Squalirium pigment, pigment dispersion, ink composition, optical filter, and display device

Abstract

To provide a squarylium colorant that has excellent light resistance and shows reduced absorption (sub-absorption) of light of other wavelengths different from the maximum absorption wavelength, and a colorant dispersant, an ink composition, an optical filter, and a display device each containing the squarylium colorant.SOLUTION: A squarylium colorant comprises a salt-forming compound of a squarylium dye represented by, for example, the following formula, a colorless organic cation and heteropoly acid.SELECTED DRAWING: None

Description

Technical Field

[0001] The present disclosure relates to squarylium colorants, colorant dispersions, ink compositions, optical filters, and display devices.

Background Art

[0002] In recent years, LEDs have been increasingly used as light sources for lighting devices and display devices. For example, there are several types of light emission methods when using white LEDs. There is a method of arranging LEDs that emit light of each of R (red), G (green), and B (blue) to obtain white light, and a method of obtaining white light by combining blue light from a blue LED and yellow light emission from a yellow phosphor. Among these methods, when using a method of obtaining white light by combining a blue LED and a yellow phosphor, the spectrum of the obtained white light contains light showing orange color in the region around 590 nm and cyan color in the region around 490 nm, and it is known that the color rendering property deteriorates when the emission intensity of the light in this region is high. Conventionally, an optical filter has been installed on the front surface of a display device to remove unnecessary light emission components and make the display color vivid.

[0003] In Patent Documents 1 and 2, squarylium compounds are disclosed as useful compounds for optical filters such as display devices.

[0004] On the other hand, the present inventors have also disclosed a colorant dispersion and composition capable of forming a film excellent in light resistance while selectively and effectively reducing light in an unnecessary wavelength region, and a film and an optical filter excellent in light resistance containing a salt-forming compound of squarylium while selectively and effectively reducing light in an unnecessary wavelength region.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

[0006] In order to suppress light in an unnecessary wavelength region caused by a light source, an optical member, or external light reflection, it is considered effective to use a dye compound that selectively absorbs light in the unnecessary wavelength region. When a squarylium dye alone is used for an optical filter or the like as in Patent Documents 1 and 2, there is a problem that the light resistance is poor. When a dye is used as a salt-forming compound for an optical filter or the like as in Patent Document 3, the light resistance is improved. However, when a squarylium dye is made into a salt-forming compound, absorption (secondary absorption) occurs easily at a wavelength different from the maximum absorption wavelength, resulting in problems such as a decrease in color reproducibility (color purity) and brightness.

[0007] The present disclosure has been made in view of the above circumstances, and an object thereof is to provide a squarylium colorant having good light resistance and reduced absorption (secondary absorption) at a wavelength different from the maximum absorption wavelength, a colorant dispersion liquid containing the squarylium colorant, an ink composition, an optical filter, and a display device. [Means for Solving the Problems]

[0008] One embodiment of the present disclosure provides a squarylium colorant comprising a squarylium dye, a colorless organic cation, and a salt-forming compound of a heteropolyacid.

[0009] Another embodiment of the present disclosure provides a colorant dispersion liquid containing a squarylium colorant comprising a squarylium dye, a colorless organic cation, and a salt-forming compound of a heteropolyacid, a dispersant, and a solvent.

[0010] Other embodiments of the present disclosure provide an ink composition containing a squarylium pigment, a colorant dispersion, an ink composition containing a squarylium colorant composed of a squarylium pigment, a colorless organic cation, and a salt-forming compound of a heteropolyacid, and a binder component.

[0011] Other embodiments of the present disclosure provide an optical filter containing a squarylium colorant composed of a squarylium pigment, a colorless organic cation, and a salt-forming compound of a heteropolyacid.

[0012] Other embodiments of the present disclosure provide a display device including the optical filter of the present disclosure.

[0013] In the squarylium colorant, colorant dispersion, ink composition, optical filter, and display device according to the embodiments of the present disclosure, the squarylium colorant may be a squarylium colorant in which the colorless organic cation is a phosphonium compound.

[0014] In the squarylium colorant, colorant dispersion, ink composition, optical filter, and display device according to the embodiments of the present disclosure, the squarylium colorant may be a squarylium colorant in which the colorless organic cation is a phosphonium compound represented by the following general formula (A). Formula (A): A―[P + R A 3 a (In formula (A), A is an a-valent organic group, and each R A is independently a hydrocarbon group having 1 to 6 carbon atoms which may have a substituent, and a is an integer of 2 to 4.)

[0015] In the squarylium colorant, colorant dispersion, ink composition, optical filter, and display device according to the embodiments of the present disclosure, the squarylium colorant may be a squarylium colorant in which the squarylium pigment is a squarylium pigment represented by the following general formula (3-1).

[0016] [Chemical formula] ​ (In formula (3-1), R 1 and R 4 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms which may have a substituent, and R 2 , R 3 , R 5 and R 6 each independently represent a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms which may have a substituent, a halogen atom, a nitro group, a cyano group, a hydroxy group, -OR 7 , -OCOR 8 , -COOR 9 , -CONHR 10 , -NHCOR 11 , or -NR 12 R 13 represents, and R 7 , R 8 , R 9 , R 10 and R 11 each independently represent a hydrocarbon group having 1 to 6 carbon atoms which may have a substituent, and R 12 and R 13 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms which may have a substituent. Q each independently represents a direct bond or a divalent aromatic ring group. Y each independently represents a divalent organic group, and Z 0 each independently represents a group that can be derived into an organic cation group or an organic cation group. Represents an organic cation group. E each independently represents a substituent, and adjacent substituents E may form a ring. m and n each independently represent an integer of 0 to 4.) [Advantages of the Invention]

[0017] According to an embodiment of the present disclosure, a squarylium colorant having good light resistance and reduced absorption (sub-absorption) at a wavelength different from the maximum absorption wavelength, a colorant dispersion liquid containing the squarylium colorant, an ink composition, an optical filter, and a display device can be provided. [Brief Description of the Drawings]

[0018]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

Figure 7

MODE FOR CARRYING OUT THE INVENTION

[0019] Hereinafter, embodiments, examples, etc. of the present disclosure will be described with reference to the drawings and the like. However, the present disclosure can be implemented in many different modes, and is not to be construed as being limited to the description contents of the embodiments, examples, etc. exemplified below. In addition, for the purpose of making the description clearer, the drawings may schematically represent the width, thickness, shape, etc. of each part compared to the actual mode, but this is only an example and does not limit the interpretation of the present disclosure. Further, in this specification and each drawing, the same reference numerals may be given to the same elements as those described above with respect to the already shown drawings, and the detailed description may be omitted as appropriate. Further, for the sake of convenience of explanation, the terms "above" or "below" may be used in the explanation, but the up and down directions may be reversed. "In this specification, when a certain configuration of a certain member or a certain region, etc. is said to be "above (or below)" another configuration of another member or another region, etc., unless otherwise specified, this includes not only the case where it is directly above (or directly below) the other configuration, but also the case where it is above (or below) the other configuration, that is, the case where another component is included between above (or below) the other configuration.

[0020] In the present disclosure, "(meth)acrylic" represents each of acrylic or methacrylic, and "(meth)acrylate" represents each of acrylate or methacrylate. Also, in this specification, the terms "plate", "sheet", and "film" are not distinguished from each other based only on the difference in name, and the "film surface (plate surface, sheet surface)" refers to the surface that coincides with the planar direction of the target film-like (plate-like, sheet-like) member when the target film-like (plate-like, sheet-like) member is viewed as a whole and globally. In the present disclosure, the "organic dye" is a dye compound containing a carbon atom, and refers to a compound that absorbs at least a part of visible light (light with a wavelength of 400 nm to 700 nm) and near-infrared light (light with a wavelength of 700 nm to 1100 nm), and the "colorant" refers to a compound that absorbs at least a part of visible light (light with a wavelength of 400 nm to 700 nm) and near-infrared light (light with a wavelength of 700 nm to 1100 nm), and also includes a compound that absorbs only near-infrared light. Also, the "organic group" refers to a group containing a carbon atom. The "organic cation" refers to a cationic moiety containing a carbon atom. Hereinafter, the squarylium colorant, colorant dispersion, ink composition, optical filter, and display device of the present disclosure will be described in detail in order.

[0021] I. Squarylium Colorant The squarylium colorant of one embodiment of the present disclosure is a squarylium colorant composed of a squarylium dye, a colorless organic cation, and a salt-forming compound of a heteropolyacid. The squarylium colorant of one embodiment of the present disclosure is a squarylium colorant having good light resistance and reduced absorption (secondary absorption) at a wavelength different from the maximum absorption wavelength by forming a salt compound with a colorless organic cation and a heteropolyacid with respect to the squarylium dye.

[0022] Organic dyes dissolve in solvents to form films. However, since they tend to aggregate and precipitate in the film, it is difficult to create a uniform film. As a result, the function of selectively absorbing light of unwanted emission wavelengths cannot be effectively and uniformly exerted. Conventionally, organic dyes have poor light resistance, which has been a problem in actual use. On the other hand, when an organic dye forms a salt-forming compound with a heteropolyacid, two or more cationized predetermined organic dyes ionically bond to one polyvalent heteropolyacid anion. Therefore, in the salt-forming compound of the organic dye and the heteropolyacid, a plurality of organic dyes form one molecule around the heteropolyacid anion, and further, ion pair formation between molecules becomes possible, so that the association between molecules is promoted, and as a result, fine particles that are hardly soluble in the solvent are formed. When the coloring material exists in the form of fine particles, photo-degradation is likely to occur only on the particle surface, and the progress of photo-degradation is suppressed. Therefore, it is presumed that the light resistance is improved compared to organic dyes. However, the salt-forming compound tends to have absorption (secondary absorption) at a wavelength different from the maximum absorption wavelength. FIG. 4 is a schematic diagram showing an example of a conventional salt-forming compound. In FIG. 4, as an example, a salt-forming compound 120 in which a divalent organic dye cation 101 and a trivalent heteropolyacid anion 103 form a salt by ionic bonding is schematically shown. In such a conventional salt-forming compound 120, since the distance between the organic dye cations 101 is close and they easily interact with each other in the associated state of the molecules, it is presumed that secondary absorption is likely to occur. Secondary absorption appears at a wavelength slightly away from the maximum absorption wavelength, or if it is a wavelength close to the maximum absorption wavelength, it overlaps with the peak of the maximum absorption wavelength and the peak of the maximum absorption wavelength becomes broad and appears. When secondary absorption exists, it not only selectively absorbs light in the unwanted wavelength region but also absorbs light in the necessary wavelength region. Therefore, it is desirable to reduce secondary absorption.

[0023] Figure 3 is a schematic diagram showing an example of the squarylium coloring material of the present disclosure. In Figure 3, as an example, a salt-forming compound (the squarylium coloring material of the present disclosure) 110 is schematically shown in which a divalent organic dye cation (squarylium dye cation) 101, a divalent colorless organic cation 102, and a trivalent heteropolyacid anion 103 form a salt by ionic bonding. Thus, in the salt-forming compound 110 of the squarylium coloring material of the present disclosure, it becomes possible to increase the distance between squarylium dye cations 101 without affecting the absorption wavelength by the colorless organic cation 102, and it is presumed that the interaction between squarylium dyes is suppressed and side absorption hardly occurs. When the side absorption of the squarylium coloring material is reduced, the film containing the squarylium coloring material suppresses the absorption of light in the necessary wavelength region and can selectively absorb light in the unnecessary wavelength region, and only the light in the unnecessary wavelength region can be selectively and effectively reduced. The squarylium coloring material of the present disclosure with reduced side absorption is a coloring material with improved wavelength selectivity. When the squarylium coloring material of the present disclosure is used, the decrease in color purity and brightness due to the side absorption is suppressed, and the color purity and brightness are improved.

[0024] <Squarylium-based dye> Squarylium-based dyes refer to dyes having a four-membered ring derived from squaric acid. Examples of squarylium-based dyes include compounds represented by the following formula (1-1).

[0025] [Chemical formula] (In formula (1-1), A 1 and A 2 each independently represent an aromatic ring group which may have a substituent or a group represented by the general formula (1-2);

[0026] [Chemical formula] In formula (1-2), W 1represents a non-metal atomic group forming a nitrogen-containing heterocyclic ring, and R 20 represents an alkyl group, an alkenyl group or an aralkyl group, d represents 0 or 1, and the wavy line represents a connecting bond.)

[0027] A in the general formula (1-1) 1 and A 2 each independently represents an aromatic ring group which may have a substituent, or a group represented by the general formula (1-2). As the aromatic ring group, it may be an aromatic hydrocarbon group, that is, an aryl group, or an aromatic heterocyclic group, that is, a heteroaryl group. A 1 and A 2 The number of carbon atoms of the aromatic hydrocarbon group represented by is preferably 6 to 48, more preferably 6 to 24, and particularly preferably 6 to 12. The aromatic hydrocarbon group may be a monocyclic or condensed ring. A 1 and A 2 As the aromatic heterocyclic group represented by, a 5-membered ring or a 6-membered ring is preferable. Further, the aromatic heterocyclic group may be a monocyclic or condensed ring, preferably a monocyclic or condensed ring having 2 to 8 condensed rings, more preferably a monocyclic or condensed ring having 2 to 4 condensed rings, and still more preferably a monocyclic or condensed ring having 2 or 3 condensed rings. Examples of the heteroatom contained in the aromatic heterocyclic group include a nitrogen atom, an oxygen atom, and a sulfur atom, and a nitrogen atom and a sulfur atom are preferable. The number of heteroatoms is preferably 1 to 3, and more preferably 1 to 2. Specifically, examples include an aromatic heterocyclic group derived from a monocyclic or polycyclic aromatic ring such as a 5-membered ring or a 6-membered ring containing at least one of a nitrogen atom, an oxygen atom, and a sulfur atom.

[0028] Specific examples of the aromatic ring in the aromatic ring group include benzene ring, naphthalene ring, pentalene ring, indene ring, azulene ring, heptalene ring, indacene ring, perylene ring, pentacene ring, acenaphthylene ring, phenanthrene ring, anthracene ring, naphthacene ring, chrysene ring, triphenylene ring, fluorene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indolizine ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolidine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthridine ring, acridine ring, phenanthroline ring, pyrrolo[2,1-b]benzothiazole ring, pyrrolo[2,1-a]isoquinoline ring, thianthrene ring, chromene ring, xanthene ring, phenoxathiin ring, phenothiazine ring, and phenazine ring, etc. Among them, benzene ring or naphthalene ring is preferred.

[0029] A 1 and A 2 The aromatic ring group in may have substituents. When the aromatic ring group has two or more substituents, the plurality of substituents may be the same or different. Examples of the substituent include, for example, halogen atom, cyano group, nitro group, alkyl group, alkenyl group, alkynyl group, aromatic ring group, aralkyl group, -OR 100 , -COR 101 , -COOR 102 , -OCOR 103 , -NR 104 R 105 , -NHCOR 106 , -CONR 107 R 108 , -NHCONR 109 R 110 , -NHCOOR 111 , -SR 112 , -SO 2 R 113 , -SO 2 OR 114 , -NHSO 2 R 115 , -SO2 NR 116 R 117 、 -(R 118 O) n R 119 、 and groups such as these combinations thereof. R 100 ~R 117 、 and R 119 each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aromatic ring group, or an aralkyl group, and R 118 each independently represents a divalent hydrocarbon group. -COOR 102 When the R 102 of is a hydrogen atom (i.e., a carboxy group), the hydrogen atom may dissociate or may be in a salt state. Also, -SO 2 OR 104 When the R 104 of is a hydrogen atom (i.e., a sulfo group), the hydrogen atom may dissociate or may be in a salt state. From the viewpoint of improving solvent solubility, as the divalent hydrocarbon group of R 118 may be either saturated or unsaturated, and may be linear, branched, cyclic, or a combination of cyclic and linear or branched. From the viewpoint of improving solvent solubility, the divalent hydrocarbon group of R 118 is preferably a linear or branched hydrocarbon group, and the divalent hydrocarbon group of R 118 preferably has 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 3 carbon atoms. Also, n is exemplified by 1 to 18, preferably 1 to 12, and more preferably 1 to 6.

[0030] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and even more preferably 1 to 8 carbon atoms. The alkyl group may be linear, branched, or cyclic, and linear or branched is preferred. The alkenyl group preferably has 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, and particularly preferably 2 to 8 carbon atoms. The alkenyl group may be linear, branched, or cyclic, and linear or branched is preferred. The number of carbon atoms in the alkynyl group is preferably from 2 to 40, more preferably from 2 to 30, and particularly preferably from 2 to 25. The alkynyl group may be linear, branched or cyclic, with linear or branched being preferred. Among the aromatic ring groups, the number of carbon atoms in the aromatic hydrocarbon group is preferably from 6 to 30, more preferably from 6 to 20, and still more preferably from 6 to 12. The alkyl portion of the aralkyl group is the same as the above alkyl group. The aryl portion of the aralkyl group is the same as the above aromatic hydrocarbon group. The number of carbon atoms in the aralkyl group is preferably from 7 to 40, more preferably from 7 to 30, and still more preferably from 7 to 25. Among the aromatic ring groups, the aromatic heterocyclic group is preferably a monocyclic or condensed ring, more preferably a monocyclic or condensed ring with 2 to 8 condensed rings, and still more preferably a monocyclic or condensed ring with 2 to 4 condensed rings. The number of heteroatoms constituting the ring of the aromatic heterocyclic group is preferably 1 to 3. The heteroatoms constituting the ring of the aromatic heterocyclic group are preferably nitrogen atoms, oxygen atoms or sulfur atoms. The aromatic heterocyclic group is preferably a 5-membered or 6-membered ring. The number of carbon atoms constituting the ring of the aromatic heterocyclic group is preferably from 3 to 30, more preferably from 3 to 18, and still more preferably from 3 to 12. The alkyl group, alkenyl group, alkynyl group, aralkyl group, and aromatic ring group may or may not have a substituent, and may be unsubstituted. Examples of the substituent include the above-described substituents.

[0031] On the other hand, A 1 and A 2 In the group represented by the general formula (1-2), R 20 represents an alkyl group, an alkenyl group or an aralkyl group, with an alkyl group being preferred. The number of carbon atoms in the alkyl group is preferably from 1 to 30, more preferably from 1 to 20, still more preferably from 1 to 12, and particularly preferably from 2 to 8. The number of carbon atoms in the alkenyl group is preferably from 2 to 30, more preferably from 2 to 20, and still more preferably from 2 to 12. The alkyl group and the alkenyl group may be linear, branched or cyclic, with linear or branched being preferred. The number of carbon atoms in the aralkyl group is preferably from 7 to 30, more preferably from 7 to 20.

[0032] In the general formula (1-2), W 1 As the nitrogen-containing heterocyclic ring formed by [it], a 5-membered ring or a 6-membered ring is preferable. Further, the nitrogen-containing heterocyclic ring is preferably a monocyclic ring or a condensed ring, more preferably a monocyclic ring or a condensed ring having 2 to 8 condensed rings, still more preferably a monocyclic ring or a condensed ring having 2 to 4 condensed rings, and particularly preferably a condensed ring having 2 or 3 condensed rings. The nitrogen-containing heterocyclic ring may contain a sulfur atom in addition to the nitrogen atom. Further, the nitrogen-containing heterocyclic ring may have a substituent. Examples of the substituent include the above-described substituents. For example, a halogen atom, an alkyl group, a hydroxy group, an amino group, and an acylamino group are preferable, and a halogen atom and an alkyl group are more preferable. The halogen atom is preferably a chlorine atom. The number of carbon atoms of the alkyl group is preferably 1 to 30, more preferably 1 to 20, and still more preferably 1 to 12. The alkyl group is preferably linear or branched.

[0033] In the general formula (1-1), the cation exists in a delocalized manner as follows.

[0034]

Chemical formula

[0035] Regarding the details of the above formulas (1-1) and (1-2), the descriptions in paragraph numbers 0055 to 0071 of JP-A-2017-181705 and paragraph numbers 0020 to 0049 of JP-A-2011-208101 can also be referred to, and this content is incorporated herein.

[0036] As the squarylium-based dye, it may have a structure having two or more 4-membered rings derived from squaric acid in one molecule. For example, A of the compound represented by the above formula (1-1) 1 and A 2 either one of them is replaced with A of another compound represented by the above formula (1-1) 1 and A 2Examples thereof include a structure bonded with a linking group to any one of them. As the squarylium-based dye having a structure having two or more four-membered rings derived from squaric acid in one molecule, the compounds described in paragraphs 0018 to 0019 and 0048 to 0093 of JP-A-2009-40860 may be used.

[0037] Specific examples of the squarylium-based dye include, for example, the compounds described in paragraph numbers 0044 to 0049 of JP-A-2011-208101 and the compounds described in paragraphs 0018 to 0019 and 0048 to 0110 of JP-A-2009-40860, the contents of which are incorporated herein.

[0038] The squarylium-based dye used in the present invention preferably contains an organic cation group as a substituent so as to easily form a salt with a heteropolyacid described later, and a compound represented by the following general formula (2-1) is preferable.

[0039] [Chemical formula] (In the general formula (2-1), X 1 and X 2 each independently represent an aromatic ring group which may have a substituent, Y represents a divalent organic group, and Z 0 represents a group which can be derived from an organic cation group or an organic cation group. e represents an integer of 1 to 4, and when e is 2 or more, a plurality of Ys and a plurality of Zs 0 may be the same or different from each other.)

[0040] In the general formula (2-1), the aromatic ring group which may have a substituent in X 1 and X 2 may be the same as the aromatic ring group which may have a substituent in A 1 and A 2 in the general formula (1-1). Further, from the viewpoint of improving the solvent solubility, X 1 and X 2 are -(R 118 O) n R 119, an aralkyl group, -OR 100 , -COR 101 , -COOR 102 , -OCOR 103 , -NR 104 R 105 , -NHCOR 106 , -CONR 107 R 108 , -NHCONR 109 R 110 , -NHCOOR 111 , -SR 112 , -SO 2 R 113 , -SO 2 OR 114 , -NHSO 2 R 115 , and -SO 2 NR 116 R 117 may have at least one substituent selected from the group consisting of. Note that the -(R 118 O) n R 119 , -OR 100 , -COR 101 , -COOR 102 , -OCOR 103 , -NR 104 R 105 , -NHCOR 106 , -CONR 107 R 108 , -NHCONR 109 R 110 , -NHCOOR 111 , -SR 112 , -SO 2 R 113 , -SO 2 OR 114 , -NHSO 2 R 115 or -SO 2 NR 116 R 117 may be the same as the substituents described in A 1 and A 2 . From the viewpoint of easily providing a dye skeleton having absorption in the visible region (400 nm to 700 nm), preferred X 1 and X 2Examples include, but are not limited to, the following chemical formulas (x-1) to (x-11) and combinations thereof. Examples of combinations of chemical formulas (x-1) to (x-11) include, for example, the combination of (x-1) and (x-10), the combination of (x-1), (x-10), and (x-10), etc.

[0041] [Chemical Formula] (In chemical formulas (x-1) to (x-11), R, R’, and R” each independently represent a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms which may have a substituent, a halogen atom, a nitro group, a cyano group, a hydroxy group, -OR 100 , -COR 101 , -COOR 102 , -OCOR 103 , -NR 104 R 105 , -NHCOR 106 , -CONR 107 R 108 , or -(CH 2 CH 2 O) n” -R 120 . n” is 2 to 12, and R 100 to R 108 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aromatic ring group, or an aralkyl group, and R 120 represents a hydrocarbon group having 1 to 4 carbon atoms. n represents 2 and n’ represents 3. In the formula, * indicates a 4-membered ring derived from squaric acid or the bonding position with Y. In the case of a combination of two or more of (x-1) to (x-11), * indicates a 4-membered ring derived from squaric acid, the bonding position with any of (x-1) to (x-11), or the bonding position with Y.)

[0042] Examples of the hydrocarbon group having 1 to 6 carbon atoms for R, R’, and R” in chemical formulas (x-1) to (x-11) include a saturated hydrocarbon group or an unsaturated hydrocarbon group having 1 to 6 carbon atoms. Examples of the saturated hydrocarbon groups having 1 to 6 carbon atoms include linear alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, or hexyl group; branched alkyl groups such as isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isopentyl group, or neopentyl group; and alicyclic saturated hydrocarbon groups such as cyclopropyl group, cyclopentyl group, or cyclohexyl group. Examples of the unsaturated hydrocarbon groups having 1 to 6 carbon atoms include phenyl group which is an aromatic hydrocarbon group; unsaturated aliphatic hydrocarbon groups such as vinyl group, propenyl group, butenyl group, or pentenyl group; and monovalent alicyclic unsaturated hydrocarbon groups such as cyclopropenyl group, cyclopentenyl group, or cyclohexenyl group. Examples of the substituents of the hydrocarbon group include, for example, halogen atom, hydroxy group, amino group, nitro group, sulfamoyl group, sulfo group, etc. Examples of the halogen atom include fluorine atom, chlorine atom, bromine atom, or iodine atom. Also, the halogen atoms in R, R’, and R” may be the same as described above, and R 100 ~R 108 may be the same as described above.

[0043] From the viewpoint of improving solvent solubility, at least one of R, R’, and R” in Chemical Formulas (x-1) to (x-11) may be -(CH 2 CH 2 O) n” -R 120 In -(CH 2 CH 2 O) n” -R 120 , n” is preferably 1 to 8, more preferably 1 to 6. R 120 may be a methyl group, ethyl group, n-propyl group, i-propyl group, or n-butyl group.

[0044] In General Formula (2-1), Y represents a divalent organic group, and at least one of X 1 and X 2 in the squarylium-based dye moiety and Z 0functions as a linking group to [it]. Examples of the divalent organic group in Y include divalent hydrocarbon groups which may contain heteroatoms, and divalent hydrocarbon groups which may contain O, S, N in the carbon chain. Examples of the divalent organic group in Y include, for example, divalent hydrocarbon groups, and divalent groups which are combinations of divalent hydrocarbon groups and -CONH-, -COO-, -O-, -S- and the like. The divalent hydrocarbon group may be either saturated or unsaturated, and may be linear, branched, cyclic, or a combination of cyclic and linear or branched. The number of carbon atoms of the divalent hydrocarbon group is preferably 1 to 30, more preferably 1 to 20, still more preferably 1 to 15, even more preferably 1 to 12, and particularly preferably 2 to 8. From the viewpoint of optical stability, the divalent organic group in Y is preferably a divalent hydrocarbon group. It is more preferable that the squarylium dye moiety related to color development and the cationic group are electronically independent, because it can suppress the spread of the electron distribution related to color development and give a sharp absorption with a narrow half-value width. Among them, Y is 1 or X 2 It is preferably a hydrocarbon group in which the carbon atom directly bonded to [it] does not have a π bond. X 1 or X 2 An aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at the terminal directly bonded to [it], or an aromatic hydrocarbon group having a saturated aliphatic hydrocarbon group at the terminal directly bonded to X 1 or X 2 is preferred, and among them, an aliphatic saturated hydrocarbon group is preferably used. X 1 or X 2 and Z 0 are inert to oxidation, reduction, or hydrolysis reactions that can cause dye degradation, and are chemically stably linked. Preferred examples of Y include, but are not limited to, the following chemical formulas (y-1) to (y-6). Among them, from the viewpoint of providing a sharp absorption with a narrow half-value width, it is preferably (y-1), (y-3), (y-5), or (y-6), and more preferably (y-1), (y-3), or (y-5). Further, similar to (y-1), it may be a linear or branched alkylene group having 3 to 6 carbon atoms.

[0045] [Chemical formula] (In the formula, * represents the bonding position of one of X 1 and X 2 with Z 0 .)

[0046] In the general formula (2-1), Z 0 is a group that can be derived from an organic cationic group (Z + ) or an organic cationic group. Among Z 0 , examples of the group that can be derived from the organic cationic group (Z + ) include a monovalent nitrogen-containing compound group, a sulfur-containing compound group, a phosphorus-containing compound group, etc. that can form an onium. Note that the organic cationic group (Z + ) is not limited to a protonated onium, and may be an onium substituted with a hydrocarbon group instead of a proton. Examples of the nitrogen-containing compound that can form an onium include, for example, tertiary amines, piperidine, pyrrolidine, pyridine, imidazoline, morpholine, etc. Examples of the sulfur-containing compound that can form an onium include, for example, thiol, thioether, etc. Examples of the phosphorus-containing compound that can form an onium include, for example, phosphine, etc. Among Z 0 , examples of the organic cationic group (Z + ) include the group that can be derived from the cationic group (Z 0) includes a structure in which it becomes an onium, and examples thereof include ammonium cations such as tetraalkylammonium cations and trialkylammonium cations, piperidinium cations, pyrrolidinium cations, pyridinium cations, imidazolium cations, morpholinium, sulfonium cations such as trialkylsulfonium cations, and phosphonium cations such as tetraalkylphosphonium cations. Among them, since cationization by proton addition is easy and the raw materials are relatively inexpensive and easily available, Z 0 Preferably, a tertiary amino group, a pyridyl group, an imidazolyl group, etc. are used. From the point that the formed onium exists stably as a cation, preferred Z 0 Examples include the following chemical formulas (z-1) to (z-9), but are not limited thereto.

[0047]

Chemical formula

[0048] -(CH 2 CH 2 O) n” -R 120 in chemical formulas (z-1) to (z-9) may be the same as -(CH 2 CH 2 O) n” -R 120 in the above (x-1) to (x-11). e represents an integer from 1 to 4, and among them, from the viewpoint of forming continuous ion pairs, increasing the molecular weight of the ion pair aggregate, and improving the durability to heat and light, it is preferably 2 to 4, more preferably 2 to 3, and even more preferably 2. When e is 2 or more, a plurality of Ys and a plurality of Zs 0 may be the same or different from each other. From the point that the symmetry of the electronic state related to the color development of the squarylium-based dye increases and the dye gives a sharp absorption with a narrow half-value width, X 1 and X 2 , a plurality of Ys, and a plurality of Zs 0 are preferably the same as each other.

[0049] -Y-Z used in the present invention 0 Examples of the combination of include, but are not limited to, the following.

[0050]

Table 1

[0051] Examples of the compound represented by the general formula (2-1) include, but are not limited to, the compounds represented by the following general formula (3-1).

[0052]

Chemical formula

[0053] R 1 ~R 6 The hydrocarbon group having 1 to 6 carbon atoms which may have a substituent in may be the same as the hydrocarbon group having 1 to 6 carbon atoms which may have a substituent of R in the formula (2-1). Also, R 2 , R 3 , R 5 and R 6 The halogen atom in may be the same as above, and R 7 , R 8 , R 9 , R 10 , R 11 , R 12 and R 13 The hydrocarbon group having 1 to 6 carbon atoms which may have a substituent in may be the same as the hydrocarbon group having 1 to 6 carbon atoms which may have a substituent, may be a hydrocarbon group having 1 to 3 carbon atoms, and may be unsubstituted.

[0054] Q each independently represents a direct bond or a divalent aromatic ring group. A direct bond means a covalent bond without intervening atoms or groups. As the divalent aromatic ring group in Q, the above A 1and A 2 In Q, the aromatic ring similar to the aromatic ring in the divalent aromatic group can be used. The aromatic ring in the divalent aromatic group in Q preferably has 5 to 10 ring-constituting atoms, and examples thereof include benzene ring, naphthalene ring, pyrrole ring, furan ring, thiophene ring, pyridine ring, indole ring, benzofuran ring, benzothiophene ring, etc. From the viewpoint of easy synthesis by obtaining raw materials, it may be a benzene ring.

[0055] Y and Z in formula (3-1) 0 may be the same as Y and Z in the formula (2-1) 0 respectively.

[0056] E each independently represents a substituent. As the substituent, it may be the same as the substituent that the aromatic group in the above A 1 and A 2 may have. Further, adjacent substituents E may form a ring. That is, adjacent substituents E may be bonded to each other to form a condensed ring with the benzene ring to which the substituent E is bonded. Examples of the condensed ring formed by adjacent substituents E include naphthalene ring, benzofuran ring, benzothiophene ring, etc. m and n each independently represent an integer of 0 to 4, may be an integer of 0 to 2, and may be 0 or 1.

[0057] Among the compounds represented by the general formula (3-1), the compounds represented by the following general formula (3-2) are preferable because they are likely to reduce side absorption.

[0058]

Chemical formula

[0059] Like the compound represented by the formula (3-2), -Y-Z 0 When it is substituted at the ortho position with respect to the bonding position with Q, -Y-Z 0 with respect to the bispyrrolosquarylium plane, the twist angle of the benzene ring to which -Y-Z 0 is attached tends to increase, and the tilt angle of -Y-Z 0 with respect to the bispyrrolosquarylium plane tends to increase. In the compound represented by the formula (3-2), one -Y-Z 0 is located diagonally upward, and the other -Y-Z

[0060] The squarylium dye used in the present invention can be produced with reference to the known production methods described in the above-mentioned publications and other known production methods described in the literature. The production method of the compound represented by the general formula (2-1) is not particularly limited. For example, reactions using Grignard reagents, coupling reactions using palladium catalysts, etc., carbon-carbon formation reactions such as Ullmann reactions, Friedel-Crafts reactions, aldol reactions, Wittig reactions, etc. are used to introduce Y and Z 0 into X 1 and X 2 A method of reacting the compound for inducing with squaric acid in the presence of a base can be mentioned.

[0061] <Colorless organic cation> The colorless organic cation used in the squarylium colorant of the present invention may be an organic cation having an absorption maximum in the wavelength region of 400 nm or less. Further, the colorless organic cation may be a compound having no absorption in the wavelength region exceeding 400 nm and 780 nm or less. The colorless organic cations used in the present invention are derived from nitrogen-containing compounds, sulfur-containing compounds, and phosphorus-containing compounds that can form onium. The organic cations are not limited to protonated onium, and may be onium substituted with hydrocarbon groups instead of protons. Examples of nitrogen-containing compounds that can form onium include tertiary amines, piperidine, pyrrolidine, pyridine, imidazoline, morpholine, and the like. Examples of sulfur-containing compounds that can form onium include thiol, thioether, and the like. Examples of phosphorus-containing compounds that can form onium include phosphine, and the like.

[0062] Examples of the colorless organic cations used in the present invention include structures in which nitrogen-containing compounds, sulfur-containing compounds, and phosphorus-containing compounds that can form onium become onium, and include ammonium groups, pyridinium groups, piperidinium groups, pyrrolidinium groups, pyridinium groups, imidazolium groups, morpholinium groups, sulfonium groups such as trialkylsulfonium cation groups, and phosphonium groups such as triarylalkylphosphonium groups and tetraalkylphosphonium groups. Compounds containing at least one cation group selected from the group consisting of are mentioned.

[0063] The colorless organic cations used in the present invention are preferably divalent or higher cations, and preferably contain two or more cation groups in one molecule. The upper limit of the valence of the colorless organic cations used in the present invention is not particularly limited, but may be tetravalent or less, or trivalent or less.

[0064] Among them, the colorless organic cations used in the present invention are preferably phosphonium compounds, and more preferably divalent or higher phosphonium compounds, in that they have no absorption in the visible region.

[0065] As the colorless organic cation used in the present invention, among others, from the viewpoint of molecular bulkiness for suppressing the association and interaction between dye cations when a dye cation, a heteropolyacid, and a colorless organic cation form a salt, a phosphonium compound represented by the following general formula (A) is preferable. Formula (A): A―[P + R A 3 a (In formula (A), A is an a-valent organic group, and each R A is independently a hydrocarbon group having 1 to 6 carbon atoms which may have a substituent, and a is an integer of 2 to 4.)

[0066] In formula (A), each R A is independently a hydrocarbon group having 1 to 6 carbon atoms which may have a substituent, and examples of the hydrocarbon group having 1 to 6 carbon atoms include a saturated hydrocarbon group or an unsaturated hydrocarbon group having 1 to 6 carbon atoms. Examples of the saturated hydrocarbon group having 1 to 6 carbon atoms include linear alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, or hexyl group; branched-chain alkyl groups such as isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isopentyl group, or neopentyl group; alicyclic saturated hydrocarbon groups such as cyclopropyl group, cyclopentyl group, or cyclohexyl group, etc. Examples of the unsaturated hydrocarbon group having 1 to 6 carbon atoms include an aromatic hydrocarbon group, phenyl group; unsaturated aliphatic hydrocarbon groups such as vinyl group, propenyl group, butenyl group, or pentenyl group; alicyclic unsaturated hydrocarbon groups such as cyclopropenyl group, cyclopentenyl group, or cyclohexenyl group, etc. Examples of the substituent of the hydrocarbon group include, for example, a halogen atom, nitro group, cyano group, hydroxy group, -OR a1 , -OCOR a2 , -COOR a3 , -CONHR a4 , -NHCOR a5 , or -NR a6 R a7 (Here, R a1 , R a2 , R​a3 , R a4 and R a5 each independently represents a hydrocarbon group having 1 to 6 carbon atoms which may have a substituent, and R a6 and R a7 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms which may have a substituent), etc. are exemplified. R a1 , R a2 , R a3 , R a4 , R a5 , R a6 and R a7 The hydrocarbon group having 1 to 6 carbon atoms which may have a substituent in may be the same as described above, may be a hydrocarbon group having 1 to 3 carbon atoms, and may or may not have a substituent.

[0067] In formula (A), A is an a-valent organic group, and the organic group may be an aliphatic hydrocarbon group, an aromatic ring group, or a combination thereof, and may contain heteroatoms such as O (oxygen atom), S (sulfur atom), N (nitrogen atom), etc. in the carbon chain. In A, the aliphatic hydrocarbon group may be linear, branched or cyclic, the carbon atoms may have an unsaturated bond, may have a substituent, and may contain O, S, N in the carbon chain. For example, an ether group, a carbonyl group, an oxycarbonyl group, an amide group, etc. may be contained. Also, the aromatic ring group in A may be the same as described above, and among them, a monocyclic or polycyclic aromatic group having an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at the terminal directly bonded to P is exemplified, may have a substituent, and may be a heterocyclic ring containing O, S, N. Examples of the substituent that A may have include, for example, the same as the substituent in the above R A may be the same. Among them, A is preferably an a-valent aliphatic hydrocarbon group, which may be linear, branched or cyclic, and the carbon atoms may have an unsaturated bond.

[0068] <Heteropoly acid> The heteropolyacid used in the present invention is one of the polyacids in which the central atomic species of the constituent oxoacids are two or more. In a salt-forming compound, the heteropolyacid becomes a heteropolyacid anion. The heteropolyacid anion has the formula (L l M m O n ) a- (where a represents a number of 2 or more). In the ion formula, L is a heteroatom, M is a polyatom, O is an oxygen atom, and l, m, and n represent the composition ratios of the respective atoms. The polyatom M includes Mo (molybdenum), W (tungsten), V (vanadium), Ti (titanium), Nb (niobium), etc., and the polyatom M may contain two or more transition metal atoms. The heteroatom L is not particularly limited, and examples include Si, P, As, S, Fe, Co, etc. Also, it may contain counter cations such as Na + and H + etc.

[0069] Among them, from the viewpoint of excellent heat resistance, it is preferably a polyacid having one or more elements selected from tungsten (W) and molybdenum (Mo). Examples of such heteropolyacids include phosphotungstic acid ion [PW 12 O 40 3- , [P 2 W 18 O 62 6- , silicotungstic acid ion [SiW 12 O 40 4- , phosphomolybdic acid ion [PMo 12 O 40 3- , silicomolybdic acid ion [SiMo 12 O 40 4- , phosphotungstomolybdic acid ion [PW 12-s Mo s O 40 3- (s is an integer of 1 or more and 11 or less), [P 2 W 18-t Mo t O​​​​​​62 6- (t is an integer from 1 to 17), silicotungstomolybdic acid ion [SiW 12-u Mo u O 40 4- (u is an integer from 1 to 11), etc. can be mentioned.

[0070] From the viewpoint of improving light resistance, the heteropoly acid is preferably a heteropoly acid having a redox potential greater than -0.3 V based on the silver / silver chloride electrode standard. By using such a heteropoly acid anion having a redox potential greater than a specific value as the counter anion, the energy generated when the photoexcited organic dye returns to the ground state is absorbed by the heteropoly acid having a property of being easily reduced, among others, whereby the generation of singlet oxygen during light irradiation can be suppressed, and the light resistance of the colorant is further improved.

[0071] Examples of the heteropoly acid used in the present disclosure having a redox potential greater than -0.3 V based on the silver / silver chloride electrode standard include, for example, H 4 SiMo 12 O 40 (-0.232 V), H 3 PW 6 Mo 6 O 40 (-0.197 V), H 3 PW 3 Mo 9 O 40 (-0.153 V), H 3 PMo 12 O 40 (-0.082 V), H 6 PW 9 V 3 O 40 (0.045 V), H 5 PW 10 V 2 O 40 (0.050 V), H 6 PMo 9 V 3 O 40 (0.168 V), H 3 AsMo 12 O 40 (0.183 V), H 4 PW​​11 V 1 O 40 (0.224 V), H 5 PMo 10 V 2 O 40 (0.233 V), H 4 PMo 11 V 1 O 40 (0.261 V), etc. may be mentioned. Here, the redox potential specified in the present disclosure refers to the measured value of an aqueous solution of a heteropolyacid using a silver / silver chloride standard electrode (saturated aqueous KCl solution) with platinum as the working electrode. As the aqueous solution of the heteropolyacid, an aqueous solution in which 1 mM of the heteropolyacid is dissolved in a 0.5 M aqueous sodium sulfate electrolyte solution can be used. As the redox potential of the heteropolyacid under the above measurement conditions, the values of the redox potential (V) in Fig. 9 of Journal of Moleculer Catalysis A: Chemical 212 (2004) 229 - 236 can also be referred to, and the values in the parentheses above are the values of that literature.

[0072] <Method for producing squarylium colorant> The squarylium colorant (salt-forming compound) of the present disclosure can be obtained, for example, by mixing a squarylium dye having a desired structure, a colorless organic cation, and a heteropolyacid in a solvent and heating if necessary. The squarylium dye, the colorless organic cation, and the heteropolyacid may each be used alone or in combination of two or more.

[0073] In the squarylium colorant (salt-forming compound) of the present disclosure, the content ratio of the squarylium dye serving as a cation and the colorless organic cation may be adjusted to a desired color and is not particularly limited. Although it depends on the valence of the cation, from the viewpoint of suppressing the generation of side absorption by keeping a distance between dye molecules, the molar ratio of the squarylium dye to the colorless organic cation may be 6:4 to 2:8 for the squarylium dye:colorless organic cation, and may be 5:5 to 3:7.

[0074] Further, when the squarylium coloring material (salt-forming compound) of the present disclosure is a normal salt, it is preferable to adjust the number of cations of the squarylium dye and the colorless organic cation and the number of anions of the heteropolyacid so as to form a normal salt, in view of higher dispersibility and dispersion stability compared with the case where an acidic salt or the like is used.

[0075] <Properties of Squarylium Coloring Material> From the viewpoint of improving color purity in the visible region of the display device, the maximum absorption wavelength (λmax) in the wavelength range of 400 nm to 700 nm in the absorption spectrum, that is, the minimum transmission wavelength in the wavelength range of 400 nm to 700 nm in the transmission spectrum, of the squarylium coloring material may be 550 nm to 630 nm, may be 560 nm to 620 nm, and may be 570 nm to 610 nm. The maximum absorption wavelength to minimum transmission wavelength in the wavelength range of 380 nm to 750 nm of the squarylium coloring material can be appropriately changed by changing the substituents of the squarylium dye. Further, the half-value width of the maximum absorption wavelength to minimum transmission wavelength in the wavelength range of 400 nm to 700 nm may be 85 nm or less, and may be 70 nm or less, from the viewpoint of cutting only unnecessary light of the display device.

[0076] II. Coloring Material Dispersion Liquid The coloring material dispersion liquid according to one embodiment of the present disclosure is characterized by containing the squarylium coloring material of the present disclosure, a dispersant, and a solvent. The coloring material dispersion liquid of the present disclosure contains the squarylium coloring material of the present disclosure having good light resistance and reduced secondary absorption, so that a film or molded body having improved color purity, brightness, and good light resistance and reduced secondary absorption can be formed.

[0077] The coloring material dispersion liquid of the present disclosure contains at least the squarylium coloring material of the present disclosure, a dispersant, and a solvent, and may contain other components as necessary. Hereinafter, each component of such a coloring material dispersion liquid of the present disclosure will be described in detail in order.

[0078] <Colorant> The squarylium colorant of the present disclosure used in the colorant dispersion of the present disclosure may be the same as described above, and thus the description here is omitted. In the colorant dispersion of the present disclosure, the squarylium colorant of the present disclosure can be used alone or in combination of two or more. Other colorants may be included. Other colorants are blended as needed for the purpose of controlling the color tone. Other colorants can be selected as appropriate from those conventionally known, such as pigments and dyes, and can be used alone or in combination of two or more. The blending amount of other colorants is not particularly limited as long as the effects of the present disclosure are not impaired, and can be the same as in the case of using in the composition described later. In the colorant dispersion of the present disclosure, the content of the colorant is not particularly limited. From the viewpoints of dispersibility and dispersion stability, the content of the colorant is preferably in the range of 5 to 40% by mass, more preferably 10 to 20% by mass, based on the total amount of the colorant dispersion.

[0079] <Dispersant> In the colorant dispersion according to the present disclosure, the colorant is used by being dispersed in a solvent. In the present disclosure, a dispersant is used to disperse the colorant well. As the dispersant, it can be appropriately selected from those conventionally used as pigment dispersants. As the dispersant, for example, surfactants such as cationic, anionic, nonionic, amphoteric, silicone-based, and fluorine-based can be used. Among the surfactants, polymer surfactants (polymer dispersants) are preferred from the viewpoint of being able to disperse uniformly and finely.

[0080] Examples of the polymer dispersant include (co)polymers of unsaturated carboxylic acid esters such as polyacrylate esters; (co)polymers of unsaturated carboxylic acids such as polyacrylic acid; (partial) amine salts, (partial) ammonium salts, and (partial) alkylamine salts of (co)polymers of unsaturated carboxylic acids such as polyacrylic acid; (co)polymers of hydroxyl group-containing unsaturated carboxylic acid esters such as hydroxyl group-containing polyacrylate esters and modified products thereof; polyurethanes; unsaturated polyamides; polysiloxanes; long-chain polyaminoamide phosphates; polyethyleneimine derivatives (amides obtained by reacting poly(lower alkyleneimine) with a polyester containing a free carboxyl group and salts thereof); polyallylamine derivatives (reaction products obtained by reacting polyallylamine with one or more compounds selected from three compounds: a polyester having a free carboxyl group, a polyamide, or a copolycondensate of an ester and an amide (polyesteramide)).

[0081] Among them, as the polymer dispersant, an acidic dispersant is preferably used because it can preferably disperse the colorant which is the salt-forming compound and has good dispersion stability. Here, the acidic dispersant refers to a dispersant in which the amount of acidic groups is larger than the amount of basic groups, and the basic dispersant refers to a dispersant in which the amount of basic groups is larger than the amount of acidic groups. Among the acidic dispersants used in the present disclosure, a resin in which the amount of acidic groups occupies 80 mol% or more when the total amount of the acidic groups and the basic groups is 100 mol% is preferable, and a resin having substantially acidic groups and no basic groups is more preferable. Among the acidic dispersants used in the present disclosure, it is preferable from the viewpoint of the dispersion stability of the colorant that the acidic dispersant has an acid value and no amine value. When an acidic dispersant is used, it is presumed that it not only disperses the colorant which is the salt-forming compound well but also has an action of stably existing the colorant which is the salt-forming compound in an ion pair state.

[0082] The acid value of the acidic dispersant used in the present disclosure is preferably 30 mgKOH / g or more, more preferably 60 mgKOH / g or more, and even more preferably 90 mgKOH / g or more. In addition, the amine value of the acidic dispersant used in the present disclosure is preferably 0 mgKOH / g. Note that the acid value represents the mass (mg) of potassium hydroxide required to neutralize the acidic components contained in 1 g of the solid content of the dispersant, and is a value measured by the method described in JIS K 0070. In addition, the amine value represents the mass (mg) of potassium hydroxide equivalent to the amount of hydrochloric acid required to neutralize 1 g of the solid content of the dispersant, and is a value measured by the method described in JIS K 7237.

[0083] Examples of the acidic group of the acidic dispersant used in the present disclosure include a carboxy group, a phosphoric acid group and its salts, a sulfonic acid group and its salts, and the like. Examples of the acidic dispersant include a block or graft copolymer having an acidic group, a salt with an organic cation such as an alkylammonium salt of a block copolymer having an acidic group, a hydroxy group-containing carboxylic acid ester, a fatty acid salt such as a salt of a high molecular weight polycarboxylic acid, a polyether ester type anionic surfactant, a naphthalenesulfonic acid formalin condensate salt, a phosphate ester such as a polyoxyethylene alkyl phosphate ester and its salts, an alkyl sulfate ester salt, a polyoxyethylene alkyl ether sulfate ester salt, and a sulfonate such as an alkylbenzene sulfonate.

[0084] Examples of commercially available products of the acidic dispersant include DISPERBYKR-103, DISPERBYKR-110, DISPERBYK-118, AJISPER PN411, AJISPER PA111, and the like.

[0085] Among the acidic dispersants, from the viewpoints of the dispersibility and dispersion stability of the colorant, it is more preferable that the dispersant is a polymer having one or more selected from the structural units represented by the following general formula (I) and the structural units represented by the following general formula (I').

[0086]

Chem.

[0087] In the general formulas (I) and (I'), L 1 is a direct bond or a divalent linking group. Here, the fact that L 1 is a direct bond means that the phosphorus atom is directly bonded to the carbon atom of the main chain skeleton without passing through a linking group. L 1 There is no particular limitation on the divalent linking group in L 1 as long as it can link the carbon atom of the main chain skeleton and the phosphorus atom. Examples of the divalent linking group in L 1 include, for example, a linear, branched or cyclic alkylene group, a linear, branched or cyclic alkylene group having a hydroxyl group, an arylene group, a -CONH- group, a -COO- group, a -NHCOO- group, an ether group (-O- group), a thioether group (-S- group), and combinations thereof. In the present invention, the direction of bonding of the divalent linking group is arbitrary. That is, when -CONH- is included in the divalent linking group, -CO may be on the carbon atom side of the main chain and -NH may be on the phosphorus atom side of the side chain, or conversely, -NH may be on the carbon atom side of the main chain and -CO may be on the phosphorus atom side of the side chain.

[0088] The polymer having one or more selected from the structural unit represented by the general formula (I) and the structural unit represented by the general formula (I') may be the same as the polymer having one or more selected from the structural unit represented by the general formula (I) and the structural unit represented by the general formula (I') described in JP-A-2017-002191. For the description of each symbol of the polymer having one or more selected from the structural unit represented by the general formula (I) and the structural unit represented by the general formula (I'), refer to the description content of the corresponding symbols of the polymer having one or more selected from the structural unit represented by the general formula (I) and the structural unit represented by the general formula (I') described in JP-A-2017-002191, and this content is incorporated herein.

[0089] Among the polymers having one or more selected from the structural unit represented by the general formula (I) and the structural unit represented by the general formula (I'), in particular, the polymer in which the (B) dispersant is a reaction product of a polymer having at least one of an epoxy group and a cyclic ether group in the side chain and an acidic phosphorus compound, and at least a part of the acidic phosphorus compound group may form a salt, is preferable in terms of excellent colorant dispersibility and storage stability, and the ability to form a film excellent in heat resistance and solvent resistance.

[0090] The polymer having one or more selected from the structural unit represented by the general formula (I) and the structural unit represented by the general formula (I') preferably further has a solvent affinity site from the viewpoint of dispersibility. Among such dispersants, in particular, a graft copolymer having one or more selected from the structural unit represented by the general formula (I) and the structural unit represented by the general formula (I') and a structural unit represented by the following general formula (II), or a block copolymer having one or more selected from the structural unit represented by the general formula (I) and the structural unit represented by the general formula (I') and a structural unit represented by the following general formula (III) is preferable in terms of excellent colorant dispersibility and storage stability, and the ability to form a film excellent in heat resistance and solvent resistance.

[0091] [Chemistry] (In general formula (II), L 2 is a direct bond or a divalent linking group, R 51 is a hydrogen atom or a methyl group, and Polymer represents a polymer chain having a structural unit represented by the following general formula (IV). In general formula (III), R 52 is a hydrogen atom or a methyl group, R 53 is a hydrocarbon group, -[CH(R 54 )-CH(R 55 )-O] x2 -R 56 , -[(CH 2 ) y2 -O] z2 -R 56 , -[CO-(CH 2 ) y2 -O] z2 -R 56 , -CO-O-R 56’ or -O-CO-R 56” is a monovalent group represented by, R 54 and R 55 are each independently a hydrogen atom or a methyl group, R 56 is a hydrogen atom, a hydrocarbon group, -CHO, -CH 2 CHO or -CH 2 COOR 57 is a monovalent group represented by, R 56’ is a hydrocarbon group, -[CH(R 54 )-CH(R 55 )-O] x2’ -R 56 , -[(CH 2 ) y2’ -O] z2’ -R 56 , -[CO-(CH 2 ) y2’ -O] z2’ -R 56 is a monovalent group represented by, R 56” is an alkyl group having 1 to 18 carbon atoms, R 57 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. The hydrocarbon group may have a substituent. x2 and x2' represent integers from 1 to 18, y2 and y2' represent integers from 1 to 5, and z2 and z2' represent integers from 1 to 18.)

[0092] [Chemical formula] (In general formula (IV), R 61 is a hydrogen atom or a methyl group, and R 62 is a hydrocarbon group, -[CH(R 63 )-CH(R 64 )-O] x3 -R 65 , -[(CH 2 ) y3 -O] z3 -R 65 , -[CO-(CH 2 ) y3 -O] z3 -R 65 , -CO-O-R 66 or -O-CO-R 67 represents a monovalent group, and R 63 and R 64 are each independently a hydrogen atom or a methyl group. R 65 is a hydrogen atom, a hydrocarbon group, -CHO, -CH 2 CHO or -CH 2 COOR 68 represents a monovalent group. R 66 is a hydrocarbon group, -[CH(R 63 )-CH(R 64 )-O] x4 -R 65 , -[(CH 2 ) y4 -O] z4 -R 65 , -[CO-(CH 2 ) y4 -O] z4 -R 65 represents a monovalent group. R 67 is an alkyl group having 1 to 18 carbon atoms, and R 68 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and the hydrocarbon group may have substituents.) n represents an integer from 5 to 200. x3 and x4 represent integers from 1 to 18, y3 and y4 represent integers from 1 to 5, and z3 and z4 represent integers from 1 to 18.)

[0093] Examples of the graft copolymer having at least one selected from the structural units represented by the general formula (I) and the structural units represented by the general formula (I') and the structural unit represented by the general formula (II), or the block copolymer having at least one selected from the structural units represented by the general formula (I) and the structural units represented by the general formula (I') and the structural unit represented by the general formula (III) include the graft copolymers and block copolymers described in JP-A-2017-002191 and the like, which are preferably used.

[0094] In the present disclosure, the dispersant can be used alone or in combination of two or more. The content of the dispersant is appropriately selected according to the type of the colorant used and the like. In the colorant dispersion of the present disclosure, the dispersant is usually in the range of 5 to 200 parts by mass, preferably 10 to 100 parts by mass, and more preferably 20 to 80 parts by mass with respect to 100 parts by mass of the colorant. If the content is within the above range, the colorant can be uniformly dispersed. Further, in the composition described later, the blending ratio of the binder component does not relatively decrease, and a film having sufficient hardness can be formed. In the colorant dispersion of the present disclosure, the content of the dispersant is preferably in the range of 1 to 50% by mass, more preferably 1 to 20% by mass, based on the total amount of the dispersion, from the viewpoints of dispersibility and dispersion stability.

[0095] <Solvent> The colorant dispersion liquid according to the present disclosure uses the squarylium colorant dispersed as particles (aggregates) in a solvent. Since the colorant is a salt-forming compound of the specific dye and the heteropolyacid, it is hardly soluble in an organic solvent. The colorant, which is the salt-forming compound used in the present disclosure, is excellent in light resistance by being dispersed in a solvent while maintaining its aggregated state. The solvent used in the present disclosure is a solvent that does not substantially dissolve the colorant which is the salt-forming compound or a poorly soluble solvent, and preferably has a solubility of the colorant at 23 °C of 0.1 (mg / 10 g solvent) or less. Among them, a solvent having a solubility of the colorant at 23 °C of 0.01 (mg / 10 g solvent) or less is preferable, and further, a solvent that does not substantially dissolve the colorant is more preferable.

[0096] In the present disclosure, the solvent in which the solubility of the squarylium colorant at 23 °C is 0.1 (mg / 10 g solvent) or less can be easily determined by the following evaluation method. Put 10 g of the solvent to be evaluated into a 20 mL sample tube, further add 0.1 g of the colorant, cover the lid and shake well for 20 seconds, and then let it stand in a water bath at 23 °C for 10 minutes. Filter 5 g of this supernatant to remove insoluble matters. Measure the absorption spectrum of the solution obtained by further diluting the obtained filtrate 1000 times using a UV-visible near-infrared spectrophotometer (for example, UV-3100PC manufactured by Shimadzu Corporation) with a 1 cm cell, and determine the absorbance at the maximum absorption wavelength. At this time, if the absorbance at the maximum absorption wavelength is less than 2, the solvent can be evaluated as a solvent in which the solubility of the colorant at 23 °C is 0.1 (mg / 10 g solvent) or less (a poorly soluble solvent).

[0097] Also, in the above evaluation method, without diluting the obtained filtrate, measure the absorption spectrum in the same manner as above, and determine the absorbance at the maximum absorption wavelength. At this time, if the absorbance at the maximum absorption wavelength is less than 2, the solvent can be evaluated as a solvent that does not substantially dissolve the colorant which is the salt-forming compound.

[0098] As the solvent in which the solubility of the squarylium pigment at 23°C is 0.1 (mg / 10 g solvent) or less, any solvent that does not substantially dissolve the squarylium pigment or is a poorly soluble solvent is not particularly limited, and it may be appropriately selected from solvents that do not react with each component in the pigment dispersion liquid and can dissolve or disperse them.

[0099] In the pigment dispersion liquid of the present disclosure, among others, it is preferable to use an ester-based solvent from the viewpoint of dispersion stability. Examples of the ester-based solvent include ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, ethyl lactate, methoxyethyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-1-butyl acetate, 3-methoxybutyl acetate, methoxybutyl acetate, ethoxyethyl acetate, ethyl cellosolve acetate, and the like. These solvents may be used alone or in combination of two or more.

[0100] The pigment dispersion liquid of the present disclosure is prepared by using the above solvents in a proportion of usually 50 to 95% by mass, preferably 60 to 85% by mass, based on the total amount of the pigment dispersion liquid containing the solvent. If the amount of the solvent is too small, the viscosity increases and the dispersibility tends to decrease. On the other hand, if the amount of the solvent is too large, the pigment concentration decreases, and there may be a risk that a sufficient absorption effect of light of a specific wavelength cannot be obtained depending on the application.

[0101] <Other Components> In the pigment dispersion liquid of the present disclosure, a dispersion auxiliary resin and other components may be further blended as necessary. Examples of the dispersion auxiliary resin include alkali-soluble resins. Due to the steric hindrance of the alkali-soluble resin, it becomes difficult for the pigment particles to come into contact with each other, which may have the effect of stabilizing the dispersion and reducing the dispersant due to the dispersion stabilizing effect. Examples of the other components include surfactants for improving wettability, silane coupling agents for improving adhesion, defoaming agents, anti-floating agents, antioxidants, anti-aggregation agents, ultraviolet absorbers, and the like.

[0102] <Method for producing colorant dispersion liquid> The colorant dispersion liquid of the present disclosure can be prepared by mixing the dispersant with the solvent, stirring to prepare a dispersant solution, and then mixing the colorant according to the present disclosure and other compounds as necessary with the dispersant solution and dispersing them using a disperser. Further, the colorant dispersion liquid of the present disclosure may be prepared by mixing a colorant and a dispersant with a solvent and dispersing them using a known disperser.

[0103] Examples of the disperser for performing the dispersion treatment include roll mills such as two-roll and three-roll mills, ball mills such as ball mills and vibration ball mills, paint conditioners, bead mills such as continuous disk type bead mills and continuous annular type bead mills. As preferable dispersion conditions for the bead mill, the bead diameter to be used is preferably 0.03 to 2.00 mm, more preferably 0.10 to 1.0 mm.

[0104] Specifically, preliminary dispersion is performed with 2 mm zirconia beads having a relatively large bead diameter, and further main dispersion is performed with 0.1 mm zirconia beads having a relatively small bead diameter. Further, after dispersion, it is preferable to filter with a membrane filter having a pore size of 0.1 to 0.5 μm.

[0105] In the present disclosure, the dispersion time for dispersion using a known disperser is appropriately adjusted and not particularly limited. For example, from the viewpoint of refining the colorant and achieving high absorbency for light in an unnecessary wavelength region, it is preferably set to 5 to 40 hours. In this way, a colorant dispersion liquid excellent in the dispersibility of colorant particles can be obtained.

[0106] The average dispersed particle size of the colorant used in the present disclosure in the colorant dispersion liquid is not particularly limited and may be appropriately set depending on the application, but is preferably within the range of 10 to 150 nm, more preferably within the range of 20 to 125 nm, in terms of excellent light resistance. When the average dispersed particle size of the colorant is within the above range, the surface coated with the colorant dispersion liquid of the present disclosure exhibits uniform and excellent absorption performance against light in unnecessary wavelength ranges. The average dispersed particle size of the colorant in the colorant dispersion is the dispersed particle size of the colorant particles dispersed in a dispersion medium containing at least a solvent, and is measured by a laser light scattering particle size distribution meter. The particle size can be measured by diluting the colorant dispersion with the solvent used in the colorant dispersion to a concentration that can be measured by the laser light scattering particle size distribution meter (for example, 1000 times), and measuring the particle size at 23°C by dynamic light scattering using a laser light scattering particle size distribution meter (for example, a nano track particle size distribution measuring device UPA-EX150 manufactured by Nikkiso Co., Ltd.). The average dispersed particle size here is the volume average particle size.

[0107] The colorant dispersion can be used as a preparatory product for preparing the composition described later. That is, the colorant dispersion is a colorant dispersion having a high ratio of (mass of colorant content in the composition) / (mass of solid content other than colorant content in the composition) that is preparatoryly prepared in a stage prior to the preparation of the composition described later. Specifically, the ratio of (mass of colorant content in the composition) / (mass of solid content other than colorant content in the composition) is usually 1.0 or more. By mixing the colorant dispersion with at least a binder component, a composition with excellent dispersibility can be prepared.

[0108] III. Ink Composition The ink composition according to one embodiment of the present disclosure is characterized by containing the squarylium colorant according to the present disclosure and a binder component.

[0109] By using the squarylium pigment of the present disclosure having good light resistance and reduced secondary absorption in combination with a binder component, a film or molded article having good light resistance, reduced secondary absorption, and improved color purity and brightness can be formed. The ink composition of the present disclosure contains at least the squarylium pigment of the present disclosure and a binder component, and may optionally have other components. Further, the ink composition of the present disclosure may be used by combining a binder component with the pigment dispersion. In this case, the ink composition of the present disclosure contains the squarylium pigment of the present disclosure, a binder component, a dispersant, and a solvent. Hereinafter, each component of the composition of the present disclosure will be described in detail. Regarding the components that can be included in the pigment dispersion according to the present disclosure, the same components as those described in the section of the pigment dispersion can be used, and thus the description here is omitted. However, the solvent is not limited to the preferred solvent, and a solvent having high solubility for the binder component and other components added as necessary can be appropriately selected and used.

[0110] <Binder component> The ink composition of the present disclosure contains a binder component in order to impart film-forming properties, moldability, and adhesion to the coated surface. The binder component preferably contains at least a resin. The resin may be any of an adhesive, a thermoplastic resin, a thermosetting resin, and a photocurable resin. The resin here is not limited to a high molecular compound or polymer, and may be a low molecular compound or monomer. Further, it may be particles of a synthetic resin that constitute a resin emulsion. The binder component preferably has light transmissivity, and when a film having a thickness of 3 μm is formed using only the binder component, the transmittance in the visible light region is preferably 80% or more, more preferably 84% or more. The transmittance can be measured according to JIS K7361-1 (Test method for total light transmittance of transparent plastics).

[0111] Examples of the adhesive include acrylic adhesives, silicone adhesives, urethane adhesives, polyvinyl butyral adhesives, ethylene-vinyl acetate adhesives, polyvinyl ethers, saturated amorphous polyesters, melamine resins, and other adhesives. Examples of the thermoplastic resin include acrylic resins such as poly(meth)acrylic acid, poly(meth)acrylic acid esters, polyacrylonitrile, and polyacrylamide; polystyrene resins; cellulose resins such as nitrocellulose, ethyl cellulose, and triacetyl cellulose; polyester resins such as polyethylene terephthalate; polycarbonate resins; thermoplastic urethane resins; modified olefin resins such as chlorinated polyethylene and chlorinated polypropylene; vinyl resins such as vinyl acetate resins, vinyl chloride-vinyl acetate copolymers, and butyral resins; polyamide resins; polyimide resins; olefin resins such as cyclic polyolefins and polyolefins.

[0112] From the viewpoint of imparting sufficient hardness to the coating film, it is preferable to contain a curable binder component containing a thermosetting resin or a photocurable resin. The curable binder component is not particularly limited, and conventionally known curable binder components can be appropriately used. Examples of the curable binder component include a photocurable binder component containing a photocurable resin that can be polymerized and cured by visible light, ultraviolet light, electron beams, etc., and a thermosetting binder component containing a thermosetting resin that can be polymerized and cured by heating.

[0113] As the thermosetting binder, a combination of a compound having two or more thermosetting functional groups in one molecule and a curing agent is usually used, and a catalyst that can accelerate the thermosetting reaction may be added. Examples of the thermosetting functional group include an epoxy group, an oxetanyl group, an isocyanate group, an ethylenic unsaturated bond, etc. The epoxy group is preferably used as the thermosetting functional group. Specific examples of the thermosetting binder component can include those described in International Publication No. WO2012 / 144521.

[0114] On the one hand, as the photocurable binder, a combination of a compound having one or more photocurable functional groups in one molecule and a photoinitiator is usually used. These compounds and photoinitiators can be appropriately selected from those known in the art and used. Examples of the photocurable functional group include a radically polymerizable ethylenically unsaturated bond-containing group, a cationically polymerizable epoxy group, an oxetanyl group, etc. As the photocurable functional group, an ethylenically unsaturated bond-containing group is preferably used, and specifically, a vinyl group, a (meth)acryloyl group, etc. can be mentioned. From the viewpoint of improving the hardness, the number of photocurable functional groups contained in the photocurable compound in one molecule is preferably two or more, and more preferably three or more. Among the radical polymerizable compounds, from the viewpoint of high reactivity, compounds having a (meth)acryloyl group are particularly preferred. Compounds called polyfunctional (meth)acrylate monomers having two or more (meth)acryloyl groups in one molecule, oligomers having a molecular weight of several hundred to several thousand having two or more (meth)acryloyl groups in the molecule, such as urethane (meth)acrylate, polyester (meth)acrylate, epoxy (meth)acrylate, melamine (meth)acrylate, polyfluoroalkyl (meth)acrylate, and silicone (meth)acrylate, can be preferably used. Also, polyfunctional (meth)acrylate polymers having two or more (meth)acryloyl groups in the side chain of the acrylate polymer can be preferably used. Among them, from the viewpoint of improving the hardness, polyfunctional (meth)acrylate monomers having two or more (meth)acryloyl groups in one molecule can be preferably used.

[0115] Examples of the resin emulsion include acrylic emulsions, styrene-acrylic emulsions, vinyl acetate emulsions, ethylene-vinyl acetate emulsions, etc.

[0116] When the film has a pattern and a photolithography process is used in forming the film, a photosensitive binder component having alkali developability is preferably used. Examples of the photosensitive binder component include a positive photosensitive binder component and a negative photosensitive binder component. Examples of the positive photosensitive binder component include a system containing an alkali-soluble resin and a compound containing an o-quinonediazide group as a photosensitive imparting component. Examples of the alkali-soluble resin include a polyimide precursor and the like.

[0117] As the negative photosensitive binder component, a system containing at least an alkali-soluble resin, a polyfunctional monomer, and a photoinitiator is preferably used. Specific examples of the alkali-soluble resin, the polyfunctional monomer, and the photoinitiator can include, for example, those described in International Publication No. 2012 / 144521.

[0118] <Optional additive component> The ink composition of the present disclosure may contain other light-absorbing compounds and various additives as necessary, as long as the object of the present disclosure is not impaired. Examples of other light-absorbing compounds can include, for example, compounds having a desired absorption in the visible light region, such as squarylium compounds, anthraquinone compounds, phthalocyanine compounds, methine compounds, azomethine compounds, oxazine compounds, azo compounds, styryl compounds, coumarin compounds, porphyrin compounds, dibenzofuranone compounds, diketopyrrolopyrrole-based compounds, rhodamine compounds, xanthene compounds, pyromethene compounds, and the like.

[0119] Examples of the additives include, for example, polymerization inhibitors, chain transfer agents, leveling agents, plasticizers, surfactants, defoaming agents, silane coupling agents, ultraviolet absorbers, adhesion promoters, antistatic agents, fillers, and the like. The additives may further include inorganic or organic fine particles for adjusting hardness and refractive index, antiglare agents, antifouling agents, flame retardants, antioxidants, light stabilizers, surface modifiers, and the like.

[0120] <Mixing ratio of each component in the composition> The total content of the specific colorant used in the present disclosure and other colorants compounded as required may be appropriately selected according to the purpose and is not particularly limited. For example, it may be 0.01% by mass or more, 0.05% by mass or more, 0.1% by mass or more, 0.2% by mass or more, 20% by mass or less, or 10% by mass or less based on the total solid content of the composition. If the amount of the colorant is too small, it may be difficult to obtain the desired absorbency for light in the unnecessary wavelength regions. On the other hand, if there is too much colorant or the like, the properties of the coating film such as the adhesion to the substrate, the surface roughness of the cured film, and the coating film hardness may become insufficient when the composition is applied to the substrate and cured. In the present disclosure, the solid content includes all components other than the above-described solvent and also includes polyfunctional monomers that are liquid at 25°C. Also, when using a dispersant, the content of the dispersant may be appropriately adjusted within the range where the colorant can be uniformly dispersed. For example, it is preferably 10 to 150 parts by mass, more preferably 15 to 45 parts by mass, and even more preferably 15 to 40 parts by mass with respect to 100 parts by mass of the colorant. Further, the content of the dispersant is preferably in the range of 0.01 to 30% by mass, and particularly preferably in the range of 0.03 to 10% by mass with respect to the total solid content of the composition. If the content of the dispersant is less than 0.01% by mass with respect to the total solid content of the composition, the effect of using the dispersant may not be fully exhibited. If it exceeds 30% by mass, it may cause a decrease in curability and developability. The binder component is preferably compounded in a proportion such that its total content is 24 to 94% by mass, more preferably 40 to 90% by mass with respect to the total solid content of the composition. Also, when using a solvent, its content may be appropriately adjusted from the viewpoints of the dispersibility of the colorant and the coatability of the composition. The solvent is preferably usually in the range of 65 to 95% by mass, and more preferably in the range of 75 to 88% by mass with respect to the total amount of the composition containing the solvent.

[0121] <Manufacture of Ink Composition> The method for manufacturing the ink composition is not particularly limited. When using an adhesive or a thermoplastic resin as the binder component, a specific colorant used in the present disclosure may be added to the adhesive or the thermoplastic resin, followed by kneading and use. Alternatively, methods include adding a binder component and various optional additive components to a solvent, mixing them, and then adding and mixing the colorant used in the present disclosure thereto. When preparing a composition using the colorant dispersion according to the present disclosure, for example, methods include simultaneously introducing the colorant dispersion according to the present disclosure, a binder component, and various optional additive components into a solvent and mixing them, or adding a binder component and various optional additive components to a solvent, mixing them, and then adding and mixing the colorant dispersion according to the present disclosure thereto.

[0122] <Film or molded article> The film or molded article according to one embodiment of the present disclosure is a film or molded article containing at least one of the ink composition according to one embodiment of the present disclosure and its cured product. The film or molded article according to one embodiment of the present disclosure contains at least one of the ink composition according to one embodiment of the present disclosure and its cured product, thereby having good light resistance, reduced secondary absorption, and improved color purity and brightness. The film of the present disclosure may have a pattern or may be a film without a pattern (flat film). Further, the film of the present disclosure may be used in a state laminated on a support, or the film of the present disclosure may be peeled off from the support and used.

[0123] The film of the present disclosure may be referred to as a sheet or a plate, and the film thickness can be appropriately adjusted according to the purpose. The film thickness may be 200 μm or less, and more preferably 150 μm or less. Among them, from the viewpoint of ensuring the total light transmittance, the film of the present disclosure is preferably 100 μm or less, more preferably 80 μm or less, and still more preferably 50 μm or less. The lower limit of the film thickness is preferably 0.1 μm or more, more preferably 0.2 μm or more, and still more preferably 0.3 μm or more.

[0124] As a method for manufacturing a film according to one embodiment of the present disclosure, for example, a method including a step of forming a composition layer on a support using the ink composition according to one embodiment of the present disclosure, and, if necessary, a step of further curing the composition layer can be mentioned.

[0125] The support is not particularly limited, and in addition to supports made of materials such as glass, silicon, polycarbonate, polyester, polyacrylic, aromatic polyamide, polyamideimide, polyimide, cycloolefin polymer, and cellulose acylate, other optical members used in display devices may also be used.

[0126] As a method for applying the ink composition to the support, a known method can be appropriately selected and used. For example, coating methods such as gravure coating method, reverse coating method, knife coating method, dip coating method, spray coating method, air knife coating method, spin coating method, roll coating method, printing method, dip and pull-up method, curtain coating method, die coating method, casting method, bar coating method, extrusion coating method, E-type coating method, etc., and various printing methods such as inkjet, nozzle jet, etc. discharge system printing, flexographic printing, screen printing, gravure printing, reverse offset printing, metal mask printing method, etc., transfer methods using a mold, etc., and nanoimprint method, etc. can be mentioned.

[0127] The composition layer applied on the support can be made into a film by appropriately removing (drying) the solvent as necessary.

[0128] As the step of curing the composition layer, a known method can be appropriately selected, such as applying at least one of heating and light irradiation according to the curability of the binder component contained in the composition, to cure the binder component. Further, after manufacturing the film, the support may be removed.

[0129] As a manufacturing method when the film of one embodiment of the present disclosure has a pattern, a method including a step of forming a pattern on the composition layer by a photolithography method or a dry etching method can be mentioned. Regarding the photolithography method or the dry etching method, there are no particular limitations, and a known method can be appropriately selected and applied according to the binder component contained in the composition.

[0130] As a manufacturing method of the molded body of one embodiment of the present disclosure, for example, a method of thermoforming using the ink composition of one embodiment of the present disclosure can be mentioned. As the molding method, a known method can be appropriately selected and applied according to the binder component contained in the ink composition.

[0131] The film or molded body of one embodiment of the present disclosure can be used in various devices such as solid-state imaging devices such as CCD (charge-coupled device) and CMOS (complementary metal-oxide semiconductor) in addition to image display devices. Further, the film or molded body of one embodiment of the present disclosure is preferably used for an optical filter described later, which is intended to transmit, reflect, absorb light rays and give various effects, and can also be used for a recording medium that utilizes selective absorption heat of a wavelength. In addition, the film or molded body of one embodiment of the present disclosure can also be used as an optical material that transmits, reflects, absorbs light rays and gives various effects. As the optical material, for example, it can also be used for lenses such as plastic spectacle lenses, sunglass lenses, and goggles.

[0132] IV. Optical Filter The optical filter of one embodiment of the present disclosure is an optical filter containing the squarylium colorant of the present disclosure. The optical filter of one embodiment of the present disclosure may have a single-layer structure composed of a layer containing the squarylium colorant of the present disclosure, or may be a laminate having a multilayer structure including a layer containing the squarylium colorant of the present disclosure. The layer containing the squarylium coloring material of the present disclosure may be the same as the film of one embodiment of the present disclosure described above. In the optical filter of one embodiment of the present disclosure, the layer containing the squarylium coloring material of the present disclosure may be one layer or two or more layers, and the squarylium coloring materials of the present disclosure included in two or more layers may be the same or different.

[0133] The optical filter of one embodiment of the present disclosure containing the squarylium coloring material of the present disclosure may be used, for example, as a specific wavelength absorption filter that selectively absorbs light in an unnecessary wavelength region, a color correction filter that adjusts color tone, or the like. As the optical filter, for example, in addition to display devices, it is applied to lighting devices, window materials, and the like.

[0134] The optical filter of one embodiment of the present disclosure may include a support, and further, an adhesive layer or a peelable release film may be laminated. As the support, the adhesive layer, and the peelable release film, conventionally known configurations can be appropriately selected and applied. Specific examples of the adhesive layer and the peelable release film include, for example, those described in JP-A-2009-251511.

[0135] The optical filter of one embodiment of the present disclosure may further have other functional layers. Examples of other functional layers include a polarizer, a retardation film, a protective film, an antireflection layer, an antiglare layer, an antifouling layer, an antistatic layer, a hard coat layer, an adhesive layer, an adhesive layer, and the like. As the polarizer, the retardation film, the protective film, the antireflection layer, the antiglare layer, the antifouling layer, the antistatic layer, the hard coat layer, the adhesive layer, and the adhesive layer, conventionally known configurations can be adopted respectively.

[0136] Also, in the optical filter according to one embodiment of the present disclosure, the layer containing the squarylium coloring material of the present disclosure may be further provided with another function. Examples of the other function include functions possessed by one or more selected from the group consisting of a protective film, an antireflection layer, an antiglare layer, an antifouling layer, an antistatic layer, a hard coat layer, an adhesive layer, and an adhesive layer.

[0137] In the optical filter according to one embodiment of the present disclosure, the squarylium coloring material of the present disclosure may be incorporated into the configuration of a conventionally known optical filter. For example, an optical filter in which the squarylium coloring material of the present disclosure is incorporated into at least one of the functional layers can be mentioned.

[0138] The optical filter according to one embodiment of the present disclosure may be a display surface film installed on the observer-side surface of the display panel in a display device. The display surface film usually has a surface functional layer necessary for the display surface, and may further have a support for the surface functional layer and a surface functional layer, an adhesive layer, or an adhesive layer on the surface opposite to the surface functional layer of the support. Examples of the surface functional layer include at least one or more of a polarizer, a retardation film, a protective film, a hard coat layer, an antireflection layer, an antiglare layer, an antifouling layer, and an antistatic layer. Among them, as the surface functional layer, a layer having the function of a hard coat layer may be included from the viewpoints of improving the surface hardness of the display surface film and being able to form a coating film by a solution process, and a layer having at least the functions of a hard coat layer and an antireflection layer may be included.

[0139] The hard coat layer generally has a higher hardness than the protective film and is a layer that imparts at least scratch resistance. The hard coat layer preferably exhibits a hardness of "H" or higher in the pencil hardness test (4.9 N load) defined in JIS K5600-5-4 (1999). The hard coat layer preferably has an antireflection function or an antiglare function for improving visibility, and may further have an antifouling function or an antistatic function. The hard coat layer can be appropriately selected from the hard coat layers used in the optical filters or optical films of conventionally known display devices. As the hard coat layer, for example, the hard coat layers described in International Publication No. 2012 / 018087, International Publication No. 2011 / 065531, Japanese Patent Application Laid-Open No. 2018-51918, etc. can be referred to, and this content is incorporated herein, but is not limited thereto.

[0140] As the configurations of the polarizer, retardation film, protective film, antireflection layer, antiglare layer, antifouling layer, and antistatic layer employed in the surface functional layer, conventionally known configurations can also be appropriately selected and employed. For example, Patent No. 6070195, Patent No. 6040936, Japanese Patent Application Laid-Open No. 2017-21293, Japanese Patent Application Laid-Open No. 2013-142817, Japanese Patent Application Laid-Open No. 2011-90301, etc. can be referred to.

[0141] FIG. 1 is a schematic cross-sectional view showing an example of the optical filter of the present disclosure. As shown in FIG. 1, the optical filter 40 can function as a display surface film, and a laminate having a surface functional layer 30 on one side of the support 1 and an adhesive layer or an adhesive layer 2 on the other side of the support 1 can be mentioned. On the other side of the support 1, a surface functional layer 30 may further be provided between the support 1 and the adhesive layer or the adhesive layer 2 (not shown). FIG. 1 is only an example, and the optical filter of the present disclosure is not limited to this configuration. The optical filter of the present disclosure may be composed only of a film corresponding to the surface functional layer 30. However, the surface functional layer 30 may be a single layer or a laminate composed of two or more layers. Examples of the configuration when the surface functional layer 30 is a laminate include a configuration in which an antireflection layer composed of a low refractive index layer and a high refractive index layer and a hard coat layer are laminated in this order.

[0142] In the optical filter of the present disclosure shown in FIG. 1, the squarylium colorant of the present disclosure may be contained in any of the surface functional layer 30, the support 1, and the adhesive layer or adhesive layer 2, or may be contained in two or more layers. From the viewpoint of further improving light resistance, the optical filter of the present disclosure may contain the squarylium colorant of the present disclosure in a layer located closer to the display element side than the surface functional layer 30 containing an ultraviolet absorber or the support 1 containing an ultraviolet absorber. The surface functional layer 30, the support 1, and the adhesive layer or adhesive layer 2 containing the squarylium colorant of the present disclosure can be produced in the same manner as the method for producing the film of one embodiment of the present disclosure by appropriately selecting a binder component and, if necessary, other necessary components. As the material of the support 1, it is preferably appropriately selected from thermoplastic resins among the binder components of the ink composition of one embodiment of the present disclosure described above, and may be the same as the support of the film of one embodiment of the present disclosure described above. Among others, from the viewpoint of optical properties, a triacetyl cellulose film (TAC film), a cycloolefin polymer film, etc. are preferably used as the support 1. Further, as the material of the adhesive layer or adhesive layer 2, a binder component having a high transmittance in the visible light region may be appropriately selected from among the adhesive or curable binder components of the binder components of the ink composition of one embodiment of the present disclosure described above.

[0143] Since the existing manufacturing process of the display device can be used, the squarylium colorant of the present disclosure may be contained in the surface functional layer 30. Among the surface functional layers 30, for example, the squarylium colorant of the present disclosure may be contained in the hard coat layer. As the material of the hard coat layer, a binder component having a high transmittance in the visible light region may be appropriately selected from among the photocurable binder components of the binder components of the ink composition of one embodiment of the present disclosure described above.

[0144] In the optical filter used as the display surface film of the present disclosure, the total thickness of the surface functional layers may be appropriately selected, and for example, 10 to 150 μm can be mentioned, but usually it is 20 to 100 μm. In the optical filter used as the display surface film of the present disclosure, when having a support, the thickness of the support may be appropriately selected. For example, it may be 10 to 150 μm, but usually it is 20 to 100 μm. In the optical filter used as the display surface film of the present disclosure, when having an adhesive layer or an adhesive layer, the thickness of the adhesive layer or the adhesive layer may be appropriately selected. For example, it may be 10 to 150 μm, but usually it is 20 to 100 μm.

[0145] The optical filter used as the display surface film of the present disclosure may have a transmittance of 80% or more, or may be 90% or more in the visible light region (380 nm to 750 nm) measured according to JIS K7361-1.

[0146] By using the squarylium coloring material of the present disclosure, the optical filter of the present disclosure can be an optical filter having a maximum absorption wavelength (minimum transmittance wavelength) in the wavelength region around 570 to 590 nm, and can selectively absorb the wavelength around 570 to 590 nm. For example, by disposing such an optical filter of the present disclosure on the viewing side of the display element of the display device, the wavelength around 570 to 590 nm can be selectively absorbed from the light incident on the optical filter, and the light transmitted through the optical filter can improve the color purity of green light and red light compared with the light incident on the optical filter.

[0147] V. Display device The display device according to one embodiment of the present disclosure is a display device including the optical filter according to one embodiment of the present disclosure. The optical filter of the present disclosure may be incorporated and used in a display device, and the incorporation method is not particularly limited. The display device is not particularly limited and is applicable. Examples of display elements constituting the display device include liquid crystal display elements, EL (inorganic EL, organic EL) display elements, plasma display elements, electronic paper display elements, LED display elements (such as micro LEDs), and display elements using quantum dot light-emitting diodes (QLEDs). That is, examples of the display device include a liquid crystal display device, an EL (inorganic EL, organic EL) display device, a plasma display device, an electronic paper display device, an LED display device (such as micro LEDs), and a display device using quantum dot light-emitting diodes (QLEDs). In the case of a liquid crystal display device, it is necessary to arrange a backlight on the side opposite to the molded body of the display element. Among them, the display device according to one embodiment of the present disclosure is preferably a display device provided with an optical filter containing the squarylium colorant of the present disclosure on the viewing side of the display element, from the viewpoint of high color purity of the display color. The optical filter containing the squarylium colorant of the present disclosure may be provided as a display surface film.

[0148] An example of the display device according to one embodiment of the present disclosure will be described with reference to the drawings. As shown in FIG. 2, the image display device 100 mainly includes a display panel 10 for displaying an image, and a backlight device 20 disposed on the back side of the display panel 10. In the present embodiment, since the display panel 10 is a liquid crystal display panel, the image display device 100 includes the backlight device 20, but depending on the type of the display panel (display element), the backlight device 20 may not be provided.

[0149] (Display panel) As shown in FIG. 2, the display panel 10 has a structure in which a protective film 11, a polarizer 12, a protective film 13, a light-transmissive adhesive layer 14, a display element 15, a light-transmissive adhesive layer 16, a protective film 17, a polarizer 18, a light-transmissive adhesive layer 16', a protective film 19, and a surface functional layer 30 are laminated in this order from the backlight device 20 side toward the observer side. In FIG. 2, the laminate of the light-transmissive adhesive layer 16', the protective film 19, and the surface functional layer 30 corresponds to the display surface film 40. The optical filter of the present disclosure may be the display surface film 40, or may be a laminate in which a light-transmissive adhesive layer 16, a protective film 17, a polarizer 18, a light-transmissive adhesive layer 16', a protective film 19, and a surface functional layer 30 are laminated in this order. Note that the display panel 10 only needs to include the display element 15, and does not necessarily need to include the protective film 11 or the like.

[0150] The display element 15 in FIG. 2 is a liquid crystal display element. However, the display element 15 is not limited to a liquid crystal display element, and may be, for example, a display element as described above. The liquid crystal display element has a liquid crystal layer, an alignment film, an electrode layer, a color filter, etc. disposed between two glass substrates. Conventionally known protective films, polarizers, and light-transmissive adhesive layers can be appropriately selected and used. Preferred examples of the protective film include a triacetyl cellulose film (TAC film) and a cycloolefin polymer film. Preferred examples of the light-transmissive adhesive layer include an adhesive sheet such as OCA (Optical Clear Adhesive), and may also be a cured product of a liquid curable adhesive layer composition containing a polymerizable compound such as OCR (Optically Clear Resin).

[0151] The surface functional layer 30 in FIG. 2 is located on the surface of the display panel in the display device and is a layer that imparts various functions. It may be a single layer or two or more layers. The surface functional layer 30 may be the same as the surface functional layer described in the optical filter of one embodiment of the present disclosure above, and may be a layer having at least one function of a hard coat layer, an antireflection layer, an antiglare layer, an antifouling layer, and an antistatic layer.

[0152] (Backlight device) The backlight device 20 illuminates the display panel 10 from the back side of the display panel 10. As the backlight device 20, a known backlight device can be used, and the backlight device 20 may be either an edge light type or a direct bottom type backlight device. Further, examples of the light source of the backlight include an LED, a CCFL (cold cathode fluorescent tube), etc. A backlight using quantum dots as the light source is likely to enhance color reproducibility.

[0153] Since the display device according to one embodiment of the present disclosure includes an optical filter containing the squarylium colorant of the present disclosure, it can be suitably used for a display device using a white LED or a blue LED as a light source. When the optical filter containing the squarylium colorant of the present disclosure is used, light in the vicinity of 570 to 590 nm is preferably removed, and the chromaticity of white light can be corrected to a preferable one. Therefore, the display device may have a light source of a method of obtaining white light by combining blue light of a blue light-emitting LED and a phosphor that emits yellow light, or a method of obtaining white light by combining a blue light-emitting LED and phosphors that emit green and red light. Further, when the optical filter containing the squarylium colorant of the present disclosure is used, light in the vicinity of 570 to 590 nm is preferably removed, and the color purity of green light and red light can be improved. Therefore, the display device may have a light source of a blue light-emitting LED.

[0154] In the display device according to one embodiment of the present disclosure, the installation position of the optical filter may be any position as long as it is arranged between the light source as the backlight and the observer of the display device, and is not particularly limited. In a display device according to an embodiment of the present disclosure, for example, in FIG. 2, the light-transmissive adhesive layer 16 or the protective film 17 present between the display element 15 and the polarizer 18 may be an optical filter containing the squarylium colorant of the present disclosure, and the protective film 11, the protective film 13, or the light-transmissive adhesive layer 14 may be an optical filter containing the squarylium colorant of the present disclosure.

[0155] The display device according to an embodiment of the present disclosure is not limited to the above examples, and a conventionally known configuration may be appropriately selected and adopted. The display device according to an embodiment of the present disclosure may further include a touch panel, for example, on the observer side of the display panel 10 in FIG. 2 via, for example, a light-transmissive adhesive layer.

[0156] Also, the display device according to an embodiment of the present disclosure is not limited to the above examples, and a conventionally known configuration may be appropriately selected and adopted. In the display device, the optical filter according to an embodiment of the present disclosure may be provided, for example, at a position suitable for reducing light in an unnecessary wavelength region, and can be set as appropriate.

Example

[0157] Hereinafter, the present disclosure will be specifically described with reference to examples. These descriptions do not limit the embodiments of the present disclosure.

[0158] Hereinafter, the present disclosure will be specifically described with reference to examples. These descriptions do not limit the embodiments of the present disclosure. The following 1 1H-NMR measurement was performed using JEOL JNM-LA400WB manufactured by JEOL Ltd. The following MALDI-MS measurement was performed using REFLEX II manufactured by BRUKER. In the following elemental analysis, organic trace element analysis was performed using CE440 manufactured by Exeter Analytical Inc.

[0159] (Synthesis Example 1: Synthesis of Squarylium Dye A) Squalirium dye A was obtained in the same manner according to the method of Synthesis Example 6 of the same document, except that triethylene glycol monomethyl ether in Intermediate 1 described in International Publication No. 2019-216282 was changed to 2-methoxyethanol. 1 It was confirmed by 1H-NMR that the obtained squalirium dye A had the following structure. The obtained 1 1H-NMR spectrum is shown in Fig. 6.

[0160]

Chemical formula

[0161] (Synthesis Example 2: Synthesis of squalirium dye B) (1) Step 1 2-Bromobenzaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd., 225 g, 1.22 mol) and acetic acid (manufactured by Kanto Chemical Co., Inc., 650 mL) were added to a 2 L flask. Then, it was cooled to 10 °C, 1-nitropropane (manufactured by Tokyo Chemical Industry Co., Ltd., 217 g, 2.43 mol) was added, and butylamine (manufactured by Tokyo Chemical Industry Co., Ltd., 102 g, 1.40 mol) was slowly added dropwise at 11 °C. Then, the temperature was raised to 80 °C and stirred for 2 hours. The reaction solution cooled to room temperature was poured into ice water (1300 mL), and the oil and solid were separated. After washing the oil and solid with water (1300 mL) again, water (2170 mL) and ethyl acetate (2170 mL) were added to extract the organic matter. The extracted organic layer was washed with water and concentrated under reduced pressure. The obtained crude product was subjected to silica gel column chromatography to obtain the target intermediate 1 (yield: 293 g, yield 87%).

[0162] (2) Step 2 To a 5 L flask, intermediate 1 (270 g, 1.05 mol), ethyl isocyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd., 119 g, 1.05 mol), and dehydrated tetrahydrofuran (2700 mL) were added, and the mixture was cooled to 0 °C. Then, potassium t-butoxide (manufactured by Tokyo Chemical Industry Co., Ltd., 124 g, 1.11 mol) was added portionwise, and the mixture was stirred at room temperature for 17 hours. Toluene (2700 mL) and water (2700 mL) were poured into the reaction solution, the organic layer was separated, and concentrated under reduced pressure. The obtained crude product was subjected to silica gel column chromatography to obtain the target intermediate 2 (yield: 295 g, yield rate: 87%).

[0163] (3) Step 3 To a 3 L flask, dehydrated dimethylformamide (manufactured by Tokyo Chemical Industry Co., Ltd., 1760 mL) and intermediate 2 (295 g, 914 mol) were added. The temperature was raised to 65 °C, tris(t-butylphosphonium) tetrafluoroborate (manufactured by Tokyo Chemical Industry Co., Ltd., 52.7 g, 182 mol) and tris(dibenzylideneacetone) dipalladium(0) (manufactured by Tokyo Chemical Industry Co., Ltd., 83.2 g, 90.8 mmol) were added, the temperature was raised to 100 °C, and the mixture was stirred for 2 hours. The reaction solution was cooled to room temperature, and the reaction solution was poured into a mixed solution of toluene (2100 mL), heptane (200 mL), and water (4200 mL), and the precipitated solid was removed by suction filtration. The organic layer was separated from the filtrate, washed with water, and concentrated under reduced pressure. The crude product was subjected to silica gel chromatography to obtain the target intermediate 3 (yield: 214 g, yield rate: 68%).

[0164] (4) Step 4 To a 3 L flask, intermediate 3 (100 g, 289 mmol) and dehydrated toluene (1500 mL) were added, and the mixture was cooled to -1 °C. Then, 3.6 M sodium bis(2-methoxyethoxy)aluminum hydride (670 g, 2.31 mol) was added dropwise. After the addition was completed, the temperature was raised to 60 °C, and the mixture was stirred for 1 hour. After cooling to -20 °C, 20% Rochelle salt (200 mL) was slowly added dropwise. Then, the reaction solution was poured into the remaining 20% Rochelle salt (200 mL), and the mixture was stirred at room temperature for 10 minutes. Tetrahydrofuran (220 mL) was added to obtain a solution containing intermediate 4.

[0165] (5) Step 5 A solution containing intermediate 4 (586 mmol as intermediate 4), 4-dimethylaminopyridine (manufactured by Tokyo Chemical Industry Co., Ltd., 3.58 g, 29.3 mmol), and dehydrated tetrahydrofuran (1000 mL) were added to a 5 L flask, stirred, and then di-t-butyl dicarbonate (140.8 g, 644 mmol) and triethylamine (68.2 g, 674 mmol) were added. Then, the temperature was raised to 60 °C, stirred for 15 hours, and the reaction solution was cooled to room temperature. The concentrate of the reaction solution under reduced pressure was subjected to silica gel chromatography to obtain the target intermediate 5 (yield: 144 g, two-step yield: 63%).

[0166] (6) Step 6 Intermediate 5 (142 g, 365 mmol), THF (560 mL), and methanol (940 mL) were added to a 3 L flask, and Ar gas was bubbled for 30 minutes. Then, palladium / carbon (Pd 5%) (14.2 g) was added, and hydrogen gas was bubbled for 4.5 hours. After completion of the reaction, Ar gas was bubbled for 1 hour, the reaction solution was filtered, and the filtrate was concentrated under reduced pressure. The concentrate under reduced pressure was subjected to silica gel column chromatography to obtain the target intermediate 6 (yield: 38.7 g, yield 27%).

[0167] (7) Step 7 Intermediate 6 (33.0 g, 84.5 mmol) and dehydrated tetrahydrofuran (330 mL) were added to a 500 mL flask and cooled to 0 °C. Then, a sodium methoxide / methanol solution (manufactured by Tokyo Chemical Industry Co., Ltd., 26.4 g, 137 mmol) was added dropwise at 2 °C or lower, the temperature was raised to room temperature, and stirred for 2 hours to obtain a reaction solution. The reaction solution was poured into a 15% ammonium chloride solution, ethyl acetate was added, and the organic layer was separated. The separated product was washed with water and concentrated under reduced pressure to obtain the target intermediate 7 (yield: 29.3 g, yield: 97%).

[0168] (8) Step 8 To a 2 L flask, intermediate 7 (31.7 g, 89.1 mmol) and toluene / butanol = 1 / 1 (both manufactured by Tokyo Chemical Industry Co., Ltd., 720 mL) were added, and the temperature was raised to an external temperature of 125°C. Then, squaric acid (manufactured by Tokyo Chemical Industry Co., Ltd., 3.45 g, 30.3 mmol) was added. After stirring for 3 hours, the mixture was cooled to an internal temperature of 0°C. The reaction solution was filtered, and the filtrate was concentrated under reduced pressure. Then, crystallization was performed using ethyl acetate and heptane. The obtained solid was subjected to silica gel column chromatography to obtain the target squarylium dye B (yield 8.66 g, yield: 43%). 1 By 1H-NMR, it was confirmed that the obtained squarylium dye B had the following structure. The obtained 1 1H-NMR spectrum is shown in Figure 7.

[0169] [Chemical formula]

[0170] (Preparation Example 1: Preparation of Dispersant Solution) (1) Preparation of Block Copolymer Into a reactor equipped with a condenser, an addition funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer, 100 parts by mass of dehydrated tetrahydrofuran (THF) and 3.00 parts by mass of dimethylketene methyltrimethylsilyl acetal were charged, and sufficient nitrogen substitution was performed. After injecting 0.25 part by mass of a 1M acetonitrile solution of tetrabutylammonium m-chlorobenzoate with a syringe, a mixed solution of 50.0 parts by mass of methyl methacrylate, 30.0 parts by mass of n-butyl methacrylate, and 20.0 parts by mass of benzyl methacrylate was added dropwise over 60 minutes. The temperature of the reactor was maintained below 40°C by cooling it in an ice bath. After 1 hour, 50.0 parts by mass of glycidyl methacrylate (GMA) was added dropwise over 30 minutes. After reacting for 1 hour, 1 part by mass of methanol was added to stop the reaction. 450.0 parts by mass of propylene glycol methyl ether acetate (PGMEA) was added to the obtained THF solution of the block copolymer, and solvent substitution was performed by evaporation to obtain a 25.0% by mass PGMEA solution of the block copolymer. The obtained block copolymer had a weight-average molecular weight (Mw) of 11,320, a number-average molecular weight (Mn) of 8,950, and a molecular weight distribution (Mw / Mn) of 1.26. (2) Preparation of Phosphorus-based Block Copolymer Solution Into a reactor equipped with a condenser, an addition funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer, 27.80 parts by mass of PGMEA and 9.27 parts by mass of phenylphosphonic acid (PPA) were charged, and while stirring under a nitrogen stream, the temperature was raised to 90 °C. 100.0 parts by mass of the block copolymer was added dropwise over 30 minutes, and by heating and stirring for 2 hours, a phosphorus-based block copolymer (dispersant) solution (solid content 25% by mass) was obtained. The progress of the esterification reaction between GMA of the block copolymer and PPA was confirmed by acid value measurement and 1 1H-NMR measurement. The acid value of the obtained phosphorus-based block copolymer was 100 mgKOH / g.

[0171] (Preparation Example 2: Preparation of Binder Composition) A binder composition (solid content 40% by mass) was prepared by mixing 60.0 parts by mass of PGMEA, 38.40 parts by mass of a polyfunctional monomer (Aronix M305, manufactured by Toagosei Co., Ltd.), and 1.60 parts by mass of a photoinitiator (Irgacure 184, manufactured by BASF).

[0172] (Example 1) (1) Production of Squarylium Colorant 1 1.88 g (0.58 mmol) of 1-vanado-11-tungstophosphoric acid·n hydrate (manufactured by Nippon Inorganic Chemical Industry) was dissolved in 100 mL of methanol at 60 °C, 0.50 g (0.93 mmol) of the squarylium dye A obtained in Synthesis Example 1, and 0.29 g (0.80 mmol) of bisacodyl (manufactured by Tokyo Chemical Industry Co., Ltd., maximum absorption wavelength 220 nm) (spa1) as a colorless organic cation were added, and the mixture was stirred for 1 hour. The precipitate was collected by filtration and washed with water. The obtained precipitate was dried under reduced pressure to obtain squarylium colorant 1 (yield 96%). The obtained compound was confirmed to be the target compound from the following analysis results. ·MS (MALDI) (m / z): 543.3 (MH + )、362.4 (MH +)、2747(M 3- ) ·Elemental analysis values: Measured values of CHN (45.38% / 50.18% / 4.44%); Theoretical values (45.42% / 50.25% / 4.33%) ·X-ray fluorescence analysis: Measured ratio of V / W / Mo (8.40% / 91.60% / 0.00%); Theoretical values (8.33% / 91.67% / 0.00%)

[0173] (2) Preparation of pigment dispersion 10.00 parts by mass of squarylium pigment 1, 20.0 parts by mass of the dispersant solution of Preparation Example 1 (solid content 25.0%), and 185 parts by mass of PGMEA were mixed, and pre-dispersed with 2 mm zirconia beads for 1 hour using a paint shaker (manufactured by Asada Iron Works), and further dispersed with 0.1 mm zirconia beads for 6 hours for main dispersion to obtain pigment dispersion 1.

[0174] (3) Preparation of ink composition 3.64 parts by mass of the pigment dispersion 1 obtained in (2) above, 4.32 parts by mass of the binder composition of Preparation Example 2, 2.05 parts by mass of PGMEA, 0.05 parts by mass of surfactant R08MH (manufactured by DIC), and 0.05 parts by mass of silane coupling agent KBM503 (manufactured by Shin-Etsu Silicone) were added and mixed, and pressure filtration was performed to obtain ink composition 1 of Example 1.

[0175] (Example 2) (1) Preparation of squarylium pigment 2 Squarylium pigment 2 was obtained in the same manner as the preparation of squarylium pigment 1 in Example 1, except that bisacodyl as the colorless organic cation in the preparation of squarylium pigment 1 in Example 1 was changed to an equimolar amount of ethyl viologen dibromide (manufactured by Tokyo Chemical Industry Co., Ltd., maximum absorption wavelength 250 nm) (spa2). The obtained compound was confirmed to be the target compound from the following analysis results. ·MS (MALDI) (m / z): 543.3 (MH + )、214.3 (M + )、2747 (M 3- ) ·Elemental analysis values: Measured values of CHN (41.75%, 52.77%, 5.49%); Theoretical values (41.85%, 52.72%, 5.44%) ·X-ray fluorescence analysis: Measured ratio of V / W / Mo (8.27% / 91.72% / 0.00%); Theoretical values (8.33% / 91.67% / 0.00%) (2) Preparation of colorant dispersion In the preparation of the colorant dispersion of Example 1, a colorant dispersion 2 was obtained in the same manner as the preparation of the colorant dispersion of Example 1, except that squarylium colorant 1 was changed to squarylium colorant 2. (3) Preparation of ink composition In the preparation of the ink composition of Example 1, an ink composition 2 was obtained in the same manner as the preparation of the ink composition of Example 1, except that colorant dispersion 1 was changed to colorant dispersion 2.

[0176] (Example 3) (1) Preparation of squarylium colorant 3 Squarylium colorant 3 was obtained in the same manner as the preparation of squarylium colorant 1 of Example 1, except that bisacodyl as the colorless organic cation in the preparation of squarylium colorant 1 of Example 1 was changed to an equimolar amount of allyltriphenylphosphonium chloride (manufactured by Tokyo Chemical Industry Co., Ltd., maximum absorption wavelength 304 nm) (spa3). The obtained compound was confirmed to be the target compound from the following analysis results. ·MS (MALDI) (m / z): 543.3 (MH + )、303.3 (MH + )、2747 (M 3- ) ·Elemental analysis values: Measured values of CHN (44.90%, 51.45%, 3.64%); Theoretical values (44.99%, 51.41%, 3.59%) ·X-ray fluorescence analysis: Measured ratio of V / W / Mo (8.25% / 91.74% / 0.00%); Theoretical values (8.33% / 91.67% / 0.00%) (2) Preparation of colorant dispersion In the preparation of the colorant dispersion of Example 1, a colorant dispersion 3 was obtained in the same manner as the preparation of the colorant dispersion of Example 1, except that squarylium colorant 1 was changed to squarylium colorant 3. (3) Production of Ink Composition In the production of the ink composition of Example 1, an ink composition 3 was obtained in the same manner as the production of the ink composition of Example 1, except that the colorant dispersion liquid 1 was changed to the colorant dispersion liquid 3.

[0177] (Example 4) (1) Production of Squarylium Colorant 4 Squarylium colorant 4 was obtained in the same manner as the production of squarylium colorant 1 of Example 1, except that bisacodyl as the colorless organic cation in the production of squarylium colorant 1 of Example 1 was changed to an equimolar amount of trans-2-butene-1,4-bis(triphenylphosphonium chloride) (manufactured by Tokyo Chemical Industry Co., Ltd., maximum absorption wavelength 224 nm) (spa4). The obtained compound was confirmed to be the target compound from the following analysis results. · MS (MALDI) (m / z): 543.3 (MH + )、578.6 (MH + )、2747 (M 3- ) · Elemental analysis values: CHN measured values (46.90%, 50.25%, 2.85%); theoretical values (46.97%, 50.20%, 2.83%) · X-ray fluorescence analysis: V / W / Mo measured ratio (8.37% / 91.63% / 0.00%); theoretical values (8.33% / 91.67% / 0.00%) (2) Production of Colorant Dispersion Liquid In the production of the colorant dispersion liquid of Example 1, a colorant dispersion liquid 4 was obtained in the same manner as the production of the colorant dispersion liquid of Example 1, except that squarylium colorant 1 was changed to squarylium colorant 4. (3) Production of Ink Composition In the production of the ink composition of Example 1, an ink composition 4 was obtained in the same manner as the production of the ink composition of Example 1, except that the colorant dispersion liquid 1 was changed to the colorant dispersion liquid 4.

[0178] (Example 5) (1) Production of Squarylium Colorant 5 In the production of squarylium colorant 1 of Example 1, squarylium dye A was changed to an equimolar amount of squarylium dye B, and viscogli was changed to an equimolar amount of trans-2-butene-1,4-bis(triphenylphosphonium chloride) (spa4). Squarylium colorant 5 was obtained in the same manner as in the production of squarylium colorant 1 of Example 1, except for the above changes. The obtained compound was confirmed to be the target compound from the following analysis results. ·MS(MALDI) (m / z):663(MH + )、578.6(MH + )、2747(M 3- ) ·Elemental analysis values: CHN measured values (48.50%, 48.96%, 2.54%); theoretical values (48.59%, 48.93%, 2.48%) ·X-ray fluorescence analysis: V / W / Mo measured ratio (8.27% / 91.73% / 0.00%); theoretical values (8.33% / 91.67% / 0.00%) (2) Production of colorant dispersion In the production of the colorant dispersion of Example 1, colorant dispersion 5 was obtained in the same manner as in the production of the colorant dispersion of Example 1, except that squarylium colorant 1 was changed to squarylium colorant 5. (3) Production of ink composition In the production of the ink composition of Example 1, ink composition 5 was obtained in the same manner as in the production of the ink composition of Example 1, except that colorant dispersion 1 was changed to colorant dispersion 5.

[0179] (Example 6) (1) Production of squarylium colorant 6 In the production of squarylium colorant 5 of Example 5, 1 vanado-11 tungstophosphoric acid·n hydrate (manufactured by Nippon Inorganic Chemical Industry Co., Ltd.) was changed to 2.30 g of phosphomolybdic acid (manufactured by Nippon Inorganic Chemical Industry Co., Ltd.). Squarylium colorant 6 was obtained in the same manner as in the production of squarylium colorant 5 of Example 5, except for the above change. The obtained compound was confirmed to be the target compound from the following analysis results. ·MS(MALDI) (m / z):663(MH + )、578.6(MH +)、1824(MH 3 - ) ·Elemental analysis values: Measured values of CHN (32.90%, 34.12%, 1.80%); Theoretical values (32.96%, 34.08%, 1.78%) ·X-ray fluorescence analysis: Measured ratio of V / W / Mo (0.00% / 0.00% / 100%); Theoretical value (0.00% / 0.00% / 100%) (2) Preparation of colorant dispersion In the preparation of the colorant dispersion of Example 1, a colorant dispersion 6 was obtained in the same manner as in the preparation of the colorant dispersion of Example 1, except that squarylium colorant 1 was changed to squarylium colorant 6. (3) Preparation of ink composition In the preparation of the ink composition of Example 1, an ink composition 6 was obtained in the same manner as in the preparation of the ink composition of Example 1, except that colorant dispersion 1 was changed to colorant dispersion 6.

[0180] (Comparative Example 1) (1) Preparation of comparative squarylium colorant 1 1.31 g (0.41 mmol) of 1-banaod 11 tungstophosphate · n hydrate (manufactured by Nippon Inorganic Chemical Industry) was dissolved in 100 mL of methanol at 60°C, 0.50 g (0.93 mmol) of squarylium dye A obtained in Synthesis Example 1 was added, and the mixture was stirred for 1 hour. The precipitate was collected by filtration and washed with water. The obtained precipitate was dried under reduced pressure to obtain comparative squarylium colorant 1 (yield 97%). The obtained compound was confirmed to be the target compound from the following analysis results. ·MS (MALDI) (m / z): 543.3 (MH + )、2747(MH 3 - ) ·Elemental analysis values: Measured values of CHN (42.01%, 52.68%, 5.31%); Theoretical values (42.11%, 52.63%, 5.26%) ·X-ray fluorescence analysis: Measured ratio of V / W / Mo (8.43% / 91.57% / 0.00%); Theoretical value (8.33% / 91.67% / 0.00%)

[0181] (2) Preparation of colorant dispersion 10.00 parts by mass of the comparative squarylium coloring material 1, 20.0 parts by mass of the dispersant solution of Preparation Example 1 (solid content 25.0 mass%), and 185 parts by mass of PGMEA were mixed, and pre-dispersed with 2 mm zirconia beads for 1 hour using a paint shaker (manufactured by Asada Iron Works), and further dispersed with 0.1 mm zirconia beads for 6 hours for main dispersion to obtain a comparative coloring material dispersion liquid 1.

[0182] (3) Production of Ink Composition 3.64 parts by mass of the comparative coloring material dispersion liquid 1 obtained in the above (2), 4.32 parts by mass of the binder composition of Preparation Example 2, 2.05 parts by mass of PGMEA, 0.05 parts by mass of surfactant R08MH (manufactured by DIC), and 0.05 parts by mass of silane coupling agent KBM503 (manufactured by Shin-Etsu Silicone) were added and mixed, and pressure filtration was performed to obtain a comparative ink composition 1 of Comparative Example 1.

[0183] [Evaluation] <Film Production and Initial Spectral Measurement> The ink compositions obtained in the examples and comparative examples were applied onto a glass substrate (manufactured by Nippon Electric Glass, "OA-10G") with a thickness of 0.7 mm using a spin coater. Then, heat drying was performed on a hot plate at 80 °C for 3 minutes to obtain a coating film. The coating film was irradiated with ultraviolet rays of 500 mJ / cm 2 using an ultra-high pressure mercury lamp to obtain a cured film. The transmittance spectrum, chromaticity (x, y), luminance (Y), and L, a, b (L 1 , a 1 , b 1 ) of the obtained cured film were measured using an Olympus "Micro Spectrophotometer OSP-SP200". In the measured transmittance spectrum, when the film thickness was adjusted so that the transmittance at the maximum absorption wavelength in the visible region (400 nm to 700 nm), that is, the minimum transmittance wavelength (the wavelength at which the transmittance takes the minimum value), was 40%, the transmittance at the wavelength of [minimum transmittance wavelength (nm) - 50 nm] and the transmittance at the wavelength of [minimum transmittance wavelength (nm) + 50 nm] were used to evaluate the secondary absorption. (Evaluation Criteria) ◎: The transmittance at the wavelength of [minimum transmittance wavelength (nm) - 50 nm] and the transmittance at the wavelength of [minimum transmittance wavelength (nm) + 50 nm] are both 70% or more. 〇: The transmittance at the wavelength of [minimum transmittance wavelength (nm) - 50 nm] and the transmittance at the wavelength of [minimum transmittance wavelength (nm) + 50 nm] both exceed 60%, and at least one of them is less than 70%. ×: At least one of the transmittance at the wavelength of [minimum transmittance wavelength (nm) - 50 nm] and the transmittance at the wavelength of [minimum transmittance wavelength (nm) + 50 nm] is less than 60%.

[0184] <Light resistance test> Using a xenon lamp (Atlas Suntest XLS+ (1.7 kW air-cooled xenon lamp)) under atmospheric pressure on the cured film obtained above, at a wavelength of 300 - 400 nm, with an illuminance of 58 W / m 2 And irradiate for 60 hours (equivalent to 11000 kJ / m 2 ). The transmittance spectrum and color coordinates (L 2 , a 2 , b 2 ) of the cured film after light irradiation were measured again. The retention rate of the maximum absorption wavelength of the colorant or dye, that is, the value of the transmittance at the minimum transmittance wavelength in the transmittance spectrum, was calculated from the following formula (1). Retention rate = (100 - transmittance at the minimum transmittance wavelength after the test (%)) / (100 - transmittance at the minimum transmittance wavelength before the test (%)) × 100...(1)

[0185]

Table 2

[0186] (Summary of results) It was clarified that the films of Examples 1 - 6 using the squarylium colorants 1 - 6 of the present invention had good light resistance and films with suppressed secondary absorption were obtained. For the films of Examples 1 to 6 using squarylium colorants 1 to 6 containing the colorless organic cation of the present invention, compared with the film of Comparative Example 1 using Comparative Squarylium Colorant 1 not containing the colorless organic cation, the retention rate of the transmittance at the minimum transmittance wavelength before and after the light resistance test is equivalent, but since there is no secondary absorption, it is excellent as an optical filter that cuts (absorbs) only specific light. This is because when the squarylium dye cation and the heteropolyacid anion form a salt to form a continuous ion pair aggregate to form a salt-forming compound, the inclusion of the colorless organic cation increases the distance between the dye cations, presumably suppressing the generation of secondary absorption due to the interaction between the dye cations. Further, in Squarylium Colorant 5 of Example 5, a dye cation having an S-shaped skeleton is used as the squarylium dye cation, and since the cationic group that forms a salt with the heteropolyacid is located in a direction perpendicular to the dye plane, it is presumed that the effect of preventing the association of the dyes is high and the secondary absorption can be further suppressed. And the effect of reducing the secondary absorption considered to be caused by the association of the dyes using the colorless organic cation can be confirmed even with phosphomolybdic acid, which is a different heteropolyacid, as shown in Example 6, and it is possible to achieve both improvement in light resistance.

Explanation of Reference Numerals

[0187] 100 Image display device 10 Display panel 11, 13, 17, 19 Protective film 12, 18 Polarizer 14, 16, 16’ Light-transmissive adhesive layer 15 Display element 20 Backlight device 30 Surface functional layer 40 Display surface film (an example of an optical filter) 1 Support 2 Adhesive layer or adhesive bonding layer 101 Organic dye cation 102 Colorless organic cation 103 Heteropolyacid anion 110 Salt-forming compound (squarylium colorant of the present disclosure) 120 Salt-forming compound

Claims

1. It consists of a squarylium dye, a colorless organic cation, and a salt-forming compound of a heteropolyacid, wherein the squarylium dye is a squarylium dye represented by the following general formula (3-1), and the colorless organic cation is a compound containing at least one cation group selected from the group consisting of a pyridinium group, a piperidinium group, a pyrrolidinium group, an imidazolium group, and a morpholinium group, and a phosphonium compound represented by the following general formula (A), and is at least one compound selected from the group consisting of a squarylium colorant. Formula (A): A—[P⁺Rₐ₃]ₐ (In formula (A), A is an a-valent organic group, Rₐ is each independently a hydrocarbon group having 1 to 6 carbon atoms which may have a substituent, and a is an integer of 2 to 4.) 【Chemical 1】 (In formula (3-1), R₁ and R₄ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms which may have a substituent, and R₂, R₃, R₅, and R₆ each independently represent a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms which may have a substituent, a halogen atom, a nitro group, a cyano group, a hydroxy group, —OR₇, —O COR₈, —COOR₉, —CONHR₁₀, —NH COR₁₁, or —NR₁₂R₁₃, R₇, R₈, R₉, R₁₀, and R₁₁ each independently represent a hydrocarbon group having 1 to 6 carbon atoms which may have a substituent, and R₁₂ and R₁₃ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms which may have a substituent. Q each independently represents a direct bond or a divalent aromatic ring group. Y each independently represents a divalent organic group, and Z₀ each independently represents a group that can be derived into an organic cation group or an organic cation group. E each independently represents a substituent, and adjacent substituents E may form a ring. m and n each independently represent an integer of 0 to 4.)

2. The squarylium colorant according to claim 1, wherein the colorless organic cation is a phosphonium compound represented by the following general formula (A). Formula (A): A - [P ＋ R Ａ ３ ａ ​ (In formula (A), A is an a-valent organic group, and each R Ａ is independently a hydrocarbon group having 1 to 6 carbon atoms which may have a substituent, and a is an integer of 2 to 4.)

3. In the general formula (A), Rₐ is each independently a phenyl group, a cyclopentyl group, a cyclohexyl group, a cyclopentenyl group, or a cyclohexenyl group which may have a substituent. The squarylium colorant according to claim 1 or 2.

4. A colorant dispersion liquid containing the squarylium colorant according to any one of Claims 1 to 3, a dispersant, and a solvent.

5. An ink composition containing the squarylium colorant according to any one of Claims 1 to 3 and a binder component.

6. An optical filter containing the squarylium colorant according to any one of Claims 1 to 3.

7. A display device including the optical filter according to Claim 6.

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