO BE SOLVED BY THE INVENTION

[0016] However, it was found that in the colored resin compositions described in the above Patent Documents 1 to 3, a coagulum derived from a color material (hereinafter referred to as a foreign matter) is precipitated in the obtained colored layer. Patent Document 3 describes an object to provide a colored resin composition capable of forming a pattern having a brightness sufficient for practical use and in which the generation of foreign matters is suppressed. However, in the technology of this colored resin composition, there is also a problem that foreign matters are easily precipitated after a heat treatment (after a post-baking process), and the contrast is poor, as shown in the following Comparative Example.

[0017] The present application was made in view of the above actual situation, and an object thereof is to provide a halogenated phthalocyanine color material capable of forming a colored layer in which the precipitation of foreign matters is suppressed and the contrast is improved, and a colored curable composition. In addition, an object of the present application is to provide a color filter and a display device formed using the colored curable composition.

[0018] MEANS FOR SOLVING THE PROBLEM

[0019] The halogenated phthalocyanine color material of the present application is a halogenated phthalocyanine color material represented by the following General Formula (1).

[0020] [Chemical Formula 1]

[0021]

[0022] [In General Formula (1), X 1 ~X 16 independently represent 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),

[0023] X 1 ~X16 At least one of them is a fluorine atom, X 1 ~X 16 At least one of them is a monovalent group represented by the following general formulas (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).

[0024] General formula (2): *-OR P

[0025] General formula (2-1): *-OR L1 -R a

[0026] General formula (2-2): *-O-(R L2 -O) n -R b

[0027] General formula (2-3): *-OR L2 -COO-R b

[0028] General formula (2-4): *-OR L2 -OCO-R b

[0029] General formula (2-5): *-OR c

[0030] General formula (2-6): *-OR a

[0031] (in general formulas (2) and (2-1) to (2-6),

[0032] R P This refers to a straight-chain or branched aliphatic hydrocarbon group with 1 to 6 carbon atoms (substituted or unsubstituted), an alicyclic hydrocarbon group with 5 to 14 carbon atoms (substituted or unsubstituted), an aromatic hydrocarbon group with 6 to 14 carbon atoms (substituted or unsubstituted), a heterocyclic group with 5 to 14 cyclic atoms (substituted or unsubstituted), or -R. L1 -R a 、-(R L2 -O) n -R b -R L2 -COO-R b , or -R L2 -OCO-R b R L1 R represents an aliphatic hydrocarbon group or -CO- group with 1 to 6 carbon atoms. L2 Each of the following groups independently represents an aliphatic hydrocarbon group having 1 to 6 carbon atoms: R arepresents a substituted or unsubstituted aromatic hydrocarbon group having 6 to 14 carbon atoms, R b represents a hydrogen atom, a substituted or unsubstituted 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 a phthalocyanine skeleton.

[0033] The colored curable composition of the present application 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 application.

[0034] The color filter of the present application is characterized by comprising at least a transparent substrate, and a colored layer provided on the transparent substrate, at least one of the colored layers being a colored layer that is a cured product of the colored curable composition of the present application.

[0035] The present application provides a display device characterized by comprising the color filter of the present application.

[0036] Effects of the Invention

[0037] According to the present application, it is possible to provide a halogenated phthalocyanine color material capable of forming a colored layer in which the precipitation of foreign matter is suppressed and the contrast is improved, a colored curable composition capable of forming a colored layer in which the contrast is improved, using the halogenated phthalocyanine color material, a color filter using the colored curable composition, and a display device using the color filter. BRIEF DESCRIPTION OF DRAWINGS

[0038] Figure 1 is a schematic diagram showing an example of the color filter of the present application.

[0039] Figure 2 is a schematic diagram showing an example of the display device of the present application.

[0040] Figure 3 is a schematic diagram showing another example of the display device of the present application. DETAILED DESCRIPTION

[0041] Hereinafter, the halogenated phthalocyanine color material, the colored curable composition, the color filter, and the display device of the present application will be described in detail in turn.

[0042] Note that, in the present application, light includes electromagnetic waves of wavelengths in the visible and non-visible regions, and also includes radiation, which includes microwaves, electron beams, for example. Specifically, it refers to electromagnetic waves having wavelengths of 5 μm or less, and electron beams.

[0043] In the present application, (meth)acrylic acid represents any of acrylic acid and methacrylic acid, (meth)acrylate represents any of acrylate and methacrylate, and (meth)acryloyl represents any of acryloyl and methacryloyl.

[0044] In addition, in the present specification, "~" indicating a numerical range is used in the meaning that the numerical values recited before and after it are included as lower limit values and upper limit values.

[0045] In the present specification, "substituted or unsubstituted" means that a substituent group can be present. For example, "substituted or unsubstituted alkyl group" includes an alkyl group having a substituent group and an alkyl group having no substituent group.

[0046] I. Halogenated phthalocyanine color material

[0047] The halogenated phthalocyanine color material of the present application is a halogenated phthalocyanine color material represented by the following general formula (1).

[0048] [Chemical Formula 2]

[0049]

[0050] [In 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),

[0051] X 1 ~X 16 at least one of X 1 ~X 16 at least one of X 1 ~X 16 at least one of X

[0052] General formula (2): *-O-R P

[0053] General formula (2-1): *-O-R L1 -R a

[0054] General formula (2-2): *-O-(R L2 -O) n -R b

[0055] General formula (2-3): *-O-R L2 -COO-R b

[0056] General Formula (2-4): *-O-R L2 -OCO-R b

[0057] General Formula (2-5): *-O-R c

[0058] General Formula (2-6): *-O-R a

[0059] (In General Formulae (2) and (2-1) to (2-6),

[0060] R P represents a substituted or unsubstituted 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 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 a phthalocyanine skeleton.)]

[0061] The phthalocyanine color material easily forms a stacked structure by π-π interaction through the planar structure of the phthalocyanine ring, and has high crystallinity. Therefore, the colored layer containing the phthalocyanine color material has a problem that after a heat treatment (post-baking process), foreign matter is easily precipitated due to crystal growth and aggregation of the phthalocyanine color material, and contrast is deteriorated.

[0062] In contrast, in the halogenated phthalocyanine color material represented by General Formula (1) of the present application, X 1~X 16 At least one of them is a fluorine atom, and X 1 ~X 16 At least one of them is a monovalent group represented by the above general formula (2-1) to (2-5), and X 1 ~X 16 At least one of them is a monovalent group represented by the above general formula (2-6).

[0063] Since at least one of X 1 ~X 16 is a fluorine atom, due to the electron-withdrawing effect, the color derived from the phthalocyanine skeleton of the hue (Japanese: hue) as the blue region undergoes a long-wavelength shift, becoming a color suitable for the green coloring layer of the color filter. In addition, the monovalent groups represented by the above general formula (2-1) to (2-6) are all groups that are bonded to the phthalocyanine skeleton through an ether bond and are movable, so the crystallinity can be reduced. In the phthalocyanine colorant of the present invention, by mixing a monovalent group represented by the above general formula (2-1) to (2-5) and a monovalent group represented by the above general formula (2-6) in one molecule, the regularity of the compound is reduced compared to, for example, a compound containing only the monovalent group represented by the above general formula (2-6), and thus the crystallinity is reduced. As a result, it is presumed that in the colored and cured composition using the halogenated phthalocyanine colorant represented by the above general formula (1), after the heat treatment (post-baking step) of the coloring layer, the crystal growth and aggregation of the phthalocyanine colorant are suppressed, and thus a coloring layer with suppressed precipitation of foreign substances and improved contrast can be formed.

[0064] In the general formula (1), as X 1 ~X 16 Among the halogen atoms, examples include fluorine atom, chlorine atom, bromine atom, iodine atom, etc. Among them, from the aspect of hue (Japanese: color tone), a fluorine atom is preferred, and X 1 ~X 16 At least one of them is a fluorine atom.

[0065] Among them, from the aspects of hue and maximum absorption wavelength region, it is preferred that 6 to 10, especially 7 to 9, of X 1 ~X 16 are fluorine atoms.

[0066] X 1 ~X 16 can also be a hydrogen atom. The number of hydrogen atoms in X 1 ~X 16 can be appropriately selected according to the adjustment of hue, and can be 0 to 8, can be 0 to 4, and can be 0 to 2.

[0067] X 1 ~X 16Also, the number of hydroxyl groups in X 1 ~X 16 may be appropriately selected and can be 0 to 4 or 0 to 2.

[0068] In General Formula (1), X 1 ~X 16 may be a substituted or unsubstituted hydrocarbon group having 1 to 6 carbon atoms. As the hydrocarbon group, a linear or branched aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group can be exemplified. The aliphatic hydrocarbon group can be a saturated aliphatic hydrocarbon group (alkyl group) or an unsaturated aliphatic hydrocarbon group (alkenyl group, alkynyl group).

[0069] As the linear or branched aliphatic hydrocarbon group, for example, a methyl group, an ethyl group, a linear or branched propyl group, a linear or branched butyl group, a linear or branched pentyl group, a linear or branched hexyl group, a vinyl group, a propenyl group, a 1-butenyl group, or the like can be exemplified. As the alicyclic hydrocarbon group, for example, a cyclopentyl group, a cyclohexyl group, or the like can be exemplified. As the aromatic hydrocarbon group, for example, a phenyl group can be exemplified.

[0070] In the case where the hydrocarbon group has a substituent, as the substituent, a halogen atom, an -OR s1 group, an -COR s1 group, an -COOR s1 group (here, 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), or the like can be exemplified. Specifically, 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, or the like can be exemplified. As the hydrocarbon group having 1 to 14 carbon atoms in R s1 , the same as the alicyclic hydrocarbon group and the aromatic hydrocarbon group described below can be exemplified in addition to the hydrocarbon group having 1 to 6 carbon atoms described above. As the heterocyclic group having 5 to 14 ring-forming atoms, the same as the heterocyclic group having 5 to 14 ring-forming atoms described below can be exemplified. s1 The hydrocarbon group in R s1 may be a hydrocarbon group having 1 to 6 carbon atoms, a hydrocarbon group having 1 to 4 carbon atoms, or a methyl group, an ethyl group, a linear or branched propyl group.

[0071] As the substituent of the hydrocarbon group or the heterocyclic group in R s1 , an alkoxy group having 1 to 5 carbon atoms can be exemplified.

[0072] In General Formula (1), X 1 ~X 16 may be a monovalent group represented by General Formula (2) below.1 ~ X 16 at least one of the groups represented by the following general formulae (2-1) to (2-5), X 1 ~ X 16 at least one of the groups represented by the following general formula (2-6).

[0073] General formula (2) : *-O-R P

[0074] General formula (2-1) : *-O-R L1 -R a

[0075] General formula (2-2) : *-O- (R L2 -O) n -R b

[0076] General formula (2-3) : *-O-R L2 -COO-R b

[0077] General formula (2-4) : *-O-R L2 -OCO-R b

[0078] General formula (2-5) : *-O-R c

[0079] General formula (2-6) : *-O-R a

[0080] (in the general formulae (2) and (2-1) to (2-6),

[0081] R P represents a substituted or unsubstituted 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 aR represents an aromatic hydrocarbon group with 6 to 14 carbon atoms, whether substituted or unsubstituted. b R represents a hydrogen atom, a straight-chain or branched aliphatic hydrocarbon group with 1 to 6 substituted or unsubstituted carbon atoms, an alicyclic hydrocarbon group with 5 to 14 substituted or unsubstituted carbon atoms, an aromatic hydrocarbon group with 6 to 14 substituted or unsubstituted carbon atoms, or a heterocyclic group with 5 to 14 substituted or unsubstituted cyclic atoms. c This indicates an alicyclic hydrocarbon group with 5 to 14 carbon atoms, either substituted or unsubstituted. n represents an integer from 1 to 5. * indicates the bonding position with the phthalocyanine skeleton.

[0082] In general formula (2) R P In this context, the substituted or unsubstituted aliphatic hydrocarbon groups with 1 to 6 carbon atoms, whether straight-chain or branched, can be either saturated or unsaturated.

[0083] Examples of aliphatic hydrocarbon groups with 1 to 6 carbon atoms, either straight-chain or branched, include: methyl, ethyl, straight-chain or branched propyl, straight-chain or branched butyl, straight-chain or branched pentyl, straight-chain or branched hexyl, vinyl, propenyl, 1-butenyl, etc. Aliphatic hydrocarbon groups with 1 to 6 carbon atoms can also be straight-chain or branched aliphatic hydrocarbon groups with 1 to 4 carbon atoms, or straight-chain or branched aliphatic hydrocarbon groups with 1 to 3 carbon atoms.

[0084] In general formula (2) R P Among the alicyclic hydrocarbon groups with 5 to 14 carbon atoms, whether substituted or unsubstituted, examples of alicyclic hydrocarbon groups with 5 to 14 carbon atoms include cyclopentyl, cyclohexyl, norbornyl, and adamantyl. Alicyclic hydrocarbon groups can also be alicyclic hydrocarbon groups with 5 to 10 carbon atoms or alicyclic hydrocarbon groups with 5 to 6 carbon atoms.

[0085] In general formula (2) R P Among the aromatic hydrocarbon groups in the group, those with 6 to 14 carbon atoms, whether substituted or unsubstituted, examples of aromatic hydrocarbon groups with 6 to 14 carbon atoms include: phenyl, naphthyl, biphenyl, fluorenyl, anthracene, etc. Aromatic hydrocarbon groups can also be those with 6 to 10 carbon atoms, such as phenyl.

[0086] In general formula (2) R PAmong heterocyclic groups with 5 to 14 cyclic atoms, whether substituted or unsubstituted, examples of heterocyclic groups with 5 to 14 cyclic atoms include: furan rings, thiophene rings, pyrrole rings, 2H-pyran rings, 4H-thiaran rings, pyridine rings, 1,3-oxazole rings, isoxazole rings, 1,3-thiazole rings, isothiazole rings, imidazole rings, pyrazole rings, furazon rings, pyrazine rings, pyrimidine rings, pyridazine rings, carbazole rings, acridine rings, etc., having one free valence. Heterocyclic groups with 5 to 6 cyclic atoms can also be heterocyclic groups.

[0087] In R P When a straight-chain or branched aliphatic hydrocarbon group with 1 to 6 carbon atoms has a substituent, examples of such substituents include halogen atoms, -OR... s1 -COR s1 -COOR s1 (Here, R) s1 It can be a hydrogen atom, a hydrocarbon group with 1 to 14 substituted or unsubstituted carbon atoms, or a heterocyclic group with 5 to 14 substituted or unsubstituted cyclic atoms, etc., and can be a halogen atom, hydroxyl group, aldehyde group, carboxyl group, alkoxy group, aryloxy group, heteroaryloxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, heteroaryloxycarbonyl group, etc.

[0088] In R P When the alicyclic hydrocarbon group, aromatic hydrocarbon group, or heterocyclic group in the compound has a substituent, examples of such substituents include halogen atoms, substituted or unsubstituted straight-chain or branched alicyclic hydrocarbon groups with 1 to 6 carbon atoms, and -OR. s1 -COR s1 -COOR s1 (Here, R) s1 It can be a hydrogen atom, a hydrocarbon group with 1 to 14 carbon atoms (substituted or unsubstituted), or a heterocyclic group with 5 to 14 cyclic atoms (substituted or unsubstituted), or a halogen atom, a straight-chain or branched alkyl group with 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.

[0089] Regarding the above R s1 Hydrocarbon groups with 1 to 14 carbon atoms, excluding the above-mentioned X 1 ~X 16 In addition to hydrocarbon groups having 1 to 6 carbon atoms, it can be combined with the above-mentioned R P The alicyclic hydrocarbon group in it is the same as the aromatic hydrocarbon group mentioned above. Additionally, heterocyclic groups with 5 to 14 ring atoms can be the same as the R group mentioned above. P The heterocyclic groups with 5 to 14 cyclic atoms are the same.

[0090] From the perspective of solvent solubility, R s1The hydrocarbon group in R can be a hydrocarbon group with 1 to 6 carbon atoms, or a straight-chain or branched aliphatic hydrocarbon group with 1 to 4 carbon atoms. The heterocyclic group can be a heterocyclic group with 5 to 6 cyclic atoms. s1 It can be a hydrocarbon group with 1 to 6 carbon atoms, or a hydrocarbon group with 1 to 4 carbon atoms, and can be methyl, ethyl, straight-chain or branched propyl.

[0091] Additionally, regarding R P The alicyclic hydrocarbon group, aromatic hydrocarbon group, and heterocyclic group in the substituent can be a straight-chain or branched aliphatic hydrocarbon group with 1 to 6 carbons. It can be the same as the above-mentioned straight-chain or branched aliphatic hydrocarbon group with 1 to 6 carbons, or a straight-chain or branched aliphatic hydrocarbon group with 1 to 4 carbons.

[0092] Additionally, as R s1 The substituents of the hydrocarbon group or heterocyclic group in it can be alkoxy groups with 1 to 5 carbon atoms.

[0093] In general formulas (2) and (2-1) to (2-4), R L1 It represents an aliphatic hydrocarbon group or a -CO- group with 1 to 6 carbon atoms. Additionally, R... L2 Each of the following groups can be independently represented as an aliphatic hydrocarbon group with 1 to 6 carbon atoms.

[0094] R L1 and R L2 Aliphatic hydrocarbon groups with 1 to 6 carbon atoms are divalent aliphatic hydrocarbon groups. Examples include: divalent straight-chain, branched saturated or unsaturated aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, divalent straight-chain or branched aliphatic hydrocarbon groups, and saturated aliphatic hydrocarbon groups.

[0095] Examples of straight-chain or branched aliphatic hydrocarbon groups include: methylene, ethylene, straight-chain or branched propylene, straight-chain or branched butylene, straight-chain or branched pentylene, straight-chain or branched hexylene, etc.

[0096] R L1 and R L2 The aliphatic hydrocarbon groups with 1 to 6 carbon atoms can be aliphatic hydrocarbon groups with 1 to 3 carbon atoms.

[0097] R in general formula (2-2) L2 The aliphatic hydrocarbon groups with 1 to 6 carbon atoms can be ethylene or branched propylene.

[0098] In the general formula (2-2), n represents an integer from 1 to 5, which can be 1 to 3.

[0099] In general formulas (2), (2-1) and (2-6), R a This indicates an aromatic hydrocarbon group with 6 to 14 carbon atoms, whether substituted or unsubstituted. As R aThe substituted or unsubstituted aromatic hydrocarbon group having 6 to 14 carbon atoms in R P may be the same as the above R

[0100] In General Formula (2) and (2-2) to (2-4), R b represents a hydrogen atom, a substituted or unsubstituted linear 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.

[0101] R b may be the same as the above R P .

[0102] From the viewpoint of easily reducing the crystallinity of the color material, R b may 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 viewpoint of solvent solubility, R b 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, may be a substituted or unsubstituted cyclopentyl group, a substituted or unsubstituted cyclohexyl group, or a substituted or unsubstituted phenyl group.

[0103] In addition, from the viewpoint of solvent solubility, R b may be an unsubstituted aliphatic hydrocarbon group having 1 to 3 carbon atoms.

[0104] In addition, from the viewpoint of good solubility in a high-polarity solvent, R b may be a hydrogen atom.

[0105] In General Formula (2-5), R c represents a substituted or unsubstituted alicyclic hydrocarbon group having 5 to 14 carbon atoms. As the substituted or unsubstituted alicyclic hydrocarbon group having 5 to 14 carbon atoms in R c may be the same as the above R P .

[0106] wherein R p , R a , and R b in the general formula (2) can be a monovalent group represented by the following general formula (3) from the viewpoint of suppressing the precipitation of foreign matter and improving the contrast of the colored layer.

[0107] [Chemical Formula 3]

[0108]

[0109] (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 s2 is a halogen atom, an alkyl group having 1 to 4 carbons, or an alkoxy group having 1 to 4 carbons. p is an integer of 1 to 3, and q is an integer of 0 to 2. In the case where p is 2 or 3, the plurality of W, R s1 may be the same or different, and in the case where q is 2, the plurality of R s2 may be the same or different. * indicates the bonding position.)

[0110] In the above general formula (3), R s1 may be the same as described above.

[0111] From the viewpoint of solvent solubility, R s1 may be a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 6 carbons, and may be a substituted or unsubstituted alkyl group having 1 to 6 carbons. The alkyl group is preferably an alkyl group having 1 to 5 carbons, and more preferably a straight-chain alkyl group having 1 to 5 carbons. In the case where R s1 is a substituted alkyl group, it can be a group having an alkoxy group having 1 to 5 carbons as a substituent.

[0112] p can be 1 or 2, and can be 1. In the case where p = 1, -CO-W-R s1 may be bonded to the 3-position or the 4-position with respect to the -O- to which the monovalent group represented by the general formula (3) is bonded, and can be bonded to the 4-position. In the case where p = 2, the 2 -CO-W-R s1 may be bonded to the 3,5-positions or the 2,4-positions with respect to the -O- to which the monovalent group represented by the general formula (3) is bonded, and can be bonded to the 3,5-positions.

[0113] q can be 0 or 1, and can be 0.

[0114] wherein R p , R b , and R cThe alicyclic hydrocarbon group in the above formula (4) can be a monovalent group represented by the following general formula (4).

[0115] [Chemical Formula 4]

[0116]

[0117] (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 s2 is a halogen atom, an alkyl group having 1 to 4 carbons, or an alkoxy group having 1 to 4 carbons. p is an integer of 1 to 3, and q is an integer of 0 to 2. In the case where p is 2 or 3, the plurality of W, R s1 may be the same or different, and in the case where q is 2, the plurality of R s2 may be the same or different. * indicates a bonding position.

[0118] In the above general formula (4), R s1 may be the same as described above.

[0119] From the viewpoint of solvent solubility, R s1 may be a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 6 carbons, and can be a substituted or unsubstituted alkyl group having 1 to 6 carbons. The alkyl group is preferably an alkyl group having 1 to 5 carbons, and more preferably a straight-chain alkyl group having 1 to 5 carbons. In the case where R s1 is a substituted alkyl group, it is preferable to have an alkoxy group having 1 to 5 carbons as a substituent.

[0120] p can be 1 or 2, and can be 1. In the case where p = 1, -CO-W-R s1 may be bonded to the 3-position or the 4-position with respect to the -O- to which the monovalent group represented by the general formula (4) is bonded, and can be bonded to the 4-position. In the case where p = 2, the 2 -CO-W-R s1 may be bonded to the 3, 5-positions or the 2, 4-positions with respect to the -O- to which the monovalent group represented by the general formula (4) is bonded, and can be bonded to the 3, 5-positions.

[0121] q can be 0 or 1, and can be 0.

[0122] In the monovalent group represented by the above general formula (2-1) to (2-5), the above general formula (2-1) is preferable from the viewpoint that the crystal growth is easily inhibited by steric hindrance because the terminal volume is large and the large volume terminal moves more easily. In the above general formula (2-1), R aIn the case where the aromatic hydrocarbon group in the above general formula (3) is a monovalent group represented by the above general formula (3), it is preferable from the viewpoint of obtaining a colored layer in which the generation of foreign matter is inhibited and the contrast is improved.

[0123] Among the monovalent groups represented by the above general formulae (2-1) to (2-5), the above general formula (2-5) is preferable from the viewpoint that the crystal growth is easily inhibited by steric hindrance due to the large end volume. Among them, in the above general formula (2-5), R c In the case where the aliphatic hydrocarbon group in the above general formula (4) is a monovalent group represented by the above general formula (4), it is preferable from the viewpoint of obtaining a colored layer in which the generation of foreign matter is inhibited and the contrast is improved.

[0124] Among the monovalent groups represented by the above general formulae (2-1) to (2-5), the above general formula (2-2), the above general formula (2-3), and the above general formula (2-4) are preferable from the viewpoint that the affinity with a polymer or a polymerizable compound is easily improved by the oxyalkylene chain or the ester moiety, and the aggregation of the color material is easily inhibited.

[0125] Among the above general formula (2-2), the above general formula (2-3), and the above general formula (2-4), in the case where R b is 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 from the viewpoint that the affinity with a polymer or a polymerizable compound is easily improved, the aggregation of the color material is easily inhibited, and the crystal growth is easily inhibited by steric hindrance due to the large end volume. Among them, in the case where R b is a monovalent group represented by the above general formula (3) or a monovalent group represented by the above general formula (4), it is preferable from the viewpoint of obtaining a colored layer in which the generation of foreign matter is inhibited and the contrast is improved.

[0126] In the halogenated phthalocyanine color material of the present application, from the viewpoint of obtaining a colored layer in which the generation of foreign matter is inhibited, the contrast is improved, and when color is adjusted to various color standards, color characteristics exhibiting excellent brightness and coloring power are exhibited, it is preferable that 6 to 10, particularly 7 to 9, of X 1 to X 16 be a monovalent group represented by the above general formula (2).

[0127] In the halogenated phthalocyanine color material of the present application, from the viewpoint of obtaining a colored layer in which the generation of foreign matter is inhibited and the contrast is improved, it is preferable that X 1 to X 16The number of monovalent groups is 3 to 5, with an average of 3.5 to 4.5, and especially 4, which are represented by the general formulas (2-1) to (2-5) above.

[0128] Furthermore, in the halogenated phthalocyanine pigment of the present invention, from the perspective of suppressing the precipitation of foreign matter that is prone to form and improving the contrast of the coloring layer, X is preferred. 1 ~X 16 The number of monovalent groups is 3 to 5, with an average of 3.5 to 4.5, and especially 4, which are represented by the general formula (2-6) above.

[0129] In the halide phthalocyanine colorant of the present invention, from the perspective of suppressing the precipitation of foreign matter that easily forms and improving the contrast of the coloring layer, the above-mentioned X is preferred. 1 ~X 4 either of the above X 5 ~X 8 either of the above X 9 ~X 12 Any of the above, and X 13 ~X 16 Each of them has a total of 4 monovalent groups represented by the above general formulas (2-1) to (2-5), and the above X 1 ~X 4 either of the above X 5 ~X 8 either of the above X 9 ~X 12 Any of the above, and X 13 ~X 16 Each of them has a total of four monovalent groups represented by the above general formulas (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 A total of four sites each have a monovalent group represented by the above general formulas (2-1) to (2-5), and a total of four sites each have a monovalent group represented by the above general formula (2-6).

[0130] Furthermore, in this case, from the perspective of chromaticity enhancement, the aforementioned X is preferred. 1 ~X 4 The other two, and the aforementioned X 5 ~X 8 The other two, and the aforementioned X 9 ~X 12 The other two, and the aforementioned X 13 ~X16 of the remaining two, at least one contains a fluorine atom, and the remaining one is selected from the group consisting of a halogen atom and a hydrogen atom, more preferably from the group consisting of a halogen atom, further preferably all are fluorine atoms.

[0131] As the method for producing the halogenated phthalocyanine color material, a conventionally known production method can be appropriately selected and used. For example, a production method in which a phthalonitrile compound and a metal salt are subjected to a cyclization reaction in a molten state or in an organic solvent can be appropriately used, for example, can be produced with reference to Japanese Patent Application Publication No. 2014-43556 or Japanese Patent Application Publication No. 2020-42263. As the phthalonitrile compound used in the starting material, a conventionally known production method can be appropriately selected and used for synthesis, or a commercially available product can be used.

[0132] II. Colored curable composition

[0133] The colored curable composition of the present application 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 application.

[0134] The colored curable composition of the present application contains the halogenated phthalocyanine color material of the present application, and thus a colored layer in which the deposition of foreign matter is suppressed and the contrast is improved can be formed.

[0135] The colored curable composition of the present application contains at least a color material, a polymer, a polymerizable compound, an initiator, and a solvent, and can also contain other components within a range not impairing the effects of the present application.

[0136] < Color material >

[0137] In the present application, the color material can also contain other color materials in addition to the halogenated phthalocyanine color material represented by the above general formula (1).

[0138] The other color material is not particularly limited as long as the desired color development can be achieved, and various organic pigments, inorganic pigments, dyes, salted compounds of dyes, and the like can be used alone or in a mixture of two or more. Among them, the organic pigments have high color development and high heat resistance, and thus are preferably used. As the organic pigments, for example, compounds classified as pigments (Pigment) in the color index (C.I.; published by The Society of Dyers and Colourists) can be exemplified, and specifically, those having a color index (C.I.) number described below can be exemplified.

[0139] As the color material, a yellow color material can also be contained.

[0140] In addition, as the color material, a green color material different from the halogenated phthalocyanine color material represented by the above general formula (1) can also be contained.

[0141] As the yellow color material, for example, 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, and derivative pigments of these, and the like yellow pigments; coumarin-based dyes, cyanine-based dyes, merocyanine-based dyes, azo-based dyes, methine-based dyes, azomethine-based dyes, quinophthalone-based dyes, and the like yellow dyes can be exemplified.

[0142] As the yellow color material, from the viewpoint of good heat resistance and light resistance, and high transmittance, a quinophthalone-based color material is preferable. In addition, a quinophthalone-based color material is also preferable from the viewpoint of having a hue suitable for a filter use.

[0143] The quinophthalone-based color material refers to a color material synthesized by condensation of a quinoline derivative such as quinophthalone and a phthalic anhydride derivative or a naphthalic anhydride derivative, and can be any of a pigment, a dye, and a salt compound of a dye.

[0144] As the quinophthalone pigment, for example, C.I. Pigment Yellow 138 and the like can be exemplified.

[0145] As the quinophthalone dye, for example, C.I. Disperse Yellow 54, 64, 67, 134, 149, 160; C.I. Solvent Yellow 114, 157, and the like can be exemplified, of which C.I. Disperse Yellow 54 is preferable.

[0146] On the other hand, as the green color material different from the halogenated phthalocyanine color material of the present application described above, 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, and the like green pigments; squarilium, triarylmethane, anthraquinone, coumarin, cyanine, or azo dyes, and the like green dyes can be exemplified.

[0147] From the viewpoint of easy adjustment of chroma, as the green color material different from the halogenated phthalocyanine color material described above, a phthalocyanine green pigment is preferable.

[0148] As the phthalocyanine green pigment, for example, C.I. Pigment Green 7, 36, 58, 59, 62, 63, etc. can be exemplified. From the aspect of easy adjustment of the brightness, as the phthalocyanine green pigment, C.I. Pigment Green 7, 58, 59, 62 or 63 is preferable, C.I. Pigment Green 58, 59, 62 or 63 is more preferable, and C.I. Pigment Green 59 is further more preferable.

[0149] As the other color material, for example, a blue color material, an orange color material, etc. can be exemplified.

[0150] As the orange color material, C.I. Pigment Orange 1, 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 61, 63, 64, 71, 73, etc. can be exemplified.

[0151] As the blue color material, C.I. Pigment Blue 15, 15:3, 15:4, 15:6, 60, etc. can be exemplified.

[0152] In the colored curable composition of the present application, the content ratio of the above-mentioned halogenated phthalocyanine color material of the present application with respect to the entire color material is not particularly limited, and is appropriately adjusted according to the desired color. Among them, from the aspect of adjustment to the desired color, the content ratio of the above-mentioned halogenated phthalocyanine color material of the present application with respect to the entire color material is preferably 30 to 95 mass%, more preferably 40 to 85 mass%, and further more preferably 50 to 80 mass%.

[0153] In the colored curable composition of the present application, in the case where a yellow color material is contained, the yellow color material can be appropriately selected and used alone or in combination of two or more.

[0154] In the colored curable composition of the present application, the content ratio of the yellow color material with respect to the above-mentioned halogenated phthalocyanine color material of the present application is not particularly limited, and is appropriately adjusted according to the desired color. Among them, from the aspect of adjustment to the desired color, with respect to 100 mass parts of the above-mentioned halogenated phthalocyanine color material of the present application, the yellow color material is preferably 5 to 233 mass parts, more preferably 18 to 150 mass parts, and further more preferably 25 to 100 mass parts.

[0155] In the colored curable composition of the present application, in the case where a green color material different from the above-mentioned halogenated phthalocyanine color material is contained, the green color material different from the above-mentioned halogenated phthalocyanine color material can be appropriately selected and used alone or in combination of two or more.

[0156] In the colored curable composition of the present application, the proportion of the green color material other than the above-mentioned halogenated phthalocyanine color material with respect to the above-mentioned halogenated phthalocyanine color material of the present application is not particularly limited, and is appropriately adjusted to the desired color density. Among them, from the viewpoint of adjusting to the desired color density and adjusting the brightness, with respect to 100 parts by mass of the above-mentioned halogenated phthalocyanine color material of the present application, the green color material other than the above-mentioned halogenated phthalocyanine color material is preferably contained in an amount of 5 to 900 parts by mass, more preferably in an amount of 18 to 567 parts by mass, and even more preferably in an amount of 25 to 400 parts by mass.

[0157] In addition, in the colored curable composition of the present application, in the case where a green color material other than the above-mentioned halogenated phthalocyanine color material of the present application is also contained, the proportion of the green color material containing the above-mentioned halogenated phthalocyanine color material of the present application with respect to the entire color material is not particularly limited, and is appropriately adjusted according to the desired color density. Among them, from the viewpoint of adjusting to the desired color density and adjusting the brightness, with respect to the entire color material, the green color material containing the above-mentioned halogenated phthalocyanine color material of the present application is preferably contained in an amount of 30 to 95% by mass, and more preferably in an amount of 50 to 80% by mass.

[0158] In addition, the proportion of the yellow color material with respect to the green color material containing the above-mentioned halogenated phthalocyanine color material of the present application is not particularly limited, and is appropriately adjusted according to the desired color density. Among them, from the viewpoint of adjusting to the desired color density and adjusting the brightness, with respect to 100 parts by mass of the green color material containing the above-mentioned halogenated phthalocyanine color material of the present application, the yellow color material is preferably contained in an amount of 5 to 70 parts by mass, and more preferably in an amount of 20 to 50 parts by mass.

[0159] In addition, in the colored curable composition of the present application, other color materials other than the green color material and the yellow color material can also be contained in the color material within a range that does not impair the effects of the present application, and the total content of the green color material and the yellow color material containing the above-mentioned halogenated phthalocyanine color material of the present application with respect to the entire color material is preferably 70 to 100% by mass, and more preferably 80 to 100% by mass.

[0160] The total content of the color material with respect to the total amount of the solid components of the colored curable composition is, for example, preferably in the range of 3% by mass to 65% by mass, and more preferably in the range of 4% by mass to 60% by mass. If it is equal to or greater than the above lower limit value, the colored layer when the colored curable composition is applied to a prescribed film thickness (typically 1.0 to 5.0 μm) has sufficient color density. In addition, if it is equal to or less than the above upper limit value, the storage stability is excellent, and a colored layer having sufficient hardness and adhesion to a substrate can be obtained. In particular, in the case of forming a colored layer having a high color material concentration, the content of the color material with respect to the total amount of the solid components of the colored curable composition is preferably in the range of 15% by mass to 65% by mass, and more preferably in the range of 25% by mass to 60% by mass.

[0161] Note that, in the present application, the solid content is all components other than the above-mentioned solvent, and also includes monomers and the like dissolved in the solvent.

[0162] [Binder component]

[0163] The polymer, the polymerizable compound, and the initiator contained in the colored curable composition of the present application serve as a binder component of the colored curable composition, and impart film-forming properties and adhesion to a coated surface.

[0164] As the above-mentioned binder component, a binder component used when forming a colored layer known in the past can be appropriately used, and is not particularly limited, and examples thereof include: a photosensitive binder component that can be polymerization-cured by visible light, ultraviolet rays, electron beams, or the like; a thermosetting binder component that can be polymerization-cured by heating, and a mixture of these can also be used.

[0165] As the thermosetting binder component, a system containing at least: a polymer having a thermopolymerizable functional group as a polymer, a compound having a thermopolymerizable functional group in the molecule as a polymerizable compound, and a thermopolymerization initiator containing a curing agent that reacts with the above-mentioned thermopolymerizable functional group as an initiator, and the like can be exemplified. As the thermopolymerizable functional group, an epoxy group, an isocyanate group, a carboxyl group, an amino group, a hydroxyl group, and the like can be exemplified.

[0166] In the case of using a photolithography process when forming a colored layer using the colored curable composition of the present application, a photosensitive binder component having alkali developability is suitably used. Note that, the photosensitive binder component can also use a thermosetting binder component.

[0167] As the photosensitive binder component, a positive photosensitive binder component and a negative photosensitive binder component can be exemplified. As the positive photosensitive binder component, a system containing: an alkali-soluble resin as a polymer; a compound having a bond that is cleaved by an acid and an ethylenic unsaturated group in the molecule as a polymerizable compound; a thermal radical polymerization initiator as an initiator; and a photo-acid generator can be exemplified.

[0168] As the negative photosensitive binder component, a system containing at least: an alkali-soluble resin as a polymer, a compound having an ethylenic unsaturated group in the molecule as a polymerizable compound, and a photopolymerization initiator as an initiator is suitably used.

[0169] As the binder component contained in the colored curable composition of the present application, from the aspect that a pattern can be formed using an existing process by a photolithography method with ease, the above-mentioned negative photosensitive binder component is preferred.

[0170] <Polymers>

[0171] As a polymer, in the case where a photolithography process is used when forming the colored layer, an alkali-soluble resin which is soluble in an alkali developer is suitably used.

[0172] The alkali-soluble resin has an acidic group, which is appropriately selected and used as long as it functions as a binder resin and is soluble in an alkali developer used when forming a pattern.

[0173] In the present application, the alkali-soluble resin can be standardized by an acid value of 30 mgKOH / g or more.

[0174] As the acidic group possessed by the alkali-soluble resin, for example, a carboxyl group can be exemplified. As the alkali-soluble resin having a carboxyl group, a carboxyl group-containing copolymer having a carboxyl group, an epoxy (meth)acrylate resin having a carboxyl group, and the like can be exemplified. As the carboxyl group-containing copolymer, a (meth)acrylic copolymer having a carboxyl group, a styrene-(meth)acrylic copolymer having a carboxyl group, and the like can be exemplified.

[0175] In addition, these (meth)acrylic copolymers, the styrene-(meth)acrylic copolymers having a carboxyl group, and the like (meth)acrylic copolymers, and the epoxy (meth)acrylate resins can be used by mixing two or more kinds.

[0176] The (meth)acrylic copolymers having a carboxyl group, the styrene-(meth)acrylic copolymers having a carboxyl group, and the like (meth)acrylic copolymers are, for example, (co)polymers obtained by (co)polymerizing a carboxyl group-containing olefinically unsaturated monomer and, if necessary, other copolymerizable monomers by a publicly known method.

[0177] As the carboxyl group-containing olefinically unsaturated monomer, for example, a (meth)acrylic acid, a vinylbenzoic acid, a maleic acid, a maleic acid monoalkyl ester, a fumaric acid, an itaconic acid, a crotonic acid, a cinnamic acid, a (meth)acrylic acid dimer, and the like can be exemplified. In addition, an adduct of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate and a cyclic anhydride such as maleic anhydride, phthalic anhydride, or cyclohexane dicarboxylic anhydride; an ω-carboxyl-poly caprolactone mono(meth)acrylate; and the like can be used. In addition, an anhydride-containing monomer such as maleic anhydride, itaconic anhydride, or citraconic anhydride can be used as a precursor of a carboxyl group. Among them, a (meth)acrylic acid is particularly preferable in terms of copolymerizability, cost, solubility, glass transition temperature, and the like.

[0178] From the viewpoint of excellent adhesion to a substrate, the alkali-soluble resin preferably has a hydrocarbon ring. By having a hydrocarbon ring as a bulky group, shrinkage at the time of curing is suppressed, peeling from a substrate is mitigated, and adhesion to a substrate 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 is particularly preferable in terms of suppressing swelling of the colored layer.

[0179] As such a hydrocarbon ring, a cyclic aliphatic hydrocarbon ring which can have a substituent, an aromatic ring which can have a substituent, and combinations of these can be exemplified, and the hydrocarbon ring can have a substituent such as a carbonyl group, a carboxyl group, an oxycarbonyl group, an amido group, and the like.

[0180] As specific examples of the hydrocarbon ring, aliphatic hydrocarbon rings such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, norbornane, tricyclo[5.2.1.0(2,6)]decane (bicyclopentane), adamantane, and the like, aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, phenanthrene, fluorene, and the like, chain polycyclics such as biphenyl, terphenyl, diphenylmethane, triphenylmethane, stilbene, and the like, and Cardo structures (9,9-diarylfluorene) and the like can be exemplified.

[0181] Among them, in the case of including an aliphatic hydrocarbon ring as the hydrocarbon ring, it is preferable from the viewpoints of improving the heat resistance and adhesion of the colored layer, and improving the brightness of the obtained colored layer.

[0182] In addition, in the case of including a structure in which two benzene rings are bonded to a fluorene skeleton (Cardo structure), it is particularly preferable from the viewpoints of improving the curing properties of the colored layer, improving the solvent resistance, and particularly suppressing swelling against NMP.

[0183] The hydrocarbon ring can be included as a monovalent group, or can be included as a divalent or higher group.

[0184] As for the alkali-soluble resin used in the present application, a (meth)acrylic copolymer which includes a structural unit having the above-described hydrocarbon ring in addition to a structural unit having a carboxyl group is preferably used in terms of easily adjusting the amounts of each structural unit, and increasing the amount of the structural unit having the above-described hydrocarbon ring to easily improve the function of the structural unit.

[0185] The (meth)acrylic copolymer which includes a structural unit having a carboxyl group and the above-described hydrocarbon ring can be produced by using an olefinically unsaturated monomer having a hydrocarbon ring as the above-described "other copolymerizable monomer".

[0186] As the olefinically unsaturated monomer having a hydrocarbon ring used as the alkali-soluble resin having a hydrocarbon ring, for example, (methyl) acrylate cyclohexyl, (methyl) acrylate dicyclopentyl, (methyl) acrylate adamantyl, (methyl) acrylate isobornyl, (methyl) acrylate phenoxyethyl, styrene, monomers having the above Cardo structure and an olefinically unsaturated group, and the like can be preferably used, from the viewpoint of the effect of more suppressing the excretion of foreign substances derived from the color material after the heat treatment, among which, (methyl) acrylate cyclohexyl, (methyl) acrylate dicyclopentyl, (methyl) acrylate adamantyl, (methyl) acrylate benzyl, styrene, monomers having the above Cardo structure and an olefinically unsaturated group are preferable.

[0187] Further, the alkali-soluble resin used in the present application is also preferably one having an olefinically unsaturated bond in the side chain. In the case of having an olefinically unsaturated bond, the alkali-soluble resin can 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 film strength of the cured film is further improved, the development resistance is improved, further, the thermal shrinkage of the cured film is suppressed, and the adhesion to the substrate is excellent.

[0188] Note that the olefinically unsaturated group refers to a group containing a carbon-carbon double bond which can undergo radical polymerization, and examples thereof include a (methyl) acryloyl group, a vinyl group, an allyl group, and the like.

[0189] The method of introducing an olefinically unsaturated bond in the alkali-soluble resin can be appropriately selected from the methods known in the art. For example, a method of introducing an olefinically unsaturated bond in the side chain by adding a compound having both an epoxy group and an olefinically unsaturated bond to a carboxyl group possessed by the alkali-soluble resin, such as glycidyl (meth) acrylate, and the like; a method of introducing an olefinically unsaturated bond in the side chain by adding a compound having both an isocyanate group and an olefinically unsaturated bond to a structural unit having a hydroxyl group introduced in advance in the copolymer; and the like can be exemplified.

[0190] The alkali-soluble resin used in the present application can further contain other structural units such as a structural unit having an ester group such as methyl (meth) acrylate, ethyl (meth) acrylate, and the like. The structural unit having an ester group functions not only as a component for suppressing the alkali-solubility of the colored and cured composition, but also as a component for improving the solubility in a solvent, and further improving the re-solubility in a solvent.

[0191] The alkali-soluble resin used in the present application is preferably a (meth)acrylic copolymer or a styrene-(meth)acrylic copolymer, and more preferably a (meth)acrylic copolymer or a styrene-(meth)acrylic copolymer containing a structural unit having a carboxyl group and a structural unit having a hydrocarbon ring.

[0192] The alkali-soluble resin used in the present application can be obtained by appropriately adjusting the amount of each structural unit derived monomer to be added to obtain the desired properties.

[0193] The copolymerization ratio of the carboxyl group-containing olefinically unsaturated monomer in the carboxyl group-containing copolymer is usually 5% by mass or more and 50% by mass or less, and preferably 10% by mass or more and 40% by mass or less. In this case, if the copolymerization ratio of the carboxyl group-containing olefinically unsaturated monomer is 5% by mass or more, the solubility of the obtained coating film in an alkaline developer can be inhibited from decreasing, and the pattern can be easily formed. In addition, if the copolymerization ratio is 50% by mass or less, the pattern can be less likely to be damaged or the film on the surface of the pattern can be less likely to be roughened when developed by an alkaline developer. Note that the above copolymerization ratio is a value calculated from the amount of each monomer to be added.

[0194] In addition, in the (meth)acrylic copolymer or the styrene-(meth)acrylic copolymer, etc., which is more preferably used as the alkali-soluble resin and contains a structural unit having an olefinically unsaturated bond, the amount of the monomer having both an epoxy group and an olefinically unsaturated bond to be added 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, with respect to 100% by mass of the amount of the carboxyl group-containing olefinically unsaturated monomer to be added.

[0195] The preferred weight average molecular weight (Mw) of the carboxyl group-containing copolymer is preferably in the range of 1,000 or more and 50,000 or less, and further preferably 3,000 or more and 20,000 or less. If 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 if it is 50,000 or less, the pattern can be easily formed when developed by an alkaline developer.

[0196] Note that the weight average molecular weight (Mw) in the present application is a value calculated by gel permeation chromatography (GPC) in the form of a standard polystyrene conversion value.

[0197] As a specific example of the (meth)acrylic copolymer having a carboxyl group, for example, those described in Japanese Patent Application Publication No. 2013-029832 can be given.

[0198] The epoxy (meth) acrylate resin having a carboxyl group is not particularly limited, and is, for example, an epoxy (meth) acrylate compound obtained by reacting an epoxy compound with a reactant of a monocarboxylic acid containing an unsaturated group, with an acid anhydride. The epoxy compound, the monocarboxylic acid containing an unsaturated group, and the acid anhydride can be appropriately selected from known ones and used.

[0199] The epoxy (meth) acrylate resin having a carboxyl group is preferably one containing the Cardo structure described above in view of the fact that the adverse effect is suppressed and the curability of the colored layer is improved, and the fact that the residual film rate of the colored layer is high.

[0200] The acid value of the alkali-soluble resin is preferably 30 mgKOH / g or more, and more preferably 40 mgKOH / g or more, from the viewpoint of the developability (solubility) to the alkaline aqueous solution used in the developer. The acid value of the carboxyl group-containing copolymer is preferably 50 mgKOH / g or more and 300 mgKOH / g or less, more preferably 60 mgKOH / g or more and 280 mgKOH / g or less, and further more preferably 70 mgKOH / g or more and 250 mgKOH / g or less, from the viewpoint of the developability (solubility) to the alkaline aqueous solution used in the developer and the adhesion to the substrate.

[0201] Note that in the present application, the acid value can be measured in accordance with JIS K 0070.

[0202] The equivalent of the ethylenic unsaturated bond in the case where the alkali-soluble resin has an ethylenic unsaturated group in the side chain is preferably in the range of 100 or more and 2000 or less, and particularly preferably in the range of 140 or more and 1500 or less, from the viewpoint of improving the film strength of the cured film and further suppressing the precipitation of the color material. If the equivalent of the ethylenic unsaturated bond is 2000 or less, the development resistance and the adhesion are excellent. In addition, if it is 100 or more, the proportion of other structural units such as the structural unit having a carboxyl group and the structural unit having a hydrocarbon ring can be relatively increased, and thus the developability and the heat resistance are excellent. Here, the equivalent of the ethylenic unsaturated bond is the weight average molecular weight per 1 mole of the ethylenic unsaturated bond in the alkali-soluble resin, and is represented by the following mathematical expression (1).

[0203] Mathematical expression (1) Equivalent of ethylenic unsaturated bond (g / mol) = W (g) / M (mol)

[0204] (In mathematical expression (1), W represents the mass (g) of the alkali-soluble resin, and M represents the number of moles (mol) of the ethylenic unsaturated bond contained in the alkali-soluble resin W (g))

[0205] The above-mentioned ethylenic unsaturated bond equivalent can be calculated, for example, by measuring the number of ethylenic unsaturated bonds contained in 1 g of the alkali-soluble resin according to the test method for iodine value described in JIS K 0070: 1992.

[0206] The content of the alkali-soluble resin used in the colored curable composition is not particularly limited, and is, for example, preferably in the range of 5 to 60% by mass, more preferably 10 to 40% by mass, relative to the total amount of solid components of the colored curable composition. If the content of the alkali-soluble resin is equal to or greater than the above lower limit, sufficient alkali development is easily obtained, and if the content of the alkali-soluble resin is equal to or less than the above upper limit, film roughness and pattern defects at the time of development are easily suppressed.

[0207] In addition, the content of the polymer having an ethylenic unsaturated group in the colored curable composition is, for example, preferably 5 to 60% by mass, more preferably 10 to 45% by mass, relative to the total amount of solid components of the colored curable composition. If the content of the polymer having an ethylenic unsaturated group is equal to or greater than the above lower limit, sufficient curing is obtained, and peeling of the coating film of the patterned colored curable composition is suppressed. In addition, if the content of the polymer having an ethylenic unsaturated group is equal to or less than the above upper limit, peeling caused by curing shrinkage is suppressed.

[0208] In addition, the colored curable composition of the present application can contain, for example, 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 co-condensed resin, a silicone resin, a polysiloxane resin, or the like as the above-mentioned polymer.

[0209] Note that the above-mentioned polymer can be used alone or in combination of two or more.

[0210] The content of the polymer in the colored curable composition is not particularly limited, and is, for example, preferably 5 to 60% by mass, more preferably 10 to 50% by mass, relative to the total amount of solid components of the colored curable composition. If the content of the polymer is equal to or greater than the above lower limit, film strength is suppressed from decreasing, and if the content of the polymer is equal to or less than the above upper limit, components other than the polymer are sufficiently contained.

[0211] <Polymehzable Compound>

[0212] The polymerizable compound is not particularly limited as long as it is capable of polymerization by the following initiator, and for example, a photopolymerizable compound, a thermal polymerizable compound can be used. As the thermal polymerizable compound, a compound having a thermal polymerization functional group such as a carboxyl group, an amino group, an epoxy group, a hydroxyl group, a glycidyl group, an isocyanate group, and an alkoxy group in the molecule can be used. In addition, by using a compound having an ethylenically unsaturated group in combination with a thermal radical polymerization initiator, a thermal polymerizable compound can also be used. Among the polymerizable compounds, from the aspect that a pattern can be easily formed using an existing process by a photolithography method, a photopolymerizable compound capable of polymerization by the following photoinitiator is preferable.

[0213] The photopolymerizable compound used in the colored curable composition is not particularly limited as long as it is capable of polymerization by the following photoinitiator, and generally a compound having two or more ethylenically unsaturated bonds is used, and a multifunctional (meth)acrylate having two or more acryl groups or methacryl groups is particularly preferable.

[0214] As such a multifunctional (meth)acrylate, one can be appropriately selected from those known in the past and used. As specific examples, for example, multifunctional (meth)acrylates described in Japanese Patent Application Publication No. 2013-029832, and the like can be exemplified.

[0215] These photopolymerizable compounds can be used alone or in combination of two or more. In addition, in the case where excellent photocurability (high sensitivity) is required for the colored curable composition of the present application, the photopolymerizable compound is preferably one having three or more (trifunctional) polymerizable ethylenically unsaturated bonds, and a poly(meth)acrylate of a trihydric or higher polyol, a dicarboxylic acid-modified product of these, specifically, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, a succinic acid-modified product of pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, a succinic acid-modified product of dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and the like are preferable.

[0216] The content of the polymerizable compound in the colored curable composition is, for example, preferably 5% by mass or more and 60% by mass or less, more preferably 10% by mass or more and 50% by mass or less, and still more preferably 20% by mass or more and 40% by mass or less, relative to the total amount of the solid components of the colored curable composition. If the content of the polymerizable compound is the above lower limit or more, curing failure can be suppressed, and thus the case where the exposed portion dissolves at the time of development can be suppressed, and if the content of the polymerizable compound is the above upper limit or less, development failure can be suppressed, and thus thermal shrinkage can be suppressed, and thus fine wrinkles are less likely to occur on the entire surface of the colored layer.

[0217] <Initiator>

[0218] As the initiator used in the colored curable composition of the present application, there is no particular limitation, and one or a combination of two or more kinds can be used from among various initiators known heretofore. As the initiator, for example, polymerization initiators such as thermal polymerization initiators, photopolymerization initiators, and the like can be exemplified, and specifically, for example, those described in Japanese Patent Application Publication No. 2013-029832 and the like can be exemplified.

[0219] As the photoinitiator, aromatic ketones, benzoin ethers, halomethyl oxadiazole compounds, a-amino ketones, bisimidazoles, N,N-dimethylamino benzophenone, halomethyl-hetrazine-based compounds, thioxanthone, and the like can be exemplified. As specific examples of the photoinitiator, benzophenone, 4,4'-bisdiethylaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, and the like aromatic ketones, benzoin methyl ether, and the like benzoin ethers, ethyl benzoin, and the like benzoin, 2-(o-chlorophenyl)-4,5-phenylimidazole dimer, and the like bisimidazoles, 2-trichloromethyl-5-(p-methoxystyryl)-1,3,4-oxadiazole, and the like halomethyl oxadiazole compounds, 2-(4-butoxy-naphthalen-1-yl)-4,6-bis-trichloromethyl-hetrazine, and the like halomethyl-hetrazine-based compounds, 2,2-dimethoxy-1,2-diphenylethan-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropanone, 1,2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-, 1-hydroxycyclohexyl phenyl ketone, benzil, benzoylbenzoic acid, benzoylbenzoic acid methyl ester, 4-benzoyl-4'-methyl diphenyl sulfide, benzil methyl ketal, dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, 2-n-butoxyethyl-4-dimethylaminobenzoate, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2,4-dimethylthioxanthone, isopropyl thioxanthone, 4-benzoyl-methyl diphenyl sulfide, 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, a-dimethoxy-a-phenylacetophenone, phenyl bis(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 can be exemplified.

[0220] Among them, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-(dimethylamino)-1-(4-morpholinophenyl)-1-butanone, 4,4'-bis(dimethylamino)benzophenone, and diethylthioxanthone are preferably used. From the viewpoint of adjusting sensitivity, suppressing water stains, and improving development resistance, further preferably, an α-aminoacetophenone-based initiator such as 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one is combined with a thioxanthone-based initiator such as diethylthioxanthone.

[0221] As for the total content of these in the case of using an α-aminoacetophenone-based initiator and a thioxanthone-based initiator, it is preferably 5 to 15 mass% with respect to the total amount of solid components of the color-curable composition. If it is below the upper limit value, sublimates in the manufacturing process are reduced, and thus it is preferred. If it is above the lower limit value, water stains and the like are improved, and development resistance is improved.

[0222] In the present application, among them, from the viewpoint of improving sensitivity, the photoinitiator preferably contains an oxime ester-based photoinitiator. In addition, by using an oxime ester-based photoinitiator, it is easy to suppress the difference in line width in the plane when forming a fine line pattern. Furthermore, by using an oxime ester-based photoinitiator, there is a tendency that the residual film rate is improved, and the effect of suppressing water stains is high.

[0223] As the oxime ester-based photoinitiator, from the viewpoint of reducing contamination of the color-curable composition and contamination of the device caused by decomposition products, among them, an oxime ester-based photoinitiator having an aromatic ring is preferred, an oxime ester-based photoinitiator having a condensed ring including an aromatic ring is more preferred, and an oxime ester-based photoinitiator having a condensed ring including a benzene ring and a heterocycle is further preferred.

[0224] As the oxime ester-based photoinitiator, one described in Japanese Patent Application Publication No. 2000-80068, Japanese Patent Application Publication No. 2001-233842, Japanese Patent Application Laid-Open No. 2010-527339, Japanese Patent Application Laid-Open No. 2010-527338, Japanese Patent Application Laid-Open No. 2013-041153, and the like can be appropriately selected. As commercially available 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, and the like (Irgacure series is manufactured by BASF Corporation, Adeka Arkls series is manufactured by ADEKA Corporation, and TR series is manufactured by Changzhou Qiangli Electronics New Material Co., Ltd.) can be used. From the aspect of brightness, it is particularly preferable to use an oxime ester-based photoinitiator having a diphenyl sulfide skeleton or a fluorene skeleton. In addition, from the aspect of higher sensitivity, it is preferable to use an oxime ester-based photoinitiator having a carbazole skeleton. From the aspects of sensitivity and brightness, it is preferable to use an oxime ester-based photoinitiator having a diphenyl sulfide skeleton in combination with an oxime ester-based photoinitiator having a fluorene skeleton. In addition, from the aspects of sensitivity and brightness, it is preferable to use an oxime ester-based photoinitiator having a diphenyl sulfide skeleton in combination with an oxime ester-based photoinitiator having a carbazole skeleton.

[0225] In addition, from the aspect of suppressing water stains and improving sensitivity, a photoinitiator having a tertiary amine structure can be used in combination with the oxime ester-based photoinitiator. The reason for this is that the photoinitiator having a tertiary amine structure is less likely to be deactivated by oxygen due to the tertiary amine structure as an oxygen quencher within the molecule, and thus the sensitivity can be improved. As commercially available products of the above-described photoinitiator having a tertiary amine structure, for example, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (for example, Irgacure 907, manufactured by BASF Corporation), 2-benzyl-2-(dimethylamino)-1-(4-morpholinophenyl)-1-butanone (for example, Irgacure 369, manufactured by BASF Corporation), 4,4'-bis(diethylamino)benzophenone (for example, Hicure ABP, manufactured by Kawaguchi Yakuhin), and the like can be exemplified.

[0226] In addition, from the viewpoint of adjusting sensitivity, suppressing water stains, and improving development resistance, the oxime ester-based photoinitiator and the thioxanthone-based initiator can be combined, and from the viewpoint of improving brightness, residual film rate, easily adjusting sensitivity, suppressing the generation of water stains, and improving development resistance, two or more kinds of oxime ester-based photoinitiators and the thioxanthone-based initiator can be combined.

[0227] The content of the initiator in the colored curable composition is, for example, preferably in the range of 0.1 to 15% by mass, and more preferably in the range of 1 to 10% by mass, relative to the total amount of solid components of the colored curable composition. If the content of the initiator is equal to or more than the lower limit of the above range, curing sufficiently proceeds, and if the content of the initiator is equal to or less than the upper limit of the above range, side reactions can be suppressed, and the stability over time can be maintained.

[0228] <Sensitizer>

[0229] In the present application, the dye diffusing in the system easily absorbs the exposed light, and the generation of radicals from the initiator easily occurs with a loss, and therefore, from the viewpoint of compensating for this, a sensitizer is preferably combined with the above-mentioned photoinitiator. Among them, from the viewpoint of good reactivity of the (meth)acrylic polymer system, a thiol-based sensitizer is preferably contained, and more preferably a thiol-based sensitizer is combined with the above-mentioned oxime ester-based initiator.

[0230] As the thiol-based sensitizer, a monofunctional thiol compound having one thiol group, and a polyfunctional thiol compound having two or more thiol groups can be exemplified.

[0231] As the monofunctional thiol compound, for example, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-5-methoxybenzothiazole, 2-mercapto-5-methoxybenzimidazole, 3-mercaptopropionic acid, 3-mercaptopropionic acid methyl ester, 3-mercaptopropionic acid ethyl ester, 3-mercaptopropionic acid octyl ester, and the like can be exemplified.

[0232] As the polyfunctional thiol compound, for example, 1,4-bis(3-mercaptopropionyloxy)butane, 1,3,5-tris(3-mercapto-butoxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, trimethylolpropane tri(3-mercaptopropionate), pentaerythritol tetra(3-mercaptopropionate), pentaerythritol tetra(3-mercaptopropionate), dipentaerythritol hexa(3-mercaptopropionate), and tetraethylene glycol bis(3-mercaptopropionate), and the like can be exemplified.

[0233] In the colored curable composition of the present application, the content in the case where a sensitizer is contained, for example, 0.5 to 10% by mass, relative to the total amount of solid components of the colored curable composition, can be used from the viewpoint of curability improvement. The content in the case where a sensitizer is contained, relative to the total amount of solid components of the colored curable composition, is more preferably in the range of 1 to 6% by mass, and further preferably in the range of 2 to 5% by mass.

[0234] With respect to the binder component (polymer, polymerizable compound, initiator, sensitizer, if necessary) used in the colored curable composition of the present application, the total content of these is preferably in the range of 35 to 97% by mass, and more preferably in the range of 40 to 96% by mass, relative to the total amount of solid components of the colored curable composition. If it is equal to or more than the above lower limit value, a colored layer having excellent hardness and adhesion to a substrate can be obtained. In addition, if it is equal to or less than the above upper limit value, development properties are excellent, and minute wrinkles due to heat shrinkage are also suppressed.

[0235] < Solvent >

[0236] As the solvent used in the present application, there is no particular limitation, and any organic solvent that does not react with the components in the colored curable composition and can dissolve or disperse these can be used. The solvent can be used alone or in combination of two or more.

[0237] As specific examples of the solvent, for example, alcohol-based solvents such as methanol, ethanol, isopropanol, methoxy alcohol, and the like; carbitol-based solvents such as methoxyethoxyethanol, ethoxyethoxyethanol, and the like; ester-based solvents such as ethyl acetate, butyl acetate, methoxypropyl acetate, ethoxypropyl acetate, ethyl lactate, methyl hydroxypropylate, ethyl hydroxypropylate, n-butyl acetate, isobutyl acetate, n-butyl butyrate, cyclohexyl acetate, and the like; ketone-based solvents such as acetone, methyl ethyl ketone, cyclohexanone, 2-heptanone, and the like; glycol ether acetate-based solvents such as methoxyethyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-l-butyl acetate, 3-methoxybutyl acetate, ethoxyethyl acetate, and the like; carbitol acetate-based solvents such as methoxyethoxyethyl acetate, ethoxyethoxyethyl acetate, butyl carbitol acetate (BCA), and the like; diacetate-based solvents such as propylene glycol diacetate, 1,3-butanediol diacetate, and the like; glycol ether-based solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, dipropylene glycol dimethyl ether, and the like; aprotic amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, and the like; lactone-based solvents such as γ-butyrolactone, and the like; cyclic ether-based solvents such as tetrahydrofuran, and the like; unsaturated hydrocarbon-based solvents such as benzene, toluene, xylene, naphthalene, and the like; saturated hydrocarbon-based solvents such as n-heptane, n-hexane, n-octane, and the like; and organic solvents such as aromatic hydrocarbons such as toluene, xylene, and the like. Among these solvents, from the viewpoint of solubility of other components, it is appropriate to use a glycol ether acetate-based solvent, a carbitol acetate-based solvent, a glycol ether-based solvent, an ester-based solvent. Among these, as the solvent used in the present application, from the viewpoint of solubility of other components and coating suitability, it is preferable to use one or more selected from the group consisting of 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-l-butyl acetate, ethyl lactate, methyl 2-hydroxypropylate, and 3-methoxybutyl acetate.

[0238] In addition, from the viewpoints of development properties, solvent redissolution properties, and the like, a mixed solvent containing two or more kinds of solvents can be used.

[0239] In addition, the content of the solvent can be appropriately set within a range in which a colored layer can be formed with good precision. In general, it is preferable that the content of the solvent be in a range of 55% by mass to 95% by mass, and more preferably 65% by mass to 88% by mass, with respect to the total amount of the colored curable composition containing the solvent. By setting the content of the solvent within the above range, the coating properties can be made excellent.

[0240] <Dispersant>

[0241] In the colored curable composition of the present application, a dispersant can be further included in view of dispersibility and stability of the colorant in the case of dispersing the colorant.

[0242] In the present application, the dispersant can be appropriately selected from conventionally known dispersants and used. As the dispersant, for example, a cationic, anionic, nonionic, amphoteric, silicone, fluorine, or the like surfactant can be used. Among the surfactants, a high-molecular dispersant is preferable in view of uniform and fine dispersion.

[0243] As the high-molecular dispersant, for example, the following can be exemplified: (co)polymers of unsaturated carboxylate esters such as polyacrylate; (partial) amine salts, (partial) ammonium salts, (partial) alkylamine salts of (co)polymers of unsaturated carboxylic acids such as polyacrylic acid; (co)polymers of hydroxyl-containing unsaturated carboxylate esters such as hydroxyl-containing polyacrylate, and modifications of these; polyurethanes; unsaturated polyamides; polysiloxanes; long-chain polyaminoamide phosphates; polyethyleneimine derivatives (amides obtained by reacting poly(lower alkylene imine) with a polyester containing a free carboxyl group, and bases of these); polyallylamine derivatives (reaction products obtained by reacting polyallylamine with one or more compounds selected from the group consisting of a polyester having a free carboxyl group, a polyamide, and a co-condensate (polyester amide) of an ester and an amide); and the like.

[0244] In addition, as the high-molecular dispersant, for example, a high-molecular dispersant having an amine value and containing a nitrogen atom in the main chain or side chain can be used, and among them, a high-molecular dispersant containing a polymer containing a repeating unit having a tertiary amine can be used. Among them, for example, a dispersant having at least one of a polymer having a structural unit represented by the following general formula (I) as described in Japanese Patent Application Publication No. 2016-224447, a block copolymer and a salt-type block copolymer having a structural unit represented by the following general formula (I) as described in International Publication No. 2016 / 104493 can be used in view of the fact that the main chain skeleton is less likely to be thermally decomposed and has high heat resistance.

[0245] [Chemical Formula 5]

[0246]

[0247] (In the general formula (I), R 1 represents a hydrogen atom or a methyl group, A represents a divalent linking group, R 2 and R 3 each independently represent a hydrogen atom, or a hydrocarbon group which can contain a hetero atom, R 2 and R 3 may be bonded to each other to form a ring structure.)

[0248] The above-described symbols are described in Japanese Patent Application Publication No. 2016-224447.

[0249] In addition, as the high-molecular dispersant, for example, a high-molecular dispersant having an acid value and containing an acidic group in a main chain or a side chain can be used. Among them, from the viewpoint of being less likely to be thermally decomposed from a main chain skeleton and having high heat resistance, for example, a non-aqueous dispersant that is a graft copolymer or a block copolymer can be used, the graft copolymer being a graft copolymer having at least one selected from a structural unit represented by the following general formula (I') and a structural unit represented by the following general formula (I"), and a structural unit represented by the following general formula (II), the block copolymer having a block portion containing at least one selected from a structural unit represented by the following general formula (I') and a structural unit represented by the following general formula (I"), and a block portion containing a structural unit represented by the following general formula (III).

[0250] [Chemical Formula 6]

[0251]

[0252] (In general formula (I') and general formula (I"), L 1 is a direct bond or a divalent linking group, R 1 is a hydrogen atom or a methyl group, R 2 is a hydrocarbon group, -[CH(R 6 )-CH(R 7 )-O] x1 -R 8 or -[(CH2) y1 -O] z1 -R 8 is a monovalent group represented by -R 6 and R 7 are each independently a hydrogen atom or a methyl group, R 8 is a hydrogen atom, a hydrocarbon group, -CHO, -CH2CHO, -CO-CH=CH2, -CO-C(CH3)=CH2, or -CH2COOR 9 is a monovalent group represented by -R 9 is a hydrogen atom or an alkyl group having a carbon number of 1 to 5, and the hydrocarbon group can have a substituent. 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.

[0253] In general formula (I'), X + represents an organic cation.

[0254] In general formula (II), L 2 represents a direct bond or a divalent linking group, R 3represents a hydrogen atom or a methyl group, and Polymer represents a polymer chain having one or more kinds of structural units represented by General Formula (IV) and structural units represented by General Formula (V).

[0255] In General Formula (III), R 4 represents a hydrogen atom or a methyl group, R 5 represents a hydrocarbon group, -[CH(R 10 )-CH(R 11 )-O] x2 -R 12 , -[(CH2) y2 -O] z2 -R 12 , -[CO-(CH2) y2 -O] z2 -R 12 , -CO-O-R 12 , or -O-CO-R 12 , R 10 and R 11 each independently represent a hydrogen atom or a methyl group, R 12 represents a hydrogen atom, a hydrocarbon group, -CHO, -CH2CHO, or -CH2COOR 13 , R 12 represents a hydrocarbon group, -[CH(R 10 )-CH(R 11 )-O] x2' -R 12 , -[(CH2) y2' -O] z2' -R 12 , -[CO-(CH2) y2' -O] z2' -R 12 , or -O-CO-R 12 , R 13 represents an alkyl group having 1 to 18 carbon atoms, and R 14 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and the above hydrocarbon group can have a substituent. x2 and x2' represent an integer of 1 to 18, y2 and y2' represent an integer of 1 to 5, and z2 and z2' represent an integer of 1 to 18.

[0256] [Chemical Formula 7]

[0257]

[0258] (In General Formula (IV) and General Formula (V), R 14 represents a hydrogen atom or a methyl group, R 15 represents a hydrocarbon group, -[CH(R 16 )-CH(R 17 )-O] x3-R 18 , -[(CH2) y3 -O] z3 -R 18 , -[CO-(CH2) y3 -O] z3 -R 18 , -CO-O-R 19 or -O-CO-R 20 a monovalent group represented by -R 16 and R 17 are each independently a hydrogen atom or a methyl group, R 18 is a hydrogen atom, a hydrocarbon group, -CHO, -CH2CHO or -CH2COOR 21 a monovalent group represented by -R 19 is a hydrocarbon group, -[CH(R 16 )-CH(R 17 )-O] x4 -R 18 , -[(CH2) y4 -O] z4 -R 18 , -[CO-(CH2) y4 -O] z4 -R 18 a monovalent group represented by -R 20 is an alkyl group having a carbon number of 1 to 18, R 21 is a hydrogen atom or an alkyl group having a carbon number of 1 to 5, and the above hydrocarbon group can have a substituent.

[0259] m represents an integer of 1 to 5, n 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.

[0260] The above symbols are explained in Japanese Patent Application Publication No. 2015-107471.

[0261] In the colored curable composition of the present application, the content of the dispersant is appropriately selected depending on the kind of the color material used, and further depending on the solid content concentration and the like in the colored curable composition.

[0262] The content of the dispersant in the colored curable composition of the present application is not particularly limited, and is preferably, for example, 1 to 40 mass%, more preferably 2 to 30 mass%, and further preferably 3 to 25 mass%, relative to the total amount of the solid components of the colored curable composition. If the content is equal to or greater than the lower limit, the dispersibility and dispersion stability of the color material are excellent, and the storage stability of the colored curable composition is more excellent. If the content is equal to or less than the upper limit, 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, for example, 2 to 25 mass%, and more preferably 3 to 20 mass%, relative to the total amount of the solid components of the colored curable composition. Note that, in the case of a salt-type block copolymer, the mass of the dispersant is the total mass of the block copolymer before salification and the compound(s) selected from the above general formulae (1) to (3).

[0263] <Optional Additives>

[0264] Various additives can be included in the colored curable composition as needed.

[0265] As the additives, for example, antioxidants, leveling agents, polymerization terminators, plasticizers, surfactants, defoaming agents, silane coupling agents, ultraviolet absorbers, adhesion promoters, and the like can be exemplified.

[0266] From the viewpoint of heat resistance, the colored curable composition of the present application preferably further contains an antioxidant. The antioxidant can be appropriately selected from those known in the art. As specific examples of the antioxidant, for example, hindered phenol-based antioxidants, amine-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, hydrazine-based antioxidants, and the like can be exemplified. From the viewpoint of heat resistance, a hindered phenol-based antioxidant is preferably used.

[0267] In addition, as specific examples of the surfactants and plasticizers, those described in Japanese Patent Application Publication No. 2013-029832 can be exemplified.

[0268] In the colored curable composition of the present application, from the viewpoints of degassing and heat shrinkage, the P / V ratio ((mass of the color material component in the composition) / (mass of the solid components other than the color material component in the composition)) is preferably 0.1 or greater, and further preferably 0.2 or greater, and on the other hand, from the viewpoints of excellent display defects and ease of manufacture, i.e., excellent solvent redissolution, development residue, development adhesion, development resistance, water mark generation suppression effect, and the like, the P / V ratio is preferably 0.6 or less, and more preferably 0.5 or less.

[0269] <Method for Producing Colored Curable Composition>

[0270] The method for producing the colored curable composition of the present application is not particularly limited, and for example, the color material, the polymer, the polymerizable compound, the initiator, the solvent, and various additive ingredients used as necessary can be mixed by using a publicly known mixing method to produce the colored curable composition.

[0271] In the case where the colored curable composition of the present application contains a color material, a polymer, a polymerizable compound, an initiator, a dispersant, a solvent, and various additive ingredients used as necessary, as the method for producing the resin composition, for example, the following methods can be exemplified: (1) a method in which a color material dispersing solution is first prepared by adding a color material and a dispersant in a solvent, and a polymer, a polymerizable compound, an initiator, and various additive ingredients used as necessary are mixed in the dispersing solution; (2) a method in which a color material, a dispersant, a polymer, a polymerizable compound, an initiator, and various additive ingredients used as necessary are simultaneously put in a solvent and mixed; (3) a method in which a dispersant, a polymer, a polymerizable compound, an initiator, and various additive ingredients used as necessary are added in a solvent, mixed, and then a color material is added and dispersed; (4) a method in which a color material dispersing solution is prepared by adding a color material, a dispersant, and a polymer in a solvent, and a polymer, a solvent, a polymerizable compound, an initiator, and various additive ingredients used as necessary are further added in the dispersing solution and mixed; and the like.

[0272] Among these methods, from the viewpoint of effectively preventing the aggregation of the color material and uniformly dispersing, the methods of (1) and (4) described above are preferred.

[0273] The method for producing the color material dispersing solution can be appropriately selected from publicly known dispersing methods.

[0274] For example, the method for producing the color material dispersing solution includes a step of preparing the dispersant described above, and a step of dispersing a color material in the presence of the dispersant described above in a solvent. Two or more color materials can be co-dispersed in the presence of the dispersant described above in a solvent, or two or more color material dispersing solutions can be mixed after dispersing or co-dispersing one or more color materials, thereby obtaining a color material dispersing solution.

[0275] In the case of dispersing a color material, a publicly known disperser can be used for the dispersion.

[0276] As a specific example of the disperser, a roll mill such as a two-roll mill or a three-roll mill; a ball mill such as a ball mill or a vibration ball mill; a paint conditioner; a continuous disk-type bead mill; and a continuous ring-type bead mill can be exemplified. As the preferred dispersing conditions for the bead mill, the bead diameter used is preferably 0.03 to 3.0 mm, and more preferably 0.05 to 2.0 mm.

[0277] Specifically, for example, pre-dispersion by 2.0 mm zirconia beads having a relatively large bead diameter, and further, formal dispersion by 0.1 mm zirconia beads having a relatively small bead diameter can be exemplified. In addition, it is preferable that after dispersion, filtration by a filter of 0.5 to 2 μm is performed.

[0278] As the color material, in the case of using only a color material dissolved in the color-curable composition other than the halogenated phthalocyanine color material of the present application, a color material solution in which a color material is dissolved in a solvent can be used instead of the color material dispersion liquid containing the above-described dispersant. As to the pattern of "color material solution" in which a color material is present in a state of being dissolved in a solvent, and "color material dispersion liquid" in which particles of a color material are dispersed in a solvent, it is sometimes referred to as "color material liquid" in the present application.

[0279] The color-curable composition of the present application can be particularly suitably used for a color filter use because it can form a colored layer in which the precipitation of foreign matters is inhibited and the contrast is improved, and can form a colored layer in which the brightness is also excellent by containing the above-described halogenated phthalocyanine color material of the present application.

[0280] The color-curable composition of the present application can be used for various uses in which the precipitation of foreign matters is inhibited and a good contrast is required, and can be used for an inkjet ink or a printing ink.

[0281] III. Color Filter

[0282] The color filter of the present application at least has a transparent substrate, and a colored layer provided on the transparent substrate, and at least one of the colored layers is a colored layer which is a cured product of the above-described color-curable composition of the present application.

[0283] The color filter of the present application is described with reference to the drawings. Figure 1 is a schematic cross-sectional view showing an example of the color filter of the present application. According to the present application, Figure 1 , the color filter 10 has a transparent substrate 1, a light-shielding portion 2, and a colored layer 3.

[0284] <Colored Layer>

[0285] At least one of the colored layers used in the color filter of the present application is a colored layer formed by curing the above-described color-curable composition of the present application.

[0286] The colored layer is generally formed on an opening portion of the light-shielding portion of the following transparent substrate, and is generally composed of 3 or more colored patterns.

[0287] In addition, the arrangement of the colored layer is not particularly limited, and for example, a general arrangement such as a stripe type, a mosaic type, a triangle type, a four-pixel configuration type (Japanese: 4-pixel configuration type), and the like can be adopted. In addition, the width, the area, and the like of the colored layer can be arbitrarily set.

[0288] The thickness of the colored layer is appropriately controlled by adjusting the coating method, the solid content concentration of the colored curable composition, the viscosity, and the like, and is preferably in the range of 1 to 5 μm in general.

[0289] The colored layer can be formed, for example, by the following method.

[0290] First, the colored curable composition of the present application is coated on the following transparent substrate 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, a die coating method, and the like, to form a wet coating film. Among them, the spin coating method and the die coating method can be preferably used.

[0291] Next, the wet coating film is dried using a hot plate or an oven, and the like, and is exposed to light through a mask having a predetermined pattern, to cause the alkali-soluble resin and the polyfunctional monomer, and the like, to undergo photopolymerization, thereby producing a cured coating film. As a light source for the exposure, ultraviolet rays of a low-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, and the like, an electron beam, and the like, can be exemplified. The exposure amount is appropriately adjusted depending on the light source used, the thickness of the coating film, and the like.

[0292] In addition, heating treatment can be performed after the exposure, to promote the polymerization. The heating conditions are appropriately selected depending on the blending ratio of each component in the colored curable composition used, the thickness of the coating film, and the like.

[0293] Then, development treatment is performed using a developing solution, to dissolve and remove the unexposed portions, thereby forming a coating film in a desired pattern. As the developing solution, a solution in which an alkali is dissolved in water or a water-soluble solvent is generally used. A surfactant, and the like, can be appropriately added to the alkali solution. In addition, the developing method can employ a general method.

[0294] After the development treatment, the developing solution is generally washed off, and the cured coating film of the colored curable composition is dried, to form a colored layer. Note that heating treatment can be performed after the development treatment, to sufficiently cure the coating film. The heating conditions are not particularly limited, and are appropriately selected depending on the use of the coating film.

[0295]

[0296] The light-shielding portion in the color filter of the present application is formed in a pattern on the following transparent substrate, and can be the same as that used as a light-shielding portion in a general color filter.

[0297] ​The pattern shape of the light-shielding portion is not particularly limited, and examples include a stripe shape and a matrix shape. The light-shielding portion can be a metal thin film such as chromium formed by a sputtering method, a vacuum evaporation method, or the like. Alternatively, the light-shielding portion can be a resin layer containing light-shielding particles such as carbon particles, metal oxides, inorganic pigments, organic pigments, or the like in a 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 using an inkjet ink containing light-shielding particles, a method of thermal transfer printing a photosensitive resist, and the like.

[0298] The film thickness of the light-shielding portion is set to a range of 0.2 to 0.4 μm in the case of a metal thin film, and is set to a range of 0.5 to 2 μm in the case of a black pigment dispersed or dissolved in a binder resin.

[0299] <Substrate>

[0300] As the substrate, a transparent substrate, a silicon substrate, and a substrate on which an aluminum thin film, a silver thin film, a silver / copper / palladium alloy thin film, or the like is formed on a transparent substrate or a silicon substrate are used. On these substrates, a color filter layer, a resin layer, a transistor such as a TFT, a circuit, or the like can be further formed.

[0301] The transparent substrate in the color filter of the present application is not particularly limited as long as it is a substrate transparent to visible light, and a transparent substrate used in a general color filter can be used. Specifically, examples include a transparent rigid material such as quartz glass, alkali-free glass, and synthetic quartz plate, which has no flexibility; and a transparent flexible material such as a transparent resin film, an optical resin plate, and flexible glass, which has flexibility.

[0302] The thickness of the transparent substrate is not particularly limited, and a transparent substrate having a thickness of, for example, 100 μm to 1 mm can be used depending on the use of the color filter of the present application.

[0303] Note that the color filter of the present application can be formed with an overcoat layer, a transparent electrode layer, and further an alignment film, a column spacer, or the like, in addition to the above-described substrate, light-shielding portion, and colored layer.

[0304] IV. Display device

[0305] The display device of the present application is characterized by having the above-mentioned color filter of the present application. In the present application, the constitution of the display device is not particularly limited and can be appropriately selected from conventionally known display devices, and for example, a liquid crystal display device, an organic light emitting display device, or the like can be exemplified. In terms of the present application, various display malfunctions such as liquid crystal alignment disorder caused by the electrical characteristics of green pixels, afterimage phenomenon (Japanese: yaki-ki phenomenon) caused by threshold value deviation of switching, and the like are also suppressed in a liquid crystal display device of the lateral electric field mode, and thus a liquid crystal display device is suitably selected.

[0306] < Liquid crystal display device >

[0307] The liquid crystal display device of the present application is characterized by having the above-mentioned color filter of the present application, a counter substrate, and a liquid crystal layer formed between the above-mentioned color filter and the above-mentioned counter substrate.

[0308] The liquid crystal display device of the present application is described with reference to the drawings. Figure 2 is a schematic diagram showing an example of the display device of the present application, and is a schematic diagram showing an example of a liquid crystal display device. As Figure 2 exemplified, the liquid crystal display device 40 of the present application has a color filter 10, a counter substrate 20 having a TFT array substrate or the like, and a liquid crystal layer 30 formed between the above-mentioned color filter 10 and the above-mentioned counter substrate 20.

[0309] Note that the liquid crystal display device of the present application is not limited to the constitution shown in Figure 2 and a constitution known as a liquid crystal display device in which a color filter is generally used can be employed.

[0310] As the driving mode of the liquid crystal display device of the present application, there is no particular limitation and a driving mode generally used for a liquid crystal display device can be employed. As such a driving mode, for example, a TN mode, an IPS mode, an OCB mode, and an MVA mode, or the like can be exemplified. In the present application, any of these modes can be suitably used.

[0311] In addition, as the counter substrate, a conventionally known counter substrate can be used according to the driving mode of the liquid crystal display device of the present application or the like.

[0312] Further, as the liquid crystal constituting the liquid crystal layer, various liquid crystals having different dielectric anisotropies and mixtures thereof can be used according to the driving mode of the liquid crystal display device of the present application or the like.

[0313] As the method of forming the liquid crystal layer, a method generally used as a method of manufacturing a liquid crystal cell can be used, and for example, a vacuum injection method or a liquid crystal dropping method, or the like can be exemplified.

[0314] As for the vacuum injection method, for example, the liquid crystal layer can be formed as follows: a liquid crystal cell is prepared in advance using the color filter and the counter substrate, the liquid crystal is made into an isotropic liquid by heating, the liquid crystal is injected into the liquid crystal cell in the state of the isotropic liquid by capillary action, and the liquid crystal layer is formed by sealing with an adhesive. Thereafter, the liquid crystal can be oriented by slowly cooling the liquid crystal cell to room temperature.

[0315] In addition, as for the liquid crystal dropping method, for example, the liquid crystal layer can be formed as follows: a sealant is applied to the periphery of the color filter, the color filter is heated to a temperature at which the liquid crystal becomes an isotropic phase, the liquid crystal is dropped in the state of an isotropic liquid using a dispenser or the like, the color filter and the counter substrate are overlapped under reduced pressure, and the liquid crystal layer is formed by adhesion with the sealant. Thereafter, the liquid crystal can be oriented by slowly cooling the liquid crystal cell to room temperature.

[0316] <Organic light emitting display device>

[0317] The organic light emitting display device of the present application is characterized by having the above-described color filter of the present application and an organic light emitter.

[0318] The organic light emitting display device of the present application will be described with reference to the drawings. Figure 3 is a schematic view showing another example of the display device of the present application, and is a schematic view showing an example of an organic light emitting display device. As shown in the drawing, Figure 3 The organic light emitting display device 100 of the present application has a color filter 10 and an organic light emitter 80, as exemplified. An organic protective layer 50 and an inorganic oxide film 60 can be provided between the color filter 10 and the organic light emitter 80.

[0319] As a method of laminating the organic light emitter 80, for example, 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 can be exemplified, a method of attaching the organic light emitter 80 formed on another substrate to the inorganic oxide film 60, and the like. The transparent anode 71, the hole injection layer 72, the hole transport layer 73, the light emitting layer 74, the electron injection layer 75, and the cathode 76, and other components of the organic light emitter 80 can be suitably used as known. The organic light emitting display device 100 thus produced can be applied to an organic EL display of a passive drive type, for example, and can be applied to an organic EL display of an active drive type.

[0320] Note that the organic light emitting display device of the present application is not limited to the Figure 3 configuration shown in the drawing, and a configuration known as a conventional organic light emitting display device using a color filter can be employed.

[0321] Example

[0322] Hereinafter, the present application will be specifically described with examples. The present application is not limited by these descriptions.

[0323] The halogenated phthalocyanine color material intermediate was analyzed by LC-MS (Agilent, Quadrupole LC / MS, Agilent 1260 Infinity).

[0324] (Synthetic Example 1: Synthesis of Alkali-soluble Resin A Solution)

[0325] A mixed solution of benzyl methacrylate (BzMA) 40 parts by mass, methyl methacrylate (MMA) 15 parts by mass, methacrylic acid (MAA) 25 parts by mass, and azobisisobutyronitrile (AIBN) 3 parts by mass was dropped into a polymerization tank to which propylene glycol monomethyl ether acetate (PGMEA) 150 parts by mass was added under a stream of nitrogen at 100°C over 3 hours. After the dropping was completed, further heating was performed at 100°C for 3 hours, and a polymer solution was obtained. The weight average molecular weight of the polymer solution was 7000.

[0326] Next, glycidyl methacrylate (GMA) 20 parts by mass, triethylamine 0.2 parts by mass, and p-methoxyphenol 0.05 parts by mass were added to the obtained polymer solution, and heating was performed at 110°C for 10 hours, whereby the reaction of the carboxylic acid group of the main chain methacrylic acid and the epoxy group of the glycidyl methacrylate was performed. In the reaction, air was bubbled in the reaction solution in order to prevent the polymerization of the glycidyl methacrylate. Note that the reaction was traced by measuring the acid value of the solution. The obtained alkali-soluble resin A was a resin in which GMA was introduced into the main chain formed by the copolymerization of BzMA and MMA, MAA to have a side chain having an ethylenic unsaturated bond, and the acid value was 74 mgKOH / g, and the weight average molecular weight was 12000. The solid content of the alkali-soluble resin A solution was 40% by mass.

[0327] (Example 1)

[0328] (1) Production of Halogenated Phthalocyanine Color Material 1

[0329] In a 100-ml flask, tetrachlorophthalonitrile 5.0 g (25.0 mmol) and N,N-dimethylformamide 25 ml were put, and stirring was performed at 40°C until it was dissolved. Next, methyl 4-(hydroxymethyl)benzoate 4.15 g (25.0 mmol) was put, and stirring was performed at 40°C until it was dissolved. Next, potassium carbonate 5.18 g (37.5 mmol) was put, and reaction was performed at 100°C for 6 hours. After the reaction was completed, the potassium carbonate was removed by filtration, and for the obtained reaction solution, the solvent was removed by distillation using an evaporator, and the obtained solid was dissolved in chloroform, and liquid-liquid treatment was performed using pure water.

[0330] The organic layer after the separation was recrystallized in acetone to obtain intermediate 1-1.

[0331] Intermediate 1-1 was analyzed by LC-MS. A representative chemical structural formula of intermediate 1-1 is shown below.

[0332] [Chemical Formula 8]

[0333] Intermediate 1-1

[0334]

[0335] In a 50-ml flask, 5.19 g (15.0 mmol) of intermediate 1-1 and 15.97 ml of acetone were placed and stirred at 0°C. Next, 3.11 g (22.5 mmol) of potassium carbonate was placed, and next, 2.49 g (15.0 mmol) of ethyl 4-hydroxybenzoate, which was dissolved in 10 g of acetone, was added dropwise while stirring at 0°C for 2 hours. Further, stirring was continued for 1 hour, and the reaction was completed. After the completion of the reaction, the potassium carbonate was removed by filtration, and the solvent was distilled off from the obtained reaction solution by an evaporator. The obtained solid was dissolved in chloroform, and the solution was subjected to a liquid separation treatment with pure water.

[0336] The organic layer after the separation was recrystallized in acetone to obtain intermediate 1-2.

[0337] Intermediate 1-2 was analyzed by LC-MS. A representative chemical structural formula of intermediate 1-2 is shown below.

[0338] [Chemical Formula 9]

[0339] Intermediate 1-2

[0340]

[0341] In a 50-ml flask, 3.94 g (8.00 mmol) of intermediate 1-2 and 19.70 g of benzonitrile were placed, and next, 0.64 g (2.00 mmol) of zinc iodide was placed. The reaction was carried out while stirring at 150°C for 16 hours. After the reaction solution was cooled to room temperature, 20 ml of a mixed solvent of water and methanol (3:7) was placed, and the precipitate produced was recovered by a filter paper, and the stirring and filtration in a beaker were repeated several times with isopropyl alcohol and washed.

[0342] The obtained product was dried to obtain halogenated phthalocyanine color material 1. A representative chemical structural formula is shown below.

[0343] [Chemical Formula 10]

[0344] Color material 1

[0345]

[0346] (2) Production of colorant liquid G1

[0347] As the dispersant, a dispersant b (salt-type block copolymer) solution was prepared in the same manner as the production of the dispersant b of Synthetic Example II-2 described in paragraph 0302 of International Publication No. 2016 / 104493.

[0348] Into a mayonnaise jar were put 8.13 parts by mass of the above-described dispersant b solution as a dispersant, 7.8 parts by mass of halogenated phthalocyanine colorant 1 as a colorant, 5.2 parts by mass of C.I. Pigment Yellow 138 (PY138, trade name: Chromofine Yellow 6206EC, manufactured by Okitsu Kogyo Co., Ltd.) as a yellow colorant, 14.63 parts by mass of the alkali-soluble resin A solution obtained in Synthetic Example 1, 64.25 parts by mass of PGMEA, and 100 parts by mass of zirconia beads of 2.0 mm in particle diameter, and the mixture was shaken for 1 hour by a paint shaker (manufactured by Hatta Tekko Co., Ltd.) as a pre-dispersion. Next, the zirconia beads of 2.0 mm in particle diameter were removed, and 200 parts by mass of zirconia beads of 0.1 mm in particle diameter were added, and the mixture was dispersed for 4 hours by the paint shaker as a main dispersion, to obtain a colorant liquid G1.

[0349] (3) Production of colored curable composition G1

[0350] To 43.43 parts by mass of the colorant liquid G1 obtained in the above-described (2), 4.23 parts by mass of the alkali-soluble resin A solution obtained in Synthetic Example 1, 3.95 parts by mass of a multifunctional monomer (trade name: ARONIX M-403, manufactured by Toagosei Co., Ltd.), 0.50 parts by mass of a photoinitiator (trade name: TR-PBG-3057, manufactured by Changzhou Qiangli Electronic New Material Co., Ltd.), 0.50 parts by mass of a photoinitiator (trade name: Adeka Arkls NCI-831, manufactured by ADEKA Corporation), 0.13 parts by mass of a sensitizer (pentaerythritol tetra(3-mercaptobutyrate), trade name: Karenz MT-PE1, manufactured by Showa Denko), 0.03 parts by mass of a fluorine-based surfactant (trade name: MEGAFAC F559, manufactured by DIC Corporation), 0.34 parts by mass of a silane coupling agent (trade name: KBM503, manufactured by Shin-Etsu Silicone), 26.24 parts by mass of PGMEA, and 20.65 parts by mass of propylene glycol monomethyl ether (PGME) were added, to obtain a colored curable composition G1.

[0351] (4) Formation of colored layer

[0352] The coloring and curing composition G1 obtained in (3) above was coated to a thickness of 0.7 mm onto a 100 mm × 100 mm glass substrate (manufactured by NH TECHNO GLASS Co., Ltd., "NA35") using a spin coater. After drying at 80°C for 3 minutes using a heating plate, it was irradiated with a 60 mJ / cm² ultra-high pressure mercury lamp. 2 The film is then exposed to ultraviolet light and further baked in a clean oven at 230°C for 30 minutes, thereby adjusting the film thickness to 2.5 μm to form the colored layer G1.

[0353] (Example 2)

[0354] (1) Manufacturing of halogenated phthalocyanine pigment 2

[0355] In a 100 mL flask, 5.0 g (25.0 mmol) of tetrachlorophthalonitrile and 25 mL of N,N-dimethylformamide were added and stirred at 40 °C until dissolved. Next, 3.35 g (25.0 mmol) of diethylene glycol monoethyl ether was added and stirred at 40 °C until dissolved. Then, 5.18 g (37.5 mmol) of potassium carbonate was added, and the reaction was carried out at 100 °C for 6 hours. After the reaction was complete, the potassium carbonate was removed by filtration. The solvent in the resulting reaction solution was removed by distillation using an evaporator, and the resulting solid was dissolved in chloroform and separated by distillation with pure water.

[0356] The organic layer after separation was purified by silica gel column chromatography to obtain intermediate 2-1.

[0357] Intermediate 2-1 was analyzed by LC-MS. The representative chemical structure of intermediate 2-1 is shown below.

[0358] [Chemical Formula 11]

[0359] Intermediate 2-1

[0360]

[0361] In a 50 ml flask, 6.29 g (20.0 mmol) of intermediate 2-1 and 17.0 ml of acetone were added and stirred at 0 °C. Next, 4.15 g (30.0 mmol) of potassium carbonate was added. Then, 3.32 g (20.0 mmol) of ethyl 4-hydroxybenzoate was dissolved in 10 g of acetone, and the mixture was added dropwise over 2 hours while stirring at 0 °C. The reaction was then continued for an additional hour of stirring to complete the reaction. After the reaction was complete, the potassium carbonate was removed by filtration. The solvent in the resulting reaction solution was removed by distillation using an evaporator. The resulting solid was dissolved in chloroform and separated by distillation with pure water.

[0362] The organic layer after the separation was recrystallized in acetone to obtain intermediate 2-2.

[0363] Intermediate 2-2 was analyzed by LC-MS. A representative chemical structural formula of intermediate 2-2 is shown below.

[0364] [Chemical Formula 12]

[0365] Intermediate 2-2

[0366]

[0367] In a 50 ml flask, intermediate 2-2 3.68 g (8.00 mmol) and benzonitrile 16.66 g were placed, and then, zinc iodide 0.64 g (2.00 mmol) was placed, and the reaction was performed at 150°C for 16 hours while stirring. After the reaction solution was cooled to room temperature, a mixed solvent of water and methanol (3:7) 20 ml was placed, and the generated precipitate was recovered by filter paper, and stirring and filtration were repeatedly performed several times in a beaker using isopropyl alcohol and washed.

[0368] The obtained product was dried to obtain halogenated phthalocyanine color material 2. A representative chemical structural formula is shown below.

[0369] [Chemical Formula 13]

[0370] Color material 2

[0371]

[0372] (2) Production of color material liquid G2

[0373] In (2) of Example 1, the above obtained halogenated phthalocyanine color material 2 was used instead of halogenated phthalocyanine color material 1 in an equimolar amount, and otherwise, color material liquid G2 was obtained in the same manner as in (2) of Example 1.

[0374] (3) Production of colored curable composition G2

[0375] The above color material liquid G2 was used instead of color material liquid G1 in (3) of Example 1, and otherwise, colored curable composition G2 was obtained in the same manner as in (3) of Example 1.

[0376] (4) Formation of colored layer

[0377] In (4) of Example 1, the above colored curable composition G2 was used instead of colored curable composition G1, and otherwise, colored layer G2 was obtained in the same manner as in (4) of Example 1.

[0378] (Example 3)

[0379] (1) Production of halogenated phthalocyanine color material 3

[0380] Into a 100-ml flask was placed tetrachlorophthalonitrile 5.0 g (25.0 mmol) and N,N-dimethylformamide 25 ml, and stirring was performed at 40°C until it was dissolved. Next, ethyl glycolate 2.60 g (25.0 mmol) was placed, and stirring was performed at 40°C until it was dissolved. Next, potassium carbonate 5.18 g (37.5 mmol) was placed, and reaction was performed at 100°C for 6 hours. After the completion of the reaction, the potassium carbonate was removed by filtration, and, for the obtained reaction solution, the solvent was distilled off by an evaporator, the obtained solid was dissolved in chloroform, and liquid-liquid separation was performed using purified water.

[0381] For the organic layer after liquid-liquid separation, purification treatment was performed by a silica gel column, and intermediate 3-1 was obtained.

[0382] Intermediate 3-1 was analyzed by LC-MS. The representative chemical structural formula of intermediate 3-1 is shown below.

[0383] [Chemical Formula 14]

[0384] Intermediate 3-1

[0385]

[0386] Into a 50-ml flask was placed intermediate 3-1 5.68 g (20.0 mmol) and acetone 18.4 ml, and stirring was performed at 0°C. Next, potassium carbonate 4.15 g (30.0 mmol) was placed, and, next, ethyl 4-hydroxybenzoate 3.32 g (20.0 mmol) was dissolved in acetone 10 g, and, while stirring was performed at 0°C, it was dropped for 2 hours. Further, stirring was performed for 1 hour, and the reaction was completed. After the completion of the reaction, the potassium carbonate was removed by filtration, and, for the obtained reaction solution, the solvent was distilled off by an evaporator, the obtained solid was dissolved in chloroform, and liquid-liquid separation was performed using purified water.

[0387] For the organic layer after liquid-liquid separation, recrystallization treatment was performed in acetone, and intermediate 3-2 was obtained.

[0388] Intermediate 3-2 was analyzed by LC-MS. The representative chemical structural formula of intermediate 3-2 is shown below.

[0389] [Chemical Formula 15]

[0390] Intermediate 3-2

[0391]

[0392] In a 50-ml flask, intermediate 3-2 3.44 g (8.00 mmol) and benzonitrile 17.2 g were placed, and then, zinc iodide 0.64 g (2.00 mmol) was placed, and the reaction was carried out at 150°C for 16 hours while stirring. After the reaction solution was cooled to room temperature, a mixed solvent of water and methanol (3:7) 20 ml was placed, and the generated precipitate was recovered by filter paper, and repeatedly stirred and filtered in a beaker using isopropyl alcohol and washed.

[0393] The obtained product was dried to obtain halogenated phthalocyanine colorant 3. The chemical structural formula is shown below.

[0394] [Chemical Formula 16]

[0395] Colorant 3

[0396]

[0397] (2) Production of colorant solution G3

[0398] In (2) of Example 1, the above obtained halogenated phthalocyanine colorant 3 was used instead of halogenated phthalocyanine colorant 1 in an equimolar amount, and otherwise, colorant solution G3 was obtained in the same manner as in (2) of Example 1.

[0399] (3) Production of colored curable composition G3

[0400] Colored curable composition G3 was obtained using the above colorant solution G3 instead of colorant solution G1 in (3) of Example 1, and otherwise, in the same manner as in (3) of Example 1.

[0401] (4) Formation of colored layer

[0402] In (4) of Example 1, the above colored curable composition G3 was used instead of colored curable composition G1, and otherwise, colored layer G3 was obtained in the same manner as in (4) of Example 1.

[0403] (Example 4)

[0404] (1) Production of halogenated phthalocyanine colorant 4

[0405] In a 100-ml flask, tetrachloro-phthalonitrile 5.0 g (25.0 mmol) and N,N-dimethylformamide 25 ml were put, and stirred at 40°C until it was dissolved. Next, ethyl trans-4-hydroxycyclohexanecarboxylate 4.31 g (25.0 mmol) was put, and stirred at 40°C until it was dissolved. Next, potassium carbonate 5.18 g (37.5 mmol) was put, and reacted at 100°C for 6 hours. After the reaction was completed, the potassium carbonate was removed by filtration, and the obtained reaction solution was subjected to distillative removal of the solvent by an evaporator, and the obtained solid was dissolved in chloroform, and subjected to liquid separation treatment with pure water.

[0406] The organic layer after the liquid separation was subjected to purification treatment by a silica gel column, and intermediate 4-1 was obtained.

[0407] Intermediate 4-1 was analyzed by LC-MS. A representative chemical structural formula of intermediate 4-1 is shown below.

[0408] [Chemical Formula 17]

[0409] Intermediate 4-1

[0410]

[0411] In a 50-ml flask, intermediate 4-1 7.03 g (20.0 mmol) and acetone 25.1 ml were put, and stirred at 0°C. Next, potassium carbonate 4.15 g (30.0 mmol) was put, and next, ethyl 4-hydroxybenzoate 3.32 g (20.0 mmol) was dissolved in acetone 10 g, and dropped while being stirred at 0°C for 2 hours. Further, stirring was performed for 1 hour, and the reaction was completed. After the reaction was completed, the potassium carbonate was removed by filtration, and the obtained reaction solution was subjected to distillative removal of the solvent by an evaporator, and the obtained solid was dissolved in chloroform, and subjected to liquid separation treatment with pure water.

[0412] The organic layer after the liquid separation was subjected to recrystallization treatment in acetone, and intermediate 4-2 was obtained.

[0413] Intermediate 4-2 was analyzed by LC-MS. A representative chemical structural formula of intermediate 4-2 is shown below.

[0414] [Chemical Formula 18]

[0415] Intermediate 4-2

[0416]

[0417] In a 50-ml flask, intermediate 4-2 3.99 g (8.00 mmol) and benzonitrile 19.9 g were charged, followed by zinc iodide 0.64 g (2.00 mmol), and the reaction was carried out at 150°C for 16 hours while stirring. After the reaction solution was cooled to room temperature, a mixed solvent of water and methanol (3:7) 20 ml was charged, and the resulting precipitate was recovered by filter paper, and repeatedly stirred and filtered in a beaker using isopropyl alcohol and washed.

[0418] The obtained product was dried to obtain halogenated phthalocyanine colorant 4. The chemical structural formula is shown below.

[0419] [Chemical Formula 19]

[0420] Colorant 4

[0421]

[0422] (2) Production of colorant solution G4

[0423] In (2) of Example 1, the above-obtained halogenated phthalocyanine colorant 4 was used instead of halogenated phthalocyanine colorant 1 in an equimolar amount, and otherwise, colorant solution G4 was obtained in the same manner as in (2) of Example 1.

[0424] (3) Production of colored curable composition G4

[0425] Colored curable composition G4 was obtained in the same manner as in (3) of Example 1, using the above colorant solution G4 instead of colorant solution G1 in (3) of Example 1.

[0426] (4) Formation of colored layer

[0427] In (4) of Example 1, the above colored curable composition G4 was used instead of colored curable composition G1, and otherwise, colored layer G4 was obtained in the same manner as in (4) of Example 1.

[0428] (Comparative Example 1)

[0429] (1) Production of comparative halogenated phthalocyanine colorant 1

[0430] In a 100-ml flask, tetrachlorophthalonitrile 5.0 g (25.0 mmol) and N,N-dimethylformamide 25 ml were put in and stirred at 40°C until it was dissolved. Next, ethyl 4-hydroxybenzoate 8.31 g (50.0 mmol) was put in and stirred at 40°C until it was dissolved. Next, potassium carbonate 5.18 g (37.5 mmol) was put in and reacted at 0°C for 3 hours. After the completion of the reaction, the potassium carbonate was removed by filtration, and, for the obtained reaction solution, the solvent was distilled off by an evaporator, the obtained solid was dissolved in chloroform, and the solution was subjected to a liquid-liquid separation treatment with pure water.

[0431] For the organic layer after the liquid-liquid separation, a recrystallization treatment was performed in acetone, and comparative intermediate 1 was obtained.

[0432] Comparative intermediate 1 was analyzed by LC-MS. The representative chemical structural formula of comparative intermediate 1 is shown below.

[0433] [Chemical Formula 20]

[0434] Comparative intermediate 1

[0435]

[0436] In a 50-ml flask, comparative intermediate 1 3.94 g (8.00 mmol) and benzonitrile 19.7 g were put in, and, next, zinc iodide 0.64 g (2.00 mmol) was put in and reacted at 150°C while stirring for 16 hours. After the reaction liquid was cooled to room temperature, a mixed solvent of water and methanol (3:7) 20 ml was put in, the generated precipitate was recovered by a filter paper, and stirring and filtration in a beaker were repeatedly performed several times and washed with isopropyl alcohol.

[0437] The obtained product was dried, and comparative halogenated phthalocyanine color material 1 was obtained.

[0438] The representative chemical structural formula of comparative halogenated phthalocyanine color material 1 is shown below.

[0439] [Chemical Formula 21]

[0440]

[0441] (2) Production of Comparative Color Material Liquid CG1

[0442] In (2) of Example 1, the above obtained comparative halogenated phthalocyanine color material 1 was used instead of halogenated phthalocyanine color material 1 in an equimolar amount, and, other than that, comparative color material liquid CG1 was obtained in the same manner as in (2) of Example 1.

[0443] (3) Production of Comparative Colored Curing Property Composition CG1

[0444] A comparative colored curable composition CG1 was obtained in the same manner as in (3) of Example 1, except that the above-described comparative colorant liquid CG1 was used instead of the colorant liquid G1 in (3) of Example 1.

[0445] (4) Formation of a colored layer

[0446] A colored layer CG1 was obtained in the same manner as in (4) of Example 1, except that the above-described comparative colored curable composition CG1 was used instead of the colored curable composition G1 in (4) of Example 1.

[0447] (Comparative Example 2)

[0448] (1) Production of Comparative Halogenated Phthalocyanine Colorant 2

[0449] In a 100-ml flask, 5.0 g (25.0 mmol) of tetrachlorophthalonitrile and 25 ml of N,N-dimethylformamide were charged, and stirring was performed at 40°C until it was dissolved. Next, 4.40 g (50.0 mmol) of 1-pentanol was charged, and stirring was performed at 40°C until it was dissolved. Next, 5.18 g (37.5 mmol) of potassium carbonate was charged, and reaction was performed at 100°C for 15 hours. After the completion of the reaction, the potassium carbonate was removed by filtration, and, for the obtained reaction solution, the solvent was distilled off by an evaporator, the obtained solid was dissolved in chloroform, and liquid-liquid separation was performed with pure water.

[0450] For the organic layer after the liquid-liquid separation, purification treatment was performed by a silica gel column, and comparative intermediate 2 was obtained.

[0451] Comparative intermediate 2 was analyzed by LC-MS. The representative chemical structural formula of comparative intermediate 2 is shown below.

[0452] [Chemical Formula 22]

[0453] Comparative intermediate 2

[0454]

[0455] In a 50-ml flask, 3.66 g (10.0 mmol) of comparative intermediate 2 and 18.3 g of benzonitrile were charged, and next, 0.80 g (2.50 mmol) of zinc iodide was charged, and reaction was performed at 150°C while stirring for 16 hours. After the reaction liquid was cooled to room temperature, a mixed solvent of water and methanol (3:7) 20 ml was charged, the generated precipitate was recovered by filter paper, and stirring and filtration in a beaker were repeatedly performed several times with isopropyl alcohol and washing.

[0456] The obtained product was dried, and comparative halogenated phthalocyanine colorant 2 was obtained.

[0457] A representative chemical structural formula of the comparative halogenated phthalocyanine colorant 2 is shown below.

[0458] [Chemical Formula 23]

[0459]

[0460] (2) Production of Comparative Colorant Liquid CG2

[0461] In (2) of Example 1, the above-obtained comparative halogenated phthalocyanine colorant 2 was used instead of the halogenated phthalocyanine colorant 1 in an equimolar amount, and otherwise, the comparative colorant liquid CG2 was obtained in the same manner as in (2) of Example 1.

[0462] (3) Production of Comparative Colored Curing Property Composition CG2

[0463] The above comparative colorant liquid CG2 was used instead of the colorant liquid G1 in (3) of Example 1, and otherwise, the comparative colored curing property composition CG2 was obtained in the same manner as in (3) of Example 1.

[0464] (4) Formation of Colored Layer

[0465] In (4) of Example 1, the above comparative colored curing property composition CG2 was used instead of the colored curing property composition G1, and otherwise, the colored layer CG2 was obtained in the same manner as in (4) of Example 1.

[0466] (Comparative Example 3)

[0467] (1) Production of Comparative Halogenated Phthalocyanine Colorant 3

[0468] In a 50-ml flask, tetrafluoroterephthalonitrile 2.40 g (12.0 mmol) and benzonitrile 12.0 g were charged, and then, zinc iodide 0.96 g (3.00 mmol) was charged, and the reaction was carried out at 150°C for 16 hours while stirring. After the reaction liquid was cooled to room temperature, a mixed solvent of water and methanol (3:7) 20 ml was charged, and the produced precipitate was recovered by filter paper, and stirring and filtration in a beaker were repeated several times with isopropanol and washed.

[0469] The obtained product was dried to obtain the comparative halogenated phthalocyanine colorant 3. A representative chemical structural formula of the comparative halogenated phthalocyanine colorant 3 is shown below.

[0470] [Chemical Formula 24]

[0471]

[0472] (2) Production of Comparative Colorant Liquid CG3

[0473] In (2) of Example 1, Comparative Halogenated Phthalocyanine Colorant 3 obtained above was used instead of Halogenated Phthalocyanine Colorant 1 in an equimolar amount, and otherwise, Comparative Colorant Liquid CG3 was obtained in the same manner as in (2) of Example 1.

[0474] (3) Production of Comparative Coloration and Curing Composition CG3

[0475] Comparative Coloration and Curing Composition CG3 was obtained in the same manner as in (3) of Example 1, using Comparative Colorant Liquid CG3 described above instead of Colorant Liquid G1 in (3) of Example 1.

[0476] (4) Formation of Coloration Layer

[0477] In (4) of Example 1, Comparative Coloration and Curing Composition CG3 described above was used instead of Coloration and Curing Composition G1, and otherwise, Coloration Layer CG3 was obtained in the same manner as in (4) of Example 1.

[0478] (Comparative Example 4)

[0479] (1) Production of Comparative Halogenated Phthalocyanine Colorant 4

[0480] In a 100 ml flask, tetrachlorophthalonitrile 5.0 g (25.0 mmol) and N,N-dimethylformamide 25 ml were put in, and stirring was performed at 40°C until it was dissolved. Next, 4-(hydroxymethyl)benzoic acid methyl ester 8.31 g (50.0 mmol) was put in, and stirring was performed at 40°C until it was dissolved. Next, potassium carbonate 5.18 g (37.5 mmol) was put in, and reaction was performed at 100°C for 15 hours. After the end of the reaction, the potassium carbonate was removed by filtration, and for the obtained reaction solution, the solvent was distilled off by an evaporator, the obtained solid was dissolved in chloroform, and liquid-liquid separation was performed with pure water.

[0481] For the organic layer after liquid-liquid separation, purification treatment was performed by a silica gel column, and Comparative Intermediate 4 was obtained.

[0482] Comparative Intermediate 4 was analyzed by LC-MS. The representative chemical structural formula of Comparative Intermediate 4 is shown below.

[0483] [Chemical Formula 25]

[0484] Comparative Intermediate 4

[0485]

[0486] In a 50-ml flask, Comparative Intermediate 4 3.94 g (8.00 mmol) and benzonitrile 19.7 g were charged, followed by the charging of zinc iodide 0.64 g (2.00 mmol), and the reaction was carried out at 150°C for 16 hours while stirring. After the reaction solution was cooled to room temperature, a mixed solvent of water and methanol (3:7) 20 ml was charged, and the resulting precipitate was recovered by filter paper, and repeatedly stirred and filtered in a beaker using isopropyl alcohol and washed.

[0487] The obtained product was dried to obtain Comparative Halogenated Phthalocyanine Colorant 4.

[0488] The representative chemical structural formula of Comparative Halogenated Phthalocyanine Colorant 4 is shown below.

[0489] [Chemical Formula 26]

[0490]

[0491] (2) Production of Comparative Colorant Liquid CG4

[0492] In (2) of Example 1, Comparative Halogenated Phthalocyanine Colorant 4 obtained above was used instead of Halogenated Phthalocyanine Colorant 1 in an equimolar amount, and otherwise, Comparative Colorant Liquid CG4 was obtained in the same manner as in (2) of Example 1.

[0493] (3) Production of Comparative Colored Curing Property Composition CG4

[0494] Comparative Colored Curing Property Composition CG4 was obtained in the same manner as in (3) of Example 1, using the above Comparative Colorant Liquid CG4 instead of Colorant Liquid G1 in (3) of Example 1.

[0495] (4) Formation of Colored Layer

[0496] In (4) of Example 1, Colored Layer CG4 was obtained in the same manner as in (4) of Example 1, using the above Comparative Colored Curing Property Composition CG4 instead of Colored Curing Property Composition G1.

[0497] (Comparative Example 5)

[0498] (1) Production of Comparative Halogenated Phthalocyanine Colorant 5

[0499] In a 100-ml flask, tetrachlorophthalonitrile 6.0 g (30.0 mmol) and N,N-dimethylformamide 30 ml were put in and stirred at 40°C until it was dissolved. Next, diethylene glycol monoethyl ether 8.05 g (60.0 mmol) was put in and stirred at 40°C until it was dissolved. Next, potassium carbonate 6.22 g (45.0 mmol) was put in and reacted at 100°C for 15 hours. After the completion of the reaction, the potassium carbonate was removed by filtration, and, for the obtained reaction solution, the solvent was distilled off by an evaporator, the obtained solid was dissolved in chloroform, and the solution was subjected to a liquid-liquid separation treatment with pure water.

[0500] For the organic layer after the liquid-liquid separation, a purification treatment was performed by a silica gel column to obtain comparative intermediate 5.

[0501] Comparative intermediate 5 was analyzed by LC-MS. The representative chemical structural formula of the comparative intermediate is shown below.

[0502] [Chemical Formula 27]

[0503] Comparative intermediate 5

[0504]

[0505] In a 50-ml flask, comparative intermediate 5 4.28 g (10.00 mmol) and benzonitrile 17.0 g were put in, and next, zinc iodide 0.80 g (2.50 mmol) was put in and reacted at 150°C while stirring for 16 hours. After the reaction solution was cooled to room temperature, a mixed solvent of water and methanol (3:7) 20 ml was put in, the generated precipitate was recovered by a filter paper, and stirring and filtration in a beaker were repeatedly performed several times with isopropyl alcohol and washed.

[0506] The obtained product was dried to obtain comparative halogenated phthalocyanine color material 5.

[0507] The representative chemical structural formula of comparative halogenated phthalocyanine color material 5 is shown below.

[0508] [Chemical Formula 28]

[0509]

[0510] (2) Production of Comparative Color Material Liquid CG5

[0511] In (2) of Example 1, the above obtained comparative halogenated phthalocyanine color material 5 was used instead of halogenated phthalocyanine color material 1 in an equimolar amount, and, other than that, comparative color material liquid CG5 was obtained in the same manner as in (2) of Example 1.

[0512] (3) Production of Comparative Colored Curing Property Composition CG5

[0513] A comparative colored curable composition CG5 was obtained in the same manner as in (3) of Example 1, except that the comparative colorant liquid CG5 described above was used instead of the colorant liquid G1 in (3) of Example 1.

[0514] (4) Formation of a colored layer

[0515] A colored layer CG5 was obtained in the same manner as in (4) of Example 1, except that the comparative colored curable composition CG5 described above was used instead of the colored curable composition G1 in (4) of Example 1.

[0516] (Comparative Example 6)

[0517] (1) Production of Comparative Halogenated Phthalocyanine Colorant 6

[0518] In a 100-ml flask, 5.0 g (25.0 mmol) of tetrachlorophthalonitrile and 25 ml of N,N-dimethylformamide were charged, and stirring was performed at 40°C until it was dissolved. Next, 5.21 g (50.0 mmol) of ethyl glycolate was charged, and stirring was performed at 40°C until it was dissolved. Next, 5.18 g (37.5 mmol) of potassium carbonate was charged, and reaction was performed at 100°C for 15 hours. After the completion of the reaction, the potassium carbonate was removed by filtration, and, for the obtained reaction solution, the solvent was distilled off by an evaporator, the obtained solid was dissolved in chloroform, and liquid-liquid separation was performed with pure water.

[0519] For the organic layer after the liquid-liquid separation, purification treatment was performed by a silica gel column, and comparative intermediate 6 was obtained.

[0520] Comparative intermediate 6 was analyzed by LC-MS. The representative chemical structural formula of comparative intermediate 6 is shown below.

[0521] [Chemical Formula 29]

[0522] Comparative intermediate 6

[0523]

[0524] In a 50-ml flask, 3.68 g (10.00 mmol) of comparative intermediate 6 and 18.4 g of benzonitrile were charged, and next, 0.80 g (2.50 mmol) of zinc iodide was charged, and reaction was performed at 150°C while stirring for 16 hours. After the reaction liquid was cooled to room temperature, a mixed solvent of water and methanol (3:7) 20 ml was charged, and the generated precipitate was recovered by filter paper, and stirring and filtration in a beaker were repeatedly performed several times with isopropyl alcohol and washing.

[0525] The obtained product was dried, and comparative halogenated phthalocyanine colorant 6 was obtained.

[0526] A representative chemical structural formula of the comparative halogenated phthalocyanine colorant 6 is shown below.

[0527] [Chemical Formula 30]

[0528]

[0529] (2) Production of Comparative Colorant Liquid CG6

[0530] In (2) of Example 1, the above obtained comparative halogenated phthalocyanine colorant 6 was used instead of the halogenated phthalocyanine colorant 1 in an equimolar amount, and otherwise, the comparative colorant liquid CG6 was obtained in the same manner as in (2) of Example 1.

[0531] (3) Production of Comparative Colored Curing Property Composition CG6

[0532] The above comparative colorant liquid CG6 was used instead of the colorant liquid G1 in (3) of Example 1, and otherwise, the comparative colored curing property composition CG6 was obtained in the same manner as in (3) of Example 1.

[0533] (4) Formation of Colored Layer

[0534] In (4) of Example 1, the above comparative colored curing property composition CG6 was used instead of the colored curing property composition G1, and otherwise, the colored layer CG6 was obtained in the same manner as in (4) of Example 1.

[0535] (Comparative Example 7)

[0536] (1) Production of Comparative Halogenated Phthalocyanine Colorant 7

[0537] In a 100 ml flask, tetrachlorophthalonitrile 5.0 g (25.0 mmol) and N,N-dimethylformamide 25 ml were put, and stirring was performed at 40°C until it was dissolved. Next, methyl trans-4-hydroxycyclohexanecarboxylate 8.61 g (50.0 mmol) was put, and stirring was performed at 40°C until it was dissolved. Next, potassium carbonate 5.18 g (37.5 mmol) was put, and reaction was performed at 100°C for 15 hours. After the end of the reaction, the potassium carbonate was removed by filtration, and for the obtained reaction solution, the solvent was distilled off by an evaporator, the obtained solid was dissolved in chloroform, and liquid-liquid treatment was performed with pure water.

[0538] For the organic layer after liquid-liquid separation, purification treatment was performed by a silica gel column, and comparative intermediate 7 was obtained.

[0539] The comparative intermediate 7 was analyzed by LC-MS. A representative chemical structural formula of the comparative intermediate 7 is shown below.

[0540] [Chemical Formula 31]

[0541] Comparative intermediate 7

[0542]

[0543] In a 50 ml flask, Comparative Intermediate 7 3.68 g (10.00 mmol) and benzonitrile 18.4 g were charged, followed by zinc iodide 0.80 g (2.50 mmol), and then the reaction was carried out with stirring at 150°C for 16 hours. After the reaction solution was cooled to room temperature, a mixed solvent of water and methanol (3:7) 20 ml was charged, and the resulting precipitate was recovered by filter paper, and repeatedly stirred and filtered in a beaker using isopropyl alcohol and washed.

[0544] The obtained product was dried to obtain Comparative Halogenated Phthalocyanine Colorant 7.

[0545] The representative chemical structural formula of Comparative Halogenated Phthalocyanine Colorant 7 is shown below.

[0546] [Chemical Formula 32]

[0547]

[0548] (2) Production of Comparative Colorant Liquid CG7

[0549] In (2) of Example 1, Comparative Halogenated Phthalocyanine Colorant 7 obtained above was used instead of Halogenated Phthalocyanine Colorant 1 in an equimolar amount, and otherwise, Comparative Colorant Liquid CG7 was obtained in the same manner as in (2) of Example 1.

[0550] (3) Production of Comparative Colored Curing Property Composition CG7

[0551] Comparative Colored Curing Property Composition CG7 was obtained in the same manner as in (3) of Example 1, using the above Comparative Colorant Liquid CG7 instead of Colorant Liquid G1 in (3) of Example 1.

[0552] (4) Formation of Colored Layer

[0553] In (4) of Example 1, Comparative Colored Curing Property Composition CG7 was used instead of Colored Curing Property Composition G1, and otherwise, Colored Layer CG7 was obtained in the same manner as in (4) of Example 1.

[0554] [Method of Evaluation]

[0555] (1) Evaluation of Solubility of Colored Curing Property Composition

[0556] The presence or absence of insolubles was observed visually immediately after the preparation of the colored curing property composition, and after standing at 25°C under a humidity of 50% for 2 weeks.

[0557] (Evaluation Criteria)

[0558] O: No insoluble matter

[0559] X: Insoluble matter

[0560] (2) Evaluation of colored layer

[0561] Foreign matter and contrast were evaluated for the dried layer at the time of forming the colored layer, the cured film after exposure (cured film before the heating step), and the colored layer (cured film after the heating step).

[0562] <Foreign matter>

[0563] The dried layer at the time of forming the colored layer, the cured film after exposure (cured film before the heating step), and the colored layer (cured film after the heating step) were observed under a reflected light of an optical microscope at 200 times, and evaluated according to the following evaluation criteria.

[0564] (Evaluation criteria of foreign matter)

[0565] A: No foreign matter was observed under a reflected light of an optical microscope at 200 times.

[0566] B: 10 or less of minute foreign matter of 1 μm or less was observed per 1 mm square under a reflected light of an optical microscope at 200 times.

[0567] C: More than 10 of minute foreign matter of 1 μm or less was observed per 1 mm square under a reflected light of an optical microscope at 200 times, and / or 10 or less of foreign matter of 1 μm or more was observed per 1 mm square under a reflected light of an optical microscope at 200 times.

[0568] D: More than 10 of foreign matter of 1 μm or more was observed per 1 mm square under a reflected light of an optical microscope at 200 times.

[0569] <Contrast>

[0570] For each colored layer (cured film before and after the heating step), the contrast was measured using a contrast measuring device CT-1B manufactured by Koshaka Electric Co., Ltd. and a microspectrophotometer OSP-SP200 manufactured by Olympus Corporation, with a blank sample set to 18000.

[0571] (Evaluation criteria of contrast)

[0572] A: Contrast was more than 10000

[0573] B: Contrast was 8000 to 10000

[0574] C: Contrast was less than 8000

[0575] D: Measurement was impossible (data was not reliable because of much foreign matter)

[0576] [Table 1]

[0577]

[0578] [Results]

[0579] As for the halogenated phthalocyanine color materials of Comparative Examples 1 to 3 which correspond to the halogenated phthalocyanine color materials of the past, foreign matter was precipitated from the cured film after the heating step, and the contrast was poor. As for the halogenated phthalocyanine color materials of Comparative Examples 2 and 3, foreign matter was precipitated from the cured film after drying and exposure, and the solubility stability of the composition was also poor.

[0580] As for the halogenated phthalocyanine color materials of Comparative Examples 4 to 7, foreign matter was precipitated from the cured film after the heating step, and the contrast was poor. As for the halogenated phthalocyanine color materials of Comparative Examples 5 and 6, foreign matter was precipitated from the cured film after drying and exposure.

[0581] In contrast, as for the halogenated phthalocyanine color materials of Examples 1 to 4 which are the halogenated phthalocyanine color materials of the present application, foreign matter was not precipitated from the cured film after the heating step, and the contrast was good.

[0582] Explanation of Reference Numerals

[0583] 1 transparent substrate

[0584] 2 light shielding portion

[0585] 3 colored layer

[0586] 10 color filter

[0587] 20 counter substrate

[0588] 30 liquid crystal layer

[0589] 40 liquid crystal display device

[0590] 50 organic protective layer

[0591] 60 inorganic oxide film

[0592] 71 transparent anode

[0593] 72 hole injection layer

[0594] 73 hole transport layer

[0595] 74 light emitting layer

[0596] 75 electron injection layer

[0597] 76 cathode

[0598] 80 organic light emitting body

[0599] 100 organic light emitting display device

Claims

1. A halide phthalocyanine pigment, represented by the following general formula (1), In general formula (1), in X 2 or X 3 either of them, X 6 or X 7 either of them, X 10 or X 11 either of them, and X 14 or X 15 Each of them has a total of 4 monovalent groups represented by the following general formulas (2-1) to (2-5), and in X 2 or X 3 either of them, X 6 or X 7 either of them, X 10 or X 11 either of them, and X 14 or X 15 Each of them has a total of 4 monovalent groups represented by the following general formula (2-6), X 1 X 4 X 5 X 8 X 9 X 12 X 13 and X 16 It is a fluorine atom; General formula (2-1): -OR L1 -R a General formula (2-2): -O-(R L2 -O) n -R b General formula (2-3): -OR L2 -COO-R b General formula (2-4): -OR L2 -OCO-R b General formula (2-5): -OR c General formula (2-6): -OR a In general formulas (2-1) to (2-6), R L1 R represents an aliphatic hydrocarbon group or -CO- group with 1 to 6 carbon atoms. L2 Each of the following groups independently represents an aliphatic hydrocarbon group having 1 to 6 carbon atoms: R a R represents an aromatic hydrocarbon group with 6 to 14 carbon atoms, whether substituted or unsubstituted. b R represents a hydrogen atom, a straight-chain or branched aliphatic hydrocarbon group with 1 to 6 substituted or unsubstituted carbon atoms, an alicyclic hydrocarbon group with 5 to 14 substituted or unsubstituted carbon atoms, or an aromatic hydrocarbon group with 6 to 14 substituted or unsubstituted carbon atoms. c It represents an alicyclic hydrocarbon group with 5 to 14 carbon atoms, whether substituted or unsubstituted; n represents an integer from 1 to 5; Indicates the bonding position with the phthalocyanine backbone; The substituents in the substituted or unsubstituted aliphatic hydrocarbon groups with 1 to 6 carbon atoms, whether straight-chain or branched, are halogen atoms or -OR. s1 -COR s1 -COOR s1 R s1 It consists of hydrogen atoms or hydrocarbon groups having 1 to 6 carbon atoms. The substituted or unsubstituted alicyclic hydrocarbon group with 5 to 14 carbon atoms, and the substituted or unsubstituted aromatic hydrocarbon group with 6 to 14 carbon atoms, each having a halogen atom as a substituent, and the substituted or unsubstituted alicyclic hydrocarbon group with 1 to 6 carbon atoms, are all straight-chain or branched aliphatic hydrocarbon groups. s1 -COR s1 -COOR s1 R s1 It consists of a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms.

2. A coloring curable composition comprising a colorant, a polymer, a polymeric compound, an initiator, and a solvent, wherein the colorant comprises the halogenated phthalocyanine colorant as described in claim 1.

3. The coloring and curing composition according to claim 2, further comprising a sensitizer.

4. The coloring and curing composition according to claim 2 or 3, wherein, The initiator comprises an oxime ester-based photoinitiator.

5. The coloring and curing composition according to claim 2 or 3, further comprising a yellow colorant.

6. A color filter comprising at least a substrate and a coloring layer disposed on the substrate, wherein at least one of the coloring layers is a cured product of the coloring curable composition according to any one of claims 2 to 5.

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

Images