Light-absorbing filter, light filter, method for manufacturing light filter, organic electroluminescent display device, inorganic electroluminescent display device, and liquid crystal display device

Abstract

The present invention provides a light absorption filter, a light filter using the light absorption filter, a method for manufacturing the light filter, an organic electroluminescent display device, an inorganic electroluminescent display device or a liquid crystal display device including the light filter, and a method for manufacturing the organic electroluminescent display device, the inorganic electroluminescent display device or the liquid crystal display device. The light absorption filter contains a resin, a specific dye, and a compound that generates radicals by irradiation with ultraviolet light, and a polymer constituting the resin contains a crosslinkable group. The light absorption filter includes a resin, a compound A having an acid group, a compound B that forms a hydrogen bond with the acid group included in the compound A and generates a radical by ultraviolet irradiation, and a specific dye. The compound A is included in a side chain of a polymer constituting the resin.

Description

Technical Field

[0001] The present invention relates to a light absorption filter, an optical filter and a manufacturing method thereof, an organic electroluminescent display device, an inorganic electroluminescent display device and a liquid crystal display device. Background Art

[0002] As image display devices, organic electroluminescence (OLED) display devices, inorganic electroluminescence display devices (inorganic EL display devices), liquid crystal display devices, and the like are mainly known.

[0003] Liquid crystal display devices are used more and more as image display devices that consume little power and save space. In a liquid crystal display device, the liquid crystal panel itself that displays images is a non-luminous element, so it has a backlight unit that is arranged on the back of the liquid crystal panel and supplies light to the liquid crystal panel.

[0004] OLED display devices are devices that display images using the self-luminescence of OLED elements. Therefore, compared with various display devices such as liquid crystal display devices and plasma display devices, they have advantages such as being able to achieve high contrast ratio, high color reproduction, wide viewing angle, high-speed response, and thin and light weight. In addition to these advantages, from the perspective of flexibility, they are also attracting attention as the protagonist of the next generation of display devices.

[0005] Inorganic EL display devices are devices that use the self-luminescence of inorganic EL elements as fluorescent materials to display images instead of OLED elements in OLED display devices. According to recent research, it is expected that display devices that are superior to OLED display devices in terms of larger screens and longer lifespans can be realized.

[0006] In an image display device, there is known a technique of incorporating a light absorption filter into an optical system.

[0007] For example, in a liquid crystal display device, when a white light emitting diode (LED) is used as a light source for a backlight unit, an attempt is made to provide a light absorption filter to block light of an unnecessary wavelength emitted from the white LED. Also, in an OLED display device, an attempt is made to provide a light absorption filter from the viewpoint of suppressing reflection of external light.

[0008] As another form of a light absorption filter incorporated in an image display device, a filter having both a light absorption portion having a light absorption effect and a portion where the light absorption is eliminated (hereinafter, also referred to as a "light absorption eliminated portion") by eliminating the light absorption of a desired portion has been studied. In particular, as a form of an optical filter incorporated in an image display device, a light absorption property close to colorless is required for the light absorption eliminated portion in the filter.

[0009] For example, Patent Document 1 discloses a light absorption filter comprising a resin, a dye having a main absorption wavelength band at a wavelength of 400 to 700 nm, and a compound that generates free radicals by ultraviolet irradiation, wherein the dye comprises a squarylium dye represented by the general formula (1) or a benzylidene dye or a cinnamylene dye represented by the general formula (V) described in Patent Document 1. According to the light absorption filter disclosed in Patent Document 1, a high decolorization rate due to ultraviolet irradiation is exhibited, and absorption (hereinafter also referred to as "secondary absorption") derived from a new coloring structure accompanying decomposition of the dye due to ultraviolet irradiation is almost non-existent, thereby achieving high decolorization performance.

[0010] Previous technical literature

[0011] Patent Literature

[0012] Patent Document 1: International Publication No. 2021 / 132674 Summary of the invention

[0013] Technical issues to be solved by the invention

[0014] However, when the light absorption filter described in Patent Document 1 is used, high decolorization performance can be obtained, but the light absorption filter needs to be heated during ultraviolet irradiation, and improvement in the productivity of the filter is required.

[0015] The research results of the present inventors and others show that by setting the structure of a light absorption filter including a resin, a compound A having an acid group, a compound B that forms a hydrogen bond with the acid group contained in the above-mentioned compound A and generates free radicals when irradiated with ultraviolet rays, and a dye having a main absorption wavelength band at a wavelength of 400 to 700 nm, excellent decolorization properties can be obtained even when irradiated with ultraviolet rays at room temperature.

[0016] On the other hand, if one wishes to obtain a more practical optical filter having a light-absorbing portion and a light-absorbing extinguishing portion, one may consider increasing the concentration of the dye contained in the light-absorbing filter, or increasing the concentration of the compound that generates free radicals by ultraviolet irradiation in order to decolorize the dye contained at a high concentration.

[0017] However, as a result of research conducted by the present inventors, it was found that when the concentration of the compound generating free radicals is increased in a light absorption filter comprising the above-mentioned resin, a compound A having an acid group, a compound B that forms a hydrogen bond with the acid group contained in the above-mentioned compound A and generates free radicals upon ultraviolet irradiation, and a dye having a main absorption wavelength band at a wavelength of 400 to 700 nm, a problem that a substantially circular cavity of a size of about several mm is generated in the filter at a portion where the light absorption disappears after ultraviolet irradiation occurs. It is desired to develop a light absorption filter that does not cause such a problem even when the compound generating free radicals is contained at a high concentration.

[0018] That is, the object of the present invention is to provide a light absorption filter which can obtain excellent decolorization even when irradiated with ultraviolet rays at room temperature, and can obtain a filter in which the generation of cavities in the filter due to ultraviolet irradiation is suppressed even when a compound generating free radicals is contained at a high concentration.

[0019] Furthermore, the present invention aims to provide an optical filter, an OLED display device, an inorganic electroluminescent display device, a liquid crystal display device having the optical filter, and a method for manufacturing the optical filter, wherein the optical filter uses the above-mentioned light absorption filter and has a light absorption portion and a light absorption disappearance portion at a desired position.

[0020] Means for solving technical problems

[0021] That is, the above-mentioned problems were solved by the following means.

[0022] <1>

[0023] A light absorption filter comprises a resin, a dye having a main absorption wavelength band at a wavelength of 400 to 700 nm, and a compound generating free radicals by ultraviolet irradiation, wherein the polymer constituting the resin contains a crosslinking group.

[0024] <2>

[0025] according to <1> The light absorption filter, wherein

[0026] The compound that generates a radical by the ultraviolet irradiation includes a combination of a compound A having an acid group and a compound B having a structure capable of forming a hydrogen bond with the acid group included in the compound A.

[0027] <3>

[0028] A light absorption filter comprises a resin, a compound A having an acid group, a compound B which forms a hydrogen bond with the acid group contained in the compound A and generates a free radical when irradiated with ultraviolet light, and a dye having a main absorption wavelength band at a wavelength of 400 to 700 nm, wherein the compound A is contained in a side chain of a polymer constituting the resin.

[0029] <4>

[0030] according to <1> to <3> The light absorption filter as described in any one of the preceding claims, wherein:

[0031] The dye having a main absorption wavelength band at the wavelength of 400 to 700 nm includes a heterocyclic azo dye.

[0032] <5>

[0033] according to <4> The light absorption filter, wherein

[0034] The heterocyclic azo dye includes an azo dye represented by the following general formula (III).

[0035] [Chemical formula 1]

[0036]

[0037] In the above formula, R 17 and R 18 Each independently represents a hydrogen atom or a monovalent substituent.

[0038] R 19 represents a hydrogen atom, an aliphatic group, an aryl group, a heterocyclic group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyl group, an alkylsulfonyl group, an arylsulfonyl group or a sulfamoyl group.

[0039] Q represents a diazo component residue.

[0040] <6>

[0041] according to <1> to <5> The light absorption filter as described in any one of the preceding claims, wherein:

[0042] The dye having a main absorption wavelength band at the wavelength of 400 to 700 nm includes a squarylium dye represented by the following general formula (1).

[0043] [Chemical formula 2]

[0044]

[0045] In the above formula, A and B each independently represent an aryl group which may have a substituent, a heterocyclic group which may have a substituent, or -CH=G. G represents a heterocyclic group which may have a substituent.

[0046] <7>

[0047] according to <1> to <6> The light absorption filter as described in any one of the preceding claims, wherein:

[0048] The light absorption filter causes the dye having the main absorption wavelength band at the wavelength of 400 to 700 nm to undergo chemical changes and decolorize by irradiation with ultraviolet rays.

[0049] <8>

[0050] A filter that uses ultraviolet light to <1> to <7> The light absorption filter described in any one of the above is formed by performing mask exposure.

[0051] <9>

[0052] An organic electroluminescent display device, an inorganic electroluminescent display device or a liquid crystal display device, comprising <8> The optical filter.

[0053] <10>

[0054] According to the method <9> The organic electroluminescent display device, inorganic electroluminescent display device or liquid crystal display device, wherein:

[0055] The optical filter has a layer on the viewer's side that blocks light absorption by the compound that generates radicals when irradiated with the ultraviolet rays.

[0056] <11>

[0057] A method for manufacturing an optical filter comprises the following steps: <1> to <7> The light absorption filter described in any one of the above is irradiated with ultraviolet rays and subjected to mask exposure.

[0058] In the present invention, when there are multiple substituents or linking groups represented by specific symbols or formulas (hereinafter referred to as substituents, etc.) or when multiple substituents, etc. are specified at the same time, unless otherwise specified, each substituent, etc. may be the same or different from each other. This is also the same for the number of substituents, etc. In addition, when multiple substituents, etc. are close (especially, when adjacent), unless otherwise specified, they can be linked to each other to form a ring. In addition, unless otherwise specified, rings such as alicyclic rings, aromatic rings, and heterocyclic rings can be further fused to form condensed rings.

[0059] In the present invention, unless otherwise specified, the components constituting the light absorption filter (resin, dye, compound that generates free radicals by ultraviolet irradiation (including a combination of compound A and compound B), and other components that may be appropriately contained, etc.) may be contained in the light absorption filter alone or in combination of two or more. This also has the same meaning for the optical filter produced using the light absorption filter of the present invention.

[0060] The optical filter of the present invention can preferably be applied to the description of the light absorption filter of the present invention unless otherwise specified, except that the optical filter of the present invention has a light absorption disappearance portion formed by ultraviolet irradiation.

[0061] In the present invention, unless otherwise specified, when a double bond exists in a molecule, it may be either E-type or Z-type, and may be a mixture thereof.

[0062] In the present invention, the expression of a compound (including a complex) is used to include, in addition to the compound itself, its salt and its ion. Furthermore, within the scope of not damaging the effect of the present invention, the expression of a compound means a compound including a part of the structure that has been changed. Furthermore, with respect to a compound that is not indicated to be substituted or unsubstituted, it means that it may have any substituent within the scope of not damaging the effect of the present invention. This is also the same for substituents and linking groups.

[0063] Furthermore, in the present invention, a numerical range expressed using "to" means a range including the numerical values ​​described before and after "to" as the lower limit and the upper limit.

[0064] In the present invention, the composition includes not only a mixture in which the concentration of the components is constant (each component is uniformly dispersed) but also a mixture in which the concentration of the components varies within a range that does not impair the intended function.

[0065] In the present invention, having a main absorption wavelength band at wavelengths XX to YY nm means that the wavelength showing maximum absorption (i.e., the maximum absorption wavelength) exists in the wavelength range XX to YY nm. Therefore, if the maximum absorption wavelength is within the above wavelength range, the entire absorption band including the wavelength may be within the above wavelength range or may extend outside the above wavelength range. Furthermore, in the case where there are multiple maximum absorption wavelengths, it is sufficient as long as the maximum absorption wavelength showing the maximum absorbance exists in the above wavelength range. That is, the maximum absorption wavelength other than the maximum absorption wavelength showing the maximum absorbance may exist in any one of the above wavelength ranges XX to YY nm.

[0066] Effects of the Invention

[0067] The light absorption filter of the present invention can obtain excellent decolorization even when irradiated with ultraviolet rays at room temperature, and can obtain a filter in which the generation of cavities in the filter due to ultraviolet irradiation is suppressed even when a compound generating free radicals is contained at a high concentration.

[0068] Furthermore, the optical filter of the present invention and the OLED display device, inorganic electroluminescent display device, and liquid crystal display device of the present invention including the same can have a light-absorbing portion and a light-absorbing non-accepting portion at desired positions. BRIEF DESCRIPTION OF THE DRAWINGS

[0069] Figure 1 This is a schematic diagram schematically showing an embodiment of a liquid crystal display device including the optical filter of the present invention. DETAILED DESCRIPTION

[0070] [Light absorption filter]

[0071] In one embodiment, the light absorption filter of the present invention contains a resin, a dye having a main absorption wavelength band at a wavelength of 400 to 700 nm (hereinafter also referred to as "dye"), and a compound that generates free radicals upon ultraviolet irradiation, wherein the polymer constituting the resin contains a crosslinking group.

[0072] In the present invention, the main absorption wavelength band of the dye refers to the main absorption wavelength band of the dye measured in the state of the light absorption filter. Specifically, in the examples described below, the measurement is performed in the state of the light absorption filter with the substrate under the conditions described in the absorbance of the light absorption filter.

[0073] In the light absorption filter of the present invention, the "dye" is dispersed (preferably dissolved) in the resin to form a layer showing a specific absorption spectrum derived from the dye. The dispersion may be random or regular.

[0074] Furthermore, the "compound A having an acid group" described later can be bonded to the polymer constituting the resin. Furthermore, the "compound B having a structure capable of forming a hydrogen bond with the acid group contained in the compound A" described later forms a hydrogen bond with the compound A and is dispersed (preferably dissolved) in the resin, or forms a hydrogen bond with the compound A in the polymer constituting the resin when the compound A having the acid group is bonded to the polymer constituting the resin. Thus, the compound A and the compound B in the light absorption filter of the present invention generate free radicals when irradiated with ultraviolet rays, and the mechanism in which the generated free radicals react with the dye can more effectively decolorize and discolor the dye.

[0075] The light absorption filter of the present invention contains a dye having a main absorption wavelength band at a wavelength of 400 to 700 nm, a compound that generates free radicals by ultraviolet irradiation, and a resin, and the polymer constituting the above-mentioned resin contains a crosslinking group. The light absorption filter of the present invention having such a structure can obtain excellent decolorization even when irradiated with ultraviolet rays at room temperature (referring to 10 to 30°C) as a mild environment, and can suppress the generation of cavities in the filter by ultraviolet irradiation even when the compound that generates free radicals is contained at a high concentration. Although the reason is inferred, it is believed that the reason why cavities are generated in the filter by ultraviolet irradiation is that the free radicals generated by ultraviolet irradiation not only attack the dye but also attack the polymer constituting the resin, causing the depolymerization of the polymer. In contrast, it is believed that by introducing a crosslinking group into the polymer constituting the resin, the polymer can be crosslinked in the decolorization reaction based on ultraviolet irradiation, and the generation of cavities in the filter by ultraviolet irradiation can be suppressed.

[0076] In the light absorption filter of the present invention, when a compound A having an acid group and a compound B having a structure capable of forming a hydrogen bond with the acid group of the compound A are contained as compounds that generate free radicals by ultraviolet irradiation, the efficiency of generating free radical species by ultraviolet irradiation is improved compared with the case of using a common photo-free radical generator such as a benzophenone compound. Therefore, even when ultraviolet irradiation is performed under mild temperature conditions such as room temperature (i.e., 10 to 30° C.), sufficient free radical species are generated, and the free radical species react directly or indirectly with the above-mentioned dye to decompose the dye, thereby fading and discoloring the dye, and a more excellent decolorization rate can be shown.

[0077] Furthermore, in the light absorption filter of the present invention, when the compound A having an acid group is bonded to the polymer constituting the resin, free radicals are generated near the dye by ultraviolet irradiation, and the free radicals are easily reacted with the dye.

[0078] Thus, in the light absorption filter of the present invention, the dye undergoes a chemical change and is decolorized by irradiation with ultraviolet rays. That is, the light absorption filter has a characteristic that the dye undergoes a chemical change and is decolorized by irradiation with ultraviolet rays.

[0079] <Dyes having a main absorption wavelength band at a wavelength of 400 to 700 nm>

[0080] Specific examples of dyes having a main absorption wavelength band at a wavelength of 400 to 700 nm used in the present invention include, for example, tetraazaporphyrin (TAP) series, squaraine (SQ) series, cyanine (CY) series, benzylidene series, cinnamylene series and azo series pigments (dyes).

[0081] Among these, the light absorption filter of the present invention preferably contains a heterocyclic azo dye and / or a squarylium dye represented by the following general formula (1) as the above-mentioned dye from the viewpoint that it is not easy to generate a secondary coloring structure accompanying the decomposition of the dye. These dyes are not easy to generate a secondary coloring structure accompanying the decomposition of the dye, so by using them as dyes, the part irradiated with ultraviolet light can be effectively made colorless.

[0082] Specifically, when a heterocyclic azo dye and / or a squarylium dye represented by the following general formula (1) is used as the dye, the optical filter of the present invention can be preferably produced by mask-exposing the light absorption filter of the present invention by ultraviolet irradiation.

[0083] Furthermore, by adjusting the mixing ratio of the heterocyclic azo dye and the squarylium dye represented by the following general formula (1), the light absorption filter of the present invention and the light absorption site in the optical filter of the present invention can suppress the change in the hue of the reflected light compared to the case where no dye is contained (hereinafter referred to as "adjusting the hue of the reflected light to be neutral"), which is therefore preferred.

[0084] The dye that can be contained in the light absorption filter of the present invention may be one or more than one dye. For example, when the light absorption filter of the present invention contains a heterocyclic azo dye, the heterocyclic azo dye may be one or more than one dye, and when the light absorption filter of the present invention contains a squarylium dye represented by the following general formula (1), the squarylium dye represented by the following general formula (1) may be one or more than one dye.

[0085] The light absorption filter of the present invention may contain dyes other than the above-mentioned dyes.

[0086] In the present invention, in the pigment represented by each following general formula, cation exists in the mode of delocalization, and has a plurality of tautomeric structures.Therefore, in the present invention, at least 1 tautomeric structure of some pigment is applicable to the situation of each general formula, and a certain pigment is made as the pigment represented by each general formula.Therefore, the pigment represented by specific general formula also can be called the pigment that can represent at least 1 tautomeric structure by specific general formula.In the present invention, about the pigment represented by general formula, as long as at least 1 of its tautomeric structure is applicable to this general formula, then can adopt any tautomeric structure.

[0087] (1) Heterocyclic azo pigments

[0088] In the present invention, the heterocyclic azo colorant refers to a dye having a structure in which a heterocyclic group is directly bonded to at least one of the nitrogen atoms constituting an azo group (—N═N—).

[0089] The above heterocyclic group may be a saturated or unsaturated aliphatic heterocyclic group or an aromatic heterocyclic group.

[0090] The heterocyclic ring in the heterocyclic group may be a monocyclic ring or a condensed ring, and is preferably a monocyclic ring. The heterocyclic ring in the heterocyclic group is preferably a 5-membered ring or a 6-membered ring.

[0091] The heterocyclic ring in the heterocyclic group may be any heterocyclic ring containing at least one of heteroatoms (atoms other than carbon atoms) such as a nitrogen atom, a sulfur atom, and an oxygen atom as a ring-constituting atom, preferably a heterocyclic ring containing at least one of a nitrogen atom and a sulfur atom as a ring-constituting atom, and more preferably a heterocyclic ring containing at least a nitrogen atom as a ring-constituting atom.

[0092] The heterocyclic ring in the heterocyclic group may contain one or more hetero atoms as ring-constituting atoms, and preferably contains 1 to 4 hetero atoms, more preferably 1 to 3 hetero atoms.

[0093] Examples of the heterocyclic ring in the heterocyclic group include aromatic heterocyclic rings such as pyrrole ring, pyrazole ring, imidazole ring, pyridine ring, pyrimidine ring, pyrazine ring, pyridazine ring, triazine ring, tetrazine ring, thiazole ring, isothiazole ring, and thiophene ring. In addition, examples of the heterocyclic ring include pyridin-2-one rings in which a part of these aromatic heterocyclic rings is substituted with an oxo group (=O).

[0094] Preferred examples of the heterocyclic azo dye include azo dyes represented by the following general formula (III).

[0095] [Chemical formula 3]

[0096]

[0097] In the above formula, R 17 and R 18 Each independently represents a hydrogen atom or a monovalent substituent.

[0098] R 19 represents a hydrogen atom, an aliphatic group, an aryl group, a heterocyclic group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyl group, an alkylsulfonyl group, an arylsulfonyl group or a sulfamoyl group.

[0099] Q represents a diazo component residue.

[0100] As can be used as R 17 and R 18The monovalent substituent of the compound may include a halogen atom, an aliphatic group, an aryl group, a heterocyclic group, a cyano group, a carboxyl group, a carbamoyl group, an aliphatic oxycarbonyl group, an aryloxycarbonyl group, an acyl group, a hydroxyl group, an aliphatic oxy group, an aryloxy group, an acyloxy group, a carbamoyloxy group, a heterocyclic oxy group, an amino group (-NH2), an aliphatic amino group, an arylamino group, a heterocyclic amino group, an acylamino group, a carbamoylamino group, a sulfamoylamino group, an aliphatic oxycarbonylamino group, an aryloxycarbonylamino group, an aliphatic sulfonylamino group, an arylsulfonylamino group, a nitro group, an aliphatic thiol group, an arylthio group, an aliphatic sulfonyl group, an arylsulfonyl group, a sulfamoyl group, a sulfo group, an imido group, and a heterocyclic thiol group. Among these, from the viewpoint of mainly imparting solubility, an aliphatic group, an aryl group, a heterocyclic group, a cyano group, a carbamoyl group, an aliphatic oxycarbonyl group, an aryloxy group, an aliphatic amino group, or an arylamino group is preferred.

[0101] These can be used as R 17 and R 18 The substituent may be further substituted.

[0102] Can be used as R 17 ~R 19 The aliphatic group may further have a monovalent substituent, which may be saturated, unsaturated, or cyclic. Specifically, for example, alkyl, substituted alkyl, alkenyl, substituted alkenyl, alkynyl, substituted alkynyl, aralkyl, and substituted aralkyl may be mentioned. The total number of carbon atoms in the aliphatic group is preferably 1 to 30, more preferably 1 to 16. As specific examples of the aliphatic group, for example, methyl, ethyl, butyl, isopropyl, tert-butyl, hydroxyethyl, methoxyethyl, cyanoethyl, trifluoromethyl, 3-sulfopropyl, 4-sulfobutyl, 2-(2-hydroxyethoxy)ethyl, 2-(2-(acetoxy)ethoxy)ethyl, cyclohexyl, benzyl, 2-phenylethyl, vinyl, and allyl may be mentioned.

[0103] In addition, examples of the monovalent substituent that may be present include: 17 and R 18 The monovalent substituent of the present invention is the same in the following description related to the monovalent substituent that may be possessed. As the monovalent substituent that may be possessed, for example, alkoxy, acyloxy, hydroxyl, etc. are preferred. Moreover, these substituents may further have a substituent, for example, alkoxy, acyloxy, hydroxyl, etc. are preferably mentioned.

[0104] Can be used as R 17 ~R 19The aryl group may further have a monovalent substituent, and is preferably an aryl group having a total carbon number of 6 to 30, and more preferably an aryl group having 6 to 16. Specific examples thereof include phenyl, 4-tolyl, 4-methoxyphenyl, 2-chlorophenyl, 3-(3-sulfopropylamino)phenyl, 4-sulfamoylphenyl, 4-(ethoxyethylsulfamoyl)phenyl, and 3-(dimethylcarbamoyl)phenyl.

[0105] As can be used as R 17 ~R 19 The heterocyclic group may be a saturated or unsaturated aliphatic ring group or an aromatic ring group, and is preferably an aromatic heterocyclic group. Examples of the ring constituting the heterocyclic group include a ring containing at least one of heteroatoms such as a nitrogen atom, a sulfur atom, and an oxygen atom as a ring-constituting atom, and may further have a monovalent substituent, preferably a heterocyclic group having a total carbon number of 1 to 30, and more preferably a heterocyclic group having 1 to 15. Specifically, for example, 2-pyridyl, 2-thienyl, 2-thiazolyl, 2-benzothiazolyl, 2-benzoxazolyl, and 2-furanyl may be mentioned.

[0106] As can be used as R 17 ~R 19 The carbamoyl group includes, in addition to an unsubstituted carbamoyl group (-CONH2), a carbamoyl group substituted with an aliphatic group, an aromatic group, or the like.

[0107] Can be used as R 17 ~R 19 The carbamoyl group may further have a monovalent substituent, and is preferably a carbamoyl group having a total carbon number of 1 to 30, and more preferably a carbamoyl group having a carbon number of 1 to 16. Specific examples thereof include methylcarbamoyl, dimethylcarbamoyl, phenylcarbamoyl, and N-methyl-N-phenylcarbamoyl.

[0108] As can be used as R 17 and R 18 The aliphatic group in the aliphatic oxycarbonyl group can be used as R 17 ~R 19 Record of aliphatic groups.

[0109] Can be used as R 17 and R 18 The aliphatic oxycarbonyl group may further have a monovalent substituent, may be saturated or unsaturated, and may be cyclic, and preferably has a total carbon number of 2 to 30, and more preferably has a total carbon number of 2 to 16. Specific examples thereof include methoxycarbonyl, ethoxycarbonyl, and 2-methoxyethoxycarbonyl.

[0110] Can be used as R 19The alkoxycarbonyl group may further have a monovalent substituent, may be saturated or unsaturated, and may be cyclic, and preferably has a total carbon number of 2 to 30, and more preferably has a total carbon number of 2 to 16. Specific examples thereof include methoxycarbonyl, ethoxycarbonyl, and 2-methoxyethoxycarbonyl.

[0111] Can be used as R 17 ~R 19 The aryloxycarbonyl group may further have a monovalent substituent, and is preferably an aryloxycarbonyl group having a total carbon number of 7 to 30, and more preferably an aryloxycarbonyl group having a total carbon number of 7 to 16. Specific examples thereof include a phenoxycarbonyl group, a 4-methylphenoxycarbonyl group, and a 3-chlorophenoxycarbonyl group.

[0112] Available as R 17 ~R 19 The acyl group includes an aliphatic carbonyl group, an aryl carbonyl group and a heterocyclic carbonyl group, and preferably has a total carbon number of 1 to 30, and more preferably has a total carbon number of 1 to 16. Specific examples thereof include acetyl, methoxyacetyl, thienoyl and benzoyl.

[0113] As can be used as R 17 and R 18 The aliphatic group in the aliphatic sulfonyl group can be used as R 17 ~R 19 Record of aliphatic groups.

[0114] Can be used as R 17 and R 18 The aliphatic sulfonyl group may further have a monovalent substituent, may be saturated or unsaturated, may be cyclic, and preferably has a total carbon number of 1 to 30, more preferably a total carbon number of 1 to 16. Specific examples thereof include methylsulfonyl, methoxymethylsulfonyl, and ethoxyethylsulfonyl.

[0115] Can be used as R 19 The alkylsulfonyl group may further have a monovalent substituent, may be saturated or unsaturated, may be cyclic, and preferably has a total carbon number of 1 to 30, more preferably a total carbon number of 1 to 16. Specific examples thereof include methylsulfonyl, methoxymethylsulfonyl, and ethoxyethylsulfonyl.

[0116] Can be used as R 17 ~R 19 The arylsulfonyl group may further have a monovalent substituent, and preferably has a total carbon number of 6 to 30, and more preferably has a total carbon number of 6 to 18. Specific examples thereof include a benzenesulfonyl group and a toluenesulfonyl group.

[0117] As can be used as R 17 ~R 19 The sulfamoyl group includes, in addition to an unsubstituted sulfamoyl group (-SO2NH2), a carbamoyl group substituted with an aliphatic group, an aromatic group, or the like.

[0118] Can be used as R 17 ~R 19 The sulfamoyl group may further have a monovalent substituent, and preferably has a total carbon number of 0 to 30, and more preferably has a total carbon number of 0 to 16. Specific examples thereof include an unsubstituted sulfamoyl group, a dimethylsulfamoyl group, and a di-(2-hydroxyethyl)sulfamoyl group.

[0119] Can be used as R 17 and R 18 The imide group may further have a monovalent substituent, and is preferably a 5- to 6-membered ring imide group. The imide group preferably has a total carbon number of 4 to 30, and more preferably 4 to 20. Specifically, for example, succinimide and phthalimide groups are mentioned.

[0120] As can be used as R 17 and R 18 The aliphatic groups in the aliphatic oxy, aliphatic oxy, aliphatic amino, aliphatic oxycarbonylamino, aliphatic sulfonylamino and aliphatic thio groups can be used as R 17 ~R 19 Record of aliphatic groups.

[0121] As can be used as R 17 and R 18 The aryl group in the aryloxy group, arylamino group, aryloxycarbonylamino group, arylsulfonylamino group and arylthio group can be used as R 17 ~R 19 The record of aromatic group.

[0122] As can be used as R 17 and R 18 The acyl group in the acyloxy group and the acylamino group can be used as R 17 ~R 19 The acyl group of

[0123] As can be used as R 17 and R 18 The carbamoyl group in the carbamoyloxy group and the carbamoylamino group can be used as R 17 ~R 19 No record of carbamoyl group.

[0124] As can be used as R 17 and R 18The heterocyclic group in the heterocyclic oxy, heterocyclic amino and heterocyclic thio group can be used as R 17 ~R 19 The heterocyclic group of

[0125] As can be used as R 17 and R 18 The sulfamoyl group in the sulfamoylamino group can be used as R 17 ~R 19 No record of the sulfamoyl group.

[0126] The diazo component residue represented by Q means a residue of a diazo component "Q-NH2". In particular, from the viewpoint of the target color reproducibility, Q is preferably an aryl group or an aromatic heterocyclic group.

[0127] The aromatic hydrocarbon ring constituting the aryl group that can be used as Q may be a monocyclic ring or a condensed ring, and is preferably a monocyclic ring. An aryl group having a total carbon number of 6 to 30 is preferred, and an aryl group having a total carbon number of 6 to 16 is more preferred. Specifically, a phenyl group is preferred. The aryl group that can be used as Q may have a substituent, and examples of the substituent that may have include a sulfamoyl group (preferably an alkylsulfamoyl group or a dialkylsulfamoyl group), a sulfonyl group (preferably an alkylsulfonyl group), and a cyano group.

[0128] The aromatic heterocyclic group that can be used as Q is preferably an aromatic ring group containing at least one of heteroatoms such as a nitrogen atom, a sulfur atom, and an oxygen atom as a ring-constituting atom constituting the heterocyclic group, and is composed of a 5- to 6-membered ring. The number of carbon atoms in the aromatic heterocyclic group is preferably 1 to 25, and more preferably 1 to 15. The aromatic heterocyclic ring constituting the aromatic heterocyclic group may be a monocyclic ring or a condensed ring, and is preferably a monocyclic ring.

[0129] Specific examples of the aromatic heterocyclic group include pyrazolyl, 1,2,4-triazolyl, isothiazolyl, benzisothiazolyl, thiazolyl, benzothiazolyl, oxazolyl, and 1,2,4-thiadiazolyl.

[0130] In addition, R 17 ~R 19 And Q preferably does not have a squaric acid structure.

[0131] The above-mentioned squaric acid structure refers to the structure of a squaric acid-based pigment. A squaric acid-based pigment refers to a pigment having a structure having a skeleton derived from squaric acid in the central part of a π-conjugated system. For example, a squaric acid-based pigment represented by the general formula (1) described in Patent Document 1 can be cited.

[0132] Examples of heterocyclic azo dyes include the following exemplary compounds (B-12) to (B-16), (B-18), and (B-19), but the present invention is not limited thereto.

[0133] [Chemical formula 4]

[0134]

[0135] (2) Squaric acid pigment represented by general formula (1)

[0136] [Chemical formula 5]

[0137]

[0138] In the general formula (1), A and B each independently represent an aryl group which may have a substituent, a heterocyclic group which may have a substituent, or -CH=G. G represents a heterocyclic group which may have a substituent.

[0139] The aryl group that can be used as A or B is not particularly limited, and may be a group containing a single ring or a group containing a condensed ring. The number of carbon atoms in the aryl group is preferably 6 to 30, more preferably 6 to 20, and further preferably 6 to 12. Examples of the aryl group include groups containing a benzene ring or a naphthalene ring, and groups containing a benzene ring are more preferred.

[0140] As a heterocyclic group that can be used as A or B, there is no particular limitation, including a group comprising an aliphatic heterocycle or an aromatic heterocycle, preferably a group comprising an aromatic heterocycle. As a heteroaryl of an aromatic heterocyclic group, for example, a heteroaryl that can be used as a substituent X described later can be cited. Aromatic heterocyclic groups that can be used as A or B are preferably groups of 5-membered rings or 6-membered rings, more preferably groups of nitrogen-containing 5-membered rings. Specifically, a group comprising any one of a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, a pyrazole ring, a thiazole ring, an oxazole ring, a triazole ring, an indole ring, an indolenine ring, a pyridine ring, a pyrimidine ring, a quinoline ring, a benzothiazole ring, a benzoxazole ring and a pyrazolotriazole ring can be preferably cited. Among them, a group comprising any one of a pyrrole ring, a pyrazole ring, a thiazole ring, a pyridine ring, a pyrimidine ring and a pyrazolotriazole ring is preferred. The pyrazolotriazole includes a condensed ring of a pyrazole ring and a triazole ring, and any condensed ring may be formed by condensing at least one of these rings. Examples of the condensed rings include the condensed rings in the general formulae (4) and (5) described below.

[0141] A and B may be bonded to the squarylium acid moiety (the four-membered ring represented by the general formula (1)) at any position (ring-constituting atom) without particular limitation, but are preferably bonded to a carbon atom.

[0142] G in -CH=G which can be used as A or B represents a heterocyclic group which may have a substituent, and preferred examples include those exemplified as the heterocyclic groups which can be used as A or B. Among them, groups containing any one of a benzoxazole ring, a benzothiazole ring and an indoline ring are preferred.

[0143] At least one of A and B may have a hydrogen-bonding group that forms a hydrogen bond in the molecule.

[0144] A, B, and G may each have a substituent X. When having a substituent X, adjacent substituents may be bonded to each other to further form a ring structure. In addition, a plurality of substituents X may exist.

[0145] As the substituent X, for example, there can be mentioned those which can be used as R in the general formula (2) described below. 1 Specific examples include halogen atoms, cyano groups, nitro groups, alkyl groups (including cycloalkyl groups), alkenyl groups, alkynyl groups, aryl groups, heteroaryl groups, aralkyl groups, ferrocenyl groups, -OR 10 、-C(=O)R 11 、-C(=O)OR 12 、-OC(=O)R 13 、-NR 14 R 15 、-NHCOR 16 、--CONR 17 R 18 、-NHCONR 19 R 20 、-NHCOOR 21 、-SR 22 、-SO2R 23 、-SO3R 24 、-NHSO2R 25 and-SO2NR 26 R 27 Furthermore, the substituent X preferably has a quencher moiety described below in addition to the above-mentioned ferrocenyl group.

[0146] In the general formula (1), R 10 ~R 27 Each independently represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group. 10 ~R 27 The aliphatic group and the aromatic group are not particularly limited and can be appropriately selected from the group consisting of R 1 Among the substituents of , alkyl, cycloalkyl, alkenyl, and alkynyl, which are classified as aliphatic groups, and aryl, which are classified as aromatic groups, can be selected. 10 ~R 27 The heterocyclic group may be aliphatic or aromatic. For example, it can be appropriately selected from the following general formula (2) 1 The invention can be selected from a heteroaryl group or a heterocyclic group.

[0147] In addition, in -COOR 12 R 12 In the case of a hydrogen atom (i.e., a carboxyl group), the hydrogen atom may be dissociated (i.e., a carbonate group) or in the form of a salt.24 R 24 When it is a hydrogen atom (ie, a sulfo group), the hydrogen atom may be dissociated (ie, a sulfonate group) or may be in the state of a salt.

[0148] Examples of the halogen atom which can be used as the substituent X include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

[0149] The number of carbon atoms of the alkyl group which can be used as the substituent X is preferably 1 to 20, more preferably 1 to 15, and even more preferably 1 to 8. The number of carbon atoms of the alkenyl group is preferably 2 to 20, more preferably 2 to 12, and even more preferably 2 to 8. The number of carbon atoms of the alkynyl group is preferably 2 to 40, more preferably 2 to 30, and even more preferably 2 to 25. The alkyl group, alkenyl group, and alkynyl group may be linear, branched, or cyclic, and are preferably linear or branched.

[0150] The aryl group which can be used as the substituent X includes a monocyclic or condensed ring group. The number of carbon atoms of the aryl group is preferably 6 to 30, more preferably 6 to 20, and further preferably 6 to 12.

[0151] The alkyl part of the aralkyl group which can be used as the substituent X is the same as the above-mentioned alkyl group. The aryl part of the aralkyl group is the same as the above-mentioned aryl group. The number of carbon atoms of the aralkyl group is preferably 7 to 40, more preferably 7 to 30, and further preferably 7 to 25.

[0152] The heteroaryl group that can be used as the substituent X includes a group containing a monocyclic ring or a condensed ring, preferably a group containing a monocyclic ring or a condensed ring having 2 to 8 rings, and more preferably a group containing a monocyclic ring or a condensed ring having 2 to 4 rings. The number of heteroatoms constituting the ring of the heteroaryl group is preferably 1 to 3. The heteroatoms constituting the ring of the heteroaryl group can be exemplified by a nitrogen atom, an oxygen atom or a sulfur atom. The heteroaryl group preferably contains a group of a 5-membered ring or a 6-membered ring. The number of carbon atoms constituting the ring of the heteroaryl group is preferably 3 to 30, more preferably 3 to 18, and further preferably 3 to 12. Examples of the heteroaryl group include groups containing any one of a pyridine ring, a piperidine ring, a furan ring, a furfuran ring, a thiophene ring, a pyrrole ring, a quinoline ring, a morpholine ring, an indole ring, an imidazole ring, a pyrazole ring, a carbazole ring, a phenothiazine ring, a phenoxazine ring, an indoleline ring, a thiazole ring, a pyrazine ring, a thiadiazine ring, a benzoquinoline ring and a thiadiazole ring.

[0153] The ferrocenyl group which can be used as the substituent X is preferably represented by the general formula (2M).

[0154] [Chemical formula 6]

[0155]

[0156] In the general formula (2M), L represents a single bond or a divalent linking group that is not conjugated with A, B or G in the general formula (1). 1m ~R 9mand (c) and (d) represent a hydrogen atom or a substituent. M is an atom that can constitute a metallocene compound and represents Fe, Co, Ni, Ti, Cu, Zn, Zr, Cr, Mo, Os, Mn, Ru, Sn, Pd, Rh, V or Pt. * represents a bonding portion with A, B or G.

[0157] In the present invention, when L in the general formula (2M) is a single bond, the cyclopentadiene ring directly bonded to A, B or G (having R in the general formula (2M)) 1m The ring) is not included in the conjugated structure conjugated with A, B or G.

[0158] As a divalent linking group that can be used as L, there is no particular limitation as long as it is a linking group that is not conjugated with A, B or G, and the above-mentioned conjugated structure may be contained in the inside or at the end of the cyclopentadiene ring side in the general formula (2M). As a divalent linking group, for example, an alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, a divalent heterocyclic group obtained by removing two hydrogen atoms from a heterocyclic ring, -CH=CH-, -CO-, -CS-, -NR- (R represents a hydrogen atom or a monovalent substituent.), -O-, -S-, -SO2- or -N=CH-, or a divalent linking group formed by combining a plurality of them (preferably 2 to 6). Preferably, it is a group selected from the group consisting of an alkylene group having 1 to 8 carbon atoms, an arylene group having 6 to 12 carbon atoms, -CH=CH-, -CO-, -NR- (R is as described above), -O-, -S-, -SO2- and -N=CH-, or a divalent linking group formed by combining two or more (preferably 2 to 6) groups selected from the group. Particularly preferably, it is a group selected from the group consisting of an alkylene group having 1 to 4 carbon atoms, a phenylene group, -CO-, -NH-, -O- and -SO2-, or a linking group formed by combining two or more (preferably 2 to 6) groups selected from the group. As the divalent linking group of the combination, there is no particular limitation, but it is preferred to include -CO-, -NH-, -O- or -SO2- groups, and examples include -CO-, -NH-, -O- or -SO2- combinations of two or more linking groups, or -CO-, -NH-, -O- and -SO2- at least one and an alkylene or arylene group. As the linking group of -CO-, -NH-, -O- or -SO2- combinations of two or more, examples include -COO-, -OCO-, -CONH-, -NHCOO-, -NHCONH-, -SO2NH-. As the linking group of -CO-, -NH-, -O- and -SO2- at least one and an alkylene or arylene group, examples include -CO-, -COO- or -CONH- and an alkylene or arylene group.

[0159] The substituent that can be used as R is not particularly limited and has the same meaning as the substituent X that A in the general formula (2) may have.

[0160] L is preferably a single bond, or a group selected from the group consisting of an alkylene group having 1 to 8 carbon atoms, an arylene group having 6 to 12 carbon atoms, -CH=CH-, -CO-, -NR- (R is as described above), -O-, -S-, -SO2- and -N=CH-, or a group consisting of a combination of two or more groups selected from this group.

[0161] L may have one or more substituents. There are no particular restrictions on the substituents that L may have, and for example, they have the same meaning as the above-mentioned substituent X. When L has multiple substituents, the substituents bonded to adjacent atoms may bond to each other to further form a ring structure.

[0162] The alkylene group which can be used as L may be any of linear, branched or cyclic groups as long as it has 1 to 20 carbon atoms, and examples thereof include methylene, ethylene, propylene, methylethylene, methylmethylene, dimethylmethylene, 1,1-dimethylethylene, butylene, 1-methylpropylene, 2-methylpropylene, 1,2-dimethylpropylene, 1,3-dimethylpropylene, 1-methylbutylene, 2-methylbutylene, 3-methylbutylene, 4-methylbutylene, 2,4-dimethylbutylene, 1,3-dimethylbutylene, pentylene, hexylene, heptylene, octylene, ethane-1,1-diyl, propane-2,2-diyl, cyclopropane-1,1-diyl, cyclopropane-1,2-diyl, cyclobutane-1,1-diyl, cyclobutane-1,2-diyl, cyclopentane-1,1-diyl, cyclopentane-1,2-diyl, cyclopentane-1,3-diyl, cyclohexane-1,1-diyl, cyclohexane-1,2-diyl, cyclohexane-1,3-diyl, cyclohexane-1,4-diyl, methylcyclohexane-1,4-diyl and the like.

[0163] When L is used as a linking group containing at least one of -CO-, -CS-, -NR- (R is as described above), -0-, -S-, -SO2- and -N=CH- in the alkylene group, a group such as -CO- can be introduced at any position in the alkylene group, and the number of introduction is not particularly limited.

[0164] The arylene group that can be used as L is not particularly limited as long as it is a group having 6 to 20 carbon atoms. For example, it includes a group obtained by further removing one hydrogen atom from each of the groups exemplified as the aryl group having 6 to 20 carbon atoms that can be used as A in the general formula (1).

[0165] The heterocyclic group that can be used as L is not particularly limited, and examples thereof include groups obtained by further removing one hydrogen atom from the groups exemplified as the heterocyclic group that can be used as A.

[0166] In the general formula (2M), the remaining partial structure after removing the linking group L is equivalent to a structure (metallocene structure) formed by removing one hydrogen atom from the metallocene compound. In the present invention, the metallocene compound as the metallocene structure can be used without particular limitation as long as it is a compound that conforms to the partial structure defined by the general formula (2M) (a compound in which a hydrogen atom is bonded instead of L). The metallocene structure defined by the general formula (2M) is specifically described below.

[0167] In the general formula (2M), R 1m ~R 9m represents a hydrogen atom or a substituent. 1m ~R 9m The substituents of are not particularly limited, but can be selected from the group consisting of R 1 The substituents are selected from the following: 1m ~R 9m A hydrogen atom, a halogen atom, an alkyl group, an acyl group, an alkoxy group, an amino group or an amide group is preferred, a hydrogen atom, a halogen atom, an alkyl group, an acyl group or an alkoxy group is more preferred, a hydrogen atom, a halogen atom, an alkyl group or an acyl group is further preferred, a hydrogen atom, a halogen atom or an alkyl group is particularly preferred, and a hydrogen atom is most preferred.

[0168] As can be used as R 1m ~R 9m Alkyl groups can be used as R 1 Among the alkyl groups, those having 1 to 8 carbon atoms are preferred, and examples thereof include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, isobutyl, pentyl, tert-pentyl, hexyl, octyl and 2-ethylhexyl.

[0169] The alkyl group may have a halogen atom as a substituent. Examples of the alkyl group substituted with a halogen atom include chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, fluoromethyl, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, perfluoroethyl, perfluoropropyl, and perfluorobutyl.

[0170] And, can be used as R 1mIn the alkyl groups of the following, at least one methylene group forming the carbon chain may be substituted with -O- or -CO-. Examples of the alkyl group in which the methylene group is substituted with -O- include methoxy, ethoxy, propoxy, isopropoxy, isobutoxy, sec-butoxy, tert-butoxy, 2-methoxyethoxy, chloromethoxy, dichloromethoxy, trichloromethoxy, bromomethoxy, dibromomethoxy, tribromomethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, perfluoroethoxy, perfluoropropoxy, and alkyl groups in which the methylene group at the end of the carbon chain is substituted with, and examples of the alkyl group in which the methylene group inside the carbon chain is substituted with, such as 2-methoxyethyl. Examples of the alkyl group in which the methylene group is substituted with -CO- include acetyl, propionyl, monochloroacetyl, dichloroacetyl, trichloroacetyl, trifluoroacetyl, propan-2-on-1-yl, butan-2-on-1-yl, and the like.

[0171] In the general formula (2M), M is an atom that can constitute a metallocene compound and represents Fe, Co, Ni, Ti, Cu, Zn, Zr, Cr, Mo, Os, Mn, Ru, Sn, Pd, Rh, V or Pt. Among them, M is preferably Fe, Ti, Co, Ni, Zr, Ru or Os, more preferably Fe, Ti, Ni, Ru or Os, further preferably Fe or Ti, and most preferably Fe.

[0172] As the group represented by the general formula (2M), it is preferred that L, R 1m ~R 9m and M are preferably combined with each other, for example, a single bond as L or a group selected from the group consisting of an alkylene group having 2 to 8 carbon atoms, an arylene group having 6 to 12 carbon atoms, -CH=CH-, -CO-, -NR- (R is as described above), -0-, -S-, -SO2- and -N=CH-, or a group consisting of a combination of two or more groups selected from the group, as R 1m ~R 9m A group consisting of a hydrogen atom, a halogen atom, an alkyl group, an acyl group or an alkoxy group and Fe as M.

[0173] Alkyl, alkenyl, alkynyl, aralkyl, aryl and heteroaryl groups which can be used as the substituent X, and 10 ~R 27The aliphatic group, aromatic group and heterocyclic group may further have a substituent, respectively, or may be unsubstituted. There are no particular restrictions on the substituents that may be further possessed, but preferably a substituent selected from an alkyl group, an aryl group, an amino group, an alkoxy group, an aryloxy group, an aromatic heterocyclic oxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, an acylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfonylamino group, an alkylthio group, an arylthio group, an aromatic heterocyclic thio group, a sulfonyl group, a ferrocenyl group, a hydroxyl group, a mercapto group, a halogen atom, a cyano group, a sulfo group and a carboxyl group, and more preferably a substituent selected from an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an aromatic heterocyclic oxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, an alkylthio group, an arylthio group, an aromatic heterocyclic thio group, a sulfonyl group, a ferrocenyl group, a hydroxyl group, a mercapto group, a halogen atom, a cyano group, a sulfo group and a carboxyl group. These groups can be appropriately selected from R which can be used as the general formula (2) described later. 1 Select from the substituents.

[0174] As a preferred embodiment of the dye represented by the above general formula (1), there is mentioned a dye represented by the following general formula (2).

[0175] [Chemical formula 7]

[0176] General formula (2)

[0177] In the general formula (2), A 1 The same as A in the general formula (1). Among them, a nitrogen-containing 5-membered heterocyclic group is preferred.

[0178] In the general formula (2), R 1 and R 2 Each independently represents a hydrogen atom or a substituent. 1 With R 2 They may be the same or different and may be bonded to each other to form a ring.

[0179] As can be used as R 1 and R 2The substituent of is not particularly limited, but for example, alkyl (methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, isobutyl, pentyl, hexyl, octyl, dodecyl, trifluoromethyl, etc.), cycloalkyl (cyclopentyl, cyclohexyl, etc.), alkenyl (vinyl, allyl, etc.), alkynyl (ethynyl, propargyl, etc.), aryl (phenyl, naphthyl, etc.), heteroaryl (furanyl, thienyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, imidazolyl, pyrazolyl, thiazolyl, benzimidazolyl, benzoxazolyl, quinazolinyl, phthalazinyl, etc.), heterocyclic group (also referred to as heterocyclic group, for example,pyrrolidinyl, imidazolidinyl, morpholinyl, oxazolidinyl, etc.), alkoxy (methoxy, ethoxy, propoxy, etc.), cycloalkyloxy (cyclopentyloxy, cyclohexyloxy, etc.), aryloxy (phenoxy, naphthyloxy, etc.), heteroaryloxy (aromatic heterocyclic oxy), alkylthio (methylthio, ethylthio, propylthio, etc.), cycloalkylthio (cyclopentylthio, cyclohexylthio, etc.), arylthio (phenylthio, naphthylthio, etc.), heteroarylthio (aromatic heterocyclic thio), alkoxycarbonyl (methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl, octyloxycarbonyl, etc.), aryloxycarbonyl (phenoxycarbonyl, naphthyloxycarbonyl, etc.), phosphoryl (dimethylphosphinoyl, diphenylphosphinoyl), acyl), sulfamoyl (aminosulfonyl, methylaminosulfonyl, dimethylaminosulfonyl, butylaminosulfonyl, cyclohexylaminosulfonyl, octylaminosulfonyl, phenylaminosulfonyl, 2-pyridylaminosulfonyl, etc.), acyl (acetyl, ethylcarbonyl, propylcarbonyl, cyclohexylcarbonyl, octylcarbonyl, 2-ethylhexylcarbonyl, phenylcarbonyl, naphthylcarbonyl, pyridylcarbonyl, etc.), acyloxy (acetyloxy, ethylcarbonyloxy, butylcarbonyloxy, octylcarbonyloxy, phenylcarbonyloxy, etc.), amide (methylcarbonylamino, ethylcarbonylamino, dimethylcarbonylamino, propylcarbonylamino, pentylcarbonylamino, cyclohexylcarbonylamino 1-amino-4-yl, 1-amino-6-yl, 1-amino-7-yl, 1-amino-1-nitro, 1-amino-2-nitro, 1-amino-3-nitro, 1-amino-6-yl, 1-amino-7-yl, 1-amino-1-nitro, 1-amino-2-nitro, 1-amino-3-nitro, 1-amino-4-yl, 1-amino-5-nitro, 1-amino-6-yl, 1-amino-7-yl, 1-amino-8-yl, 1-amino-9-yl, 1-amino-10-nitro, 1-amino-11-yl, 1-amino-12-yl, 1-amino-13-yl, 1-amino-14-yl, 1-amino-15-nitro, 1-amino-16-yl, 1-amino-17-yl, 1-amino-18-yl, 1-amino-19-yl, 1-amino-21-yl, 1-amino-22-yl, 1-amino-19-yl, 1-amino-1 alkylsulfonyl group (methylsulfonyl, ethylsulfonyl, butylsulfonyl, cyclohexylsulfonyl, 2-ethylhexylsulfonyl, etc.), arylsulfonyl group (phenylsulfonyl, naphthylsulfonyl, 2-pyridylsulfonyl, etc.), amino group (amino, ethylamino, dimethylamino, butylamino, dibutylamino, cyclopentylamino, 2-ethylhexylamino, dodecylamino, anilino, naphthylamino, 2-pyridylamino, etc.), alkylsulfonyloxy group (methanesulfonyloxy), cyano group, nitro group, halogen atom (fluorine atom, chlorine atom, bromine atom, etc.), hydroxyl group, etc.

[0180] Among them, an alkyl group, an alkenyl group, an aryl group or a heteroaryl group is preferred, an alkyl group, an aryl group or a heteroaryl group is more preferred, and an alkyl group is further preferred.

[0181] Can be used as R 1 and R 2The substituent of may further have a substituent. As the substituent that may further have, there can be mentioned those that can be used as R 1 and R 2 The above substituents and the substituents X that A, B and G in the above general formula (1) may have. 1 With R 2 Can bond to each other to form a ring, R 1 or R 2 With B 2 or B 3 The substituents may be bonded to form a ring.

[0182] The ring formed at this time is preferably a heterocyclic ring or a heteroaryl ring. The size of the ring formed is not particularly limited, but preferably a 5-membered ring or a 6-membered ring. In addition, the number of rings formed is not particularly limited, and may be 1 or 2 or more. As a form of forming 2 or more rings, for example, R 1 With B 2 Substituents and R 2 With B 3 The substituents possessed are respectively bonded to form two rings.

[0183] In the general formula (2), B 1 , B 2 , B 3 and B 4 Each independently represents a carbon atom or a nitrogen atom. 1 , B 2 , B 3 and B 4 The ring of is an aromatic ring. 1 ~B 4 At least 2 of them are carbon atoms, more preferably B 1 ~B 4 All carbon atoms.

[0184] Can be used as B 1 ~B 4 The carbon atoms have hydrogen atoms or substituents. 1 ~B 4 The number of carbon atoms having a substituent among the carbon atoms in is not particularly limited, but is preferably 0, 1 or 2, and more preferably 1. In particular, B is preferably 1 and B 4 are carbon atoms, and at least one of them has a substituent.

[0185] As can be used as B 1 ~B 4 The substituents on the carbon atoms of are not particularly limited, and examples thereof include 1 and R 2The above-mentioned substituents. Among them, preferably, it is an alkyl group, an alkoxy group, an alkoxycarbonyl group, an aryl group, an acyl group, an amide group, a sulfonamide group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, an amino group, a cyano group, a nitro group, a halogen atom or a hydroxyl group, and more preferably, it is an alkyl group, an alkoxy group, an alkoxycarbonyl group, an aryl group, an acyl group, an amide group, a sulfonamide group, a carbamoyl group, an amino group, a cyano group, a nitro group, a halogen atom or a hydroxyl group.

[0186] Can be used as B 1 ~B 4 The substituent on the carbon atom of may further have a substituent. Examples of the substituent that may further have include R in the general formula (2): 1 and R 2 The substituent that may be further possessed and the substituent X that A, B and G in the general formula (1) may have are preferably ferrocenyl.

[0187] As can be used as B 1 and B 4 The substituents on the carbon atoms of are preferably alkyl, alkoxy, hydroxy, amide, sulfonamide or carbamoyl, and particularly preferably alkyl, alkoxy, hydroxy, amide or sulfonamide, and most preferably hydroxy, amide or sulfonamide. These can be used as B 1 and B 4 The substituent possessed by the carbon atom of may further have a ferrocenyl group.

[0188] As can be used as B 2 and B 3 The substituents possessed by the carbon atoms are further preferably alkyl, alkoxy, alkoxycarbonyl, acyl, amino, cyano, nitro or halogen atoms, and it is particularly preferred that any one of the substituents is an electron withdrawing group (for example, alkoxycarbonyl, acyl, cyano, nitro or halogen atom).

[0189] The dye represented by the above general formula (2) is preferably a dye represented by any one of the following general formulas (3), (4) and (5).

[0190] [Chemical formula 8]

[0191] General formula (3)

[0192] In the general formula (3), R 1 and R 2 Each independently represents a hydrogen atom or a substituent, and R 1 and R 2 The meanings are the same, and the preferred ranges are also the same.

[0193] In the general formula (3), B 1 ~B 4Each independently represents a carbon atom or a nitrogen atom, and B in the above general formula (2) 1 ~B 4 The meanings are the same, and the preferred ranges are also the same.

[0194] In the general formula (3), R 3 and R 4 Each independently represents a hydrogen atom or a substituent. 3 and R 4 The substituents of are not particularly limited, and examples thereof include those that can be used as the above R 1 and R 2 The substituents are the same as the group.

[0195] However, it can be used as R 3 The substituent of is preferably an alkyl group, an alkoxy group, an amino group, an amide group, a sulfonamide group, a cyano group, a nitro group, an aryl group, a heteroaryl group, a heterocyclic group, an alkoxycarbonyl group, a carbamoyl group or a halogen atom, more preferably an alkyl group, an aryl group or an amino group, and further preferably an alkyl group. These can be used as R 3 The substituent may further have a ferrocenyl group.

[0196] As can be used as R 4 The substituent is preferably an alkyl group, an aryl group, a heteroaryl group, a heterocyclic group, an alkoxy group, an alkoxycarbonyl group, an acyl group, an acyloxy group, an amide group, a carbamoyl group, an amino group or a cyano group, more preferably an alkyl group, an alkoxycarbonyl group, an acyl group, a carbamoyl group or an aryl group, and further preferably an alkyl group.

[0197] Can be used as R 3 and R 4 The alkyl group may be any of linear, branched and cyclic, preferably linear or branched. The number of carbon atoms in the alkyl group is preferably 1 to 12, more preferably 1 to 8. Examples of the alkyl group include preferably methyl, ethyl, n-propyl, isopropyl, tert-butyl, 2-ethylhexyl and cyclohexyl, more preferably methyl and tert-butyl.

[0198] [Chemical formula 9]

[0199] General formula (4)

[0200] In the general formula (4), R 1 and R 2 Each independently represents a hydrogen atom or a substituent, and R 1 and R 2 The meanings are the same, and the preferred ranges are also the same.

[0201] In general formula (4), B 1 ~B 4 Each independently represents a carbon atom or a nitrogen atom, and B in the above general formula (2) 1 ~B4 The meanings are the same, and the preferred ranges are also the same.

[0202] In the general formula (4), R 5 and R 6 Each independently represents a hydrogen atom or a substituent. 5 and R 6 The substituents of are not particularly limited, and examples thereof include those that can be used as the above R 1 and R 2 The substituents are the same as the group.

[0203] However, it can be used as R 5 The substituent is preferably an alkyl group, an alkoxy group, an aryloxy group, an amino group, a cyano group, an aryl group, a heteroaryl group, a heterocyclic group, an acyl group, an acyloxy group, an amide group, a sulfonamide group, a urea group or a carbamoyl group, more preferably an alkyl group, an alkoxy group, an acyl group, an amide group or an amino group, further preferably an alkyl group.

[0204] Can be used as R 5 The alkyl group can be used as R in the general formula (3) 3 The alkyl group has the same meaning and the preferred range is also the same.

[0205] In the general formula (4), it can be used as R 6 The substituent is preferably an alkyl group, an alkenyl group, an aryl group, a heteroaryl group, a heterocyclic group, an alkoxy group, a cycloalkyloxy group, an aryloxy group, an alkoxycarbonyl group, an acyl group, an acyloxy group, an amide group, a sulfonamide group, an alkylsulfonyl group, an arylsulfonyl group, a carbamoyl group, an amino group, a cyano group, a nitro group or a halogen atom, more preferably an alkyl group, an aryl group, a heteroaryl group or a heterocyclic group, further preferably an alkyl group or an aryl group.

[0206] Can be used as R 6 The alkyl group can be used as R in the general formula (3) 4 The alkyl group has the same meaning and the preferred range is also the same.

[0207] Can be used as R 6 The aryl group is preferably an aryl group having 6 to 12 carbon atoms, and more preferably a phenyl group. The aryl group may have a substituent, and examples of such a substituent include groups included in the following substituent group A, and particularly preferably an alkyl group having 1 to 10 carbon atoms, a sulfonyl group, an amino group, an acylamino group, and a sulfonylamino group. These substituents may further have a substituent. Specifically, the substituent is preferably an alkylsulfonylamino group.

[0208] -Substituent Group A-

[0209] a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkoxy group, an aminooxy group, an aryloxy group, a silyloxy group, a heterocyclic group, an acyloxy group, a carbamoyloxy group, an amino group, an acylamino group, an aminocarbonylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfamoylamino group, a sulfonylamino group (including an alkyl or arylsulfonylamino group), a mercapto group, an alkylthio group, an arylthio group, a heterocyclic thio group, a sulfamoyl group, a sulfo group, an alkyl or arylsulfinyl group, a sulfonyl group (including an alkyl or arylsulfonyl group), an acyl group, an aryloxycarbonyl group, an alkoxycarbonyl group, a carbamoyl group, an aryl or heterocyclic azo group, an imide group, a phosphinyl group, a phosphinyl group, a phosphinyloxy group, a phosphinylamino group, a silyl group, and the like.

[0210] [Chemical formula 10]

[0211] General formula (5)

[0212] In the general formula (5), R 1 and R 2 Each independently represents a hydrogen atom or a substituent, and R 1 and R 2 The meanings are the same, and the preferred ranges are also the same.

[0213] In the general formula (5), B 1 ~B 4 Each independently represents a carbon atom or a nitrogen atom, and B in the above general formula (2) 1 ~B 4 The meanings are the same, and the preferred ranges are also the same.

[0214] In the general formula (5), R 7 and R 8 Each independently represents a hydrogen atom or a substituent. 7 and R 8 The substituents of are not particularly limited, and examples thereof include those that can be used as the above R 1 and R 2 The substituents are the same as the group.

[0215] However, it can be used as R 7 The preferred range, more preferred range and further preferred range of the substituents of can be used as R in the general formula (4) 5 The substituents are the same as those of 5 The alkyl group can be used as the above R 3 The alkyl group has the same meaning and the preferred range is also the same.

[0216] In the general formula (5), it can be used as R 8 The preferred range, more preferred range and further preferred range of the substituents of can be used as R in the general formula (4) 6The substituents are the same as those of 8 The preferred ranges of the alkyl and aryl groups are similar to those that can be used as R in the above general formula (4). 6 The alkyl and aryl groups have the same meanings and the preferred ranges are also the same.

[0217] As the square acid pigment used in the above-mentioned dye, as long as it is the square acid pigment represented by any one of the general formula (1)~(5), it can be used without particular restriction. As its example, for example, can enumerate the compound described in any one of the communiques in Japanese Unexamined Patent Publication No. 2006-160618, International Publication No. 2004 / 005981, International Publication No. 2004 / 007447, Dyes and Pigment, 2001,49,p.161-179, International Publication No. 2008 / 090757, International Publication No. 2005 / 121098 and Japanese Unexamined Patent Publication No. 2008-275726.

[0218] Specific examples of the dye represented by any of the general formulae (1) to (5) include the compounds described in

[0067] to

[0070] of International Publication No. 2021 / 132674. However, the present invention is not limited thereto.

[0219] In addition to the above specific examples, specific examples of the coloring matter represented by any one of the general formulae (3) to (5) include the compounds described in

[0071] to

[0080] of International Publication No. 2021 / 132674. However, the present invention is not limited thereto.

[0220] As a preferred embodiment of the dye represented by the general formula (1), the dye represented by any one of the general formulas (6) to (9) and the description of specific examples described in

[0081] to

[0095] of International Publication No. 2021 / 132674 can be applied as is.

[0221] (Quencher built-in pigment)

[0222] The square acid-based pigment represented by the general formula (1) can be a built-in quencher pigment formed by linking the quencher portion and the pigment through a linking group through a covalent bond. The built-in quencher pigment can also be preferably used as the dye. That is, the built-in quencher pigment is listed as the dye according to the wavelength having the main absorption wavelength band.

[0223] Examples of the quencher-internal dye include an electron-donating quencher-internal dye whose quencher moiety is an electron-donating quencher moiety and an electron-accepting quencher moiety whose quencher moiety is an electron-accepting quencher moiety.

[0224] The electron-donating quencher part refers to a structural part that, after donating electrons to the lower-energy SOMO of the two SOMOs (Singly Occupied Molecular Orbital) of the excited-state pigment, receives electrons from the higher-energy SOMO of the pigment, thereby inactivating the excited-state pigment to the ground state. The electron-accepting quencher part refers to a structural part that, after accepting electrons from the higher-energy SOMO of the two SOMOs of the excited-state pigment, donates electrons to the lower-energy SOMO of the pigment, thereby inactivating the excited-state pigment to the ground state.

[0225] As the electron-donating quencher moiety, for example, a ferrocenyl group in the substituent X, and the quencher moieties in the quencher compounds described in paragraphs

[0199] to

[0212] and

[0234] to

[0287] of International Publication No. 2019 / 066043 can be cited, and the ferrocenyl group in the substituent X is preferred. Furthermore, as the electron-accepting quencher moiety, for example, the quencher moieties in the quencher compounds described in paragraphs

[0288] to

[0310] of International Publication No. 2019 / 066043 can be cited.

[0226] In the light absorption filter of the present invention, from the viewpoint of the light resistance of the light absorbing site, the dye having a main absorption wavelength band at a wavelength of 400 to 700 nm preferably includes an electron-donating quencher built-in dye, and more preferably includes a squarylium dye represented by the following general formula (1A).

[0227] [Chemical formula 11]

[0228]

[0229] In the above formula, A and B each independently represent an aryl group which may have a substituent, a heterocyclic group which may have a substituent, or -CH=G. G represents a heterocyclic group which may have a substituent. However, at least one of A and B includes an electron donating quencher moiety.

[0230] The pigment represented by the general formula (1A) is the same as the pigment represented by the general formula (1) except that at least one of A and B includes an electron-donating quencher portion in the pigment represented by the general formula (1). Therefore, the description related to A, B and G in the general formula (1) can be applied. And, as a preferred embodiment of the pigment represented by the general formula (1A), in the description of the pigment represented by any one of the general formulas (2) to (9) as a preferred embodiment of the pigment represented by the general formula (1), the description that at least one of the structures equivalent to A and B in the general formula (1) includes an electron-donating quencher portion can be applied.

[0231] The electron donating quencher moiety included in at least one of A and B is preferably a ferrocenyl group among the substituents X described above.

[0232] Specific examples of the pigment corresponding to the quencher-internal pigment among the squarylium pigments represented by the general formula (1) include the compounds described in

[0097] to

[0114] of International Publication No. 2021 / 132674. However, the present invention is not limited thereto.

[0233] The total content of the above-mentioned dyes in the light absorption filter of the present invention is preferably 0.10 mass % or more, more preferably 0.15 mass % or more, further preferably 0.20 mass % or more, particularly preferably 0.25 mass % or more, and particularly preferably 0.30 mass % or more. When the total content of the above-mentioned dyes in the light absorption filter of the present invention is greater than the above-mentioned preferred lower limit, a good antireflection effect can be obtained.

[0234] Furthermore, the total content of the dyes in the light absorption filter of the present invention is usually 50 mass % or less, preferably 40 mass % or less, more preferably 30 mass % or less, further preferably 15 mass % or less, and particularly preferably 10 mass % or less.

[0235] That is, the total content of the above dyes in the light absorption filter of the present invention is preferably 0.10 to 50 mass %, more preferably 0.15 to 40 mass %, further preferably 0.20 to 30 mass %, particularly preferably 0.25 to 15 mass %, and particularly preferably 0.30 to 10 mass %.

[0236] In the light absorption filter of the present invention, when the above-mentioned dye contains a heterocyclic azo dye and does not contain a squarylium dye represented by the above-mentioned general formula (1), the proportion of the heterocyclic azo dye in the total of the above-mentioned dyes is preferably 80% by mass or more, more preferably 90% by mass or more, and may also be 100% by mass.

[0237] Furthermore, in the light absorption filter of the present invention, when the above-mentioned dye contains a squarylium dye represented by the above-mentioned general formula (1) and does not contain a heterocyclic azo dye, the proportion of the squarylium dye represented by the above-mentioned general formula (1) in the total of the above-mentioned dyes is preferably 80% by mass or more, more preferably 90% by mass or more, and may also be 100% by mass.

[0238] In addition, when the light absorption filter of the present invention contains both the heterocyclic azo dye and the squarylium dye represented by the above general formula (1), the total proportion of the heterocyclic azo dye and the squarylium dye represented by the above general formula (1) in the total of the above dyes is preferably 80% by mass or more, more preferably 90% by mass or more, and may also be 100% by mass.

[0239] In addition, when the dye contains the built-in quencher pigment, from the viewpoint of imparting light absorption properties such as anti-reflection effect, the content of the built-in quencher pigment in the light absorption filter of the present invention is preferably 0.10% by mass or more, more preferably 0.15% by mass or more, further preferably 0.20% by mass or more, particularly preferably 0.25% by mass or more, and particularly preferably 0.30% by mass or more. The upper limit is preferably 45% by mass or less, preferably 40% by mass or less, more preferably 30% by mass or less, further preferably 15% by mass or less, and particularly preferably 10% by mass or less. That is, the content of the built-in quencher pigment in the light absorption filter is preferably 0.10 to 45% by mass, more preferably 0.15 to 40% by mass, further preferably 0.20 to 30% by mass, particularly preferably 0.25 to 15% by mass, and particularly preferably 0.30 to 10% by mass.

[0240] <Compounds that generate free radicals upon ultraviolet irradiation>

[0241] The light absorption filter of the present invention contains a compound that generates radicals by ultraviolet irradiation (also simply referred to as a "radical generator" in the present invention).

[0242] The radical generator is a compound that generates radicals by ultraviolet irradiation and is not particularly limited as long as it has a function of decolorizing the dye. For example, the following photoradical generators can be used.

[0243] (1) Photoradical generator

[0244] The photoradical generator is not particularly limited as long as it is a compound that generates radicals by ultraviolet irradiation and has the function of decolorizing the dye. In addition, the generated radicals may be diradicals in addition to ordinary radicals.

[0245] As the photoradical generator, compounds commonly used as photoradical polymerization initiators or photoradical generators can be used without particular limitation, and examples thereof include acetophenone generators, benzoin generators, benzophenone generators, phosphine oxide generators, oxime generators, ketal generators, anthraquinone generators, thioxanthone generators, azo compound generators, peroxide generators, disulfide generators, lophanine dimer generators, onium salt generators, borate generators, active ester generators, active halogen generators, inorganic complex generators, and coumarin generators. In addition, the "○○ generator" in the specific examples of the photoradical generators is sometimes referred to as "○○ compound" or "○○ class", etc., and is hereinafter referred to as "○○ compound".

[0246] Specific examples, preferred embodiments, and commercial products of the photoradical generator are described in paragraphs

[0133] to

[0151] of JP-A-2009-098658 as specific examples, preferred embodiments, and commercial products of the photoradical generator, and these can be similarly preferably used in the present invention.

[0247] The photoradical generator is preferably a compound that generates free radicals by intramolecular cleavage or a compound that generates free radicals by removing hydrogen atoms from nearby compounds. From the viewpoint of further improving the decolorization rate, a compound that generates free radicals by removing hydrogen atoms from nearby compounds is more preferred.

[0248] The compound that generates radicals by intramolecular cleavage (hereinafter also referred to as an "intramolecular cleavage type photo-radical generator") refers to a compound that generates radicals by homolytic bond cleavage of a compound that absorbs light.

[0249] As intramolecular cleavage type photo-radical generators, for example, acetophenone compounds, benzoin compounds, phosphine oxide compounds, oxime compounds, ketal compounds, azo compounds, peroxide compounds, disulfide compounds, onium salt compounds, borate compounds, active ester compounds, active halogen compounds, inorganic complex compounds and coumarin compounds can be cited. Among these, acetophenone compounds, benzoin compounds or phosphine oxide compounds are also preferred as carbonyl compounds. As a photodecomposition reaction of intramolecular cleavage type carbonyl compounds, Norrish I type reaction is known, and this reaction can be referred to for the free radical generation mechanism.

[0250] The compound that generates free radicals by abstracting a hydrogen atom from a nearby compound (hereinafter also referred to as a "hydrogen abstraction type photoradical generator") refers to a compound that generates free radicals by abstracting a hydrogen atom from a nearby compound using a carbonyl compound in an excited triplet state obtained by light absorption.

[0251] As hydrogen abstraction type photo-radical generators, carbonyl compounds are known, for example, benzophenone compounds, anthraquinone compounds and thioxanthone compounds. As the photodecomposition reaction of hydrogen abstraction type carbonyl compounds, the Norrish II reaction is known, and the radical generation mechanism can be referred to this reaction.

[0252] Examples of the compound existing in the vicinity include various components existing in the light absorption filter, such as resins, dyes, and radical generators.

[0253] The compound existing nearby becomes a compound having free radicals by removing hydrogen atoms. The dye whose hydrogen atoms are removed by the hydrogen-abstraction photo-radical generator becomes an active compound having free radicals, and thus the dye can also fade or decolorize by reactions such as decomposition of the dye having the free radicals.

[0254] Furthermore, when the hydrogen abstraction type photo-radical generator abstracts a hydrogen atom in a molecule, a diradical is generated.

[0255] As the hydrogen abstraction type photo-radical generator, benzophenone compounds are preferred from the viewpoint of the quantum yield of the hydrogen abstraction reaction.

[0256] Various examples of photoradical generators are described in "Latest UV Curing Technology", TECHNICAL INFORMATION INSTITUTE CO., LTD., 1991, p. 159 and "Ultraviolet Curing System", written by Kato Kiyoshi, published by Sogo Technical Center in 1989, pp. 65 to 148, which can also be preferably used in the present invention.

[0257] In the photoradical generator, the maximum absorption wavelength of ultraviolet rays absorbed is preferably in the range of 250 to 400 nm, more preferably in the range of 240 to 400 nm, and further preferably in the range of 270 to 400 nm.

[0258] When the photoradical generator is a benzophenone compound, the photoradicals at the longest wavelength side belonging to n-π * The maximum absorption wavelength of the transition is preferably in the range of 260 to 400 nm, more preferably in the range of 285 to 345 nm. * The absorption maximum wavelength is preferably in the range of 240 to 380 nm, more preferably in the range of 270 to 330 nm. By setting the absorption maximum wavelength in the above range, the light from the light source such as the metal halide lamp used in exposure is well absorbed, and on the other hand, it is difficult to absorb ultraviolet rays intruding from the outside when assembled in a display device, and it is possible to take into account both the light resistance of the unexposed part and the decolorization of the exposed part.

[0259] As a photoradical generator having absorption in a longer wavelength range among benzophenone compounds, for example, an alkoxybenzophenone compound can be mentioned.

[0260] The maximum absorption wavelength of ultraviolet light absorbed by the photoradical generator is preferably separated from the main absorption wavelength band of the dye having a main absorption wavelength band at a wavelength of 400 to 700 nm by 30 nm or more. The upper limit is not particularly limited.

[0261] Commercially available photocleavage-type photoradical generators are listed under trade names, such as "Irgacure 651", "Irgacure 184", "Irgacure 819", "Irgacure 907", "Irgacure 1870" (CGI-403 / Irgacure 184 = 7 / 3 mixed initiator), "Irgacure 500", "Irgacure 369", "Irgacure 1173", "Irgacure 2959", "Irgacure 4265", "Irgacure 4263", "Irgacure 127", or "OXE01" manufactured by BASF (formerly Ciba Specialty Chemicals Co., Ltd.); and "KAYACURE DETX-S", "KAYACURE BP-100", "KAYACURE BDMK", "KAYACURE CTX", "KAYACUREBMS", "KAYACURE 2-EAQ", "KAYACURE ABQ", "KAYACURE CPTX", "KAYACURE EPD", "KAYACUREITX", "KAYACURE QTX", "KAYACURE BTC" or "KAYACURE MCA", etc.; and "Esacure (KIP100F, KB1, EB3, BP, X33, KT046, KT37, KIP150 or TZT)" manufactured by Sartomer Company, Inc. In addition, a combination of two or more of them can also be cited as a preferred example.

[0262] When the light absorption filter of the present invention contains a photo radical generator, the content of the photo radical generator in the light absorption filter of the present invention is preferably 0.01 to 30% by mass, and more preferably 0.1 to 20% by mass.

[0263] As for the above-mentioned free radical generator, it is also preferred to cite a combination of two or more compounds, and a combination in which free radicals are generated by ultraviolet irradiation as a result of the interaction of the two or more compounds such as complex formation in the light absorption filter. As for the type of the combined compound, in the mechanism of generating free radicals by ultraviolet irradiation, it is sufficient to use two or more compounds showing different functions, preferably two. As such a combination, it is preferred to cite a combination of a compound A having an acid group and a compound B having a structure capable of forming a hydrogen bond with the acid group contained in the compound A.

[0264] In the light absorption filter of the present invention, when a compound A having an acid group and a compound B having a structure capable of forming a hydrogen bond with the acid group contained in the compound A are contained, the efficiency of generating free radical species by ultraviolet irradiation is improved compared with the case of using the above-mentioned photo-free radical generator. Therefore, even when ultraviolet irradiation is performed under mild temperature conditions such as room temperature, sufficient free radical species are generated, and the free radical species directly or indirectly react with the above-mentioned dye, and the dye is decomposed, thereby the dye can fade and decolorize, so it is preferred. In particular, when the dye contained in the light absorption filter of the present invention contains the above-mentioned heterocyclic azo dye and / or the square acid-based dye represented by the above-mentioned general formula (1), secondary absorption accompanying the decomposition of the dye hardly occurs, and decolorization can be achieved.

[0265] Hereinafter, the compound A having an acid group and the compound B having a structure capable of forming a hydrogen bond with the acid group included in the compound A will be described in detail.

[0266] (2) Compound A having an acid group

[0267] The light absorption filter of the present invention preferably contains, as the radical generator, a compound A having an acid group (also referred to simply as "compound A" in the present invention) together with a compound B having a structure capable of forming a hydrogen bond with an acid group contained in compound A described later.

[0268] As the acid group contained in compound A, a proton dissociative group having a pKa of 12 or less is preferred. Specifically, the acid group includes a carboxyl group, a sulfonamide group, a phosphonic acid group (-P(=O)(OH)2), a phosphoric acid group (-OP(=O)(OH)2), a sulfonic acid group, a phenolic hydroxyl group, and a sulfonimide group, and a carboxyl group is preferred. In addition, pKa refers to the negative common logarithm (-logKa) of the acid dissociation constant (Ka) in water at 25°C, and in the pKa of compound B described later, the calculation can be performed in the same manner except that the mixed solvent of water / methanol = 50 / 50 (volume ratio) is changed to water.

[0269] Compound A may be a low molecular weight compound or a high molecular weight compound (hereinafter also referred to as a "polymer"), and is preferably a polymer.

[0270] Compound A is a polymer, which means that Compound A is chemically bonded to a polymer constituting a resin contained in the light absorption filter of the present invention.

[0271] When compound A is chemically bonded to a polymer constituting the resin, compound A may be bonded in the form of being introduced into the main chain of the polymer, in the form of being contained in a side chain of the polymer, or in the form of being contained in a graft chain of the polymer.

[0272] Here, bonding in the form of being introduced into the main chain of the polymer means that the acid group in compound A is directly bonded to the main chain of the polymer, bonding in the form of being included in the side chain of the polymer means that the acid group in compound A is bonded to the main chain of the polymer via a linking group, and bonding in the form of being included in the graft chain of the polymer means that the polymer side chain has a polymer structure and has a structural unit derived from compound A as a structural unit constituting the polymer structure. In addition, the definitions of the main chain, side chain and graft chain are as described below.

[0273] When compound A is a low molecular weight compound, the molecular weight of compound A is less than 5000, preferably 2000 or less, more preferably 1000 or less, further preferably 500 or less, and particularly preferably 400 or less. The lower limit is not particularly limited, but is actually 100 or more, preferably 200 or more. That is, it is actually 100 or more and less than 5000, preferably 200 to 2000, more preferably 200 to 1000, further preferably 200 to 500, and particularly preferably 200 to 400.

[0274] When compound A is a polymer, the lower limit of the weight average molecular weight of compound A is 5,000 or more, preferably 10,000 or more, and more preferably 15,000 or more from the viewpoint of the physical properties of the optical filter. There is no particular limitation on the upper limit, but from the viewpoint of solubility in the solvent, it is preferably 500,000 or less, more preferably 200,000 or less, and further preferably 150,000 or less. That is, it is actually 5,000 to 500,000, preferably 10,000 to 200,000, and more preferably 15,000 to 150,000.

[0275] In addition, the weight average molecular weight is a value measured by the measurement method of the weight average molecular weight described in the Examples mentioned later.

[0276] Furthermore, part or all of the acid groups contained in compound A may be anionized or not anionized in the light absorption filter, and in the present invention, both anionized acid groups and non-anionized acid groups are included and referred to as acid groups. That is, compound A may be anionized or not anionized in the light absorption filter.

[0277] As the compound A, a compound having a carboxyl group is preferred in terms of excellent film forming properties of the light absorption filter.

[0278] The compound having a carboxyl group is preferably a monomer containing a carboxyl group (hereinafter also referred to as a "carboxyl group-containing monomer") or a polymer containing a carboxyl group (hereinafter also referred to as a "carboxyl group-containing polymer"), and is more preferably a carboxyl group-containing polymer from the viewpoint of film forming properties of the light absorption filter.

[0279] The following descriptions on carboxyl-containing monomers and carboxyl-containing polymers can be understood by replacing the carboxyl group with the acid group contained in the above compound A. That is, the carboxyl-containing monomer can be replaced with a monomer having the above acid group, and the carboxyl-containing polymer can be replaced with a polymer having the above acid group.

[0280] In addition, part or all of the carboxyl groups (-COOH) possessed by the carboxyl group-containing monomer and the carboxyl group-containing polymer may be anionized or non-anionized in the light absorption filter, and both anionized carboxyl groups (-COO) and non-anionized carboxyl groups are included in the term "carboxyl groups".

[0281] That is, the carboxyl group-containing polymer may be anionized or not anionized in the light absorption filter, and both anionized carboxyl group-containing polymers and non-anionized carboxyl group-containing polymers are included in the term "carboxyl group-containing polymer".

[0282] The content of compound A in the light absorption filter is preferably 1% by mass or more, more preferably 25% by mass or more, further preferably 30% by mass or more, particularly preferably 45% by mass or more, and particularly preferably 50% by mass or more. The upper limit of the content of compound A is preferably less than 100% by mass, more preferably 99% by mass or less, and further preferably 97% by mass or less. That is, preferably 1% by mass or more and less than 100% by mass, more preferably 25 to 99% by mass, further preferably 30 to 97% by mass, particularly preferably 45 to 97% by mass, and particularly preferably 50 to 97% by mass.

[0283] Among them, when compound A is a polymer, the content of compound A in the light absorption filter is preferably 50 mass% or more and less than 100 mass%, more preferably 60 mass% or more and less than 100 mass%, and further preferably 70 mass% or more and less than 100 mass%. The upper limit is also preferably 99 mass% or less, more preferably 97 mass% or less, further preferably 95 mass% or less, and particularly preferably 90 mass% or less.

[0284] The compound A may be used alone or in combination of two or more.

[0285] (Carboxyl group-containing monomer)

[0286] Examples of the carboxyl group-containing monomer include polymerizable compounds containing a carboxyl group and one or more (for example, 1 to 15) ethylenically unsaturated groups.

[0287] Examples of the ethylenically unsaturated group include a (meth)acryloyl group, a vinyl group, and a styryl group, and a (meth)acryloyl group is preferred.

[0288] When the ethylenically unsaturated group is a (meth)acryloyl group, the carbonyl bond in the (meth)acryloyl group and the carbonyl bond in the carboxyl group may share one carbonyl bond.

[0289] As the carboxyl group-containing monomer, a difunctional or higher-functional monomer containing a carboxyl group is preferred from the viewpoint of better film forming properties. The difunctional or higher-functional monomer refers to a polymerizable compound having two or more (eg, 2 to 15) ethylenically unsaturated groups in one molecule.

[0290] The number of carboxyl groups contained in the carboxyl group-containing monomer may be 1 or more, and is, for example, preferably 1 to 8, more preferably 1 to 4, and even more preferably 1 to 2.

[0291] The carboxyl group-containing monomer may further have an acid group other than the carboxyl group as the acid group. Examples of the acid group other than the carboxyl group include a phenolic hydroxyl group, a phosphoric acid group, and a sulfonic acid group.

[0292] The bifunctional or higher-functional monomer containing a carboxyl group is not particularly limited and can be appropriately selected from known compounds.

[0293] Examples of the bifunctional or higher-functional monomer containing a carboxyl group include ARONIX M-520 and ARONIX M-510 (both manufactured by TOAGOSEI CO., LTD.) as trade names.

[0294] Furthermore, as the monomer having two or more functions including a carboxyl group, for example, there can be mentioned a tri- to tetra-functional polymerizable compound having a carboxyl group (a compound having a carboxyl group introduced into the skeleton of pentaerythritol triacrylate and pentaerythritol tetraacrylate [PETA] (acid value = 80 to 120 mgKOH / g)) and a penta- to hexa-functional polymerizable compound having a carboxyl group (a compound having a carboxyl group introduced into the skeleton of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate [DPHA] (acid value = 25 to 70 mgKOH / g)). In addition, when using the above-mentioned tri- or more functional monomer having a carboxyl group, it is also preferred to use a bi- or more functional monomer having a carboxyl group at the same time from the viewpoint of better film forming properties.

[0295] Examples of the bifunctional or higher-functional monomer containing a carboxyl group and the bifunctional or higher-functional monomer containing an acid group include polymerizable compounds having an acid group described in paragraphs 0025 to 0030 of JP-A-2004-239942, the contents of which are incorporated herein.

[0296] (Polymer containing carboxyl group)

[0297] The carboxyl group-containing polymer may further have an acid group other than the carboxyl group as the acid group. Examples of the acid group other than the carboxyl group include a phenolic hydroxyl group, a phosphoric acid group, and a sulfonic acid group.

[0298] When the carboxyl group-containing polymer is a copolymer, the structure of the polymer may be a random polymer or an ordered polymer such as a block polymer.

[0299] <<Structural unit having a carboxyl group>>

[0300] The carboxyl group-containing polymer preferably contains a structural unit having a carboxyl group.

[0301] As the structural unit having a carboxyl group, for example, a structural unit derived from (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, 2-carboxyethyl (meth) acrylic acid, 2-acryloyloxyethyl succinic acid or fumaric acid can be mentioned. Among them, from the viewpoint of excellent decolorization of the dye, a structural unit derived from (meth) acrylic acid is preferred.

[0302] Furthermore, as the structural unit having the above-mentioned carboxyl group, in addition to the above-mentioned method in which the double bond of the monomer component having the carboxyl group is introduced into the main chain of the polymer, there can be mentioned a method in which the double bond of the monomer component having the carboxyl group is introduced into the side chain of the polymer, and a method in which the monomer component having the carboxyl group is introduced as a structural unit of the graft chain of the polymer.

[0303] In the embodiment in which a monomer component having a carboxyl group is introduced as a structural unit of a graft chain of a polymer, the weight average molecular weight of the graft chain is preferably 100 to 10,000, more preferably 300 to 5,000, and further preferably 500 to 2500. The weight average molecular weight is a value measured by the weight average molecular weight measurement method described in the Examples below.

[0304] From the viewpoint of improving production applicability, viscosity and solubility, a structural unit derived from a component other than a monomer component having a carboxyl group may be included in the graft chain. As such a structural unit, any structural unit can be mentioned, for example, a structural unit having an alicyclic structure described later, a structural unit derived from an alkyl (meth)acrylate, and a structural unit having an aromatic ring are preferably used.

[0305] In the case where the graft chain of the polymer contains a structural unit derived from a component other than a monomer component having a carboxyl group, it is preferred to adjust the acid value of the polymer containing the carboxyl group to be within the preferred range described later. When the total of all structural units constituting the graft chain is set to 100 mol%, the content of the structural unit derived from the monomer component having a carboxyl group in the graft chain can be set to, for example, 30 mol% or more, preferably 40 mol% or more, and more preferably 50 mol% or more. The upper limit is not particularly limited and can be set to 100 mol% or less.

[0306] In the method in which the double bond of a monomer component having a carboxyl group is introduced into the side chain of a polymer and in the method in which a monomer component having a carboxyl group is introduced as a structural unit of a graft chain of the above-mentioned polymer, the structure derived from the monomer component having a carboxyl group may be directly bonded to the main chain or may be bonded via a linking group, but preferably bonded via a linking group.

[0307] Examples of the linking group include -O-, -S-, >C=O, >NR A or an alkylene group, or a group formed by combining two or more of these. A Examples include a hydrogen atom or a substituent T described below, and a hydrogen atom or an alkyl group is preferred. Among them, a combination of -COO- and an alkylene group, or -COO-, an alkylene group and -NR A A linking group of a combination of COO-.

[0308] The number of atoms in the linking group that links the bonding site on the polymer main chain and the bonding site on the structure derived from the monomer component having a carboxyl group is preferably 1 to 30, more preferably 2 to 20, and further preferably 4 to 12. By setting it within this range, it is easy to manufacture and the strength of the obtained resin can be made appropriate. In addition, with respect to the above-mentioned linking group, "the number of atoms that links the bonding site on the polymer main chain and the bonding site on the structure derived from the monomer component having a carboxyl group" refers to the number of atoms that constitute the shortest chain that links the bonding site on the polymer main chain and the structure derived from the monomer component having a carboxyl group. For example, the structural unit with a carboxyl group in the resin 2 used in the later-described embodiments is a structure unit of a graft chain of a polymer in which a monomer component with a carboxyl group is introduced, and the number of atoms that constitute the shortest chain that links the polymer main chain and the structure derived from methacrylic acid as a monomer component having a carboxyl group is 11.

[0309] The acid value of the carboxyl group-containing polymer is preferably 20 to 400 mgKOH / g, more preferably 40 to 350 mgKOH / g, and further preferably 60 to 300 mgKOH / g. In addition, the acid value of the polymer is set to a value measured in accordance with Japanese Industrial Standard (JIS) K0070-1992 "Test methods for acid value, saponification value, ester value, iodine value, hydroxyl value and unsaponifiable matter of chemical products".

[0310] When the total of all structural units constituting the main chain of the polymer containing a carboxyl group is set to 100 mol%, the content of the structural unit having a carboxyl group in the polymer containing a carboxyl group is preferably 1 to 100 mol%, more preferably 3 to 65 mol%, and further preferably 5 to 45 mol%. In addition, the structural unit having a carboxyl group refers to the content of the structural unit constituting the main chain of the polymer containing a carboxyl group.

[0311] The structural unit having a carboxyl group may be used alone or in combination of two or more.

[0312] <<Structural unit having an alicyclic structure>>

[0313] The carboxyl group-containing polymer preferably includes a structural unit having an alicyclic structure in addition to the above-mentioned structural units.

[0314] Examples of the alicyclic structure include tricyclic [5.2.1.0 2，6 ] decane ring structure (also called tetrahydrodicyclopentadiene. The monovalent group is dicyclopentyl), tricyclo[5.2.1.0 2，6 ]Decan-3-ene ring structure (also called 5,6-dihydrodicyclopentadiene. The monovalent group is dicyclopentenyl), isobornane ring structure (the monovalent group is isobornyl), adamantane ring structure (the monovalent group is adamantyl) and cyclohexane ring structure (the monovalent group is cyclohexyl).

[0315] Examples of the structural unit having an alicyclic structure include structural units derived from (meth)acrylates having an alicyclic structure (specifically, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, 3,3,5-trimethylcyclohexyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, cyclohexyl (meth)acrylate, etc.).

[0316] When the total of all structural units constituting the main chain of the polymer containing a carboxyl group is set to 100 mol%, the content of the structural unit having an alicyclic structure in the polymer containing a carboxyl group is preferably 0 to 99 mol%, more preferably 10 to 97 mol%, further preferably 20 to 95 mol%, and particularly preferably 40 to 95 mol%. In addition, the structural unit having an alicyclic structure refers to the content of the structural unit constituting the main chain of the polymer containing a carboxyl group.

[0317] The structural unit having an alicyclic structure may be used alone or in combination of two or more.

[0318] <<Other structural units>>

[0319] The carboxyl group-containing polymer may have other structural units in addition to the above-mentioned structural units.

[0320] As said other structural unit, the structural unit derived from the (meth)acrylic acid alkyl ester and the structural unit which has an aromatic ring are mentioned, for example.

[0321] The alkyl group in the structural unit derived from the alkyl (meth)acrylate may be unsubstituted or may have a substituent. Examples of the substituent include a hydroxyl group, an acyloxy group, and -NR A COO-alkyl, -COONR A -alkyl. A With the aforementioned R A Furthermore, the substituent that the alkyl group in the structural unit derived from the alkyl (meth)acrylate may have may further have a substituent and may include a graft chain.

[0322] Examples of the structural unit having an aromatic ring include structural units derived from benzyl (meth)acrylate, phenethyl (meth)acrylate, styrene, 9-anthrylmethyl (meth)acrylate, 1-naphthyl (meth)acrylate, 2-naphthyl (meth)acrylate, 1-vinylnaphthalene, 2-vinylnaphthalene, 1-naphthylmethyl (meth)acrylate, 2-naphthylmethyl (meth)acrylate, nonylphenoxypolyethylene glycol (meth)acrylate, 2-(o-phenylphenoxy)ethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, phenoxyethyl (meth)acrylate, and the like.

[0323] When the total of all structural units constituting the main chain of the polymer containing the carboxyl group is set to 100 mol%, the content of other structural units in the polymer containing the carboxyl group is selected from 0 to 99 mol%, more preferably 1 to 97 mol%, and further preferably 3 to 95 mol%. In addition, other structural units refer to the content of structural units constituting the main chain of the polymer containing the carboxyl group.

[0324] The other structural units may be used alone or in combination of two or more.

[0325] (3) Compound B

[0326] The light absorption filter of the present invention preferably contains, as the radical generator, a compound B having a structure capable of forming a hydrogen bond with an acid group contained in the compound A (also referred to simply as "compound B" in the present invention) together with the compound A.

[0327] Compound B is preferably a compound having a structure that increases basicity by absorbing ultraviolet light and becoming excited. The increased basicity of compound B in the excited state can form a complex in which the acid group contained in compound A interacts more strongly with compound B, thereby improving the efficiency of generating free radicals.

[0328] The structure of compound B that can form a hydrogen bond with the acid group contained in compound A may be the entire structure of compound B or a partial structure constituting a part of compound B.

[0329] Compound B may be a high molecular compound (a compound having a molecular weight of 5000 or more) or a low molecular compound (a compound having a molecular weight of less than 5000), and is preferably a low molecular compound.

[0330] The molecular weight of the compound B as a low molecular weight compound is less than 5000, preferably less than 1000, more preferably 500 or less, and further preferably 350 or less. The lower limit is not particularly limited, but is preferably 65 or more, and more preferably 75 or more. The preferred range of the molecular weight of the compound B as a low molecular weight compound is, for example, 65 to 500, and more preferably 75 to 350.

[0331] From the viewpoint of having a large molar absorption coefficient with respect to ultraviolet rays, the compound B is preferably an aromatic compound.

[0332] Here, the aromatic compound refers to a compound having one or more aromatic rings.

[0333] The aromatic ring may be present in only one or in plurality in the compound B. When the aromatic ring is present in plurality, for example, the aromatic ring may be present in a side chain of a polymer constituting a resin.

[0334] The aromatic ring may be any of an aromatic hydrocarbon ring and an aromatic heterocyclic ring. In the case of an aromatic heterocyclic ring (also referred to as a heteroaromatic ring), it is a compound having one or more (e.g., 1 to 4) heteroatoms (at least one of a nitrogen atom, an oxygen atom, or a sulfur atom) as ring atoms (ring-constituting atoms), preferably one or more (e.g., 1 to 4) nitrogen atoms as ring atoms.

[0335] In addition, the unsubstituted aromatic hydrocarbon does not have a structure capable of forming a hydrogen bond with the acid group contained in the compound A, and therefore does not have a function of generating free radicals by ultraviolet irradiation, and does not correspond to the compound B. Furthermore, the unsubstituted aromatic hydrocarbon ring in the form of being bonded to the side chain of the polymer constituting the resin does not have a structure capable of forming a hydrogen bond with the acid group contained in the compound A, and therefore does not have a function of generating free radicals by ultraviolet irradiation, and does not correspond to the compound B.

[0336] The aromatic ring preferably has 5 to 15 ring member atoms.

[0337] Examples of the aromatic ring include monocyclic aromatic rings such as a pyridine ring, a pyrazine ring, a pyrimidine ring, and a triazine ring; aromatic rings formed by condensing two rings such as a quinoline ring, an isoquinoline ring, a quinoxaline ring, and a quinazoline ring; and aromatic rings formed by condensing three rings such as an acridine ring, a phenanthridine ring, a phenanthroline ring, and a phenazine ring.

[0338] The aromatic ring may have one or more (e.g., 1 to 5) substituents, and examples of the substituents include alkyl groups, aryl groups, halogen atoms, acyl groups, alkoxycarbonyl groups, arylcarbonyl groups, carbamoyl groups, hydroxyl groups, cyano groups, and nitro groups. In addition, when the aromatic ring has two or more substituents, the multiple substituents may be bonded to each other to form a non-aromatic ring.

[0339] In addition, when multiple aromatic rings (for example, 2 to 5 aromatic rings) form a series of aromatic ring structures bonded by structures selected from single bonds, carbonyl bonds and multiple bonds (for example, vinylene groups that may have substituents, -C≡C-, -N=N-, etc.), the above series of aromatic ring structures as a whole are regarded as one specific structure.

[0340] The series of aromatic ring structures in which the above-mentioned multiple aromatic rings are bonded by a structure selected from a single bond, a carbonyl bond and a multiple bond do not correspond to the above-mentioned unsubstituted aromatic hydrocarbon ring, nor do they correspond to the unsubstituted aromatic hydrocarbon ring in the form in which the unsubstituted aromatic hydrocarbon ring is bonded to the side chain of the polymer constituting the resin.

[0341] Furthermore, it is preferred that at least one of the plurality of aromatic rings constituting the series of aromatic ring structures is the heteroaromatic ring.

[0342] Specific examples of compound B include monocyclic aromatic compounds such as pyridine compounds (pyridine and pyridine derivatives), pyrazine compounds (pyrazine and pyrazine derivatives), pyrimidine compounds (pyrimidine and pyrimidine derivatives), and triazine compounds (triazine and triazine derivatives); compounds having two rings fused together to form an aromatic ring, such as quinoline compounds (quinoline and quinoline derivatives), isoquinoline compounds (isoquinoline and isoquinoline derivatives), quinoxaline compounds (quinoxaline and quinoxaline derivatives), and quinazoline compounds (quinazoline and quinazoline derivatives); and compounds having three or more rings fused together to form an aromatic ring, such as acridine compounds (acridine and acridine derivatives), phenanthridine compounds (phenanthridine and phenanthridine derivatives), phenanthroline compounds (phenanthroline and phenanthroline derivatives), and phenazine compounds (phenazine and phenazine derivatives). In the specific examples of compound B, the compound is used to include not only the compound itself but also unsubstituted compounds having a part of the structure changed and compounds having a substituent (referred to as "derivative") within the range not impairing the effects of the present invention.

[0343] It is presumed that these compounds B form a complex with the aforementioned compound A, and two molecules of free radicals are generated by the following mechanism upon irradiation with ultraviolet rays.

[0344] 1) Compound B is generated in an excited state by absorbing ultraviolet rays.

[0345] 2) Holes move from the excited state of compound B to the ground state of compound A (electrons of compound A move to the orbital on the lower energy side of the two half-occupied orbitals of compound B in the excited state).

[0346] 3) As a proton moves from compound A to compound B, a radical in which a hydrogen radical is supported on compound B and a radical in which the hydrogen radical is separated from compound A are generated.

[0347] When compound A is a compound having a carboxyl group, the following reaction further occurs, and a free radical is generated by a photodecarbonation reaction.

[0348] 4) Hydrogen radicals are separated from the radicals separated from compound A to carbon dioxide.

[0349] Among them, compound B is preferably one or more of quinoline compounds (quinoline and quinoline derivatives) and isoquinoline compounds (isoquinoline and isoquinoline derivatives).

[0350] Preferred examples of the substituent which these compounds may have include an alkyl group, an aryl group, a halogen atom, an acyl group, an alkoxycarbonyl group, an arylcarbonyl group, a carbamoyl group, a hydroxyl group, a cyano group and a nitro group.

[0351] When compound B is a polymer, it may be a polymer in which the above-mentioned specific structure is bonded to the polymer main chain via a single bond or a linking group.

[0352] Compound B as a polymer is obtained, for example, by polymerizing a monomer having a heteroaromatic ring (specifically, a (meth)acrylate monomer having a vinyl heteroaromatic ring and / or having a specific structure (preferably a heteroaromatic ring)) and may be copolymerized with other monomers as required.

[0353] Specific examples of the compound B include quinoline, 2-methylquinoline, 4-methylquinoline, 2,4-dimethylquinoline, 2-methyl-4-phenylquinoline, isoquinoline, 1-methylisoquinoline, 3-methylisoquinoline, and 1-phenylisoquinoline.

[0354] From the viewpoint of achieving both the decolorization of the ultraviolet irradiated portion and the durability of the dye in the ultraviolet non-irradiated portion, the content of compound B is preferably 0.1 to 50 mass %, more preferably 2.0 to 40 mass %, further preferably 4 to 35 mass %, and particularly preferably 8 to 30 mass %, relative to the total mass of the light absorption filter.

[0355] Furthermore, similarly, from the viewpoint of taking into account both the bleaching resistance of the ultraviolet irradiated portion and the durability of the dye of the ultraviolet non-irradiated portion, the pKaH (pKa of the conjugate acid) which is a measure of the basicity of compound B is preferably greater than 2.0 and less than 7.0, more preferably greater than 3.0 and less than 6.0, and further preferably greater than 4.3 and less than 5.5.

[0356] In the present invention, pKa refers to the negative common logarithm (-logKa) of the acid dissociation constant (Ka) in a mixed solvent of water / methanol = 50 / 50 (volume ratio) at 25° C. pKa can be calculated by dropping 0.0 mol / L of an aqueous sodium hydroxide solution to a mixed solution of a sample for measurement (conjugate acid of compound B) of water / methanol = 50 / 50 (volume ratio), and reading the amount of the aqueous sodium hydroxide solution added to the half-equivalent point.

[0357] The compound B may be used alone or in combination of two or more.

[0358] From the viewpoint of further improving the decolorization rate, the amount of the free radical generator in the light absorption filter of the present invention is preferably 0.1 to 20 moles relative to 1 mole of the dye having a main absorption wavelength band at a wavelength of 400 to 700 nm. The lower limit is more preferably 0.25 moles or more, and more preferably 0.50 moles or more. The upper limit is more preferably 17.5 moles or less, and more preferably 15 moles or less. That is, it is more preferably 0.25 to 17.5 moles, and more preferably 0.50 to 15 moles. The amount of the free radical generator mentioned here refers to the amount of the above-mentioned light free radical generator or the amount of compound B, and does not include the amount of compound A.

[0359] The light absorption filter of the present invention may contain one type of radical generator, or may contain two or more types of radical generators.

[0360] <Resin>

[0361] There are no particular limitations on the resin contained in the light absorption filter of the present invention (hereinafter also referred to as "matrix resin") as long as it can disperse (preferably dissolve) the above-mentioned dye, can show the decolorization effect of the dye caused by free radicals generated from a compound that generates free radicals by ultraviolet irradiation (preferably a free radical generator containing compound B that hydrogen bonds with the acid group contained in compound A), can obtain excellent decolorization properties even when irradiated with ultraviolet rays at room temperature, can suppress the generation of cavities in the filter caused by ultraviolet irradiation even when containing a compound that generates free radicals at a high concentration, and has the desired light transmittance (in the visible region with a wavelength of 400 to 800 nm, the transmittance is preferably 80% or more).

[0362] In the light absorption filter of the present invention, the polymer constituting the above-mentioned resin contains a crosslinking group to suppress the decrease in molecular weight of the resin due to ultraviolet irradiation.

[0363] The crosslinkable group is not particularly limited as long as it is a group that can be crosslinked using free radicals generated by ultraviolet irradiation, and examples thereof include free radical polymerizable groups, specifically, epoxy groups, vinyl groups, groups having free radical polymerizable double bonds (styryl groups, (meth)acryloyl groups, (meth)acryloyloxy groups, (meth)acrylamide groups, etc.), and the like.

[0364] Among these, the crosslinkable group is preferably a vinyl group or a group having a radical polymerizable double bond (such as a styryl group, a (meth)acryloyl group, a (meth)acryloyloxy group, and a (meth)acrylamide group).

[0365] The method for introducing the crosslinkable group into the polymer constituting the resin is not particularly limited, and the crosslinkable group can be introduced by a conventional method. For example, the following methods (i) to (iii) are mentioned.

[0366] (i) a method of reacting a compound having an epoxy group and a radical polymerizable group with a carboxyl group in a polymer, or a method of reacting a compound having a carboxyl group and a radical polymerizable group with an epoxy group in a polymer, utilizing bond formation based on a reaction between a carboxyl group and an epoxy group;

[0367] (ii) a method of reacting a compound having an isocyanate group and a radical polymerizable group with a hydroxyl group in a polymer, or a method of reacting a compound having a hydroxyl group and a radical polymerizable group with an isocyanate group in a polymer, utilizing bond formation based on a reaction between a hydroxyl group and an isocyanate group;

[0368] (iii) A method of removing HCl from 2-chloroethylcarbonyl groups in a polymer or a method of removing HBr from 2-bromoethylcarbonyl groups in a polymer by utilizing the formation of a radical polymerizable double bond by removing HCl or HBr.

[0369] Among them, the method (i) or (ii) is preferred. More specifically, there is a method of reacting glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, or the like with a carboxyl group in a polymer.

[0370] The crosslinkable group may be directly bonded to the polymer main chain or may be bonded via a linking group, and is preferably bonded via a linking group.

[0371] The linking group is not particularly limited and can be a linking group corresponding to the method of introducing the crosslinking group, and examples thereof include -0-, -S-, >C=O, >NR A , an alkylene group, an alkenylene group, an arylene group or a heteroarylene group, or a group formed by combining two or more of these. A With the aforementioned RA Among them, preferably, a combination of -COO- and an alkylene group, or -COO-, an alkylene group and -NR A A linking group of a combination of COO-.

[0372] The number of atoms in the linking group that links the bonding site on the polymer main chain and the bonding site on the crosslinking group is not particularly limited, and is, for example, preferably 1 to 30, more preferably 1 to 20, and further preferably 2 to 15. In addition, with respect to the above-mentioned linking group, "the number of atoms that links the bonding site on the polymer main chain and the bonding site on the crosslinking group" refers to the number of atoms constituting the shortest chain linking the bonding site on the polymer main chain and the crosslinking group. For example, in the resin 3 used in the examples described below, the number of atoms constituting the shortest chain linking the polymer main chain and the methacryloyloxy group as the crosslinking group is 5.

[0373] The content of the structural unit having a crosslinkable group in all the structural units constituting the polymer is preferably 3 to 30 mol %, more preferably 5 to 25 mol %, and even more preferably 5 to 20 mol %.

[0374] The content of the structural unit having a crosslinkable group among all the structural units constituting the above-mentioned polymer can be calculated by NMR (Nuclear Magnetic Resonance) or IR (infrared absorption spectrometry). For example, deuterated chloroform is used as a solvent for NMR, and mesitylene of a known concentration is added as a standard sample and measured, thereby inferring the structure and existence ratio of all the structural units constituting the polymer. In addition, the content (molar fraction) of the structural unit having a crosslinkable group in the polymer can be calculated based on the ratio of the structural unit containing a crosslinkable group therein.

[0375] In addition, when the values ​​calculated by NMR and IR measurement are different, the value of NMR is adopted.

[0376] Among the polymers constituting the above resins, polymers having an aromatic ring or an alicyclic structure in a side chain are preferred, and (meth)acrylic polymers containing a structural unit having an aromatic ring or an alicyclic structure are more preferred, because of their suitability for production and / or the physical properties of the obtained coating film. Among them, (meth)acrylic polymers containing a structural unit having an aromatic ring or an alicyclic structure are more preferred, because they can further improve the decolorization rate and further improve the heat resistance and light resistance.

[0377] Here, the (meth)acrylic polymer refers to a polymer containing at least one of a structural unit derived from (meth)acrylic acid and a structural unit derived from (meth)acrylic acid ester. In addition, when the polymer contains a structural unit derived from (meth)acrylic acid, the structural unit derived from (meth)acrylic acid becomes a structural unit having a carboxyl group as an acid group in the above-mentioned compound A, which corresponds to a polymer in which the above-mentioned compound A is chemically bonded to the polymer constituting the above-mentioned resin.

[0378] Furthermore, in the present invention, the "main chain" refers to the relatively longest connecting chain in the molecule of the polymer, and the "side chain" refers to an atomic group branched from the main chain.

[0379] In the present invention, the "main chain" of a polymer refers to a linear molecular chain that can be regarded as a branch chain or a side group relative to the main chain, and all other molecular chains constituting the polymer. Although it depends on the mass average molecular weight of the branched chain regarded as a branch chain or a side group, as a typical example, the longest chain among the molecular chains constituting the polymer becomes the main chain.

[0380] In contrast, the "side chain" of a polymer refers to a branched chain other than the main chain, including a short chain and a long chain (grafted chain). The terminal group of the polymer is not particularly limited, and an appropriate group can be adopted according to the polymerization method, etc. For example, a hydrogen atom, an alkyl group, an aryl group, a hydroxyl group, and a polymerization initiator residue can be cited.

[0381] In the present invention, the "grafted chain" of a polymer refers to an atomic group having a polymer structure in the structure of a polymer side chain, which is typically introduced into the polymer main chain by graft polymerization. However, in the present invention, the grafted chain is not limited to a polymer chain introduced by graft polymerization.

[0382] Examples of the monomer for introducing a structural unit having an aromatic ring include benzyl acrylate, benzyl methacrylate, naphthyl acrylate, naphthyl methacrylate, naphthyl methyl acrylate, naphthyl methyl methacrylate, styrene, 9-anthrylmethyl (meth)acrylate, 1-naphthyl (meth)acrylate, 2-naphthyl (meth)acrylate, 1-vinylnaphthalene, 2-vinylnaphthalene, 1-naphthylmethyl (meth)acrylate, 2-naphthylmethyl (meth)acrylate, nonylphenoxypolyethylene glycol (meth)acrylate, 2-(o-phenylphenoxy)ethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, etc. When the polymer does not contain a structural unit derived from (meth)acrylic acid, the content of the structural unit having an aromatic ring is preferably 5 to 100 mol %, more preferably 10 to 100 mol %, and even more preferably 20 to 100 mol % relative to all structural units of the polymer.

[0383] Examples of the monomer for introducing a structural unit having an alicyclic structure include dicyclopentanyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, and 3,3,5-trimethylcyclohexyl (meth)acrylate, and cyclohexyl (meth)acrylate is preferred.

[0384] When the polymer does not contain a structural unit derived from (meth)acrylic acid, the content of the structural unit having an alicyclic structure is preferably 1 to 90 mol %, more preferably 5 to 90 mol %, and further preferably 5 to 80 mol % based on all structural units of the polymer.

[0385] From the viewpoint of adjusting the glass transition temperature, the polymer constituting the above resin may contain a structural unit having an alkyl group with 1 to 14 carbon atoms. As the structural unit having an alkyl group with 1 to 14 carbon atoms, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, tert-butyl (meth)acrylate, sec-butyl (meth)acrylate, pentyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-ethylbutyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, isononyl (meth)acrylate, lauryl (meth)acrylate, isobornyl (meth)acrylate and tetradecyl (meth)acrylate can be cited. In the present invention, the structural unit having an alkyl group with 1 to 14 carbon atoms can be used alone, or two or more can be used in combination. The content of the structural unit having an alkyl group with 1 to 14 carbon atoms is preferably 0 to 30 mol% relative to all the structural units of the polymer.

[0386] Furthermore, in the light absorption filter of the present invention, the polymer constituting the resin may include a structural unit bonded to the compound A having an acid group. Examples of the structural unit bonded to the compound A having an acid group include a structural unit in which the acid group of the compound A is directly bonded to the polymer main chain and a structural unit in which the compound A is introduced into a polymer side chain, preferably a structural unit derived from (meth)acrylic acid or a structural unit containing a structure derived from (meth)acrylic acid in a side chain.

[0387] In the case where the polymer constituting the above-mentioned resin contains a structural unit bonded to a compound A having an acid group, regarding the content of the structural unit bonded to the compound A having an acid group, the content of the structural unit having an alicyclic structure, and the total content of the structural unit having an aromatic ring and the structural unit having an alkyl group having 1 to 14 carbon atoms, the description related to the content of the structural unit having a carboxyl group, the content of the structural unit having an alicyclic structure, and the content of other structural units (the total content of the structural unit derived from an alkyl (meth)acrylate and the structural unit having an aromatic ring) in the carboxyl group-containing polymer of the above-mentioned compound A shall be applied.

[0388] The weight average molecular weight (Mw) of the polymer constituting the resin is preferably 10,000 or more, more preferably 10,000 to 200,000, and even more preferably 15,000 to 150,000. The weight average molecular weight is a value measured by the weight average molecular weight measurement method described in Examples below.

[0389] The specific examples of the polymer used in the present invention are shown below, but the present invention is not limited to these polymers. In addition, polymers in which the ratio of each structural unit in the following specific examples, the weight average molecular weight, and the acid value are appropriately adjusted can also be preferably cited as specific examples of the polymer used in the present invention.

[0390] In the specific examples of the graft polymer, it refers to a graft polymer structure in which * in the structure described in the column of the structural unit constituting the main chain and * in the structure described in the column of the structural unit constituting the graft chain are linked.

[0391] In addition, the ratio of the structural units enclosed by () is a molar basis (mol%), and in the graft polymer, the total of the structural units constituting the main chain is 100 mol%, and the total of the structural units constituting the graft chain is 100 mol%. In addition, the copolymer composed of each structural unit may be a random polymer or an ordered polymer such as a block.

[0392] The unit of acid value is mgKOH / g.

[0393] [Table A]

[0394] Specific Example <Graft Polymer>

[0395]

[0396] Specific Example <Polymer containing a crosslinkable group>

[0397]

[0398] <Other ingredients>

[0399] The light absorption filter of the present invention may contain an anti-fading agent, a matting agent, a leveling agent (surfactant), and the like in addition to the above-mentioned dye, the above-mentioned compound that generates radicals by ultraviolet irradiation, and the above-mentioned resin (matrix polymer).

[0400] <Anti-fading agent>

[0401] In the light absorption filter of the present invention, the anti-fading agent is preferably one that does not inhibit discoloration caused by ultraviolet irradiation but has the effect of suppressing decomposition of the dye caused by visible light.

[0402] As the anti-fading agent, a compound represented by the following general formula (IV) can be preferably used.

[0403] [Chemical formula 12]

[0404]

[0405] In formula (IV), R 10 represents an alkyl group, an alkenyl group, an aryl group, a heterocyclic group or a 18 CO-、R 19 SO2- or R 20 A group represented by NHCO-. Here, R 18 , R 19 and R 20 Each independently represents an alkyl group, an alkenyl group, an aryl group or a heterocyclic group. 11 and R 12 Each independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group or an alkenyloxy group, and R 13 , R 14 , R 15 , R 16 and R 17 Each independently represents a hydrogen atom, an alkyl group, an alkenyl group or an aryl group.

[0406] Among them, R 10 ~R 20 The alkyl group in the above-mentioned group includes an aralkyl group.

[0407] The compound represented by the above general formula (IV) is the same as the compound represented by the general formula (IV) described in

[0215] to

[0221] of International Publication No. 2021 / 221122. Therefore, the description of each substituent in the general formula (IV) and the specific examples of the compound represented by the general formula (IV) can be directly applied to the description of

[0217] to

[0221] of International Publication No. 2021 / 221122.

[0408] As the anti-fading agent, a compound represented by the following general formula [III] can also be preferably used.

[0409] [Chemical formula 13]

[0410] General formula [III]

[0411]

[0412] In the general formula [III], R 31 represents an aliphatic group or an aromatic group, and Y represents a non-metal atom group required to form a 5- to 7-membered ring together with the nitrogen atom.

[0413] The compound represented by the general formula [III] is the same as the compound represented by the general formula [III] described in

[0223] to

[0227] of International Publication No. 2021 / 221122. Therefore, the description of each substituent in the general formula [III] and the specific examples of the compound represented by the general formula [III] can be directly applied to the description of

[0225] to

[0227] of International Publication No. 2021 / 221122.

[0414] In addition to the above specific examples, specific examples of the compound represented by the above general formula [III] include the illustrative compounds B-1 to B-65 described on pages 8 to 11 of the specification of Japanese Unexamined Patent Publication No. 2-167543 and the illustrative compounds (1) to (120) described on pages 4 to 7 of the specification of Japanese Unexamined Patent Publication No. 63-95439.

[0415] The content of the anti-fading agent in the light absorption filter of the present invention is preferably 1 to 15% by mass, more preferably 5 to 15% by mass, further preferably 5 to 12.5% ​​by mass, and particularly preferably 10 to 12.5% ​​by mass.

[0416] By containing the anti-fading agent within the above preferred range, the light absorption filter of the present invention can improve the light resistance of the dye (pigment) without causing side effects such as discoloration.

[0417] (Matting agent)

[0418] In the range that does not damage the effect of the present invention, microparticles can be added to the surface of the light absorption filter of the present invention to impart slidability and prevent adhesion. As the microparticles, preferably silicon dioxide (silicon dioxide, SiO2) whose surface is coated with hydrophobic groups and adopts the mode of secondary particles is used. In addition, among the microparticles, microparticles such as titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, magnesium silicate and calcium phosphate can be used together with or instead of silicon dioxide. As commercially available microparticles, R972 and NX90S (both manufactured by NIPPONAEROSIL CO., LTD., trade names) etc. can be cited.

[0419] The fine particles function as so-called matting agents. By adding the fine particles, minute irregularities are formed on the surface of the light absorption filter of the present invention. Even if the light absorption filters of the present invention overlap with each other or with other films due to the irregularities, they will not adhere to each other, thereby ensuring slip properties.

[0420] In the case where the light absorption filter of the present invention contains a matting agent as fine particles, if there are 10 4 Pieces / mm 2 The above-mentioned protrusions with a height of 30 nm or more have a particularly large effect of improving the sliding property and the adhesion property.

[0421] From the viewpoint of improving the adhesion and the slipping property, the matting agent fine particles are preferably applied to the surface layer. As a method of applying the fine particles to the surface layer, there can be mentioned a method based on multilayer casting and coating.

[0422] The content of the matting agent in the light absorption filter of the present invention can be appropriately adjusted depending on the purpose.

[0423] However, when the light absorption filter of the present invention is provided with a gas barrier layer described later, it is preferred that the matting agent fine particles are provided on the surface of the light absorption filter that is in contact with the gas barrier layer within a range that does not impair the effects of the present invention.

[0424] (Leveling agent)

[0425] A leveling agent (surfactant) can be appropriately mixed in the light absorption filter of the present invention. As the leveling agent, commonly used compounds can be used, and fluorinated surfactants are particularly preferred. Specifically, for example, the compounds described in paragraphs

[0028] to

[0056] in the specification of Japanese Patent Publication No. 2001-330725 can be cited. In addition, as a commercially available product, the Megaface F (trade name) series manufactured by DIC Corporation can also be used.

[0426] The content of the leveling agent in the light absorption filter of the present invention can be appropriately adjusted depending on the purpose.

[0427] The light absorption filter of the present invention may contain, in addition to the above-mentioned components, a low molecular plasticizer, an oligomer plasticizer, a retardation regulator, a degradation inhibitor, a peeling accelerator, an infrared absorber, an antioxidant, a filler, a compatibilizer, and the like.

[0428] Furthermore, the light absorption filter of the present invention may contain a reaction accelerator or a reaction retardant as described in paragraphs

[0020] and

[0021] of Japanese Patent Application Laid-Open No. 09-286979.

[0429] In the present invention, the light absorption filter described below is also suitable as the light absorption filter of the present invention. The light absorption filter of the present invention described above is regarded as a first embodiment, and the light absorption filter of the present invention described below is regarded as a second embodiment.

[0430] As another embodiment of the light absorption filter of the present invention, there can be cited a light absorption filter comprising a resin, a compound A having an acid group, a compound B that forms a hydrogen bond with the acid group contained in the compound A and generates a free radical by ultraviolet irradiation, and a dye having a main absorption wavelength band at a wavelength of 400 to 700 nm, wherein the compound A is contained in a side chain of a polymer constituting the resin. The light absorption filter of the present invention having such a structure can obtain excellent decolorization even when irradiated with ultraviolet rays at room temperature (referring to 10 to 30° C.) as a mild environment, and can suppress the generation of cavities in the filter by ultraviolet irradiation even when a compound that generates free radicals is contained at a high concentration. Although the reason is inferred, it is considered as follows.

[0431] In the light absorption filter of the present invention, when a compound A having an acid group and a compound B forming a hydrogen bond with the acid group contained in the compound A are contained, the generation efficiency of free radical species by ultraviolet irradiation is improved compared with the case of using a common photo-free radical generator such as a benzophenone compound. Therefore, even when ultraviolet irradiation is performed under mild temperature conditions such as room temperature, sufficient free radical species are generated, and the free radical species directly or indirectly react with the above-mentioned dye, and the dye is decomposed, thereby fading and discoloring the dye. In addition, it is believed that the reason why cavities are generated in the filter by ultraviolet irradiation is that the free radicals generated by ultraviolet irradiation not only attack the dye but also attack the polymer constituting the resin, causing the depolymerization of the polymer. By introducing the compound A into the side chain of the polymer constituting the resin, the depolymerization of the polymer main chain caused by the free radicals generated by ultraviolet irradiation can be suppressed, and the generation of cavities in the filter by ultraviolet irradiation can be suppressed.

[0432] Regarding the dye in the second embodiment of the light absorption filter of the present invention, the description of the dye in the first embodiment of the light absorption filter of the present invention can be applied as it is.

[0433] With regard to the compound A having an acid group in the second embodiment of the light absorption filter of the present invention and the compound B that forms a hydrogen bond with the acid group contained in the compound A and generates a radical by ultraviolet irradiation, the description of the compound A and the compound B in the first embodiment of the light absorption filter of the present invention can be applied unless otherwise specified, except that the compound A is contained in the side chain of the polymer constituting the resin. Among them, the compound A is more preferably bonded in the form of being contained in the graft chain of the polymer constituting the resin.

[0434] Regarding the resin in the second embodiment of the light absorption filter of the present invention, the description of the resin in the first embodiment of the light absorption filter of the present invention can be applied unless otherwise specified, except that the polymer constituting the resin does not need to contain a crosslinking group and the compound A is contained in the side chain of the polymer constituting the resin.

[0435] <Method for Manufacturing Light Absorption Filter>

[0436] The light absorption filter of the present invention can be produced by a conventional method by a solution film forming method, a melt extrusion method or a method (coating method) of forming a coating on a substrate film (support film) by any method, and can also be appropriately combined with stretching. The light absorption filter of the present invention is preferably produced by a coating method.

[0437] As the above-mentioned solution film forming method and melt extrusion method, the description of the solution film forming method and melt extrusion method in

[0197] to

[0203] of International Publication No. 2021 / 132674 can be directly applied.

[0438] (Coating method)

[0439] In the coating method, a solution of the material of the light absorption filter is applied on the support film to form a coating. In order to control the adhesion between the coating and the support film, a release agent or the like may be appropriately applied on the surface of the support film in advance. The coating can be used by peeling off the support film after being laminated with other components via an adhesive layer in a later process. As for the adhesive constituting the adhesive layer, any adhesive can be appropriately used. In addition, the support film can be appropriately stretched together with the support film in a state where the solution of the material of the light absorption filter is applied on the support film or in a state where the coating is laminated.

[0440] The solvent used in the solution of the light absorption filter material can be appropriately selected from the viewpoints of being able to dissolve or disperse the light absorption filter material; being easy to form a uniform surface in the coating process and the drying process; being able to ensure liquid storage properties; and having an appropriate saturated vapor pressure.

[0441] -Addition of dyes (pigments) and free radical generators-

[0442] There is no particular limitation on the timing of adding the dye and the free radical generator to the material of the light absorption filter, as long as they are added at the time of film formation. For example, they can be added at the time of synthesizing the matrix polymer, or mixed with the material of the light absorption filter when preparing the coating liquid of the material of the light absorption filter. In addition, when the free radical generator comprises a combination of compound A and compound B, and compound A is bonded to the polymer constituting the resin, compound A is added when the polymer constituting the resin is added.

[0443] -Supporting film-

[0444] The film thickness of the support film used to form the light absorption filter of the present invention by a coating method or the like is preferably 5 to 100 μm, more preferably 10 to 75 μm, and further preferably 15 to 55 μm. If the film thickness is above the above preferred lower limit, it is easy to ensure sufficient mechanical strength and it is not easy to cause problems such as curling, wrinkling, and buckling. In addition, if the film thickness is below the above preferred upper limit, when the multilayer film of the light absorption filter of the present invention and the support film is stored in the form of a long roll, for example, it is easy to adjust the surface pressure applied to the multilayer film within an appropriate range, and it is difficult to cause adhesion problems.

[0445] The surface energy of the support film is not particularly limited, but the adhesion between the light absorption filter of the present invention and the support film can be adjusted by adjusting the correlation between the surface energy of the material of the light absorption filter of the present invention and the coating solution and the surface energy of the surface of the support film on the side where the light absorption filter of the present invention is formed. If the surface energy difference is reduced, there is a tendency for the adhesion to increase, and if the surface energy difference is increased, there is a tendency for the adhesion to decrease, and the surface energy difference can be appropriately set.

[0446] Furthermore, the surface roughness of the support film is not particularly limited, but can be adjusted based on the surface energy, hardness, and correlation between the surface roughness of the light absorption filter of the present invention and the surface energy and hardness of the surface of the support film on the side opposite to the side on which the light absorption filter of the present invention is formed, for example, to prevent adhesion failure when a multilayer film of the light absorption filter of the present invention and the support film is stored in a long roll form. If the surface roughness is increased, there is a tendency to suppress adhesion failure, and if the surface roughness is reduced, there is a tendency to reduce the surface roughness of the light absorption filter of the present invention and reduce the haze of the light absorption filter of the present invention, and it can be appropriately set.

[0447] As such a support film, any material and film can be appropriately used. As specific materials, polyester polymers (including polyethylene terephthalate), olefin polymers, cycloolefin polymers, (meth) acrylic polymers, cellulose polymers, polyamide polymers, etc. can be cited. In addition, in order to adjust the surface properties of the support film, surface treatment can be appropriately performed. In order to reduce the surface energy, for example, corona treatment, normal temperature plasma treatment, saponification treatment, etc. can be performed, and in order to increase the surface energy, silicone treatment, fluorine treatment, olefin treatment, etc. can be performed.

[0448] <Film Thickness of the Light Absorption Filter of the Present Invention>

[0449] The film thickness of the light absorption filter of the present invention is not particularly limited, but is preferably 1 to 18 μm, more preferably 1 to 12 μm, and further preferably 2 to 8 μm. If it is below the above preferred upper limit, by adding a high concentration of dye to the film, the decrease in polarization caused by the fluorescence emitted by the dye (pigment) can be suppressed. In addition, the effect of the quencher is also easy to show. On the other hand, if it is above the above preferred lower limit, it is easy to maintain the uniformity of the absorbance within the surface.

[0450] In the present invention, the film thickness of 1 to 18 μm means that the thickness of the light absorption filter of the present invention is within the range of 1 to 18 μm regardless of where it is measured. This also applies to film thicknesses of 1 to 12 μm and 2 to 8 μm. The film thickness can be measured using an electronic micrometer manufactured by ANRITSUCORPORATION.

[0451] <Absorbance of the Light Absorption Filter of the Present Invention>

[0452] In the light absorption filter of the present invention, the absorbance at the maximum absorption wavelength showing the maximum absorbance at a wavelength of 400 to 700 nm (hereinafter also referred to as "Ab(λ max )”.) is preferably 0.3 or more, more preferably 0.5 or more, and further preferably 0.7 or more.

[0453] However, the absorbance of the light absorption filter of the present invention can be adjusted by the type, addition amount or film thickness of the dye.

[0454] In the light absorption filter of the present invention, the decolorization rate due to ultraviolet irradiation at 25° C. is preferably 85% or more, more preferably 87% or more, further preferably 90% or more, and particularly preferably 95% or more. The upper limit is not particularly limited, but is preferably 100%.

[0455] In addition, regarding the above-mentioned decolorization rate, the above-mentioned Ab(λ max ) is calculated using the following formula.

[0456] Decolorization rate (%) = 100-(Ab after ultraviolet irradiation (λ max ) / Ab(λ before UV irradiation max ))×100

[0457] In the ultraviolet irradiation test, an ultrahigh pressure mercury lamp (manufactured by HOYA, trade name: UL750) was used under atmospheric pressure (101.33 kPa) and the light absorption filter was irradiated at an illuminance of 100 mW / cm at room temperature (25°C). 2 , irradiation dose is 3J / cm 2 of ultraviolet rays.

[0458] The absorbance, ultraviolet irradiation test, and decolorization rate can be measured and calculated by the methods described in the Examples.

[0459] Furthermore, it is preferred that the light absorption filter of the present invention hardly generates absorption (secondary absorption) derived from a new coloring structure accompanying decomposition of a pigment.

[0460] For example, the absorbance at a specific wavelength can be compared with the Ab(λ max ) ratio to confirm whether there is absorption from the new coloring structure accompanying the decomposition of the pigment. Regarding the specific wavelength, the wavelength at which the pigment before ultraviolet irradiation hardly shows absorption and the new absorption caused by the decomposition of the pigment is observed is selected.

[0461] As a specific example, as described in the examples below, it is possible to determine the absorbance at a specific wavelength and the Ab(λ max ) ratio to confirm whether there is absorption from the new coloring structure accompanying the decomposition of the pigment. Regarding the specific wavelength, the wavelength at which the pigment before ultraviolet irradiation hardly shows absorption and the new absorption caused by the decomposition of the pigment is observed is selected.

[0462] As a specific example, as described in the examples below, the absorbance at a wavelength of 450 nm (hereinafter also referred to as "Ab(450)") can be compared with the above Ab(λ max ) ratio to confirm the presence or absence of absorption from the new coloring structure accompanying the decomposition of the pigment. That is, the smaller the value obtained by subtracting the ratio of the following (I) from the ratio of the following (II), the less absorption from the new coloring structure accompanying the decomposition of the pigment occurs, and the value is preferably less than 8.5%, more preferably less than 7.0%, and further preferably less than 5.0%. The lower limit is not particularly limited, but from the perspective of making the evaluation of the secondary absorption associated with the decomposition of the pigment appropriate, it is actually more than -10%, preferably more than -6%.

[0463] (I) [Ab(450) before UV irradiation / Ab(λ before UV irradiation max )]×100%

[0464] (II) [Ab(450) after UV irradiation / Ab(λ before UV irradiation max )]×100%

[0465] The presence or absence of absorption derived from a new coloring structure accompanying the decomposition of the pigment can be confirmed by measuring and calculating by the method described in the Examples.

[0466] In addition, the absorbance at a wavelength of 650 nm (hereinafter, also referred to as "Ab (650)") can be used instead of the absorbance at a wavelength of 450 nm, and the evaluation can be performed based on the value obtained by subtracting the ratio of the following (III) from the ratio of the following (IV). The preferred range of the value obtained by subtracting the ratio of the following (III) from the ratio of the following (IV) has the same meaning as the value obtained by subtracting the ratio of (I) from the ratio of the above formula (II).

[0467] (III) [Ab(650) before UV irradiation / Ab(λ max )]×100%

[0468] (IV) [Ab (650) after UV irradiation / Ab (λ before UV irradiation max )]×100%

[0469] Here, regarding the ultraviolet irradiation test, the description of the ultraviolet irradiation test in the above-mentioned quenching rate can be preferably applied.

[0470] The presence or absence of absorption derived from a new coloring structure accompanying the decomposition of the pigment can be confirmed by measuring and calculating by the method described in the Examples.

[0471] The light absorption filter of the present invention can exhibit excellent decolorization properties when both the decolorization rate and the values ​​for confirming the presence or absence of absorption derived from a new colored structure accompanying the decomposition of the pigment satisfy the preferred ranges.

[0472] The light absorbing part having a light absorbing effect in the optical filter of the present invention preferably satisfies the Ab(λ) related to the light absorbing filter of the present invention. max ) records.

[0473] <Processing of the Light Absorption Filter of the Present Invention>

[0474] The light absorption filter of the present invention can be hydrophilized by any glow discharge treatment, corona discharge treatment or alkali saponification treatment, and corona discharge treatment is preferably used. It is also preferable to apply the method disclosed in Japanese Patent Application Laid-Open No. 6-94915 or Japanese Patent Application Laid-Open No. 6-118232.

[0475] Furthermore, the obtained film may be subjected to a heat treatment step, a superheated water vapor contact step, an organic solvent contact step, etc. as necessary. Furthermore, a surface treatment may be appropriately performed.

[0476] Furthermore, as the adhesive layer, a layer made of an adhesive composition containing a (meth)acrylic resin, a styrene resin, a silicone resin or the like as a base polymer and a crosslinking agent such as an isocyanate compound, an epoxy compound or an aziridine compound added thereto can be used.

[0477] Preferably, the description of the pressure-sensitive adhesive layer in the OLED display device described later can be applied.

[0478] <Gas Barrier Layer>

[0479] The light absorption filter of the present invention may have a gas barrier layer on at least one side. When the light absorption filter of the present invention has a gas barrier layer, the light absorption filter of the present invention can be set to have excellent decolorization even when irradiated with ultraviolet rays at room temperature, and even when containing a compound that generates free radicals at a high concentration, the light absorption filter can suppress the generation of cavities in the filter by ultraviolet irradiation, and the light absorption filter that achieves excellent decolorization and excellent light resistance can be preferably used for the production of the optical filter described later.

[0480] The material forming the gas barrier layer is not particularly limited, and examples thereof include organic materials such as polyvinyl alcohol and polyvinylidene chloride (preferably crystalline resins), organic-inorganic hybrid materials such as sol-gel materials, SiO2, SiO x 、SiON、SiN x The gas barrier layer may be a single layer or a multilayer. In the case of a multilayer, a structure such as an inorganic dielectric multilayer film or a multilayer film in which organic materials and inorganic materials are alternately stacked can be cited.

[0481] The light absorption filter of the present invention has at least a gas barrier layer on the surface in contact with air when the light absorption filter of the present invention is used, so that the reduction in the absorption intensity of the dye in the light absorption filter of the present invention can be suppressed. As long as the gas barrier layer is provided at the interface in contact with air of the light absorption filter of the present invention, the gas barrier layer may be provided only on one side of the light absorption filter of the present invention, or may be provided on both sides.

[0482] In the case where the gas barrier layer contains a crystalline resin, the gas barrier layer contains a crystalline resin, preferably has a thickness of 0.1 μm to 10 μm, and an oxygen permeability of 60 cc / m 2 ·day·atm or less.

[0483] In the gas barrier layer, the “crystalline resin” is a resin having a melting point at which it changes from a crystal phase to a liquid when the temperature is increased, and can impart gas barrier properties with respect to oxygen to the gas barrier layer.

[0484] (Crystalline resin)

[0485] As the crystalline resin contained in the gas barrier layer, any crystalline resin can be used without particular limitation as long as it has gas barrier properties and can provide the gas barrier layer with a desired oxygen permeability.

[0486] Examples of the crystalline resin include polyvinyl alcohol and polyvinylidene chloride. Polyvinyl alcohol is preferred because the crystal portion can effectively suppress gas permeation.

[0487] The polyvinyl alcohol may be modified or unmodified. Examples of the modified polyvinyl alcohol include modified polyvinyl alcohols into which groups such as acetoacetyl groups and carboxyl groups are introduced.

[0488] From the viewpoint of further improving oxygen barrier properties, the saponification degree of the polyvinyl alcohol is preferably 80.0 mol% or more, more preferably 90.0 mol% or more, further preferably 97.0 mol% or more, and particularly preferably 98.0 mol% or more. There is no particular restriction on the upper limit, but in practice it is 99.99 mol% or less. The saponification degree of the polyvinyl alcohol is a value calculated according to the method described in JIS K67261994.

[0489] The gas barrier layer may generally contain any component contained in the gas barrier layer within the range that does not impair the effect of the present invention. For example, in addition to the above-mentioned crystalline resin, it may also contain an amorphous resin material, an organic-inorganic hybrid material such as a sol-gel material, SiO2, SiO x 、SiON、SiN x And inorganic materials such as Al2O3.

[0490] Furthermore, the gas barrier layer may contain solvents such as water and organic solvents generated during the production process within a range not impairing the effects of the present invention.

[0491] The content of the crystalline resin in the gas barrier layer is, for example, preferably 90% by mass or more, more preferably 95% by mass or more in 100% by mass of the total mass of the gas barrier layer. The upper limit is not particularly limited, but may be 100% by mass.

[0492] The oxygen permeability of the gas barrier layer is preferably 60 cc / m 2 ·day·atm or less, more preferably 50cc / m 2 ·day·atm or less, more preferably 30cc / m 2 ·day·atm or less, particularly preferably 10cc / m 2 ·day·atm or less, preferably 5cc / m 2 ·day·atm or less, most preferably 1cc / m 2 ·day·atm or less. The actual lower limit is 0.001cc / m 2 ·day·atm or more, for example, preferably more than 0.05cc / m 2When the oxygen permeability is within the above-described preferred range, the light resistance can be further improved.

[0493] The oxygen permeability of the gas barrier layer is a value measured by a gas permeability test method based on JIS K 7126-22006. As a measuring device, for example, an oxygen permeability tester, OX-TRAN2 / 21 (trade name) manufactured by MOCON can be used. In addition, the measuring conditions are set to a temperature of 25° C. and a relative humidity of 50%.

[0494] The oxygen permeability can be expressed using the SI unit (fm) / (s·Pa). 2 ·day·atm). fm is pronounced as femtometer, and means 1fm=10 -15 m.

[0495] From the viewpoint of further improving light resistance, the thickness of the gas barrier layer is preferably 0.5 μm to 5 μm, more preferably 1.0 μm to 4.0 μm.

[0496] The thickness of the gas barrier layer is measured by taking a cross-sectional photograph using a field emission scanning electron microscope S-4800 (trade name) manufactured by Hitachi High-Technologies Corporation or the like.

[0497] The crystallinity of the crystalline resin contained in the gas barrier layer is preferably 25% or more, more preferably 40% or more, and further preferably 45% or more. The upper limit is not particularly limited, but is practically 55% or less, and preferably 50% or less.

[0498] The crystallinity of the crystalline resin contained in the gas barrier layer is a value measured and calculated by the following method according to the method described in J. Appl. Pol. Sci., 81, 762 (2001).

[0499] The sample peeled from the gas barrier layer was heated at 10°C / min in the range of 20°C to 260°C using a DSC (differential scanning calorimeter) to measure the heat of fusion 1. In addition, as the heat of fusion 2 of complete crystallization, the value described in J. Appl. Pol. Sci., 81, 762 (2001) was used. Using the obtained heat of fusion 1 and heat of fusion 2, the crystallinity was calculated by the following formula.

[0500] [Crystallinity (%)] = ([Heat of Melting 1] / [Heat of Melting 2]) × 100

[0501] In addition, the heat of fusion 1 and the heat of fusion 2 may be in the same unit, and are usually Jg.

[0502] <Method for producing gas barrier layer>

[0503] The method for forming the gas barrier layer is not particularly limited, but according to conventional methods, for example, in the case of organic materials, a method of producing by a casting method such as spin coating and slit coating can be cited. In addition, a method of attaching a commercially available resin gas barrier film or a pre-made resin gas barrier film to the light absorption filter of the present invention can be cited. In addition, in the case of inorganic materials, a plasma CVD (Plasma Enhanced Chemical Vapor Deposition) method, a sputtering method, and a vapor deposition method can be cited.

[0504] When the light absorption filter of the present invention is provided with the above-mentioned gas barrier layer, for example, a method of directly forming the above-mentioned gas barrier layer on the light absorption filter of the present invention produced by the above-mentioned production method can be cited. In this case, it is also preferable to subject the surface of the light absorption filter of the present invention where the gas barrier layer is provided to corona treatment.

[0505] Furthermore, when any of the above optical functional films is provided, it is also preferable to bond them via an adhesive layer. For example, it is also preferable to bond an optical functional film via an adhesive layer after providing a gas barrier layer on the light absorption filter of the present invention.

[0506] <Optically functional film>

[0507] The light absorption filter of the present invention may appropriately include the above-mentioned gas barrier layer or any optically functional film within a range not impairing the effects of the present invention.

[0508] Regarding any of the above optical functional films, there are no particular restrictions on optical properties and materials, but a film containing at least one of cellulose ester resin, acrylic resin, cyclic olefin resin and polyethylene terephthalate resin (or as a main component) can be preferably used. In addition, an optically isotropic film can be used, and an optically anisotropic phase difference film can also be used.

[0509] As for the above-mentioned arbitrary optical functional films, as an optical film containing a cellulose ester resin, for example, FUJITAC TD80UL (manufactured by Fujifilm Corporation) or the like can be used.

[0510] Regarding any of the above-mentioned optical functional films, as an optical film containing an acrylic resin, an optical film containing a (meth) acrylic resin containing a styrene resin described in Japanese Patent No. 4570042, an optical film containing a (meth) acrylic resin having a glutarimide ring structure on the main chain described in Japanese Patent No. 5041532, an optical film containing a (meth) acrylic resin having a lactone ring structure described in Japanese Patent Publication No. 2009-122664, and an optical functional film containing a (meth) acrylic resin having a glutaric anhydride unit described in Japanese Patent Publication No. 2009-139754.

[0511] Furthermore, regarding any of the above-mentioned optical functional films, as an optical film containing a cyclic olefin resin, the cyclic olefin resin film described in paragraph

[0029] and thereafter of Japanese Patent Publication No. 2009-237376, the cyclic olefin resin film containing an additive for lowering Rth described in Japanese Patent Publication No. 4881827, and Japanese Patent Publication No. 2008-063536 can be utilized.

[0512] Furthermore, any of the above optically functional films may contain an ultraviolet absorber. As the ultraviolet absorber, commonly used compounds can be used without particular limitation.

[0513] The content of the ultraviolet absorber in the ultraviolet absorbing layer can be appropriately adjusted depending on the purpose.

[0514] [Filter]

[0515] The optical filter of the present invention is obtained by subjecting the light absorption filter of the present invention to mask exposure by ultraviolet irradiation.

[0516] The optical filter of the present invention includes a light-absorbing portion having a light-absorbing effect and a portion where the light-absorbing property is eliminated (light-absorbing eliminated portion) according to a mask exposure pattern (hereinafter also referred to as a "mask pattern").

[0517] That is, the light absorption filter of the present invention is exposed through a mask by ultraviolet irradiation, whereby the masked portion of the light absorption filter of the present invention is not exposed and exists as a light absorbing portion having a light absorbing effect, while the unmasked portion is exposed and becomes a light absorbing non-existent portion.

[0518] The light-absorbing site can exhibit desired absorbance.

[0519] Regarding the light absorption disappearance site, even when the light absorption filter of the present invention contains a compound that generates radicals at a high concentration, the generation of cavities in the filter due to ultraviolet irradiation can be suppressed, so that cavities are hardly generated in the filter.

[0520] Furthermore, the light absorption filter of the present invention exhibits an excellent decolorization rate for the above-mentioned light absorption disappearance site, and since secondary absorption accompanying dye decomposition hardly occurs, it can exhibit optical characteristics close to colorless.

[0521] <Optical filter manufacturing method>

[0522] The optical filter of the present invention is obtained by irradiating the light absorption filter of the present invention with ultraviolet rays and performing mask exposure.

[0523] The mask pattern can be appropriately adjusted to obtain the optical filter of the present invention having a desired pattern consisting of light-absorbing regions and light-absorbing non-regions.

[0524] The conditions for ultraviolet irradiation can be appropriately adjusted to obtain the optical filter of the present invention having a light absorption disappearance portion. For example, the pressure conditions can be carried out under atmospheric pressure (101.33 kPa), and the temperature conditions can be carried out under mild temperature conditions instead of heating at room temperature (10 to 30° C.), and the lamp output can be set to 10 to 320 W / cm, and as the lamp used, an air-cooled metal halide lamp, an ultra-high pressure mercury lamp, or other mercury lamp can be used.

[0525] Furthermore, the light absorption filter of the present invention can suppress the free radicals generated by ultraviolet irradiation from attacking the polymer constituting the resin and causing the depolymerization of the polymer, so that the ultraviolet irradiation dose can be increased, for example, even when the ultraviolet irradiation dose is set to 0.2 to 10 J / cm 2 In the case of ultraviolet irradiation, it is also possible to suppress the generation of cavities in the filter due to ultraviolet irradiation.

[0526] The optical filter of the present invention may include the optically functional film described in the light absorption filter of the present invention.

[0527] Furthermore, the optical filter of the present invention may have a layer containing an ultraviolet absorber. The ultraviolet absorber is not particularly limited, and commonly used compounds can be used, for example, the ultraviolet absorber in the ultraviolet absorbing layer described below can be cited. The resin constituting the layer containing an ultraviolet absorber is also not particularly limited, and for example, the resin in the ultraviolet absorbing layer described below can be cited.

[0528] The content of the ultraviolet absorber in the layer containing the ultraviolet absorber can be appropriately adjusted depending on the purpose.

[0529] [OLED display device]

[0530] The organic electroluminescent display device of the present invention (referred to as an organic EL (electroluminescence) display device or an OLED (Organic Light Emitting Diode) display device, and in the present invention, also simply referred to as an OLED display device) includes the optical filter of the present invention.

[0531] As the OLED display device of the present invention, as long as it includes the optical filter of the present invention, the structure of a commonly used OLED display device can be used as other structures without particular limitation. As a structural example of the OLED display device of the present invention, there is no particular limitation, but for example, a display device including glass, a layer including a TFT (thin film transistor), an OLED display element, a barrier film, a color filter, glass, an adhesive layer, the optical filter of the present invention, and a surface film in this order from the side opposite to the external light can be cited.

[0532] The above-mentioned OLED display element has a structure in which an anode electrode, a light-emitting layer and a cathode electrode are stacked in sequence. Between the anode electrode and the cathode electrode, in addition to the light-emitting layer, a Hall injection layer, a Hall transport layer, an electron transport layer and an electron injection layer are included. In addition, for example, the records in Japanese Patent Publication No. 2014-132522 can also be referred to.

[0533] Furthermore, as the color filter, in addition to a normal color filter, a color filter on which quantum dots are stacked can be used.

[0534] A resin film can also be used instead of the above-mentioned glass.

[0535] <Adhesive Layer>

[0536] In the OLED display device of the present invention, the surface of the optical filter of the present invention on the external light side can be bonded to an optical functional film having an antireflection layer or the like or a polarizing plate including a polarizer and a polarizing plate protective film via an adhesive layer. Furthermore, the surface of the optical filter of the present invention on the side opposite to the external light is preferably bonded to glass (substrate) via an adhesive layer.

[0537] As the above-mentioned adhesive layer, the description related to the adhesive layer and the formation method in the OLED display device described in

[0239] to

[0290] of International Publication No. 2021 / 132674 can be directly applied.

[0538] In addition, from the viewpoint of the light resistance of the optical filter, the adhesive composition described in International Publication No. 2021 / 132674 preferably contains the aforementioned ultraviolet absorber.

[0539] <Base Material>

[0540] In the OLED display device of the present invention, the optical filter of the present invention may be bonded to the optical functional film via an adhesive layer on the surface located on the external light side. Furthermore, the optical filter of the present invention is preferably bonded to the glass (substrate) via an adhesive layer on the surface located on the side opposite to the external light.

[0541] The method for forming the above-mentioned adhesive layer is not particularly limited, and for example, the following methods can be used: a method in which the adhesive composition is applied to the light absorption filter or optical filter of the present invention using a common device such as a rod coater, and then dried and cured; and a method in which the adhesive composition is first applied to the surface of a removable substrate, dried, and then the adhesive layer is transferred to the light absorption filter of the present invention using a removable substrate, and then matured and cured.

[0542] The releasable substrate is not particularly limited, and any releasable substrate can be used. For example, the support film in the method for producing the light absorption filter of the present invention can be mentioned.

[0543] In addition, the conditions for coating, drying, aging, and curing can also be appropriately adjusted according to conventional methods.

[0544] [Inorganic electroluminescent display device]

[0545] The inorganic electroluminescent display device of the present invention (hereinafter, also referred to as “inorganic EL display device”) includes the optical filter of the present invention.

[0546] As the inorganic EL display device of the present invention, as long as it includes the filter of the present invention, as other structures, the structure of commonly used inorganic EL display devices can be used without particular restrictions. For example, the inorganic EL elements and inorganic electroluminescent display devices described in Japanese Patent Gazette No. 2005-338640 can be preferably used.

[0547] [Liquid crystal display device]

[0548] The liquid crystal display device of the present invention includes the optical filter of the present invention.

[0549] As described later, the optical filter of the present invention may be used as at least one of a polarizing plate protective film and an adhesive layer, and may be included in a backlight unit used in a liquid crystal display device.

[0550] The liquid crystal display device preferably includes the filter of the present invention, a polarizer including a polarizer and a polarizer protective film, an adhesive layer, and a liquid crystal cell, and the polarizer is preferably bonded to the liquid crystal cell via an adhesive layer. In the liquid crystal display device, the filter of the present invention can also serve as a polarizer protective film or an adhesive layer. That is, the liquid crystal display device is divided into the following cases: a polarizer including a polarizer and the filter of the present invention (polarizer protective film), an adhesive layer, and a liquid crystal cell; and a polarizer including a polarizer and a polarizer protective film, an optical filter of the present invention (adhesive layer), and a liquid crystal cell.

[0551] Figure 1 1 is a schematic diagram showing an example of a liquid crystal display device of the present invention. Figure 1 In the embodiment, the liquid crystal display device 10 includes a liquid crystal cell having a liquid crystal layer 5, and a liquid crystal cell upper electrode substrate 3 and a liquid crystal cell lower electrode substrate 6 disposed above and below the liquid crystal cell, and an upper polarizer 1 and a lower polarizer 8 disposed on both sides of the liquid crystal cell. A color filter layer may be stacked on the upper electrode substrate 3 or the lower electrode substrate 6. A backlight is disposed on the back side of the above-mentioned liquid crystal display device 10. As a light source of the backlight, the light source described in the above-mentioned backlight unit can be used.

[0552] The upper polarizing plate 1 and the lower polarizing plate 8 each have a structure in which a polarizer is laminated with two polarizing plate protective films sandwiched therebetween. In the liquid crystal display device 10, it is preferred that at least one polarizing plate is a polarizing plate including the optical filter of the present invention.

[0553] Furthermore, in the liquid crystal display device 10, the liquid crystal cell and the polarizing plates (upper polarizing plate 1 and / or lower polarizing plate 8) may be bonded together via an adhesive layer (not shown). In this case, the optical filter of the present invention may also serve as the adhesive layer.

[0554] The liquid crystal display device 10 includes an image direct view type, an image projection type, or a light modulation type. An active matrix liquid crystal display device using a three-terminal or two-terminal semiconductor element such as TFT (Thin Film Transistor) or MIM (Metal Insulator Metal) is effective for the present invention. Of course, a passive matrix liquid crystal display device represented by a STN (Super Twisted Nematic) mode called time-sharing drive is also effective.

[0555] When the optical filter of the present invention is included in the backlight unit, the polarizer of the liquid crystal display device may be a conventional polarizer (not including the optical filter of the present invention) or a polarizer including the optical filter of the present invention. Furthermore, the adhesive layer may be a conventional adhesive layer (not the optical filter of the present invention) or an adhesive layer based on the optical filter of the present invention.

[0556] In addition to preferably using the optical filter of the present invention, an IPS (In Plane Switching) mode liquid crystal display device described in paragraphs 0128 to 0136 of Japanese Patent Application Laid-Open No. 2010-102296 is also preferably used as the liquid crystal display device of the present invention.

[0557] <Polarizing Plate>

[0558] The polarizing plate used in the present invention includes a polarizer and at least one polarizing plate protective film.

[0559] The polarizer used in the present invention preferably has a polarizer and polarizer protective films located on both sides of the polarizer, and preferably includes the optical filter of the present invention as the polarizer protective film on at least one side. A conventional polarizer protective film may be provided on the side of the polarizer opposite to the side having the optical filter of the present invention (polarizer protective film of the present invention).

[0560] The film thickness of the polarizer protective film is preferably 5 to 120 μm, more preferably 10 to 100 μm. The film is not easy to produce uneven display after high temperature and high humidity for a long time when assembled into a liquid crystal display device, so it is preferred. On the other hand, if it is too thin, it is difficult to stably transport when manufacturing the film and making the polarizer. In the case where the filter of the present invention also serves as a polarizer protective film, the thickness of the filter preferably satisfies the above range.

[0561] As the polarizer used in the present invention, the descriptions related to the performance, shape, structure, polarizer, lamination method of polarizer and polarizer protective film, functionalization of polarizer, etc. described in

[0299] to

[0309] of International Publication No. 2021 / 132674 can be directly applied.

[0562] <Adhesive Layer>

[0563] In the liquid crystal display device of the present invention, the polarizing plate is preferably bonded to the liquid crystal cell via an adhesive layer. The optical filter of the present invention may also serve as the adhesive layer. When the optical filter of the present invention does not also serve as the adhesive layer, a common adhesive layer may be used as the adhesive layer.

[0564] The pressure-sensitive adhesive layer is not particularly limited as long as it can bond the polarizing plate and the liquid crystal cell together, but for example, acrylic, urethane, polyisobutylene, and the like are preferred.

[0565] When the optical filter of the present invention also serves as an adhesive layer, the adhesive layer contains the above-mentioned dye and the above-mentioned base polymer, and further contains a cross-linking agent, a coupling agent, etc. to impart adhesiveness.

[0566] When the optical filter of the present invention also serves as a pressure-sensitive adhesive layer, the pressure-sensitive adhesive layer preferably contains 90 to 100% by mass of the base polymer, and more preferably 95 to 100% by mass. The content of the pigment is as described above.

[0567] The thickness of the pressure-sensitive adhesive layer is not particularly limited, but is, for example, preferably 1 to 50 μm, more preferably 3 to 30 μm.

[0568] <Liquid Crystal Unit>

[0569] The liquid crystal cell is not particularly limited, and a common liquid crystal cell can be used.

[0570] <Ultraviolet absorbing layer>

[0571] The organic electroluminescent display device, inorganic electroluminescent display device or liquid crystal display device including the optical filter of the present invention preferably has a layer (hereinafter also referred to as "ultraviolet absorption layer") that blocks light absorption (ultraviolet absorption) of the compound that generates free radicals by ultraviolet irradiation on the viewer side relative to the optical filter of the present invention. By providing the above-mentioned ultraviolet absorption layer, fading of the optical filter of the present invention caused by external light can be prevented.

[0572] Hereinafter, the ultraviolet absorbing layer used in the present invention will be described.

[0573] (Ultraviolet light absorber)

[0574] The ultraviolet absorbing layer generally contains a resin and an ultraviolet absorber.

[0575] Specific examples of the ultraviolet absorber preferably used in the present invention include hindered phenol compounds, benzophenone compounds such as hydroxybenzophenone compounds, benzotriazole compounds, salicylate compounds, cyanoacrylate compounds, and nickel complex salt compounds.

[0576] Examples of hindered phenol compounds include 2,6-di-tert-butyl-p-cresol, pentaerythritol ester-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis(3,5-di-tert-butyl-4-hydroxy-oxycinnamic acid amide), 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, and tris-(3,5-di-tert-butyl-4-hydroxybenzyl)-isocyanurate.

[0577] Examples of benzotriazole compounds include 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2,2-methylenebis(4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazol-2-yl)phenol), 2,4-bis(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butylanilino)-1,3,5-triazine, triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis( 3,5-di-tert-butyl-4-hydroxy-oxidized cinnamic acid), 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-amylphenyl)-5-chlorobenzotriazole, 2,6-di-tert-butyl-p-cresol, pentaerythritol ester-tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) and the like.

[0578] The amount of these ultraviolet absorbers added is preferably 0.1 to 30.0 parts by mass based on 100 parts by mass of the resin.

[0579] Furthermore, from the viewpoint of further improving the light resistance of the optical filter of the present invention, the compound (1) represented by the following formula (1) is particularly preferably used as an ultraviolet absorber.

[0580] <<Compound represented by formula (1) (Compound (1))>>

[0581] The resin composition for forming the ultraviolet absorbing layer preferably contains a compound represented by formula (1) (hereinafter, also referred to as compound (1)).

[0582] [Chemical formula 14]

[0583]

[0584] In formula (1), R 1 and R 2 Each independently represents an alkyl group, an aryl group or a heterocyclic group,

[0585] R 3 and R 6 each independently represents an alkoxy group, an acyloxy group, a carbamoyloxy group or an alkoxycarbonyloxy group,

[0586] R 4 represents an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyloxy group, an alkylamino group, an anilino group, an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkylthio group or an arylthio group,

[0587] R 5It represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyloxy group, an alkylamino group, an anilino group, an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkylthio group or an arylthio group.

[0588] R 1 With R 2 Can bond to each other to form a ring, R 3 With R 4 Can bond to each other to form a ring, R 4 With R 5 Can bond to each other to form a ring, R 5 With R 6 They may be bonded to each other to form a ring. The formed ring may be aromatic or may not show aromaticity.

[0589] However, in R 3 and R 6 When each independently represents an acyloxy group or a carbamoyloxy group, R 4 and R 5 At least one of them is an aryl group, an alkoxy group, an aryloxy group, an acyloxy group, an alkylamino group, an anilino group, an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkylthio group or an arylthio group.

[0590] In formula (1), R 1 and R 2 Each independently represents an alkyl group, an aryl group or a heterocyclic group, and is preferably an alkyl group or an aryl group. 1 and R 2 Furthermore, from the viewpoint of the absorption of ultraviolet light near a wavelength of 400 nm, it is preferred that R 1 and R 2 are each independently an aryl group.

[0591] R 1 and R 2 The number of carbon atoms of the alkyl group represented is preferably 1 to 30, more preferably 1 to 20, further preferably 1 to 15, particularly preferably 1 to 10, and most preferably 1 to 8. The alkyl group may be any of linear, branched, and cyclic, preferably linear or branched. The alkyl group may have a substituent. As the substituent, the groups described in the substituent T described later may be mentioned, for example, preferably a halogen atom, an alkoxy group, an alkenyl group, and an aryl group may be mentioned.

[0592] R 1 and R 2The number of carbon atoms of the aryl group represented is preferably 6 to 40, more preferably 6 to 30, further preferably 6 to 20, particularly preferably 6 to 15, and most preferably 6 to 12. As the aryl group, phenyl or naphthyl is preferred, and phenyl is more preferred. The aryl group may have a substituent. As the substituent, the groups described in the substituent T described later can be mentioned, for example, an alkoxy group can be preferably mentioned.

[0593] R 1 and R 2 The heterocyclic ring in the represented heterocyclic group preferably includes a 5-membered or 6-membered saturated or unsaturated heterocyclic ring. The heterocyclic ring may be condensed with an aliphatic ring, an aromatic ring or other heterocyclic ring. As heteroatoms constituting the heterocyclic ring, B, N, O, S, Se and Te can be mentioned, preferably at least one of N, O and S. The heterocyclic ring preferably has a free atomic valence (monovalent) on the carbon atom constituting the ring (the heterocyclic group is bonded to the carbon atom). The preferred number of carbon atoms in the heterocyclic group is 1 to 40, more preferably 1 to 30, and further preferably 1 to 20. Examples of saturated heterocyclic rings in heterocyclic groups include pyrrolidine rings, morpholine rings, 2-borano-1,3-dioxolane rings and 1,3-thiazolidine rings. Examples of unsaturated heterocyclic rings in heterocyclic groups include imidazole rings, thiazole rings, benzothiazole rings, benzoxazole rings, benzotriazole rings, benzoselenazole rings, pyridine rings, pyrimidine rings and quinoline rings. The heterocyclic group may have a substituent. Examples of the substituent include the groups described in the substituent T described later.

[0594] R 1 With R 2 They may be bonded to each other to form a ring. 1 With R 2 The ring formed by bonding is preferably a 5-membered ring or a 6-membered ring, and preferably does not exhibit aromaticity. 1 With R 2 The ring formed by bonding may have a substituent. Examples of the substituent include the groups described in the substituent T described later.

[0595] In formula (1), R 3 and R 6 Each independently represents an alkoxy group, an acyloxy group, a carbamoyloxy group or an alkoxycarbonyloxy group, preferably an alkoxy group or an acyloxy group, and R is more preferably R 1 or R 2 because it can suppress coloration and more easily improve the absorption of ultraviolet light near a wavelength of 400 nm. 3 and R 6 At least one of them is an alkoxy group. According to the research of the present inventors, it was found that the higher the electron-donating ability (electron-donating property) of the substituent on the benzene ring of benzodithiol, the easier it is to shift the maximum absorption wavelength of the compound to the long wavelength side. Since the alkoxy group is a substituent with higher electron-donating ability, it is speculated that it is more likely to shift the maximum absorption wavelength of the compound to the long wavelength side. In particular, R 3 and R6 Both are alkoxy groups.

[0596] R 3 and R 6 The number of carbon atoms of the alkoxy group represented is preferably 1 to 30, more preferably 1 to 20, further preferably 1 to 15, particularly preferably 1 to 10, and most preferably 1 to 8. The alkoxy group may be either a straight chain or a branched chain. The alkoxy group may have a substituent. As the substituent, the groups described in the substituent T described later can be cited.

[0597] R 3 and R 6 The number of carbon atoms of the acyloxy group represented is preferably 2 to 30, more preferably 2 to 20, further preferably 2 to 15, and particularly preferably 2 to 10. The acyloxy group may have a substituent. Examples of the substituent include the groups described in the substituent T described below.

[0598] R 3 and R 6 The number of carbon atoms of the represented carbamoyloxy group is preferably 2 to 30, more preferably 2 to 20, further preferably 2 to 15, particularly preferably 2 to 10, and most preferably 2 to 8. The carbamoyloxy group may be either a straight chain or a branched chain. The carbamoyloxy group may have a substituent. As the substituent, the groups described in the substituent T described later can be mentioned.

[0599] R 3 and R 6 The number of carbon atoms of the alkoxycarbonyloxy group represented is preferably 2 to 30, more preferably 2 to 20, further preferably 2 to 15, particularly preferably 2 to 10, and most preferably 2 to 8. The alkoxycarbonyloxy group may be either a straight chain or a branched chain. The alkoxycarbonyloxy group may have a substituent. As the substituent, the groups described in the substituent T described later can be mentioned.

[0600] In formula (1), R 4 represents an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyloxy group, an alkylamino group, an anilino group, an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkylthio group or an arylthio group, and R 5 It represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyloxy group, an alkylamino group, an anilino group, an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkylthio group or an arylthio group.

[0601] R 4 and R 5The number of carbon atoms of the alkyl group represented is preferably 1 to 30, more preferably 1 to 20, further preferably 1 to 15, particularly preferably 1 to 10, and most preferably 1 to 8. The alkyl group may be any of a straight chain, a branched chain, and a cyclic chain, and is preferably a straight chain or a branched chain. The alkyl group may have a substituent. As the substituent, the groups described in the substituent T described later can be cited, and for example, an alkenyl group can be preferably cited.

[0602] R 4 and R 5 The number of carbon atoms of the aryl group represented is preferably 6 to 40, more preferably 6 to 30, further preferably 6 to 20, particularly preferably 6 to 15, and most preferably 6 to 12. The aryl group is preferably phenyl or naphthyl, more preferably phenyl. The aryl group may have a substituent. As the substituent, the groups described in the substituent T described later can be cited.

[0603] R 4 and R 5 The number of carbon atoms of the alkoxy group represented is preferably 1 to 30, more preferably 1 to 20, further preferably 1 to 15, particularly preferably 1 to 10, and most preferably 1 to 8. The alkoxy group may be either a straight chain or a branched chain. The alkoxy group may have a substituent. As the substituent, the groups described in the substituent T described later can be cited.

[0604] R 4 and R 5 The number of carbon atoms of the aryloxy group represented is preferably 6 to 40, more preferably 6 to 30, further preferably 6 to 20, particularly preferably 6 to 15, and most preferably 6 to 12. The aryloxy group may have a substituent. Examples of the substituent include the groups explained in the substituent T described below.

[0605] R 4 and R 5 The number of carbon atoms of the acyloxy group represented is preferably 2 to 30, more preferably 2 to 20, further preferably 2 to 15, and particularly preferably 2 to 10. The acyloxy group may have a substituent. Examples of the substituent include the groups described in the substituent T described below.

[0606] R 4 and R 5 The number of carbon atoms of the alkylamino group represented is preferably 1 to 30, more preferably 1 to 20, further preferably 1 to 15, particularly preferably 1 to 10, and most preferably 1 to 8. The alkyl portion in the alkylamino group may be either a straight chain or a branched chain. The alkylamino group may have a substituent. As the substituent, the groups described in the substituent T described later can be cited.

[0607] R 4 and R 5The number of carbon atoms of the anilino group represented is preferably 6 to 40, more preferably 6 to 30, further preferably 6 to 20, particularly preferably 6 to 15, and most preferably 6 to 12. The anilino group may have a substituent. Examples of the substituent include the groups described in the substituent T described later, and preferably an alkyl group is used.

[0608] R 4 and R 5 The number of carbon atoms of the acylamino group is preferably 2 to 30, more preferably 2 to 20, further preferably 2 to 15, and particularly preferably 2 to 10. The acylamino group may have a substituent. Examples of the substituent include the groups described in the substituent T described below.

[0609] R 4 and R 5 The number of carbon atoms in the alkylsulfonylamino group is preferably 2 to 30, more preferably 2 to 20, further preferably 2 to 15, and particularly preferably 2 to 10. The alkylsulfonylamino group may have a substituent. Examples of the substituent include the groups described in the substituent T described below.

[0610] R 4 and R 5 The number of carbon atoms of the arylsulfonylamino group is preferably 6 to 40, more preferably 6 to 30, further preferably 6 to 20, particularly preferably 6 to 15, and most preferably 6 to 12. The arylsulfonylamino group may have a substituent. Examples of the substituent include the groups described in the substituent T described below.

[0611] R 4 and R 5 The number of carbon atoms of the alkylthio group represented is preferably 1 to 30, more preferably 1 to 20, further preferably 1 to 15, particularly preferably 1 to 10, and most preferably 1 to 8. The alkylthio group may be either linear or branched. The alkylthio group may have a substituent. Examples of the substituent include the groups described in the substituent T described later.

[0612] R 4 and R 5 The number of carbon atoms of the arylthio group represented is preferably 6 to 40, more preferably 6 to 30, further preferably 6 to 20, particularly preferably 6 to 15, and most preferably 6 to 12. The arylthio group may have a substituent. Examples of the substituent include the groups explained in the substituent T described below.

[0613] In formula (1), R 3 With R 4 Can bond to each other to form a ring, R 4 With R 5 Can bond to each other to form a ring, R 5 With R 6The ring formed by these groups bonding to each other is preferably a 5-membered ring or a 6-membered ring. The ring formed by these groups bonding to each other may have a substituent. As a substituent, the group described in the substituent T described later can be cited.

[0614] From the perspective of suppressing coloration and making it easier to improve the absorption of ultraviolet rays near a wavelength of 400 nm, R 4 is an alkyl group, an aryl group, an alkoxy group or an aryloxy group, R 5 is a hydrogen atom, an alkyl group, an aryl group, an alkoxy group or an aryloxy group, and more preferably R 4 is an alkyl group or an alkoxy group, R 5 is a hydrogen atom, an alkyl group or an alkoxy group.

[0615] Furthermore, from the viewpoint of easy synthesis, R 4 is an alkyl group, an aryl group, an alkoxy group or an aryloxy group, R 5 is a hydrogen atom, more preferably R 4 is an alkyl group or an alkoxy group, R 5 A hydrogen atom.

[0616] Furthermore, from the viewpoint of increasing the wavelength of the absorption spectrum, it is preferred that R 4 and R 5 are independently alkyl, aryl, alkoxy or aryloxy, more preferably alkyl or alkoxy, and further preferably R 4 and R 5 Both are alkyl or R 4 and R 5 Both are alkoxy groups.

[0617] Also, R is preferred 4 With R 5 They are bonded to each other to form a ring.

[0618] The compound represented by the above formula (1) (compound (1)) is preferably a compound represented by the following formula (1a).

[0619] [Chemical formula 15]

[0620]

[0621] In formula (1a), R 1a and R 2a Each independently represents an alkyl group,

[0622] R 3a and R 6a each independently represents an alkoxy group or an acyloxy group,

[0623] R 4a represents an alkyl group or an alkoxy group,

[0624] R5a represents a hydrogen atom, an alkyl group or an alkoxy group.

[0625] R 1a With R 2a Can bond to each other to form a ring, R 3a With R 4a Can bond to each other to form a ring, R 4a With R 5a Can bond to each other to form a ring, R 5a With R 6a They may be bonded to each other to form a ring.

[0626] However, in R 3a and R 6a In the case of an acyloxy group, R 4a and R 5a At least one of them is an alkoxy group.

[0627] R 1a and R 2a The number of carbon atoms of the alkyl group represented is preferably 1 to 30, more preferably 1 to 20, further preferably 1 to 15, particularly preferably 1 to 10, and most preferably 1 to 8. The alkyl group may be any of linear, branched, and cyclic, preferably linear or branched. The alkyl group may have a substituent. As the substituent, the groups described in the substituent T described later can be cited.

[0628] R 1a With R 2a They may be bonded to each other to form a ring. 1a With R 2a The ring formed by bonding is preferably a 5-membered ring or a 6-membered ring. 1a With R 2a The ring formed by bonding may have a substituent. Examples of the substituent include the groups described in the substituent T described later.

[0629] In formula (1a), R 3a and R 6a Each independently represents an alkoxy group or an acyloxy group. From the viewpoint of suppressing coloration and making it easier to improve the absorption of ultraviolet rays near a wavelength of 400 nm, R 3a and R 6a At least one of them is an alkoxy group, and more preferably R 3a and R 6a Both are alkoxy groups.

[0630] R 3a and R 6aThe number of carbon atoms of the alkoxy group represented is preferably 1 to 30, more preferably 1 to 20, further preferably 1 to 15, particularly preferably 1 to 10, and most preferably 1 to 8. The alkoxy group may be either a straight chain or a branched chain. The alkoxy group may have a substituent. As the substituent, the groups described in the substituent T described later can be cited.

[0631] R 3a and R 6a The number of carbon atoms of the acyloxy group represented is preferably 2 to 30, more preferably 2 to 20, further preferably 2 to 15, and particularly preferably 2 to 10. The acyloxy group may have a substituent. Examples of the substituent include the groups described in the substituent T described below.

[0632] In formula (1a), R 4a represents an alkyl group or an alkoxy group, R 5a represents a hydrogen atom, an alkyl group or an alkoxy group.

[0633] R 4a and R 5a The number of carbon atoms of the alkyl group represented is preferably 1 to 30, more preferably 1 to 20, further preferably 1 to 15, particularly preferably 1 to 10, and most preferably 1 to 8. The alkyl group may be any of linear, branched, and cyclic, preferably linear or branched. The alkyl group may have a substituent. As the substituent, the groups described in the substituent T described later can be cited.

[0634] R 4a and R 5a The number of carbon atoms of the alkoxy group represented is preferably 1 to 30, more preferably 1 to 20, further preferably 1 to 15, particularly preferably 1 to 10, and most preferably 1 to 8. The alkoxy group may be either a straight chain or a branched chain. The alkoxy group may have a substituent. As the substituent, the groups described in the substituent T described later can be cited.

[0635] In formula (1a), R 3a With R 4a Can bond to each other to form a ring, R 4a With R 5a Can bond to each other to form a ring, R 5a With R 6a The ring formed by these groups bonding to each other is preferably a 5-membered ring or a 6-membered ring. The ring formed by these groups bonding to each other may have a substituent. As a substituent, the group described in the substituent T described later can be cited.

[0636] (Substituent T)

[0637] As the substituent T, the following groups can be mentioned.

[0638] Halogen atoms (e.g., chlorine atoms, bromine atoms, iodine atoms);

[0639] Alkyl [straight-chain, branched or cyclic alkyl. Specifically, it includes straight-chain or branched alkyl (preferably straight-chain or branched alkyl having 1 to 30 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-octyl, eicosyl, 2-chloroethyl, 2-cyanoethyl, 2-ethylhexyl), cycloalkyl (preferably cycloalkyl having 3 to 30 carbon atoms, such as cyclohexyl, cyclopentyl, 4-n-dodecylcyclohexyl), bicycloalkyl (preferably bicycloalkyl having 5 to 30 carbon atoms, i.e., a monovalent group obtained by removing one hydrogen atom from a bicycloalkane having 5 to 30 carbon atoms. For example, bicyclo[1,2,2]heptane-2-yl, bicyclo[2,2,2]octane-3-yl), and further includes a monovalent group obtained by removing one hydrogen atom from a tricycloalkane structure having multiple ring structures. The alkyl group in the substituent described below (such as an alkyl group of an alkylthio group) also represents an alkyl group of this concept. ];

[0640] Alkenyl [straight-chain, branched or cyclic alkenyl. Specifically, it includes straight-chain or branched alkenyl (preferably straight-chain or branched alkenyl having 2 to 30 carbon atoms, for example, vinyl, allyl, isoprenyl, geranyl, oleyl), cycloalkenyl (preferably cycloalkenyl having 3 to 30 carbon atoms. That is, a monovalent group obtained by removing one hydrogen atom of a cycloolefin having 3 to 30 carbon atoms. For example, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl), bicycloalkenyl (preferably bicycloalkenyl having 5 to 30 carbon atoms, that is, a monovalent group obtained by removing one hydrogen atom of a bicycloolefin having one double bond. For example, bicyclo[2,2,1]hept-2-en-1-yl, bicyclo[2,2,2]oct-2-en-4-yl). ];

[0641] Alkynyl (preferably a straight-chain or branched alkynyl group having 2 to 30 carbon atoms. For example, ethynyl and propargyl);

[0642] Aryl group (preferably an aryl group having 6 to 30 carbon atoms. For example, phenyl, p-tolyl, naphthyl, m-chlorophenyl, o-hexadecanoylaminophenyl);

[0643] Heterocyclic group (preferably a monovalent group obtained by removing one hydrogen atom from a 5-membered or 6-membered aromatic or non-aromatic heterocyclic compound, more preferably a 5-membered or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms. For example, 2-furanyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl);

[0644] Cyano;

[0645] Hydroxyl;

[0646] Nitro;

[0647] carboxyl;

[0648] Alkoxy (preferably a linear or branched alkoxy group having 1 to 30 carbon atoms. For example, methoxy, ethoxy, isopropoxy, tert-butoxy, n-octyloxy, 2-methoxyethoxy);

[0649] An aryloxy group (preferably an aryloxy group having 6 to 30 carbon atoms. For example, a phenoxy group, a 2-methylphenoxy group, a 4-tert-butylphenoxy group, a 3-nitrophenoxy group, and a 2-tetradecanoylaminophenoxy group);

[0650] A heterocyclic oxy group (preferably a heterocyclic oxy group having 2 to 30 carbon atoms, for example, 1-phenyltetrazol-5-oxy group and 2-tetrahydropyranyloxy group);

[0651] acyloxy (preferably formyloxy, alkylcarbonyloxy having 2 to 30 carbon atoms, arylcarbonyloxy having 6 to 30 carbon atoms. For example, formyloxy, acetyloxy, pivaloyloxy, stearoyloxy, benzoyloxy, p-methoxyphenylcarbonyloxy);

[0652] Carbamoyloxy (preferably a carbamoyloxy group having 1 to 30 carbon atoms, for example, N,N-dimethylcarbamoyloxy, N,N-diethylcarbamoyloxy, morpholinylcarbonyloxy, N,N-di-n-octylaminocarbonyloxy, N-n-octylcarbamoyloxy);

[0653] An alkoxycarbonyloxy group (preferably an alkoxycarbonyloxy group having 2 to 30 carbon atoms, for example, a methoxycarbonyloxy group, an ethoxycarbonyloxy group, a tert-butoxycarbonyloxy group, and an n-octylcarbonyloxy group);

[0654] An aryloxycarbonyloxy group (preferably an aryloxycarbonyloxy group having 7 to 30 carbon atoms, for example, a phenoxycarbonyloxy group, a p-methoxyphenoxycarbonyloxy group, and a p-n-hexadecyloxyphenoxycarbonyloxy group);

[0655] An amino group (preferably an unsubstituted amino group (-NH2), an alkylamino group having 1 to 30 carbon atoms, or an anilino group having 6 to 30 carbon atoms. For example, an unsubstituted amino group (-NH2), a methylamino group, a dimethylamino group, an anilino group, an N-methyl-anilino group, or a diphenylamino group);

[0656] Acylamino (preferably formylamino, alkylcarbonylamino having 2 to 30 carbon atoms, arylcarbonylamino having 6 to 30 carbon atoms. For example, formylamino, acetylamino, pivaloylamino, lauroylamino, benzylamino, 3,4,5-tri-n-octyloxyphenylcarbonylamino);

[0657] An aminocarbonylamino group (preferably an aminocarbonylamino group having 1 to 30 carbon atoms, for example, carbamoylamino, N,N-dimethylaminocarbonylamino, N,N-diethylaminocarbonylamino, and morpholinecarbonylamino);

[0658] an alkoxycarbonylamino group (preferably an alkoxycarbonylamino group having 2 to 30 carbon atoms, for example, a methoxycarbonylamino group, an ethoxycarbonylamino group, a tert-butoxycarbonylamino group, an n-octadecyloxycarbonylamino group, and an N-methyl-methoxycarbonylamino group);

[0659] An aryloxycarbonylamino group (preferably an aryloxycarbonylamino group having 7 to 30 carbon atoms, for example, a phenoxycarbonylamino group, a p-chlorophenoxycarbonylamino group, and a m-n-octyloxyphenoxycarbonylamino group);

[0660] A sulfamoylamino group (preferably a sulfamoylamino group having 0 to 30 carbon atoms. For example, a sulfamoylamino group, an N,N-dimethylaminosulfonylamino group, and an N-n-octylaminosulfonylamino group);

[0661] an alkylsulfonylamino group or an arylsulfonylamino group (preferably an alkylsulfonylamino group having 1 to 30 carbon atoms or an arylsulfonylamino group having 6 to 30 carbon atoms. For example, methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino, 2,3,5-trichlorophenylsulfonylamino, and p-tolylsulfonylamino);

[0662] thiol;

[0663] an alkylthio group (preferably an alkylthio group having 1 to 30 carbon atoms, for example, methylthio, ethylthio, and n-hexadecylthio);

[0664] an arylthio group (preferably an arylthio group having 6 to 30 carbon atoms, for example, a phenylthio group, a p-chlorophenylthio group, and a m-methoxyphenylthio group);

[0665] a heterocyclic thio group (preferably a heterocyclic thio group having 2 to 30 carbon atoms, for example, 2-benzothiazolylthio and 1-phenyltetrazolyl-5-ylthio);

[0666] a sulfamoyl group (preferably a sulfamoyl group having 0 to 30 carbon atoms, for example, N-ethylsulfamoyl, N-(3-dodecyloxypropyl)sulfamoyl, N,N-dimethylsulfamoyl, N-acetylsulfamoyl, N-benzoylsulfamoyl, N-(N'-phenylcarbamoyl)sulfamoyl);

[0667] Sulfonic acid;

[0668] an alkylsulfinyl group or an arylsulfinyl group (preferably an alkylsulfinyl group having 1 to 30 carbon atoms or an arylsulfinyl group having 6 to 30 carbon atoms. For example, methylsulfinyl, ethylsulfinyl, phenylsulfinyl, p-tolylsulfinyl);

[0669] an alkylsulfonyl group or an arylsulfonyl group (preferably an alkylsulfonyl group having 1 to 30 carbon atoms or an arylsulfonyl group having 6 to 30 carbon atoms. For example, methylsulfonyl, ethylsulfonyl, phenylsulfonyl, p-tolylsulfonyl);

[0670] Acyl group (preferably formyl, alkylcarbonyl having 2 to 30 carbon atoms, arylcarbonyl having 7 to 30 carbon atoms, heterocyclic carbonyl having 4 to 30 carbon atoms and bonded to a carbonyl group via a carbon atom. For example, acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, p-octyloxyphenylcarbonyl, 2-pyridylcarbonyl, 2-furylcarbonyl);

[0671] an aryloxycarbonyl group (preferably an aryloxycarbonyl group having 7 to 30 carbon atoms, for example, a phenoxycarbonyl group, an o-chlorophenoxycarbonyl group, a m-nitrophenoxycarbonyl group, and a p-tert-butylphenoxycarbonyl group);

[0672] an alkoxycarbonyl group (preferably an alkoxycarbonyl group having 2 to 30 carbon atoms, for example, a methoxycarbonyl group, an ethoxycarbonyl group, a tert-butoxycarbonyl group, and an n-octadecyloxycarbonyl group);

[0673] Carbamoyl group (preferably a carbamoyl group having 1 to 30 carbon atoms. For example, carbamoyl group, N-methylcarbamoyl group, N,N-dimethylcarbamoyl group, N,N-di-n-octylcarbamoyl group, N-(methylsulfonyl)carbamoyl group);

[0674] an arylazo group or a heterocyclic azo group (preferably an arylazo group having 6 to 30 carbon atoms or a heterocyclic azo group having 3 to 30 carbon atoms. For example, a phenylazo group, a p-chlorophenylazo group, and a 5-ethylthio-1,3,4-thiadiazol-2-ylazo group);

[0675] An imide group (preferably an N-succinimidyl group or an N-phthalimide group);

[0676] A phosphino group (preferably a phosphino group having 2 to 30 carbon atoms, for example, a dimethylphosphino group, a diphenylphosphino group, a methylphenoxyphosphino group);

[0677] A phosphinyl group (preferably a phosphinyl group having 2 to 30 carbon atoms. For example, a phosphinyl group, a dioctyloxyphosphinyl group, a diethoxyphosphinyl group);

[0678] A phosphinyloxy group (preferably a phosphinyloxy group having 2 to 30 carbon atoms. For example, a diphenoxyphosphinyloxy group and a dioctyloxyphosphinyloxy group);

[0679] A phosphinylamino group (preferably a phosphinylamino group having 2 to 30 carbon atoms, for example, a dimethoxyphosphinylamino group and a dimethylaminophosphinylamino group);

[0680] In the above-mentioned groups, one or more hydrogen atoms may be substituted by the above-mentioned substituent T. Examples of such substituents include alkylcarbonylaminosulfonyl, arylcarbonylaminosulfonyl, alkylsulfonylaminocarbonyl, and arylsulfonylaminocarbonyl. Specific examples include methylsulfonylaminocarbonyl, p-tolylsulfonylaminocarbonyl, acetylaminosulfonyl, and benzoylaminosulfonyl.

[0681] As specific examples of compound (1), the following compounds can be cited. However, the present invention is not limited to these compounds. In the structural formula shown below, Me is a methyl group, Et is an ethyl group, Bu is a butyl group, tBu is a tert-butyl group, Pr is a propyl group, and Ph is a phenyl group.

[0682] [Chemical formula 16]

[0683]

[0684] [Chemical formula 17]

[0685]

[0686] [Chemical formula 18]

[0687]

[0688] The compound (1) can be preferably used as an ultraviolet absorber. The maximum absorption wavelength of the compound (1) preferably exists in the wavelength range of 370 to 420 nm, and more preferably exists in the wavelength range of 380 to 400 nm.

[0689] The molar absorption coefficient ε of compound (1) at a wavelength of 405 nm was calculated according to the following formula: 405 It is preferably 500 or more, more preferably 1000 or more, further preferably 2000 or more, and particularly preferably 3000 or more.

[0690] ε 405 =ε max ×(A 405 / A max )

[0691] ε 405 is the molar absorption coefficient of compound (1) at a wavelength of 405 nm, ε max is the molar absorption coefficient of compound (1) at the maximum absorption wavelength, A 405 is the absorbance of compound (1) at a wavelength of 405 nm, A max is the absorbance of compound (1) at the maximum absorption wavelength. In addition, the unit of the above molar absorption coefficient is L / (mol·cm). 405 and A maxThe absorbance is taken as the absorbance in the spectroscopic absorption spectrum of the compound (1) measured in ethyl acetate.

[0692] In the optical absorption spectrum of compound (1) measured in ethyl acetate, the absorbance A at a wavelength of 405 nm is 405 and the absorbance A at a wavelength of 430 nm 430 The ratio (A 430 / A 405 ) is preferably less than 0.13, more preferably less than 0.10. The lower limit of the above ratio is not particularly limited, and can be set to be greater than 0. The compound having such an absorbance ratio has excellent light transmittance in the visible region near the ultraviolet region, regardless of the high absorption near the wavelength of 405nm, and therefore has excellent absorptivity of ultraviolet rays on the longer wavelength side and excellent visible transparency. In addition, when the absorption region of ultraviolet rays in the compound is shifted to the longer wavelength side, the light transmittance in the visible region (especially, the light transmittance in the visible region near the ultraviolet region) also tends to decrease, but according to the above compound (1), it is possible to exert an excellent effect of maintaining the light transmittance in the visible region at a high level and improving the absorptivity of ultraviolet rays on the longer wavelength side.

[0693] The compound (1) can be synthesized by referring to the synthesis methods described in JP-A-2016-081035, Japanese Patent No. 5376885, and the like.

[0694] The content of compound (1) in the total solid content of the resin composition for forming the ultraviolet absorbing layer is preferably 0.01 to 50% by mass. The lower limit is more preferably 0.05% by mass or more, and further preferably 0.10% by mass or more. The upper limit is more preferably 40% by mass or less, further preferably 30% by mass or less, and particularly preferably 20% by mass or less.

[0695] The content of compound (1) is preferably 0.01 to 50 parts by mass relative to 100 parts by mass of the resin. The lower limit is more preferably 0.05 parts by mass or more, and further preferably 0.10 parts by mass or more. The upper limit is more preferably 40 parts by mass or less, further preferably 30 parts by mass or less, and particularly preferably 20 parts by mass or less.

[0696] The resin composition may contain only one compound (1) or two or more compounds (1). When containing two or more compounds (1), the total amount thereof is preferably within the above range.

[0697] (resin)

[0698] As the resin used in the ultraviolet absorbing layer, known resins can be used without particular limitation unless it violates the gist of the present invention. Examples of the resin include cellulose acylate resins, acrylic resins, cycloolefin resins, polyester resins, and epoxy resins.

[0699] (Setting position of ultraviolet absorbing layer)

[0700] The configuration of the ultraviolet absorbing layer is not particularly limited as long as it is on the viewer side relative to the optical filter of the present invention, and can be provided at any position. For example, an ultraviolet absorber can be added to a protective film, an anti-reflection film, or other components of the polarizer to give it the function of an ultraviolet absorbing layer. Furthermore, an ultraviolet absorber can be added to the aforementioned adhesive layer.

[0701] Example

[0702] Below, the present invention is further described in detail according to embodiment. About the material, dosage, ratio, processing content, processing sequence etc. shown in the following embodiment, as long as do not depart from the gist of the present invention, then can be appropriately changed.Therefore, the scope of the present invention is not limited to the embodiment shown below.

[0703] In the following examples, "parts" and "%" representing the composition are by mass unless otherwise specified. Room temperature refers to "25°C". The abbreviations of solvents, compounds, substituents, etc. used in each synthesis mean that the solvents, compounds, substituents, etc. are the same even in the description of other parts. The trade names of the compounds used in each synthesis also refer to the same products in the description of other parts.

[0704] Furthermore, all the steps from the preparation step of the light absorption filter forming liquid to the production step of the light absorption filter with a substrate using the light absorption filter forming liquid and the steps until the ultraviolet irradiation test were performed under yellow light to avoid exposure to ultraviolet rays.

[0705] [Fabrication of light absorption filter]

[0706] Materials used to make the light absorption filter are shown below.

[0707] <Matrix polymer (resin)>

[0708] As resins 1 to 6, resin polymers having the structural units, weight average molecular weights, and acid values ​​shown in the following Table B were used. The methacrylic acid moieties of resins 1 to 6 correspond to compound A having an acid group as defined in the present invention.

[0709] In the case of the graft polymer resin 2, it refers to a graft polymer structure in which * in the structure described in the column of the structural unit constituting the main chain and * in the structure described in the column of the structural unit constituting the graft chain are linked.

[0710] The ratio of the structural units enclosed in parentheses is a molar basis (mol %), and in the graft polymer, the total of the structural units constituting the main chain is 100 mol %, and the total of the structural units constituting the graft chain is 100 mol %.

[0711] The acid value is a value measured by the above method, and the unit is mgKOH / g. The weight average molecular weight is a value measured by the method described below.

[0712]

[0713] (Synthesis Examples of Resins 1, 5 and 6)

[0714] Resins 1, 5, and 6 were synthesized by conventional methods to obtain the polymers described in Table B above.

[0715] (Synthesis Example of Resin 2)

[0716] (Synthesis of Macromonomers)

[0717] In a 300 mL three-necked flask equipped with a stirring blade, a cooling tube, a thermometer, and a nitrogen inlet tube, 7.2 g of tert-butyl methacrylate, 1.4 g of mercaptopropanol, and 8.1 g of cyclohexanone were placed and heated to 80° C. 0.06 g of polymerization initiator V-601 (trade name, manufactured by FUJIFILM Wako Pure Chemical Corporation, the same meaning below) was added and stirred for 3 hours under a nitrogen stream. Furthermore, 0.03 g of polymerization initiator V-601 was added and aged at 90° C. for 4 hours.

[0718] After stopping the nitrogen supply to the obtained solution, a mixed solution of 2.3 g of Karenz MOI (trade name, manufactured by SHOWA DE NKOK.K.), 0.01 g of NEOSTANN U-600 (trade name, manufactured by NITTO KASEI CO., LTD.) and 2.0 g of cyclohexanone was added and reacted at 85° C. for 8 hours to prepare a macromonomer solution.

[0719] (Synthesis of Graft Polymer)

[0720] In a 300 mL three-necked flask equipped with a stirring blade, a cooling tube, a thermometer, and a nitrogen inlet tube, 4.0 g of cyclohexanone was placed and heated to 80° C. A mixed solution of 13.1 g of cyclohexyl methacrylate, 20.0 g of the macromonomer solution obtained above, 4.0 g of cyclohexanone, and 0.36 g of V-60 was added dropwise over 150 minutes, and after stirring for 1 hour, a mixed solution of 0.3 g of V-601 and 2.0 g of cyclohexanone was added and aged at 90° C. for 4 hours.

[0721] After stopping the supply of nitrogen to the obtained solution, 26 g of trifluoroacetic acid was added and stirred at 70° C. for 8 hours. After confirming the progress of the reaction by NMR, the reaction solution was added dropwise to a large amount of hexane for purification and dried to obtain 16.2 g of a light brown polymer (resin 2). The MEK solution of resin 2 was prepared by dissolving in MEK (methyl ethyl ketone).

[0722] (Synthesis Example of Resin 3)

[0723] In a 300 mL three-necked flask equipped with a stirring blade, a cooling tube, a thermometer, and a nitrogen inlet tube, 9.0 g of cyclohexanone was placed and heated to 80° C. A mixed solution of 21.81 g of cyclohexyl methacrylate, 8.2 g of methacrylic acid, 10.62 g of polymerization initiator V-60, and 36 g of cyclohexanone was added dropwise over 150 minutes under a nitrogen stream. After aging for 1 hour, a mixed solution of 10.75 g of V-60 and 3.6 g of cyclohexanone was added and aged at 90° C. for 3 hours.

[0724] The reaction solution was cooled to 85° C., and after the nitrogen flow was stopped, 5.0 g of glycidyl methacrylate, 1.8 g of tetrabutylammonium bromide, 0.8 g of a polymerization inhibitor MEHQ (hydroquinone monomethyl ether), and 80 mL of cyclohexanone were added and reacted for 8 hours to obtain a polymer (resin 3) solution.

[0725] (Synthesis of Resin 4)

[0726] In a 300 mL three-necked flask equipped with a stirring blade, a cooling tube, a thermometer, and a nitrogen inlet tube, 6.0 g of cyclohexanone was placed and heated to 80° C. A mixed solution of 14.6 g of cyclohexyl methacrylate, 3.6 g of methacrylic acid, 1.8 g of 2-hydroxyethyl methacrylate, 0.39 g of V-60, and 24.0 g of cyclohexanone was added dropwise over 150 minutes, and after stirring for 1 hour, a mixed solution of 0.4 g of V-601 and 2.1 g of cyclohexanone was added and aged at 90° C. for 4 hours.

[0727] After stopping the supply of nitrogen to the obtained solution, a mixed solution of 2.2 g of Karenz MOI, 0.01 g of NEOSTANN U-6000, 0.5 g of a polymerization inhibitor MEHQ, and 40 mL of cyclohexanone was added, and the mixture was reacted at 85° C. for 8 hours. The obtained solution was added dropwise to a large amount of excess hexane for purification, and dried to obtain 19.8 g of a solid white polymer (resin 4). The MEK solution of resin 4 was prepared by dissolving it in MEK.

[0728] It was confirmed by NMR and IR that each of the obtained resins (polymers) had a polymer having a desired structure.

[0729] (Resin 201)

[0730] Cyclic polyolefin resin (manufactured by Mitsui Chemicals, Inc., APL6509T (trade name), a copolymer of ethylene and norbornene, Tg: 80°C)

[0731] <Compound B>

[0732] 4-Methylquinoline (manufactured by Sigma-Aldrich Co. LLC., Lepidine, pKaH: 5.1)

[0733] <Dye>

[0734] [Chemical formula 19]

[0735]

[0736] (Leveling agent 1)

[0737] A polymer surfactant composed of the following components was used as the leveling agent 1. In the following structural formula, the ratio of each component is a molar ratio, and t-Bu means a tert-butyl group.

[0738] [Chemical formula 20]

[0739]

[0740] (Substrate 1)

[0741] Polyethylene terephthalate (manufactured by TORAY INDUSTRIES, INC., trade name: Lumirr or XD-510P, film thickness: 50 μm)

[0742] (Substrate 2)

[0743] Cellulose acylate film (manufactured by Fujifilm Corporation, trade name: ZRD40SL)

[0744] Example

[0745] <1. Preparation of Light Absorption Filter No. 101 with Substrate>

[0746] (1) Preparation of resin solution (light absorption filter forming solution)

[0747] The components were mixed in the following composition to prepare a light absorption filter forming liquid (composition) Ba-1. In addition, resin 2 was prepared as a MEK solution, and the amount of resin in the solution was adjusted to the following blending amount. The same applies to the case where the above-mentioned resin 1, 3 or 4 is used.

[0748]

[0749]

[0750] Next, the obtained light absorption filter forming liquid Ba-1 was filtered using filter paper with an absolute filtration accuracy of 10 μm (#63, manufactured by TOYO ROSHI KAISHA, Ltd.), and further filtered using a metal sintered filter with an absolute filtration accuracy of 2.5 μm (trade name: PALL Filter PMF, media code: FH025, manufactured by NIHON PALL LTD.).

[0751] (2) Fabrication of light absorption filter with substrate

[0752] The light absorption filter forming liquid Ba-1 after the filtration treatment was applied on the substrate 1 using a bar coater so that the film thickness after drying was 2.2 μm, and dried at 100° C., thereby producing a light absorption filter No. 101 with a substrate.

[0753] <2. Preparation of light absorption filters No. 102 to 104, R201 to R204, C205, C208, C209, R210, and R211 with substrate>

[0754] In the preparation of the light absorption filter No. 101 with a substrate, light absorption filters Nos. 102 to 104, c205, c208, and c209 with a substrate were prepared in the same manner as the preparation of the light absorption filter No. 101 with a substrate, except that at least one of the type of the base polymer (resin), the type of the dye, and the amount thereof was changed to the contents described in Table 1. In addition, while the amount of the leveling agent 1 and 4-methylquinoline in the light absorption filter No. 101 with a substrate was kept constant, the amount of the resin was changed according to the change in the amount of the dye, and the adjustment was made so that the mass of the entire filter did not change.

[0755] Furthermore, in the production of the light absorption filter No. 101 with a substrate, 4-methylquinoline and dye were not added, and the type and / or amount of the resin added was changed in a manner that did not change the overall quality of the filter. Otherwise, light absorption filters Nos. R201 to R204, R210, and R211 with a substrate were produced in the same manner.

[0756] Here, Nos. 101 to 104 are light absorption filters of the present invention, Nos. c205, c208, and c209 are light absorption filters for comparison, and Nos. r201 to r204, r210, and r211 are reference light absorption filters.

[0757] <3. Preparation of Light Absorption Filter No. C206 and R207 with Substrate>

[0758] (1) Preparation of resin solution (light absorption filter forming solution)

[0759] The components were mixed in the following composition to prepare a light absorption filter forming liquid (composition) Ba-2.

[0760]

[0761] Next, the obtained light absorption filter forming liquid Ba-2 was filtered using filter paper with an absolute filtration accuracy of 10 μm (#63, manufactured by TOYO ROSHI KAISHA, Ltd.), and further filtered using a metal sintered filter with an absolute filtration accuracy of 2.5 μm (product name: PALL Filter PMF, media code: FH025, manufactured by NIHON PALL LTD.).

[0762] (2) Fabrication of light absorption filter with substrate

[0763] The light absorption filter forming liquid Ba-2 after the filtration treatment was applied on the substrate 2 using a bar coater so that the film thickness after drying was 2.2 μm, and dried at 120° C., thereby producing a light absorption filter No. c206 with a substrate.

[0764] In the preparation of the light absorption filter No. c206 with a substrate, a light absorption filter No. r207 with a substrate was prepared in the same manner as the light absorption filter No. c206 with a substrate, except that the dye and the photoradical generator were not added.

[0765] Here, No. c206 is a light absorption filter for comparison, and No. r207 is a light absorption filter for reference.

[0766] [Fabrication of a light-absorbing filter having a gas-barrier layer]

[0767] Regarding light absorption filters No. 101 to 104, R201 to R204, R207, R210, R211, C205, C206, C208, and C209 with a substrate, a light absorption filter (a light absorption filter with a substrate having a gas barrier layer) in which a gas barrier layer is further stacked on the light absorption filter was prepared in the following manner, and the evaluation described below was carried out.

[0768] (1) Preparation of substrate 3

[0769] A corona treatment device (trade name: Corona-Plus, manufactured by VETAPHONE) was used at a discharge rate of 1000 W·min / m 2 The light absorption filter with substrate produced above was subjected to corona treatment on its light absorption filter side under the conditions of a treatment speed of 3.2 m / min, thereby using it as substrate 3.

[0770] (2) Preparation of resin solution

[0771] The components shown below were mixed and stirred in a thermostatic chamber at 90° C. for 1 hour to dissolve Kuraray Poval AQ-4105 (trade name, manufactured by KURARAY CO., LTD., modified polyvinyl alcohol, saponification degree 98 to 99 mol%) to prepare a gas barrier layer forming liquid.

[0772]

[0773] Next, the obtained gas barrier layer forming liquid was filtered using a filter having an absolute filtration accuracy of 5 μm (trade name: Hydrophobic Fluor epore Membrane, manufactured by Millex).

[0774] (3) Lamination of gas barrier layers

[0775] The gas barrier layer forming liquid after the filtration treatment was applied to the corona treated surface of the substrate 3 using a bar coater so that the film thickness after drying was 1.6 μm, and dried at 120° C. for 60 seconds to produce a light absorption filter having a gas barrier layer.

[0776] The light absorption filter having the gas barrier layer has a structure in which a substrate 1 or a substrate 2, a light absorption filter, and a gas barrier layer are stacked in this order.

[0777] <Evaluation of Physical Properties of Gas Barrier Layer>

[0778] The physical properties of the gas barrier layer measured by the above method were: crystallinity 53%, oxygen permeability 0.4 cc / m 2 ·day·atm, thickness 1.6μm.

[0779] <Absorbance of light absorption filter (before ultraviolet irradiation)>

[0780] (1) Determination of absorbance

[0781] The absorbance in the wavelength range of 380 to 800 nm was measured for each 1 nm of the light absorption filter having a gas barrier layer and the standard filter using a UV3600 spectrophotometer (trade name) manufactured by SHIMADZU CORPORATION. The optical path length was 2.2 μm.

[0782] The standard filter for the light absorption filters No. 101 and No. 104 containing the resin 2 was changed to a light absorption filter No. r201 containing no dye and compound B.

[0783] The standard filter for the light absorption filter No. 102 containing the resin 3 is changed to the light absorption filter No. r202 containing no dye and compound B.

[0784] The standard filter for the light absorption filter No. 103 containing the resin 4 was changed to the light absorption filter No. r203 containing no dye and compound B.

[0785] The standard filter for the light absorption filter No. c205 containing the resin 1 was changed to the light absorption filter No. r204 containing no dye and compound B.

[0786] The standard filter for the light absorption filter No. c208 containing the resin 5 is changed to the light absorption filter No. r210 containing no dye and compound B.

[0787] The standard filter for the light absorption filter No. c209 containing the resin 6 is changed to the light absorption filter No. r211 containing no dye and compound B.

[0788] The standard filter for the light absorption filter No. c206 containing the resin 201 is changed to the light absorption filter No. r207 containing no dye and no photo-radical generator.

[0789] (2) Calculation of absorbance

[0790] The absorbance value Ab of the light absorption filter having a gas barrier layer measured above at each wavelength λnm is used. xThe absorbance Ab(λ) of the light absorption filter before ultraviolet irradiation is calculated by the following formula using the absorbance value Ab0(λ) of a standard filter containing the same resin at each wavelength λnm.

[0791] Ab(λ)=Ab x (λ)-Ab0(λ)

[0792] Hereinafter, the wavelength showing the maximum absorbance Ab(λ) of the light absorption filter in the wavelength range of 400 to 700 nm is referred to as the maximum absorption wavelength (hereinafter also referred to as “λ”). max ”), the λ max The absorbance under the condition of max )”.).

[0793] <<Evaluation 1>>

[0794] Each light absorption filter was evaluated for the decolorization rate, the ratio of components having a molecular weight of 10,000 or more after ultraviolet irradiation, and the presence or absence of failure due to ultraviolet irradiation.

[0795] The results are collectively shown in Table 1 described later.

[0796] (Ultraviolet irradiation test)

[0797] The light absorption filter having a gas barrier layer and the standard filter were irradiated with an illumination of 100 mW / cm from the gas barrier layer side (the side opposite to the substrate 1 or substrate 2) at room temperature using an ultra-high pressure mercury lamp (manufactured by HOYA, trade name: UL750) under atmospheric pressure (101.33 kPa). 2 , irradiation dose is 3J / cm 2 of ultraviolet rays (UV).

[0798] <Absorbance of light absorption filter (after ultraviolet irradiation)>

[0799] The absorbance Ab(λ) of the light absorption filter after ultraviolet irradiation was calculated by the same method as described in the above <Absorbance of light absorption filter (before ultraviolet irradiation)> using the light absorption filter having a gas barrier layer after ultraviolet irradiation and the standard filter.

[0800] [1. Evaluation of decolorization rate]

[0801] The absorption maximum value (Ab(λ) before and after the ultraviolet irradiation test was used. max )) and the decolorization rate was calculated by the following formula. max= The absorbance value at 593 nm was calculated. For dye B-18, λ max =The absorbance value at 431 nm was calculated. In Table 1 described below, it is recorded as "Decolorization rate @ 3 J / cm 2 " column.

[0802] Decolorization rate (%) = 100-(Ab after ultraviolet irradiation (λ max ) / Ab(λ before UV irradiation max ))×100

[0803] [2. Absorption from the new coloring structure accompanying dye decomposition (secondary absorption)]

[0804] In addition, in light absorption filters Nos. 101 to 104, the value obtained by subtracting the ratio of (I) from the ratio of (II) specified in the aforementioned paragraph

[0176] was 5.0% or less, and secondary absorption accompanying dye decomposition caused by ultraviolet irradiation was suppressed.

[0805] [3. Evaluation of the ratio of components having a molecular weight of 10,000 or more after ultraviolet irradiation]

[0806] <Preparation of Assay Solution>

[0807] Place the light absorption filter 8cm 2 The resin was dissolved by immersion in 1.5 mL of methyl ethyl ketone for 24 hours. Then, the supernatant was collected from the solution and filtered with a filter having a pore size of 0.45 μm for the following determination of the weight average molecular weight. In Table 1 described below, in the columns of "before ultraviolet irradiation" and "after ultraviolet irradiation" related to "the ratio of components with a molecular weight of 10,000 or more", the "ratio of components with a molecular weight of 10,000 or more before ultraviolet irradiation" and "ratio of components with a molecular weight of 10,000 or more after ultraviolet irradiation" are recorded respectively.

[0808] <Measurement of Weight Average Molecular Weight and Calculation of Ratio of Components Having a Molecular Weight of 10,000 or More>

[0809] The weight average molecular weight (polystyrene standard) of the light absorption filter before and after the ultraviolet irradiation test was measured under the following measurement conditions using HLC-8320GPC (trade name) manufactured by TOSOH CORPORATION, and the ratio of components having a molecular weight of 10,000 or more was calculated by the following calculation formula (I).

[0810] Column: TSKgel GMHHR-H and GMHHR-M

[0811] Column temperature: 40℃

[0812] Determination solvent: tetrahydrofuran

[0813] Flow rate: 1mL / min

[0814] Injection volume: 100 μL

[0815] Detector: RI (Refractive Index Detector)

[0816] Calculation formula (I)

[0817] Ratio of components with a molecular weight of 10,000 or more (%) = 100% x ((cumulative value of the strength of components with a molecular weight of 10,000 or more) / (cumulative value of the strength of all components))

[0818] [4. Evaluation of surface failure caused by ultraviolet irradiation]

[0819] The light absorption filter (8 cm x 8 cm) after the ultraviolet irradiation test was observed for planar failure, and the following criteria were used to evaluate the presence of planar failure caused by ultraviolet irradiation. Planar failure refers to cavities generated in the film at the level of several mm to an optical microscope.

[0820] -Evaluation Criteria-

[0821] A: No planar failure was observed by either the naked eye or an optical microscope (magnification 40 times).

[0822] B: No planar failure was observed with the naked eye, but planar failure was observed by observation with an optical microscope (magnification: 40 times).

[0823] C: 1 to 5 surface defects were observed with the naked eye.

[0824] D: Six or more surface defects were observed with the naked eye.

[0825]

[0826] (Notes to table)

[0827] The amount of the dye added is parts by mass relative to 10,000 parts by mass of the filter.

[0828] "-" in light absorption filter Nos. r2001 to r2004, r2007, r2100, and r211 means that they were standard filters and were not evaluated.

[0829] Light absorption filter No. c2006 contains benzophenone as a photoradical generator, and corresponds to light absorption filter No. 1003 described in International Publication No. 20021 / 132674.

[0830] From the results in Table 1 above, the following can be seen.

[0831] Comparative Example light absorption filters No. c2005, c2008, and c2009 contain resin 1, resin 5, or resin 6, in which the polymer constituting the resin does not contain a crosslinking group, and the methacrylic acid unit corresponding to the compound A in the present invention is not contained in the side chain of the polymer constituting the resin but is introduced into the main chain. In the light absorption filters No. c2005, c2008, and c2009 of these comparative examples, the ratio of components having a molecular weight of 10,000,000 or more after ultraviolet irradiation is as low as 5% or less, and the defect of 6 or more surface defects observed by naked eyes by ultraviolet irradiation occurs. In addition, it is known that although the weight average molecular weights of resin 5 and resin 6 before ultraviolet irradiation are as large as 6400,000,000 and 11,790,000, respectively, the ratio of components having a molecular weight of 100,000,000 or more after ultraviolet irradiation is reduced to the same level as that of resin 1 having a weight average molecular weight of 33,600,000 before ultraviolet irradiation. Furthermore, in the light absorption filter No. c2006 of the comparative example, a compound that generates free radicals by ultraviolet irradiation is contained in the filter, but the polymer constituting the resin is the resin 2001 that does not contain a crosslinking group and does not contain the compound A of the present invention. In the light absorption filter No. c2006 of the comparative example, sufficient free radicals are not generated by ultraviolet irradiation at room temperature, so the decolorization rate is originally low and the decolorization property is poor.

[0832] In contrast, light absorption filters Nos. 1001 and 1004 of the present invention containing resin 2 containing methacrylic acid units corresponding to compound A of the present invention in the polymer side chain, and light absorption filters Nos. 1002 and 1003 of the present invention containing resin 3 or resin 4 containing a methacrylate group as a crosslinking group in the polymer all show excellent decolorization when irradiated with ultraviolet rays at room temperature, and the ratio of components with a molecular weight of 100,000,000 or more after ultraviolet irradiation is also high. Moreover, no planar failure that can be observed with the naked eye or an optical microscope occurs after ultraviolet irradiation, and they are excellent in suppressing the generation of cavities in the filter by ultraviolet irradiation.

[0833] The present invention has been described together with its embodiments, but unless otherwise indicated, we do not intend our invention to be limited to any of the details described and should be broadly construed without departing from the spirit and scope of the invention as set forth in the appended claims.

[0834] This application claims priority based on Japanese patent application No. 2022-142576 filed in Japan on September 7, 2022, the contents of which are incorporated herein by reference as part of the description of this specification.

[0835] Explanation of symbols

[0836] 1-upper polarizer, 2-direction of absorption axis of upper polarizer, 3-upper electrode substrate of liquid crystal unit, 4-orientation control direction of upper substrate, 5-liquid crystal layer, 6-lower electrode substrate of liquid crystal unit, 7-orientation control direction of lower substrate, 8-lower polarizer, 9-direction of absorption axis of lower polarizer, B-backlight unit, 10-liquid crystal display device.

Claims

1. A light absorption filter comprising a resin, a dye having a main absorption wavelength band at a wavelength of 400 to 700 nm, and a compound that generates free radicals when irradiated with ultraviolet rays, The polymer constituting the resin contains a crosslinkable group.

2. The light absorption filter according to claim 1, wherein The compound that generates free radicals by ultraviolet irradiation includes a combination of a compound A having an acid group and a compound B having a structure capable of forming a hydrogen bond with the acid group included in the compound A.

3. A light absorption filter comprising a resin, a compound A having an acid group, a compound B which forms a hydrogen bond with the acid group contained in the compound A and generates a free radical by ultraviolet irradiation, and a dye having a main absorption wavelength band at a wavelength of 400 to 700 nm, The compound A is contained in a side chain of a polymer constituting the resin.

4. The light absorption filter according to claim 1 or 3, wherein: The dye having a main absorption wavelength band at a wavelength of 400 to 700 nm includes a heterocyclic azo dye.

5. The light absorption filter according to claim 4, wherein The heterocyclic azo dye includes an azo dye represented by the following general formula (III): In the above formula, R 17 and R 18 each independently represents a hydrogen atom or a monovalent substituent, R 19 represents a hydrogen atom, an aliphatic group, an aryl group, a heterocyclic group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyl group, an alkylsulfonyl group, an arylsulfonyl group or a sulfamoyl group, Q represents a diazo component residue.

6. The light absorption filter according to claim 1 or 3, wherein: The dye having a main absorption wavelength band at a wavelength of 400 to 700 nm comprises a squarylium dye represented by the following general formula (1): In the above formula, A and B each independently represent an aryl group which may have a substituent, a heterocyclic group which may have a substituent, or -CH=G, and G represents a heterocyclic group which may have a substituent.

7. The light absorption filter according to claim 1 or 3, wherein: The light absorption filter causes the dye having a main absorption wavelength band at a wavelength of 400 to 700 nm to undergo chemical changes and decolorize by irradiation with ultraviolet rays.

8. An optical filter obtained by irradiating the light absorption filter according to claim 1 or 3 with ultraviolet rays and performing mask exposure. 9 . An organic electroluminescent display device, an inorganic electroluminescent display device or a liquid crystal display device, comprising the filter according to claim 8 .

10. The organic electroluminescent display device, inorganic electroluminescent display device or liquid crystal display device according to claim 9, wherein: The optical filter has a layer on the viewer's side that blocks light absorption by the compound that generates radicals when irradiated with ultraviolet rays.

11. A method for manufacturing an optical filter, comprising the step of: irradiating the light absorption filter according to claim 1 or 3 with ultraviolet rays to perform mask exposure.

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