Light absorption filter, optical filter and method for producing same, organic electroluminescent display device, inorganic electroluminescent display device and liquid crystal display device

Abstract

The present invention provides: a light absorption filter which contains a resin, a dye that has a main absorption wavelength range of 400 nm to 700 nm, while containing at least one of a specific azo dye represented by one of general formulae (i) to (iv) and a specific indoaniline dye represented by general formula (v), and a compound which generates radicals upon irradiation of ultraviolet light; an optical filter which uses this light absorption filter, and a method for producing this optical filter; and an organic electroluminescent display device, an inorganic electroluminescent display device and a liquid crystal display device, each of which comprises this optical filter.

Description

Light-absorbing filter, optical filter and manufacturing method thereof, organic electroluminescent display device, inorganic electroluminescent display device, and liquid crystal display device

[0001] The present invention relates to a light-absorbing 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.

[0002] 2. Description of the Related Art In recent years, organic electroluminescence (OLED) display devices, inorganic electroluminescence display devices (inorganic EL display devices), liquid crystal display devices, and the like have been used as image display devices.

[0003] Liquid crystal display devices (LCDs) are becoming increasingly popular as space-saving, low-power image display devices. Because the LCD panel that displays images is a non-emissive element, LCDs are equipped with a backlight unit located behind the LCD panel to supply light to the LCD panel. OLED display devices utilize the spontaneous emission of OLED elements to display images. Therefore, compared to various display devices such as LCDs and plasma display devices, they offer advantages such as a high contrast ratio, excellent color reproducibility, a wide viewing angle, fast response, and a thin, lightweight design. In addition to these advantages, they are also being actively researched and developed as next-generation display devices due to their flexibility. Inorganic EL display devices utilize the spontaneous emission of inorganic EL elements as a fluorescent material to display images, replacing the OLED elements used in OLED display devices. Recent research has raised hopes for the realization of display devices superior to OLED display devices in terms of larger screen sizes and longer lifespans.

[0004] In the development of image display devices, a technique of incorporating a light-absorbing filter as a component is known. 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 has been made to provide a light-absorbing filter to block light of unnecessary wavelengths emitted from the white LED. Also, in an OLED display device, an attempt has been made to provide a light-absorbing filter from the viewpoint of suppressing external light reflection.

[0005] As another form of light-absorbing filter incorporated into an image display device, research is also being conducted on optical filters that have both light-absorbing portions that have a light-absorbing effect and portions where light absorption has been eliminated by eliminating the light absorption properties in desired portions (hereinafter simply referred to as "light-absorption-eliminated portions"). In particular, when an optical filter is incorporated into an image display device, the light-absorption-eliminated portions of the optical filter are required to have light absorption characteristics that are close to colorless. For example, Patent Document 1 describes a light-absorbing filter that contains a resin, a dye having a main absorption wavelength band in the wavelength range of 400 to 700 nm, and a compound that generates radicals upon ultraviolet irradiation, wherein the dye includes a squaraine-based dye represented by general formula (1) described in Patent Document 1, or a benzylidene-based dye or cinnamylidene-based dye represented by general formula (V). The light-absorbing filter described in Patent Document 1 is said to exhibit a high decolorization rate due to ultraviolet irradiation, and to produce almost no absorption due to a new colored structure accompanying decomposition of the dye due to ultraviolet irradiation (hereinafter also referred to as "secondary absorption"), thereby achieving high decolorization properties.

[0006] International Publication No. 2021 / 132674

[0007] However, although high decolorization properties are obtained when the light-absorbing filter described in Patent Document 1 is used, when a benzylidene dye or a cinnamylidene dye represented by general formula (V) is used, the light-absorbing filter needs to be heated during ultraviolet irradiation, and improvements are needed in terms of the productivity of optical filters. That is, an object of the present invention is to provide a light-absorbing filter that exhibits an excellent decolorization rate even when irradiated with ultraviolet light at room temperature and that hardly generates secondary absorption associated with dye decomposition due to ultraviolet irradiation. Another object of the present invention is to provide an optical filter using the above light-absorbing filter, which has light-absorbing sites and light-absorbency-eliminating sites at desired positions, as well as OLED display devices, inorganic electroluminescent display devices, and liquid crystal display devices that include this optical filter, and a method for manufacturing the optical filter.

[0008] As a result of intensive research in view of the above-mentioned problems, the present inventors have found that by configuring a light-absorbing filter containing an azo dye or an indoaniline dye having a specific structure, excellent decolorization properties can be obtained even when irradiated with ultraviolet light at room temperature. Based on this finding, further research has led to the completion of the present invention.

[0009] That is, the above-mentioned problems have been solved by the following means: <1> A light-absorbing filter containing a resin, a dye having a main absorption wavelength band in the wavelength range of 400 to 700 nm, and a compound that generates radicals upon irradiation with ultraviolet light, wherein the dye contains at least one of an azo dye represented by any one of the following general formulas (i) to (iv) and an indoaniline dye represented by the following general formula (v): In the above formula, R １７ and R １８ R each independently represents a hydrogen atom or a monovalent substituent. 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. １７ ~R １９ and Q cannot have a squaraine structure. In the above formula, R ２１ ~R ２４ , R ２６ and R ２７ represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, a carboxy group, a sulfo group, -OR １０８ , -SR １０９ , -NR １１０ R １１１ , -S(=O) ２ NR １１２ R １１３ , —C(═O)NR １１４ R １１５ , -NHC(=O)R １１６ , -C(=O)OR １１７ , -O(CH ２ CH ２ O) ｎ R １１８ , -O(CH ２ CH２ S) ｎ R １１９ , -S(CH ２ CH ２ O) ｎ R １２０ , -S(CH ２ CH ２ S) ｎ R １２１ , acyclic hydrocarbon group, monocyclic hydrocarbon group, condensed polycyclic hydrocarbon group, or heterocyclic group. １０８ ~R １２１ represents a hydrogen atom, an acyclic hydrocarbon group, a monocyclic hydrocarbon group, a condensed polycyclic hydrocarbon group, or a heterocyclic group. n is a positive integer. The acyclic hydrocarbon group, the monocyclic hydrocarbon group, the condensed polycyclic hydrocarbon group, and the heterocyclic group may each be a halogen atom, a cyano group, a nitro group, a carboxy group, a sulfo group, an -OR １０８ , -SR １０９ , -NR １１０ R １１１ , -S(=O) ２ NR １１２ R １１３ , —C(═O)NR １１４ R １１５ , -NHC(=O)R １１６ , -C(=O)OR １１７ , -O(CH ２ CH ２ O) ｎ R １１８ , -O(CH ２ CH ２ S) ｎ R １１９ , -S(CH ２ CH ２ O) ｎ R １２０ , -S(CH ２ CH ２ S) ｎ R １２１ The aryl group may have one or more substituents selected from the group consisting of acyclic hydrocarbon groups, monocyclic hydrocarbon groups, condensed polycyclic hydrocarbon groups, and heterocyclic groups. In the above formula, R ３１ represents a hydrogen atom, an alkyl group, an alkoxy group, a cyano group, a carbonyl group, an aromatic group, or a heterocyclic group. ３２represents a hydrogen atom, an alkyl group, an alkoxy group, a cyano group, a nitro group, a carbonyl group, an aromatic group, or a heterocyclic group. ３４ and R ３５ R each independently represents a hydrogen atom, an alkyl group, or an aromatic group. ３７ represents a hydrogen atom, an alkyl group, an alkoxy group, a cyano group, a carbonyl group, an acylamino group, or an aromatic group. In the above formula, R ４１ ~R ４４ , R ４６ and R ４７ represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, a carboxy group, a sulfo group, -OR ２０８ , -SR ２０９ , -NR ２１０ R ２１１ , -S(=O) ２ NR ２１２ R ２１３ , —C(═O)NR ２１４ R ２１５ , -NHC(=O)R ２１６ , -C(=O)OR ２１７ , -O(CH ２ CH ２ O) ｎ R ２１８ , -O(CH ２ CH ２ S) ｎ R ２１９ , -S(CH ２ CH ２ O) ｎ R ２２０ , -S(CH ２ CH ２ S) ｎ R ２２１ , acyclic hydrocarbon group, monocyclic hydrocarbon group, condensed polycyclic hydrocarbon group, or heterocyclic group. ２０８ ~R ２２１ represents a hydrogen atom, an acyclic hydrocarbon group, a monocyclic hydrocarbon group, a condensed polycyclic hydrocarbon group, or a heterocyclic group. n is a positive integer. The acyclic hydrocarbon group, the monocyclic hydrocarbon group, the condensed polycyclic hydrocarbon group, and the heterocyclic group may each be a halogen atom, a cyano group, a nitro group, a carboxy group, a sulfo group, an -OR ２０８ , -SR ２０９ , -NR ２１０ R ２１１, -S(=O) ２ NR ２１２ R ２１３ , —C(═O)NR ２１４ R ２１５ , -NHC(=O)R ２１６ , -C(=O)OR ２１７ , -O(CH ２ CH ２ O) ｎ R ２１８ , -O(CH ２ CH ２ S) ｎ R ２１９ , -S(CH ２ CH ２ O) ｎ R ２２０ , -S(CH ２ CH ２ S) ｎ R ２２１ The aryl group may have one or more substituents selected from the group consisting of acyclic hydrocarbon groups, monocyclic hydrocarbon groups, condensed polycyclic hydrocarbon groups, and heterocyclic groups. In the above formula, Q １ represents a group of atoms necessary to form a 5- to 7-membered nitrogen-containing heterocycle together with the carbon atom to which it is attached, including at least one nitrogen atom. ５１ represents an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an aminocarbonyl group, or a sulfonyl group; R ５２ represents a hydrogen atom or an alkyl group, and R ５３ ~R ５７ represents a hydrogen atom, an alkyl group, an alkoxy group, an acylamino group, an alkylsulfonylamino group, or a halogen atom; R ５８ and R ５９ represents a hydrogen atom, an alkyl group, or an aryl group. <2> The light-absorbing filter according to <1>, wherein the compound that generates radicals upon irradiation with ultraviolet light comprises a combination of compound A having an acid group and compound B having a structure that can form a hydrogen bond with the acid group contained in compound A. <3> The light-absorbing filter according to <1> or <2>, wherein the dye having a main absorption wavelength band in a wavelength range of 400 to 700 nm comprises a squaraine 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. G represents a heterocyclic group which may have a substituent. <4> The light-absorbing filter according to <2>, in which the compound A having an acid group is chemically bonded to a polymer constituting the resin. <5> The light-absorbing filter according to any one of <1> to <4>, in which the dye having a main absorption wavelength band in the wavelength range of 400 to 700 nm undergoes a chemical change and loses its color when irradiated with ultraviolet light. <6> An optical filter obtained by mask-exposing the light-absorbing filter according to any one of <1> to <5> with ultraviolet light irradiation. <7> An organic electroluminescent display device, an inorganic electroluminescent display device, or a liquid crystal display device, comprising the optical filter according to <6>. <8> The organic electroluminescent display device, the inorganic electroluminescent display device, or the liquid crystal display device according to <7>, further comprising a layer on the viewer's side of the optical filter that inhibits light absorption by the compound that generates radicals when irradiated with ultraviolet light. <9> A method for producing an optical filter, comprising irradiating the light-absorbing filter according to any one of <1> to <5> with ultraviolet light and exposing it using a mask.

[0010] In the present invention, when there are multiple substituents or linking groups, etc. (hereinafter referred to as substituents, etc.) represented by a specific symbol or formula, or when multiple substituents, etc. are specified simultaneously, unless otherwise specified, the respective substituents, etc. may be the same or different from one another. The same applies to the specification of the number of substituents, etc. Furthermore, when multiple substituents, etc. are adjacent (especially when they are adjacent), they may be linked to each other to form a ring, unless otherwise specified. Furthermore, unless otherwise specified, rings, such as alicyclic rings, aromatic rings, and heterocyclic rings, may be further condensed to form a fused ring. In the present invention, unless otherwise specified, the components constituting the light-absorbing filter (e.g., dyes, compounds that generate radicals upon ultraviolet irradiation, and other components that may be appropriately contained) may each be contained in the light-absorbing filter in one type or in two or more types. The same applies to an optical filter produced using the light-absorbing filter of the present invention. Unless otherwise specified, the description of the light-absorbing filter of the present invention can be preferably applied to the optical filter of the present invention, except that the optical filter has a light-absorption disappearance site formed by ultraviolet irradiation. In the present invention, unless otherwise specified, the double bond may be either E-type or Z-type in the molecule, or a mixture thereof. In the present invention, the term "compound" (including complexes) refers to the compound itself, its salts, and its ions. It also includes compounds with partially modified structures, provided that the effects of the present invention are not impaired. Furthermore, compounds that are not specified as substituted or unsubstituted may have any substituent, provided that the effects of the present invention are not impaired. This also applies to substituents and linking groups. In the present invention, a numerical range expressed using "to" refers to a range that includes the numerical values ​​before and after "to" as the lower and upper limits. In the present invention, the term "composition" encompasses not only mixtures with constant component concentrations (each component uniformly dispersed) but also mixtures with component concentrations that vary within a range that does not impair the intended function.In the present invention, having a main absorption wavelength band in the wavelength range of XX to YY nm means that the wavelength showing maximum absorption (i.e., the maximum absorption wavelength) is present in the wavelength range of XX to YY nm. Therefore, as long as this maximum absorption wavelength is within the above wavelength range, the entire absorption band including this wavelength may be within the above wavelength range, or may extend outside the above wavelength range. Furthermore, when there are multiple maximum absorption wavelengths, it is sufficient that the maximum absorption wavelength showing the greatest absorbance is present in the above wavelength range. In other words, maximum absorption wavelengths other than the maximum absorption wavelength showing the greatest absorbance may be present either inside or outside the above wavelength range of XX to YY nm. In the present invention, "(meth)acrylate" refers to either or both of acrylate and methacrylate, "(meth)acrylic acid" refers to either or both of acrylic acid and methacrylic acid, and "(meth)acryloyl" refers to either or both of acryloyl and methacryloyl.

[0011] The light-absorbing filter of the present invention exhibits an excellent decolorization rate when irradiated with ultraviolet light at room temperature, and furthermore, there is almost no secondary absorption associated with decomposition of the dye due to ultraviolet light irradiation. Furthermore, the optical filter of the present invention can have light-absorbing portions and light-absorption-eliminating portions at desired positions. Furthermore, the OLED display device, inorganic electroluminescence display device, and liquid crystal display device of the present invention are equipped with the optical filter of the present invention. The optical filter of the present invention can be preferably manufactured by the manufacturing method of the present invention.

[0012] Fig. 1 is a schematic diagram showing an outline of one embodiment of a liquid crystal display device having an optical filter of the present invention, and Fig. 2 is a schematic diagram showing a configuration for simulating ambient light reflection using a light-absorbing filter of the present invention.

[0013] [Light-Absorption Filter] The light-absorbing filter of the present invention contains a resin, a dye (hereinafter also simply referred to as "dye") having a main absorption wavelength band in the wavelength range of 400 to 700 nm, and a compound that generates radicals upon irradiation with ultraviolet light, and the dye contains at least one of an azo dye represented by any one of general formulas (i) to (iv) described below and an indoaniline dye represented by general formula (v) described below.

[0014] In the present invention, the main absorption wavelength band of a dye is the main absorption wavelength band of the dye measured in the state of a light-absorbing filter. Specifically, it is measured in the state of a light-absorbing filter with a substrate under the conditions described in the section on absorbance of a light-absorbing filter in the Examples described later.

[0015] In the light-absorbing filter of the present invention, the "dye" is dispersed (preferably dissolved) in the resin, thereby making the light-absorbing filter a layer that exhibits a specific absorption spectrum derived from the dye. This dispersion may be random, regular, or the like.

[0016] The light-absorbing filter of the present invention contains a resin, a dye having a main absorption wavelength band in the wavelength range of 400 to 700 nm, the dye including at least one of an azo dye represented by any one of general formulas (i) to (iv) below and an indoaniline dye represented by general formula (v) below, and a compound that generates radicals upon ultraviolet irradiation. The azo dye represented by general formula (i) below is a dye having a main absorption wavelength band in the wavelength range of approximately 400 to 500 nm, the azo dye represented by any one of general formulas (ii) to (iv) below is a dye having a main absorption wavelength band in the wavelength range of approximately 450 to 600 nm, and the indoaniline dye represented by general formula (v) below is a dye having a main absorption wavelength band in the wavelength range of approximately 580 to 700 nm. The light-absorbing filter of the present invention having such a configuration can exhibit excellent decolorization properties even when irradiated with ultraviolet light in a mild environment such as room temperature (meaning 10 to 30°C). Although the reason for this is speculation, it is believed that the azo dye represented by general formula (i) exhibits excellent decolorization rates even when irradiated with ultraviolet light at moderate temperatures, such as room temperature, because the hydroxy group on the pyridine ring bonded to the azo group (-N=N-) contributes to the generation of radical species, and the azo dye represented by general formula (i) itself exhibits almost no secondary absorption associated with dye decomposition, thereby exhibiting excellent decolorization properties. The azo dye represented by any of general formulas (ii) to (iv) has a structure in which an electron-donating group (amino group) is substituted at one end of the chromophore and an electron-withdrawing group (thiazole group or isothiazole group) is substituted at the other end. The effect of stabilizing a radical by substituting both an electron-donating group and an electron-withdrawing group for the radical center is generally known as the "captodative effect," and is described, for example, in Acc. Chem. Res., Vol. 18 (1985), pp. 148-154. The azo dyes represented by any of the general formulae (ii) to (iv) also easily generate radicals due to the above-mentioned "Captodative Effect," and therefore are thought to be able to obtain an excellent decolorization rate when irradiated with ultraviolet light.Furthermore, the indoaniline dye represented by general formula (v) also has a structure in which an electron-donating group (amino group) is substituted at one end of the chromophore and an electron-withdrawing group (carbonyl group) is substituted at the other end, and due to the above-mentioned "Captodative Effect," an excellent decolorization rate is obtained even when irradiated with ultraviolet light under mild temperature conditions such as room temperature, and the azo dye represented by any of general formulas (ii) to (iv) and the indoaniline dye represented by general formula (v) themselves hardly exhibit secondary absorption associated with dye decomposition, and are therefore thought to exhibit excellent decolorization properties. Meanwhile, among the dyes having a main absorption wavelength band in the wavelength range of 400 to 700 nm described in Patent Document 1, benzylidene dyes or cinnamylidene dyes represented by general formula (V) described in Patent Document 1 are described as dyes having a main absorption wavelength band in the wavelength range of approximately 400 to 500 nm. However, when a light-absorbing filter containing this dye is irradiated with ultraviolet light in a mild environment, such as at room temperature (10 to 30°C), the decolorization rate is as low as 84%, as shown in Comparative Example No. c202 described below, and the decolorization property at room temperature is poor. The light-absorbing filter of the present invention contains an azo dye represented by the general formula (i) described below instead of the benzylidene dye or cinnamylidene dye represented by the general formula (V) described in Patent Document 1, and therefore has a main absorption wavelength band in the wavelength range of approximately 400 to 500 nm, and can exhibit excellent decolorization property even when irradiated with ultraviolet light in a mild environment, such as at room temperature (10 to 30°C). Furthermore, the light-absorbing filter of the present invention contains an azo dye represented by any one of (ii) to (iv) below or an indoaniline dye represented by general formula (v), and therefore has a main absorption wavelength band in the wavelength region of approximately 450 to 700 nm, and can exhibit excellent decolorization properties comparable to those of a light-absorbing filter containing a squaraine dye represented by general formula (1) described in Patent Document 1, even when irradiated with ultraviolet light in a mild environment such as room temperature (meaning 10 to 30° C.).

[0017] In the light-absorbing filter of the present invention, when the compound that generates radicals upon UV irradiation contains 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 compound A, as described below, the efficiency of generating radical species upon UV irradiation is improved compared to when a commonly used photoradical generator such as a benzophenone compound is used. Therefore, even when UV irradiation is performed under mild temperature conditions such as room temperature, sufficient radical species are generated, and these radical species react directly or indirectly with the dye, causing the dye to decompose, resulting in fading and decolorization of the dye, thereby achieving a superior decolorization rate. Furthermore, in the light-absorbing filter of the present invention, when compound A having an acid group is bonded to a polymer that constitutes the resin, radicals are generated near the dye upon UV irradiation, which has the effect of making the radicals more likely to react with the dye. Furthermore, the "compound A having an acid group" described below may be bonded to a polymer that constitutes the resin. Furthermore, "compound B having a structure capable of forming a hydrogen bond with the acid group contained in compound A" described below forms a hydrogen bond with compound A and is dispersed (preferably dissolved) in the resin, or when compound A containing the acid group is bonded to a polymer constituting the resin, forms a hydrogen bond with compound A in the resin, and when irradiated with ultraviolet light, generates a radical, and the generated radical reacts with a nearby dye, making the radical more likely to react with the dye, thereby more efficiently fading and decolorizing the dye.

[0018] In this way, the light-absorbing filter of the present invention undergoes a chemical change of the dye when irradiated with ultraviolet light, resulting in decolorization. That is, the light-absorbing filter has the property that the dye undergoes a chemical change and can be decolorized when irradiated with ultraviolet light.

[0019] <Dye Having a Main Absorption Wavelength Band in a Wavelength Range of 400 to 700 nm> Specific examples of dyes used in the present invention having a main absorption wavelength band in a wavelength range of 400 to 700 nm include tetraazaporphyrin (TAP)-based, squaraine (SQ)-based, cyanine (CY)-based, benzylidene-based, cinnamylidene-based, azo-based, and indoaniline-based dyes. In the present invention, the dye contains at least one of an azo-based dye represented by any one of the following general formulas (i) to (iv) and an indoaniline-based dye represented by the following general formula (v), and as described above, exhibits excellent decolorization properties even when irradiated with ultraviolet light in a mild environment at room temperature (meaning 10 to 30° C.):

[0020] Among these, the light-absorbing filter of the present invention preferably includes, as the dye, at least one of an azo dye represented by any one of the following general formulas (i) to (iv) and an indoaniline dye represented by the following general formula (v), and may optionally include a squaraine dye represented by the following general formula (1), because these dyes are unlikely to form secondary colored structures due to dye decomposition. Since these dyes are all unlikely to form secondary colored structures due to dye decomposition, their use as dyes can efficiently decolorize and colorless areas irradiated with ultraviolet light. That is, when at least one of an azo dye represented by any one of the following general formulas (i) to (iv) and an indoaniline dye represented by the following general formula (v) is used as the dye, and when a squaraine dye represented by the following general formula (1) is further used as an optional component, the optical filter of the present invention can be suitably produced by exposing the light-absorbing filter of the present invention to ultraviolet light through a mask. Furthermore, by adjusting the compounding ratio of two or more dyes selected from at least one of an azo dye represented by any one of the following general formulas (i) to (iv) and an indoaniline dye represented by the following general formula (v), and a squaraine dye represented by the following general formula (1) (however, the squaraine dye represented by the following general formula (1) is an optional component), it is possible to suppress a change in the color of the reflected light in the light-absorbing filter of the present invention and the light-absorbing site in the optical filter of the present invention compared to when no dye is contained (hereinafter referred to as "adjusting the color of the reflected light to be neutral").

[0021] The dye contained in the light-absorbing filter of the present invention may be one type or two or more types. The azo dye represented by the following general formula (i), the azo dye represented by the following general formula (ii), the azo dye represented by the following general formula (iii), the azo dye represented by the following general formula (iv), and the indoaniline dye represented by the following general formula (v), which may be contained in the light-absorbing filter of the present invention, may each be one type or two or more types. Furthermore, when the light-absorbing filter of the present invention contains a squaraine dye represented by the following general formula (1), the squaraine dye represented by the following general formula (1) may be one type or two or more types. The light-absorbing filter of the present invention may also contain dyes other than the above-mentioned dyes.

[0022] In the present invention, in the dyes represented by the following general formulas, the cations are delocalized and multiple tautomeric structures exist. Therefore, in the present invention, if at least one tautomeric structure of a dye corresponds to each general formula, the dye is considered to be a dye represented by that general formula. Therefore, a dye represented by a specific general formula can also be said to be a dye whose at least one tautomeric structure can be represented by a specific general formula. In the present invention, the dye represented by a general formula may have any tautomeric structure as long as at least one of its tautomeric structures corresponds to this general formula.

[0023] (1-1) Azo dye represented by general formula (i)

[0024]

[0025] In the above formula, R １７ and R １８ R each independently represents a hydrogen atom or a monovalent substituent. 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. １７ ~R １９and Q do not have a squaraine structure. The squaraine structure refers to the structure of a squaraine dye. A squaraine dye is a dye having a structure in which a skeleton derived from squaric acid is located at the center of a π-conjugated system. For example, a squaraine dye represented by the general formula (1) described below can be mentioned.

[0026] R １７ and R １８ Examples of the monovalent substituent that can be taken as the substituent include a halogen atom, an aliphatic group, an aryl group, a heterocyclic group, a cyano group, a carboxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aryloxycarbonyl group, an acyl group, a hydroxy group, an aliphatic oxy group, an aryloxy group, an acyloxy group, a carbamoyloxy group, a heterocyclic oxy group, an amino group (-NH ２ ), 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 thio group, an arylthio group, an aliphatic sulfonyl group, an arylsulfonyl group, a sulfamoyl group, a sulfo group, an imido group, and a heterocyclic thio group. Among these, mainly from the viewpoint of imparting solubility, an aliphatic group, an aryl group, a heterocyclic group, a cyano group, a carbamoyl group, an aliphatic oxycarbonyl group, an aryloxycarbonyl group, an acyl group, an aliphatic oxy group, an aryloxy group, an aliphatic amino group, or an arylamino group is preferred. １７ and R １８ The substituents which may be taken as may be further substituted.

[0027] R １７ ~R １９The aliphatic group which can be taken as may further have a monovalent substituent, and may be saturated or unsaturated, or may be cyclic. Specific examples include alkyl groups, substituted alkyl groups, alkenyl groups, substituted alkenyl groups, alkynyl groups, substituted alkynyl groups, aralkyl groups, and substituted aralkyl groups. The total number of carbon atoms in the aliphatic group is preferably 1 to 30, and more preferably 1 to 16. Specific examples of the aliphatic group include a methyl group, an ethyl group, a butyl group, an isopropyl group, a t-butyl group, a hydroxyethyl group, a methoxyethyl group, a cyanoethyl group, a trifluoromethyl group, a 3-sulfopropyl group, a 4-sulfobutyl group, a 2-(2-hydroxyethoxy)ethyl group, a 2-(2-(acetyloxy)ethoxy)ethyl group, a cyclohexyl group, a benzyl group, a 2-phenethyl group, a vinyl group, and an allyl group. The monovalent substituent which may be taken as R １７ and R １８ The same applies to the following description of the monovalent substituent that may be possessed. Preferred examples of the monovalent substituent that may be possessed include an alkoxy group, an acyloxy group, and a hydroxy group. These substituents may further have a substituent, and preferred examples thereof include an alkoxy group, an acyloxy group, and a hydroxy group.

[0028] R １７ ~R １９ The aryl group which can be taken as may further have a monovalent substituent, and is preferably an aryl group having a total of 6 to 30 carbon atoms, more preferably an aryl group having a total of 6 to 16 carbon atoms. Specific examples include a phenyl group, a 4-tolyl group, a 4-methoxyphenyl group, a 2-chlorophenyl group, a 3-(3-sulfopropylamino)phenyl group, a 4-sulfamoylphenyl group, a 4-(ethoxyethylsulfamoyl)phenyl group, and a 3-(dimethylcarbamoyl)phenyl group.

[0029] R １７ ~R １９The heterocyclic group that can be taken as the heterocyclic group may be a saturated or unsaturated aliphatic ring group or an aromatic ring group, with an aromatic heterocyclic group being preferred. Examples of ring-constituting atoms that constitute the heterocyclic group include those containing at least one heteroatom such as a nitrogen atom, a sulfur atom, or an oxygen atom, and may further have a monovalent substituent. The heterocyclic group is preferably a heterocyclic group having a total of 1 to 30 carbon atoms, and more preferably a heterocyclic group having 1 to 15 carbon atoms. Specific examples include a 2-pyridyl group, a 2-thienyl group, a 2-thiazolyl group, a 2-benzothiazolyl group, a 2-benzoxazolyl group, and a 2-furyl group.

[0030] R １７ ~R １９ The carbamoyl group that can be taken as the ２ ), and also includes carbamoyl groups substituted with aliphatic groups, aryl groups, etc. １７ ~R １９ The carbamoyl group which can be taken as may further have a monovalent substituent, and is preferably a carbamoyl group having a total of 1 to 30 carbon atoms, more preferably a carbamoyl group having 1 to 16 carbon atoms. Specific examples include a methylcarbamoyl group, a dimethylcarbamoyl group, a phenylcarbamoyl group, and an N-methyl-N-phenylcarbamoyl group.

[0031] R １７ and R １８ The aliphatic group in the aliphatic oxycarbonyl group that can be taken as R １７ ~R １９ The description of the aliphatic groups that can be taken as R １７ and R １８ The aliphatic oxycarbonyl group which can be taken as R may further have a monovalent substituent, may be saturated or unsaturated, or may be cyclic, and is preferably an aliphatic oxycarbonyl group having a total of 2 to 30 carbon atoms, more preferably an aliphatic oxycarbonyl group having a total of 2 to 16 carbon atoms. Specific examples include a methoxycarbonyl group, an ethoxycarbonyl group, and a 2-methoxyethoxycarbonyl group. １９The alkoxycarbonyl group which can be taken as may further have a monovalent substituent, may be saturated or unsaturated, may be cyclic, and is preferably an alkoxycarbonyl group having a total of 2 to 30 carbon atoms, more preferably an alkoxycarbonyl group having a total of 2 to 16 carbon atoms. Specific examples include a methoxycarbonyl group, an ethoxycarbonyl group, and a 2-methoxyethoxycarbonyl group.

[0032] R １７ ~R １９ The aryloxycarbonyl group represented by the formula (I) may further have a monovalent substituent, and is preferably an aryloxycarbonyl group having a total of 7 to 30 carbon atoms, more preferably an aryloxycarbonyl group having 7 to 16 carbon atoms. Specific examples include a phenoxycarbonyl group, a 4-methylphenoxycarbonyl group, and a 3-chlorophenoxycarbonyl group.

[0033] R １７ ~R １９ The acyl group that can be taken as (III) includes an aliphatic carbonyl group, an arylcarbonyl group, and a heterocyclic carbonyl group, and preferably has a total of 1 to 30 carbon atoms, more preferably has a total of 1 to 16 carbon atoms. Specific examples include an acetyl group, a methoxyacetyl group, a thienoyl group, and a benzoyl group.

[0034] R １７ and R １８ The aliphatic group in the aliphatic sulfonyl group that can be taken as R １７ ~R １９ The description of the aliphatic groups that can be taken as R １７ and R １８ The aliphatic sulfonyl group which can be taken as R may further have a monovalent substituent, may be saturated or unsaturated, may be cyclic, and preferably has a total of 1 to 30 carbon atoms, more preferably 1 to 16 carbon atoms. Specific examples include a methanesulfonyl group, a methoxymethanesulfonyl group, and an ethoxyethanesulfonyl group. １９The alkylsulfonyl group which can be taken as may further have a monovalent substituent, may be saturated or unsaturated, may be cyclic, and preferably has a total of 1 to 30 carbon atoms, more preferably 1 to 16. Specific examples include a methanesulfonyl group, a methoxymethanesulfonyl group, and an ethoxyethanesulfonyl group.

[0035] R １７ ~R １９ The arylsulfonyl group which can be taken as may further have a monovalent substituent, and preferably has a total of 6 to 30 carbon atoms, more preferably 6 to 18 carbon atoms. Specific examples include benzenesulfonyl and toluenesulfonyl groups.

[0036] R １７ ~R １９ The sulfamoyl group that can be taken as the ２ NH ２ ), and also includes carbamoyl groups substituted with aliphatic groups, aryl groups, etc. １７ ~R １９ The sulfamoyl group which can be taken as may further have a monovalent substituent, and preferably has a total of 0 to 30 carbon atoms, more preferably 0 to 16 carbon atoms. Specific examples include an unsubstituted sulfamoyl group, a dimethylsulfamoyl group, and a di-(2-hydroxyethyl)sulfamoyl group.

[0037] R １７ and R １８ The imido group may further have a monovalent substituent, and is preferably a 5- or 6-membered ring imido group. The imido group preferably has a total of 4 to 30 carbon atoms, more preferably 4 to 20 carbon atoms. Specific examples include succinimide and phthalimide groups.

[0038] R １７ and R １８ The aliphatic groups in the aliphatic oxy group, aliphatic amino group, aliphatic oxycarbonylamino group, aliphatic sulfonylamino group and aliphatic thio group that can be taken as R １７~R １９ The description of the aliphatic groups that can be taken as R １７ and R １８ The aryl group in the aryloxy group, arylamino group, aryloxycarbonylamino group, arylsulfonylamino group and arylthio group that can be taken as R １７ ~R １９ The description of the aryl group that can be taken as R can be applied. １７ and R １８ The acyl group in the acyloxy group and acylamino group that can be taken as R １７ ~R １９ The description of the acyl group that can be taken as R １７ and R １８ The carbamoyl group in the carbamoyloxy group and carbamoylamino group that can be taken as R １７ ~R １９ The description of the carbamoyl group that can be taken as R １７ and R １８ The heterocyclic group in the heterocyclic oxy group, heterocyclic amino group and heterocyclic thio group that can be taken as R １７ ~R １９ The description of the heterocyclic group that can be taken as R can be applied. １７ and R １８ The sulfamoyl group in the sulfamoylamino group that can be taken as R １７ ~R １９ The description of the sulfamoyl group that can be taken as the above can be applied.

[0039] The diazo component residue represented by Q is the diazo component "Q-NH ２". In particular, from the viewpoint of the target color reproducibility, Q is preferably an aryl group or an aromatic heterocyclic group. The aromatic hydrocarbon ring constituting the aryl group that can be taken as Q may be a monocyclic or fused ring, and is preferably a monocyclic ring. An aryl group having a total of 6 to 30 carbon atoms is preferred, and an aryl group having a total of 6 to 16 carbon atoms is more preferred. Specifically, a phenyl group is preferred. The aryl group that can be taken as Q may have a substituent, and preferred examples of the substituent that may be taken as Q include a sulfamoyl group (preferably an alkylsulfamoyl group or a dialkylsulfamoyl group), a sulfonyl group (preferably an alkylsulfonyl group), and a cyano group.

[0040] The aromatic heterocyclic group that can be taken as Q is preferably an aromatic ring group containing at least one heteroatom such as a nitrogen atom, a sulfur atom, or an oxygen atom as a ring-constituting atom constituting the heterocyclic group, and is preferably constituted by a 5- or 6-membered ring. The number of carbon atoms in the aromatic heterocyclic group is preferably 1 to 25, more preferably 1 to 15. The aromatic heterocycle constituting the aromatic heterocyclic group may be a monocycle or a condensed ring, and is preferably a monocycle. Specific examples of the aromatic heterocyclic group include a pyrazole group, a 1,2,4-triazole group, an isothiazole group, a benzisothiazole group, a thiazole group, a benzothiazole group, an oxazole group, and a 1,2,4-thiadiazole group.

[0041] Examples of the azo dye represented by the general formula (i) include the following exemplary compounds (B-12) to (B-16), (B-18), and (B-19), although the present invention is not limited to these.

[0042]

[0043] (1-2) Azo dyes represented by the following general formula (ii):

[0044]

[0045] In the above formula, R ２１ ~R ２４ , R ２６ and R ２７represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, a carboxy group, a sulfo group, -OR １０８ , -SR １０９ , -NR １１０ R １１１ , -S(=O) ２ NR １１２ R １１３ , —C(═O)NR １１４ R １１５ , -NHC(=O)R １１６ , -C(=O)OR １１７ , -O(CH ２ CH ２ O) ｎ R １１８ , -O(CH ２ CH ２ S) ｎ R １１９ , -S(CH ２ CH ２ O) ｎ R １２０ , -S(CH ２ CH ２ S) ｎ R １２１ , acyclic hydrocarbon group, monocyclic hydrocarbon group, condensed polycyclic hydrocarbon group, or heterocyclic group. １０８ ~R １２１ represents a hydrogen atom, an acyclic hydrocarbon group, a monocyclic hydrocarbon group, a condensed polycyclic hydrocarbon group, or a heterocyclic group. n is a positive integer. The acyclic hydrocarbon group, the monocyclic hydrocarbon group, the condensed polycyclic hydrocarbon group, and the heterocyclic group may each be a halogen atom, a cyano group, a nitro group, a carboxy group, a sulfo group, an -OR １０８ , -SR １０９ , -NR １１０ R １１１ , -S(=O) ２ NR １１２ R １１３ , —C(═O)NR １１４ R １１５ , -NHC(=O)R １１６ , -C(=O)OR １１７ , -O(CH ２ CH ２ O) ｎ R １１８ , -O(CH ２ CH ２ S) ｎ R １１９, -S(CH ２ CH ２ O) ｎ R １２０ , -S(CH ２ CH ２ S) ｎ R １２１ The aryl group may have one or more substituents selected from the group consisting of acyclic hydrocarbon groups, monocyclic hydrocarbon groups, condensed polycyclic hydrocarbon groups, and heterocyclic groups.

[0046] R ２１ ~R ２４ , R ２６ , R ２７ and R １０８ ~R １２１ The acyclic hydrocarbon group that can be taken as R means an acyclic alkyl group in which one hydrogen atom has been removed from an acyclic alkane. However, the acyclic alkyl group may have a ring structure as a substituent. The number of carbon atoms in the acyclic alkyl group is preferably 1 to 30, more preferably 1 to 20, even more preferably 1 to 12, particularly preferably 1 to 8, and of these, 1 to 6 is preferred. ２１ ~R ２４ , R ２６ , R ２７ and R １０８ ~R １２１ The monocyclic hydrocarbon group that can be taken as R means a monocyclic cycloalkyl group, a monocyclic cycloalkenyl group, a monocyclic cycloalkynyl group, or a monocyclic aryl group, which is a group in which one hydrogen atom has been removed from a monocyclic aliphatic hydrocarbon ring (which may be a monocyclic cycloalkane, a monocyclic cycloalkene, or a monocyclic cycloalkyne) or a monocyclic aromatic hydrocarbon ring. The number of carbon atoms in the monocyclic cycloalkyl group, the monocyclic cycloalkenyl group, and the monocyclic cycloalkynyl group is not particularly limited as long as it is structurally possible, but is more preferably 3 to 30, more preferably 3 to 20, and even more preferably 3 to 16. The number of carbon atoms in the monocyclic aryl group is more preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 16. R ２１ ~R ２４ , R ２６ , R ２７ and R １０８ ~R １２１The fused polycyclic hydrocarbon group that can be taken as R means a fused polycyclic cycloalkyl group, a fused polycyclic cycloalkenyl group, a fused polycyclic cycloalkynyl group, or a fused polycyclic aryl group, which is a group in which one hydrogen atom has been removed from a fused polycyclic aliphatic hydrocarbon ring (which may be a fused polycyclic cycloalkane, a fused polycyclic cycloalkene, or a fused polycyclic cycloalkyne) or a fused polycyclic aromatic hydrocarbon ring. The number of carbon atoms in the fused polycyclic cycloalkyl group, the fused polycyclic cycloalkenyl group, and the fused polycyclic cycloalkynyl group is not particularly limited as long as it is structurally possible, but is more preferably 8 to 30, and more preferably 8 to 20. The number of carbon atoms in the fused polycyclic aryl group is more preferably 12 to 30, and more preferably 12 to 20. ２１ ~R ２４ , R ２６ , R ２７ and R １０８ ~R １２１ The heterocyclic group that can be used as the heterocyclic group is R １７ ~R １９ The description of the heterocyclic group that can be taken as: can be applied. n is preferably an integer of 1 to 12, more preferably an integer of 1 to 6, and even more preferably an integer of 1 to 3.

[0047] Specific groups of each substituent in the general formula (ii) are the same as those of R in the compound represented by the general formula [1] described in JP-A-5-257180, unless otherwise specified. １ ~R ４ , R ６ , R ７ , R ８ ~R ２１ The descriptions regarding R ２１ ~R ２４ , R ２６ , R ２７ , R １０８ ~R １２１ can be applied as is.

[0048] R ２１ represents a cyano group, a nitro group, -OR １０８, an acyclic hydrocarbon group (preferably an acyclic alkyl group or an acyclic alkenyl group) or a heterocyclic group is preferred, a cyano group or a nitro group, or an acyclic alkyl group substituted with a halogen atom (preferably an alkyl group substituted with a fluorine atom) is more preferred, and a cyano group is even more preferred. ２２ is preferably a hydrogen atom, a cyano group, an acyclic hydrocarbon group (preferably an acyclic alkyl group) or a monocyclic hydrocarbon group, more preferably a hydrogen atom or an alkyl group, and even more preferably an alkyl group. ２１ and R ２２ At least one of R is preferably a cyano group or a nitro group, or an acyclic alkyl group substituted with a halogen atom, a cyano group, or a nitro group. ２３ represents a hydrogen atom, -OR １０８ , -SR １０９ , -NR １１０ R １１１ , —C(═O)NR １１４ R １１５ , -NHC(=O)R １１６ , -O(CH ２ CH ２ O) ｎ R １１８ , -O(CH ２ CH ２ S) ｎ R １１９ , -S(CH ２ CH ２ O) ｎ R １２０ , -S(CH ２ CH ２ S) ｎ R １２１ or a non-cyclic hydrocarbon group (preferably a non-cyclic alkyl group), and a hydrogen atom, -OR １０８ , -SR １０９ , -NR １１０ R １１１ , -NHC(=O)R １１６ or acyclic alkyl groups are more preferred, -NHC(=O)R １１６ More preferably, R １０８ ~R １１１ , R １１６ , R １１８ ~R １２１ is preferably an acyclic alkyl group.２４ and R ２７ is preferably a hydrogen atom. ２６ represents a hydrogen atom, -OR １０８ , -SR １０９ , -NR １１０ R １１１ , -NHC(=O)R １１６ , -O(CH ２ CH ２ O) ｎ R １１８ , -O(CH ２ CH ２ S) ｎ R １１９ , -S(CH ２ CH ２ O) ｎ R １２０ , -S(CH ２ CH ２ S) ｎ R １２１ or a non-cyclic hydrocarbon group (preferably a non-cyclic alkyl group), and a hydrogen atom, -OR １０８ or -SR １０９ is more preferred, and a hydrogen atom is even more preferred. １０８ ~R １１１ , R １１６ , R １１８ ~R １２１ is preferably an acyclic alkyl group. ２４ and R ２６ -NR located at the ortho position relative to １１０ R １１１ In this case, R １１０ is preferably an acyclic alkyl group, and R １１１ is preferably an acyclic alkyl group, and is preferably an unsubstituted acyclic alkyl group or —OR １０８ , a non-cyclic alkyl group having a monocyclic hydrocarbon group or a condensed polycyclic hydrocarbon group as a substituent is more preferred. １０８ is preferably a hydrogen atom or an acyclic alkyl group.

[0049] Specific examples of the dye represented by general formula (ii) include the compounds used in the examples described later, as well as the compounds described in paragraphs

[0023] to

[0034] of JP-A No. 5-257180, and the compounds described in paragraphs

[0050] and

[0052] of JP-A No. 2013-129712, compound D-18 described in paragraph

[0055] , and the compound described in paragraph

[0056] . However, the present invention is not limited to these.

[0050] (1-3) Azo dyes represented by the following general formula (iii):

[0051]

[0052] In the above formula, R ３１ represents a hydrogen atom, an alkyl group, an alkoxy group, a cyano group, a carbonyl group (preferably an alkyloxycarbonyl group or an aryloxycarbonyl group), an aromatic group, or a heterocyclic group. ３２ represents a hydrogen atom, an alkyl group, an alkoxy group, a cyano group, a nitro group, a carbonyl group (preferably an alkyloxycarbonyl group or an aryloxycarbonyl group), an aromatic group, or a heterocyclic group. ３４ and R ３５ R each independently represents a hydrogen atom, an alkyl group, or an aromatic group. ３７ represents a hydrogen atom, an alkyl group, an alkoxy group, a cyano group, a carbonyl group (preferably an alkyloxycarbonyl group or an aryloxycarbonyl group), an acylamino group, or an aromatic group. ３４ and R ３５ may be bonded to each other to form a ring.

[0053] The definition and preferred range of each substituent in the general formula (iii) are the same as those of R in the general formula (1) described in JP-A-2013-129712, unless otherwise specified. １ and R ２ The descriptions regarding R ３１ and R ３２ R relating to general formula (3) described in JP-A-2013-129712 ４ , R ５ and R ７ The descriptions regarding R ３４ , R３５ and R ３７ In the present invention, R ３７ R in the general formula (3) described in JP-A-2013-129712 ７ In addition to the hydrogen atom, alkyl group, alkoxy group, cyano group, carbonyl group and aromatic group that R can take, it can also take the following acylamino group: ３７ The number of carbon atoms in the acylamino group that can be taken as R is preferably 1 to 12, more preferably 1 to 6. ３１ , R ３２ and R ３７ The number of carbon atoms in the alkyl group that can be taken as R is more preferably 1 to 20, further preferably 1 to 12, and particularly preferably 1 to 6. ３１ , R ３２ and R ３７ The number of carbon atoms in the alkoxy group that can be taken as R is more preferably 1 to 20, further preferably 1 to 12, and particularly preferably 1 to 6. ３１ , R ３２ and R ３７ The number of carbon atoms in the alkyloxycarbonyl group that can be taken as R is preferably 2 to 30, more preferably 2 to 20, still more preferably 2 to 12, and particularly preferably 2 to 7. ３４ and R ３５ The alkyl group that can be taken as the alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and even more preferably 1 to 12 carbon atoms.

[0054] R ３１ is preferably an alkyl group or an aryl group, more preferably an alkyl group. ３２ is preferably an alkyl group or a cyano group, more preferably a cyano group. ３４ and R ３５ is preferably a hydrogen atom or an alkyl group, more preferably an alkyl group. ３７ is preferably a hydrogen atom, an alkyl group, an acylamino group or an aromatic group, more preferably a hydrogen atom or an alkyl group, and even more preferably an alkyl group.

[0055] Specific examples of the dye represented by formula (iii) include the compounds shown below, although the present invention is not limited to these.

[0056]

[0057]

[0058]

[0059] (1-4) Azo dyes represented by the following general formula (iv):

[0060]

[0061] In the above formula, R ４１ ~R ４４ , R ４６ and R ４７ represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, a carboxy group, a sulfo group, -OR ２０８ , -SR ２０９ , -NR ２１０ R ２１１ , -S(=O) ２ NR ２１２ R ２１３ , —C(═O)NR ２１４ R ２１５ , -NHC(=O)R ２１６ , -C(=O)OR ２１７ , -O(CH ２ CH ２ O) ｎ R ２１８ , -O(CH ２ CH ２ S) ｎ R ２１９ , -S(CH ２ CH ２ O) ｎ R ２２０ , -S(CH ２ CH ２ S) ｎ R ２２１ , acyclic hydrocarbon group, monocyclic hydrocarbon group, condensed polycyclic hydrocarbon group, or heterocyclic group. ２０８ ~R ２２１ represents a hydrogen atom, an acyclic hydrocarbon group, a monocyclic hydrocarbon group, a condensed polycyclic hydrocarbon group, or a heterocyclic group. n is a positive integer. The acyclic hydrocarbon group, the monocyclic hydrocarbon group, the condensed polycyclic hydrocarbon group, and the heterocyclic group may each be a halogen atom, a cyano group, a nitro group, a carboxy group, a sulfo group, an -OR ２０８ , -SR２０９ , -NR ２１０ R ２１１ , -S(=O) ２ NR ２１２ R ２１３ , —C(═O)NR ２１４ R ２１５ , -NHC(=O)R ２１６ , -C(=O)OR ２１７ , -O(CH ２ CH ２ O) ｎ R ２１８ , -O(CH ２ CH ２ S) ｎ R ２１９ , -S(CH ２ CH ２ O) ｎ R ２２０ , -S(CH ２ CH ２ S) ｎ R ２２１ The aryl group may have one or more substituents selected from the group consisting of acyclic hydrocarbon groups, monocyclic hydrocarbon groups, condensed polycyclic hydrocarbon groups, and heterocyclic groups.

[0062] R in general formula (iv) ４１ ~R ４４ , R ４６ , R ４７ , R ２０８ ~R ２２１ and n are the same as R in the general formula (ii) above unless otherwise specified. ２１ ~R ２４ , R ２６ , R ２７ , R １０８ ~R １２１ The descriptions of R and n can be applied as they are. ４３ represents a hydrogen atom, -OR ２０８ , -SR ２０９ , -NR ２１０ R ２１１ , -NHC(=O)R ２１６ , -O(CH ２ CH ２ O) ｎ R ２１８ , -O(CH ２ CH ２ S) ｎ R ２１９, -S(CH ２ CH ２ O) ｎ R ２２０ , -S(CH ２ CH ２ S) ｎ R ２２１ or a non-cyclic hydrocarbon group (preferably a non-cyclic alkyl group), and a hydrogen atom, -OR ２０８ , -SR ２０９ , -NR ２１０ R ２１１ , -NHC(=O)R ２１６ or acyclic alkyl groups are more preferred, -NHC(=O)R ２１６ or acyclic alkyl group is more preferred. ２０８ ~R ２１１ , R ２１６ , R ２１８ ~R ２２１ is preferably an acyclic alkyl group. ４４ and R ４６ -NR located at the ortho position relative to ２１０ R ２１１ In this case, R ２１０ is preferably an acyclic alkyl group, and R ２１１ is preferably an acyclic alkyl group, and is preferably an unsubstituted acyclic alkyl group (including an acyclic alkyl group substituted with an acyclic alkyl group), or -OR ２０８ , a non-cyclic alkyl group having a monocyclic hydrocarbon group or a condensed polycyclic hydrocarbon group as a substituent is more preferred. ２０８ is preferably a hydrogen atom or an acyclic alkyl group. ４４ and / or R ４６ is R on the benzene ring ４４ and R ４６ -NR located at the ortho position relative to ２１０ R ２１１ R in ２１０ and / or R ２１１ and may be bonded to form a ring. The ring that may be formed is preferably a 5- or 6-membered ring, and may be saturated or unsaturated, and is preferably a saturated 6-membered ring. The ring that may be formed may further have a substituent, and preferably has, for example, an alkyl group. Among these, as a form of forming a ring, R４６ and R on the benzene ring ４４ and R ４６ -NR located at the ortho position relative to ２１０ R ２１１ R in ２１１ and preferably combine to form a saturated six-membered ring.

[0063] Specific examples of the dye represented by general formula (iv) include the compounds used in the examples described later and the compounds described in paragraph

[0053] of JP-A-2013-129712, although the present invention is not limited thereto.

[0064] (1-5) Indoaniline dyes represented by the following general formula (v):

[0065]

[0066] In the above formula, Q １ represents a group of atoms necessary to form a 5- to 7-membered nitrogen-containing heterocycle together with the carbon atom to which it is attached, including at least one nitrogen atom. ５１ represents an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an aminocarbonyl group, or a sulfonyl group; R ５２ represents a hydrogen atom or an alkyl group, and R ５３ ~R ５７ represents a hydrogen atom, an alkyl group, an alkoxy group, an acylamino group, an alkylsulfonylamino group, or a halogen atom; R ５８ and R ５９ represents a hydrogen atom, an alkyl group, or an aryl group. ５１ and R ５３ But, R ５４ and R ５５ and / or R ５５ and R ５９ But, or R ５８ and R ５９ may be bonded to each other to form a ring.

[0067] The definition and preferred range of each substituent in the general formula (v) are the same as those of R relating to the general formula (I) described in JP-A-2-92686, unless otherwise specified. １ ~R ６ , R ８ , R９ and Q １ The descriptions regarding R ５１ ~R ５６ , R ５８ , R ５９ and Q １ In the present invention, R ５３ ~R ５６ R in the general formula (I) described in JP-A-2-92686 ３ ~R ６ In addition to the hydrogen atom, alkyl group, alkoxy group, and halogen atom that R can take, R can take the following acylamino group and alkylsulfonylamino group. ５３ ~R ５７ The number of carbon atoms in the acylamino group that can be taken as R is preferably 1 to 12, and more preferably 1 to 6. ５３ ~R ５７ The number of carbon atoms in the alkylsulfonylamino group that can be taken as R is preferably 1 to 12, and more preferably 1 to 6. ５７ The alkyl group, alkoxy group and halogen atom that can be taken as R ５３ ~R ５６ The descriptions of the alkyl group, alkoxy group and halogen atom that can be taken as the alkyl group, alkoxy group and halogen atom can be applied as they are.

[0068] Q １ is preferably —NR １６ C(=O)-Q ２ It is expressed as -. ２ is -NR １６ C(=O)-Q ２ The carbon atom to which - is bonded and -NR １６ R represents a group of atoms necessary to form a 5- to 7-membered nitrogen-containing heterocycle together with C(═O)—, and examples thereof include a divalent amino group, an ether bond, a thioether bond, an alkylene bond, an ethylene bond, an imino bond, a sulfonyl bond, a carbonyl bond, an arylene bond, or a divalent heterocyclic group, or a group formed by combining two or more of these. １６ represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and preferably a hydrogen atom. １６ The definition and preferred range of each substituent of R in general formula (I) described in JP-A-2-92686 are also the same as those described in１６ The descriptions regarding R can be applied as they are. ５１ is preferably an acyl group having 2 to 7 carbon atoms or an alkoxycarbonyl group having 2 to 7 carbon atoms. ５２ is preferably a hydrogen atom, and R ５３ ~R ５６ is preferably a hydrogen atom. ５７ is preferably an alkoxy group, an acylamino group, or an alkylsulfonylamino group, and more preferably an alkoxy group or an acylamino group. ５８ and R ５９ is preferably an alkyl group having 1 to 6 carbon atoms.

[0069] In particular, the indoaniline dye represented by the above general formula (v) is preferably represented by the following general formula (va).

[0070]

[0071] In the above formula, R ５１ , R ５３ , R ５７ ~R ５９ and Q ２ is R in the above general formula (v). ５１ , R ５３ , R ５７ ~R ５９ and Q ２ It is synonymous with: ２ is -CR １１ R １２ CR １３ R １４ -, -CR １１ R １２ -or-NR １１ - is preferred, and -CR １１ R １２ CR １３ R １４ - is more preferred. １１ ~R １４ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R １１ and R １２ is a hydrogen atom and R １３ and R １４ is preferably an alkyl group having 1 to 4 carbon atoms. １１ R １２ CR １３R １４ - is R １１ and R １２ is preferably bonded to >C=O on the side of the carbon atom to which it is bonded.

[0072] Specific examples of the dye represented by formula (v) include the compounds used in the examples described later, as well as compounds No. 1 to 51 described on pages 5 and 6 of JP-A No. 2-92686, although the present invention is not limited to these.

[0073] (2) Squaraine dyes represented by general formula (1)

[0074]

[0075] In 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, where G represents a heterocyclic group which may have a substituent.

[0076] The aryl group that can be used as A or B is not particularly limited and may be a group consisting of a single ring or a group consisting of a fused ring. The number of carbon atoms in the aryl group is preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 12. Examples of the aryl group include groups consisting of a benzene ring or a naphthalene ring, and more preferably a group consisting of a benzene ring.

[0077] The heterocyclic group that can be taken as A or B is not particularly limited, and includes a group consisting of an aliphatic heterocycle or an aromatic heterocycle, and a group consisting of an aromatic heterocycle is preferred. Examples of heteroaryl groups that are aromatic heterocyclic groups include the heteroaryl groups that can be taken as the substituent X described below. The aromatic heterocyclic group that can be taken as A or B is preferably a 5-membered or 6-membered ring group, and more preferably a nitrogen-containing 5-membered ring group. Specific examples of suitable groups include 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, an indoline ring, a pyridine ring, a pyrimidine ring, a quinoline ring, a benzothiazole ring, a benzoxazole ring, and a pyrazolotriazole ring. Among them, a group consisting of a pyrrole ring, a pyrazole ring, a thiazole ring, a pyridine ring, a pyrimidine ring, and a pyrazolotriazole ring is preferred. The pyrazolotriazole ring is a fused ring formed by condensing at least one pyrazole ring and one triazole ring, and examples thereof include the fused rings in the general formulae (4) and (5) described below.

[0078] A and B may be bonded to the squaric acid moiety (the four-membered ring shown in general formula (1)) at any site (atom constituting the ring) without any particular limitation, but are preferably bonded to a carbon atom.

[0079] G in -CH=G which can be taken as A or B represents a heterocyclic group which may have a substituent, and suitable examples thereof include the examples shown above for the heterocyclic group which can be taken as A or B. Among these, a group consisting of any one of a benzoxazole ring, a benzothiazole ring, and an indoline ring is preferred.

[0080] At least one of A and B may have a hydrogen-bonding group that forms an intramolecular hydrogen bond. A, B, and G may each have a substituent X, and when they have a substituent X, adjacent substituents may be bonded to each other to form a ring structure. In addition, there may be a plurality of substituents X. Examples of the substituent X include R １Specific examples of the substituent include a halogen atom, a cyano group, a nitro group, an alkyl group (including a cycloalkyl group), an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an aralkyl group, a ferrocenyl group, and —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 , -SO ２ R ２３ , -SO ３ R ２４ , -NHSO ２ R ２５ and -SO ２ NR ２６ R ２７ In addition to the ferrocenyl group, the substituent X preferably has a quencher moiety as described below.

[0081] In general formula (1), R １０ ~R ２７ R each independently represents a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group. １０ ~R ２７ The aliphatic group and aromatic group that can be taken as R １ The substituents that can be taken as R can be appropriately selected from alkyl groups, cycloalkyl groups, alkenyl groups and alkynyl groups, which are classified as aliphatic groups, and aryl groups, which are classified as aromatic groups. １０ ~R ２７ The heterocyclic group that can be used as the heterocyclic group may be aliphatic or aromatic. For example, R １ The heteroaryl group or heterocyclic group can be appropriately selected from the heteroaryl groups or heterocyclic groups that can be taken as —COOR. １２ R １２When —SO 3 is a hydrogen atom (i.e., a carboxy group), the hydrogen atom may be dissociated (i.e., a carbonate group) or may be in the form of a salt. ３ R ２４ R ２４ When is a hydrogen atom (i.e., a sulfo group), the hydrogen atom may be dissociated (i.e., a sulfonate group) or may be in the form of a salt.

[0082] Examples of halogen atoms that can be used as the substituent X include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The number of carbon atoms in the alkyl group that 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 in 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 in the alkynyl group is preferably 2 to 40, more preferably 2 to 30, and particularly preferably 2 to 25. The alkyl group, alkenyl group, and alkynyl group may each be linear, branched, or cyclic, with linear or branched being preferred. The aryl group that can be used as the substituent X includes a monocyclic or fused ring group. The number of carbon atoms in the aryl group is preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 12. The alkyl portion of the aralkyl group that can be used as the substituent X is the same as the alkyl group described above. The aryl portion of the aralkyl group is the same as the aryl group described above. The number of carbon atoms in the aralkyl group is preferably 7 to 40, more preferably 7 to 30, and even more preferably 7 to 25. The heteroaryl group that can be used as the substituent X includes a group consisting of a monocycle or a fused ring, preferably a monocycle or a group consisting of 2 to 8 fused rings, and more preferably a monocycle or a group consisting of 2 to 4 fused rings. The number of heteroatoms constituting the ring of the heteroaryl group is preferably 1 to 3. Examples of heteroatoms constituting the ring of the heteroaryl group include a nitrogen atom, an oxygen atom, and a sulfur atom. The heteroaryl group is preferably a group consisting of a 5- or 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 even more preferably 3 to 12. Examples of heteroaryl groups include groups consisting of a pyridine ring, piperidine ring, furan ring, furfuran ring, thiophene ring, pyrrole ring, quinoline ring, morpholine ring, indole ring, imidazole ring, pyrazole ring, carbazole ring, phenothiazine ring, phenoxazine ring, indoline ring, thiazole ring, pyrazine ring, thiadiazine ring, benzoquinoline ring, and thiadiazole ring.

[0083] The ferrocenyl group which can be used as the substituent X is preferably represented by the general formula (2M).

[0084]

[0085] In general formula (2M), L represents a single bond or a divalent linking group that is not conjugated with A, B, or G in general formula (1). １ｍ ~R ９ｍ represents 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 site with A, B, or G. In the present invention, when L in general formula (2M) is a single bond, the cyclopentadienyl ring (R in general formula (2M)) directly bonding to A, B, or G is a cyclopentadienyl ring. １ｍ The ring having the formula (A) is not included in the conjugated structure conjugated with A, B or G.

[0086] The divalent linking group that can be taken as L is not particularly limited as long as it is a linking group that is not conjugated with A, B, or G, and may contain the above-mentioned conjugated structure inside it or at the end of the cyclopentadiene ring in general formula (2M). Examples of the divalent linking group include 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 heterocycle, -CH=CH-, -CO-, -CS-, -NR- (wherein R represents a hydrogen atom or a monovalent substituent), -O-, -S-, and -SO ２ - or -N=CH-, or a divalent linking group formed by combining a plurality of these (preferably 2 to 6). Preferred are alkylene groups having 1 to 8 carbon atoms, arylene groups having 6 to 12 carbon atoms, -CH=CH-, -CO-, -NR- (wherein R is as defined above), -O-, -S-, and -SO ２ - and -N=CH- or a divalent linking group formed by combining two or more (preferably 2 to 6) groups selected from this group, and particularly preferred are alkylene groups having 1 to 4 carbon atoms, phenylene groups, -CO-, -NH-, -O- and -SO ２ - or a linking group formed by combining two or more (preferably 2 to 6) groups selected from this group. The combined divalent linking group is not particularly limited, but may be -CO-, -NH-, -O-, or -SO ２ A group containing - is preferred, and is -CO-, -NH-, -O- or -SO ２A linking group formed by combining two or more types of -, or -CO-, -NH-, -O- and -SO ２ - is a linking group formed by combining at least one of - with an alkylene group or an arylene group. ２ Examples of the linking group formed by combining two or more types of - include -COO-, -OCO-, -CONH-, -NHCOO-, -NHCONH-, and -SO ２ -NH-, -CO-, -NH-, -O- and -SO ２ Examples of the linking group formed by combining at least one of - with an alkylene group or an arylene group include groups formed by combining -CO-, -COO-, or -CONH- with an alkylene group or an arylene group. The substituent that can be taken as R is not particularly limited and has the same meaning as the substituent X that A in general formula (2) may have.

[0087] L is a single bond, an alkylene group having 1 to 8 carbon atoms, an arylene group having 6 to 12 carbon atoms, —CH═CH—, —CO—, —NR— (wherein R is as defined above), —O—, —S—, or —SO ２ A group selected from the group consisting of - and -N=CH- or a group formed by combining two or more groups selected from this group is preferred.

[0088] L may have one or more substituents. The substituent that L may have is not particularly limited and has the same meaning as the above-mentioned substituent X, for example. When L has multiple substituents, the substituents bonded to adjacent atoms may further bond to each other to form a ring structure.

[0089] The alkylene group that can be taken as L may be any of linear, branched, or cyclic, so 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, Examples of L include 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, etc. In the alkylene group, L may contain -CO-, -CS-, -NR- (wherein R is as defined above), -O-, -S-, -SO ２ When a linking group containing at least one of - and -N=CH- is adopted, the group such as -CO- may be incorporated at any position in the alkylene group, and the number of groups incorporated is not particularly limited.

[0090] The arylene group that can be taken as L is not particularly limited as long as it is a group having 6 to 20 carbon atoms, and examples thereof include groups in which one hydrogen atom has been further removed from each of the groups exemplified as the aryl group having 6 to 20 carbon atoms that can be taken as A in general formula (1). The heterocyclic group that can be taken as L is not particularly limited, and examples thereof include groups in which one hydrogen atom has further removed from each of the groups exemplified as the heterocyclic group that can be taken as A above.

[0091] In general formula (2M), the remaining partial structure excluding the linking group L corresponds to a structure (metallocene structural part) obtained by removing one hydrogen atom from a metallocene compound. In the present invention, the metallocene compound that serves as the metallocene structural part can be any known metallocene compound without any particular limitation, as long as it is a compound that conforms to the partial structure defined by general formula (2M) above (a compound in which a hydrogen atom is bonded in place of L). The metallocene structural part defined by general formula (2M) will be specifically described below.

[0092] In general formula (2M), R １ｍ ~R ９ｍ R each represents a hydrogen atom or a substituent. １ｍ ~R ９ｍ The substituents that can be used as the substituent are not particularly limited, but for example, R １ The substituents R can be selected from those which can be taken as R １ｍ ~R ９ｍ are each preferably a hydrogen atom, a halogen atom, an alkyl group, an acyl group, an alkoxy group, an amino group, or an amide group, more preferably a hydrogen atom, a halogen atom, an alkyl group, an acyl group, or an alkoxy group, still more preferably a hydrogen atom, a halogen atom, an alkyl group, or an acyl group, particularly preferably a hydrogen atom, a halogen atom, or an alkyl group, and most preferably a hydrogen atom.

[0093] R １ｍ ~R ９ｍ Examples of alkyl groups that can be used as R １Among the alkyl groups that can be taken as R, alkyl groups 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. This alkyl group may have a halogen atom as a substituent. Examples of alkyl groups substituted with a halogen atom include chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, fluoromethyl, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, perfluoroethyl, perfluoropropyl, and perfluorobutyl. In addition, R １ｍ In the alkyl group which can be taken as the above, at least one methylene group forming the carbon chain may be substituted with -O- or -CO-. Examples of the alkyl group in which a methylene group is substituted with -O- include alkyl groups in which a terminal methylene group is substituted, such as methoxy, ethoxy, propoxy, isopropoxy, isobutoxy, sec-butoxy, tert-butoxy, 2-methoxyethoxy, chloromethyloxy, dichloromethyloxy, trichloromethyloxy, bromomethyloxy, dibromomethyloxy, tribromomethyloxy, fluoromethyloxy, difluoromethyloxy, trifluoromethyloxy, 2,2,2-trifluoroethyloxy, perfluoroethyloxy, perfluoropropyloxy, and perfluorobutyloxy, as well as alkyl groups in which an internal methylene group of the carbon chain, such as 2-methoxyethyl, is substituted. Examples of the alkyl group in which a methylene group is substituted with —CO— include acetyl, propionyl, monochloroacetyl, dichloroacetyl, trichloroacetyl, trifluoroacetyl, propan-2-one-1-yl, and butan-2-one-1-yl.

[0094] In 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 these, M is preferably Fe, Ti, Co, Ni, Zr, Ru, or Os, more preferably Fe, Ti, Ni, Ru, or Os, still more preferably Fe or Ti, and most preferably Fe.

[0095] The group represented by general formula (2M) includes L, R １ｍ ~R ９ｍ and a group formed by combining the preferred ones of M and M together are preferred, and for example, L is a single bond, an alkylene group having 2 to 8 carbon atoms, an arylene group having 6 to 12 carbon atoms, -CH=CH-, -CO-, -NR- (wherein R is as defined above), -O-, -S-, -SO ２ - and -N=CH- or a combination of two or more groups selected from this group, and R １ｍ ~R ９ｍ Examples of the group include a group formed by combining a hydrogen atom, a halogen atom, an alkyl group, an acyl group, or an alkoxy group with Fe as M.

[0096] The alkyl group, alkenyl group, alkynyl group, aralkyl group, aryl group, and heteroaryl group that can be taken as the substituent X, and R １０ ~R ２７The aliphatic group, aromatic group and heterocyclic group which can be taken as may each further have a substituent or may be unsubstituted. The substituents that may be further substituted are not particularly limited, but are preferably 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 hydroxy group, a mercapto group, a halogen atom, a cyano group, a sulfo group, and a carboxy group, and more preferably 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 hydroxy group, a mercapto group, a halogen atom, a cyano group, a sulfo group, and a carboxy group. These groups are represented by the R １ The substituent can be appropriately selected from the substituents that can be taken as the substituent.

[0097] A preferred embodiment of the dye represented by the above general formula (1) is a dye represented by the following general formula (2).

[0098]

[0099] In general formula (2), A １ is the same as A in general formula (1). Among them, a nitrogen-containing five-membered heterocyclic group is preferred.

[0100] In general formula (2), R １ and R ２ R each independently represents a hydrogen atom or a substituent. １ and R ２ may be the same or different, and may be bonded to each other to form a ring. １ and R ２The substituents that can be adopted as the aryl group are not particularly limited, and examples thereof include alkyl groups (methyl groups, ethyl groups, propyl groups, isopropyl groups, butyl groups, t-butyl groups, isobutyl groups, pentyl groups, hexyl groups, octyl groups, dodecyl groups, trifluoromethyl groups, etc.), cycloalkyl groups (cyclopentyl groups, cyclohexyl groups, etc.), alkenyl groups (vinyl groups, allyl groups, etc.), alkynyl groups (ethynyl groups, propargyl groups, etc.), aryl groups (phenyl groups, naphthyl groups, etc.), heteroaryl groups (furyl groups, thienyl groups, pyridyl groups, pyridazyl groups, pyrimidyl groups, pyrazinyl groups, a phenyl group, a triazyl group, an imidazolyl group, a pyrazolyl group, a thiazolyl group, a benzimidazolyl group, a benzoxazolyl group, a quinazolyl group, a phthalazyl group, etc.), a heterocyclic group (also called a heterocyclic group, for example, a pyrrolidyl group, an imidazolidyl group, a morpholyl group, an oxazolidyl group, etc.), an alkoxy group (a methoxy group, an ethoxy group, a propyloxy group, etc.), a cycloalkoxy group (a cyclopentyloxy group, a cyclohexyloxy group, etc.), an aryloxy group (a phenoxy group, a naphthyloxy group, etc.), a heteroaryloxy group (aromatic heterocyclic oxy group), an alkylthio group (methylthio group, ethylthio group, propylthio group, etc.), cycloalkylthio group (cyclopentylthio group, cyclohexylthio group, etc.), arylthio group (phenylthio group, naphthylthio group, etc.), heteroarylthio group (aromatic heterocyclic thio group), alkoxycarbonyl group (methyloxycarbonyl group, ethyloxycarbonyl group, butyloxycarbonyl group, octyloxycarbonyl group, etc.), aryloxycarbonyl group (phenyloxycarbonyl group, naphthyloxycarbonyl group, etc.), phosphoryl group (dimethoxyphosphonyl, diphenylphosphoryl ), sulfamoyl groups (aminosulfonyl groups, methylaminosulfonyl groups, dimethylaminosulfonyl groups, butylaminosulfonyl groups, cyclohexylaminosulfonyl groups, octylaminosulfonyl groups, phenylaminosulfonyl groups, 2-pyridylaminosulfonyl groups, etc.), acyl groups (acetyl groups, ethylcarbonyl groups, propylcarbonyl groups, cyclohexylcarbonyl groups, octylcarbonyl groups, 2-ethylhexylcarbonyl groups, phenylcarbonyl groups, naphthylcarbonyl groups, pyridylcarbonyl groups, etc.), acyloxy groups (acetyloxy groups,ethylcarbonyloxy group, butylcarbonyloxy group, octylcarbonyloxy group, phenylcarbonyloxy group, etc.), amide group (methylcarbonylamino group, ethylcarbonylamino group, dimethylcarbonylamino group, propylcarbonylamino group, pentylcarbonylamino group, cyclohexylcarbonylamino group, 2-ethylhexylcarbonylamino group, octylcarbonylamino group, dodecylcarbonylamino group, phenylcarbonylamino group, naphthylcarbonylamino group, etc.) , sulfonylamide groups (methylsulfonylamino groups, octylsulfonylamino groups, 2-ethylhexylsulfonylamino groups, trifluoromethylsulfonylamino groups, etc.), carbamoyl groups (aminocarbonyl groups, methylaminocarbonyl groups, dimethylaminocarbonyl groups, propylaminocarbonyl groups, pentylaminocarbonyl groups, cyclohexylaminocarbonyl groups, octylaminocarbonyl groups, 2-ethylhexylaminocarbonyl groups, dodecylaminocarbonyl groups, phenylaminocarbonyl groups, etc.), a carboxyl group, a naphthylaminocarbonyl group, a 2-pyridylaminocarbonyl group, etc.), a ureido group (a methylureido group, an ethylureido group, a pentylureido group, a cyclohexylureido group, an octylureido group, a dodecylureido group, a phenylureido group, a naphthylureido group, a 2-pyridylaminoureido group, etc.), an alkylsulfonyl group (a methylsulfonyl group, an ethylsulfonyl group, a butylsulfonyl group, a cyclohexylsulfonyl group, a 2-ethylhexylsulfonyl group, etc.), an arylsulfonyl group Examples of such groups include alkyl groups (phenylsulfonyl group, naphthylsulfonyl group, 2-pyridylsulfonyl group, etc.), amino groups (amino group, ethylamino group, dimethylamino group, butylamino group, dibutylamino group, cyclopentylamino group, 2-ethylhexylamino group, dodecylamino group, anilino group, naphthylamino group, 2-pyridylamino group, etc.), alkylsulfonyloxy groups (methanesulfonyloxy), cyano group, nitro group, halogen atoms (fluorine atom, chlorine atom, bromine atom, etc.), and hydroxy groups. Among these, alkyl groups, alkenyl groups, aryl groups, and heteroaryl groups are preferred, alkyl groups, aryl groups, and heteroaryl groups are more preferred, and alkyl groups are even more preferred.

[0101] R １ and R ２ The substituent that can be taken as R may further have a substituent. １ and R ２ and the substituent X that A, B, and G in the general formula (1) may have. １ and R ２ may be bonded to each other to form a ring, and R １ or R ２ And B ２ or B ３ may bond with the substituents possessed by R to form a ring. The ring formed in this case is preferably a hetero ring or a heteroaryl ring, and the size of the ring formed is not particularly limited, but is preferably a 5-membered or 6-membered ring. The number of rings formed is also not particularly limited, and may be one or two or more. Examples of the form in which two or more rings are formed include, for example, R １ and B ２ The substituents of and R ２ and B ３ and the substituents possessed by each of the groups may be bonded to form two rings.

[0102] 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 containing B is an aromatic ring. １ ~B ４ Among these, at least two are preferably carbon atoms, and B １ ~B ４ It is more preferable that all of B are carbon atoms. １ ~B ４ The carbon atom which can be represented by B has a hydrogen atom or a substituent. １ ~B ４The number of carbon atoms having a substituent among the carbon atoms that can be taken as B is not particularly limited, but is preferably 0, 1 or 2, and more preferably 1. １ and B ４ is a carbon atom, and at least one of them preferably has a substituent. １ ~B ４ The substituents that can be taken by the carbon atom as R are not particularly limited, and １ and R ２ Among these, preferred are alkyl groups, alkoxy groups, alkoxycarbonyl groups, aryl groups, acyl groups, amide groups, sulfonylamido groups, carbamoyl groups, alkylsulfonyl groups, arylsulfonyl groups, amino groups, cyano groups, nitro groups, halogen atoms, and hydroxy groups, and more preferred are alkyl groups, alkoxy groups, alkoxycarbonyl groups, aryl groups, acyl groups, amide groups, sulfonylamido groups, carbamoyl groups, amino groups, cyano groups, nitro groups, halogen atoms, and hydroxy groups. １ ~B ４ The substituents that can be taken as the carbon atom may further have a substituent. Examples of the further substituents that can be taken as the carbon atom include R １ and R ２ and the substituent X that A, B, and G in the general formula (1) may have, and a ferrocenyl group is preferred.

[0103] B １ and B ４ The substituent that the carbon atom may have is more preferably an alkyl group, an alkoxy group, a hydroxy group, an amide group, a sulfonylamido group, or a carbamoyl group, particularly preferably an alkyl group, an alkoxy group, a hydroxy group, an amide group, or a sulfonylamido group, and most preferably a hydroxy group, an amide group, or a sulfonylamido group. １ and B ４ The substituent on the carbon atom that can be represented by may further include a ferrocenyl group. ２ and B ３The substituent that the carbon atom may have is more preferably an alkyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, an amino group, a cyano group, a nitro group, or a halogen atom, and it is particularly preferred that either one of the substituents is an electron-withdrawing group (for example, an alkoxycarbonyl group, an acyl group, a cyano group, a nitro group, or a halogen atom).

[0104] 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).

[0105]

[0106] In general formula (3), R １ and R ２ each independently represents a hydrogen atom or a substituent, and R １ and R ２ In general formula (3), B has the same meaning as B, and the preferred range is also the same. １ ~B ４ each independently represents a carbon atom or a nitrogen atom, and B in the general formula (2) １ ~B ４ The same definition and preferred range are also the same.

[0107] In general formula (3), R ３ and R ４ R each independently represents a hydrogen atom or a substituent. ３ and R ４ The substituents that can be adopted as R １ and R ２ The substituents that can be used as R ３ The substituent that can be taken as R is preferably an alkyl group, an alkoxy group, an amino group, an amido group, a sulfonylamido 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 even more preferably an alkyl group. ３ The substituent that can be taken as R may further have a ferrocenyl group. ４The substituent that can be taken as aryl 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 amido 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 still more preferably an alkyl group.

[0108] R ３ and R ４ The alkyl group may be linear, branched, or cyclic, but is preferably linear or branched. The number of carbon atoms in the alkyl group is preferably 1 to 12, and more preferably 1 to 8. Preferred examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a t-butyl group, a 2-ethylhexyl group, and a cyclohexyl group, and more preferably a methyl group or a t-butyl group.

[0109]

[0110] In general formula (4), R １ and R ２ each independently represents a hydrogen atom or a substituent, and R １ and R ２ In general formula (4), B has the same meaning as B, and the preferred range is also the same. １ ~B ４ each independently represents a carbon atom or a nitrogen atom, and B in the general formula (2) １ ~B ４ The same definition and preferred range are also the same.

[0111] In general formula (4), R ５ and R ６ R each independently represents a hydrogen atom or a substituent. ５ and R ６ The substituents that can be adopted as R １ and R ２ The substituents that can be used as R ５The substituent that can be taken as R 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 amido group, a sulfonylamido group, a ureido group, or a carbamoyl group, more preferably an alkyl group, an alkoxy group, an acyl group, an amido group, or an amino group, and still more preferably an alkyl group. ５ The alkyl group that can be taken as is R ３ The preferred ranges are also the same as those of the alkyl groups that can be taken as above.

[0112] In general formula (4), R ６ The substituent that can be taken as R is preferably an alkyl group, an alkenyl group, an aryl group, a heteroaryl group, a heterocyclic group, an alkoxy group, a cycloalkoxy group, an aryloxy group, an alkoxycarbonyl group, an acyl group, an acyloxy group, an amido group, a sulfonylamido 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, and even more preferably an alkyl group or an aryl group. ６ The alkyl group that can be taken as is R ４ The meanings and preferred ranges of the alkyl groups are the same as those of the alkyl groups that can be taken as R ６ The aryl group that can be taken as (R) is preferably an aryl group having 6 to 12 carbon atoms, and more preferably a phenyl group. This aryl group may have a substituent, and examples of such a substituent include groups included in the following substituent group A, with alkyl groups having 1 to 10 carbon atoms, sulfonyl groups, amino groups, acylamino groups, sulfonylamino groups, and the like being particularly preferred. These substituents may further have a substituent. Specifically, the substituent is preferably an alkylsulfonylamino group.

[0113] - Substituent Group A - A halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxy group, a nitro group, a carboxy group, an alkoxy group, an aminooxy group, an aryloxy group, a silyloxy group, a heterocyclic oxy 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 imido group, a phosphino group, a phosphinyl group, a phosphinyloxy group, a phosphinylamino group, a silyl group, and the like.

[0114]

[0115] In general formula (5), R １ and R ２ each independently represents a hydrogen atom or a substituent, and R １ and R ２ In general formula (5), B has the same meaning as B, and the preferred range is also the same. １ ~B ４ each independently represents a carbon atom or a nitrogen atom, and B in the general formula (2) １ ~B ４ The same definition and preferred range are also the same.

[0116] In general formula (5), R ７ and R ８ R each independently represents a hydrogen atom or a substituent. ７ and R ８ The substituents that can be adopted as R １ and R ２ The substituents that can be used as R ７The preferred range, more preferred range, and even more preferred range of the substituents that can be taken as R in general formula (4) are ５ The substituents are the same as those that can be taken as R ５ The alkyl group that can be taken as R ３ The preferred ranges are also the same as those of the alkyl groups that can be taken as above.

[0117] In general formula (5), R ８ The preferred range, more preferred range, and even more preferred range of the substituents that can be taken as R in general formula (4) are ６ The substituents are the same as those that can be taken as R ８ The preferred range of alkyl groups and aryl groups that can be taken as R in the above general formula (4) is ６ The meanings and preferred ranges of the alkyl and aryl groups are the same as those of the alkyl and aryl groups that can be taken as the above.

[0118] The squaraine dye used in the dye is not particularly limited as long as it is a squaraine dye represented by any one of general formulas (1) to (5). Examples thereof include the compounds described in JP-A-2006-160618, WO-A-2004 / 005981, WO-A-2004 / 007447, Dyes and Pigment, 2001, 49, pp. 161-179, WO-A-2008 / 090757, WO-A-2005 / 121098, and JP-A-2008-275726.

[0119] Specific examples of the dye represented by any one of general formulas (1) to (5) include the compounds described in

[0067] to

[0070] of WO 2021 / 132674. However, the present invention is not limited to these. In addition to the above specific examples, specific examples of the dye represented by any one of general formulas (3) to (5) include the compounds described in

[0071] to

[0080] of WO 2021 / 132674. However, the present invention is not limited to these. Furthermore, as a preferred embodiment of the dye represented by the above general formula (1), the dye represented by any one of general formulas (6) to (9) described in

[0081] to

[0095] of WO 2021 / 132674 and the specific examples thereof can be applied as is.

[0120] (Quencher-Incorporated Dyes) The squaraine dye represented by the general formula (1) may be a quencher-incorporated dye in which a quencher moiety is covalently linked to the dye via a linking group. Such quencher-incorporated dyes can also be preferably used as the dye. That is, the quencher-incorporated dyes are counted as dyes according to the wavelengths of their main absorption wavelength bands. Examples of quencher-incorporated dyes include electron-donating quencher-incorporated dyes in which the quencher moiety is an electron-donating quencher moiety, and electron-accepting quencher moieties in which the quencher moiety is an electron-accepting quencher moiety. The electron-donating quencher moiety refers to a structural moiety that donates an electron to the lower-energy-level SOMO (Singly Occupied Molecular Orbital) of two SOMOs (Singly Occupied Molecular Orbitals) of the dye in an excited state, and then accepts an electron from the higher-energy-level SOMO of the dye, thereby deactivating the excited dye to the ground state. The electron-accepting quencher moiety refers to a structural moiety that receives an electron from the SOMO with the higher energy level of the two SOMOs of a dye in an excited state and then donates an electron to the SOMO with the lower energy level of the dye, thereby deactivating the excited dye to the ground state. Examples of the electron-donating quencher moiety include the ferrocenyl group in the substituent X described above, and the quencher moieties in the quencher compounds described in paragraphs

[0199] to

[0212] and

[0234] to

[0287] of WO 2019 / 066043, with the ferrocenyl group in the substituent X described above being preferred. Furthermore, examples of the electron-accepting quencher moiety include the quencher moieties in the quencher compounds described in paragraphs

[0288] to

[0310] of WO 2019 / 066043.

[0121] In the light-absorbing filter of the present invention, from the viewpoint of light resistance of the light-absorbing moiety, the dye having a main absorption wavelength band in the wavelength range of 400 to 700 nm preferably includes a dye containing an electron-donating quencher, and more preferably includes a squaraine dye represented by the following general formula (1A):

[0122]

[0123] 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, where G represents a heterocyclic group which may have a substituent, provided that at least one of A and B contains an electron-donating quencher moiety.

[0124] The dye represented by the general formula (1A) is the same as the dye represented by the general formula (1) except that at least one of A and B in the dye represented by the general formula (1) includes an electron-donating quencher moiety. Therefore, the descriptions of A, B, and G in the general formula (1A) can be applied to the descriptions of A, B, and G in the general formula (1). Furthermore, as a preferred embodiment of the dye represented by the general formula (1A), the descriptions of the dye represented by any of the general formulas (2) to (9), which are preferred embodiments of the dye represented by the general formula (1), can be applied, with the modifications made so that at least one of the structures corresponding to A and B in the general formula (1) includes an electron-donating quencher moiety. The electron-donating quencher moiety included in at least one of A and B is preferably a ferrocenyl group in the substituent X described above.

[0125] Among the squaraine dyes represented by general formula (1), specific examples of dyes that fall under the category of dyes incorporating a quencher include the compounds described in paragraphs

[0097] to

[0114] of WO 2021 / 132674. However, the present invention is not limited to these.

[0126] The total content of the dyes in the light-absorbing filter of the present invention is preferably 0.10% by mass or more, more preferably 0.15% by mass or more, even more preferably 0.20% by mass or more, particularly preferably 0.25% by mass or more, and especially preferably 0.30% by mass or more. When the total content of the dyes in the light-absorbing filter of the present invention is equal to or greater than the above-mentioned preferable lower limit, good light absorption properties such as anti-reflection effect can be obtained. Furthermore, the total content of the dyes in the light-absorbing filter of the present invention is usually 50% by mass or less, preferably 40% by mass or less, more preferably 30% by mass or less, even more preferably 15% by mass or less, and especially preferably 10% by mass or less. That is, the total content of the dyes in the light-absorbing filter of the present invention is preferably 0.10 to 50% by mass, more preferably 0.15 to 40% by mass, even more preferably 0.20 to 30% by mass, particularly preferably 0.25 to 15% by mass, and especially preferably 0.30 to 10% by mass.

[0127] The content of the azo dye represented by the general formula (i) in the light-absorbing filter of the present invention is preferably 0.01 to 30% by mass, more preferably 0.1 to 10% by mass. Similarly to the content of the azo dye represented by the general formula (i), the azo dye represented by the general formula (iii), the azo dye represented by the general formula (iv), and the indoaniline dye represented by the general formula (v) in the light-absorbing filter of the present invention, the content of each of these dyes is preferably 0.01 to 30% by mass, more preferably 0.1 to 10% by mass. In addition, in the light-absorbing filter of the present invention, all of the dyes may be composed of at least one of the azo dye represented by any one of the general formulas (i) to (iv) and the indoaniline dye represented by the general formula (v). When the light-absorbing filter of the present invention contains a squaraine dye represented by the general formula (1), the content of the squaraine dye represented by the general formula (1) in the light-absorbing filter of the present invention is preferably 0.01 to 30% by mass, more preferably 0.1 to 10% by mass. In the light-absorbing filter of the present invention, all of the dyes, except for the azo dye represented by any one of the general formulas (i) to (iv) and the indoaniline dye represented by the general formula (v), may be squaraine dyes represented by the general formula (1). When the dye contains the quencher-containing dye, the content of the quencher-containing dye in the light-absorbing filter of the present invention is preferably 0.10% by mass or more, more preferably 0.15% by mass or more, even more preferably 0.20% by mass or more, particularly preferably 0.25% by mass or more, and particularly preferably 0.30% by mass or more, from the viewpoint of imparting light absorption properties such as antireflection effect. The upper limit is preferably 45% by mass or less, more preferably 40% by mass or less, more preferably 30% by mass or less, even more preferably 15% by mass or less, and particularly preferably 10% by mass or less. That is, the total content of the quencher-containing dye in the light-absorbing filter is preferably 0.10 to 45% by mass, more preferably 0.15 to 40% by mass, even more preferably 0.20 to 30% by mass, particularly preferably 0.25 to 15% by mass, and especially preferably 0.30 to 10% by mass.

[0128] <Compound that generates radicals upon irradiation with ultraviolet light> The light-absorbing filter of the present invention contains a compound that generates radicals upon irradiation with ultraviolet light (also simply referred to as a "radical generator" in the present invention.) The radical generator is not particularly limited as long as it is a compound that generates radicals upon irradiation with ultraviolet light and has the function of decolorizing the dye. For example, a photoradical generator that may be used in combination with compound B described below can be used as the radical generator.

[0129] The radical generator is preferably a combination of two or more compounds, and a combination in which two or more compounds interact with each other, such as by complex formation, in the light-absorbing filter to generate radicals upon ultraviolet irradiation is also preferred. The types of compounds to be combined may be two or more compounds that exhibit different functions in the mechanism of generating radicals upon ultraviolet irradiation, and two types are preferred. A preferred example of such a combination is a combination of compound A having an acid group and compound B having a structure capable of forming a hydrogen bond with the acid group contained in compound A. When the light-absorbing filter of the present invention contains compound A having an acid group and compound B having a structure capable of forming a hydrogen bond with the acid group contained in compound A, the efficiency of generating radical species upon ultraviolet irradiation is improved compared to when the photoradical generator is used. Therefore, even when ultraviolet irradiation is performed under mild temperature conditions, such as room temperature, sufficient radical species are generated, and these radical species react directly or indirectly with the dye, causing the dye to decompose and fade or lose color. In particular, the azo dyes represented by any one of the general formulas (i) to (iv) and the indoaniline dyes represented by the general formula (v) contained in the light-absorbing filter of the present invention, as well as the squaraine dyes represented by the general formula (1) that may be contained therein, are decolorized with almost no secondary absorption associated with decomposition of the dyes. Compound A having an acid group and compound B having a structure capable of forming a hydrogen bond with the acid group contained in compound A will be described in detail below.

[0130] (1) Compound A Having an Acid Group The light-absorbing filter of the present invention preferably contains, as the radical generator, Compound A having an acid group (also simply referred to as "Compound A" in the present invention), together with Compound B having a structure capable of forming a hydrogen bond with the acid group contained in Compound A, which will be described later. The acid group contained in Compound A is preferably a proton-dissociating group having a pKa of 12 or less. Specific examples of the acid group include a carboxy group, a sulfonamide group, and a phosphonic acid group (-P(=O)(OH) ２ ), phosphate group (-OP(=O)(OH) ２ ), sulfo group, phenolic hydroxyl group, sulfonylimide group, etc., with carboxy group being preferred. Note that pKa refers to the negative common logarithm (-logKa) of the acid dissociation constant (Ka) in water at 25°C, and can be calculated in the same manner as in the pKa of compound B described below, except that the water / methanol = 50 / 50 (volume ratio) mixed solvent is replaced with water. Compound A may be a low molecular weight compound or a high molecular weight compound (hereinafter also referred to as "polymer"), and is preferably a polymer. Compound A being a polymer means that compound A is chemically bonded to a polymer constituting the resin contained in the light-absorbing filter of the present invention. 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, even more preferably 500 or less, and particularly preferably 400 or less. There is no particular restriction on the lower limit, but 100 or more is practical, and 200 or more is preferred. That is, a molecular weight of 100 or more but less than 5,000 is practical, with 200 to 2,000 being preferred, 200 to 1,000 being more preferred, 200 to 500 being even more preferred, and 200 to 400 being particularly preferred. When compound A is a polymer, the lower limit of the weight-average molecular weight of compound A is 5,000 or more, and from the viewpoint of the physical properties of the optical filter, 10,000 or more is preferred, and 15,000 or more is more preferred. The upper limit is not particularly limited, but from the viewpoint of solubility in solvents, 500,000 or less is preferred, 200,000 or less is more preferred, and 150,000 or less is even more preferred. That is, a molecular weight of 5,000 to 500,000 is practical and preferred, 10,000 to 200,000 is more preferred, and 15,000 to 150,000 is more preferred.

[0131] In addition, some or all of the acid groups contained in compound A may or may not be anionized in the light-absorbing filter, and in the present invention, both anionized and non-anionized acid groups are referred to as acid groups. In other words, compound A may or may not be anionized in the light-absorbing filter.

[0132] From the viewpoint of excellent film-forming properties of the light-absorbing filter, the compound A is preferably a compound having a carboxy group. The compound having a carboxy group is preferably a monomer containing a carboxy group (hereinafter also referred to as a "carboxy group-containing monomer") or a polymer containing a carboxy group (hereinafter also referred to as a "carboxy group-containing polymer"), and from the viewpoint of film-forming properties of the light-absorbing filter, it is more preferably a carboxy group-containing polymer.

[0133] In addition, a part or all of the carboxyl groups (—COOH) of the carboxyl group-containing monomer and the carboxyl group-containing polymer may or may not be anionized in the light-absorbing filter, and the anionized carboxyl groups (—COOH － In other words, the carboxy group-containing polymer may be anionized or not in the light-absorbing filter, and the carboxy group-containing polymer may be anionized or not in the light-absorbing filter, and the carboxy group-containing polymer may be anionized or not in the light-absorbing filter, and the carboxy group-containing polymer may be anionized or not in the light-absorbing filter.

[0134] The content of compound A in the light-absorbing filter is preferably 1% by mass or more, more preferably 25% by mass or more, even more preferably 30% by mass or more, particularly preferably 45% by mass or more, and especially 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 even more preferably 97% by mass or less. That is, it is preferably 1% by mass or more but less than 100% by mass, more preferably 25 to 99% by mass, even more preferably 30 to 97% by mass, particularly preferably 45 to 97% by mass, and especially preferably 50 to 97% by mass. In particular, when compound A is a polymer, the content of compound A in the light-absorbing filter is preferably 50% by mass or more but less than 100% by mass, more preferably 60% by mass or more but less than 100% by mass, and even more preferably 70% by mass or more but less than 100% by mass. The upper limit is also preferably 99% by mass or less, more preferably 97% by mass or less, even more preferably 95% by mass or less, and especially preferably 90% by mass or less. The compound A may be used alone or in combination of two or more kinds.

[0135] (Carboxy Group-Containing Monomer) Examples of the carboxy group-containing monomer include polymerizable compounds containing a carboxy group and one or more (e.g., 1 to 15) ethylenically unsaturated groups. Examples of the ethylenically unsaturated group include a (meth)acryloyl group, a vinyl group, and a styryl group, with a (meth)acryloyl group being preferred. When the ethylenically unsaturated group is a (meth)acryloyl group, the carbonyl bond in the (meth)acryloyl group and the carbonyl bond in the carboxy group may share one carbonyl bond. From the viewpoint of superior film-forming properties, the carboxy group-containing monomer is preferably a bifunctional or higher functional monomer containing a carboxy group. Note that a bifunctional or higher functional monomer refers to a polymerizable compound having two or more (e.g., 2 to 15) ethylenically unsaturated groups in one molecule. The number of carboxy groups contained in the carboxy group-containing monomer may be one or more, for example, preferably 1 to 8, more preferably 1 to 4, and even more preferably 1 to 2. The carboxyl group-containing monomer may further have an acid group other than a carboxyl group, such as a phenolic hydroxyl group, a phosphoric acid group, or a sulfonic acid group.

[0136] The difunctional or higher functional monomer containing a carboxy group is not particularly limited and can be appropriately selected from known compounds. Examples of the difunctional or higher functional monomer containing a carboxy group include trade names Aronix M-520 and Aronix M-510 (both manufactured by Toagosei Co., Ltd.).

[0137] Examples of difunctional or higher functional monomers containing a carboxy group include trifunctional to tetrafunctional polymerizable compounds having a carboxy group (compounds having a carboxy group introduced into a pentaerythritol triacrylate and pentaerythritol tetraacrylate [PETA] skeleton (acid value = 80 to 120 mg KOH / g)), and pentafunctional to hexafunctional polymerizable compounds having a carboxy group (compounds having a carboxy group introduced into a dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate [DPHA] skeleton (acid value = 25 to 70 mg KOH / g)). When using the above-mentioned trifunctional or higher functional monomers containing a carboxy group, it is also preferable to use a difunctional or higher functional monomer containing a carboxy group in combination, from the viewpoint of better film-forming properties.

[0138] Examples of the difunctional or higher functional monomer containing a carboxy group and the difunctional or higher functional monomer containing an acid group include the polymerizable compounds having an acid group described in paragraphs 0025 to 0030 of JP-A No. 2004-239942, the contents of which are incorporated herein by reference.

[0139] (Carboxy group-containing polymer) The carboxy group-containing polymer may further have an acid group other than a carboxy group as the acid group. Examples of the acid group other than a carboxy group include a phenolic hydroxyl group, a phosphoric acid group, and a sulfonic acid group. When the carboxy group-containing polymer is a copolymer, the polymer structure may be a random polymer or a regular polymer such as a block polymer.

[0140] <<Constituent Unit Having Carboxy Group>> The carboxyl group-containing polymer preferably has a constituent unit having a carboxyl group. Examples of the constituent unit having a carboxyl group include constituent units derived from (meth)acrylic acid, crotonic acid, itaconic acid, maleic acid, or fumaric acid. Among these, constituent units derived from (meth)acrylic acid are preferred because of their excellent decolorization properties.

[0141] The content of the structural unit having a carboxy group in the carboxy group-containing polymer is preferably 1 to 100 mol %, more preferably 3 to 65 mol %, even more preferably 5 to 45 mol %, and particularly preferably 10 to 45 mol %, when the total of all structural units of the carboxy group-containing polymer is 100 mol %. The structural unit having a carboxy group may be used alone or in combination of two or more types.

[0142] <Constituent Unit Having Aromatic Ring> In addition to the above-mentioned constituent units, the carboxyl group-containing polymer also preferably has a constituent unit having an aromatic ring (preferably an aromatic hydrocarbon ring). For example, a constituent unit derived from a (meth)acrylate having an aromatic ring (specifically, benzyl (meth)acrylate, phenethyl (meth)acrylate, phenoxyethyl (meth)acrylate, etc.) can be mentioned.

[0143] The content of the aromatic ring-containing structural unit in the carboxy group-containing polymer is preferably 0 to 97 mol %, more preferably 0 to 95 mol %, and even more preferably 0 to 90 mol %, when the total of all structural units in the carboxy group-containing polymer is taken as 100 mol %. The aromatic ring-containing structural unit may be used alone or in combination of two or more types.

[0144] <Constituent Unit Having Alicyclic Structure> In addition to the above-mentioned constituent units, the carboxy group-containing polymer also preferably has a constituent unit having an alicyclic structure. Examples of the alicyclic structure include tricyclo[5.2.1.0 ２，６ ] decane ring structure (also called tetrahydrodicyclopentadiene. The monovalent group is dicyclopentanyl), 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). Examples of structural units having an alicyclic structure include structural units derived from (meth)acrylates having an alicyclic structure (specifically, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, cyclohexyl (meth)acrylate, etc.).

[0145] The content of the structural unit having an alicyclic structure in the carboxy group-containing polymer is preferably 0 to 97 mol %, more preferably 0 to 95 mol %, and even more preferably 0 to 90 mol %, when the total of all structural units of the carboxy group-containing polymer is taken as 100 mol %. The structural unit having an alicyclic structure may be used alone, or two or more types may be used in combination.

[0146] <Other Structural Units> The carboxyl group-containing polymer may have other structural units in addition to the structural units described above. Examples of such other structural units include structural units derived from methyl (meth)acrylate. The content of the other structural units in the carboxyl group-containing polymer is preferably 0 to 70 mol%, more preferably 0 to 50 mol%, and even more preferably 0 to 20 mol%, when the total of all structural units in the carboxyl group-containing polymer is taken as 100 mol%. The other structural units may be used alone or in combination of two or more.

[0147] (2) Compound B The light-absorbing filter of the present invention preferably contains, as the radical generator, compound B (also referred to simply as "compound B" in the present invention) having a structure capable of forming a hydrogen bond with the acid group contained in compound A, together with compound A described above. Compound B is preferably a compound having a structure whose basicity increases when it absorbs ultraviolet light and enters an excited state. The increased basicity of compound B in the excited state allows the acid group contained in compound A to form a complex with compound B, which interacts more strongly with compound B, thereby increasing the efficiency of radical generation. The structure of compound B capable of forming 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. Compound B may be a polymer compound (meaning a compound with a molecular weight of 5,000 or more) or a low molecular weight compound (meaning a compound with a molecular weight of less than 5,000), and is preferably a low molecular weight compound. The molecular weight of compound B, which is a low molecular weight compound, is less than 5,000, preferably less than 1,000, more preferably 500 or less, and even more preferably 350 or less. Although there is no particular restriction on the lower limit, it is preferably at least 65, more preferably at least 75. A preferred range of the molecular weight of compound B, which is a low molecular weight compound, is, for example, 65 to 500, more preferably 75 to 350.

[0148] Compound B is preferably an aromatic compound because it has a large molar extinction coefficient with respect to ultraviolet light. Here, an aromatic compound is a compound having one or more aromatic rings. Compound B may contain only one aromatic ring, or multiple aromatic rings. When multiple aromatic rings are present, for example, the aromatic rings may be present in a side chain of a polymer constituting the resin. The aromatic ring may be either an aromatic hydrocarbon ring or an aromatic heterocycle. In the case of an aromatic heterocycle (also referred to as a heteroaromatic ring), the compound has one or more (e.g., 1 to 4) heteroatoms (at least one of nitrogen atom, oxygen atom, sulfur atom, etc.) as ring-membering atoms (ring-constituting atoms), and preferably has one or more (e.g., 1 to 4) nitrogen atoms as ring-membering atoms. Note that unsubstituted aromatic hydrocarbons do not have a structure capable of forming hydrogen bonds with the acid groups contained in compound A, and therefore do not have the function of generating radicals upon ultraviolet irradiation, and therefore do not fall under compound B. Furthermore, 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 does not have a structure capable of forming a hydrogen bond with the acid group contained in compound A, and therefore does not have the function of generating radicals upon ultraviolet irradiation, and does not correspond to compound B. The number of ring-member atoms of the aromatic ring is preferably 5 to 15.

[0149] 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 fused with two rings such as a quinoline ring, an isoquinoline ring, a quinoxaline ring, and a quinazoline ring; and aromatic rings fused with three rings such as an acridine ring, a phenanthridine ring, a phenanthroline ring, and a phenazine ring.

[0150] The aromatic ring may have one or more (e.g., 1 to 5) substituents, and examples of the substituents include an alkyl group, an aryl group, a halogen atom, an acyl group, an alkoxycarbonyl group, an arylcarbonyl group, a carbamoyl group, a hydroxy group, a cyano group, and a nitro group. Furthermore, when the aromatic ring has two or more substituents, the multiple substituents may be bonded to each other to form a non-aromatic ring. Note that when multiple aromatic rings (e.g., 2 to 5 aromatic rings) form a series of aromatic ring structures bonded by a structure selected from single bonds, carbonyl bonds, and multiple bonds (e.g., an optionally substituted vinylene group, -C≡C-, -N=N-, etc.), the entire series of aromatic ring structures is considered to be one specific structure. Furthermore, it is preferable that one or more of the multiple aromatic rings constituting the series of aromatic ring structures be the heteroaromatic ring.

[0151] 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 in which two rings are fused 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 in which three or more rings are fused 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 these specific examples of compound B, the term "compound" refers not only to the compound itself, but also to compounds having a substituent (referred to as "derivatives"), including unsubstituted compounds whose structure has been partially modified to the extent that the effects of the present invention are not impaired. It is believed that these compounds B form complexes with the aforementioned compound A, and generate two radical molecules through the following mechanism when irradiated with ultraviolet light: 1) Compound B in an excited state is generated by absorbing ultraviolet light; 2) A hole moves from excited compound B to compound A in the ground state (an electron from compound A moves to the lower-energy orbital of the two half-occupied orbitals of excited compound B); 3) A proton moves from compound A to compound B, generating a radical in which a hydrogen radical is added to compound B and a radical in which a hydrogen radical is released from compound A. When compound A is a compound having a carboxyl group, the following reaction further occurs, generating a radical by photodecarboxylation: 4) Carbon dioxide is released from the radical resulting from the release of a hydrogen radical from compound A.

[0152] Among these, compound B is preferably one or more of quinoline compounds (quinoline and quinoline derivatives) and isoquinoline compounds (isoquinoline and isoquinoline derivatives). Preferred substituents that these compounds may have are alkyl groups, aryl groups, halogen atoms, acyl groups, alkoxycarbonyl groups, arylcarbonyl groups, carbamoyl groups, hydroxy groups, cyano groups, and nitro groups.

[0153] When compound B is a polymer, the specific structure may be bonded to the polymer main chain via a single bond or a linking group. Compound B, which is a polymer, can be obtained, for example, by polymerizing a monomer having a heteroaromatic ring (specifically, a heteroaromatic ring having a vinyl group and / or a (meth)acrylate monomer having a specific structure (preferably a heteroaromatic ring)). If necessary, compound B may be copolymerized with other monomers.

[0154] Specific examples of compound B include quinoline, 2-methylquinoline, 4-methylquinoline, 2,4-dimethylquinoline, 2-methyl-4-phenylquinoline, isoquinoline, 1-methylisoquinoline, 3-methylisoquinoline, and 1-phenylisoquinoline.

[0155] From the viewpoint of achieving both the decolorization property of the UV-irradiated portion and the durability of the dye in the UV-unirradiated portion, the content of compound B is preferably 0.1 to 50 mass% relative to the total mass of the light-absorbing filter, more preferably 2.0 to 40 mass%, even more preferably 4 to 35 mass%, and particularly preferably 8 to 30 mass%. Furthermore, from the viewpoint of achieving both the decolorization property of the UV-irradiated portion and the durability of the dye in the UV-unirradiated portion, the pKaH (pKa of the conjugate acid), which is a measure of the basicity of compound B, is preferably 2.0 to 7.0, more preferably 3.0 to 6.0, and even more preferably 4.3 to 5.5. 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. The pKa can be calculated by adding 0.01 mol / L of aqueous sodium hydroxide solution dropwise to a 50 / 50 (volume ratio) water / methanol mixed solution of a measurement sample (conjugate acid of compound B) and reading the amount of aqueous sodium hydroxide added dropwise up to the half-equivalent point. Compound B may be used singly or in combination of two or more types.

[0156] In addition to the compound B, the light-absorbing filter of the present invention may contain a compound that generates radicals upon irradiation with ultraviolet light (also referred to as a "photoradical generator" in the present invention). The photoradical generator is not particularly limited as long as it is a compound that generates radicals upon irradiation with ultraviolet light and has the function of decolorizing the dye. The radical generated may be a biradical in addition to a normal radical. As the photoradical generator, compounds commonly used as photoradical polymerization initiators or photoradical generators can be used without any 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, lophine dimer generators, onium salt generators, borate salt generators, active ester generators, active halogen generators, inorganic complex generators, and coumarin generators. Note that the "XX generator" in the specific examples of the photoradical generators may be referred to as "XX compound" or "XX type", etc., and will hereinafter be referred to as "XX compound". Specific examples, preferred forms, commercially available products, etc. of photoradical generators are described in paragraphs

[0133] to

[0151] of JP 2009-098658 A as specific examples, preferred forms, commercially available products, etc. of photoradical initiators, and these can also be suitably used in the present invention.

[0157] The photoradical generator is preferably a compound that generates radicals by intramolecular cleavage, or a compound that generates radicals by abstracting a hydrogen atom from a nearby compound. From the viewpoint of further improving the decolorization rate, a compound that generates radicals by abstracting a hydrogen atom from a nearby compound is more preferable. The compound that generates radicals by intramolecular cleavage (hereinafter also referred to as "intramolecular cleavage-type photoradical generator") refers to a compound that generates radicals by homolytic bond cleavage of a compound that absorbs light. Examples of intramolecular cleavage-type photoradical generators include acetophenone compounds, benzoin compounds, phosphine oxide compounds, oxime compounds, ketal compounds, azo compounds, peroxide compounds, disulfide compounds, onium salt compounds, borate salt compounds, active ester compounds, active halogen compounds, inorganic complex compounds, and coumarin compounds. Among these, carbonyl compounds such as acetophenone compounds, benzoin compounds, or phosphine oxide compounds are preferred. The Norrish type I reaction is known as a photodecomposition reaction of intramolecular cleavage-type carbonyl compounds, and this reaction can be used as a reference for the radical generation mechanism.

[0158] The above-mentioned compound that generates radicals by abstracting hydrogen atoms from nearby compounds (hereinafter also referred to as "hydrogen abstraction photoradical generator") refers to a compound in which a carbonyl compound in an excited triplet state obtained by light absorption abstracts a hydrogen atom from a nearby compound, thereby generating radicals. Known examples of hydrogen abstraction photoradical generators include carbonyl compounds, such as benzophenone compounds, anthraquinone compounds, and thioxanthone compounds. The Norrish II reaction is known as a photodecomposition reaction of hydrogen abstraction carbonyl compounds, and this reaction can be used to explain the radical generation mechanism. Examples of nearby compounds include various components present in light-absorbing filters, such as resins, dyes, and radical generators. Nearby compounds become compounds containing radicals by abstracting hydrogen atoms. Dyes that have had their hydrogen atoms abstracted by a hydrogen abstraction photoradical generator become active compounds containing radicals, and reactions such as decomposition of the dye containing these radicals can also cause fading or discoloration of the dye. Furthermore, when a hydrogen abstraction photoradical generator abstracts a hydrogen atom within a molecule, a biradical is generated. As the hydrogen abstraction type photoradical generator, a benzophenone compound is preferred from the viewpoint of the quantum yield of the hydrogen abstraction reaction.

[0159] Various examples of photoradical generators are described in "Latest UV Curing Technology," published by Technical Information Association, Inc., 1991, p. 159, and "Ultraviolet Curing System," by Kiyomi Kato, published by the General Technology Center, 1989, pp. 65-148, and these can also be suitably used in the present invention.

[0160] In the photoradical generator, the maximum absorption wavelength of the ultraviolet light to be absorbed is preferably in the range of 250 to 400 nm, more preferably in the range of 240 to 400 nm, and even more preferably in the range of 270 to 400 nm. When the photoradical generator is a benzophenone compound, the maximum absorption wavelength of the ultraviolet light to be absorbed is in the range of n-π ＊ The wavelength of the absorption maximum attributable to the transition is preferably in the range of 260 to 400 nm, more preferably in the range of 285 to 345 nm.＊ The wavelength of the absorption maximum attributable to 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 within the above range, the compound can effectively absorb light from a light source such as a metal halide lamp used during exposure, while being less likely to absorb ultraviolet light entering from the outside when incorporated into a display device, thereby achieving both light resistance in the unexposed area and decolorization in the exposed area. Among benzophenone compounds, examples of photoradical generators having absorption in the longer wavelength region include alkoxybenzophenone compounds.

[0161] The maximum absorption wavelength of ultraviolet light absorbed by the photoradical generator and the main absorption wavelength band of the dye having a main absorption wavelength band in the wavelength range of 400 to 700 nm are usually preferably at least 30 nm apart, with no particular upper limit.

[0162] Commercially available photocleavage type photoradical generators include, by trade name, "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," and "OXE01," all of which are manufactured by BASF (formerly Chiba Specialty Chemicals). Examples include "Kayacure DETX-S," "Kayacure BP-100," "Kayacure BDMK," "Kayacure CTX," "Kayacure BMS," "Kayacure 2-EAQ," "Kayacure ABQ," "Kayacure CPTX," "Kayacure EPD," "Kayacure ITX," "Kayacure QTX," "Kayacure BTC," and "Kayacure MCA," all manufactured by Kayaku Co., Ltd., and also "Esacure (KIP100F, KB1, EB3, BP, X33, KTO46, KT37, KIP150, or TZT)" manufactured by Sartomer Co., Ltd. Combinations of two or more of these are also preferred examples.

[0163] When the light-absorbing filter of the present invention contains a photoradical generator, the content of the photoradical generator in the light-absorbing filter of the present invention is preferably 0.01 to 30% by mass, more preferably 0.1 to 20% by mass.

[0164] From the viewpoint of further improving the decolorization rate, the amount of radical generator in the light-absorbing filter of the present invention is preferably 0.1 to 20 moles per mole of dye having a main absorption wavelength band in the wavelength range of 400 to 700 nm. The lower limit is more preferably 0.25 moles or more, and even more preferably 0.50 moles or more. The upper limit is more preferably 17.5 moles or less, and even more preferably 15 moles or less. The amount of radical generator referred to here means the amount of the above-mentioned photoradical generator or the amount of compound B, and does not include the amount of compound A. The light-absorbing filter of the present invention may contain one type of radical generator, or two or more types of radical generators.

[0165] <Resin> The resin (hereinafter also referred to as "matrix resin") contained in the light-absorbing filter of the present invention is not particularly limited as long as it can disperse (preferably dissolve) the dye, can exert the decolorizing action of the dye by radicals generated from a compound that generates radicals upon ultraviolet irradiation (preferably compound B that is hydrogen-bonded with an acid group contained in compound A), and has the desired light transmittance (it is preferable that the light transmittance is 80% or more in the visible region of wavelengths of 400 to 800 nm).

[0166] Various polymers can be used as the polymer constituting the resin, but from the viewpoint of preventing the molecular weight of the resin from decreasing due to ultraviolet irradiation, polymers having an aromatic ring or alicyclic structure in the side chain are preferred, and (meth)acrylic polymers containing structural units having an aromatic ring or alicyclic structure are more preferred. Among them, from the viewpoint of further improving the decolorization rate and further improving heat resistance and light resistance, (meth)acrylic polymers containing structural units having an alicyclic structure are even more preferred. Here, (meth)acrylic polymer refers to a polymer containing at least one structural unit derived from (meth)acrylic acid and a structural unit derived from a (meth)acrylic acid ester. Note that 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 carboxy group as the acid group in the above-mentioned compound A, and corresponds to the above-mentioned polymer in which the above-mentioned compound A is chemically bonded to the polymer constituting the resin. Furthermore, in the present disclosure, the "main chain" refers to the relatively longest bonded chain in the molecule of the polymer compound, and the "side chain" refers to an atomic group branched from the main chain.

[0167] Examples of monomers that derive structural units having an aromatic ring include benzyl acrylate, benzyl methacrylate, naphthyl acrylate, naphthyl methacrylate, naphthyl methyl acrylate, naphthyl methyl methacrylate, 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% by mass, more preferably 10 to 100% by mass, and even more preferably 20 to 100% by mass, relative to the total mass of the polymer.

[0168] Examples of monomers that derive a structural unit having an alicyclic structure include dicyclopentanyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, etc. When the polymer contains a structural unit having an alicyclic structure, the content of the structural unit having an alicyclic structure is preferably 1 to 90 mass%, more preferably 5 to 90 mass%, and even more preferably 5 to 80 mass%, relative to the total mass of the polymer.

[0169] Furthermore, in the light-absorbing filter of the present invention, the polymer constituting the resin may contain a structural unit bonded to a compound A having an acid group. The structural unit bonded to a compound A having an acid group is preferably a structural unit derived from (meth)acrylic acid. The content of the structural unit derived from (meth)acrylic acid is preferably 1 to 70 mass% and more preferably 1 to 60 mass% relative to the total mass of the polymer. More preferably, the description of the content of structural units having a carboxy group in the carboxy group-containing polymer of compound A described above applies. When the polymer constituting the resin contains a structural unit bonded to a compound A having an acid group, the content of structural units having an aromatic ring, and the content of structural units having an alicyclic structure in the carboxy group-containing polymer of compound A described above apply to the content of structural units bonded to a compound A having an acid group, the content of structural units having an aromatic ring, and the content of structural units having an alicyclic structure.

[0170] The polymer constituting the resin may contain a structural unit having an alkyl group having 1 to 14 carbon atoms from the viewpoint of adjusting the glass transition temperature, etc. Examples of structural units having an alkyl group having 1 to 14 carbon atoms include structural units derived from alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, t-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, and tetradecyl (meth)acrylate. In the present invention, structural units having an alkyl group having 1 to 14 carbon atoms may be used alone, or two or more types may be used in combination. The content of the structural unit having an alkyl group having 1 to 14 carbon atoms is preferably 0 to 95% by mass relative to the total mass of the polymers constituting the resin.

[0171] 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.

[0172] <Other Components> The absorption filter of the present invention may contain, in addition to the above-mentioned dye, the above-mentioned compound that generates radicals upon irradiation with ultraviolet light, and the above-mentioned resin (matrix polymer), an anti-fading agent, a matting agent, a leveling agent (surfactant), and the like.

[0173] <Anti-Fading Agent> In the light-absorbing filter of the present invention, the anti-fading agent is preferably one that does not inhibit discoloration due to ultraviolet irradiation, and that has the effect of suppressing decomposition of the dye due to visible light.

[0174] As the anti-fading agent, a compound represented by the following general formula (IV) can be preferably used.

[0175]

[0176] In formula (IV), R １０ is an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, or R １８ CO-, R １９ SO ２ - or R ２０ represents a group represented by NHCO-. １８ , R １９ and R ２０ R 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; 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, provided that R １０ ~R ２０ The alkyl group in the formula (I) includes an aralkyl group.

[0177] The compound represented by the general formula (IV) is the same as the compound represented by the general formula (IV) described in

[0215] to

[0221] of WO 2021 / 221122. Therefore, for the description of each substituent in the general formula (IV) and specific examples of the compound represented by the general formula (IV), the description of

[0217] to

[0221] of WO 2021 / 221122 can be applied as is.

[0178] As the above-mentioned anti-fading agent, a compound represented by the following general formula [III] can also be preferably used.

[0179]

[0180] In general formula [III], R ３１ represents an aliphatic group or an aromatic group, and Y represents a group of non-metallic atoms necessary to form a 5- to 7-membered ring together with the nitrogen atom.

[0181] 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 WO 2021 / 221122. Therefore, for the description of each substituent in the general formula [III], and specific examples of compounds represented by the general formula [III], the description of

[0225] to

[0227] of WO 2021 / 221122 can be applied as is. In addition to the above specific examples, specific examples of the compound represented by the general formula [III] include the exemplary compounds B-1 to B-65 described on pages 8 to 11 of JP-A-2-167543, and the exemplary compounds (1) to (120) described on pages 4 to 7 of JP-A-63-95439.

[0182] The content of the anti-fading agent in the light-absorbing filter of the present invention is preferably 1 to 15 mass %, more preferably 5 to 15 mass %, even more preferably 5 to 12.5 mass %, and particularly preferably 10 to 12.5 mass %. By containing the anti-fading agent within the above preferred range, the light resistance of the dye (pigment) can be improved without causing side effects such as discoloration.

[0183] (Matting Agent) Fine particles may be added to the surface of the light-absorbing filter of the present invention to provide slipperiness and prevent blocking, within the range that does not impair the effects of the present invention. These fine particles include silica (silicon dioxide, SiO ) whose surface is coated with hydrophobic groups and which takes the form of secondary particles. ２ ) is preferably used. As the fine particles, fine particles 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 may be used together with or instead of silica. Examples of commercially available fine particles include R972 and NX90S (both manufactured by Nippon Aerosil Co., Ltd., trade names).

[0184] These fine particles function as a so-called matting agent, and by adding the fine particles, minute irregularities are formed on the surface of the light-absorbing filter of the present invention, and due to these irregularities, even when the light-absorbing filters of the present invention are overlapped with each other or with other films, etc., they do not stick to each other, and smoothness is ensured. When the light-absorbing filter of the present invention contains a matting agent as fine particles, the minute irregularities caused by the protrusions of the fine particles protruding from the filter surface are such that the number of protrusions of 30 nm or more in height is 10 or more. ４ pieces / mm ２ When the above amount is present, the effect of improving the slipperiness and blocking properties is particularly great.

[0185] It is particularly preferable to apply the matting agent (fine particles) to the surface layer in terms of improving blocking properties and slip properties. Methods for applying fine particles to the surface layer include multilayer casting and coating. The content of the matting agent in the light-absorbing filter of the present invention is appropriately adjusted depending on the purpose. However, when the light-absorbing filter of the present invention is provided with a gas barrier layer described below, it is preferable to apply the above-mentioned matting agent fine particles to the surface of the light-absorbing filter that comes into contact with the gas barrier layer, within a range that does not impair the effects of the present invention.

[0186] (Leveling Agent) A leveling agent (surfactant) can be appropriately mixed into the light-absorbing filter of the present invention. Commonly used compounds can be used as the leveling agent, and fluorine-containing surfactants are particularly preferred. Specific examples include the compounds described in paragraphs

[0028] to

[0056] of the specification of JP-A No. 2001-330725. Furthermore, as a commercially available product, the Megafac F (trade name) series manufactured by DIC Corporation can also be used. The content of the leveling agent in the light-absorbing filter of the present invention is appropriately adjusted depending on the purpose.

[0187] In addition to the above components, the light-absorbing filter of the present invention may contain a low-molecular-weight plasticizer, an oligomeric plasticizer, a retardation regulator, a deterioration inhibitor, a release promoter, an infrared absorber, an antioxidant, a filler, a compatibilizer, etc. Furthermore, the light-absorbing filter of the present invention may contain a reaction accelerator or a reaction retarder described in paragraphs

[0020] and

[0021] of JP-A-09-286979.

[0188] <Method for manufacturing a light-absorbing filter> The light-absorbing filter of the present invention can be produced by a conventional method, such as a solution film-forming method, a melt extrusion method, or a method (coating method) of forming a coating layer on a substrate film (support film) by any method, and stretching can also be combined as appropriate. The light-absorbing filter of the present invention is preferably produced by a coating method. As the above-mentioned solution film-forming method and melt extrusion method, the descriptions of the solution film-forming method and melt extrusion method in

[0197] to

[0203] of WO 2021 / 132674 can be applied as is.

[0189] (Coating Method) In the coating method, a solution of the material of the light-absorbing filter is applied to a support film to form a coating layer. A release agent or the like may be applied in advance to the surface of the support film as needed to control adhesion to the coating layer. The coating layer can be used by laminating it to another member via an adhesive layer in a later step, and then peeling off the support film. Any adhesive can be used as the adhesive constituting the adhesive layer. The support film can be stretched as needed with the solution of the material of the light-absorbing filter applied to it or with the coating layer laminated on it.

[0190] The solvent used for the solution of the material of the light-absorbing filter can be appropriately selected from the viewpoints of being able to dissolve or disperse the material of the light-absorbing filter, being able to easily form a uniform surface in the coating step and drying step, being able to ensure liquid preservation properties, having an appropriate saturated vapor pressure, etc.

[0191] -Addition of dye (pigment) and radical generator- The timing of adding the dye and the radical generator to the material of the light-absorbing filter is not particularly limited as long as they are added at the time of film formation. For example, they may be added at the time of synthesis of the matrix polymer, or they may be mixed with the material of the light-absorbing filter when preparing a coating liquid for the material of the light-absorbing filter. Note that when the radical generator contains a combination of compound A and compound B, and compound A is bonded to the polymer that constitutes the resin, compound A is added when the polymer that constitutes the resin is added.

[0192] -Support Film- The support film used to form the light-absorbing filter of the present invention by a coating method or the like preferably has a film thickness of 5 to 100 μm, more preferably 10 to 75 μm, and even more preferably 15 to 55 μm. When the film thickness is equal to or greater than the above-mentioned preferable lower limit, sufficient mechanical strength is easily ensured, and defects such as curling, wrinkling, and buckling are unlikely to occur. Furthermore, when the film thickness is equal to or less than the above-mentioned preferable upper limit, when a multilayer film of the light-absorbing filter of the present invention and a support film is stored, for example, in the form of a long roll, the surface pressure applied to the multilayer film is easily adjusted to an appropriate range, and adhesion defects are unlikely to occur.

[0193] The surface energy of the support film is not particularly limited, but the adhesive strength between the light-absorbing filter of the present invention and the support film can be adjusted by adjusting the relationship between the surface energies of the material and coating solution of the light-absorbing filter of the present invention and the surface energy of the surface of the support film on which the light-absorbing filter of the present invention is formed. If the difference in surface energy is reduced, the adhesive strength tends to increase, and if the difference in surface energy is increased, the adhesive strength tends to decrease, and can be set appropriately.

[0194] In addition, the surface unevenness of the support film is not particularly limited, but can be adjusted according to the relationship between the surface energy, hardness, and surface unevenness of the light-absorbing filter of the present invention and the surface energy and hardness of the surface opposite to the side where the light-absorbing filter of the present invention is formed of the support film, for example, for the purpose of preventing adhesion failure when storing the multilayer film of the light-absorbing filter of the present invention and the support film in a long roll form.If the surface unevenness is increased, adhesion failure tends to be suppressed, and if the surface unevenness is reduced, the surface unevenness of the light-absorbing filter of the present invention tends to be reduced, and the haze of the light-absorbing filter of the present invention tends to be reduced, and can be set appropriately.

[0195] Any material or film can be used as the support film. Specific examples of the material include polyester polymers (including polyethylene terephthalate), olefin polymers, cycloolefin polymers, (meth)acrylic polymers, cellulose polymers, and polyamide polymers. Furthermore, the support film can be subjected to a surface treatment to adjust its surface properties. For example, corona treatment, room temperature plasma treatment, saponification treatment, etc. can be performed to reduce the surface energy, and silicone treatment, fluorine treatment, olefin treatment, etc. can be performed to increase the surface energy.

[0196] <Film Thickness of the Light-Absorption Filter of the Present Invention> The film thickness of the light-absorbing filter of the present invention is not particularly limited, but is preferably 1 to 18 μm, more preferably 1 to 12 μm, and even more preferably 2 to 8 μm. When the film thickness is equal to or less than the above-mentioned preferred upper limit, adding a dye at a high concentration to a thin film can suppress a decrease in polarization degree due to fluorescence emitted by the dye (pigment). The effect of the quencher is also easily manifested. On the other hand, when the film thickness is equal to or greater than the above-mentioned preferred lower limit, it becomes easier to maintain uniformity of in-plane absorbance. In the present invention, a film thickness of 1 to 18 μm means that the thickness of the light-absorbing filter of the present invention is within the range of 1 to 18 μm regardless of the location 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 Anritsu Corporation.

[0197] <Absorbance of the Light-Absorbing Filter of the Present Invention> In the light-absorbing filter of the present invention, the absorbance at the maximum absorption wavelength (hereinafter simply referred to as "Ab(λ")) exhibiting the largest absorbance in the wavelength range of 400 to 700 nm is ｍａｘ ) is preferably 0.3 or more, more preferably 0.5 or more, and even more preferably 0.7 or more. However, the absorbance of the light-absorbing filter of the present invention can be adjusted by the type of dye, the amount added, or the film thickness. The light-absorbing filter of the present invention preferably has a decolorization rate by ultraviolet irradiation at 25°C of 85% or more, more preferably 87% or more, and even more preferably 90% or more. There is no particular upper limit, and 100% is also preferable. The decolorization rate is determined by the above Ab(λ) before and after the ultraviolet irradiation test. ｍａｘ ) is calculated by the following formula: Decolorization rate (%) = 100 - (Ab(λ) after ultraviolet irradiation) ｍａｘ ) / Ab(λ ｍａｘ )) × 100 Here, the ultraviolet irradiation test was carried out under atmospheric pressure (101.33 kPa) using an ultra-high pressure mercury lamp (manufactured by HOYA Corporation, product name: UL750) with an illuminance of 100 mW / cm ２ , irradiation amount 750-1500mJ / cm ２The light-absorbing filter is irradiated with ultraviolet light at room temperature (25° C.) The absorbance, ultraviolet irradiation test, and decolorization rate can be measured and calculated by the methods described in the examples.

[0198] Furthermore, it is preferable that the light-absorbing filter of the present invention hardly generates absorption (secondary absorption) derived from a new colored structure accompanying decomposition of the dye. For example, the presence or absence of absorption derived from a new colored structure accompanying decomposition of the dye can be determined by the above-mentioned Ab(λ ｍａｘ The specific wavelength is selected at which the dye before UV irradiation shows almost no absorption and at which new absorption due to decomposition of the dye is observed. As a specific example, as described in the Examples below, the presence or absence of absorption due to the new colored structure accompanying decomposition of the dye can be confirmed based on the ratio of the absorbance at the specific wavelength to the absorbance at the specific wavelength Ab(λ ｍａｘ The specific wavelength is selected at which the dye before UV irradiation shows almost no absorption and at which new absorption due to decomposition of the dye is observed. As a specific example, as described in the Examples below, the presence or absence of absorption due to a new colored structure accompanying decomposition of the dye can be confirmed based on the ratio of the absorbance at the specific wavelength to the Ab(λ ｍａｘ The absorbance at a wavelength of 450 nm (hereinafter also referred to simply as "Ab(450)") to the ... ｍａｘ ) × 100% (II) Ab(450) after UV irradiation / Ab(λ) before UV irradiation ｍａｘ) × 100% The presence or absence of absorption due to the new colored structure accompanying the decomposition of the dye can be confirmed by measurement and calculation using the method described in the Examples. Furthermore, as described in the Examples below, the absorbance at a wavelength of 650 nm (hereinafter also simply referred to as "Ab(650)") can be used instead of the absorbance at a wavelength of 450 nm, and the evaluation can also be performed based on the value obtained by subtracting the ratio (III) below from the ratio (IV) below. The preferred range of the value obtained by subtracting the ratio (III) below from the ratio (IV) below is the same as the value obtained by subtracting the ratio (I) from the ratio in the above formula (II). (III) Ab(650) before ultraviolet irradiation / Ab(λ before ultraviolet irradiation) ｍａｘ ) × 100% (IV) Ab(650) after UV irradiation / Ab(λ) before UV irradiation ｍａｘ ) × 100% Here, the description of the ultraviolet irradiation test for the quenching rate can be preferably applied to the ultraviolet irradiation test. The presence or absence of absorption due to the new colored structure accompanying the decomposition of the dye can be measured and calculated by the method described in the Examples.

[0199] The light-absorbing filter of the present invention can exhibit excellent decolorization properties when the above-mentioned decolorization rate and the value confirming the presence or absence of absorption derived from a new colored structure accompanying decomposition of the dye both fall within preferred ranges.

[0200] The light-absorbing portion having a light-absorbing effect in the optical filter of the present invention is Ab(λ ｍａｘ ) is preferably satisfied.

[0201] <Treatment of the Light-Absorbing Filter of the Present Invention> The light-absorbing filter of the present invention may be subjected to hydrophilization treatment by any of glow discharge treatment, corona discharge treatment, alkaline saponification treatment, etc., and corona discharge treatment is preferably used. It is also preferable to apply the methods disclosed in JP-A-6-94915 or JP-A-6-118232, etc.

[0202] The obtained film may be subjected to a heat treatment step, a superheated steam contact step, an organic solvent contact step, etc., as required. In addition, a surface treatment may be appropriately performed.

[0203] Furthermore, the pressure-sensitive adhesive layer may be a layer made of a pressure-sensitive adhesive composition having a base polymer such as a (meth)acrylic resin, a styrene resin, a silicone resin, or the like, to which a crosslinking agent such as an isocyanate compound, an epoxy compound, or an aziridine compound has been added. Preferably, the description of the pressure-sensitive adhesive layer in the OLED display device described below can be applied.

[0204] <Gas barrier layer> The light-absorbing filter of the present invention may have a gas barrier layer on at least one side. When the light-absorbing filter of the present invention has a gas barrier layer, the light-absorbing filter of the present invention can be a light-absorbing filter that achieves both excellent decolorization properties and excellent light resistance, and can be suitably used for producing optical filters, which will be described later. The material for forming the gas barrier layer is not particularly limited, and examples thereof include organic materials (preferably crystalline resins) such as polyvinyl alcohol and polyvinylidene chloride, organic-inorganic hybrid materials such as sol-gel materials, SiO ２ , SiO ｘ , SiON, SiN ｘ and Al ２ O ３ The gas barrier layer may be a single layer or a multilayer, and in the case of a multilayer, examples of the gas barrier layer include an inorganic dielectric multilayer film and a multilayer film in which organic materials and inorganic materials are alternately laminated.

[0205] The light-absorbing filter of the present invention has a gas barrier layer at least on the surface that comes into contact with air when the light-absorbing filter of the present invention is used, thereby making it possible to suppress a decrease in the absorption intensity of the dye in the light-absorbing filter of the present invention. As long as a gas barrier layer is provided on the interface of the light-absorbing filter of the present invention that comes into contact with air, the gas barrier layer may be provided on only one surface of the light-absorbing filter of the present invention or on both surfaces.

[0206] In particular, when the gas barrier layer contains a crystalline resin, the gas barrier layer contains a crystalline resin, has a layer thickness of 0.1 μm to 10 μm, and has an oxygen permeability of 60 cc / m ２In the gas barrier layer, the "crystalline resin" is a resin that has a melting point at which it undergoes a phase transition from crystal to liquid when the temperature is increased, and is capable of imparting gas barrier properties related to oxygen gas to the gas barrier layer. ２ The "gas barrier layer having a viscosity of 1000 psi / day atm or less" is the same as the gas barrier layer described in paragraphs

[0180] to

[0184] of WO 2022 / 149510, and the description of the gas barrier layer described in paragraphs

[0180] to

[0184] of WO 2022 / 149510 can be applied as is.

[0207] <Method for manufacturing gas barrier layer> The method for forming the gas barrier layer is not particularly limited, but may be a conventional method, for example, in the case of an organic material, a casting method such as spin coating or slit coating may be used. Also, a method of laminating a commercially available resin gas barrier film or a pre-prepared resin gas barrier film to the light-absorbing filter of the present invention may be used. Furthermore, in the case of an inorganic material, a plasma CVD (Plasma Enhanced Chemical Vapor Deposition) method, a sputtering method, a vapor deposition method, etc. may be used.

[0208] When providing the above-mentioned gas barrier layer on the light-absorbing filter of the present invention, for example, a method of directly forming the above-mentioned gas barrier layer on the light-absorbing filter of the present invention produced by the above-mentioned production method can be mentioned.In this case, it is also preferable to subject the surface of the light-absorbing filter of the present invention on which the gas barrier layer is to be provided to a corona treatment.In addition, when providing any of the above-mentioned optically functional films, it is also preferable to attach them via an adhesive layer.For example, it is also preferable to provide a gas barrier layer on the light-absorbing filter of the present invention, and then further attach an optically functional film via an adhesive layer.

[0209] <Optical Functional Film> The light-absorbing filter of the present invention may appropriately have the gas barrier layer or any optical functional film as long as the effects of the present invention are not impaired. The optical properties and materials of the optional optical functional film are not particularly limited, but a film containing (or having as its main component) at least one of cellulose ester resin, acrylic resin, cyclic olefin resin, and polyethylene terephthalate resin can be preferably used. An optically isotropic film or an optically anisotropic retardation film may be used. As the optional optical functional film containing a cellulose ester resin, for example, Fujitac TD80UL (manufactured by Fujifilm Corporation) can be used. Examples of the optically functional film containing an acrylic resin include an optical film containing a (meth)acrylic resin containing a styrene-based resin as described in Japanese Patent No. 4,570,042, an optical film containing a (meth)acrylic resin having a glutarimide ring structure in the main chain as described in Japanese Patent No. 5,041,532, an optical film containing a (meth)acrylic resin having a lactone ring structure as described in Japanese Patent Laid-Open No. 2009-122664, and an optically functional film containing a (meth)acrylic resin having a glutaric anhydride unit as described in Japanese Patent Laid-Open No. 2009-139754. Examples of the optically functional film containing a cyclic olefin resin include a cyclic olefin resin film as described in paragraph

[0029] and subsequent paragraphs of Japanese Patent Laid-Open No. 2009-237376, and a cyclic olefin resin film containing an additive that reduces Rth as described in Japanese Patent No. 4,881,827 and Japanese Patent Laid-Open No. 2008-063536.

[0210] [Optical Filter] The optical filter of the present invention is obtained by masked exposure of the light-absorbing filter of the present invention with ultraviolet irradiation. The optical filter of the present invention has light-absorbing portions having a light-absorbing effect and portions in which the light-absorbing property has been eliminated (light-absorbency-eliminated portions) according to the pattern of the masked exposure (hereinafter also referred to as "mask pattern"). That is, by masked exposure of the light-absorbing filter of the present invention with ultraviolet irradiation, the masked portions of the light-absorbing filter of the present invention are not exposed and exist as light-absorbing portions having a light-absorbing effect, while the unmasked portions are exposed and become light-absorbency-eliminated portions. The light-absorbency-eliminated portions can exhibit a desired absorbance. Furthermore, the light-absorbency-eliminated portions can exhibit optical properties that are close to colorless, since the light-absorbing filter of the present invention exhibits an excellent decolorization rate and there is almost no secondary absorption associated with dye decomposition.

[0211] <Method for Manufacturing Optical Filter> The optical filter of the present invention can be obtained by irradiating the light-absorbing filter of the present invention with ultraviolet light and exposing it to a mask. The mask pattern can be adjusted appropriately so as to obtain an optical filter of the present invention having a desired pattern composed of light-absorbing portions and light-absorbency-eliminating portions. The conditions for ultraviolet irradiation can be adjusted appropriately so as to obtain an optical filter of the present invention having light-absorbency-eliminating portions. For example, the pressure conditions can be atmospheric pressure (101.33 kPa), and the temperature conditions can be mild, such as room temperature (10 to 30°C), without heating. The lamp output can be 10 to 320 W / cm. The lamp used can be an air-cooled metal halide lamp, a mercury lamp such as an ultra-high pressure mercury lamp, or the like. The irradiation dose can be 200 to 2000 mJ / cm. ２ It can be said that:

[0212] The optical filter of the present invention may have an optically functional film as described in the light-absorbing filter of the present invention. The optical filter of the present invention may also have a layer containing an ultraviolet absorber. The ultraviolet absorber is not particularly limited and a commonly used compound can be used, for example, the ultraviolet absorber in the ultraviolet absorbing layer described below. 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 used. The content of the ultraviolet absorber in the layer containing the ultraviolet absorber is appropriately adjusted depending on the purpose.

[0213] [OLED Display Device] The organic electroluminescence display device of the present invention (also referred to as an organic EL (electroluminescence) display device or OLED (organic light-emitting diode) display device, and in the present invention, also abbreviated as an OLED display device) includes the optical filter of the present invention. The OLED display device of the present invention can be configured with any commonly used OLED display device, without any particular limitations, as long as it includes the optical filter of the present invention. Examples of the configuration of the OLED display device of the present invention are not particularly limited, and include, for example, a display device including, from the side opposite to external light, glass, a layer including a TFT (thin film transistor), an OLED display element, a barrier film, a color filter, glass, an adhesive layer, and the optical filter and surface film of the present invention. The OLED display element has a configuration in which an anode electrode, a light-emitting layer, and a cathode electrode are laminated in this order. In addition to the light-emitting layer, a hole injection layer, a hole transport layer, an electron transport layer, an electron injection layer, etc. are included between the anode electrode and the cathode electrode. In addition, for example, the description in JP 2014-132522 A can be referred to. Furthermore, as the color filter, in addition to a normal color filter, a color filter in which quantum dots are laminated can also be used. A resin film can also be used instead of the glass.

[0214] <Adhesive Layer> In the OLED display device of the present invention, the surface of the optical filter of the present invention facing the external light may be bonded to an optically 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. The surface of the optical filter of the present invention facing the external light is preferably bonded to glass (substrate) via an adhesive layer. The adhesive layer may be the same as described in paragraphs

[0239] to

[0290] of WO 2021 / 132674, which relate to the adhesive layer and forming method for the OLED display device. The adhesive composition described in WO 2021 / 132674 preferably contains the aforementioned ultraviolet absorber in terms of the light resistance of the optical filter.

[0215] <Substrate> In the OLED display device of the present invention, the optical filter of the present invention may be bonded to an optically functional film via a pressure-sensitive adhesive layer on the surface facing the external light side. Also, the optical filter of the present invention is preferably bonded to glass (substrate) via a pressure-sensitive adhesive layer on the surface facing the external light side.

[0216] The method for forming the pressure-sensitive adhesive layer is not particularly limited, and for example, a method of applying a pressure-sensitive adhesive composition to the light-absorbing filter or optical filter of the present invention by a conventional means such as a bar coater, followed by drying and curing; a method of first applying the pressure-sensitive adhesive composition to the surface of a release substrate, drying, and then transferring the pressure-sensitive adhesive layer to the light-absorbing filter of the present invention using the release substrate, followed by aging and curing, etc. can be used.The release substrate is not particularly limited, and any release substrate can be used, such as the support film in the above-mentioned method for producing the light-absorbing filter of the present invention.In addition, the conditions for application, drying, aging and curing can also be appropriately adjusted based on conventional methods.

[0217] [Inorganic Electroluminescence Display Device] The inorganic electroluminescence display device of the present invention (referred to as an inorganic EL (electroluminescence) display device, and in the present invention, also abbreviated as inorganic EL display device) includes the optical filter of the present invention. As the inorganic EL display device of the present invention, as long as it includes the optical filter of the present invention, the configuration of a commonly used inorganic EL display device can be used as other configuration without particular limitation. For example, the description of the inorganic EL element and inorganic electroluminescence display device described in JP 2005-338640 A can be preferably applied.

[0218] [Liquid Crystal Display Device] The liquid crystal display device of the present invention includes the optical filter of the present invention. The optical filter of the present invention may be used as at least one of a polarizing plate protective film and a pressure-sensitive adhesive layer, as described below, or may be included in a backlight unit used in the liquid crystal display device.

[0219] The liquid crystal display device preferably includes the optical filter of the present invention, a polarizing plate including a polarizer and a polarizing plate protective film, a pressure-sensitive adhesive layer, and a liquid crystal cell, and the polarizing plate is preferably attached to the liquid crystal cell via the pressure-sensitive adhesive layer. In this liquid crystal display device, the optical filter of the present invention may also serve as the polarizing plate protective film or the pressure-sensitive adhesive layer. That is, the liquid crystal display device can be divided into a case where the liquid crystal display device includes a polarizing plate including a polarizer and the optical filter of the present invention (polarizing plate protective film), a pressure-sensitive adhesive layer, and a liquid crystal cell, and a case where the liquid crystal display device includes a polarizing plate including a polarizer and a polarizing plate protective film, the optical filter of the present invention (pressure-sensitive adhesive layer), and a liquid crystal cell.

[0220] Fig. 1 is a schematic diagram showing an example of a liquid crystal display device of the present invention. In Fig. 1, the liquid crystal display device 10 comprises 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 arranged above and below the liquid crystal layer 5, and an upper polarizing plate 1 and a lower polarizing plate 8 arranged on either side of the liquid crystal cell. A color filter layer may be laminated on the upper electrode substrate 3 or the lower electrode substrate 6. A backlight is arranged on the rear of the liquid crystal display device 10. The light source for the backlight can be the same as that described above for the backlight unit.

[0221] The upper polarizing plate 1 and the lower polarizing plate 8 each have a laminated structure in which a polarizer is sandwiched between two polarizing plate protective films. In the liquid crystal display device 10, at least one of the polarizing plates preferably includes the optical filter of the present invention. Furthermore, in the liquid crystal display device 10, the liquid crystal cell and the polarizing plate (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. The liquid crystal display device 10 may be of a direct-view type, an image projection type, or an optical modulation type. The present invention is effective for active matrix liquid crystal displays using three-terminal or two-terminal semiconductor elements such as TFTs (Thin Film Transistors) or MIMs (Metal Insulator Metals). Of course, the present invention is also effective for passive matrix liquid crystal displays, typified by the STN (Super Twisted Nematic) mode, known as time-division driving. When the optical filter of the present invention is included in a backlight unit, the polarizing plate of the liquid crystal display device may be a normal polarizing plate (a polarizing plate not including the optical filter of the present invention) or a polarizing plate including the optical filter of the present invention, and the pressure-sensitive adhesive layer may be a normal pressure-sensitive adhesive layer (not including the optical filter of the present invention) or a pressure-sensitive adhesive layer including the optical filter of the present invention.

[0222] The IPS (In Plane Switching) mode liquid crystal display device described in paragraphs 0128 to 0136 of JP-A No. 2010-102296 is preferable as the liquid crystal display device of the present invention, except that it uses the optical filter of the present invention.

[0223] <Polarizing Plate> The polarizing plate used in the present invention includes a polarizer and at least one polarizing plate protective film. The polarizing plate used in the present invention preferably includes a polarizer and polarizing plate protective films on both sides of the polarizer, and preferably includes the optical filter of the present invention as a polarizing plate protective film on at least one side. The polarizer may have a conventional polarizing plate protective film on the side opposite to the side having the optical filter of the present invention (polarizing plate protective film of the present invention). The thickness of the polarizing plate protective film is preferably 5 to 120 μm, more preferably 10 to 100 μm. A thinner film is preferred because it is less likely to cause display unevenness after aging at high temperature and high humidity when incorporated into a liquid crystal display device. On the other hand, if the film is too thin, it becomes difficult to stably transport the film during film production and polarizing plate production. When the optical filter of the present invention also serves as a polarizing plate protective film, the thickness of the optical filter preferably satisfies the above range. The polarizing plate used in the present invention can be the same as described in paragraphs

[0299] to

[0309] of International Publication No. 2021 / 132674, including the performance, shape, configuration, polarizer, lamination method of polarizer and polarizing plate protective film, and functionalization of polarizing plate.

[0224] <Adhesive Layer> 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 conventional adhesive layer can be used. The adhesive layer is not particularly limited as long as it can bond the polarizing plate and the liquid crystal cell, but for example, acrylic, urethane, polyisobutylene, etc. are preferred. When the optical filter of the present invention also serves as the adhesive layer, this adhesive layer contains the dye and the base polymer and further contains a crosslinking agent, coupling agent, etc. to impart adhesive properties. When the optical filter of the present invention also serves as the adhesive layer, the adhesive layer preferably contains 90 to 100% by mass, and more preferably 95 to 100% by mass, of the base polymer. The dye content is as described above. The thickness of the adhesive layer is not particularly limited, but is preferably 1 to 50 μm, and more preferably 3 to 30 μm.

[0225] <Liquid Crystal Cell> The liquid crystal cell is not particularly limited, and a conventional one can be used.

[0226] <Ultraviolet absorbing layer> An 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 absorbing layer") that inhibits light absorption (ultraviolet absorption) of the compound that generates radicals upon ultraviolet irradiation on the viewer side of the optical filter of the present invention. By providing the ultraviolet absorbing layer, it is possible to prevent fading of the optical filter of the present invention due to external light. The ultraviolet absorbing layer used in the present invention will be described below.

[0227] (Ultraviolet Absorber) The ultraviolet absorbing layer usually contains a resin and an ultraviolet absorber. Specific examples of the ultraviolet absorber preferably used in the present invention include hindered phenol compounds, benzophenone compounds such as hydroxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, cyanoacrylate compounds, and nickel complex salt compounds. Examples of hindered phenol compounds include 2,6-di-tert-butyl-p-cresol, pentaerythrityl-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis(3,5-di-tert-butyl-4-hydroxy-hydrocinnamide), 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. 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) Examples of such ultraviolet absorbers include 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2,6-di-tert-butyl-p-cresol, and pentaerythrityl-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]. The amount of these ultraviolet absorbers added is preferably 0.1 to 30.0 parts by mass per 100 parts by mass of the resin.

[0228] Furthermore, the compound (1) represented by the following formula (1) is particularly preferably used as an ultraviolet absorber from the viewpoint of further improving the light resistance of the optical filter of the present invention.

[0229] <<Compound Represented by Formula (1) (Compound (1))>> The resin composition for forming the ultraviolet absorbing layer preferably contains a compound represented by Formula (1) (hereinafter also referred to as compound (1)).

[0230]

[0231] In formula (1), R １ and R ２ each independently represents an alkyl group, an aryl group, or a heterocyclic group; R ３ and R ６ each independently represents an alkoxy group, an acyloxy group, a carbamoyloxy group, or an alkoxycarbonyloxy group; 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; R ５ 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. １ and R ２ may be bonded to each other to form a ring, and R ３ and R ４ may be bonded to each other to form a ring, and R ４ and R ５ may be bonded to each other to form a ring, and R ５ and R ６ may be bonded to each other to form a ring. The ring formed may or may not be aromatic. However, R ３ and R ６ are each independently an acyloxy group or a carbamoyloxy group, R４ and R ５ At least one of the groups 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.

[0232] In formula (1), R １ and R ２ Each of R 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 are each independently an alkyl group. From the viewpoint of the absorption of ultraviolet light having a wavelength of about 400 nm, R １ and R ２ is preferably each independently an aryl group.

[0233] R １ and R ２ The number of carbon atoms in the alkyl group represented by is preferably 1 to 30, more preferably 1 to 20, even more preferably 1 to 15, particularly preferably 1 to 10, and most preferably 1 to 8. The alkyl group may be linear, branched, or cyclic, and is preferably linear or branched. The alkyl group may have a substituent. Examples of the substituent include the groups explained for the substituent T described below, and preferred examples include a halogen atom, an alkoxy group, an alkenyl group, and an aryl group.

[0234] R １ and R ２ The number of carbon atoms in the aryl group represented by is preferably 6 to 40, more preferably 6 to 30, even more preferably 6 to 20, particularly preferably 6 to 15, and most preferably 6 to 12. The aryl group is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. The aryl group may have a substituent. Examples of the substituent include the groups explained for the substituent T described below, and a preferred example is an alkoxy group.

[0235] R １ and R ２The heterocyclic ring in the heterocyclic group represented by the formula (I) preferably contains a 5- or 6-membered saturated or unsaturated heterocyclic ring. An aliphatic ring, an aromatic ring, or another heterocyclic ring may be condensed with the heterocyclic ring. Heteroatoms constituting the heterocyclic ring include B, N, O, S, Se, and Te, and at least one of N, O, and S is preferred. In the heterocyclic ring, the carbon atoms constituting the ring preferably have a free valence (monovalent) (the heterocyclic group is bonded at a carbon atom). The number of carbon atoms in the heterocyclic group is preferably 1 to 40, more preferably 1 to 30, and even more preferably 1 to 20. Examples of saturated heterocyclic rings in the heterocyclic group include a pyrrolidine ring, a morpholine ring, a 2-bora-1,3-dioxolane ring, and a 1,3-thiazolidine ring. Examples of the unsaturated heterocyclic ring in the heterocyclic group include an imidazole ring, a thiazole ring, a benzothiazole ring, a benzoxazole ring, a benzotriazole ring, a benzoselenazole ring, a pyridine ring, a pyrimidine ring, and a quinoline ring. The heterocyclic group may have a substituent. Examples of the substituent include the groups described below for the substituent T.

[0236] R １ and R ２ may be bonded to each other to form a ring. １ and R ２ The ring formed by bonding of R is preferably a 5- or 6-membered ring, and preferably does not exhibit aromaticity. １ and R ２ The ring formed by bonding may have a substituent. Examples of the substituent include the groups explained for the substituent T described below.

[0237] In formula (1), R ３ and R ６ R each independently represents an alkoxy group, an acyloxy group, a carbamoyloxy group, or an alkoxycarbonyloxy group, and is preferably an alkoxy group or an acyloxy group, since this makes it easier to increase the absorbency of ultraviolet light with a wavelength of around 400 nm while suppressing coloration. ３ and R ６It is more preferable that at least one of R is an alkoxy group. Through investigations by the present inventors, it has been 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 a longer wavelength side. Since an alkoxy group is a substituent with a higher electron-donating ability, it is presumed that it can shift the maximum absorption wavelength of the compound to a longer wavelength side. ３ and R ６ It is particularly preferred that both of the groups are alkoxy groups.

[0238] R ３ and R ６ The number of carbon atoms in the alkoxy group represented by is preferably 1 to 30, more preferably 1 to 20, even more preferably 1 to 15, particularly preferably 1 to 10, and most preferably 1 to 8. The alkoxy group may be either linear or branched. The alkoxy group may have a substituent. Examples of the substituent include the groups explained in the substituent T below. R ３ and R ６ The number of carbon atoms in the acyloxy group represented by is preferably 2 to 30, more preferably 2 to 20, still more preferably 2 to 15, and particularly preferably 2 to 10. The acyloxy group may have a substituent. Examples of the substituent include the groups explained in the substituent T below. R ３ and R ６ The number of carbon atoms in the carbamoyloxy group represented by is preferably 2 to 30, more preferably 2 to 20, even more preferably 2 to 15, particularly preferably 2 to 10, and most preferably 2 to 8. The carbamoyloxy group may be either linear or branched. The carbamoyloxy group may have a substituent. Examples of the substituent include the groups explained in the substituent T below. R ３ and R ６ The number of carbon atoms in the alkoxycarbonyloxy group represented by is preferably 2 to 30, more preferably 2 to 20, still more preferably 2 to 15, particularly preferably 2 to 10, and most preferably 2 to 8. The alkoxycarbonyloxy group may be either linear or branched. The alkoxycarbonyloxy group may have a substituent. Examples of the substituent include the groups described below for the substituent T.

[0239] 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; R ５ 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.

[0240] R ４ and R ５ The number of carbon atoms in the alkyl group represented by is preferably 1 to 30, more preferably 1 to 20, even more preferably 1 to 15, particularly preferably 1 to 10, and most preferably 1 to 8. The alkyl group may be linear, branched, or cyclic, and is preferably linear or branched. The alkyl group may have a substituent. Examples of the substituent include the groups explained for the substituent T described below, and a preferred example is an alkenyl group.

[0241] R ４ and R ５ The number of carbon atoms in the aryl group represented by is preferably 6 to 40, more preferably 6 to 30, even more preferably 6 to 20, particularly preferably 6 to 15, and most preferably 6 to 12. The aryl group is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. The aryl group may have a substituent. Examples of the substituent include the groups described below for the substituent T.

[0242] R ４ and R ５ The number of carbon atoms in the alkoxy group represented by is preferably 1 to 30, more preferably 1 to 20, still more preferably 1 to 15, particularly preferably 1 to 10, and most preferably 1 to 8. The alkoxy group may be either linear or branched. The alkoxy group may have a substituent. Examples of the substituent include the groups explained for the substituent T below.

[0243] R ４ and R ５The number of carbon atoms in the aryloxy group represented by is preferably 6 to 40, more preferably 6 to 30, still more 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 described below for the substituent T.

[0244] R ４ and R ５ The number of carbon atoms in the acyloxy group represented by is preferably 2 to 30, more preferably 2 to 20, still more 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 below for the substituent T.

[0245] R ４ and R ５ The number of carbon atoms in the alkylamino group represented by is preferably 1 to 30, more preferably 1 to 20, still more preferably 1 to 15, particularly preferably 1 to 10, and most preferably 1 to 8. The alkyl moiety in the alkylamino group may be either linear or branched. The alkylamino group may have a substituent. Examples of the substituent include the groups explained for the substituent T below.

[0246] R ４ and R ５ The number of carbon atoms in the anilino group represented by is preferably 6 to 40, more preferably 6 to 30, still more 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 explained for the substituent T described below, and a preferred example is an alkyl group.

[0247] R ４ and R ５ The number of carbon atoms in the acylamino group represented by is preferably 2 to 30, more preferably 2 to 20, still more 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 below for the substituent T.

[0248] R ４ and R ５The number of carbon atoms in the alkylsulfonylamino group represented by is preferably 2 to 30, more preferably 2 to 20, still more 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 below for the substituent T.

[0249] R ４ and R ５ The number of carbon atoms in the arylsulfonylamino group represented by is preferably 6 to 40, more preferably 6 to 30, still more 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 below for the substituent T.

[0250] R ４ and R ５ The number of carbon atoms in the alkylthio group represented by is preferably 1 to 30, more preferably 1 to 20, still more 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 explained for the substituent T below.

[0251] R ４ and R ５ The number of carbon atoms in the arylthio group represented by is preferably 6 to 40, more preferably 6 to 30, still more 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 described below for the substituent T.

[0252] In formula (1), R ３ and R ４ may be bonded to each other to form a ring, and R ４ and R ５ may be bonded to each other to form a ring, and R ５ and R ６ may be bonded to each other to form a ring. The ring formed by bonding these groups to each other is preferably a 5- or 6-membered ring. The ring formed by bonding these groups to each other may have a substituent. Examples of the substituent include the groups explained below for the substituent T.

[0253] R is used because it is easier to increase the absorption of ultraviolet light with a wavelength of around 400 nm while suppressing coloration. ４ is an alkyl group, an aryl group, an alkoxy group, or an aryloxy group, and R ５ is preferably a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, or an aryloxy group, and R ４ is an alkyl group or an alkoxy group, and R ５ is more preferably a hydrogen atom, an alkyl group or an alkoxy group.

[0254] In addition, from the viewpoint of ease of synthesis, R ４ is an alkyl group, an aryl group, an alkoxy group, or an aryloxy group, and R ５ is preferably a hydrogen atom, and R ４ is an alkyl group or an alkoxy group, and R ５ is more preferably a hydrogen atom.

[0255] In addition, from the viewpoint of increasing the wavelength of the absorption spectrum, R ４ and R ５ are each independently preferably an alkyl group, an aryl group, an alkoxy group, or an aryloxy group, more preferably an alkyl group or an alkoxy group, and R ４ and R ５ are both alkyl groups, or R ４ and R ５ It is more preferred that both of the groups are alkoxy groups.

[0256] Also, R ４ and R ５ are also preferably bonded to each other to form a ring.

[0257] The compound represented by the above formula (1) (compound (1)) is preferably a compound represented by the following formula (1a):

[0258]

[0259] In formula (1a), R １ａ and R ２ａ each independently represents an alkyl group; ３ａ and R ６ａeach independently represents an alkoxy group or an acyloxy group; R ４ａ represents an alkyl group or an alkoxy group, R ５ａ represents a hydrogen atom, an alkyl group, or an alkoxy group. １ａ and R ２ａ may be bonded to each other to form a ring, and R ３ａ and R ４ａ may be bonded to each other to form a ring, and R ４ａ and R ５ａ may be bonded to each other to form a ring, and R ５ａ and R ６ａ may be bonded to each other to form a ring. ３ａ and R ６ａ is an acyloxy group, R ４ａ and R ５ａ At least one of them is an alkoxy group.

[0260] R １ａ and R ２ａ The number of carbon atoms in the alkyl group represented by is preferably 1 to 30, more preferably 1 to 20, still more preferably 1 to 15, particularly preferably 1 to 10, and most preferably 1 to 8. The alkyl group may be linear, branched, or cyclic, and is preferably linear or branched. The alkyl group may have a substituent. Examples of the substituent include the groups described below for the substituent T.

[0261] R １ａ and R ２ａ may be bonded to each other to form a ring. １ａ and R ２ａ The ring formed by bonding of R is preferably a 5- or 6-membered ring. １ａ and R ２ａ The ring formed by bonding may have a substituent. Examples of the substituent include the groups explained for the substituent T described below.

[0262] In formula (1a), R ３ａ and R ６ａ R each independently represents an alkoxy group or an acyloxy group, and is selected from R because it is easy to enhance the absorbance of ultraviolet light with a wavelength of around 400 nm while suppressing coloration. ３ａ and R６ａ At least one of R is preferably an alkoxy group. ３ａ and R ６ａ It is more preferable that both of the groups are alkoxy groups.

[0263] R ３ａ and R ６ａ The number of carbon atoms in the alkoxy group represented by is preferably 1 to 30, more preferably 1 to 20, even more preferably 1 to 15, particularly preferably 1 to 10, and most preferably 1 to 8. The alkoxy group may be either linear or branched. The alkoxy group may have a substituent. Examples of the substituent include the groups explained in the substituent T below. R ３ａ and R ６ａ The number of carbon atoms in the acyloxy group represented by is preferably 2 to 30, more preferably 2 to 20, still more 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 below for the substituent T.

[0264] In formula (1a), R ４ａ represents an alkyl group or an alkoxy group, and R ５ａ represents a hydrogen atom, an alkyl group, or an alkoxy group.

[0265] R ４ａ and R ５ａ The number of carbon atoms in the alkyl group represented by is preferably 1 to 30, more preferably 1 to 20, still more preferably 1 to 15, particularly preferably 1 to 10, and most preferably 1 to 8. The alkyl group may be linear, branched, or cyclic, and is preferably linear or branched. The alkyl group may have a substituent. Examples of the substituent include the groups described below for the substituent T.

[0266] R ４ａ and R ５ａ The number of carbon atoms in the alkoxy group represented by is preferably 1 to 30, more preferably 1 to 20, still more preferably 1 to 15, particularly preferably 1 to 10, and most preferably 1 to 8. The alkoxy group may be either linear or branched. The alkoxy group may have a substituent. Examples of the substituent include the groups explained for the substituent T below.

[0267] In formula (1a), R ３ａ and R ４ａ may be bonded to each other to form a ring, and R ４ａ and R ５ａ may be bonded to each other to form a ring, and R ５ａ and R ６ａ may be bonded to each other to form a ring. The ring formed by bonding these groups to each other is preferably a 5- or 6-membered ring. The ring formed by bonding these groups to each other may have a substituent. Examples of the substituent include the groups explained below for the substituent T.

[0268] (Substituent T) Examples of the substituent T include the following groups: a halogen atom (for example, a chlorine atom, a bromine atom, or an iodine atom); an alkyl group [a linear, branched, or cyclic alkyl group; Specifically, it also includes a linear or branched alkyl group (preferably a linear or branched alkyl group having 1 to 30 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a t-butyl group, an n-octyl group, an eicosyl group, a 2-chloroethyl group, a 2-cyanoethyl group, or a 2-ethylhexyl group), a cycloalkyl group (preferably a cycloalkyl group having 3 to 30 carbon atoms, such as a cyclohexyl group, a cyclopentyl group, or a 4-n-dodecylcyclohexyl group), a bicycloalkyl group (preferably a bicycloalkyl group having 5 to 30 carbon atoms, that is, a monovalent group obtained by removing one hydrogen atom from a bicycloalkane having 5 to 30 carbon atoms, such as a bicyclo[1,2,2]heptan-2-yl group or a bicyclo[2,2,2]octan-3-yl group), or a monovalent group obtained by removing one hydrogen atom from a tricycloalkane structure having many ring structures. The alkyl groups in the substituents explained below (for example, the alkyl group of an alkylthio group) also represent alkyl groups within this concept.]; alkenyl groups [straight-chain, branched or cyclic alkenyl groups; Specifically, it includes linear or branched alkenyl groups (preferably linear or branched alkenyl groups having 2 to 30 carbon atoms, for example, vinyl, allyl, prenyl, geranyl, and oleyl), cycloalkenyl groups (preferably cycloalkenyl groups having 3 to 30 carbon atoms, that is, monovalent groups obtained by removing one hydrogen atom from a cycloalkene having 3 to 30 carbon atoms, for example, 2-cyclopenten-1-yl and 2-cyclohexen-1-yl), and bicycloalkenyl groups (preferably bicycloalkenyl groups having 5 to 30 carbon atoms, that is, monovalent groups obtained by removing one hydrogen atom from a bicycloalkene having one double bond, for example, bicyclo[2,2,1]hept-2-en-1-yl and bicyclo[2,2,2]oct-2-en-4-yl). an alkynyl group (preferably a linear or branched alkynyl group having 2 to 30 carbon atoms, for example, an ethynyl group or a propargyl group);

[0269] an aryl group (preferably an aryl group having 6 to 30 carbon atoms, for example, a phenyl group, a p-tolyl group, a naphthyl group, a m-chlorophenyl group, or an o-hexadecanoylaminophenyl group); a heterocyclic group (preferably a monovalent group obtained by removing one hydrogen atom from a 5- or 6-membered aromatic or non-aromatic heterocyclic compound, more preferably a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms, for example, a 2-furyl group, a 2-thienyl group, a 2-pyrimidinyl group, or a 2-benzothiazolyl group); a cyano group; a hydroxy group; a nitro group; a carboxy group; an alkoxy group (preferably a straight-chain or branched alkoxy group having 1 to 30 carbon atoms, for example, a methoxy group, an ethoxy group, an isopropoxy group, a t-butoxy group, an n-octyloxy group, or a 2-methoxyethoxy group); an aryloxy group (preferably an aryloxy group having 6 to 30 carbon atoms, for example, a phenoxy group, a 2-methylphenoxy group, a 4-t-butylphenoxy group, a 3-nitrophenoxy group, or a 2-tetradecanoylaminophenoxy group); a heterocyclic oxy group (preferably a heterocyclic oxy group having 2 to 30 carbon atoms, for example, a 1-phenyltetrazole-5-oxy group or a 2-tetrahydropyranyloxy group); an acyloxy group (preferably a formyloxy group, an alkylcarbonyloxy group having 2 to 30 carbon atoms, or an arylcarbonyloxy group having 6 to 30 carbon atoms, for example, a formyloxy group, an acetyloxy group, a pivaloyloxy group, a stearoyloxy group, a benzoyloxy group, or a p-methoxyphenylcarbonyloxy group);

[0270] a carbamoyloxy group (preferably a carbamoyloxy group having 1 to 30 carbon atoms, for example, an N,N-dimethylcarbamoyloxy group, an N,N-diethylcarbamoyloxy group, a morpholinocarbonyloxy group, an N,N-di-n-octylaminocarbonyloxy group, or an N-n-octylcarbamoyloxy group); an alkoxycarbonyloxy group (preferably an alkoxycarbonyloxy group having 2 to 30 carbon atoms, for example, a methoxycarbonyloxy group, an ethoxycarbonyloxy group, a t-butoxycarbonyloxy group, or an n-octylcarbonyloxy group); an aryloxycarbonyloxy group (preferably an aryloxycarbonyloxy group having 7 to 30 carbon atoms, for example, a phenoxycarbonyloxy group, a p-methoxyphenoxycarbonyloxy group, or a p-n-hexadecyloxyphenoxycarbonyloxy group); an amino group (preferably an unsubstituted amino group (—NH ２ ), alkylamino groups having 1 to 30 carbon atoms, and anilino groups having 6 to 30 carbon atoms. For example, unsubstituted amino groups (—NH ２ ), methylamino group, dimethylamino group, anilino group, N-methyl-anilino group, diphenylamino group); acylamino group (preferably formylamino group, alkylcarbonylamino group having 2 to 30 carbon atoms, arylcarbonylamino group having 6 to 30 carbon atoms, for example, formylamino group, acetylamino group, pivaloylamino group, lauroylamino group, benzoylamino group, 3,4,5-tri-n-octyloxyphenylcarbonylamino group);

[0271] an aminocarbonylamino group (preferably an aminocarbonylamino group having 1 to 30 carbon atoms, for example, a carbamoylamino group, an N,N-dimethylaminocarbonylamino group, an N,N-diethylaminocarbonylamino group, or a morpholinocarbonylamino group); an alkoxycarbonylamino group (preferably an alkoxycarbonylamino group having 2 to 30 carbon atoms, for example, a methoxycarbonylamino group, an ethoxycarbonylamino group, a t-butoxycarbonylamino group, an n-octadecyloxycarbonylamino group, or an N-methylmethoxycarbonylamino group); an aryloxycarbonylamino group (preferably an aryloxycarbonylamino group having 7 to 30 carbon atoms, for example, a phenoxycarbonylamino group, a p-chlorophenoxycarbonylamino group, or an m-n-octyloxyphenoxycarbonylamino group); a sulfamoylamino group (preferably a sulfamoylamino group having 0 to 30 carbon atoms, for example, a sulfamoylamino group, an N,N-dimethylaminosulfonylamino group, or an N-n-octylaminosulfonylamino group); an alkyl or arylsulfonylamino group (preferably an alkylsulfonylamino group having 1 to 30 carbon atoms, or an arylsulfonylamino group having 6 to 30 carbon atoms, for example, a methylsulfonylamino group, a butylsulfonylamino group, a phenylsulfonylamino group, a 2,3,5-trichlorophenylsulfonylamino group, or a p-methylphenylsulfonylamino group); a mercapto group; an alkylthio group (preferably an alkylthio group having 1 to 30 carbon atoms, for example, a methylthio group, an ethylthio group, or an n-hexadecylthio group); an arylthio group (preferably an arylthio group having 6 to 30 carbon atoms, for example, a phenylthio group, a p-chlorophenylthio group, or an m-methoxyphenylthio group); a heterocyclic thio group (preferably a heterocyclic thio group having 2 to 30 carbon atoms, for example, a 2-benzothiazolylthio group, a 1-phenyltetrazol-5-ylthio group);

[0272] a sulfamoyl group (preferably a sulfamoyl group having 0 to 30 carbon atoms, for example, an N-ethylsulfamoyl group, an N-(3-dodecyloxypropyl)sulfamoyl group, an N,N-dimethylsulfamoyl group, an N-acetylsulfamoyl group, an N-benzoylsulfamoyl group, or an N-(N'-phenylcarbamoyl)sulfamoyl group); a sulfo group; an alkyl or arylsulfinyl group (preferably an alkylsulfinyl group having 1 to 30 carbon atoms, or an arylsulfinyl group having 6 to 30 carbon atoms, for example, a methylsulfinyl group, an ethylsulfinyl group, a phenylsulfinyl group, or a p-methylphenylsulfinyl group); an alkyl or arylsulfonyl group (preferably an alkylsulfonyl group having 1 to 30 carbon atoms, or an arylsulfonyl group having 6 to 30 carbon atoms, for example, a methylsulfonyl group, an ethylsulfonyl group, a phenylsulfonyl group, or a p-methylphenylsulfonyl group);

[0273] acyl groups (preferably formyl groups, alkylcarbonyl groups having 2 to 30 carbon atoms, arylcarbonyl groups having 7 to 30 carbon atoms, and heterocyclic carbonyl groups having 4 to 30 carbon atoms and bonded to a carbonyl group at a carbon atom, such as acetyl groups, pivaloyl groups, 2-chloroacetyl groups, stearoyl groups, benzoyl groups, p-n-octyloxyphenylcarbonyl groups, 2-pyridylcarbonyl groups, and 2-furylcarbonyl groups); aryloxycarbonyl groups (preferably aryloxycarbonyl groups having 7 to 30 carbon atoms, such as phenoxycarbonyl groups, o-chlorophenoxycarbonyl groups, m-nitrophenoxycarbonyl groups, and p-t-butylphenoxycarbonyl groups); an alkoxycarbonyl group (preferably an alkoxycarbonyl group having 2 to 30 carbon atoms, for example, a methoxycarbonyl group, an ethoxycarbonyl group, a t-butoxycarbonyl group, or an n-octadecyloxycarbonyl group); a carbamoyl group (preferably a carbamoyl group having 1 to 30 carbon atoms, for example, a carbamoyl group, an N-methylcarbamoyl group, an N,N-dimethylcarbamoyl group, an N,N-di-n-octylcarbamoyl group, or an N-(methylsulfonyl)carbamoyl group); an aryl or heterocyclic azo group (preferably an aryl azo 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, or a 5-ethylthio-1,3,4-thiadiazol-2-ylazo group); an imido group (preferably an N-succinimido group, or an N-phthalimido group); a phosphinyl group (preferably a phosphinyl group having 2 to 30 carbon atoms, for example, a dimethylphosphino group, a diphenylphosphino group, or a methylphenoxyphosphinyl group); a phosphinyl group (preferably a phosphinyl group having 2 to 30 carbon atoms, for example, a phosphinyl group, a dioctyloxyphosphinyl group, or a diethoxyphosphinyl group); a phosphinyloxy group (preferably a phosphinyloxy group having 2 to 30 carbon atoms, for example, a diphenoxyphosphinyloxy group, or a dioctyloxyphosphinyloxy group); a phosphinylamino group (preferably a phosphinylamino group having 2 to 30 carbon atoms, for example, a dimethoxyphosphinylamino group, or a dimethylaminophosphinylamino group);

[0274] Of the groups listed above, in groups having a hydrogen atom, one or more hydrogen atoms may be substituted with the above-mentioned substituent T. Examples of such a substituent include an alkylcarbonylaminosulfonyl group, an arylcarbonylaminosulfonyl group, an alkylsulfonylaminocarbonyl group, and an arylsulfonylaminocarbonyl group. Specific examples include a methylsulfonylaminocarbonyl group, a p-methylphenylsulfonylaminocarbonyl group, an acetylaminosulfonyl group, and a benzoylaminosulfonyl group.

[0275] Specific examples of compound (1) include, but are not limited to, compounds having the following structures: 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.

[0276]

[0277]

[0278]

[0279] Compound (1) is preferably used as an ultraviolet absorber. The maximum absorption wavelength of compound (1) is preferably in the wavelength range of 370 to 420 nm, and more preferably in the wavelength range of 380 to 400 nm.

[0280] The molar absorption coefficient ε of compound (1) at a wavelength of 405 nm calculated from the following formula: ４０５ is preferably 500 or more, more preferably 1000 or more, even more preferably 2000 or more, and particularly preferably 3000 or more. ４０５ = ε ｍａｘ × (A ４０５ / A ｍａｘ ) ε ４０５ is the molar absorption coefficient of compound (1) at a wavelength of 405 nm, and ε ｍａｘ is the molar absorption coefficient at the maximum absorption wavelength of compound (1), and A ４０５ is the absorbance of compound (1) at a wavelength of 405 nm, and Aｍａｘ is the absorbance at the maximum absorption wavelength of compound (1). The unit of the molar absorption coefficient is L / (mol cm). ４０５ and A ｍａｘ is the absorbance in the spectroscopic absorption spectrum of compound (1) measured in ethyl acetate.

[0281] In the spectroscopic absorption spectrum of compound (1) measured in ethyl acetate, the absorbance A at a wavelength of 405 nm ４０５ and absorbance A at a wavelength of 430 nm ４３０ The ratio of (A ４３０ / A ４０５ ) is preferably less than 0.13, more preferably 0.10 or less. The lower limit of the ratio is not particularly limited, but can be 0 or more. Compounds having such an absorbance ratio have high absorption in the vicinity of 405 nm wavelength, but excellent transmittance of light in the visible region near the ultraviolet region, and therefore have excellent absorbance of ultraviolet light on the longer wavelength side and excellent visible transparency. Note that when an attempt is made to shift the ultraviolet absorption region of a compound to the longer wavelength side, the transmittance of light in the visible region (particularly the transmittance of light in the visible region near the ultraviolet region) also tends to decrease. However, the compound (1) can achieve the excellent effect of improving the absorbance of ultraviolet light on the longer wavelength side while maintaining a high level of transmittance of light in the visible region.

[0282] 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.

[0283] 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 even more preferably 0.10% by mass or more. The upper limit is more preferably 40% by mass or less, even more preferably 30% by mass or less, and particularly preferably 20% by mass or less. The content of compound (1) is preferably 0.01 to 50 parts by mass per 100 parts by mass of the resin. The lower limit is more preferably 0.05 parts by mass or more, and even more preferably 0.10 parts by mass or more. The upper limit is more preferably 40 parts by mass or less, even more preferably 30 parts by mass or less, and particularly preferably 20 parts by mass or less. The resin composition may contain only one type of compound (1), or may contain two or more types. When two or more types of compound (1) are contained, the total amount thereof is preferably within the above range.

[0284] (Resin) The resin used in the ultraviolet absorbing layer may be any known resin, and is not particularly limited as long as it does not deviate from the spirit of the present invention. Examples of the resin include cellulose acylate resin, acrylic resin, cycloolefin resin, polyester resin, and epoxy resin.

[0285] (Position of ultraviolet absorbing layer) The position of the ultraviolet absorbing layer is not particularly limited as long as it is on the viewer side of the optical filter of the present invention, and it can be installed at any position. For example, it is possible to add an ultraviolet absorber to a member such as a protective film of a polarizing plate or an anti-reflection film to give it the function of an ultraviolet absorbing layer. In addition, it is also possible to add an ultraviolet absorber to the above-mentioned pressure-sensitive adhesive layer.

[0286] The present invention will be described in more detail below based on examples. The materials, amounts used, ratios, processing details, processing procedures, etc. shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the examples shown below. In the following examples, "parts" and "%" representing compositions are based on mass unless otherwise specified. Room temperature means "25°C." All of the steps from the preparation of the light-absorbing filter-forming solution to the production of a light-absorbing filter with a substrate using the light-absorbing filter-forming solution and the use in an ultraviolet irradiation test were carried out under yellow light to prevent ultraviolet irradiation.

[0287] [Preparation of Light-Absorption Filter] The materials used in preparing the light-absorbing filter are as follows: <Matrix Polymer (Resin)> (Resin 1) Cyclohexyl methacrylate-methacrylic acid random copolymer, methacrylic acid content 29 mol%, weight average molecular weight 26,300. The methacrylic acid portion of Resin 1 corresponds to Compound A having an acid group as defined in the present invention.

[0288] <Compound B> 4-methylquinoline (Tokyo Chemical Industry Co., Ltd., Lepidine, pKaH 5.1) <Dye>

[0289]

[0290]

[0291] (Leveling Agent 1) A polymer surfactant composed of the following components was used as 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.

[0292]

[0293] (Substrate 1) Polyethylene terephthalate film (manufactured by Toray Industries, Inc., product name: Lumirror XD-510P, film thickness 50 μm)

[0294] Example 1. Preparation of Light Absorption Filter No. 101

[0295] (1) Preparation of resin solution (light-absorbing filter forming liquid) The components were mixed in the composition shown below to prepare light-absorbing filter forming liquid (composition) Ba-1. ------------------------------------------------ Composition of light-absorbing filter forming liquid Ba-1 ------------------------------------------------ Resin 1 81.1 parts by mass Leveling agent 1 0.08 parts by mass Dye B-19 1.56 parts by mass 4-methylquinoline (Tokyo Chemical Industry Co., Ltd.) 17.2 parts by mass Methyl ethyl ketone (solvent) 566.7 parts by mass ------------------------------------------------

[0296] Subsequently, the obtained light-absorbing filter-forming solution Ba-1 was filtered using a filter paper (#63, manufactured by Toyo Roshi Kaisha) having an absolute filtration accuracy of 10 μm, and further filtered using a sintered metal filter (trade name: Pall Filter PMF, media code: FH025, manufactured by Pall Corporation) having an absolute filtration accuracy of 2.5 μm.

[0297] (2) Preparation of Light-Absorbing Filter The light-absorbing filter-forming solution Ba-1 after the above-mentioned filtration treatment was applied to a substrate 1 using a bar coater so that the film thickness after drying would be 2.2 μm, and the applied film was dried at 120° C. to prepare light-absorbing filter No. 101.

[0298] <2. Preparation of Light-Absorbing Filters Nos. 102-112, r201, and c202-c206> Light-absorbing filters Nos. 102-112 and c202-c206 were prepared in the same manner as light-absorbing filter No. 101, except that in the preparation of light-absorbing filter No. 101, at least one of the type and blending amount of dye was changed as shown in Table 1. The blending amount of leveling agent 1 in light-absorbing filter No. 101 was fixed, and the blending amount of resin was changed in accordance with the change in the blending amount of dye, adjusting the weight of the filter as a whole. Furthermore, light-absorbing filter No. r201 was prepared in the same manner as light-absorbing filter No. 101, except that compound B and dye were not blended, and the blending amount of resin was changed so that the weight of the filter as a whole remained unchanged. Here, Nos. 101-112 are light-absorbing filters of the present invention, and No. c202 to c206 are light-absorbing filters for comparison, and No. r201 is a reference light-absorbing filter.

[0299] [Preparation of Light-Absorbing Filter Having Gas Barrier Layer] For light-absorbing filters Nos. 101 to 112, r201, and c202 to c206, a light-absorbing filter (light-absorbing filter having a gas barrier layer) was prepared by further laminating a gas barrier layer on the light-absorbing filter as described below, and the evaluations described below were carried out.

[0300] (1) Preparation of Substrate 3 The light-absorbing filter side of the substrate-attached light-absorbing filter prepared above was treated with a corona treatment device (product name: Corona-Plus, manufactured by VETAPHONE) at a discharge rate of 1000 W·min / m ２ The substrate was subjected to a corona treatment under the conditions of a treatment speed of 3.2 m / min and used as a substrate 3.

[0301] (2) Preparation of resin solution The components were mixed in the composition shown below and stirred in a thermostatic bath at 90°C for 1 hour to dissolve Kuraray Exeval AQ-4105 (trade name, manufactured by Kuraray Co., Ltd., modified polyvinyl alcohol, saponification degree 98-99 mol%), preparing a gas barrier layer-forming liquid. ---------------------------------------------------------------- Composition of gas barrier layer-forming liquid ---------------------------------------------------------------- Kuraray Exeval AQ-4105 (trade name, manufactured by Kuraray Co., Ltd.) 4.0 parts by mass Pure water 88.5 parts by mass Isopropyl alcohol 7.5 parts by mass ----------------------------------------------------------------

[0302] Subsequently, the resulting gas barrier layer-forming liquid was filtered using a filter with an absolute filtration accuracy of 5 μm (trade name: Hydrophobic Fluorepore Membrane, manufactured by Millex Corporation).

[0303] (3) Lamination of Gas Barrier Layer 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 as to give a film thickness of 1.6 μm after drying, and dried at 120° C. for 60 seconds to produce a light-absorbing filter having a gas barrier layer. This light-absorbing filter having a gas barrier layer has a configuration in which the substrate 1, the light-absorbing filter, and the gas barrier layer are laminated in this order.

[0304] <Evaluation of Physical Properties of Gas Barrier Layer> The physical properties of the gas barrier layer measured by the method described in

[0182] to

[0184] of WO 2022 / 149510 were a crystallinity of 53% and an oxygen permeability of 0.4 cc / m ２ ·day·atm, and the thickness was 1.6 μm.

[0305] <Absorbance of Light-Absorbing Filter (Before UV Irradiation)> (1) Measurement of Absorbance Using a UV3600 spectrophotometer (trade name) manufactured by Shimadzu Corporation, the absorbance in the wavelength range of 380 to 800 nm was measured in 1 nm increments for the light-absorbing filter having a gas barrier layer and the standard filter. The standard filter for light-absorbing filters Nos. 101 to 112 and c202 to c206 containing Resin 1 was light-absorbing filter No. r201, which was modified so as not to contain dye and compound B.

[0306] (2) Calculation of absorbance The absorbance value Ab of the light-absorbing filter having a gas barrier layer measured above at each wavelength λ nm ｘ (λ) and the absorbance value Ab of a standard filter containing the same resin at each wavelength λ nm ０ Using the absorbance Ab(λ) of the light-absorbing filter before ultraviolet irradiation, the absorbance Ab(λ) of the light-absorbing filter before ultraviolet irradiation was calculated according to the following formula: Ab(λ)=Ab ｘ (λ)-Ab ０ (λ) Hereinafter, the wavelength showing the largest absorbance Ab(λ) among the wavelengths showing maximum absorption of the light absorption filter in the wavelength range of 400 to 700 nm is referred to as the maximum absorption wavelength (hereinafter simply referred to as "λ"). ｍａｘ "), and this λ ｍａｘ The absorbance at the absorption maximum (hereinafter simply referred to as "Ab(λ ｍａｘ )). The maximum absorption wavelength and absorption maximum value were determined for each of Dye A, Dye B, and Dye C, and the decolorization rate described below was evaluated for each dye. Here, Dyes B-19 and B-18, which are azo dyes represented by the above-mentioned general formula (i), and Comparative Dyes 1 to 4 are classified as Dye A; Dye 7-23, Dye F-1, which is an azo dye represented by the above-mentioned general formula (ii); Dyes E-1 and E-2, which are azo dyes represented by the above-mentioned general formula (iii); Dyes D-1 and D-2, which are azo dyes represented by the above-mentioned general formula (iv); and Comparative Dye 5 are classified as Dye B; and Dyes G-1 and G-2, which are indoaniline dyes represented by the above-mentioned general formula (v), and Dye C-73 are classified as Dye C.

[0307] <<Evaluation 1>> The decolorization rate of each light-absorbing filter was evaluated. The results are summarized in Table 2 below.

[0308] (Ultraviolet Irradiation Test) Under atmospheric pressure (101.33 kPa), an ultra-high pressure mercury lamp (manufactured by HOYA Corporation, product name: UL750) was used at room temperature to irradiate a light-absorbing filter having a gas barrier layer and a standard filter with an illuminance of 100 mW / cm. ２ The gas barrier layer side (opposite side to the substrate 1) was irradiated with ultraviolet (UV) rays in the amount shown in Table 1.

[0309] <Absorbance of Light-Absorbing Filter (After UV Irradiation)> Using the light-absorbing filter having a gas barrier layer after UV irradiation and the standard filter, the absorbance Ab(λ) of the light-absorbing filter after UV irradiation was calculated in the same manner as described above in <Absorbance of Light-Absorbing Filter (Before UV Irradiation)>.

[0310] [1. Evaluation of decolorization rate] The maximum absorption value (Ab(λ)) before and after the ultraviolet irradiation test ｍａｘ )) was used to calculate the decolorization rate according to the following formula: Decolorization rate (%) = 100 - (Ab(λ) after ultraviolet irradiation) ｍａｘ ) / Ab(λ) before UV irradiation ｍａｘ )) x 100

[0311] [2. Evaluation of the Presence or Absence of Secondary Absorption Due to Decomposition of Dye] The presence or absence of absorption (secondary absorption) due to a new colored structure due to decomposition of the dye was evaluated by measuring the absorption maximum (Ab(λ)) before ultraviolet irradiation. ｍａｘ The absorbance at a wavelength of 450 nm (hereinafter also referred to simply as "Ab(450)") and the absorption maximum value before ultraviolet irradiation (Ab(λ ｍａｘThe evaluation was based on the ratio of the absorbance at a wavelength of 650 nm (hereinafter also referred to simply as "Ab(650)") to the absorbance at a wavelength of 650 nm (hereinafter also referred to simply as "Ab(650)"). The smaller the value obtained by subtracting the ratio of (I) below from the ratio of (II) below, and the smaller the value obtained by subtracting the ratio of (III) below from the ratio of (IV) below, the less absorption resulting from the new colored structure associated with the decomposition of the dye is generated. Note that in the description of Table 2 below, a wavelength of 450 nm can be selected for evaluation of Nos. 101, 105, 106, 109 to 111, and c203, and a wavelength of 650 nm can be selected for evaluation of Nos. 101 to 109, 112, and c202 to c206, as the wavelength at which the presence or absence of secondary absorption associated with the decomposition of the dye can be evaluated, i.e., the wavelength at which the dye shows almost no absorption before UV irradiation and new absorption due to the decomposition of the dye is observed. (I) Ab(450) before UV irradiation / Ab(λ ｍａｘ ) × 100% (II) Ab(450) after UV irradiation / Ab(λ) before UV irradiation ｍａｘ ) × 100% (III) Ab(650) before ultraviolet irradiation / Ab(λ ｍａｘ ) × 100% (IV) Ab(650) after UV irradiation / Ab(λ) before UV irradiation ｍａｘ ) x 100%

[0312] [Simulation of Color of Reflected Light] For the light-absorbing filter produced above, a simulation of the reflection of external light on the aluminum foil substrate was performed in a configuration in which the light-absorbing filter was transferred to an aluminum foil substrate via an adhesive and then the base material was peeled off. ＊ and b ＊ Specifically, in the configuration shown in FIG. 2, white light having the spectrum of standard illuminant D65 specified by the International Commission on Illumination (CIE) is transmitted through a light-absorbing filter, reflected by an aluminum foil substrate with a reflectance of 85%, and then transmitted through the light-absorbing filter again. The light intensity is calculated in 1-nm increments in the wavelength range from 380 nm to 780 nm, and this is multiplied by the photopic standard relative luminosity factor and summed (luminosity correction is performed), thereby obtaining the color tone (a ＊ , b ＊ ) was calculated. ＊ and b ＊From the viewpoint of adjusting the color tone of the reflected light to a neutral color, it is preferable that the absolute values ​​of each of these be close to 0, and for example, a level of 3.0 or less is preferable.

[0313]

[0314]

[0315] (Table notes) λ ｍａｘ means the wavelength at which the light-absorbing filter exhibits the highest absorbance Ab(λ) among the maximum absorption wavelengths that the light-absorbing filter has in the wavelength region of 400 to 700 nm. The blending amounts of the dye and compound B are expressed in parts by mass relative to 100 parts by mass of the filter. Ab(λ ｍａｘ ) is the maximum absorption wavelength λ ｍａｘ The "-" in the "decolorization rate" column indicates that the corresponding dye is not contained.

[0316] The results in Tables 1 and 2 above reveal the following. Comparative light-absorbing filters Nos. c202 to c206, which did not contain any of the azo dyes represented by general formulas (i) to (iv) or the indoaniline dyes represented by general formula (v) but contained any of Comparative Dyes 1 to 5, all had low decolorization rates upon irradiation with UV light. In contrast, light-absorbing filters Nos. 101 and 104 of the present invention, which contained dye B-19 or B-18, an azo dye represented by general formula (i); light-absorbing filters Nos. 105 and 106 of the present invention, which contained dye D-1 or D-2, an azo dye represented by general formula (iv); light-absorbing filters Nos. 107 and 108 of the present invention, which contained dye E-1 or E-2, an azo dye represented by general formula (iii); and light-absorbing filter No. 109 of the present invention, which contained dye F-1, an azo dye represented by general formula (ii), all had low decolorization rates upon irradiation with UV light. Light-absorbing filters Nos. 109, 110, and 111 of the present invention, which contain dye G-1 or G-2, an indoaniline dye represented by general formula (v), all exhibited a high decolorization rate upon irradiation with UV light, showed almost no secondary absorption due to decomposition of the dye upon irradiation with UV light, and exhibited excellent decolorization properties when irradiated with UV light at room temperature. Furthermore, light-absorbing filters Nos. 102 and 103 of the present invention, which contain dye B-19, an azo dye represented by general formula (i), in combination with dyes C-73 and 7-23, which are squaraine dyes represented by general formula (1), and light-absorbing filter No. 112 of the present invention, which contain dye B-19, an azo dye represented by general formula (i), in combination with dye E-2, an azo dye represented by general formula (iii), and dye C-73, a squaraine dye represented by general formula (1), all exhibited excellent decolorization properties when irradiated with UV light at room temperature, and were also able to adjust the color of reflected light to a neutral tone.

[0317] While the present invention has been described in connection with embodiments thereof, we do not intend to limit our invention to any of the details of the description unless otherwise specified, and believe that the claims should be construed broadly without departing from the spirit and scope of the invention as set forth in the appended claims.

[0318] This application claims priority based on Japanese Patent Application No. 2022-090495 filed in Japan on June 2, 2022, Japanese Patent Application No. 2022-122898 filed in Japan on August 1, 2022, and Japanese Patent Application No. 2022-177176 filed in Japan on November 4, 2022, the contents of which are incorporated herein by reference.

[0319] REFERENCE SIGNS LIST 1 Upper polarizer 2 Direction of absorption axis of upper polarizer 3 Upper electrode substrate of liquid crystal cell 4 Alignment control direction of upper substrate 5 Liquid crystal layer 6 Lower electrode substrate of liquid crystal cell 7 Alignment control direction of lower substrate 8 Lower polarizer 9 Direction of absorption axis of lower polarizer B Backlight unit 10 Liquid crystal display device 11 Aluminum foil substrate 91 Light-absorbing filter D65 White light having the spectrum of standard illuminant D65 defined by the International Commission on Illumination (CIE) R Reflected light

Claims

1. A light-absorbing filter comprising a resin, a dye having a main absorption wavelength band in the wavelength range of 400 to 700 nm, and a compound that generates radicals when irradiated with ultraviolet light, the dye including at least one of an azo dye represented by any one of general formulas (i) to (iv) below and an indoaniline dye represented by general formula (v) below: 【Chemistry 1】 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 residue of a diazo component. However, R １７ ~R １９ and Q cannot have a squaraine structure. 【Chemistry 2】 In the above formula, R ２１ ~R ２４ , R ２６ and R ２７ is a hydrogen atom, a halogen atom, a cyano group, a nitro group, a carboxy group, a sulfo group, -OR １０８ , -SR １０９ , -NR １１０ R １１１ , -S(=O) ２ N.R. １１２ R １１３ , -C(=O)NR １１４ R １１５ , -NHC(=O)R １１６ , -C(=O)OR １１７ , -O(CH ２ CH ２ O) ｎ R １１８ , -O(CH ２ CH ２ S) ｎ R １１９ , -S(CH ２ CH ２ O) ｎ R １２０ , -S(CH ２ CH ２ S) ｎ R １２１ , acyclic hydrocarbon groups, monocyclic hydrocarbon groups, condensed polycyclic hydrocarbon groups, or heterocyclic groups. R １０８ ~R １２１ represents a hydrogen atom, an acyclic hydrocarbon group, a monocyclic hydrocarbon group, a condensed polycyclic hydrocarbon group or a heterocyclic group, and n is a positive integer. The acyclic hydrocarbon group, the monocyclic hydrocarbon group, the condensed polycyclic hydrocarbon group and the heterocyclic group are not limited to halogen atoms, cyano groups, nitro groups, carboxy groups, sulfo groups, -OR １０８ , -SR １０９ , -NR １１０ R １１１ , -S(=O) ２ N.R. １１２ R １１３ , -C(=O)NR １１４ R １１５ , -NHC(=O)R １１６ , -C(=O)OR １１７ , -O(CH ２ CH ２ O) ｎ R １１８ , -O(CH ２ CH ２ S) ｎ R １１９ , -S(CH ２ CH ２ O) ｎ R １２０ , -S(CH ２ CH ２ S) ｎ R １２１ The aryl group may have one or more of acyclic hydrocarbon groups, monocyclic hydrocarbon groups, condensed polycyclic hydrocarbon groups, and heterocyclic groups as substituents. 【Chemistry 3】 In the above formula, R ３１ represents a hydrogen atom, an alkyl group, an alkoxy group, a cyano group, a carbonyl group, an aromatic group or a heterocyclic group. R ３２ represents a hydrogen atom, an alkyl group, an alkoxy group, a cyano group, a nitro group, a carbonyl group, an aromatic group or a heterocyclic group. R ３４ and R ３５ each independently represents a hydrogen atom, an alkyl group, or an aromatic group. R ３７ represents a hydrogen atom, an alkyl group, an alkoxy group, a cyano group, a carbonyl group, an acylamino group, or an aromatic group. 【Chemistry 4】 In the above formula, R ４１ ~R ４４ , R ４６ and R ４７ is a hydrogen atom, a halogen atom, a cyano group, a nitro group, a carboxy group, a sulfo group, -OR ２０８ , -SR ２０９ , -NR ２１０ R ２１１ , -S(=O) ２ N.R. ２１２ R ２１３ , -C(=O)NR ２１４ R ２１５ , -NHC(=O)R ２１６ , -C(=O)OR ２１７ , -O(CH ２ CH ２ O) ｎ R ２１８ , -O(CH ２ CH ２ S) ｎ R ２１９ , -S(CH ２ CH ２ O) ｎ R ２２０ , -S(CH ２ CH ２ S) ｎ R ２２１ , acyclic hydrocarbon groups, monocyclic hydrocarbon groups, condensed polycyclic hydrocarbon groups, or heterocyclic groups. R ２０８ ~R ２２１ represents a hydrogen atom, an acyclic hydrocarbon group, a monocyclic hydrocarbon group, a condensed polycyclic hydrocarbon group or a heterocyclic group, and n is a positive integer. The acyclic hydrocarbon group, the monocyclic hydrocarbon group, the condensed polycyclic hydrocarbon group and the heterocyclic group are not limited to halogen atoms, cyano groups, nitro groups, carboxy groups, sulfo groups, -OR ２０８ , -SR ２０９ , -NR ２１０ R ２１１ , -S(=O) ２ N.R. ２１２ R ２１３ , -C(=O)NR ２１４ R ２１５ , -NHC(=O)R ２１６ , -C(=O)OR ２１７ , -O(CH ２ CH ２ O) ｎ R ２１８ , -O(CH ２ CH ２ S) ｎ R ２１９ , -S(CH ２ CH ２ O) ｎ R ２２０ , -S(CH ２ CH ２ S) ｎ R ２２１ The aryl group may have one or more of acyclic hydrocarbon groups, monocyclic hydrocarbon groups, condensed polycyclic hydrocarbon groups, and heterocyclic groups as substituents. 【Chemistry 5】 In the above formula, Q １ represents a group of atoms necessary to form a 5- to 7-membered nitrogen-containing heterocycle together with the carbon atom to which it is bonded, including at least one nitrogen atom. R ５１ represents an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an aminocarbonyl group, or a sulfonyl group; R ５２ represents a hydrogen atom or an alkyl group; R ５３ ~R ５７ represents a hydrogen atom, an alkyl group, an alkoxy group, an acylamino group, an alkylsulfonylamino group, or a halogen atom; R ５８ and R ５９ represents a hydrogen atom, an alkyl group or an aryl group.

2. 2. The light absorption filter according to claim 1, wherein the compound that generates radicals when irradiated with ultraviolet light 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 contained in the compound A.

3. 3. The light absorption filter according to claim 1, wherein the dye having a main absorption wavelength band in the wavelength range of 400 to 700 nm comprises a squaraine dye represented by the following general formula (1): 【Chemistry 6】 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, where G represents a heterocyclic group which may have a substituent.

4. 3. The light absorbing filter according to claim 2, wherein the compound A having an acid group is chemically bonded to a polymer constituting the resin.

5. 3. The light absorbing filter according to claim 1, wherein the dye having a main absorption wavelength band of 400 to 700 nm undergoes a chemical change and is decolorized by irradiation with ultraviolet light.

6. 3. An optical filter obtained by exposing the light absorbing filter according to claim 1 or 2 to ultraviolet light using a mask.

7. An organic electroluminescence display device, an inorganic electroluminescence display device, or a liquid crystal display device, comprising the optical filter according to claim 6 .

8. 8. The organic electroluminescent display device, inorganic electroluminescent display device, or liquid crystal display device according to claim 7, further comprising a layer for inhibiting light absorption by a compound that generates radicals when irradiated with ultraviolet light, on the viewer side of the optical filter.

9. 3. A method for producing an optical filter, comprising irradiating the light absorbing filter according to claim 1 with ultraviolet light and exposing the light absorbing filter through a mask.

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