Light absorption filter, light filter, organic electroluminescent display device, and liquid crystal display device

Abstract

The invention relates to a light absorption filter, an optical filter, an organic electroluminescent display device, and a liquid crystal display device. The present invention provides a light absorption filter, an optical filter, an OLED display device or a liquid crystal display device, the light absorption filter containing a resin, a dye having a main absorption wavelength band at a wavelength of 400-700 nm, and a compound that generates radicals by irradiation with ultraviolet light, the dye contains a squarylium dye represented by a specific general formula (1), or a benzylidene dye or a cinnamyl dye represented by a specific general formula (V).

Description

[0001] This application is a divisional application of Chinese application number 202080089694.4, with a filing date of December 25, 2020 and an invention name of “Light absorption filter, optical filter, organic electroluminescent display device and liquid crystal display device”. Technical Field

[0002] The invention relates to a light absorption filter, an optical filter, an organic electroluminescent display device and a liquid crystal display device. Background Art

[0003] As image display devices, organic electroluminescence (OLED) display devices, liquid crystal display devices, and the like are used in recent years.

[0004] Liquid crystal display devices are used more and more as image display devices that consume little power and save space. In a liquid crystal display device, the liquid crystal panel itself that displays images is a non-luminous element, so it has a backlight unit that is arranged on the back of the liquid crystal panel and supplies light to the liquid crystal panel.

[0005] OLED display devices are devices that display images using the self-luminescence of OLED elements. Therefore, compared with various display devices such as liquid crystal display devices and plasma display devices, they have advantages such as being able to achieve high contrast ratio, high color reproduction, wide viewing angle, high-speed response, and thinness and lightness. In addition to these advantages, they are actively being researched and developed as next-generation display devices from the perspective of flexibility.

[0006] In the development of image display devices, there is known a technology for incorporating a light absorption filter as a structure.

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

[0008] Previous technical literature

[0009] Patent Literature

[0010] Patent Document 1: Japanese Patent Application Laid-Open No. 9-286979 Summary of the invention

[0011] Technical issues to be solved by the invention

[0012] As another form of a light absorption filter incorporated into an image display device, a filter having both a light absorption portion having a light absorption effect and a portion where the light absorption is eliminated (hereinafter also referred to as a "light absorption eliminated portion") is considered by eliminating the light absorption at a desired portion.

[0013] For example, Patent Document 1 describes a photodecolorizing composition comprising a dye and a compound that changes the color development mechanism of the dye by ultraviolet irradiation, and that fades or disappears by ultraviolet irradiation.

[0014] However, it is known that the light absorption filter using the photobleachable composition described in Patent Document 1 together with a resin has a low quenching rate due to ultraviolet irradiation, and there is room for improvement. In addition, it is also known that depending on the dye used, in addition to the insufficient quenching rate, the dye is decomposed by ultraviolet irradiation, and absorption from a new coloring structure accompanying the decomposition (hereinafter also referred to as "secondary absorption") may occur.

[0015] In particular, as a method of incorporating an optical filter into an image display device, a portion of the optical filter where light absorption disappears is required to have a light absorption characteristic close to colorless.

[0016] That is, an object of the present invention is to provide a light absorption filter which shows an excellent quenching rate when irradiated with ultraviolet rays and in which secondary absorption accompanying decomposition of a dye due to ultraviolet irradiation hardly occurs.

[0017] Furthermore, the present invention aims to provide an optical filter using the above-mentioned light absorption filter and having a light absorption portion and a light absorption-free portion at desired positions, and an OLED display device and a liquid crystal display device including the optical filter.

[0018] Means for solving technical problems

[0019] In view of the above problems, the present inventors conducted intensive research and found that the above-mentioned excellent light quenching property can be obtained by setting the structure of the light absorption filter containing a dye having a specific chemical structure and a compound that generates free radicals when irradiated with ultraviolet rays. The present invention was completed by further repeated research based on this knowledge.

[0020] That is, the above-mentioned problems were solved by the following means.

[0021] <1>

[0022] A light absorption filter comprising a resin, a dye having a main absorption wavelength band at a wavelength of 400 to 700 nm, and a compound that generates free radicals when irradiated with ultraviolet rays, wherein the dye comprises a squarylium dye represented by the following general formula (1).

[0023] [Chemical formula 1]

[0024]

[0025] 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.

[0026] G represents a heterocyclic group which may have a substituent.

[0027] <2>

[0028] A light absorption filter comprises a resin, a dye having a main absorption wavelength band at a wavelength of 400 to 700 nm, and a compound that generates free radicals when irradiated with ultraviolet rays, wherein the dye comprises a benzylidene or cinnamylidene pigment represented by the following general formula (V).

[0029] [Chemical formula 2]

[0030]

[0031] In the above formula, A 61 Indicates acidic nucleus, L 61 , L 62 and L 63 Each independently represents a methine group which may be substituted, L 64 and L 65 R each independently represents an alkylene group having 1 to 4 carbon atoms. 62 and R 63 Each independently represents a cyano group, a -COOR 64 、-CONR 65 R 66 、-COR 64 、-SO2R 64 or -SO2NR 65 R 66 , R 64 represents an alkyl group, an alkenyl group, a cycloalkyl group or an aryl group, R 65 and R 66 R each independently represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group or an aryl group. 61 represents a substituent, m 61 An integer of 0 or 1, n 61 An integer from 0 to 4.

[0032] <3>

[0033] according to <1> or <2> The light absorption filter, wherein

[0034] The compound that generates free radicals upon ultraviolet irradiation is a compound that generates free radicals by intramolecular cleavage.

[0035] <4>

[0036] according to <1> or <2> The light absorption filter, wherein

[0037] The compound that generates free radicals by ultraviolet irradiation is a compound that generates free radicals by abstracting a hydrogen atom from a nearby compound.

[0038] <5>

[0039] according to <4> The light absorption filter, wherein

[0040] The compound that generates a free radical by abstracting a hydrogen atom from a nearby compound is a benzophenone compound substituted with an alkoxy group.

[0041] <6>

[0042] according to <1> to <5> The light absorption filter as described in any one of the preceding claims, wherein:

[0043] The light absorption filter causes the dye to undergo a chemical change and decolorize by irradiation with light.

[0044] <7>

[0045] A filter that is used to filter <1> to <6> The light absorption filter described in any one of the above is formed by performing mask exposure.

[0046] <8>

[0047] An organic electroluminescent display device or a liquid crystal display device, comprising <7> The optical filter.

[0048] <9>

[0049] according to <8> The organic electroluminescent display device or liquid crystal display device, wherein:

[0050] The optical filter has a layer on the viewer's side that blocks light absorption by the compound that generates radicals when irradiated with ultraviolet rays.

[0051] <10>

[0052] A method for manufacturing an optical filter comprises the following steps: <1> to <6> The light absorption filter described in any one of the above is irradiated with ultraviolet rays and subjected to mask exposure.

[0053] <11>

[0054] according to <10> The method for manufacturing the optical filter, wherein:

[0055] The above-mentioned ultraviolet ray irradiation is performed under heating conditions.

[0056] <12>

[0057] according to <11> The method for manufacturing the optical filter, wherein:

[0058] The heating temperature is a temperature exceeding the glass transition temperature of the light absorption filter.

[0059] In the present invention, when there are multiple substituents or linking groups represented by specific symbols or formulas (hereinafter referred to as substituents, etc.) or when multiple substituents, etc. are specified at the same time, unless otherwise specified, each substituent, etc. may be the same or different from each other. This is also the same for the number of substituents, etc. In addition, when multiple substituents, etc. are close (especially, when adjacent), unless otherwise specified, they can be linked to each other to form a ring. In addition, unless otherwise specified, rings such as alicyclic rings, aromatic rings, and heterocyclic rings can be further fused to form condensed rings.

[0060] In the present invention, unless otherwise specified, the components constituting the light absorption filter (dye, resin, compound that generates free radicals by ultraviolet irradiation, and other components that may be appropriately contained, etc.) may be contained in the light absorption filter alone or in two or more kinds. The same applies to the optical filter produced using the light absorption filter of the present invention.

[0061] The optical filter of the present invention can preferably be applied to the description of the light absorption filter of the present invention unless otherwise specified, except that the optical filter of the present invention has a light absorption disappearance portion formed by ultraviolet irradiation.

[0062] In the present invention, unless otherwise specified, when a double bond exists in a molecule, it may be either E-type or Z-type, and may be a mixture thereof.

[0063] In the present invention, the expression of a compound (including a complex) is used to include, in addition to the compound itself, its salt and its ion. Furthermore, it refers to a substance obtained by changing a part of the structure within the scope of not damaging the effect of the present invention. Moreover, with respect to a compound not indicating substitution or unsubstituted, it means that it may have any substituent within the scope of not damaging the effect of the present invention. This is also the same for substituents and linking groups.

[0064] Furthermore, in the present invention, a numerical range expressed using "to" means a range including the numerical values ​​described before and after "to" as the lower limit and the upper limit.

[0065] In the present invention, the composition includes not only a mixture in which the concentration of the components is constant (each component is uniformly dispersed) but also a mixture in which the concentration of the components varies within a range that does not impair the intended function.

[0066] In the present invention, having a main absorption wavelength band at wavelengths XX to YYnm means that the wavelength showing maximum absorption (i.e., the maximum absorption wavelength) exists in the wavelength region XX to YYnm. Therefore, if the maximum absorption wavelength is within the above wavelength region, the entire absorption band including the wavelength may be within the above wavelength region or may extend outside the above wavelength region. Furthermore, in the case where there are multiple maximum absorption wavelengths, it is sufficient as long as the maximum absorption wavelength showing the maximum absorbance exists in the above wavelength region. That is, the maximum absorption wavelength other than the maximum absorption wavelength showing the maximum absorbance may exist in any one of the above wavelength region XX to YYnm.

[0067] Effects of the Invention

[0068] The light absorption filter of the present invention shows an excellent quenching rate when irradiated with ultraviolet rays, and also hardly causes secondary absorption accompanying decomposition of the dye due to ultraviolet irradiation.

[0069] Furthermore, the optical filter of the present invention and the OLED display device and liquid crystal display device of the present invention including the same can have a light-absorbing portion and a light-absorbing non-accepting portion at desired positions. BRIEF DESCRIPTION OF THE DRAWINGS

[0070] Figure 1 This is a schematic diagram schematically showing an embodiment of a liquid crystal display device including a polarizing plate and having a filter of the present invention in a backlight. DETAILED DESCRIPTION

[0071] [Light absorption filter]

[0072] The light absorption filter of the present invention contains a resin, a dye having a main absorption wavelength band at a wavelength of 400 to 700 nm (hereinafter also referred to as "dye"), and a compound that generates free radicals when irradiated with ultraviolet rays, wherein the dye contains a squarylium dye represented by the general formula (1) described below or a benzylidene or cinnamylene dye represented by the general formula (V) described below.

[0073] In the present invention, the main absorption wavelength band of the dye refers to the main absorption wavelength band of the dye measured in the state of the light absorption filter. Specifically, in the examples described below, the measurement is performed in the state of the light absorption filter with the substrate under the conditions described in the absorbance of the light absorption filter.

[0074] In the light absorption filter of the present invention, the "dye" is dispersed (preferably dissolved) in the resin to form a layer showing a specific absorption spectrum derived from the dye. The dispersion may be random or regular.

[0075] Furthermore, the above-mentioned "compound that generates free radicals by ultraviolet irradiation" generates free radicals when irradiated with ultraviolet rays by being dispersed (preferably dissolved) in the resin, and the generated free radicals react with the dye, thereby being able to fade and decolorize the dye. As described later, in the case where the compound that generates free radicals by ultraviolet irradiation is a compound that generates free radicals by removing hydrogen atoms from nearby compounds (hereinafter also referred to as "hydrogen-abstraction-type photo-radical generator"), the hydrogen-abstraction-type photo-radical generator excited by ultraviolet irradiation removes hydrogen atoms (hydrogen radicals) from the nearby dye, thereby generating a dye having free radicals, and as a result, the dye can also be faded and decolorized.

[0076] The light absorption filter of the present invention has a structure containing the following in a resin: a dye having a main absorption wavelength band at a wavelength of 400 to 700 nm and having a specific chemical structure; and a compound that generates free radicals by ultraviolet irradiation. The light absorption filter of the present invention having such a structure shows an excellent quenching rate when irradiated with ultraviolet rays, and also, secondary absorption accompanying the decomposition of the dye hardly occurs, and can show a decolorization characteristic close to colorless. Although the reason is inferred, it is considered as follows.

[0077] In the light absorption filter of the present invention, the compound that generates free radicals by ultraviolet irradiation generates free radical species by ultraviolet irradiation, and the free radical species reacts directly or indirectly with the above-mentioned dye to decompose the dye, thereby fading and discoloring the dye. In addition, the hydrogen abstraction type photo-free radical generator excited by ultraviolet irradiation generates a dye having free radicals by hydrogen abstraction reaction, and the active dye reacts and decomposes, etc., thereby fading and discoloring the dye. In particular, the squarylium dye represented by the general formula (1) described later or the benzylidene or cinnamylene dye represented by the general formula (V) described later contained in the light absorption filter of the present invention has a specific chemical structure, so that secondary absorption accompanying dye decomposition hardly occurs, and discoloration can be performed.

[0078] Furthermore, the squarylium dye represented by the general formula (1) described later and the benzylidene and cinnamylene dyes represented by the general formula (V) described later in the light absorption filter of the present invention can show sharp absorption. Therefore, by using the light absorption filter of the present invention, it can be preferably used to form the filter of the present invention having a light absorption portion having a light absorption effect and a light absorption disappearance portion in a desired pattern.

[0079] Thus, in the light absorption filter of the present invention, the dye undergoes a chemical change and is decolorized by irradiation with light (ultraviolet rays). That is, the light absorption filter has a characteristic that the dye undergoes a chemical change and is decolorized by irradiation with light (ultraviolet rays).

[0080] Therefore, the light absorption filter of the present invention preferably does not contain a compound having an ethylenically unsaturated bond.

[0081] <Dyes having a main absorption wavelength band at a wavelength of 400 to 700 nm>

[0082] Specific examples of dyes having a main absorption wavelength band at a wavelength of 400 to 700 nm (hereinafter also referred to as "dyes") used in the present invention include tetraazaporphyrin (TAP) series, squarine (SQ) series, cyanine (CY) series, benzylidene series and cinnamylene series pigments (dyes).

[0083] The dye that may be contained in the light absorption filter of the present invention may be one kind or two or more kinds.

[0084] The light absorption filter of the present invention may contain dyes other than the above-mentioned dyes.

[0085] Among these, from the viewpoint that it is not easy to generate a secondary coloring structure accompanying the decomposition of the dye, the light absorption filter of the present invention includes a squarylium dye represented by the following general formula (1) or a benzylidene or cinnamylene dye represented by the general formula (V) described later as the above-mentioned dye. As described above, a dye that is not easy to generate a secondary coloring structure accompanying the decomposition of the dye is used as the dye, thereby effectively making the part irradiated with ultraviolet light colorless.

[0086] Furthermore, as the dye, from the viewpoint of sharp absorption waveform in the main absorption wavelength band, a squarylium dye represented by the following general formula (1) or a benzylidene or cinnamylene dye represented by the general formula (V) described later is also preferred. As described above, by using a dye having a sharp absorption waveform, the reduction of the transmittance of the displayed light can be suppressed to a minimum and the reflection of external light can be prevented.

[0087] That is, when a squarylium dye represented by the following general formula (1) or a benzylidene dye or a cinnamylidene dye represented by the general formula (V) described later is used as the dye, the optical filter of the present invention can be preferably produced by mask-exposing the light absorption filter of the present invention by ultraviolet irradiation.

[0088] In the present invention, in the pigment represented by following each general formula, cation exists in the mode of delocalization, and has a plurality of tautomeric structures.Therefore, in the present invention, at least one tautomeric structure of some pigment is applicable to the situation of each general formula, and a certain pigment is made as the pigment represented by each general formula.Therefore, the pigment represented by specific general formula also can be called the pigment that can represent at least one tautomeric structure by specific general formula.In the present invention, about the pigment represented by general formula, as long as at least one of its tautomeric structure is applicable to this general formula, then can adopt any tautomeric structure.

[0089] (1) Squarylium dye represented by general formula (1)

[0090] [Chemical formula 3]

[0091]

[0092] In the general formula (1), A and B each independently represent an aryl group which may have a substituent, a heterocyclic group which may have a substituent, or -CH=G. G represents a heterocyclic group which may have a substituent.

[0093] The aryl group that can be used as A or B is not particularly limited, and may be a group containing a single ring or a group containing a condensed ring. The number of carbon atoms in the aryl group is preferably 6 to 30, more preferably 6 to 20, and further preferably 6 to 12. Examples of the aryl group include groups containing a benzene ring or a naphthalene ring, and groups containing a benzene ring are more preferred.

[0094] As a heterocyclic group that can be used as A or B, there is no particular limitation, including a group comprising an aliphatic heterocycle or an aromatic heterocycle, preferably a group comprising an aromatic heterocycle. As a heteroaryl of an aromatic heterocyclic group, for example, a heteroaryl that can be used as a substituent X described later can be cited. Aromatic heterocyclic groups that can be used as A or B are preferably groups of 5-membered rings or 6-membered rings, more preferably groups of nitrogen-containing 5-membered rings. Specifically, a group comprising any one of a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, a pyrazole ring, a thiazole ring, an oxazole ring, a triazole ring, an indole ring, an indolenine ring, a pyridine ring, a pyrimidine ring, a quinoline ring, a benzothiazole ring, a benzoxazole ring and a pyrazolotriazole ring can be preferably cited. Among them, a group comprising any one of a pyrrole ring, a pyrazole ring, a thiazole ring, a pyridine ring, a pyrimidine ring and a pyrazolotriazole ring is preferred. The pyrazolotriazole includes a condensed ring of a pyrazole ring and a triazole ring, and any condensed ring may be formed by condensing at least one of these rings. Examples of the condensed rings include the condensed rings in the general formulae (4) and (5) described below.

[0095] A and B may be bonded to the squarylium acid moiety (the four-membered ring represented by the general formula (1)) at any position (ring-constituting atom) without particular limitation, but are preferably bonded to a carbon atom.

[0096] G in -CH=G which can be used as A or B represents a heterocyclic group which may have a substituent, and preferred examples include those exemplified as the above-mentioned heterocyclic groups which can be used as A or B. Among them, groups containing any one of a benzoxazole ring, a benzothiazole ring and an indoline ring are preferred.

[0097] At least one of A and B may have a hydrogen-bonding group that forms a hydrogen bond in the molecule.

[0098] A, B, and G may each have a substituent X. When having a substituent X, adjacent substituents may be bonded to each other to further form a ring structure. In addition, a plurality of substituents X may exist.

[0099] As the substituent X, for example, there can be mentioned those which can be used as R in the general formula (2) described below. 1 Specific examples include halogen atoms, cyano groups, nitro groups, alkyl groups (including cycloalkyl groups), alkenyl groups, alkynyl groups, aryl groups, heteroaryl groups, aralkyl groups, ferrocenyl groups, -OR 10 、-C(=O)R 11 、-C(=O)OR 12 、-OC(=O)R 12 、-NR 14 R 15 、-NHCOR 16 、-CONR 17 R 18 、-NHCONR 19 R 20 、-NHCOOR 21 、-SR 22 、-SO2R 23 、-SO3R 24 、-NHSO2R 25 and-SO2NR 26 R 27 Furthermore, the substituent X preferably has a quencher moiety described below in addition to the above-mentioned ferrocenyl group.

[0100] In the general formula (1), R 10 ~R 27 Each independently represents a hydrogen atom, an aliphatic group, an aromatic group or a heteroatom-containing cyclic group. 10 ~R 27 The aliphatic group and the aromatic group are not particularly limited and can be appropriately selected from the group consisting of R 1 Among the substituents of , alkyl, cycloalkyl, alkenyl, and alkynyl, which are classified as aliphatic groups, and aryl, which are classified as aromatic groups, can be selected. 10 ~R 27The heteroatom-containing cyclic group may be aliphatic or aromatic. For example, it can be appropriately selected from R 1 The invention can be selected from a heteroaryl group or a heteroatom-containing cyclic group.

[0101] In addition, in -COOR 12 R 12 In the case of a hydrogen atom (i.e., a carboxyl group), the hydrogen atom may be dissociated (i.e., a carbonate group) or in the form of a salt. 24 R 24 When it is a hydrogen atom (ie, a sulfo group), the hydrogen atom may be dissociated (ie, a sulfonate group) or may be in the state of a salt.

[0102] Examples of the halogen atom which can be used as the substituent X include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

[0103] The number of carbon atoms of the alkyl group which can be used as the substituent X is preferably 1 to 20, more preferably 1 to 15, and even more preferably 1 to 8. The number of carbon atoms of the alkenyl group is preferably 2 to 20, more preferably 2 to 12, and even more preferably 2 to 8. The number of carbon atoms of the alkynyl group is preferably 2 to 40, more preferably 2 to 30, and even more preferably 2 to 25. The alkyl group, alkenyl group, and alkynyl group may be linear, branched, or cyclic, and are preferably linear or branched.

[0104] The aryl group which can be used as the substituent X includes a monocyclic or condensed ring group. The number of carbon atoms of the aryl group is preferably 6 to 30, more preferably 6 to 20, and further preferably 6 to 12.

[0105] The alkyl part of the aralkyl group which can be used as the substituent X is the same as the above-mentioned alkyl group. The aryl part of the aralkyl group is the same as the above-mentioned aryl group. The number of carbon atoms of the aralkyl group is preferably 7 to 40, more preferably 7 to 30, and further preferably 7 to 25.

[0106] The heteroaryl group that can be used as the substituent X includes a group containing a monocyclic ring or a condensed ring, preferably a group containing a monocyclic ring or a condensed ring having 2 to 8 rings, and more preferably a group containing a monocyclic ring or a condensed ring having 2 to 4 rings. The number of heteroatoms constituting the ring of the heteroaryl group is preferably 1 to 3. The heteroatoms constituting the ring of the heteroaryl group can be exemplified by a nitrogen atom, an oxygen atom or a sulfur atom. The heteroaryl group preferably contains a group of a 5-membered ring or a 6-membered ring. The number of carbon atoms constituting the ring of the heteroaryl group is preferably 3 to 30, more preferably 3 to 18, and further preferably 3 to 12. Examples of the heteroaryl group include groups containing any one of a pyridine ring, a piperidine ring, a furan ring, a furfuran ring, a thiophene ring, a pyrrole ring, a quinoline ring, a morpholine ring, an indole ring, an imidazole ring, a pyrazole ring, a carbazole ring, a phenothiazine ring, a phenoxazine ring, an indoleline ring, a thiazole ring, a pyrazine ring, a thiadiazine ring, a benzoquinoline ring and a thiadiazole ring.

[0107] The ferrocenyl group which can be used as the substituent X is preferably represented by the general formula (2M).

[0108] [Chemical formula 4]

[0109]

[0110] In the general formula (2M), L represents a single bond or a divalent linking group that is not conjugated with A, B or G in the general formula (1). 1m ~R 9m and (c) and (d) represent a hydrogen atom or a substituent. M is an atom that can constitute a metallocene compound and represents Fe, Co, Ni, Ti, Cu, Zn, Zr, Cr, Mo, Os, Mn, Ru, Sn, Pd, Rh, V or Pt. * represents a bonding portion with A, B or G.

[0111] In the present invention, when L in the general formula (2M) is a single bond, the cyclopentadiene ring directly bonded to A, B or G (having R in the general formula (2M)) 1m The ring) is not included in the conjugated structure conjugated with A, B or G.

[0112] As a divalent linking group that can be used as L, there is no particular limitation as long as it is a linking group that is not conjugated with A, B or G, and the above-mentioned conjugated structure may be contained in the interior thereof or at the end portion of the cyclopentadiene ring side in the general formula (2M). As a divalent linking group, for example, an alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, a divalent heterocyclic group obtained by removing two hydrogen atoms from a heterocyclic ring, -CH=CH-, -CO-, -CS-, -NR- (R represents a hydrogen atom or a monovalent substituent.), -o-, -S-, -So2- or -N=CH-, or a divalent linking group formed by combining a plurality thereof (preferably 2 to 6). Preferably, it is a group selected from the group consisting of an alkylene group having 1 to 8 carbon atoms, an arylene group having 6 to 12 carbon atoms, -CH=CH-, -CO-, -NR- (R is as described above), -o-, -S-, -So2- and -N=CH-, or a divalent linking group formed by combining two or more groups (preferably 2 to 6) selected from the group. Particularly preferably, it is a group selected from the group consisting of an alkylene group having 1 to 4 carbon atoms, a phenylene group, -CO-, -NH-, -O- and -SO2-, or a linking group formed by combining two or more groups (preferably 2 to 6) selected from the group. As a bivalent linking group of combination, there is no particular limitation, but it is preferred to include a group comprising -CO-, -NH-, -O- or -SO2-, and examples thereof include a linking group formed by combining two or more of -CO-, -NH-, -O- or -SO2-, or a linking group formed by combining at least one of -CO-, -NH-, -O- and -SO2- with an alkylene or arylene group. As a linking group formed by combining two or more of -CO-, -NH-, -O- or -SO2-, examples thereof include -COO-, -OCO-, -CONH-, -NHCOO-, -NHCONH-, -SO2NH-. As a linking group formed by combining at least one of -CO-, -NH-, -O- and -SO2- with an alkylene or arylene group, examples thereof include a group formed by combining -CO-, -COO- or -CONH- with an alkylene or arylene group.

[0113] The substituent that can be used as R is not particularly limited and has the same meaning as the substituent X that A in the general formula (2) may have.

[0114] L is preferably a single bond, or a group selected from the group consisting of an alkylene group having 1 to 8 carbon atoms, an arylene group having 6 to 12 carbon atoms, -CH=CH-, -CO-, -NR- (R is as described above), -O-, -S-, -SO2- and -N=CH-, or a group consisting of a combination of two or more groups selected from this group.

[0115] L may have one or more substituents. There are no particular restrictions on the substituents that L may have, and for example, they have the same meaning as the above-mentioned substituent X. When L has multiple substituents, the substituents bonded to adjacent atoms may bond to each other to further form a ring structure.

[0116] The alkylene group that can be used as L may be any of linear, branched or cyclic groups as long as it has 1 to 20 carbon atoms, and examples thereof include methylene, ethylene, propylene, methylethylene, methylmethylene, dimethylmethylene, 1,1-dimethylethylene, butylene, 1-methylpropylene, 2-methylpropylene, 1,2-dimethylpropylene, 1,3-dimethylpropylene, 1-methylbutylene, 2-methylbutylene, 3-methylbutylene, 4-methylbutylene, 2,4-dimethylbutylene, 1,3-dimethylbutylene, pentylene, hexylene, heptylene, octylene, ethane-1,1-diyl, propane-2,2-diyl, cyclopropane-1,1-diyl, cyclopropane-1,2-diyl, cyclobutane-1,1-diyl, cyclobutane-1,2-diyl, cyclopentane-1,1-diyl, cyclopentane-1,2-diyl, cyclopentane-1,3-diyl, cyclohexane-1,1-diyl, cyclohexane-1,2-diyl, cyclohexane-1,3-diyl, cyclohexane-1,4-diyl, methylcyclohexane-1,4-diyl and the like.

[0117] When L is used as a linking group containing at least one of -CO-, -CS-, -NR- (R is as described above), -O-, -S-, -SO2- and -N=CH- in the alkylene group, a group such as -CO- can be introduced into any position in the alkylene group, and the number introduced is not particularly limited.

[0118] The arylene group that can be used as L is not particularly limited as long as it is a group having 6 to 20 carbon atoms. For example, it includes a group obtained by further removing one hydrogen atom from each of the groups exemplified as the aryl group having 6 to 20 carbon atoms that can be used as A in the general formula (1).

[0119] The heterocyclic group that can be used as L is not particularly limited, and examples thereof include groups obtained by further removing one hydrogen atom from the groups exemplified as the heterocyclic group that can be used as A.

[0120] In the general formula (2M), the remaining partial structure after removing the linking group L is equivalent to a structure (metallocene structure) formed by removing one hydrogen atom from the metallocene compound. In the present invention, the metallocene compound as the metallocene structure can be used without particular limitation as long as it is a compound that conforms to the partial structure defined by the general formula (2M) (a compound in which a hydrogen atom is bonded instead of L). The metallocene structure defined by the general formula (2M) is specifically described below.

[0121] In the general formula (2M), R 1m ~R 9m represents a hydrogen atom or a substituent. 1m ~R 9m The substituents of are not particularly limited, but can be selected from the group consisting of R 1 The substituents are selected from the following: 1m ~R 9m A hydrogen atom, a halogen atom, an alkyl group, an acyl group, an alkoxy group, an amino group or an amide group is preferred, a hydrogen atom, a halogen atom, an alkyl group, an acyl group or an alkoxy group is more preferred, a hydrogen atom, a halogen atom, an alkyl group or an acyl group is further preferred, a hydrogen atom, a halogen atom or an alkyl group is particularly preferred, and a hydrogen atom is most preferred.

[0122] As can be used as R 1m ~R 9m Alkyl groups can be used as R 1 Among the alkyl groups, those having 1 to 8 carbon atoms are preferred, and examples thereof include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, isobutyl, pentyl, tert-pentyl, hexyl, octyl and 2-ethylhexyl.

[0123] The alkyl group may have a halogen atom as a substituent. Examples of the alkyl group substituted with a halogen atom include chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, fluoromethyl, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, perfluoroethyl, perfluoropropyl, and perfluorobutyl.

[0124] And, can be used as R 1mIn the alkyl groups such as , at least one methylene group forming the carbon chain may be substituted with -O- or -CO-. Examples of the alkyl group in which the methylene group is substituted with -O- include methoxy, ethoxy, propoxy, isopropoxy, isobutoxy, sec-butoxy, tert-butoxy, 2-methoxyethoxy, chloromethoxy, dichloromethoxy, trichloromethoxy, bromomethoxy, dibromomethoxy, tribromomethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, perfluoroethoxy, perfluoropropoxy, and alkyl groups in which the methylene group at the end of the perfluorobutoxy group is substituted, and examples of the alkyl group in which the methylene group inside the carbon chain is substituted with 2-methoxyethyl, etc. Examples of the alkyl group in which the methylene group is substituted with -CO- include acetyl, propionyl, monochloroacetyl, dichloroacetyl, trichloroacetyl, trifluoroacetyl, propan-2-on-1-yl, butan-2-on-1-yl, etc.

[0125] In the general formula (2M), M is an atom that can constitute a metallocene compound and represents Fe, Co, Ni, Ti, Cu, Zn, Zr, Cr, Mo, Os, Mn, Ru, Sn, Pd, Rh, V or Pt. Among them, M is preferably Fe, Ti, Co, Ni, Zr, Ru or Os, more preferably Fe, Ti, Ni, Ru or Os, further preferably Fe or Ti, and most preferably Fe.

[0126] As the group represented by the general formula (2M), it is preferred that L, R 1m ~R 9m and M are preferably combined with each other, for example, a single bond as L or a group selected from the group consisting of an alkylene group having 2 to 8 carbon atoms, an arylene group having 6 to 12 carbon atoms, -CH=CH-, -CO-, -NR- (R is as described above), -O-, -S-, -SO2- and -N=CH-, or a group consisting of a combination of two or more groups selected from the group, as R 1m ~R 9m A group consisting of a hydrogen atom, a halogen atom, an alkyl group, an acyl group or an alkoxy group and Fe as M.

[0127] Alkyl, alkenyl, alkynyl, aralkyl, aryl and heteroaryl groups which can be used as the substituent X, and 10 ~R 27The aliphatic group, aromatic group and heteroatom-containing cyclic group may further have a substituent, or may be unsubstituted. There are no particular restrictions on the substituents that may be further possessed, but preferably, a substituent selected from alkyl, aryl, amino, alkoxy, aryloxy, aromatic heterocyclic oxy, acyl, alkoxycarbonyl, aryloxycarbonyl, acyloxy, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, alkylthio, arylthio, aromatic heterocyclic thio, sulfonyl, ferrocenyl, hydroxyl, mercapto, halogen atom, cyano, sulfo and carboxyl, and more preferably a substituent selected from alkyl, aryl, alkoxy, aryloxy, aromatic heterocyclic oxy, acyl, alkoxycarbonyl, aryloxycarbonyl, acyloxy, alkylthio, arylthio, aromatic heterocyclic thio, sulfonyl, ferrocenyl, hydroxyl, mercapto, halogen atom, cyano, sulfo and carboxyl. These groups can be appropriately selected from R which can be used as the general formula (2) described later. 1 Select from the substituents.

[0128] As a preferred embodiment of the dye represented by the above general formula (1), there is mentioned a dye represented by the following general formula (2).

[0129] [Chemical formula 5]

[0130]

[0131] In the general formula (2), A 1 The same as A in the general formula (1). Among them, a nitrogen-containing 5-membered heterocyclic group is preferred.

[0132] In the general formula (2), R 1 and R 2 Each independently represents a hydrogen atom or a substituent. 1 With R 2 They may be the same or different and may be bonded to each other to form a ring.

[0133] As can be used as R 1 and R 2The substituent of is not particularly limited, but for example, alkyl (methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, isobutyl, pentyl, hexyl, octyl, dodecyl, trifluoromethyl, etc.), cycloalkyl (cyclopentyl, cyclohexyl, etc.), alkenyl (vinyl, allyl, etc.), alkynyl (ethynyl, propargyl, etc.), aryl (phenyl, naphthyl, etc.), heteroaryl (furyl, thienyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, imidazolyl, pyrazolyl, thiazolyl, benzimidazolyl, benzoxazolyl, quinazolinyl, phthalazinyl, etc.), heteroatom-containing cyclic group (also referred to as heterocyclic group, for example,pyrrolidinyl, imidazolidinyl, morpholinyl, oxazolidinyl, etc.), alkoxy (methoxy, ethoxy, propoxy, etc.), cycloalkyloxy (cyclopentyloxy, cyclohexyloxy, etc.), aryloxy (phenoxy, naphthyloxy, etc.), heteroaryloxy (aromatic heterocyclic oxy), alkylthio (methylthio, ethylthio, propylthio, etc.), cycloalkylthio (cyclopentylthio, cyclohexylthio, etc.), arylthio (phenylthio, naphthylthio, etc.), heteroarylthio (aromatic heterocyclic thio), alkoxycarbonyl (methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl, octyloxycarbonyl, etc.), aryloxycarbonyl (phenoxycarbonyl, naphthyloxycarbonyl, etc.), phosphoryl (dimethylphosphinoyl, diphenylphosphinoyl), ), sulfamoyl (aminosulfonyl, methylaminosulfonyl, dimethylaminosulfonyl, butylaminosulfonyl, cyclohexylaminosulfonyl, octylaminosulfonyl, phenylaminosulfonyl, 2-pyridylaminosulfonyl, etc.), acyl (acetyl, ethylcarbonyl, propylcarbonyl, cyclohexylcarbonyl, octylcarbonyl, 2-ethylhexylcarbonyl, phenylcarbonyl, naphthylcarbonyl, pyridylcarbonyl, etc.), acyloxy (acetyloxy, ethylcarbonyloxy, butylcarbonyloxy, octylcarbonyloxy, phenylcarbonyloxy, etc.), amide (methylcarbonylamino, ethylcarbonylamino, dimethylcarbonylamino, propylcarbonylamino, pentylcarbonylamino, cyclohexylcarbonylamino 2-ethylhexylcarbonylamino, octylcarbonylamino, dodecylcarbonylamino, phenylcarbonylamino, naphthylcarbonylamino, etc.), sulfonamide (methylsulfonylamino, octylsulfonylamino, 2-ethylhexylsulfonylamino, trifluoromethylsulfonylamino, etc.), carbamoyl (aminocarbonyl, methylaminocarbonyl, dimethylaminocarbonyl, propylaminocarbonyl, pentylaminocarbonyl, cyclohexylaminocarbonyl, octylaminocarbonyl, 2-ethylhexylaminocarbonyl, dodecylaminocarbonyl, phenylaminocarbonyl, naphthylaminocarbonyl, 2-pyridylaminocarbonyl, etc.), urea (methylurea, ethylurea, pentylurea, cyclohexylurea, octyl , alkylsulfonyl groups (methylsulfonyl, ethylsulfonyl, butylsulfonyl, cyclohexylsulfonyl, 2-ethylhexylsulfonyl, etc.), arylsulfonyl groups (phenylsulfonyl, naphthylsulfonyl, 2-pyridylsulfonyl, etc.), amino groups (amino, ethylamino, dimethylamino, butylamino, dibutylamino, cyclopentylamino, 2-ethylhexylamino, dodecylamino, phenylamino, naphthylamino, 2-pyridylamino, etc.), alkylsulfonyloxy groups (methanesulfonyloxy), cyano groups, nitro groups, halogen atoms (fluorine atoms, chlorine atoms, bromine atoms, etc.), hydroxyl groups, etc. ,

[0134] Among them, an alkyl group, an alkenyl group, an aryl group or a heteroaryl group is preferred, an alkyl group, an aryl group or a heteroaryl group is more preferred, and an alkyl group is further preferred.

[0135] Can be used as R 1 and R 2The substituent of may further have a substituent. As the substituent that may further have, there can be mentioned those that can be used as R 1 and R 2 The above substituents and the substituents X that A, B and G in the above general formula (1) may have. 1 With R 2 Can bond to each other to form a ring, R 1 or R 2 With B 2 or B 3 The substituents may be bonded to form a ring.

[0136] The ring formed at this time is preferably a heterocyclic ring or a heteroaryl ring. The size of the ring formed is not particularly limited, but preferably a 5-membered ring or a 6-membered ring. In addition, the number of rings formed is not particularly limited, and may be 1 or 2 or more. As a form of forming 2 or more rings, for example, R 1 With B 2 Substituents and R 2 With B 3 The substituents possessed are respectively bonded to form two rings.

[0137] In the general formula (2), B 1 , B 2 , B 3 and B 4 Each independently represents a carbon atom or a nitrogen atom. 1 , B 2 , B 3 and B 4 The ring of is an aromatic ring. 1 ~B 4 At least 2 of them are carbon atoms, more preferably B 1 ~B 4 All carbon atoms.

[0138] Can be used as B 1 ~B 4 The carbon atoms have hydrogen atoms or substituents. 1 ~B 4 The number of carbon atoms having a substituent among the carbon atoms in is not particularly limited, but is preferably 0, 1 or 2, and more preferably 1. In particular, B is preferably 1 and B 4 are carbon atoms, and at least one of them has a substituent.

[0139] As can be used as B 1 ~B 4 The substituents on the carbon atoms of are not particularly limited, and examples thereof include 1 and R 2The above-mentioned substituents. Among them, preferably, it is an alkyl group, an alkoxy group, an alkoxycarbonyl group, an aryl group, an acyl group, an amide group, a sulfonamide group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, an amino group, a cyano group, a nitro group, a halogen atom or a hydroxyl group, and more preferably, it is an alkyl group, an alkoxy group, an alkoxycarbonyl group, an aryl group, an acyl group, an amide group, a sulfonamide group, a carbamoyl group, an amino group, a cyano group, a nitro group, a halogen atom or a hydroxyl group.

[0140] Can be used as B 1 ~B 4 The substituent on the carbon atom of may further have a substituent. Examples of the substituent that may further have include R in the general formula (2): 1 and R 2 The substituent that may be further possessed and the substituent X that A, B and G in the general formula (1) may have are preferably ferrocenyl.

[0141] As can be used as B 1 and B 4 The substituents on the carbon atoms of are preferably alkyl, alkoxy, hydroxy, amide, sulfonamide or carbamoyl, and particularly preferably alkyl, alkoxy, hydroxy, amide or sulfonamide, and most preferably hydroxy, amide or sulfonamide. These can be used as B 1 and B 4 The substituent possessed by the carbon atom of may further have a ferrocenyl group.

[0142] As can be used as B 2 and B 3 The substituents possessed by the carbon atoms are further preferably alkyl, alkoxy, alkoxycarbonyl, acyl, amino, cyano, nitro or halogen atoms, and it is particularly preferred that any one of the substituents is an electron withdrawing group (for example, alkoxycarbonyl, acyl, cyano, nitro or halogen atom).

[0143] 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).

[0144] [Chemical formula 6]

[0145]

[0146] In the general formula (3), R 1 and R 2 Each independently represents a hydrogen atom or a substituent, and R 1 and R 2 The meanings are the same, and the preferred ranges are also the same.

[0147] In the general formula (3), B 1 ~B 4Each independently represents a carbon atom or a nitrogen atom, and B in the above general formula (2) 1 ~B 4 The meanings are the same, and the preferred ranges are also the same.

[0148] In the general formula (3), R 3 and R 4 Each independently represents a hydrogen atom or a substituent. 3 and R 4 The substituents of are not particularly limited, and examples thereof include those that can be used as the above R 1 and R 2 The substituents are the same as the group.

[0149] Among them, it can be used as R 3 The substituent of is preferably an alkyl group, an alkoxy group, an amino group, an amide group, a sulfonamide group, a cyano group, a nitro group, an aryl group, a heteroaryl group, a heteroatom-containing cyclic group, an alkoxycarbonyl group, a carbamoyl group or a halogen atom, more preferably an alkyl group, an aryl group or an amino group, and further preferably an alkyl group. These can be used as R 3 The substituent may further have a ferrocenyl group.

[0150] As can be used as R 4 The substituent is preferably an alkyl group, an aryl group, a heteroaryl group, a heteroatom-containing cyclic group, an alkoxy group, an alkoxycarbonyl group, an acyl group, an acyloxy group, an amide group, a carbamoyl group, an amino group or a cyano group, more preferably an alkyl group, an alkoxycarbonyl group, an acyl group, a carbamoyl group or an aryl group, and further preferably an alkyl group.

[0151] Can be used as R 3 and R 4 The alkyl group may be any of a linear, branched, or cyclic group, but is preferably a linear or branched group. The number of carbon atoms in the alkyl group is preferably 1 to 12, and more preferably 1 to 8. Examples of the alkyl group include preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a tert-butyl group, a 2-ethylhexyl group, and a cyclohexyl group, and more preferably a methyl group and a tert-butyl group.

[0152] [Chemical formula 7]

[0153]

[0154] In the general formula (4), R 1 and R 2 Each independently represents a hydrogen atom or a substituent, and R 1 and R 2 The meanings are the same, and the preferred ranges are also the same.

[0155] In general formula (4), B 1 ~B 4 Each independently represents a carbon atom or a nitrogen atom, and B in the above general formula (2) 1 ~B4 The meanings are the same, and the preferred ranges are also the same.

[0156] In the general formula (4), R 5 and R 6 Each independently represents a hydrogen atom or a substituent. 5 and R 6 The substituents of are not particularly limited, and examples thereof include those that can be used as the above R 1 and R 2 The substituents are the same as the group.

[0157] Among them, it can be used as R 5 The substituent is preferably an alkyl group, an alkoxy group, an aryloxy group, an amino group, a cyano group, an aryl group, a heteroaryl group, an acyl group, an acyloxy group, an amide group, a sulfonamide group, a urea group or a carbamoyl group, more preferably an alkyl group, an alkoxy group, an acyl group, an amide group or an amino group, and further preferably an alkyl group.

[0158] Can be used as R 5 The alkyl group can be used as R in the general formula (3) 3 The alkyl group has the same meaning and the preferred range is also the same.

[0159] In the general formula (4), it can be used as R 6 The substituent is preferably an alkyl group, an alkenyl group, an aryl group, a heteroaryl group, a heteroatom-containing cyclic group, an alkoxy group, a cycloalkyloxy group, an aryloxy group, an alkoxycarbonyl group, an acyl group, an acyloxy group, an amide group, a sulfonamide group, an alkylsulfonyl group, an arylsulfonyl group, a carbamoyl group, an amino group, a cyano group, a nitro group or a halogen atom, more preferably an alkyl group, an aryl group, a heteroaryl group or a heteroatom-containing cyclic group, further preferably an alkyl group or an aryl group.

[0160] Can be used as R 6 The alkyl group can be used as R in the general formula (3) 4 The alkyl group has the same meaning and the preferred range is also the same.

[0161] Can be used as R 6 The aryl group is preferably an aryl group having 6 to 12 carbon atoms, and more preferably a phenyl group. The aryl group may have a substituent, and examples of such a substituent include groups included in the following substituent group A, and particularly preferably an alkyl group having 1 to 10 carbon atoms, a sulfonyl group, an amino group, an acylamino group, and a sulfonylamino group. These substituents may further have a substituent. Specifically, the substituent is preferably an alkylsulfonylamino group.

[0162] -Substituent Group A-

[0163] a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkoxy group, an aminooxy group, an aryloxy group, a silyloxy group, a heterocyclic group, an acyloxy group, a carbamoyloxy group, an amino group, an acylamino group, an aminocarbonylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfamoylamino group, a sulfonylamino group (including an alkyl or arylsulfonylamino group), a mercapto group, an alkylthio group, an arylthio group, a heterocyclicthio group, a sulfamoyl group, a sulfo group, an alkyl or arylsulfinyl group, a sulfonyl group (including an alkyl or arylsulfonyl group), an acyl group, an aryloxycarbonyl group, an alkoxycarbonyl group, a carbamoyl group, an aryl or heterocyclic azo group, an imide group, a phosphinyl group, a phosphinyloxy group, a phosphinylamino group, a silyl group, and the like.

[0164] [Chemical formula 8]

[0165]

[0166] In the general formula (5), R 1 and R 2 Each independently represents a hydrogen atom or a substituent, and R 1 and R 2 The meanings are the same, and the preferred ranges are also the same.

[0167] In the general formula (5), B 1 ~B 4 Each independently represents a carbon atom or a nitrogen atom, and B in the above general formula (2) 1 ~B 4 The meanings are the same, and the preferred ranges are also the same.

[0168] In the general formula (5), R 7 and R 8 Each independently represents a hydrogen atom or a substituent. 7 and R 8 The substituents of are not particularly limited, and examples thereof include those that can be used as the above R 1 and R 2 The substituents are the same as the group.

[0169] Among them, it can be used as R 7 The preferred range, more preferred range and further preferred range of the substituents of can be used as R in the general formula (4) 5 The substituents are the same as those of 5 The alkyl group can be used as the above R 3 The alkyl group has the same meaning and the preferred range is also the same.

[0170] In the general formula (5), it can be used as R 8 The preferred range, more preferred range and further preferred range of the substituents of can be used as R in the general formula (4) 6The substituents are the same as those of 8 The preferred ranges of the alkyl and aryl groups are similar to those that can be used as R in the above general formula (4). 6 The alkyl and aryl groups have the same meanings and the preferred ranges are also the same.

[0171] As the squarylium cyanine pigment used in the above-mentioned dye, as long as it is a squarylium cyanine pigment represented by any one of the general formulas (1) to (5), it can be used without particular limitation. As its example, for example, compounds described in Japanese Patent Publication No. 2006-160618, International Publication No. 2004 / 005981, International Publication No. 2004 / 007447, Dyes and Pigment, 2001, 49, p.161-179, International Publication No. 2008 / 090757, International Publication No. 2005 / 121098, and Japanese Patent Publication No. 2008-275726 can be enumerated.

[0172] Specific examples of the dye represented by any of the general formulae (1) to (5) are shown below, but the present invention is not limited thereto.

[0173] In the following specific examples, Me represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group.

[0174] [Chemical formula 9]

[0175]

[0176] [Chemical formula 10]

[0177]

[0178] [Chemical formula 11]

[0179]

[0180] In addition to the above specific examples, specific examples of the pigment represented by any one of the general formulas (3) to (5) are given below. The substituent B in the following table represents the following structure. In the following structure and the following table, Me represents a methyl group, Et represents an ethyl group, i-Pr represents an isopropyl group, Bu represents a normal butyl group, t-Bu represents a tert-butyl group, and Ph represents a phenyl group. In the following structure, * represents the bonding portion to the carbon four-membered ring in each general formula.

[0181] [Chemical formula 12]

[0182]

[0183] [Chemical formula 13]

[0184]

[0185] [Chemical formula 14]

[0186]

[0187]

[0188] [Chemical formula 15]

[0189]

[0190] [Chemical formula 16]

[0191]

[0192] [Chemical formula 17]

[0193]

[0194]

[0195] [Chemical formula 18]

[0196]

[0197] [Chemical formula 19]

[0198]

[0199]

[0200] [Chemical formula 20]

[0201]

[0202] As a preferred embodiment of the dye represented by the above general formula (1), there is a dye represented by the following general formula (6).

[0203] [Chemical formula 21]

[0204]

[0205] In the general formula (6), R 3 and R 4 Each independently represents a hydrogen atom or a substituent, and R 3 and R 4 The meanings are the same, and the preferred ranges are also the same.

[0206] In the general formula (6), A 2 The same as A in the general formula (1). Among them, a nitrogen-containing 5-membered heterocyclic group is preferred.

[0207] The dye represented by the above general formula (6) is preferably a dye represented by any one of the following general formulas (7), (8) and (9).

[0208] [Chemical formula 22]

[0209]

[0210] In the general formula (7), R 3 and R 4 Each independently represents a hydrogen atom or a substituent, and R 3 and R 4 The meanings are the same, and the preferred ranges are also the same. 3 and 2 R 4 They may be the same or different.

[0211] [Chemical formula 23]

[0212]

[0213] In the general formula (8), R3 及 R 4 Each independently represents a hydrogen atom or a substituent, and R 3 The meanings are the same, and the preferred ranges are also the same.

[0214] In the general formula (8), R 5 and R 6 Each independently represents a hydrogen atom or a substituent, and R 5 and R 6 The meanings are the same, and the preferred ranges are also the same.

[0215] [Chemical formula 24]

[0216]

[0217] In the general formula (9), R 3 and R 4 Each independently represents a hydrogen atom or a substituent, and R 3 The meanings are the same, and the preferred ranges are also the same.

[0218] In the general formula (9), R 7 and R 8 Each independently represents a hydrogen atom or a substituent, and R 7 and R 8 The meanings are the same, and the preferred ranges are also the same.

[0219] Specific examples of the dye represented by any of the general formulae (6) to (9) are shown below, but the present invention is not limited to these.

[0220] In the following specific examples, Me represents a methyl group, Et represents an ethyl group, i-Pr represents an isopropyl group, t-Bu represents a tert-butyl group, and Ph represents a phenyl group. In the following structures, * represents a bonding portion to a carbon four-membered ring in each general formula.

[0221] [Chemical formula 25]

[0222]

[0223]

[0224] [Chemical formula 26]

[0225]

[0226] [Chemical formula 27]

[0227]

[0228]

[0229] [Chemical formula 28]

[0230]

[0231]

[0232] (Quencher built-in pigment)

[0233] The squarylium dye represented by the general formula (1) can be a built-in quencher dye formed by linking the quencher portion and the dye through a linking group by a covalent bond. The built-in quencher dye can also be preferably used as the dye. That is, the built-in quencher dye is listed as the dye according to the wavelength having the main absorption wavelength band.

[0234] As the quencher moiety, for example, a ferrocenyl group in the substituent X can be cited. In addition, the quencher moiety in the quencher compound described in paragraphs

[0199] to

[0212] and

[0234] to

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

[0235] Specific examples of the squarylium dyes represented by the general formula (1) corresponding to the quencher-internal type dyes are shown below. However, the present invention is not limited to these.

[0236] In the following specific examples, Me represents a methyl group, Et represents an ethyl group, and B u It represents butyl.

[0237] [Chemical formula 29]

[0238]

[0239] [Chemical formula 30]

[0240]

[0241] [Chemical formula 31]

[0242]

[0243] [Chemical formula 32]

[0244]

[0245] [Chemical formula 33]

[0246]

[0247] [Chemical formula 34]

[0248]

[0249] [Chemical formula 35]

[0250]

[0251] [Chemical formula 36]

[0252]

[0253] [Chemical formula 37]

[0254]

[0255] [Chemical formula 38]

[0256]

[0257] [Chemical formula 39]

[0258]

[0259] [Chemical formula 40]

[0260]

[0261] [Chemical formula 41]

[0262]

[0263] [Chemical formula 42]

[0264]

[0265] [Chemical formula 43]

[0266]

[0267] [Chemical formula 44]

[0268]

[0269] [Chemical formula 45]

[0270]

[0271] (2) A benzylidene or cinnamylene pigment represented by the general formula (V) [Chemical Formula 46]

[0272]

[0273] In the above formula, A 61 Indicates acidic nucleus, L 61 , L 62 and L 63 Each independently represents a methine group which may be substituted, L 64 and L 65 R each independently represents an alkylene group having 1 to 4 carbon atoms. 62 and R 63 Each independently represents a cyano group, a -COOR 64 (ie, -C(=O)OR 64 ),-CONR 65 R 66 (i.e., -C(=O)NR 65 R 66 ), -COR 64 (i.e., -C(=O)R 64 ),-SO2R 64 or -SO2NR 65 R 66 , R 64 represents an alkyl group, an alkenyl group, a cycloalkyl group or an aryl group, R 65 and R 66 R each independently represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group or an aryl group. 61 represents a substituent, m 61 An integer of 0 or 1, n 61 An integer from 0 to 4.

[0274] In the compound (pigment) represented by the above general formula (V), m 61 is an integer of 0 or 1, among which m 61 Compounds with m=0 are called benzylidene pigments, usually yellow pigments. 61 Compounds with an MnO2 of 1 are called cinnamyl pigments, usually magenta pigments.

[0275] In the present invention, m in the general formula (V) 61 It is preferably 0, and the compound represented by the general formula (V) is preferably a yellow pigment.

[0276] Hereinafter, each substituent in the general formula (V) will be described in detail.

[0277] A 61 represents an acidic core, preferably a cyclic ketomethylene compound or a compound having a methylene group sandwiched by an electron withdrawing group. 61 In the case of a cyclic ketomethylene compound, the carbon atom constituting the methylene group in the ketomethylene moiety is bonded to L via a double bond. 61 Bonding. In A 61 In the case of a compound having a methylene group sandwiched by an electron withdrawing group, the carbon atom constituting the methylene group in the methylene part sandwiched by the electron withdrawing group is bonded to L via a double bond. 61 Bonding.

[0278] Examples of cyclic ketomethylene compounds include 2-pyrazolin-5-one, 1,2,3,6-tetrahydropyridine-2,6-dione, rhodanine, hydantoin, thiohydantoin, 2,4-oxazolidinedione, isoxazolone, barbituric acid, thiobarbituric acid, indandione, dioxopyrazolopyridine, hydroxypyridine, pyrazolidinedione, 2,5-dihydrofuran-2-one, and pyrrolidine-2-one. These compounds may have a substituent.

[0279] Compounds with a methylene group sandwiched by an electron withdrawing group can be made from Z 51 -CH2-Z s2 Here, Z 51 and Z 52 Respectively represent cyano, -SO2R 51 、-COR 51 、-COOR 51 、-CON(R 52 )2、-SO2N(R 52 )2, -C〔=C(CN)2〕R 51 or -C〔=C(CN)2〕N(R 51 )2,R 51 represents an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group or a heterocyclic group, R 52 Represents a hydrogen atom or R 51 The groups listed in 51 and R 52 The substituents of can have substituents respectively, and there are multiple R in the molecule. 51 or R 52 In the case of Z, they can be the same or different. 51 With Z52 Can be the same.

[0280] A 61 The above-mentioned cyclic ketomethylene compounds are preferred, 2-pyrazol-5-one, isoxazolone, hydroxypyridine, pyrazolidinedione or barbituric acid is more preferred, isoxazolone, pyrazolidinedione or barbituric acid is further preferred, and pyrazolidinedione is particularly preferred.

[0281] The above L 61 , L 62 and L 63 It represents a methine group which may have a substituent, and the substituents which the methine group may have may be linked to each other to form a 5- or 6-membered ring (for example, cyclopentene and cyclohexene).

[0282] Examples of the substituent that the methine group may have include a sulfonamide group (e.g., methanesulfonamide, benzenesulfonamide, octanesulfonamide), a sulfamoyl group (e.g., sulfamoyl, methylsulfamoyl, phenylsulfamoyl, butylsulfamoyl), a sulfonylcarbamoyl group (e.g., methanesulfonylcarbamoyl, benzenesulfonylcarbamoyl), an acylsulfamoyl group (e.g., acetylsulfamoyl, pivaloylsulfamoyl, benzoylsulfamoyl), a chain or cyclic alkyl group (e.g., methyl, isopropyl, cyclopropyl, cyclohexyl, 2-ethylhexyl, dodecyl, octadecyl, 2-phenylethyl, benzyl), an alkenyl group (e.g., vinyl, allyl), an alkoxy group (e.g., methoxy, octyloxy, dodecyloxy, 2-methoxyethoxy), an aryloxy group (e.g., phenoxy), a halogen atom (e.g., F, Cl, Br), an amino group (e.g., amino, diethylamino, ethyldodecylamino), an alkoxy group Carbonyl (e.g., ethoxycarbonyl, octyloxycarbonyl, 2-hexyldecyloxycarbonyl), acyloxy (e.g., acetoxy), acylamino (e.g., acetylamino, pivaloylamino, benzamido), carbamoyl (e.g., unsubstituted carbamoyl, ethylcarbamoyl, diethylcarbamoyl, phenylethylcarbamoyl), aryl (e.g., phenyl, naphthyl), alkylthio (e.g., methylthio, octylthio), arylthio (e.g., phenylthio, naphthylthio), acyl (e.g., acetyl, benzoyl, pivaloyl), sulfonyl (e.g., methanesulfonyl, benzenesulfonyl), ureido (e.g., 3-propylureido, 3,3-dimethylureido), carbamate (e.g., methoxycarbonylamino, butoxycarbonylamino), cyano, hydroxyl, nitro, heterocyclic (e.g., benzoxazole ring, pyridine ring, sulfolane ring, furan ring, pyrrole ring, pyrrolidine ring, morpholine ring, piperazine ring, pyrimidine ring) and the like.

[0283] As L 61 , L 62 and L 63 , preferably by =CR 67 -(R 67represents an alkyl group having 1 to 10 carbon atoms or a hydrogen atom. ) represents.

[0284] Moreover, as L 61 , L 62 and L 63 Combination of L 61 , L 62 and L 63 Both R 67 It is a hydrogen atom of the methine or L 61 and L 63 Both R 67 is a hydrogen atom of the methine and L 62 For R 67 is a methine of a methyl group, more preferably L 61 , L 62 and L 63 Both R 67 It is the methine group of the hydrogen atom.

[0285] The above L 64 and L 65 Each independently represents an alkylene group having 1 to 4 carbon atoms, preferably a methylene group or an ethylene group. 64 and L 65 The same substituents are preferred.

[0286] The above R 62 and R 63 Each independently represents a cyano group, a -COOR 64 、-CONR 65 R 66 、-COR 64 、-SO2R 64 、-SO2NR 65 R 66 .

[0287] The above R 64 represents an alkyl group (except for a cycloalkyl group, for example, methyl, ethyl, isopropyl, tert-butyl, benzyl, trifluoromethyl, 2-chloroethyl, 2-ethoxyethyl), an alkenyl group (for example, vinyl, allyl, oleyl), a cycloalkyl group (for example, cyclopentyl, cyclohexyl) or an aryl group (for example, phenyl, 2-naphthyl, 4-chlorophenyl, 2-methoxyphenyl, 3-dimethylaminophenyl), preferably an alkyl group, a cycloalkyl group or an aryl group, and more preferably a straight-chain unsubstituted alkyl group, a cycloalkyl group or an aryl group.

[0288] The above R 65 and R 66 R 64 The groups listed in (i.e., alkyl, alkenyl, cycloalkyl or aryl) or hydrogen atom are preferably alkyl, aryl or hydrogen atom, and more preferably linear unsubstituted alkyl or hydrogen atom.

[0289] Can be used as R 65 and R 66 The number of carbon atoms in the alkyl, alkenyl and cycloalkyl groups is preferably 1 to 20, more preferably 6 to 20, and particularly preferably 8 to 16. 65 and R 66 The aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 18 carbon atoms.

[0290] R 65 With R 66 They may be linked to each other to form a nitrogen-containing heterocyclic ring.

[0291] As the above R 62 and R 63 , preferably cyano, -COOR 64 or-CONR 65 R 66 , more preferably cyano or -COOR 64 , further preferably -COOR 64 .

[0292] In addition, in R 62 and R 63 In the case of cyano, L 64 and L 65 Preferably, ethylene is 62 and R 63 -COOR 64 In the case of base, L 64 and L 65 R is preferably a methylene group. 62 With R 63 They may be the same or different, but are preferably the same.

[0293] The above R 61 represents a substituent, and preferably L 61 , L 62 and L 63 Examples of substituents that the methine group may have are described in 61 An alkyl group, an alkoxy group, a dialkylamino group or an alkoxycarbonyl group is more preferred, an alkyl group or an alkoxy group is further preferred, and a methyl group or a methoxy group is particularly preferred.

[0294] The above n 61 is an integer of 0 to 4, preferably an integer of 0 or 1, and more preferably 0. 61 When R is 1, 61 Substitution is preferably at the meta position relative to the amino group.

[0295] Specific examples of the pigment represented by the general formula (V) are shown below, but the present invention is not limited thereto. In the following structure, * represents a connecting bond. In addition, unless otherwise specified, an alkyl group refers to a linear alkyl group.

[0296] [Chemical formula 47]

[0297]

[0298]

[0299] [Chemical formula 48]

[0300]

[0301]

[0302] [Chemical formula 49]

[0303]

[0304]

[0305] [Chemical formula 50]

[0306]

[0307]

[0308] [Chemical formula 51]

[0309]

[0310]

[0311] [Chemical formula 52]

[0312] A-127

[0313]

[0314] A-128

[0315]

[0316] A-129

[0317]

[0318] A-130

[0319]

[0320] [Chemical formula 53]

[0321] A-131

[0322]

[0323] A-132

[0324]

[0325] In the light absorption filter of the present invention, the total content of the above-mentioned dye is preferably 0.10 parts by mass or more, more preferably 0.15 parts by mass or more, further preferably 0.20 parts by mass or more, particularly preferably 0.25 parts by mass or more, and particularly preferably 0.30 parts by mass or more, relative to 100 parts by mass of the resin constituting the light absorption filter of the present invention. When the total content of the above-mentioned dye in the light absorption filter of the present invention is greater than the above-mentioned preferred lower limit, a good antireflection effect can be obtained.

[0326] Furthermore, in the light absorption filter of the present invention, the total content of the dyes is usually 50 parts by mass or less, preferably 40 parts by mass or less, and more preferably 30 parts by mass or less, based on 100 parts by mass of the resin constituting the light absorption filter of the present invention.

[0327] In the light absorption filter of the present invention, the content of the squarylium dye represented by the above general formula (1) or the benzylidene or cinnamylidene dye represented by the above general formula (V) is preferably 0.01 to 30 parts by mass, and more preferably 0.1 to 10 parts by mass, relative to 100 parts by mass of the resin constituting the light absorption filter of the present invention. In addition, in the light absorption filter of the present invention, all of the above dyes may be squarylium dye represented by the above general formula (1) or the benzylidene or cinnamylidene dye represented by the above general formula (V).

[0328] In addition, when the dye contains the built-in quencher pigment, from the viewpoint of imparting light absorption properties such as an antireflection effect, the content of the built-in quencher pigment is preferably 0.1 parts by mass or more relative to 100 parts by mass of the resin constituting the light absorption filter of the present invention. The upper limit is preferably 45 parts by mass or less.

[0329] <Compounds that generate free radicals upon ultraviolet irradiation>

[0330] The compound used in the present invention that generates free radicals by ultraviolet irradiation (hereinafter, also referred to as "free radical generator") is not particularly limited as long as it is a compound that generates free radicals by ultraviolet irradiation and has the function of decolorizing the above-mentioned dye. In the present invention, a compound that absorbs light and generates free radicals (hereinafter, also referred to as "photoradical generator") can be preferably used. In addition, the generated free radical can also be a diradical in addition to a general free radical.

[0331] As the photoradical generator, compounds commonly used as photoradical polymerization initiators or photoradical generators can be used without particular limitation, and examples thereof include acetophenone generators, benzoin generators, benzophenone generators, phosphine oxide generators, oxime generators, ketal generators, anthraquinone generators, thioxanthone generators, azo compound generators, peroxide generators, disulfide generators, lophanine dimer generators, onium salt generators, borate generators, active ester generators, active halogen generators, inorganic complex generators, and coumarin generators. In addition, the "○○ generator" in the specific examples of the photoradical generators is sometimes referred to as "○○ compound" or "○○ class", etc., and is hereinafter referred to as "○○ compound".

[0332] Specific examples, preferred embodiments, and commercial products of the photoradical generator are described in paragraphs

[0133] to

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

[0333] 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 quenching rate, a compound that generates radicals by abstracting a hydrogen atom from a nearby compound is more preferred.

[0334] The compound that generates radicals by intramolecular cleavage (hereinafter also referred to as an "intramolecular cleavage type photo-radical generator") refers to a compound that generates radicals by homolytic bond cleavage of a compound that absorbs light.

[0335] As intramolecular cleavage type photo-radical generators, acetophenone compounds, benzoin compounds, phosphine oxide compounds, oxime compounds, ketal compounds, azo compounds, peroxide compounds, disulfide compounds, onium salt compounds, borate compounds, active ester compounds, active halogen compounds, inorganic complex compounds or coumarin compounds can be cited. Among these, acetophenone compounds, benzoin compounds or phosphine oxide compounds are also preferred as carbonyl compounds. As a photodecomposition reaction of intramolecular cleavage type carbonyl compounds, Norrish I type reaction is known, and this reaction can be referred to for the free radical generation mechanism.

[0336] The compound that generates free radicals by abstracting a hydrogen atom from a nearby compound (hereinafter also referred to as a "hydrogen abstraction type photoradical generator") refers to a compound that generates free radicals by abstracting a hydrogen atom from a nearby compound using a carbonyl compound in an excited triplet state obtained by light absorption.

[0337] As hydrogen abstraction type photo-radical generators, carbonyl compounds are known, and examples thereof include benzophenone compounds, anthraquinone compounds, and thioxanthone compounds. As a photodecomposition reaction of hydrogen abstraction type carbonyl compounds, Norrish II reaction is known, and the radical generation mechanism can be referred to this reaction.

[0338] Examples of the compound existing in the vicinity include various components existing in the light absorption filter, such as resins, dyes, and radical generators.

[0339] The compound existing nearby becomes a compound having free radicals by removing hydrogen atoms. The dye whose hydrogen atoms are removed by the hydrogen-abstraction photo-radical generator becomes an active compound having free radicals, and thus the dye can also fade or decolorize by reactions such as decomposition of the dye having the free radicals.

[0340] Furthermore, when the hydrogen abstraction type photo-radical generator abstracts a hydrogen atom in a molecule, a diradical is generated.

[0341] As the hydrogen abstraction type photo-radical generator, benzophenone compounds are preferred from the viewpoint of the quantum yield of the hydrogen abstraction reaction.

[0342] (Benzophenone compounds)

[0343] Examples of benzophenone compounds that can be used as hydrogen abstraction type photoradical generators include benzophenone, alkylbenzophenone compounds such as 2-methylbenzophenone, 3-methylbenzophenone or 4-methylbenzophenone, benzophenone compounds having a halogen atom such as 2-chlorobenzophenone, 4-chlorobenzophenone or 4-bromobenzophenone, benzophenone compounds substituted with a carboxyl group or an alkoxycarbonyl group such as 2-carboxybenzophenone, 2-ethoxycarbonylbenzophenone, benzophenonetetracarboxylic acid or its tetramethyl ester, 4,4'-thiazolinone, and the like. - bis(dimethylamino)benzophenone, 4,4'-bis(dicyclohexylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(dihydroxyethylamino)benzophenone, such as bis(dialkylamino)benzophenone compounds (preferably 4,4'-bis(dialkylamino)benzophenone compounds) or benzophenone compounds substituted with alkoxy groups such as 4-methoxy-4'-dimethylaminobenzophenone, 4-methoxybenzophenone, 4,4'-dimethoxybenzophenone.

[0344] Among the above benzophenone compounds, benzophenone compounds substituted with alkoxy groups (also referred to as alkoxybenzophenone compounds) are preferred from the viewpoint of achieving both high levels of light resistance of the unexposed portion and decolorization of the exposed portion while reducing the molar ratio of the radical generator to the dye.

[0345] The number of the alkoxy groups possessed by the benzophenone compound is preferably 1 to 3, more preferably 1 or 2.

[0346] The alkyl chain portion of the alkoxy group of the alkoxybenzophenone compound may be linear or branched. The alkoxy group preferably has 1 to 18 carbon atoms, more preferably 1 to 15 carbon atoms, and even more preferably 1 to 12 carbon atoms.

[0347] As for the substitution position of the alkoxy group in the above-mentioned alkoxybenzophenone compound, from the viewpoint of achieving both the light fastness of the unexposed part and the decolorization property of the exposed part at a higher level while reducing the molar ratio of the free radical generator to the dye, it is preferred that the alkoxy group be substituted at least at the 4-position, more preferably at least at the 4-position and the 4'-position, and even more preferably at both the 4-position and the 4'-position.

[0348] Various examples of photoradical generators are described in "Latest UV Curing Technology", TECHNICAL INFORMATION INSTITUTE CO., LTD., 1991, p. 159 and "Ultraviolet Curing System", written by Kato Kiyoshi, published by Sogo Technical Center in 1989, pp. 65 to 148, which can also be preferably used in the present invention.

[0349] In the photoradical generator, the maximum absorption wavelength of ultraviolet rays absorbed is preferably in the range of 250 to 400 nm, more preferably in the range of 240 to 400 nm, and further preferably in the range of 270 to 400 nm.

[0350] When the photoradical generator is a benzophenone compound, the absorption maximum wavelength attributable to n-π* migration on the longest wavelength side is preferably in the range of 260 to 400 nm, more preferably in the range of 285 to 345 nm. * The absorption maximum wavelength is preferably in the range of 240 to 380 nm, more preferably in the range of 270 to 330 nm. By setting the absorption maximum wavelength in the above range, the light from the light source such as the metal halide lamp used in exposure is well absorbed, and on the other hand, it is difficult to absorb ultraviolet rays intruding from the outside when assembled in a display device, and it is possible to take into account both the light resistance of the unexposed part and the decolorization of the exposed part.

[0351] Examples of photoradical generating agents having absorption in a longer wavelength region include alkoxybenzophenone compounds.

[0352] The maximum absorption wavelength of ultraviolet light absorbed by the photoradical generator is preferably separated from the main absorption wavelength band of the dye having a main absorption wavelength band at a wavelength of 400 to 700 nm by 30 nm or more. The upper limit is not particularly limited.

[0353] Commercially available photocleavage-type photoradical generators are listed by trade name, and include: "Irgacure 651", "Irgacure 184", "Irgacure 819", "Irgacure 907", "Irgacure 1870" (CGI-403 / Irgacure 184 = 7 / 3 mixed initiator), "Irgacure 500", "Irgacure 369", "Irgacure 1173", "Irgacure 2959", "Irgacure 4265", "Irgacure 4263", "Irgacure 127" or "OXE01" manufactured by BASF (formerly Ciba Specialty Chemicals Co., Ltd.); and "KAYACURE DETX-S", "KAYACURE BP-100", "KAYACURE BP-200" and "KAYACURE BP-300" manufactured by Nippon Kayaku Co., Ltd. BDMK", "KAYACURECTX", "KAYACURE BMS", "KAYACURE 2-EAQ", "KAYACURE ABQ", "KAYACURE CPTX", "KAYACUREEPD", "KAYACURE ITX", "KAYACURE QTX", "KAYACURE BTC" or "KAYACURE MCA", etc.; and "Esacure (KIP100F, KB1, EB3, BP, X33, KTO46, KT37, KIIP150 or TZT)" manufactured by Sartomer Company, Inc. In addition, a combination of two or more of them can also be cited as a preferred example.

[0354] In the light absorption filter of the present invention, the content of the radical generator (preferably a photoradical generator) is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 20 parts by mass, based on 100 parts by mass of the resin constituting the light absorption filter of the present invention.

[0355] From the viewpoint of further improving the quenching rate, the amount of the free radical generator (preferably a photo free radical generator) in the light absorption filter of the present invention is preferably 0.1 to 20 moles per 1 mole of the dye having a main absorption wavelength band at a wavelength of 400 to 700 nm. The lower limit is more preferably 0.25 moles or more, and more preferably 0.50 moles or more. The upper limit is more preferably 17.5 moles or less, and more preferably 15 moles or less.

[0356] The light absorption filter of the present invention may contain one radical generator (preferably a photoradical generator) or two or more radical generators.

[0357] <Resin>

[0358] There are no particular limitations on the resin contained in the light absorption filter of the present invention (hereinafter also referred to as "matrix resin"), as long as it can disperse (preferably dissolve) the above-mentioned dye and free radical generator (preferably photo radical generator), can exhibit the decolorization effect of the dye based on the free radical generator (preferably photo radical generator), and has the desired light transmittance (in the visible region with a wavelength of 400 to 800 nm, the transmittance is preferably 80% or more).

[0359] When the dye having a main absorption wavelength band at a wavelength of 400 to 700 nm is a squaryl cyanine dye represented by the general formula (1) or a benzylidene dye or a cinnamylene dye represented by the general formula (V), the matrix resin is preferably a low-polarity matrix resin in which the squaryl cyanine dye or the benzylidene dye or the cinnamylene dye can show sharper absorption. By showing sharper absorption, the light absorption filter of the present invention can suppress the reduction of the transmittance of the displayed light to a minimum and prevent the reflection of external light. Here, low polarity means that the fd value defined by the following relationship I is preferably 0.50 or more.

[0360] Relationship I: fd = δd / (δd+δp+δh)

[0361] In relational formula 1, δd, δp, and δh represent the term corresponding to the London dispersion force, the term corresponding to the dipole-dipole force, and the term corresponding to the hydrogen bonding force, respectively, relative to the solubility parameter δt calculated by the Hoy method. The specific calculation method will be described later. That is, fd represents the ratio of δd to the sum of δd, δp, and δh.

[0362] By setting the fd value to 0.50 or more, a clearer absorption waveform can be easily obtained.

[0363] Furthermore, when the light absorption filter of the present invention includes two or more types of matrix resins, the fd value is calculated as follows.

[0364] fd=∑(w i ·fd i )

[0365] Here, w i represents the mass fraction of the i-th matrix resin, fd i represents the fd value of the ith base resin.

[0366] -Term corresponding to London dispersion forceδd-

[0367] The term δd corresponding to the London dispersion force refers to the term δd in the literature “Properties of Polymers3 rd The δd was calculated based on the description in the above column of "2) Method of Hoy (1985, 1989)" on pages 214 to 220 of "ELSEVIER, (1990)" and the Amorphous Polymers described in the above column.

[0368] -The term corresponding to the dipole-dipole force δp-

[0369] The term δp corresponding to the dipole-dipole force is referred to in the literature "Properties of Polymers3 rd The δp was calculated based on the description in the above column of "2) Method of Hoy (1985, 1989)" on pages 214 to 220 of "ELSEVIER, (1990)" and the Amorphous Polymers described in the above column.

[0370] -Term corresponding to hydrogen bonding force δh-

[0371] The term δh corresponding to the hydrogen bond force refers to the reference "Properties of Polymers 3 rd The δh was calculated based on the description in the above column of "2) Method of Hoy (1985, 1989)" on pages 214 to 220 of "ELSEVIER, (1990)" and the Amorphous Polymers described in the above column.

[0372] Furthermore, if the matrix resin is a resin showing constant hydrophobicity, the water content of the light absorption filter of the present invention can be set to a low water content of, for example, 0.5% or less, which is preferable from the viewpoint of improving the light resistance of the light absorption filter of the present invention.

[0373] In addition, the resin may contain any conventional components in addition to the polymer. However, the fd of the matrix resin described above is a calculated value for the polymer constituting the matrix resin.

[0374] Preferred examples of the matrix resin include polystyrene resin and cyclic polyolefin resin, and polystyrene resin is more preferred. Generally, the fd value of polystyrene resin is 0.45 to 0.60, and the fd value of cyclic polystyrene resin is 0.45 to 0.70. As described above, the fd value is preferably 0.50 or more.

[0375] Furthermore, for example, in addition to these preferred resins, it is also preferable to use a resin component that imparts functionality to the light absorption filter of the present invention, such as a stretchable resin component and a peelable control resin component, which will be described later. That is, in the present invention, the matrix resin is used to include a stretchable resin component and a peelable control resin component in addition to the above-mentioned resins.

[0376] From the viewpoint of clarifying the absorption waveform of the dye, the matrix resin preferably contains a polystyrene resin.

[0377] (Polystyrene resin)

[0378] The polystyrene contained in the above-mentioned polystyrene resin refers to a polymer containing a styrene component. The polystyrene preferably contains a styrene component of 50% by mass or more. The light absorption filter of the present invention may contain one type of polystyrene or two or more types. Here, the styrene component refers to a structural unit derived from a monomer having a styrene skeleton in its structure.

[0379] From the viewpoint of controlling the photoelastic coefficient and hygroscopicity to values ​​within the preferred range for a light absorption filter, the polystyrene preferably contains 70% by mass or more of a styrene component, and further preferably contains 85% by mass or more. Furthermore, the polystyrene is also preferably composed only of a styrene component.

[0380] As polystyrene composed only of styrene components, homopolymers of styrene compounds and copolymers of two or more styrene compounds can be cited. Here, the styrene compound refers to a compound having a styrene skeleton in its structure, and in addition to styrene, it also includes a compound in which a substituent is introduced within the range in which the ethylenically unsaturated bond of styrene can function as a reactive (polymerizable) group.

[0381] Specific examples of styrene compounds include styrene; alkyl styrenes such as α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 3,5-dimethylstyrene, 2,4-dimethylstyrene, o-ethylstyrene, p-ethylstyrene, and tert-butylstyrene; and substituted styrenes in which a hydroxyl group, an alkoxy group, a carboxyl group, a halogen atom, and the like are introduced into the benzene nucleus of styrenes such as hydroxystyrene, tert-butoxystyrene, vinylbenzoic acid, o-chlorostyrene, and p-chlorostyrene. Among them, the polystyrene is preferably a homopolymer of styrene (i.e., polystyrene) from the viewpoint of easy availability and material price.

[0382] Furthermore, there is no particular limitation on the structural components other than the styrene component that may be contained in the above-mentioned polystyrene. That is, the polystyrene may be a styrene-diene copolymer or a styrene-polymerizable unsaturated carboxylic acid ester copolymer, etc. Furthermore, a mixture of polystyrene and a synthetic rubber (for example, polybutadiene and polyisoprene) can also be used. Furthermore, a high-impact polystyrene (HIPS) obtained by graft polymerization of styrene and a synthetic rubber is also preferred. Furthermore, it is also preferred to disperse a rubber-like elastomer in a continuous phase of a polymer containing a styrene component (for example, a copolymer of a styrene component and a (meth)acrylate component), and to obtain a polystyrene by graft polymerization of the above-mentioned copolymer and the above-mentioned rubber-like elastomer (called a grafted high-impact polystyrene "grafted HIPS"). Furthermore, the so-called styrene-based elastomer can also be preferably used.

[0383] Furthermore, the polystyrene may be hydrogenated (may be hydrogenated polystyrene). The hydrogenated polystyrene is not particularly limited, but preferably includes hydrogenated styrene-butadiene-styrene block copolymer (SEBS) obtained by adding hydrogen to SBS (styrene-butadiene-styrene block copolymer) and hydrogenated styrene-isoprene-styrene block copolymer (SEPS) obtained by adding hydrogen to SIS (styrene-isoprene-styrene block copolymer). The hydrogenated polystyrene may be used alone or in combination of two or more.

[0384] The polystyrene may be a modified polystyrene. The modified polystyrene is not particularly limited, but may be a polystyrene into which a reactive group such as a polar group is introduced, and specifically, preferably, an acid-modified polystyrene such as a maleic acid-modified polystyrene and an epoxy-modified polystyrene are mentioned.

[0385] As the polystyrene, a plurality of types of polystyrenes having different compositions, molecular weights, etc. may be used in combination.

[0386] The polystyrene resin can be obtained by anionic, bulk, suspension, emulsification or solution polymerization. In addition, in polystyrene, at least a portion of the unsaturated double bonds of the benzene ring of the conjugated diene and styrene monomers can be hydrogenated. The hydrogenation rate can be measured by a nuclear magnetic resonance device (NMR).

[0387] As the polystyrene resin, commercially available products can be used, for example, "CLEAREN 530L" and "CLEAREN 730L" manufactured by Denka Company Limited, "TUFPRENE 126S" and "ASAPRENE 411" manufactured by Asahi Kasei Corporation, "Clayton D1102A" and "Clayton D1116A" manufactured by Kraton Corporation, "Styrolux S" and "Styrolux T" manufactured by Styrolution, "ASAFLEX 840" and "ASAFLEX 860" (these are SBS) manufactured by Asahi Kasei Chemicals Corporation, "679", "HF77" and "SGP-10" manufactured by PS Japan Corporation, "DICSTYRENEX C-515" and "DICSTYRENEX C-535" (these are GPPS) manufactured by DIC Corporation, and "PS Japan "475D", "H0103", "HT478" manufactured by DICC Corporation, "DICSTYRENE GH-8300-5" manufactured by DIC Corporation (the above are HIPS), etc. Examples of hydrogenated polystyrene resins include "TUFTEC H series" manufactured by Asahi Kasei Corporation (manufactured by (former) Asahi Kasei Chemicals Corporation), "Clayton G series" manufactured by Shell Japan Ltd. (the above are SEBS), "DYNARON" (hydrogenated styrene-butadiene random copolymer) manufactured by JSR Corporation, and "SEPTON" (SEPS) manufactured by KURARAY CO., LTD. In addition, examples of modified polystyrene resins include "TUFTECM series" manufactured by Asahi Kasei Corporation (formerly manufactured by Asahi Kasei Chemicals Corporation), "EPOFRIEND" manufactured by Daicel Corporation, "Polar Group Modified DYNARON" manufactured by JSR Corporation, and "RESEDA" manufactured by TOAGOSEI CO., LTD.

[0388] The light absorption filter of the present invention preferably contains polyphenylene ether resin in addition to the above-mentioned polystyrene resin. By containing both polystyrene resin and polyphenylene ether resin, the toughness of the light absorption filter is improved, and the occurrence of defects such as cracks can be suppressed even in severe environments such as high temperature and high humidity.

[0389] As the polyphenylene ether resin, ZYLON 201A, ZYLON 202A, ZYLON S203A, etc. manufactured by Asahi Kasei Corporation can be preferably used. In addition, a resin obtained by premixing a polystyrene resin and a polyphenylene ether resin can be used. As a mixed resin of a polystyrene resin and a polyphenylene ether resin, for example, ZYLON 1002H, ZYLON 1000H, ZYLON 600H, ZYLON 500H, ZYLON 400H, ZYLON 300H, ZYLON 200H, etc. manufactured by Asahi Kasei Corporation can be preferably used.

[0390] In the light absorption filter of the present invention, when polystyrene resin and polyphenylene ether resin are contained, the mass ratio of the two is preferably 99 / 1 to 50 / 50, more preferably 98 / 2 to 60 / 40, and further preferably 95 / 5 to 70 / 30 in terms of polystyrene resin / polyphenylene ether resin. By setting the mixing ratio of the polyphenylene ether resin within the above preferred range, the light absorption filter of the present invention has sufficient toughness, and when solution film formation is performed, the solvent can be appropriately volatilized.

[0391] (Cyclic polyolefin resin)

[0392] The cyclic olefin compound forming the cyclic polyolefin contained in the cyclic polyolefin resin is not particularly limited as long as it is a compound having a ring structure containing a carbon-carbon double bond, and examples thereof include norbornene compounds, monocyclic cyclic olefin compounds other than norbornene compounds, cyclic conjugated diene compounds, and vinyl alicyclic hydrocarbon compounds.

[0393] Examples of the cyclic polyolefin include (1) polymers containing structural units derived from norbornene compounds, (2) polymers containing structural units derived from monocyclic cyclic olefin compounds other than norbornene compounds, (3) polymers containing structural units derived from cyclic conjugated diene compounds, (4) polymers containing structural units derived from vinyl alicyclic hydrocarbon compounds, and hydrogenated products of polymers containing structural units derived from each of the compounds (1) to (4).

[0394] In the present invention, the polymer including a structural unit derived from a norbornene compound and the polymer including a structural unit derived from a monocyclic cyclic olefin compound include ring-opening polymers of the respective compounds.

[0395] The cyclic polyolefin is not particularly limited, but is preferably a polymer having a structural unit derived from a norbornene compound represented by the following general formula (A-II) or (A-III). The polymer having a structural unit represented by the following general formula (A-II) is an addition polymer of a norbornene compound, and the polymer having a structural unit represented by the following general formula (A-III) is a ring-opening polymer of a norbornene compound.

[0396] [Chemical formula 54]

[0397]

[0398] In the general formulae (A-II) and (A-III), m is an integer of 0 to 4, and preferably 0 or 1.

[0399] In the general formulas (A-II) and (A-III), R 3 ~R 6 Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.

[0400] The hydrocarbon group in general formulae (AI) to (A-III) is not particularly limited as long as it is a group containing carbon atoms and hydrogen atoms, and examples thereof include alkyl groups, alkenyl groups, alkynyl groups, and aryl groups (aromatic hydrocarbon groups). Among them, alkyl groups and aryl groups are preferred.

[0401] In the general formulas (A-II) and (A-III), X 2 and X 3 , Y 2 and Y 3 each independently represents a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms substituted with a halogen atom, -(CH2) n COOR 11 、-(CH2) n OCOR 12 、-(CH2) n NCO, -(CH2) n NO2, -(CH2) n CN, -(CH2) n CONR 13 R 14 、-(CH2) n NR 12 R 14 、-(CH2) n OZ or -(CH2) n W or X 2 With Y 2 or X 3 With Y 3Bonded to each other, (-CO)2O or (-CO)2NR 15 .

[0402] Here, R 11 ~R 15 Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, Z represents a hydrocarbon group or a hydrocarbon group substituted with a halogen, and W represents Si(R 16 ) p D (3-p) (R 16 represents a hydrocarbon group having 1 to 10 carbon atoms, D represents a halogen atom, -OCOR 17 OR 17 (R 17 is a hydrocarbon group having 1 to 10 carbon atoms). p is an integer of 0 to 3). n is an integer of 0 to 10, preferably 0 to 8, more preferably 0 to 6.

[0403] In the general formulae (A-II) and (A-III), R 3 ~R 6 A hydrogen atom or -CH 3 is preferred, and a hydrogen atom is more preferred from the viewpoint of moisture permeability.

[0404] X 2 and X 3 A hydrogen atom, -CH3 or -C2H5 is preferred, respectively. From the viewpoint of moisture permeability, a hydrogen atom is more preferred.

[0405] Y 2 and Y 3 Preferably, a hydrogen atom, a halogen atom (especially a chlorine atom) or -(CH2) n COOR 11 (especially, -COOCH3), and a hydrogen atom is more preferable from the viewpoint of moisture permeability.

[0406] Other groups may be appropriately selected.

[0407] The polymer having the structural unit represented by the general formula (A-II) or (A-III) may further include at least one structural unit represented by the following general formula (AI).

[0408] [Chemical formula 55]

[0409]

[0410] In the general formula (AI), R 1 and R 2 Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and X 1 and Y 1each independently represents a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms substituted with a halogen atom, -(CH2) n COOR 11 、-(CH2) n OCOR 12 、-(CH2) n NCO, -(CH2) n NO2, -(CH2) n CN, -(CH2) n CONR 13 R 14 、-(CH2) n NR 13 R 14 、-(CH2) n OZ, -(CH2) n W, or X 1 With Y 1 Bonded to each other, (-CO)2O or (-CO)2NR 15 .

[0411] Here, R 11 ~R 15 Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, Z represents a hydrocarbon group or a hydrocarbon group substituted with a halogen, and W represents Si(R 16 ) p D (3-p) (R 16 represents a hydrocarbon group having 1 to 10 carbon atoms, D represents a halogen atom, -OCOR 17 OR 17 (R 17 is a hydrocarbon group having 1 to 10 carbon atoms). p is an integer of 0 to 3). n is an integer of 0 to 10.

[0412] From the viewpoint of adhesion to the polarizer, the cyclic polyolefin having the structural unit represented by the general formula (A-II) or (A-III) preferably contains 90% by mass or less of the structural unit derived from the above-mentioned norbornene compound relative to the total mass of the cyclic polyolefin, more preferably 30 to 85% by mass, further preferably 50 to 79% by mass, and most preferably 60 to 75% by mass. Here, the ratio of the structural unit derived from the norbornene compound represents the average value in the cyclic polyolefin.

[0413] Addition (co)polymers of norbornene compounds are described in Japanese Unexamined Patent Publication No. 10-7732, Japanese Translation of National Publication No. 2002-504184, U.S. Patent Publication No. 2004 / 229157A1, and International Publication No. 2004 / 070463.

[0414] The polymer of the norbornene compound is obtained by subjecting norbornene compounds (for example, polycyclic unsaturated compounds of norbornene) to addition polymerization.

[0415] Furthermore, as the polymer of the norbornene compound, there can be mentioned copolymers obtained by addition polymerization of the norbornene compound and olefins such as ethylene, propylene and butylene, conjugated dienes such as butadiene and isoprene, non-conjugated dienes such as ethylidene norbornene, and olefinic unsaturated compounds such as acrylonitrile, acrylic acid, methacrylic acid, maleic anhydride, acrylic acid ester, methacrylic acid ester, maleimide, vinyl acetate and vinyl chloride, as required. Among them, copolymers of the norbornene compound and propylene are preferred.

[0416] Examples of such addition (co)polymers of norbornene compounds include APL8008T (Tg 70°C), APL6011T (Tg 105°C), APL6013T (Tg 125°C), APL6015T (Tg 145°C), APL6509T (Tg 80°C), and APL6011T (Tg 105°C), which are sold under the trade name of Apel by Mitsui Chemicals, INC. and have different glass transition temperatures (Tg). In addition, particles such as TOPAS8007, TOPAS6013, and TOPAS6015 are sold by Polyplastics Co., Ltd. In addition, Appear3000 is sold by Ferrania.

[0417] The polymer of the norbornene compound may be a commercially available product, for example, it is commercially available under the trade names of Arton G or Arton F from JSR Corporation, and it is commercially available under the trade names of Zeonor ZF14, ZF16, Zeonex 250, or Zeonex 280 from Zeon Corporation.

[0418] The hydrogenated polymer of the norbornene compound can be synthesized by subjecting the norbornene compound to addition polymerization or metathesis ring-opening polymerization and then hydrogenating. The synthesis method is described in, for example, Japanese Patent Laid-Open No. 1-240517, Japanese Patent Laid-Open No. 7-196736, Japanese Patent Laid-Open No. 60-26024, Japanese Patent Laid-Open No. 62-19801, Japanese Patent Laid-Open No. 2003-159767, and Japanese Patent Laid-Open No. 2004-309979.

[0419] The molecular weight of the cyclic polyolefin can be appropriately selected according to the purpose of use, but the mass average molecular weight of polyisoprene or polystyrene converted by cyclohexane solution (toluene solution when the polymer is not dissolved) measured by gel permeation chromatography is usually in the range of 5000 to 500000, preferably 8000 to 200000, and more preferably 10000 to 100000. The polymer having a molecular weight in the above range can achieve both mechanical strength and molding processability of the molded body at a high level and in a balanced manner.

[0420] The light absorption filter of the present invention preferably contains 5 mass % or more of the above-mentioned matrix resin, more preferably 20 mass % or more, further preferably 50 mass % or more, particularly preferably 70 mass % or more, among which, preferably 80 mass % or more, most preferably 90 mass % or more.

[0421] The content of the matrix resin in the light absorption filter of the present invention is usually 99.90% by mass or less, and preferably 99.85% by mass or less.

[0422] The light absorption filter of the present invention may contain two or more cyclic polystyrenes, and polymers having different component ratios and molecular weights may be used in combination. In this case, the total content of each polymer is within the above range.

[0423] (Elongation resin component)

[0424] The light absorption filter of the present invention can appropriately select a component showing elongation (also referred to as an elongation resin component) as a resin component. Specifically, acrylonitrile-butadiene-styrene resin (ABS resin), styrene-butadiene resin (SB resin), isoprene resin, butadiene resin, polyether-urethane resin and silicone resin can be cited. In addition, these resins can be further appropriately hydrogenated.

[0425] As the elongation resin component, ABS resin or SB resin is preferably used, and SB resin is more preferably used.

[0426] As the SB resin, for example, commercially available resins can be used. Examples of such commercial products include TR2000, TR2003, and TR2250 (these are trade names, manufactured by JSR Corporation), CLEAREN 210M, 220M, and 730V (these are trade names, manufactured by Denka Company Limited), ASAFLEX 800S, 805, 810, 825, 830, and 840 (these are trade names, manufactured by Asahi Kasei Corporation), and Eporex SB2400, SB2610, and SB2710 (these are trade names, manufactured by Sumitomo Chemical Co., Ltd.).

[0427] The light absorption filter of the present invention preferably contains 15 to 95% by mass of the elongation resin component in the matrix resin, more preferably 20 to 50% by mass, and even more preferably 25 to 45% by mass.

[0428] When a sample having a thickness of 30 μm and a width of 10 mm is prepared using the elongation resin component alone as the above-mentioned elongation resin component, and the elongation at break is measured at 25° C. according to JIS 7127, the elongation at break is preferably 10% or more, more preferably 20% or more.

[0429] (Releasability Control Resin Component)

[0430] Regarding the light absorption filter of the present invention, when it is manufactured by a method including a step of peeling the light absorption filter of the present invention from a peeling film in the manufacturing method of the light absorption filter of the present invention described later, it is preferable that a component that controls peelability (peelability controlling resin component) is included as a resin component. By controlling the peelability of the light absorption filter of the present invention from the peeling film, it is possible to prevent peeling marks from being left on the light absorption filter of the present invention after peeling, and it is possible to cope with various processing speeds in the peeling process. As a result, it is possible to obtain a preferred effect in terms of improving the quality and productivity of the light absorption filter of the present invention.

[0431] The above-mentioned peelability control resin component is not particularly limited and can be appropriately selected according to the type of peeling film. As described later, when a polyester polymer film is used as the peeling film, the peelability control resin component is preferably, for example, a polyester resin (also referred to as a polyester additive). Furthermore, when a cellulose acylate film is used as the peeling film, the peelability control resin component is preferably, for example, a hydrogenated polystyrene resin (also referred to as a hydrogenated polystyrene additive).

[0432] The polyester additive can be obtained by a conventional method such as a dehydration condensation reaction of a polybasic acid and a polyol, and a dehydration condensation reaction of adding a dibasic acid anhydride to a polyol. Preferably, the polyester additive is a polycondensation ester formed from a dibasic acid and a diol.

[0433] The mass average molecular weight (Mw) of the polyester-based additive is preferably 500 to 50,000, more preferably 750 to 40,000, and even more preferably 2,000 to 30,000.

[0434] When the mass average molecular weight of the polyester additive is equal to or higher than the preferred lower limit, it is preferred from the viewpoint of brittleness and moist heat resistance, and when it is equal to or lower than the preferred upper limit, it is preferred from the viewpoint of compatibility with the resin.

[0435] The mass average molecular weight of the polyester additive is the value of the mass average molecular weight (Mw) measured under the following conditions in terms of standard polystyrene. The molecular weight distribution (Mw / Mn) can also be measured under the same conditions. In addition, Mn is the number average molecular weight in terms of standard polystyrene.

[0436] GPC: Gel permeation chromatography apparatus (HLC-8220GPC manufactured by Tosoh Corporation,

[0437] Column: HXL-H, TSK gel G7000HXL, 2 TSKgel GMHXL, TSK gel G2000HXL,

[0438] Eluent: tetrahydrofuran,

[0439] Flow rate: 1mL / min,

[0440] Sample concentration: 0.7-0.8% by mass,

[0441] Sample injection volume: 70μL,

[0442] Measuring temperature: 40℃,

[0443] Detector: Differential refractometer (RI) (40°C),

[0444] Standard material; TSK standard polystyrene manufactured by Tosoh Corporation)

[0445] As the dibasic acid component constituting the polyester-based additive, preferably, dicarboxylic acid is used.

[0446] Examples of the dicarboxylic acid include aliphatic dicarboxylic acids and aromatic dicarboxylic acids, and aromatic dicarboxylic acids or a mixture of aromatic dicarboxylic acids and aliphatic dicarboxylic acids can be preferably used.

[0447] Among the aromatic dicarboxylic acids, those having 8 to 20 carbon atoms are preferred, and those having 8 to 14 carbon atoms are more preferred. Specifically, at least one of phthalic acid, isophthalic acid, and terephthalic acid is preferably used.

[0448] Among aliphatic dicarboxylic acids, those having 3 to 8 carbon atoms are preferred, and those having 4 to 6 carbon atoms are more preferred. Specifically, at least one of succinic acid, maleic acid, adipic acid and glutaric acid is preferred, and at least one of succinic acid and adipic acid is more preferred.

[0449] Furthermore, examples of the diol component constituting the polyester-based additive include aliphatic diols and aromatic diols, and aliphatic diols are preferred.

[0450] Among aliphatic diols, aliphatic diols having 2 to 4 carbon atoms are preferred, and aliphatic diols having 2 to 3 carbon atoms are more preferred.

[0451] Examples of the aliphatic diol include ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butylene glycol, and 1,4-butylene glycol. These can be used alone or in combination of two or more.

[0452] The polyester-based additive is particularly preferably a compound obtained by condensing at least one of phthalic acid, isophthalic acid, and terephthalic acid with an aliphatic diol.

[0453] The terminal of the polyester additive can be sealed by reacting with a monocarboxylic acid. The monocarboxylic acid used for sealing is preferably an aliphatic monocarboxylic acid, and preferably acetic acid, propionic acid, butyric acid, benzoic acid and derivatives thereof are mentioned, more preferably acetic acid or propionic acid, and further preferably acetic acid.

[0454] Examples of commercially available polyester additives include ester resins manufactured by The Nippon Synthetic Chemical Industry Co., Ltd. (e.g., LP050, TP290, LP035, LP033, TP217, TP220), and ester resins BYRON manufactured by TOYOBO CO., LTD. (e.g., BYRON245, BYRONGK890, BYRON103, BYRON200, BYRON550.GK880).

[0455] The mass average molecular weight (Mw) of the hydrogenated polystyrene-based additive is preferably 500 to 50,000, more preferably 750 to 40,000, and even more preferably 2,000 to 30,000.

[0456] When the mass average molecular weight of the hydrogenated polystyrene additive is equal to or higher than the preferred lower limit, it is preferred from the viewpoint of brittleness and moist heat resistance, and when it is equal to or lower than the preferred upper limit, it is preferred from the viewpoint of compatibility with the resin.

[0457] The mass average molecular weight of the hydrogenated polystyrene additive is the value of the mass average molecular weight (Mw) measured under the following conditions in terms of standard polystyrene. The molecular weight distribution (Mw / Mn) can also be measured under the same conditions. In addition, Mn is the number average molecular weight in terms of standard polystyrene.

[0458] Examples of commercially available hydrogenated polystyrene additives include "TUFTEC H series" manufactured by Asahi Kasei Corporation (formerly manufactured by Asahi Kasei Chemicals Corporation), "Clayton G series" manufactured by Shel1 Japan Ltd. (the above are SEBS), "DYNARON" (hydrogenated styrene-butadiene random copolymer) manufactured by JSR Corporation, and "SEPTON" (SEPS) manufactured by KURARAY CO., LTD.

[0459] The content of the peelability control resin component in the light absorption filter of the present invention is preferably 0.05% by mass or more, more preferably 0.1% by mass or more in the base resin. In addition, the upper limit is preferably 25% by mass or less, more preferably 20% by mass or less, and further preferably 15% by mass or less. From the viewpoint of obtaining appropriate adhesion, the above preferred range is preferred.

[0460] <Other ingredients>

[0461] The absorption filter of the present invention may contain a matting agent, a leveling agent (surfactant), and the like in addition to the above-mentioned dye, the above-mentioned compound that generates radicals by ultraviolet irradiation, and the above-mentioned base resin.

[0462] (Matting agent)

[0463] In the range that does not damage the effect of the present invention, microparticles can be added to the surface of the light absorption filter of the present invention to impart slidability and prevent adhesion. As the microparticles, preferably silicon dioxide (silicon dioxide, SiO2) whose surface is coated with hydrophobic groups and adopts the mode of secondary particles is used. In addition, in the microparticles, microparticles such as titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, talcum, clay, calcined kaolin, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, magnesium silicate and calcium phosphate can be used together with or instead of silicon dioxide. As commercially available microparticles, R972 and NX90S (both manufactured by NIPPONAEROSIL CO., LTD., trade names) etc. can be cited.

[0464] The fine particles function as so-called matting agents. By adding the fine particles, minute irregularities are formed on the surface of the light absorption filter of the present invention. Even if the light absorption filters of the present invention overlap with each other or with other films due to the irregularities, they will not adhere to each other, thereby ensuring slip properties.

[0465] In the case where the light absorption filter of the present invention contains a matting agent as fine particles, if there are 10 4 Pieces / mm 2 The above-mentioned protrusions with a height of 30 nm or more have a particularly large effect of improving the sliding property and the adhesion property.

[0466] From the viewpoint of improving the adhesion and the slipping property, the matting agent fine particles are preferably applied to the surface layer. As a method of applying the fine particles to the surface layer, there can be mentioned a method based on multilayer casting and coating.

[0467] The content of the matting agent in the light absorption filter of the present invention can be appropriately adjusted depending on the purpose.

[0468] However, when the light absorption filter of the present invention is provided with a gas barrier layer described later, it is preferred that the matting agent fine particles are provided on the surface of the light absorption filter that is in contact with the gas barrier layer within a range that does not impair the effects of the present invention.

[0469] (Leveling agent)

[0470] A leveling agent (surfactant) can be appropriately mixed in the light absorption filter of the present invention. As the leveling agent, commonly used compounds can be used, and fluorinated surfactants are particularly preferred. Specifically, for example, the compounds described in paragraphs

[0028] to

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

[0471] The content of the leveling agent in the light absorption filter of the present invention can be appropriately adjusted depending on the purpose.

[0472] The light absorption filter of the present invention may contain, in addition to the above-mentioned components, a low molecular plasticizer, an oligomer plasticizer, a retardation regulator, a degradation inhibitor, a peeling accelerator, an infrared absorber, an antioxidant, a filler, a compatibilizer, and the like.

[0473] Furthermore, the light absorption filter of the present invention may contain a reaction accelerator or a reaction retardant as described in paragraphs

[0020] and

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

[0474] <Method for Manufacturing Light Absorption Filter>

[0475] The light absorption filter of the present invention can be produced by a conventional method by a solution film forming method, a melt extrusion method, or a method (coating method) of forming a coating on a substrate film (release film) by any method, and can also be appropriately combined with stretching. The light absorption filter of the present invention is preferably produced by a coating method.

[0476] (Solution film method)

[0477] In the solution film forming method, a solution is prepared by dissolving the material constituting the light absorption filter of the present invention in an organic solvent or water, and after appropriately performing a concentration process and a filtration process, the solution is uniformly cast onto a support. Next, the semi-dried film is peeled off from the support, and the solvent is dried in a drying zone while the two ends of the sheet are appropriately held by a clamp or the like. In addition, stretching can also be performed separately during the drying of the film or after the drying is completed.

[0478] (Melt extrusion method)

[0479] In the melt extrusion method, the material constituting the light absorption filter of the present invention (hereinafter also referred to as "the material of the light absorption filter") is melted by heat, and after appropriately performing a filtering process, the material is uniformly cast onto a support. Next, the film solidified by cooling is peeled off so that it can be stretched appropriately. In the case where the main material of the light absorption filter of the present invention is a thermoplastic polymer resin, the main material of the stripping film is also selected to be a thermoplastic polymer resin, so that the polymer resin set to a molten state can be formed into a film by a known co-extrusion method. At this time, the adhesion between the light absorption filter of the present invention and the stripping film can be controlled by adjusting the types of polymers of the light absorption filter and the stripping film of the present invention and the additives mixed in each layer, or by adjusting the stretching temperature, stretching speed, stretching ratio, etc. of the co-extruded film.

[0480] As a coextrusion method, for example, a coextrusion T-die method, a coextrusion inflation method, a coextrusion lamination method, etc. can be cited. Among them, the coextrusion T-die method is preferred. The coextrusion T-die method has a feed block method and a multi-branch method. Among them, from the viewpoint of being able to reduce thickness deviation, the multi-branch method is particularly preferred.

[0481] In the case of the co-extrusion T-die method, the melting temperature of the resin in the extruder having the T-die is preferably set to a temperature higher than the glass transition temperature (Tg) of each resin by 80° C. or more, more preferably higher by 100° C. or more, and preferably higher by 180° C. or less, more preferably higher by 150° C. or less. By setting the melting temperature of the resin in the extruder to a value higher than the lower limit of the above preferred range, the fluidity of the resin can be sufficiently improved, and by setting it to a value lower than the upper limit of the above preferred range, the degradation of the resin can be prevented.

[0482] Usually, the sheet-like molten resin extruded from the opening of the die is brought into close contact with the cooling drum. The method for bringing the molten resin into close contact with the cooling drum is not particularly limited, and examples thereof include an air knife method, a vacuum box method, and an electrostatic bonding method.

[0483] The number of cooling rollers is not particularly limited, but is usually 2 or more. Also, as the configuration method of the cooling rollers, for example, a linear type, a Z type, an L type, etc. can be cited, but there is no particular limitation. Also, the method by which the molten resin extruded from the opening of the mold passes through the cooling rollers is also not particularly limited.

[0484] The close contact state of the extruded sheet resin to the cooling roller changes according to the temperature of the cooling roller. If the temperature of the cooling roller is increased, the close contact becomes better, but if the temperature is increased too much, the sheet resin may not be peeled off from the cooling roller and may be entangled on the roller. Therefore, regarding the temperature of the cooling roller, if the glass transition temperature of the resin of the layer in contact with the roller in the resin extruded from the die is set to Tg, it is preferably set to (Tg+30)°C or less, and more preferably set to (Tg-5)°C to (Tg-45)°C. By setting the cooling roller temperature within the above preferred range, it is possible to prevent undesirable conditions such as slippage and scratches.

[0485] Here, it is preferred to reduce the content of residual solvent in the film before stretching. As methods for achieving this purpose, for example, there are: (1) reducing the residual solvent in the resin that becomes the raw material; (2) pre-drying the resin before forming the film before stretching; and other methods. Pre-drying is performed, for example, by setting the resin in the form of particles or the like and using a hot air dryer or the like. The drying temperature is preferably above 100°C, and the drying time is preferably above 2 hours. By pre-drying, the residual solvent in the film before stretching can be reduced, and the extruded sheet-like resin can be prevented from bubbling.

[0486] (Coating method)

[0487] In the coating method, a solution of the material of the light absorption filter is coated on a release film to form a coating. In order to control the adhesion between the release film and the coating, a release agent or the like may be appropriately applied in advance on the surface of the release film. The coating can be used by peeling off the release film after being laminated with other components via an adhesive layer in a later process. As for the adhesive constituting the adhesive layer, any adhesive can be appropriately used. In addition, the release film can be appropriately stretched together with the release film in a state where the solution of the material of the light absorption filter is coated on the release film or in a state where the coating is laminated.

[0488] The solvent used in the solution of the light absorption filter material can be appropriately selected from the viewpoints of being able to dissolve or disperse the light absorption filter material; being easy to form a uniform surface in the coating process and the drying process; being able to ensure liquid storage properties; and having an appropriate saturated vapor pressure.

[0489] - Addition of dye (pigment) and free radical generator (preferably photo radical generator) -

[0490] There is no particular limitation on the timing of adding the dye and the free radical generator (preferably a light free radical generator) to the light absorption filter material as long as they are added at the time of film formation. For example, they may be added at the time of synthesizing the matrix resin, or may be mixed with the light absorption filter material when preparing the coating liquid of the light absorption filter material.

[0491] -Release film-

[0492] The film thickness of the release film used to form the light absorption filter of the present invention by a coating method or the like is preferably 5 to 100 μm, more preferably 10 to 75 μm, and further preferably 15 to 55 μm. If the film thickness is above the above preferred lower limit, it is easy to ensure sufficient mechanical strength and it is not easy to cause problems such as curling, wrinkling, and buckling. In addition, if the film thickness is below the above preferred upper limit, when the multilayer film of the light absorption filter and the release film of the present invention is stored in the form of a long roll, for example, it is easy to adjust the surface pressure applied to the multilayer film within an appropriate range, and it is difficult to cause adhesion problems.

[0493] The surface energy of the release film is not particularly limited, but the bonding strength between the light absorption filter of the present invention and the release film can be adjusted by adjusting the relationship between the surface energy of the material of the light absorption filter of the present invention and the coating solution and the surface energy of the surface of the release film on the side where the light absorption filter of the present invention is formed. If the surface energy difference is reduced, the bonding strength tends to increase, and if the surface energy difference is increased, the bonding strength tends to decrease. The surface energy difference can be appropriately set.

[0494] The surface energy of the release film can be calculated from the contact angle values ​​of water and diiodomethane using the Owens method. The contact angle can be measured using, for example, DM901 (Kyowa Interface Science C o ., Ltd., contact angle measuring instrument).

[0495] The surface energy of the side of the peeling film on which the light absorption filter of the present invention is formed is preferably 41.0 to 48.0 mN / m, and more preferably 42.0 to 48.0 mN / m. If the surface energy is above the preferred lower limit, the uniformity of the thickness of the light absorption filter of the present invention can be improved, and if it is below the preferred upper limit, the peeling force between the light absorption filter of the present invention and the peeling film can be easily controlled within an appropriate range.

[0496] Furthermore, the surface roughness of the release film is not particularly limited, but can be adjusted based on the surface energy, hardness, and correlation between the surface roughness of the light absorption filter of the present invention and the surface energy and hardness of the surface of the release film on the side opposite to the side on which the light absorption filter of the present invention is formed, for example, to prevent adhesion failure when the multilayer film of the light absorption filter of the present invention and the release film is stored in a long roll form. If the surface roughness is increased, there is a tendency to suppress adhesion failure, and if the surface roughness is reduced, there is a tendency to reduce the surface roughness of the light absorption filter of the present invention and reduce the haze of the light absorption filter of the present invention, and it can be appropriately set.

[0497] As such a release film, any material and film can be appropriately used. As specific materials, polyester polymers (including polyethylene terephthalate films), olefin polymers, cycloolefin polymers, (meth) acrylic polymers, cellulose polymers, polyamide polymers, etc. can be cited. In addition, in order to adjust the surface properties of the release film, the surface treatment can be appropriately performed. In order to reduce the surface energy, for example, corona treatment, normal temperature plasma treatment, saponification treatment, etc. can be performed, and in order to increase the surface energy, silicone treatment, fluorine treatment, olefin treatment, etc. can be performed.

[0498] -Peeling force of the light absorbing filter and peeling film of the present invention-

[0499] When the light absorption filter of the present invention is formed by a coating method, the peeling force between the light absorption filter of the present invention and the peeling film can be controlled by adjusting the material of the light absorption filter of the present invention, the material of the peeling film, the internal deformation of the light absorption filter of the present invention, etc. The peeling force can be measured, for example, in a test of peeling the peeling film in a 90° direction. The peeling force when measured at a speed of 300 mm / min is preferably 0.001 to 5 N / 25 mm, more preferably 0.01 to 3 N / 25 mm, and further preferably 0.05 to 1 N / 25 mm. If it is above the above preferred lower limit, peeling of the peeling film outside the peeling process can be prevented, and if it is below the above preferred upper limit, peeling defects in the peeling process (for example, zipping or cracking of the light absorption filter of the present invention) can be prevented.

[0500] <Film Thickness of the Light Absorption Filter of the Present Invention>

[0501] The film thickness of the light absorption filter of the present invention is not particularly limited, but is preferably 1 to 18 μm, more preferably 1 to 12 μm, and further preferably 2 to 8 μm. If it is below the above preferred upper limit, by adding a high concentration of dye to the film, the decrease in polarization caused by the fluorescence emitted by the dye (pigment) can be suppressed. In addition, the effect of the quencher is also easy to show. On the other hand, if it is above the above preferred lower limit, it is easy to maintain the uniformity of the absorbance within the surface.

[0502] In the present invention, the film thickness of 1 to 18 μm means that the thickness of the light absorption filter of the present invention is within the range of 1 to 18 μm regardless of where it is measured. This also applies to film thicknesses of 1 to 12 μm and 2 to 8 μm. The film thickness can be measured using an electronic micrometer manufactured by ANRITSU CORPORATION.

[0503] <Absorbance of the Light Absorption Filter of the Present Invention>

[0504] In the light absorption filter of the present invention, the absorbance at the maximum absorption wavelength showing the maximum absorbance at a wavelength of 400 to 700 nm (hereinafter also referred to as "Ab(λ max )”.) is preferably 0.3 or more, more preferably 0.5 or more, and further preferably 0.8 or more.

[0505] However, the absorbance of the light absorption filter of the present invention can be adjusted by the type, addition amount or film thickness of the dye.

[0506] In the light absorption filter of the present invention, the quenching rate by ultraviolet irradiation is preferably 20% or more, more preferably 25% or more, further preferably 30% or more, particularly preferably 35% or more, and particularly preferably 40% or more. The upper limit is not particularly limited and may be 100%.

[0507] In addition, the quenching rate was calculated using the Ab(λ max ) is calculated using the following formula.

[0508] Quenching rate (%) = 100-(Ab after ultraviolet irradiation (λ max ) / Ab(λ before UV irradiation max ))×100

[0509] In the ultraviolet irradiation test, an air-cooled metal halide lamp (manufactured by EYE GRAPHICS Co., Ltd.) with a power of 160 W / cm2 was used under atmospheric pressure (101.33 kPa) and the light absorption filter was irradiated with a dose of 600 mJ / cm2. 2 of ultraviolet rays.

[0510] The absorbance, ultraviolet irradiation test, and quenching rate can be measured and calculated by the methods described in the Examples.

[0511] Furthermore, it is preferred that the light absorption filter of the present invention hardly generates absorption (secondary absorption) from a new coloring structure accompanying decomposition of a pigment.

[0512] For example, the absorbance at a specific wavelength can be compared with the above Ab(λ max ) ratio to confirm whether there is absorption from the new coloring structure accompanying the decomposition of the pigment. Regarding the specific wavelength, the wavelength at which the pigment before ultraviolet irradiation shows almost no absorption and new absorption caused by the decomposition of the pigment is observed is selected.

[0513] As a specific example, as described in the examples below, the absorbance at a wavelength of 450 nm (hereinafter also referred to as "Ab(450)") can be compared with the above Ab(λ max ) ratio to confirm the presence or absence of absorption from a new coloring structure accompanying the decomposition of the pigment. That is, the smaller the value obtained by subtracting the ratio of the following (I) from the ratio of the following (II), the less absorption from a new coloring structure accompanying the decomposition of the pigment occurs, and the value is preferably less than 8.5%, more preferably less than 7.0%, further preferably less than 5.0%, particularly preferably less than 3%, and preferably less than 1%. The lower limit is not particularly limited, but from the perspective of making the evaluation of the secondary absorption associated with the decomposition of the pigment appropriate, it is actually more than -10%, preferably more than -6%.

[0514] (I) Ab(450) before UV irradiation / Ab(λ before UV irradiation max )×100%

[0515] (II) Ab(450) after UV irradiation / Ab(λ before UV irradiation max )Δ100%

[0516] In addition, as described in the examples described later, the absorbance at a wavelength of 650 nm (hereinafter, also referred to as "Ab (650)") can be used instead of the absorbance at a wavelength of 450 nm, and the evaluation is performed based on the value obtained by subtracting the ratio of the following (III) from the ratio of the following (IV). The preferred range of the value obtained by subtracting the ratio of the following (III) from the ratio of the following (IV) has the same meaning as the value obtained by subtracting the ratio of (I) from the ratio of the above formula (II).

[0517] (III) Ab(650) before UV irradiation / Ab(λ max )×100%

[0518] (IV) Ab (650) after UV irradiation / Ab (λ before UV irradiation max )×100%

[0519] Here, regarding the ultraviolet irradiation test, the description of the ultraviolet irradiation test in the above-mentioned quenching rate can be preferably applied.

[0520] The presence or absence of absorption from a new colored structure accompanying the decomposition of the pigment can be confirmed by measurement and calculation by the method described in the Examples.

[0521] The light absorption filter of the present invention can exhibit excellent quenching properties when both the quenching rate and the values ​​for confirming the presence or absence of absorption from a new coloring structure accompanying the decomposition of the pigment satisfy the preferred ranges.

[0522] The light absorbing part having a light absorbing effect in the optical filter of the present invention preferably satisfies the Ab(λ) related to the light absorbing filter of the present invention. max ) records.

[0523] The light absorption disappearance portion of the optical filter of the present invention shows λ before ultraviolet irradiation. max In the absorption corresponding to the absorption of , the absorbance is preferably 0.70 or less, and more preferably 0.60 or less. The lower limit is not particularly limited, but is in practice 0.001 or more.

[0524] <Water Content of the Light Absorption Filter of the Present Invention>

[0525] The water content of the light absorption filter of the present invention is preferably 0.5 mass % or less, and more preferably 0.3 mass % or less, at 25° C. and a relative humidity of 80%, regardless of the film thickness, from the viewpoint of durability.

[0526] In this specification, the moisture content of the light absorption filter of the present invention can be measured using a sample with a thicker film as needed. After the sample is conditioned for more than 24 hours, it is measured by the Karl Fischer method using a moisture meter and a sample drying device "CA-03" and "VA-05" (both manufactured by Mitsubishi Chemical Corporation), and the moisture content (g) is calculated by dividing the sample mass (g, including the moisture content).

[0527] <Glass transition temperature (Tg) of the light absorption filter of the present invention>

[0528] The glass transition temperature of the light absorption filter of the present invention is preferably 50°C or more and 140°C or less. It is more preferably 60°C or more and 130°C or less, further preferably 60°C or more and 120°C or less, and particularly preferably 65°C or more and 120°C or less. Among them, it is preferably 70°C or more and 120°C or less. If the glass transition temperature is above the preferred lower limit, the deterioration of the polarizer when used at high temperature can be suppressed, and if the glass transition temperature is below the preferred upper limit, the organic solvent used in the coating liquid can be suppressed from easily remaining in the light absorption filter of the present invention.

[0529] The glass transition temperature of the light absorption filter of the present invention can be measured by the following method. For details, reference can be made to the description of the Examples described below.

[0530] Using a differential scanning calorimeter (X-DSC7000 (manufactured by IT Keisoku Seigyo Co., Ltd.)), 20 mg of the light absorption filter of the present invention was placed in a measuring plate, and the temperature was raised from 30°C to 120°C at a rate of 10°C / min in a nitrogen stream and maintained for 15 minutes, and then cooled to 30°C at a rate of -20°C / min. Then, the temperature was raised from 30°C to 250°C again at a rate of 10°C / min, and the temperature at which the baseline began to deviate from the low temperature side was defined as the glass transition temperature Tg.

[0531] The glass transition temperature of the light absorption filter of the present invention can be adjusted by mixing two or more polymers having different glass transition temperatures or by changing the amount of low molecular weight compound added.

[0532] <Processing of the Light Absorption Filter of the Present Invention>

[0533] The light absorption filter of the present invention can be hydrophilized by any glow discharge treatment, corona discharge treatment or alkali saponification treatment, and corona discharge treatment is preferably used. It is also preferable to apply the method disclosed in Japanese Patent Application Laid-Open No. 6-94915 or Japanese Patent Application Laid-Open No. 6-118232.

[0534] Furthermore, the obtained film may be subjected to a heat treatment step, a superheated water vapor contact step, an organic solvent contact step, etc. as necessary. Furthermore, a surface treatment may be appropriately performed.

[0535] Furthermore, as the adhesive layer, a layer made of an adhesive composition containing a (meth)acrylic resin, a styrene resin, a silicone resin or the like as a base polymer and adding a crosslinking agent such as an isocyanate compound, an epoxy compound or an aziridine compound thereto can be used.

[0536] Preferably, the description of the adhesive layer in the OLED display device described later can be applied.

[0537] <Gas Barrier Layer>

[0538] The light absorption filter of the present invention may have a gas barrier layer on at least one side. When the light absorption filter of the present invention has a gas barrier layer, the light absorption filter of the present invention can be used as a light absorption filter that achieves both excellent quenching properties and excellent light resistance, and can be preferably used to prepare the optical filter described later.

[0539] The material 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, SiO2, SiO x 、SiON、SiN x The gas barrier layer may be a single layer or a multilayer. In the case of a multilayer, a structure such as an inorganic dielectric multilayer film or a multilayer film in which organic materials and inorganic materials are alternately stacked can be cited.

[0540] The light absorption filter of the present invention has at least a gas barrier layer on the surface in contact with air when the light absorption filter of the present invention is used, so that the reduction in the absorption intensity of the dye in the light absorption filter of the present invention can be suppressed. As long as the gas barrier layer is provided at the interface in contact with air of the light absorption filter of the present invention, the gas barrier layer may be provided only on one side of the light absorption filter of the present invention, or may be provided on both sides.

[0541] In the case where the gas barrier layer contains a crystalline resin, the gas barrier layer contains a crystalline resin, preferably has a thickness of 0.1 μm to 10 μm, and an oxygen permeability of 60 cc / m 2 ·day·atm or less.

[0542] In the gas barrier layer, the “crystalline resin” is a resin having a melting point at which it changes from a crystal phase to a liquid when the temperature is increased, and can impart gas barrier properties with respect to oxygen to the gas barrier layer.

[0543] (Crystalline resin)

[0544] As the crystalline resin contained in the gas barrier layer, any crystalline resin can be used without particular limitation as long as it has gas barrier properties and can provide the gas barrier layer with a desired oxygen permeability.

[0545] Examples of the crystalline resin include polyvinyl alcohol and polyvinylidene chloride. Polyvinyl alcohol is preferred because the crystal portion can effectively suppress gas permeation.

[0546] The polyvinyl alcohol may be modified or unmodified. Examples of the modified polyvinyl alcohol include modified polyvinyl alcohols into which groups such as acetoacetyl groups and carboxyl groups are introduced.

[0547] From the viewpoint of further improving oxygen barrier properties, the saponification degree of the polyvinyl alcohol is preferably 80.0 mol% or more, more preferably 90.0 mol% or more, further preferably 97.0 mol% or more, and particularly preferably 98.0 mol% or more. There is no particular restriction on the upper limit, but in practice it is 99.99 mol% or less. The saponification degree of the polyvinyl alcohol is a value calculated according to the method described in JIS K67261994.

[0548] The gas barrier layer may generally contain any component contained in the gas barrier layer within the range that does not impair the effect of the present invention. For example, in addition to the above-mentioned crystalline resin, it may also contain an amorphous resin material, an organic-inorganic hybrid material such as a sol-gel material, SiO2, SiO x 、SiON、SiN x And inorganic materials such as Al2O3.

[0549] Furthermore, the gas barrier layer may contain solvents such as water and organic solvents generated during the production process within a range not impairing the effects of the present invention.

[0550] The content of the crystalline resin in the gas barrier layer is, for example, preferably 90% by mass or more, more preferably 95% by mass or more in 100% by mass of the total mass of the gas barrier layer. The upper limit is not particularly limited, but may be 100% by mass.

[0551] The oxygen permeability of the gas barrier layer is preferably 60 cc / m 2 ·day·atm or less, more preferably 50cc / m 2 ·day·atm or less, more preferably 30cc / m 2 ·day·atm or less, particularly preferably 10cc / m 2 ·day·atm or less, preferably 5cc / m 2·day·atm or less, most preferably 1cc / m 2 ·day·atm or less. The actual lower limit is 0.001cc / m 2 ·day·atm or more, for example, preferably more than 0.05cc / m 2 When the oxygen permeability is within the above-described preferred range, the light resistance can be further improved.

[0552] The oxygen permeability of the gas barrier layer is a value measured by a gas permeability test method based on JIS K7126-22006. As a measuring device, for example, an oxygen permeability tester, OX-TRAN2 / 21 (trade name) manufactured by MOCON can be used. In addition, the measuring conditions are set to a temperature of 25° C. and a relative humidity of 50%.

[0553] The oxygen permeability can be expressed using the SI unit (fm) / (s·Pa). 2 ·day·atm). fm is pronounced as femtometer, and means 1fm=10-1 5 m.

[0554] From the viewpoint of further improving light resistance, the thickness of the gas barrier layer is preferably 0.5 μm to 5 μm, more preferably 1.0 μm to 4.0 μm.

[0555] The thickness of the gas barrier layer is measured by taking a cross-sectional photograph using a field emission scanning electron microscope S-4800 (trade name) manufactured by Hitachi High-Technologies Corporation or the like.

[0556] The crystallinity of the crystalline resin contained in the gas barrier layer is preferably 25% or more, more preferably 40% or more, and further preferably 45% or more. The upper limit is not particularly limited, but is practically 55% or less, and preferably 50% or less.

[0557] The crystallinity of the crystalline resin contained in the gas barrier layer is a value measured and calculated by the following method according to the method described in J. Appl. Pol. Sci., 81, 762 (2001).

[0558] The sample peeled from the gas barrier layer was heated at 10°C / min in the range of 20°C to 260°C using a DSC (differential scanning calorimeter) to measure the heat of fusion 1. In addition, as the heat of fusion 2 of complete crystallization, the value described in J. Appl. Pol. Sci., 81, 762 (2001) was used. Using the obtained heat of fusion 1 and heat of fusion 2, the crystallinity was calculated by the following formula.

[0559] [Crystallinity (%)] = ([Heat of Melting 1] / [Heat of Melting 2]) × 100

[0560] In addition, the heat of fusion 1 and the heat of fusion 2 can be expressed in the same unit, usually Jg -1 .

[0561] <Method for producing gas barrier layer>

[0562] The method for forming the gas barrier layer is not particularly limited, but according to conventional methods, for example, in the case of organic materials, a method of producing by a casting method such as spin coating and slit coating can be cited. In addition, a method of attaching a commercially available resin gas barrier film or a pre-made resin gas barrier film to the light absorption filter of the present invention can be cited. In addition, in the case of inorganic materials, a plasma CVD method, a sputtering method, and a vapor deposition method can be cited.

[0563] <Optically functional film>

[0564] The light absorption filter of the present invention may appropriately include the above-mentioned gas barrier layer or any optically functional film within a range not impairing the effects of the present invention.

[0565] Regarding any of the above optical functional films, there are no particular restrictions on optical properties and materials, but a film containing at least one of cellulose ester resin, acrylic resin, cyclic olefin resin and polyethylene terephthalate resin (or as a main component) can be preferably used. In addition, an optically isotropic film can be used, and an optically anisotropic phase difference film can also be used.

[0566] As for the above-mentioned arbitrary optical functional films, as an optical film containing a cellulose ester resin, for example, FUJITAC TD80UL (manufactured by FUJIFILM Corporation) or the like can be used.

[0567] Regarding any of the above-mentioned optical functional films, as an optical film containing an acrylic resin, an optical film containing a (meth) acrylic resin containing a styrene resin described in Japanese Patent No. 4570042, an optical film containing a (meth) acrylic resin having a glutarimide ring structure on the main chain described in Japanese Patent No. 5041532, an optical film containing a (meth) acrylic resin having a lactone ring structure described in Japanese Patent Publication No. 2009-122664, and an optical functional film containing a (meth) acrylic resin having a glutaric anhydride unit described in Japanese Patent Publication No. 2009-139754.

[0568] Furthermore, regarding any of the above-mentioned optical functional films, as an optical film containing a cyclic olefin resin, the cyclic olefin resin film described in paragraph

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

[0569] [Filter]

[0570] The optical filter of the present invention is obtained by subjecting the light absorption filter of the present invention to mask exposure by ultraviolet irradiation.

[0571] The optical filter of the present invention includes a light-absorbing portion having a light-absorbing effect and a portion where the light-absorbing property is eliminated (light-absorbing eliminated portion) according to a mask exposure pattern (hereinafter also referred to as a "mask pattern").

[0572] That is, the light absorption filter of the present invention is exposed through a mask by ultraviolet irradiation, whereby the masked portion of the light absorption filter of the present invention is not exposed and exists as a light absorbing portion having a light absorbing effect, while the unmasked portion is exposed and becomes a light absorbing non-existent portion.

[0573] The light-absorbing site can exhibit desired absorbance.

[0574] Furthermore, the light absorption filter of the present invention exhibits an excellent decolorization rate for the above-mentioned light absorption disappearance site, and since secondary absorption accompanying dye decomposition hardly occurs, it can exhibit optical characteristics close to colorless.

[0575] <Optical filter manufacturing method>

[0576] The optical filter of the present invention is obtained by irradiating the light absorption filter of the present invention with ultraviolet rays and performing mask exposure.

[0577] The mask pattern can be appropriately adjusted to obtain the optical filter of the present invention having a desired pattern consisting of light-absorbing regions and light-absorbing non-regions.

[0578] The conditions for ultraviolet irradiation can be appropriately adjusted to obtain the filter of the present invention having a light absorption disappearance portion. For example, the pressure conditions can be carried out under atmospheric pressure (101.33 kPa), the lamp output can be set to 80 to 320 W / cm, and an air-cooled metal halide lamp, a mercury lamp, etc. can be used as the lamp used. In addition, the irradiation amount can be set to 200 to 1000 mJ / cm 2 .

[0579] In the method for producing the optical filter of the present invention, it is preferred to perform ultraviolet irradiation under heating conditions from the viewpoint of achieving a higher level of balance between the light fastness of the unexposed portion and the decolorization resistance of the exposed portion while reducing the molar ratio of the radical generator to the dye.

[0580] From the viewpoint of making the color from the dye more easily decolorized, the above-mentioned heating temperature is preferably a temperature exceeding the glass transition temperature of the light absorption filter irradiated with ultraviolet rays. It is believed that this is because the free radical generator is easily diffused by increasing the mobility of the molecular chain of the matrix resin component constituting the light absorption filter. By irradiating ultraviolet rays at a heating temperature exceeding the glass transition temperature, even if the amount of free radical generator added relative to the dye is reduced, it is possible to show excellent decolorization, and as a result, it is possible to obtain a filter that achieves both decolorization of the light absorption disappearance portion and light resistance of the light absorption portion at a high level.

[0581] Here, the heating temperature refers to the temperature of the light absorption filter during ultraviolet irradiation.

[0582] As described above, the glass transition temperature of the light absorption filter is a value measured by the method described in Examples described later.

[0583] From the viewpoint of further improving the ease of decolorization, the heating temperature is preferably the glass transition temperature of the light absorption filter + 5°C or more, more preferably the glass transition temperature of the light absorption filter + 10°C or more, further preferably the glass transition temperature of the light absorption filter + 20°C or more, particularly preferably the glass transition temperature of the light absorption filter + 25°C or more, and particularly preferably the glass transition temperature of the light absorption filter + 30°C or more. The upper limit of the heating temperature is not particularly limited, but is practically 200°C or less.

[0584] Heating can be appropriately performed by a conventional method. For example, a hot plate or the like can be used as a heating device. By setting the set temperature of the heating device to the above-mentioned heating temperature, the above-mentioned light absorption filter can be heated to the above-mentioned heating temperature while irradiating ultraviolet rays.

[0585] Regarding the mask, it can be performed by a conventional method according to the light absorption filter of the present invention.

[0586] The optical filter of the present invention may include the optically functional film described in the light absorption filter of the present invention.

[0587] Furthermore, the optical filter of the present invention may have a layer containing an ultraviolet absorber. The ultraviolet absorber is not particularly limited, and commonly used compounds can be used, for example, the ultraviolet absorber in the ultraviolet absorbing layer described below can be cited. The resin constituting the layer containing an ultraviolet absorber is also not particularly limited, and for example, the resin in the ultraviolet absorbing layer described below can be cited.

[0588] The content of the ultraviolet absorber in the layer containing the ultraviolet absorber can be appropriately adjusted depending on the purpose.

[0589] <<Method for producing laminate>>

[0590] When the light absorption filter of the present invention is provided with the above-mentioned gas barrier layer, for example, a method of directly forming the above-mentioned gas barrier layer on the light absorption filter of the present invention produced by the above-mentioned production method can be cited. In this case, it is also preferable to subject the surface of the light absorption filter of the present invention where the gas barrier layer is provided to corona treatment.

[0591] Furthermore, when any of the above optical functional films is provided, it is also preferable to bond them together via an adhesive layer. For example, it is also preferable to bond an optical functional film together via an adhesive layer after providing a gas barrier layer on the light absorption filter of the present invention.

[0592] [OLED display device]

[0593] The organic electroluminescent display device of the present invention (referred to as an organic EL (electroluminescence) display device or an OLED (Organic Light Emitting Diode) display device, and in the present invention, also simply referred to as an OLED display device) includes the optical filter of the present invention.

[0594] As long as the OLED display device of the present invention includes the optical filter of the present invention, the structure of a commonly used OLED display device can be used as other structures without particular limitation. As a structural example of the OLED display device of the present invention, there is no particular limitation, but for example, a display device including glass, a layer including a TFT (thin film transistor), an OLED display element, a barrier film, a color filter, glass, an adhesive layer, the optical filter of the present invention, and a surface film in this order from the side opposite to the external light can be cited.

[0595] The above-mentioned OLED display element has a structure in which an anode electrode, a light-emitting layer and a cathode electrode are stacked in sequence. Between the anode electrode and the cathode electrode, in addition to the light-emitting layer, a Hall injection layer, a Hall transport layer, an electron transport layer and an electron injection layer are included. In addition, for example, the records in Japanese Patent Publication No. 2014-132522 can also be referred to.

[0596] Furthermore, as the color filter, in addition to a normal color filter, a color filter on which quantum dots are stacked can be used.

[0597] A resin film can also be used instead of the above-mentioned glass.

[0598] <Adhesive Layer>

[0599] In the OLED display device of the present invention, the optical filter of the present invention is preferably bonded to glass (substrate) via an adhesive layer at the surface located on the side opposite to the external light.

[0600] The composition of the adhesive composition used in forming the adhesive layer is not particularly limited. For example, a composition containing a mass average molecular weight (M w ) is an adhesive composition of a base resin with a molecular weight of 500,000 or more. When the mass average molecular weight of the base resin is less than 500,000, bubbles or peeling may occur under at least one of high temperature and high humidity due to reduced cohesive force, and the durability reliability of the adhesive may be reduced. The upper limit of the mass average molecular weight of the base resin is not particularly limited, but if the mass average molecular weight is excessively increased, the coating property may be reduced due to increased viscosity, so it is preferably 2,000,000 or less.

[0601] The specific type of the base resin is not particularly limited, and examples thereof include acrylic resins, silicone resins, rubber resins, and EVA (ethylene vinyl acetate) resins. When applied to optical devices such as liquid crystal display devices, acrylic resins are mainly used due to their excellent transparency, oxidation resistance, and resistance to yellowing, but the present invention is not limited thereto.

[0602] Examples of the acrylic resin include polymers of a monomer mixture containing 80 to 99.8 parts by mass of a (meth)acrylate monomer and 0.02 to 20 parts by mass (preferably 0.2 to 20 parts by mass) of another crosslinking monomer.

[0603] The type of (meth)acrylate monomer is not particularly limited, and for example, alkyl (meth)acrylate can be cited. At this time, if the alkyl group contained in the monomer becomes an overly long chain, the cohesive force of the adhesive is reduced, and it is sometimes difficult to adjust the glass transition temperature (Tg) or adhesion, so it is preferred to use a (meth)acrylate monomer with an alkyl group of 1 to 14 carbon atoms. As for examples of such monomers, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, tert-butyl (meth)acrylate, sec-butyl (meth)acrylate, pentyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-ethylbutyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, isononyl (meth)acrylate, lauryl (meth)acrylate, isobornyl (meth)acrylate, and tetradecyl (meth)acrylate can be cited. In the present invention, the above monomers can be used alone or in combination of two or more. The (meth)acrylate monomer is preferably contained in an amount of 80 to 99.8 parts by mass in 100 parts by mass of the monomer mixture. If the (meth)acrylate monomer content is less than 80 parts by mass, initial adhesion may be reduced, while if it exceeds 99.8 parts by mass, cohesion may be reduced and durability may be reduced.

[0604] Other crosslinking monomers included in the monomer mixture can react with the multifunctional crosslinking agent described later to impart cohesive force to the binder, and impart crosslinking functional groups that play a role in regulating bonding force and durability reliability to the polymer. As such crosslinking monomers, hydroxyl-containing monomers, carboxyl-containing monomers and nitrogen-containing monomers can be cited. As hydroxyl-containing monomers, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 2-hydroxyethylene glycol (meth) acrylate or 2-hydroxypropylene glycol (meth) acrylate can be cited. As carboxyl-containing monomers, acrylic acid, methacrylic acid, 2-(meth) acryloxy acetic acid, 3-(meth) acryloxy propionic acid, 4-(meth) acryloxy butyric acid, acrylic acid dimer, itaconic acid, maleic acid and maleic anhydride can be cited. Examples of the nitrogen-containing monomer include (meth)acrylamide, N-vinylpyrrolidone, and N-vinylcaprolactam. In the present invention, these crosslinking monomers may be used alone or in combination of two or more.

[0605] The other crosslinkable monomer may be contained in an amount of 0.02 to 20 parts by mass based on 100 parts by mass of the monomer mixture. If the content is less than 0.02 parts by mass, the durability reliability of the adhesive may be reduced, while if it exceeds 20 parts by mass, at least one of the adhesiveness and the releasability may be reduced.

[0606] The monomer mixture may further contain a monomer represented by the following general formula (10). Such a monomer may be added for the purpose of adjusting the glass transition temperature of the binder or imparting other functionalities.

[0607] [Chemical formula 56]

[0608]

[0609] In the formula, R1 to R3 each independently represent a hydrogen atom or an alkyl group, R4 represents a cyano group; a phenyl group which may be substituted or unsubstituted by an alkyl group; an acetoxy group; or COR5 (here, R5 represents an amino group or a glycidyloxy group which may be substituted or unsubstituted by an alkyl group or an alkoxyalkyl group).

[0610] In the definitions of R1 to R5 in the above formula, alkyl or alkoxy refers to an alkyl or alkoxy group having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, and more preferably 1 to 12 carbon atoms, and specifically, it can be methyl, ethyl, methoxy, ethoxy, propoxy or butoxy.

[0611] As the monomer represented by the general formula (10), there can be mentioned nitrogen-containing monomers such as (meth)acrylonitrile, (meth)acrylamide, N-methyl(meth)acrylamide or N-butoxymethyl(meth)acrylamide; styrene-based monomers such as styrene or methylstyrene; epoxy-containing monomers such as glycidyl(meth)acrylate; or vinyl carboxylates such as vinyl acetate, etc., but it is not limited thereto. The monomer represented by the general formula (10) may be included in an amount of 20 parts by mass or less relative to a total of 100 parts by mass of the (meth)acrylate monomer and other crosslinking monomers. If the content exceeds 20 parts by mass, at least one of the flexibility and peelability of the adhesive may be reduced.

[0612] The method for producing a polymer using a monomer mixture is not particularly limited, and for example, it can be produced by a general polymerization method such as solution polymerization, photopolymerization, bulk polymerization, suspension polymerization or latex polymerization. In the present invention, it is particularly preferred to use a solution polymerization method, and the solution polymerization is preferably completed at a polymerization temperature of 50°C to 140°C by mixing an initiator in a state where each monomer is uniformly mixed. At this time, as the initiator used, azo-based polymerization initiators such as azobisisobutyronitrile and azobiscyclohexanecarbonitrile; and common initiators such as peroxides such as benzoyl peroxide and acetyl peroxide can be cited.

[0613] The above-mentioned adhesive composition may further include 0.1 to 10 parts by mass of a crosslinking agent relative to 100 parts by mass of the base resin. Such a crosslinking agent can impart cohesive force to the adhesive through a crosslinking reaction with the base resin. When the content of the crosslinking agent is less than 0.1 parts by mass, the cohesive force of the adhesive may sometimes decrease. Furthermore, if it exceeds 10 parts by mass, interlayer peeling and warping may sometimes occur, and the durability reliability may be reduced.

[0614] The type of the crosslinking agent is not particularly limited, and for example, any crosslinking agent such as an isocyanate compound, an epoxy compound, an aziridine compound, and a metal chelate compound can be used.

[0615] As isocyanate compounds, for example, toluene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, tetramethylxylene diisocyanate and naphthalene diisocyanate, and the reaction product of any one of them and a polyol (for example, trimethylolpropane) can be mentioned; as epoxy compounds, ethylene glycol diglycidyl ether, triglycidyl ether, trimethylolpropane triglycidyl ether, N,N,N',N'-tetraglycidylethylenediamine and glycerol diglycidyl ether can be mentioned; as aziridine compounds, N,N'-toluene-2,4-bis(1-aziridinecarboxamide), N,N'-diphenylmethane-4,4'-bis(1-aziridinecarboxamide), trithamide, bisprothaloyl-1-(2-methylaziridine) and tris-1-aziridine phosphine oxide can be mentioned. Examples of the metal chelate compound include compounds in which at least one polyvalent metal such as aluminum, iron, zinc, tin, titanium, antimony, magnesium, and vanadium is coordinated to acetylacetone or ethyl acetoacetate.

[0616] In the above-mentioned adhesive composition, 0.01 to 10 parts by mass of a silane coupling agent may also be included relative to 100 parts by mass of the base resin. Regarding the silane coupling agent, when the adhesive is placed under high temperature or high humidity conditions for a long time, it can help to improve the bonding reliability, especially when bonding with a glass substrate, it can improve the bonding stability, and can improve the heat resistance and moisture resistance. As a silane coupling agent, γ-glycidyloxypropyl trimethoxysilane, γ-glycidyloxypropyl methyl diethoxysilane, γ-glycidyloxypropyl triethoxysilane, 3-mercaptopropyl trimethoxysilane, vinyl trimethoxysilane, vinyl triethoxysilane, γ-methacryloxypropyl trimethoxysilane, γ-methacryloxypropyl triethoxysilane, γ-aminopropyl triethoxysilane, 3-isocyanate propyl triethoxysilane and γ-acetoacetate propyl trimethoxysilane can be cited. These silane coupling agents may be used alone or in combination of two or more.

[0617] The silane coupling agent is preferably contained in an amount of 0.01 to 10 parts by mass, and more preferably 0.05 to 1 part by mass, relative to 100 parts by mass of the base resin. When the content is less than 0.01 parts by mass, the effect of increasing the adhesive force may be insufficient, and when it exceeds 10 parts by mass, bubbles or peeling may occur, resulting in reduced durability and reliability.

[0618] The above-mentioned adhesive composition can also include an antistatic agent. As the antistatic agent, any compound can be used as long as it has excellent compatibility with other components included in the adhesive composition such as acrylic resin, does not adversely affect the transparency, operability and durability of the adhesive, and can impart antistatic properties to the adhesive. As the antistatic agent, inorganic salts or organic salts can be cited.

[0619] Inorganic salts are salts containing alkali metal cations or alkaline earth metal cations as cation components. Examples of cations include lithium ions (Li + ), sodium ion (Na + ), potassium ion (K + ), rubidium ions (Rb + ), cesium ion (Cs + ), beryllium ion (Be 2+ ), magnesium ion (Mg 2+ ), calcium ion (Ca 2+ ), strontium ion (Sr 2+ ) and barium ions (Ba 2+ ) or more, preferably lithium ion (Li + ), sodium ion (Na + ), potassium ion (K+), cesium ion (Cs + ), beryllium ion (Be 2+ ), magnesium ion (Mg 2+ ), calcium ions (Ca 2+ ) and barium ions (Ba 2+ The inorganic salt may be used alone or in combination of two or more. In terms of ion safety and mobility within the binder, lithium ions (Li + ).

[0620] Organic salts are salts containing onium cations as cationic components. The term "onium cation" refers to a positively charged (+) ion, wherein at least a portion of the charge is unevenly present in one or more atoms of nitrogen (N), phosphorus (P) and sulfur (S). Onium cations are cyclic or non-cyclic compounds, and in the case of cyclic compounds, they can be non-aromatic or aromatic compounds. Moreover, in the case of cyclic compounds, it is possible to contain one or more heteroatoms (e.g., oxygen) other than nitrogen, phosphorus or sulfur atoms. Moreover, cyclic or non-cyclic compounds are arbitrarily substituted by substituents such as hydrogen atoms, halogen atoms, alkyl or aryl groups. Moreover, in the case of non-cyclic compounds, it is possible to contain one or more, preferably four or more, substituents, in which case the substituents are cyclic or non-cyclic substituents, aromatic or non-aromatic substituents.

[0621] The onium cation is preferably a cation containing a nitrogen atom, and more preferably an ammonium ion. The ammonium ion is a quaternary ammonium ion or an aromatic ammonium ion.

[0622] Specifically, the quaternary ammonium ion is preferably a cation represented by the following general formula 11.

[0623] [Chemical formula 57]

[0624] Formula 11

[0625]

[0626] In Formula 11, R6 to R9 each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group.

[0627] The alkyl group or alkoxy group in the general formula 11 represents an alkyl group or alkoxy group having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, and the alkenyl group or alkynyl group represents an alkenyl group or alkynyl group having 2 to 12 carbon atoms, preferably 2 to 8 carbon atoms.

[0628] In the general formula 11, the aryl group, as a substituent derived from an aromatic compound, represents a phenyl, biphenyl, naphthalene or anthracene ring system, etc., and the heteroaryl group represents a 5- to 12-ring heterocyclic or aryl ring containing one or more heteroatoms among O, N and S, and specifically represents a furanyl, pyrrolyl, pyrrolidinyl, thienyl, pyridyl, piperidyl, indolyl, quinolyl, thiazolyl, benzothiazole and triazole, etc.

[0629] In the general formula 11, the alkyl group, alkoxy group, alkenyl group, alkynyl group, aryl group or heteroaryl group may be substituted by one or more substituents. In this case, the substituents include hydroxyl groups, halogen atoms or alkyl or alkoxy groups having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, and more preferably 1 to 4 carbon atoms.

[0630] In the present invention, as the cation represented by the general formula 11, a quaternary ammonium cation is preferably used, and in particular, a cation in which R1 to R4 are each independently a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms.

[0631] As the quaternary ammonium ion represented by the general formula 11, for example, there can be mentioned N-ethyl-N,N-dimethyl-N-(2-methoxyethyl)ammonium ion, N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium ion, N-ethyl-N,N-dimethyl-N-propylammonium ion, N-methyl-N,N,N-trioctylammonium ion, N,N,N-trimethyl-N-propylammonium ion, tetrabutylammonium ion, tetramethylammonium ion, tetrahexylammonium ion and N-methyl-N,N,N-tributylammonium ion.

[0632] As the aromatic ammonium ion, for example, one or more ions of pyridinium, pyridazinium, pyrimidinium, pyrazinium, imidazolium, pyrazolium, thiazolium, oxazolium and triazolium can be mentioned, preferably N-alkylpyridinium ion substituted with an alkyl group having 4 to 16 carbon atoms, 1,3-alkylmethylimidazolium ion substituted with an alkyl group having 2 to 10 carbon atoms, and 1,2-dimethyl-3-alkylimidazolium ion substituted with an alkyl group having 2 to 10 carbon atoms. These aromatic ammonium ions may be used alone or in combination of two or more.

[0633] Furthermore, the aromatic ammonium ion is a compound represented by the following general formula 12.

[0634] [Chemical formula 58]

[0635] Formula 12

[0636]

[0637] In general formula 12, R 10 To R 15 Each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group.

[0638] In the general formula 12, the definitions of alkyl, alkoxy, alkenyl, alkynyl, aryl, heteroaryl and their substituents are the same as those of the above general formula 11.

[0639] As the compound of general formula 12, R 11 To R 15 are each independently a hydrogen atom or an alkyl group, R 10 It is an alkyl group.

[0640] Among the examples of anions contained in the inorganic salt or organic salt containing cations in the antistatic agent, preferably fluoride (F - ), chloride (Cl - ), bromide (Br - ), iodide (I - ), perchlorate (ClO4 - ), hydroxide (OH - ), carbonate (CO3 2- ), nitrate (NO3 - )sulfonate (SO4 - ), methylbenzenesulfonate (CH3(C6H4)SO3 - ), p-toluenesulfonate (CH3C6H4SO3 - ), carboxybenzenesulfonate (COOH(C6H4)SO3 - ), trifluoromethanesulfonate (CF3SO2 - ), benzoate (C6H5COO - ), acetate (CH3COO - ), trifluoroacetate (CF3COO - ), tetrafluoroborate (BF4 - ), tetrabenzyl borate (B(C6H5)4 - ), hexafluorophosphate (PF6 - ), tris(pentafluoroethyl) trifluorophosphate (P(C2F5)3F3 - ), bis(trifluoromethanesulfonyl imide)(N(SO2CF3)2 - ), bis(pentafluoroethanesulfonyl imide) (N(SOC2F5)2 - ), bis(pentafluoroethanecarbonyl imide) (N(COC2F5)2 - ), bis(perfluorobutanesulfonyl imide) (N(SO2C4F9)2 - ), bis(perfluorobutanecarbonyl imide) (N(COC4F9)2 - ), tris(trifluoromethanesulfonyl)methyl (C(SO2CF3)3 - ) and trifluoromethane carbonyl methylate (C(SO2CF3)3 - Among the anions, it is preferred to use an imide anion which can play an electron withdrawing role and is substituted with fluorine having good hydrophobicity and high ion stability.

[0641] In the above-mentioned adhesive composition, relative to 100 parts by mass of the base resin, 0.01 to 5 parts by mass, preferably 0.01 to 2 parts by mass, and more preferably 0.1 to 2 parts by mass of the antistatic agent are included. When the content is less than 0.01 parts by mass, the target antistatic effect may not be obtained, and when it exceeds 5 parts by mass, the compatibility with other components may be reduced, and the durability reliability or transparency of the adhesive may be deteriorated.

[0642] The above-mentioned adhesive composition can also include an antistatic agent, specifically a compound that can form a coordination bond with the cation contained in the antistatic agent (hereinafter referred to as a "coordination bonding compound"). By appropriately including the coordination bonding compound, even when a relatively small amount of antistatic agent is used, the anion concentration inside the adhesive layer can be increased to effectively impart antistatic performance.

[0643] The type of the coordination bonding compound that can be used is not particularly limited as long as it has a functional group that can coordinately bond with the antistatic agent in the molecule, and examples thereof include alkylene oxide compounds.

[0644] The alkylene oxide compound is not particularly limited, but an alkylene oxide compound containing an alkylene oxide unit having 2 or more, preferably 3 to 12, and more preferably 3 to 8 carbon atoms as a basic unit is preferably used.

[0645] The molecular weight of the alkylene oxide compound is preferably 5,000 or less. The term "molecular weight" used in the present invention refers to the molecular weight or mass average molecular weight of the compound. In the present invention, if the molecular weight of the alkylene oxide compound exceeds 5,000, the viscosity may increase excessively and the coating property may deteriorate, or the ability to form a complex with a metal may decrease. On the other hand, the lower limit of the molecular weight of the alkylene oxide compound is not particularly limited, but is preferably 500 or more, more preferably 4,000 or more.

[0646] The alkylene oxide compound is not particularly limited as long as it exhibits the above-mentioned properties, and for example, a compound represented by the following general formula 13 can be used.

[0647] [Chemical formula 59]

[0648] Formula 13

[0649]

[0650] In the general formula 13, A represents an alkylene group having 2 or more carbon atoms, n represents 1 to 120, and R 16 and R 17 Each independently represents a hydrogen atom, a hydroxyl group, an alkyl group or C(═O)R 18 , the above R 18 represents a hydrogen atom or an alkyl group.

[0651] In the general formula 13, the alkylene group represents an alkylene group having 3 to 12 carbon atoms, preferably 3 to 8 carbon atoms, and specifically represents an ethylene group, a propylene group, a butylene group, or a pentylene group.

[0652] In the general formula 13, the alkyl group represents an alkyl group having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, and more preferably 1 to 4 carbon atoms; and n represents preferably 1 to 80 carbon atoms, and more preferably 1 to 40 carbon atoms.

[0653] Examples of the compound represented by the general formula 13 include polyalkylene oxides (e.g., polyethylene oxide, polypropylene oxide, polybutylene oxide or polypentene oxide, etc.), fatty acid alkyl esters of polyalkylene oxides (e.g., polyethylene oxide, polypropylene oxide, polybutylene oxide or polypentene oxide, etc.), and carboxylic acid esters of polyalkylene oxides (e.g., polyethylene oxide, polypropylene oxide, polybutylene oxide or polypentene oxide, etc.), but are not limited thereto.

[0654] In the present invention, in addition to the above-mentioned alkylene oxide compounds, various coordination bonding compounds such as ester compounds having one or more ether bonds disclosed in Korean Patent Publication No. 2006-0018495 or oxalate group-containing compounds, diamine group-containing compounds, polyvalent carboxyl group-containing compounds or ketone group-containing compounds disclosed in Korean Patent Publication No. 2006-0128659 can be appropriately selected and used.

[0655] The coordination bonding compound is contained in the adhesive composition in an amount of 3 parts by mass or less relative to 100 parts by mass of the base resin, more preferably 0.1 to 3 parts by mass, and further preferably 0.5 to 2 parts by mass. If the content exceeds 3 parts by mass, the adhesive properties such as peelability may be reduced.

[0656] In the above-mentioned binder composition, from the viewpoint of regulating bonding performance, relative to 100 mass parts of base resin, 1 mass part to 100 mass parts of adhesive imparting resin can also be included. When the content of adhesive imparting resin is less than 1 mass part, the addition effect is sometimes insufficient, and if it exceeds 100 mass parts, at least one of the intermiscibility and cohesive force improvement effect is sometimes reduced. As this adhesive imparting resin, there is no particular limitation, but for example, (hydrogenated) hydrocarbon resin, (hydrogenated) rosin resin, (hydrogenated) rosin ester resin, (hydrogenated) terpene resin, (hydrogenated) terpene phenolic resin, polymerized rosin resin or polymerized rosin ester resin can be cited. These adhesive imparting resins can be used alone or in combination of two or more.

[0657] The above-mentioned adhesive composition may also contain one or more polymerization initiators such as thermal polymerization initiators and photopolymerization initiators; epoxy resins; curing agents; ultraviolet stabilizers; antioxidants; colorants; reinforcing agents; fillers; defoaming agents; surfactants; photopolymerizable compounds such as multifunctional acrylates; and additives such as plasticizers, within the scope that will not affect the effects of the invention.

[0658] <Base Material>

[0659] In the OLED display device of the present invention, the optical filter of the present invention is preferably bonded to glass (substrate) via an adhesive layer at the surface located on the side opposite to the external light.

[0660] The method for forming the above-mentioned adhesive layer is not particularly limited, and for example, the following methods can be used: a method in which the adhesive composition is applied to the light absorption filter of the present invention using a common device such as a rod coater, and the adhesive composition is dried and cured; and a method in which the adhesive composition is first applied to the surface of a removable substrate, dried, and then the adhesive layer is transferred to the light absorption filter of the present invention using the removable substrate, and the adhesive layer is matured and cured.

[0661] The releasable substrate is not particularly limited, and any releasable substrate can be used. For example, the releasable film in the above-mentioned method for producing the light absorption filter of the present invention can be mentioned.

[0662] In addition, the conditions for coating, drying, aging, and curing can also be appropriately adjusted according to conventional methods.

[0663] [Liquid crystal display device]

[0664] The liquid crystal display device of the present invention includes the optical filter of the present invention.

[0665] As described later, the optical filter of the present invention may be used as at least one of a polarizing plate protective film and an adhesive layer, and may be included in a backlight unit used in a liquid crystal display device.

[0666] The liquid crystal display device preferably includes an optical filter, a polarizer including a polarizer and a polarizer protective film, an adhesive layer, and a liquid crystal unit, and the polarizer is preferably attached to the liquid crystal unit via an adhesive layer. In the liquid crystal display device, the optical filter can also serve as a polarizer protective film or an adhesive layer. That is, the liquid crystal display device is divided into the following cases: a polarizer including a polarizer and an optical filter (polarizer protective film), an adhesive layer, and a liquid crystal unit; and a polarizer including a polarizer and a polarizer protective film, an optical filter (adhesive layer), and a liquid crystal unit.

[0667] Figure 1 1 is a schematic diagram showing an example of a liquid crystal display device of the present invention. Figure 1In the embodiment, the liquid crystal display device 10 includes a liquid crystal cell having a liquid crystal layer 5, and a liquid crystal cell upper electrode substrate 3 and a liquid crystal cell lower electrode substrate 6 disposed above and below the liquid crystal cell, and an upper polarizer 1 and a lower polarizer 8 disposed on both sides of the liquid crystal cell. A color filter layer may be stacked on the upper electrode substrate 3 or the lower electrode substrate 6. A backlight is disposed on the back side of the above-mentioned liquid crystal display device 10. As a light source of the backlight, the light source described in the above-mentioned backlight unit can be used.

[0668] The upper polarizing plate 1 and the lower polarizing plate 8 each have a structure in which a polarizer is laminated with two polarizing plate protective films sandwiched therebetween. In the liquid crystal display device 10, it is preferred that at least one polarizing plate is a polarizing plate including the optical filter of the present invention.

[0669] Furthermore, in the liquid crystal display device 10, the liquid crystal cell and the polarizing plates (upper polarizing plate 1 and / or lower polarizing plate 8) may be bonded together via an adhesive layer (not shown). In this case, the optical filter of the present invention may also serve as the adhesive layer.

[0670] The liquid crystal display device 10 includes an image direct view type, an image projection type, or a light modulation type. An active matrix liquid crystal display device using a 3-terminal or 2-terminal semiconductor element such as TFT or MIM is effective in the present invention. Of course, a passive matrix liquid crystal display device represented by a STN mode called time-division drive is also effective.

[0671] When the optical filter of the present invention is included in the backlight unit, the polarizer of the liquid crystal display device may be a general polarizer (not including the optical filter of the present invention) or a polarizer including the optical filter of the present invention. Furthermore, the adhesive layer may be a general adhesive layer (not the optical filter of the present invention) or an adhesive layer based on the optical filter of the present invention.

[0672] In addition to preferably using the optical filter of the present invention, the IPS mode liquid crystal display device described in paragraphs 128 to 136 of Japanese Patent Application Laid-Open No. 2010-102296 is also preferably used as the liquid crystal display device of the present invention.

[0673] <Polarizing Plate>

[0674] The polarizing plate used in the present invention includes a polarizer and at least one polarizing plate protective film.

[0675] The polarizer used in the present invention preferably has a polarizer and polarizer protective films located on both sides of the polarizer, and preferably includes the optical filter of the present invention as the polarizer protective film on at least one side. A general polarizer protective film may be provided on the side of the polarizer opposite to the side having the optical filter of the present invention (polarizer protective film of the present invention).

[0676] The film thickness of the polarizer protective film is 5 μm or more and 120 μm or less, more preferably 10 μm or more and 100 μm or less. The film is not easy to produce uneven display after high temperature and high humidity for a long time when assembled into a liquid crystal display device, so it is preferred. On the other hand, if it is too thin, it is difficult to stably transmit when manufacturing the film and making the polarizer. In the case where the filter of the present invention also serves as a polarizer protective film, the thickness of the filter preferably satisfies the above range.

[0677] -Polarizer Performance-

[0678] The polarization degree of the polarizing plate used in the present invention is preferably 99.950% or more, more preferably 99.970%, and most preferably 99.990% or more.

[0679] In the present invention, the polarization degree of the polarizing plate is calculated by the following formula from the orthogonal transmittance and parallel transmittance measured at a wavelength of 380 to 700 nm using an automatic polarizing film measuring apparatus: VAP-7070 (manufactured by JASCO Corporation).

[0680] Polarization degree (%) = [(parallel transmittance - orthogonal transmittance) / (orthogonal transmittance + parallel transmittance)] 1 / 2 ×100

[0681] The polarization degree can be measured in the following manner. Prepare two samples (5 cm × 5 cm) with polarizers attached to glass via an adhesive. For the orthogonal transmittance and parallel transmittance measurements, set the glass side of the sample toward the light source and measure. Measure the two samples, and take their average values ​​as the orthogonal transmittance and parallel transmittance, respectively. When studying the effect of a polarizer protective film on the polarization degree, the polarizer protective film to be evaluated is usually configured and attached to the glass side.

[0682] Other preferred optical properties and the like of the polarizing plate used in the present invention are described in

[0238] to

[0255] of JP-A-2007-086748, and it is preferred that these properties are satisfied.

[0683] -Shape, structure-

[0684] The shape of the polarizer used in the present invention includes not only polarizers cut into thin films of a size that can be directly assembled into a liquid crystal display device, but also polarizers made into long strips and rolled into rolls by continuous production (for example, a roll length of 2500m or more or 3900m or more). In order to be used in a large-screen liquid crystal display device, the width of the polarizer is preferably set to 1470mm or more.

[0685] The polarizing plate used in the present invention is composed of a polarizer and at least one polarizing plate protective film, but is preferably further composed of a separator film bonded to one surface of the polarizing plate.

[0686] The separator film is used to protect the polarizer when the polarizer is shipped, during product inspection, etc. The separator film is used to cover the adhesive layer to be bonded to the liquid crystal panel and is used to bond the polarizer to the surface side of the liquid crystal panel.

[0687] (Polarizer)

[0688] The polarizer used for the polarizing plate of the present invention will be described.

[0689] The polarizer that can be used in the polarizing plate of the present invention is preferably composed of polyvinyl alcohol (PVA) and dichroic molecules, but a polyvinylene-based polarizer obtained by dehydrating and dechlorinating PVA and polyvinyl chloride to generate a polyene structure and orienting it as described in Japanese Patent Publication No. 11-248937 can also be used.

[0690] The film thickness of the polarizer is -

[0691] The film thickness of the polarizer before stretching is not particularly limited, but from the viewpoint of maintaining the stability of the film and the uniformity of stretching, it is preferably 1 μm to 1 mm, and particularly preferably 5 to 200 μm. In addition, a thin PVA film such that the stress generated when stretched 4 to 6 times in water is less than 10 N can be used as described in Japanese Patent Application Laid-Open No. 2002-236212.

[0692] A method for manufacturing a polarizer

[0693] There is no particular restriction on the manufacturing method of the polarizer, but for example, it is preferred that the PVA is filmized and then dichroic molecules are introduced to form the polarizer. The manufacturing of the PVA film can be carried out with reference to the method described in

[0213] to

[0237] of Japanese Patent Publication No. 2007-86748, Japanese Patent Specification No. 3342516, Japanese Patent Publication No. 09-328593, Japanese Patent Publication No. 2001-302817, Japanese Patent Publication No. 2002-144401, etc.

[0694] (Lamination method of polarizer and polarizing plate protective film)

[0695] The polarizing plate used in the present invention is produced by bonding (laminating) at least one polarizing plate protective film (preferably the optical filter of the present invention) to at least one surface of the above-mentioned polarizer.

[0696] It is preferably produced by subjecting a polarizing plate protective film to alkali treatment and bonding it to both sides of a polarizer produced by immersing and stretching a polyvinyl alcohol film in an iodine solution using a completely saponified polyvinyl alcohol aqueous solution.

[0697] Examples of the adhesive for bonding the treated surface of the polarizing plate protective film to the polarizer include polyvinyl alcohol-based adhesives such as polyvinyl alcohol and polyvinyl butyral, and vinyl latex such as butyl acrylate.

[0698] In the polarizing plate used in the present invention, the polarizing plate protective film and the polarizer are preferably laminated so that the transmission axis of the polarizer and the slow axis of the polarizing plate protective film are substantially parallel, orthogonal, or at 45°.

[0699] The slow axis can be measured by various known methods, and can be measured, for example, using a birefringence meter (KOBRADH, manufactured by Oji Scientific Instruments Co., Ltd.).

[0700] Here, substantially parallel means that the direction of the main refractive index nx of the polarizer protective film crosses with the direction of the transmission axis of the polarizer with a deviation within ±5°, preferably within ±1°, and more preferably within ±0.5°. If the angle of intersection is within 1°, the polarization performance of the polarizer under the orthogonal Nicols is not easy to decrease, and light leakage is not easy to occur, so it is preferred.

[0701] The direction of the principal refractive index nx is orthogonal to or at 45° to the direction of the transmission axis, which means that the angle at which the direction of the principal refractive index nx intersects the direction of the transmission axis is within the strict angle range of ±5° related to orthogonality and 45°, and the error from the strict angle is preferably within the range of ±1°, and more preferably within the range of ±0.5°.

[0702] (Functionalization of polarizers)

[0703] The polaroid used in the present invention can also be preferably used as a functionalized polaroid composited with an optical film having functional layers such as an anti-reflection film, a brightness enhancement film, a hard coating, a forward scattering layer, an anti-glare (anti-glare) layer, an antifouling layer, and an antistatic layer for improving the visual recognition of a display. The anti-reflection film, the brightness enhancement film, other functional optical films, the hard coating, the forward scattering layer, and the anti-glare layer used for functionalization are recorded in

[0257] to

[0276] of Japanese Patent Publication No. 2007-86748, and the functionalized polaroid can be made according to these records.

[0704] <Adhesive Layer>

[0705] 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 general adhesive layer may be used as the adhesive layer.

[0706] The adhesive layer is not particularly limited as long as it can bond the polarizing plate and the liquid crystal cell together, but for example, acrylic, urethane, polyisobutylene, and the like are preferred.

[0707] When the optical filter of the present invention also serves as an adhesive layer, the adhesive layer contains the above-mentioned dye and the above-mentioned binder resin, and further contains a crosslinking agent, a coupling agent, etc. to impart adhesiveness.

[0708] When the optical filter also serves as the adhesive layer, the adhesive layer preferably contains 90 to 100% by mass of the above-mentioned binder resin, and more preferably 95 to 100% by mass. The content of the pigment is as described above.

[0709] The thickness of the adhesive layer is not particularly limited, but is, for example, preferably 1 to 50 μm, more preferably 3 to 30 μm.

[0710] <Liquid Crystal Unit>

[0711] The liquid crystal cell is not particularly limited, and a general liquid crystal cell can be used.

[0712] <Ultraviolet absorbing layer>

[0713] The organic electroluminescent display device or liquid crystal display device including the optical filter of the present invention preferably has a layer (hereinafter also referred to as "ultraviolet absorption layer") that blocks light absorption (ultraviolet absorption) of the compound that generates free radicals by ultraviolet irradiation on the viewer side of the optical filter of the present invention. By providing the ultraviolet absorption layer, fading of the optical filter of the present invention caused by external light can be prevented.

[0714] Hereinafter, the ultraviolet absorbing layer of the present invention will be described.

[0715] (Ultraviolet light absorber)

[0716] The ultraviolet absorbing layer of the present invention comprises a resin and an ultraviolet absorber. As the ultraviolet absorber, from the viewpoint of good liquid crystal display, it is preferred to use an ultraviolet absorber that has excellent absorption capacity for ultraviolet rays with a wavelength of 370 nm or less and less absorption of visible light with a wavelength of 400 nm or more.

[0717] Specific examples of the ultraviolet absorber preferably used in the present invention include hindered phenol compounds, hydroxybenzophenone compounds, benzotriazole compounds, salicylate compounds, benzophenone compounds, cyanoacrylate compounds, and nickel complex salt compounds.

[0718] Examples of hindered phenol compounds include 2,6-di-tert-butyl-p-cresol, pentaerythritol ester-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis(3,5-di-tert-butyl-4-hydroxy-oxycinnamic acid amide), 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, and tris-(3,5-di-tert-butyl-4-hydroxybenzyl)-isocyanurate.

[0719] 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[1,2-di-( ... (3,5-di-tert-butyl-4-hydroxy-oxidized cinnamic acid), 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, (2-(2'-hydroxy-3',5'-di-tert-amylphenyl)-5-chlorobenzotriazole, 2,6-di-tert-butyl-p-cresol, pentaerythritol ester-tetrakis〔3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate〕, etc.

[0720] The amount of these ultraviolet light inhibitors added is preferably 0.1 to 30.0 parts by mass based on 100 parts by mass of the resin.

[0721] (resin)

[0722] As the resin used in the ultraviolet absorbing layer of the present invention, known resins can be used without particular limitation unless it violates the gist of the present invention. Examples of the resin include cellulose acylate resins, acrylic resins, cycloolefin resins, polyester resins, and epoxy resins.

[0723] (Setting position of ultraviolet absorbing layer)

[0724] The configuration of the ultraviolet absorbing layer of the present invention is not particularly limited as long as it is on the visual recognizer side relative to the filter of the present invention, and can be set at any position. For example, an ultraviolet absorber can be added to a protective film, an anti-reflection film, etc. of the polarizer to make it function as an ultraviolet absorbing layer.

[0725] Example

[0726] Below, the present invention is further described in detail according to embodiment. About the material, dosage, ratio, processing content, processing sequence etc. shown in the following embodiment, as long as do not depart from the gist of the present invention, then can be appropriately changed.Therefore, the scope of the present invention is not limited to the embodiment shown below.

[0727] In the following examples, "parts" and "%" indicating compositions are by mass unless otherwise specified.

[0728] Furthermore, all the steps from the preparation step of the light absorption filter forming liquid to the production step of the light absorption filter with a substrate using the light absorption filter forming liquid and the steps until the ultraviolet irradiation test were performed under yellow light to avoid exposure to ultraviolet rays.

[0729] [Fabrication of light absorption filter]

[0730] Materials used to make the light absorption filter are shown below.

[0731] <Matrix Resin (Matrix Polymer)>

[0732] (Resin 1)

[0733] A polystyrene resin (PS Japan Corporation, PSJ-polystyrene GPPS SGP-10 (trade name), Tg 100° C., fd 0.56) was heated at 110° C. and naturally cooled to room temperature (23° C.) as resin 1.

[0734] (Resin 2)

[0735] Polyphenylene ether resin (manufactured by Asahi Kasei Corporation, ZYLON S201A (trade name), poly(2,6-dimethyl-1,4-phenylene ether), Tg 210°C)

[0736] (Resin 3)

[0737] Cyclic polyolefin resin (manufactured by Mitsui Chemicals, Inc., APL6509T (trade name), a copolymer of ethylene and norbornene, Tg: 80°C)

[0738] (Resin 4)

[0739] Cyclic polyolefin resin (manufactured by Mitsui Chemicals, Inc., APL6011T (trade name), copolymer of ethylene and norbornene, Tg: 105°C)

[0740] (Releasability Controlling Resin Component 1)

[0741] BYRON550 (trade name, manufactured by TOYOBO CO., LTD., polyester additive)

[0742] <Dye>

[0743] In addition, the alkyl group in dyes A-100 and A-102 refers to a linear alkyl group.

[0744] [Chemical formula 60]

[0745]

[0746] [Chemical formula 61]

[0747]

[0748] FDG007: Trade name, manufactured by YAMADA CHEMICAL CO., LTD., porphyrin pigment

[0749] Solvent Violet 13: manufactured by Tokyo Chemical Industry Co., Ltd., Quinizarin Blue, anthraquinone pigment

[0750] Solvent Blue 35: 1,4-bis(butylamino)-9,10-anthraquinone, anthraquinone pigment

[0751] (Leveling agent 1)

[0752] A polymer surfactant composed of the following components was used as the leveling agent 1. In the following structural formula, the ratio of each component is a molar ratio, and t-Bu means a tert-butyl group.

[0753] [Chemical formula 62]

[0754]

[0755] (Substrate 1)

[0756] A polyethylene terephthalate film Lumirror XD-510P (trade name, film thickness: 50 μm, manufactured by TORAY INDUSTRIES, INC.) was used as the substrate 1 .

[0757] (Substrate 2)

[0758] Cellulose acylate film (manufactured by Fujifilm Corporation, trade name: ZRD40SL)

[0759] Example

[0760] <1. Preparation of Light Absorption Filter No. 101 with Substrate>

[0761] (1) Preparation of resin solution (light absorption filter forming solution)

[0762] The components were mixed in the following composition to prepare a light absorption filter forming liquid (composition) Ba-1.

[0763]

[0764] Next, the obtained light absorption filter forming liquid Ba-1 was filtered using filter paper with an absolute filtration accuracy of 10 μm (#63, manufactured by TOYO ROSHI KAISHA, Ltd.), and further filtered using a metal sintered filter with an absolute filtration accuracy of 2.5 μm (trade name: PALL Filter PMF, media code: FH025, manufactured by NIHON PALL LTD.).

[0765] (2) Fabrication of light absorption filter with substrate

[0766] The light absorption filter forming liquid Ba-1 after the filtration treatment was applied to the substrate 1 using a bar coater so that the film thickness after drying was 2.5 μm, and dried at 130° C. to produce a light absorption filter No. 101 with a substrate.

[0767] <2. Production of Light Absorption Filters No. 102, 121, 201, and 202 with Substrate>

[0768] Light absorption filters Nos. 102, 121, 201, and 202 with substrates were produced in the same manner as light absorption filter No. 101 with substrate, except that the type of dye or the amount of photoradical generator added was changed to that shown in Table 1.

[0769] Here, Nos. 101, 102, and 121 are light absorption filters of the present invention, and Nos. 201 and 202 are light absorption filters for comparison.

[0770] <3. Preparation of Light Absorption Filter No. 103 with Substrate>

[0771] (1) Preparation of resin solution (light absorption filter forming solution)

[0772] The components were mixed in the following composition to prepare a light absorption filter forming liquid (composition) Ba-2.

[0773]

[0774] Next, the obtained light absorption filter forming liquid Ba-2 was filtered using filter paper with an absolute filtration accuracy of 10 μm (#63, manufactured by TOYO ROSHI KAISHA, Ltd.), and further filtered using a metal sintered filter with an absolute filtration accuracy of 2.5 μm (trade name: PALL Filter PMF, media code: FH025, manufactured by NIHON PALL LTD.).

[0775] (2) Fabrication of light absorption filter with substrate

[0776] The light absorption filter forming liquid Ba-2 after the filtration treatment was applied on the substrate 2 using a bar coater so that the film thickness after drying was 2.5 μm, and dried at 120° C. to produce a light absorption filter No. 103 with a substrate.

[0777] <4. Production of Light Absorption Filters No. 104 to 109, 113 to 120, 122, 123, 203, and 204 with Substrate>

[0778] Light absorption filters Nos. 104 to 109, 113 to 120, 122, 123, 203 and 204 with substrates were manufactured in the same manner as light absorption filter No. 103 with substrate, except that at least one of the type of dye or the type or the amount of light free radical generator was changed to the contents described in Table 1.

[0779] The light absorption filter No. 204 with a substrate further contains 6.7 parts by mass (15 mol in terms of the blending ratio to 1 mol of the dye) of ethyl 4-(dimethylamino)benzoate as a decolorization accelerator.

[0780] Here, Nos. 104 to 109, 113 to 120, 122 and 123 are light absorption filters of the present invention, and Nos. 203 and 204 are light absorption filters for comparison.

[0781] <5. Preparation of Light Absorption Filters No. 110 to 112 with Substrate>

[0782] Light absorption filters Nos. 110 to 112 with substrates were produced in the same manner as in the production of light absorption filter No. 107 with substrate, except that resin 3 was changed to resin 4.

[0783] Here, Nos. 110 to 112 are light absorption filters of the present invention.

[0784] [Fabrication of a light-absorbing filter having a gas-barrier layer]

[0785] Regarding light absorption filters Nos. 103 to 123, 203, and 204 with substrates, light absorption filters in which a gas barrier layer was further laminated on the light absorption filter (light absorption filters with a gas barrier layer) were prepared as described below and evaluated as described below.

[0786] (1) Preparation of substrate 3

[0787] A corona treatment device (trade name: Corona-Plus, manufactured by VETAPHONE) was used at a discharge rate of 1000 W·min / m 2 The light absorption filter with the substrate was subjected to corona treatment on its light absorption filter side under the conditions of a treatment speed of 3.2 m / min, thereby using it as substrate 3.

[0788] (2) Preparation of resin solution

[0789] The components shown below were mixed and stirred in a thermostatic chamber at 90° C. for 1 hour to dissolve Kuraray Poval AQ-4105 (trade name, manufactured by KURARAY CO., LTD., modified polyvinyl alcohol, saponification degree 98 to 99 mol%) to prepare a gas barrier layer forming liquid.

[0790]

[0791] Next, the obtained gas barrier layer forming liquid was filtered using a filter having an absolute filtration accuracy of 5 μm (trade name: Hydrophobic Fluororepore Membrane, manufactured by Millex).

[0792] (3) Lamination of gas barrier layers

[0793] The gas barrier layer forming liquid after the filtration treatment was applied to the corona treated surface of the substrate 3 using a bar coater so that the film thickness after drying was 1.1 μm, and dried at 120° C. for 60 seconds to produce a light absorption filter having a gas barrier layer.

[0794] The light absorption filter having the gas barrier layer has a structure in which a substrate 1 or a substrate 2, a light absorption filter, and a gas barrier layer are stacked in this order.

[0795] <Absorbance of light absorption filter (before ultraviolet irradiation)>

[0796] (1) Determination of absorbance

[0797] The absorbance of the light absorption filter with a substrate and the standard filter in the wavelength range of 380 to 800 nm was measured per 1 nm using a UV3150 spectrophotometer (trade name) manufactured by SHIMADZU CORPORATION. The optical path length was 2.5 μm.

[0798] A standard filter for the light absorption filter containing resins 1 and 2 was prepared in the same manner as the light absorption filter No. 101 with a substrate, except that the light absorption filter forming liquid Ba-1 containing no dye and photoradical generator was used.

[0799] A standard filter for the light absorption filter containing resin 3 was prepared in the same manner as the light absorption filter No. 103 with substrate, except that the light absorption filter forming liquid Ba-2 containing no dye and photoradical generator was used.

[0800] Regarding the standard filter relative to the light absorption filter containing resin 4, the light absorption filter forming liquid Ba-2 was used, which was changed to not contain dye and light free radical generating agent, and the resin 3 was changed to resin 4. Except for this, it was produced in the same manner as the above-mentioned light absorption filter No. 103 with a substrate.

[0801] (2) Calculation of absorbance

[0802] The absorbance value Ab of the light absorption filter with substrate at each wavelength λnm measured above is x The absorbance Ab(λ) of the light absorption filter before ultraviolet irradiation is calculated by the following formula using the absorbance value Ab0(λ) of a standard filter containing the same resin at each wavelength λnm.

[0803] Ab(λ)=Ab x (λ)-Ab0(λ)

[0804] Hereinafter, the wavelength showing the maximum absorbance Ab(λ) of the light absorption filter in the wavelength range of 400 to 700 nm is referred to as the maximum absorption wavelength (hereinafter also referred to as “λ”). max ”), the λ max The absorbance under the condition of max )”.).

[0805] <<Evaluation 1>>

[0806] The following ultraviolet irradiation test was performed on each light absorption filter to evaluate the quenching rate and the presence or absence of secondary absorption accompanying the decomposition of the pigment.

[0807] The results are collectively shown in Table 2 described later.

[0808] (Ultraviolet irradiation test)

[0809] The light absorption filter with substrate and the standard filter were irradiated with an irradiation dose of 600 mJ / cm2 from the light absorption filter side (the side opposite to substrate 1 or substrate 2) using an air-cooled metal halide lamp (manufactured by EYE GRAPHICS Co., Ltd.) at atmospheric pressure (101.33 kPa). 2 In addition, the light absorption filter with a substrate and the standard filter were placed on a hot plate set to the UV irradiation temperature described in Table 1 below, and UV irradiation was performed while heating the filter.

[0810] (Glass transition temperature (Tg) of light absorption filter)

[0811] The glass transition temperature of the light absorption filter with a substrate produced above was measured in the following manner: In addition, a portion of the light absorption filter of the light absorption filter with a substrate produced above was scraped off and used as a sample for measurement.

[0812] Using a differential scanning calorimeter X-DSC7000 (trade name, manufactured by IT Keisoku Seigyo Co., Ltd.), 20 mg of a sample for measurement was placed in a measurement pan, and the temperature was raised from 30°C to 120°C at a rate of 10°C / min in a nitrogen stream and maintained for 15 minutes, and then cooled to 30°C at -20°C / min. Then, the temperature was raised from 30°C to 250°C at a rate of 10°C / min again, and the temperature at which the baseline began to deviate from the low temperature side was defined as the glass transition temperature Tg.

[0813] <Absorbance of light absorption filter (after ultraviolet irradiation)>

[0814] The absorbance Ab(λ) of the light absorption filter after ultraviolet irradiation was calculated by the same method as described in the above <Absorbance of light absorption filter (before ultraviolet irradiation)> using the light absorption filter with substrate after ultraviolet irradiation and the standard filter.

[0815] [1. Evaluation of decolorization rate]

[0816] The absorption maximum value (Ab(λ max)) and the quenching rate was calculated by the following formula: In the present invention, a quenching rate of 20% or more is considered acceptable.

[0817] Quenching rate (%) = 100-(Ab after ultraviolet irradiation (λ max ) / Ab(λ before UV irradiation max ))×100

[0818] [2. Evaluation of the presence or absence of secondary absorption accompanying pigment decomposition]

[0819] (About dyes C-73, C-80, 7-11, 7-22, FDG007, solvent violet 13, solvent blue 35)

[0820] The absorbance at a wavelength of 450 nm (hereinafter also referred to as "Ab(450)") is calculated relative to the maximum absorption value before ultraviolet irradiation (Ab(λ max ) ratio, the presence or absence of absorption from the new coloring structure accompanying the decomposition of the pigment (secondary absorption) was evaluated. The smaller the value obtained by subtracting the ratio of the following (I) from the ratio of the following (II), the less absorption from the new coloring structure accompanying the decomposition of the pigment occurs. In the present invention, less than 8.5% is a qualified level.

[0821] (I) Ab(450) before UV irradiation / Ab(λ before UV irradiation max )×100%

[0822] (II) Ab(450) after UV irradiation / Ab(λ before UV irradiation max )×100%

[0823] (About dyes A-100 and A-102)

[0824] The absorbance at a wavelength of 650 nm (hereinafter also referred to as "Ab(650)") is calculated relative to the maximum absorption value before ultraviolet irradiation (Ab(λ max ) ratio, the presence or absence of absorption from the new coloring structure accompanying the decomposition of the pigment (secondary absorption) was evaluated. The smaller the value obtained by subtracting the ratio of the following (III) from the ratio of the following (IV), the less absorption from the new coloring structure accompanying the decomposition of the pigment occurs. In the present invention, less than 8.5% is a qualified level.

[0825] (III) Ab(650) before UV irradiation / Ab(λ max )×100%

[0826] (IV) Ab (650) after UV irradiation / Ab (λ before UV irradiation max )×100%

[0827] <<Evaluation 2>>

[0828] The light absorption filter with substrate produced as described above was subjected to the following light resistance test, but it was used in this test without irradiating ultraviolet rays after production.

[0829] The results are collectively shown in Table 2 described later.

[0830] <Lightfastness>

[0831] (Preparation of Light Resistance Evaluation Film)

[0832] A triacetyl cellulose film (trade name: FUJITAC TD80UL, manufactured by FUJIFILM Corporation) was bonded to the side of the light absorption filter with a substrate opposite to the substrate through an adhesive 1 (trade name: SK2057, manufactured by Soken Chemical & Engineering Co., Ltd.) having a thickness of about 20 μm. Next, the substrate 1 or the substrate 2 was peeled off, and a glass was bonded to the side of the light absorption filter bonded with the substrate 1 or the substrate 2 through the adhesive 1, thereby manufacturing a light resistance evaluation film.

[0833] In addition, the side opposite to the substrate of the light absorption filter with a substrate refers to the gas barrier layer when there is a gas barrier layer, and refers to the light absorption filter when there is no gas barrier layer.

[0834] (Light resistance evaluation film absorption maximum value)

[0835] The absorbance of the light resistance evaluation film in the wavelength range of 200 nm to 1000 nm was measured per 1 nm using a UV3150 spectrophotometer (trade name) manufactured by SHIMADZU CORPORATION. The absorbance difference between the absorbance of the light resistance evaluation film at each wavelength and the absorbance of a light resistance evaluation film having the same structure except for the point not containing the dye and the radical generator was calculated, and the maximum value of the absorbance difference was defined as the absorption maximum.

[0836] (Lightfastness)

[0837] The light resistance evaluation film was irradiated with light for 200 hours at 60°C and 50% relative humidity using a super xenon weathering tester SX75 (trade name) manufactured by Suga Test Instruments Co., Ltd., and the absorption maximum before and after the irradiation was measured, and the light resistance was calculated by the following formula. In the present invention, the light resistance is preferably 30% or more when there is no gas barrier layer, and the light resistance is preferably 70% or more when there is a gas barrier layer, more preferably 80% or more, and further preferably 85% or more.

[0838] [Light resistance (%)] = ([absorption maximum value after 200 hours of light irradiation] / [absorption maximum value before light irradiation]) × 100

[0839] In addition, in the light resistance evaluation film having the same structure except for the point containing no dye, no change in absorbance at the absorption maximum value of the dye for light resistance evaluation was observed before and after the above light resistance test.

[0840]

[0841]

[0842] [Table 2-1]

[0843]

[0844] [Table 2-2]

[0845]

[0846] (Notes to table)

[0847] The molar ratio relative to the dye refers to the molar amount of the radical generator blended per 1 mol of the dye.

[0848] Light absorption filter No. 204 contains 6.7 parts by mass (15 mol in terms of a blending ratio to 1 mol of the dye) of ethyl 4-(dimethylamino)benzoate as a decolorization accelerator in addition to 6.3 parts by mass of benzophenone as a radical generator.

[0849] λ max It refers to the wavelength at which the light absorption filter shows the highest absorbance Ab(λ) among the maximum absorption wavelengths in the wavelength region of 400 to 700 nm.

[0850] The amount of dye added is parts by mass relative to 100 parts by mass of the filter. "-" means that the component is not contained.

[0851] Ab(λ max ) refers to the maximum absorption wavelength λ max The absorbance value at .

[0852] Ab(450) refers to the absorbance value at a wavelength of 450 nm, and Ab(650) refers to the absorbance value at a wavelength of 650 nm.

[0853] Ab(450) relative to Ab(λ max), the column before ultraviolet irradiation refers to the ratio calculated using Ab(450) before ultraviolet irradiation, and the column after ultraviolet irradiation refers to the ratio calculated using Ab(450) after ultraviolet irradiation.

[0854] Moreover, Ab(650) is relative to Ab(λ max ), the column before ultraviolet irradiation refers to the ratio calculated using Ab(650) before ultraviolet irradiation, and the column after ultraviolet irradiation refers to the ratio calculated using Ab(650) after ultraviolet irradiation.

[0855] The UV irradiation temperature refers to the set temperature of the hot plate in the above-mentioned ultraviolet irradiation test.

[0856] The following results are known from the results of Tables 1 and 2 above.

[0857] The light absorption filter No. 201 of the comparative example contains a porphyrazine pigment as a comparative dye. In the light absorption filter No. 201 of the comparative example, if the decolorization rate due to ultraviolet irradiation is 6%, there is almost no decolorization. The light absorption filter No. 202 of the comparative example contains an anthraquinone pigment as a comparative dye. It is known that the decolorization rate due to ultraviolet irradiation in the light absorption filter No. 202 of the comparative example is 25%, and Ab(450) / Ab(λ max ) increased from 8.9% to 17.8%, and absorption from the new colored structure occurred along with the decomposition of the pigment.

[0858] Comparative Example light absorption filter No. 203 contains an anthraquinone-based dye as a comparative dye, and Comparative Example light absorption filter No. 204 contains an anthraquinone-based dye as a comparative dye and also contains an amine-based free radical accelerator. It is known that the decolorization rates of these comparative example light absorption filters No. 203 and No. 204 are 5% and 2% respectively by ultraviolet irradiation, and that they are almost not decolorized, and that Ab(450) / Ab(λ max ) increased from 0% to 9.5% and 9.8% respectively, indicating that absorption from the new colored structure occurred as the pigment decomposed.

[0859] On the other hand, the light absorption filters No. 101 to 123 of the present invention containing the squarylium dye represented by the general formula (1) or the benzylidene dye or cinnamylidene dye represented by the general formula (V) and the radical generator are superior to the light absorption filters of the comparative examples in terms of quenching rate by ultraviolet irradiation, and there is almost no absorption from the new coloring structure accompanying the decomposition of the dye to cause decolorization, and are superior in decolorization property. In particular, as the temperature during ultraviolet irradiation is set to a temperature higher than the glass transition temperature of the light absorption filter, the decolorization rate by ultraviolet irradiation is further improved (reference: comparison of No. 107 to 109, comparison of No. 110 to 112). Furthermore, when using a benzophenone compound substituted with an alkoxy group, a more excellent decolorization rate is shown compared to an unsubstituted benzophenone compound even when the molar ratio of the radical generator to the dye is small (reference: No. 103 to 107, 110, 113 to 117).

[0860] Furthermore, the light absorption filters No. 103 to 123 having a gas barrier layer in the light absorption filter of the present invention have excellent light resistance in addition to excellent decolorization. Among them, the light absorption filters No. 103 to 120, 122 and 123 of the present invention containing a benzophenone compound as a hydrogen abstraction type light radical generator show better light resistance than the light absorption filter No. 121 of the present invention containing an α-aminoalkyl phenone compound as an intramolecular cleavage type light radical generator. Among them, the light absorption filter of the present invention containing a benzophenone compound having an alkoxy group at the 4-position and the 4'-position shows the same degree of light resistance as the light absorption filter of the present invention containing an unsubstituted benzophenone compound, and achieves a better quenching rate (reference: 113 to 117 relative to No. 103).

[0861] Thus, the light absorption filter of the present invention containing the squarylium dye represented by the general formula (1) or the benzylidene dye represented by the general formula (V) and a free radical generator can show an excellent quenching rate when subjected to ultraviolet irradiation, and also, almost no secondary absorption accompanying the decomposition of the dye due to ultraviolet irradiation occurs, thereby showing excellent decolorization properties.

[0862] Furthermore, the light absorption filter of the present invention comprising a cinnamylidene dye represented by the general formula (V) and a radical generator can show an excellent quenching rate when irradiated with ultraviolet rays, similarly to the light absorption filter comprising a squarylium dye represented by the general formula (1) or a benzylidene dye represented by the general formula (V) and a radical generator, and also exhibits excellent decolorization properties with almost no secondary absorption accompanying the decomposition of the dye due to ultraviolet irradiation.

[0863] The present invention has been described together with its embodiments, but unless otherwise indicated, we do not intend our invention to be limited to any of the details described and should be broadly construed without departing from the spirit and scope of the invention as set forth in the appended claims.

[0864] This application claims priority based on Japanese Patent Application No. 2019-236078 filed in Japan on December 26, 2019, Japanese Patent Application No. 2020-144790 filed in Japan on August 28, 2020, and Japanese Patent Application No. 2020-217111 filed in Japan on December 25, 2020, which are hereby referenced and incorporated into this specification as a part of the description of this specification.

[0865] Explanation of symbols

[0866] 1-upper polarizer, 2-direction of absorption axis of upper polarizer, 3-upper electrode substrate of liquid crystal unit, 4-orientation control direction of upper substrate, 5-liquid crystal layer, 6-lower electrode substrate of liquid crystal unit, 7-orientation control direction of lower substrate, 8-lower polarizer, 9-direction of absorption axis of lower polarizer, B-backlight unit, 10-liquid crystal display device.

Claims

1. A light absorption filter having a gas barrier layer on at least one side, comprising a resin, a dye having a main absorption wavelength band at a wavelength of 400 to 700 nm, and a compound that generates free radicals when irradiated with ultraviolet rays, wherein the dye comprises a squarylium dye represented by the following general formula (1): [Chemical formula 1] In the above formula, A and B each independently represent an aryl group which may have a substituent, a heterocyclic group which may have a substituent, or -CH=G, and G represents a heterocyclic group which may have a substituent.

2. A light absorption filter comprising a resin, a dye having a main absorption wavelength band at a wavelength of 400 to 700 nm, and a compound that generates free radicals when irradiated with ultraviolet rays, wherein the dye comprises a squarylium dye represented by the following general formula (1), and the light absorption filter decolorizes the dye by chemical changes caused by irradiation with light. [Chemical formula 1] In the above formula, A and B each independently represent an aryl group which may have a substituent, a heterocyclic group which may have a substituent, or -CH=G, and G represents a heterocyclic group which may have a substituent.

3. The light absorption filter according to claim 1 or 2, wherein: The compound that generates free radicals upon ultraviolet irradiation is a compound that generates free radicals by intramolecular cleavage.

4. The light absorption filter according to claim 1 or 2, wherein: The compound that generates free radicals by ultraviolet irradiation is a compound that generates free radicals by removing a hydrogen atom from a nearby compound.

5. The light absorption filter according to claim 4, wherein The compound that generates a free radical by removing a hydrogen atom from a nearby compound is a benzophenone compound substituted with an alkoxy group.

6. The light absorption filter according to claim 1, wherein The light absorption filter causes the dye to undergo a chemical change and decolorize by irradiation with light.

7. The light absorption filter according to claim 1 or 2, wherein: When the light absorption filter is used, the gas barrier layer is provided at least on the surface in contact with air.

8. The light absorption filter according to claim 1 or 2, wherein: The gas barrier layer contains a crystalline resin, has a thickness of 0.1 μm to 10 μm, and has an oxygen permeability of 60 cc / m 2 ·day·atm or less.

9. The light absorption filter according to claim 8, wherein The crystalline resin includes a modified polyvinyl alcohol having a saponification degree of 80.0 mol % or more and 99.99 mol % or less. 10 . An optical filter obtained by subjecting the light absorption filter according to claim 1 to mask exposure by ultraviolet irradiation. 11 . An organic electroluminescent display device or a liquid crystal display device, comprising the filter according to claim 10 .

12. The organic electroluminescent display device or liquid crystal display device according to claim 11, wherein: A layer that blocks light absorption of the compound that generates radicals when irradiated with ultraviolet rays is provided on the viewer's side relative to the optical filter.

13. A method for manufacturing an optical filter, comprising the following steps: The light absorption filter according to any one of claims 1 to 9 is irradiated with ultraviolet rays to perform mask exposure.

14. The method for manufacturing an optical filter according to claim 13, wherein: The ultraviolet ray irradiation is performed under heating conditions.

15. The method for manufacturing an optical filter according to claim 14, wherein: The heating temperature is a temperature exceeding the glass transition temperature of the light absorption filter.

Images