Stacked body and organic electroluminescent display device

Abstract

This invention provides a laminate and an organic electroluminescent display device. The laminate includes a wavelength-selective absorption layer and a gas barrier layer directly disposed on at least one side of the wavelength-selective absorption layer. The wavelength-selective absorption layer contains a resin, a dye comprising at least one of four specific dyes A to D, and an anti-fading agent for the dye. The gas barrier layer contains a crystalline resin, has a thickness of 0.1 μm to 10 μm, and an oxygen permeability of 60 cc / m². 2 •day•atm or less.

Description

[0001] This application is a divisional application of application number "202080068481.3", filed on September 30, 2020, entitled "Laminated Structure and Organic Electroluminescent Display Device". Technical Field

[0002] This invention relates to a laminate and an organic electroluminescent display device. Background Technology

[0003] Organic light-emitting diode (OLED) display devices are devices that display images using the self-emissive properties of OLED elements. Therefore, compared to various display devices such as liquid crystal displays and plasma displays, they offer advantages such as 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 a next-generation display device, focusing on flexibility.

[0004] On the other hand, when OLED display devices are used outdoors or in environments with strong external light, external light is reflected in the metal electrodes and other components of the OLED display device, resulting in display defects such as reduced contrast. A known technique for suppressing external light reflection is to use a circular polarizer with an optical anisotropy layer such as a λ / 4 retardation film; however, this technique introduces a problem of reduced brightness.

[0005] In recent years, research has been conducted on techniques that suppress external light reflection and brightness reduction by setting up a light-absorbing layer capable of absorbing external light.

[0006] For example, in Patent Document 1, a light-absorbing layer disposed between the light-emitting layer and the anti-reflective film in a color filter for an OLED of the white light source type is described as containing carbon black pigment and dye (pigment), and having a transmittance of 15% to 50% and a haze value of 1.0 or less in the wavelength region of 400 nm to 700 nm.

[0007] Furthermore, in Patent Document 2, a light absorption filter for an OLED display device is described as having an absorption spectrum that has a negative correlation with the emitted spectrum of the spectrum of each pixel that synthesizes multiple colors. However, no specific description is made of how to achieve the target absorption spectrum.

[0008] Existing technical documents Patent documents Patent Document 1: Japanese Patent Application Publication No. 2017-203810 Patent Document 2: Japanese Patent Application Publication No. 2014-132522 Patent Document 3: International Publication No. 2017 / 014272 Summary of the Invention

[0009] The technical problem to be solved by the invention According to the results of the research conducted by the inventors, it is known that in a light absorption layer (light absorption filter) as described in Patent Document 1, the color tone of the image of the OLED display device changes depending on the pigments or other colorants contained in the light absorption filter, and there is room for improvement in suppressing the color tone change.

[0010] Further research by the inventors has revealed that a wavelength-selective absorption filter containing four dyes with main absorption wavelength bands in specific wavelength regions, and whose absorbance Ab(λ) at wavelength λnm satisfies a specific relationship, can simultaneously suppress external light reflection and brightness reduction required for use in OLED display devices, and can also effectively suppress the influence on the original color tone of the displayed image.

[0011] However, when the aforementioned wavelength-selective absorption filter is used as an anti-reflection mechanism in an OLED display device to replace a circular polarizer, it results in a structure without a polarizer on the outside of the wavelength-selective absorption filter. Therefore, the dye in the wavelength-selective absorption filter is required to have high lightfastness.

[0012] For example, Patent Document 3 describes a color correction filter used in a liquid crystal display device that uses a white LED (Light Emitting Diode) as a light source. The filter contains two pigments and a resin that have maximum absorption in specific wavelength regions. Furthermore, it describes the provision of a barrier layer to suppress the decrease in pigment absorption intensity caused by light irradiation. Specifically, it describes a filter containing SiO₂, an inorganic material. x or SiN x Color correction filters with a barrier layer. Among materials with barrier properties, inorganic materials have a lower oxygen permeability and lower moisture absorption compared to organic materials, thus exhibiting superior barrier properties.

[0013] On the other hand, from the perspective of industrial productivity, barrier layers containing inorganic materials are unsuitable. Specifically, barrier layers made of inorganic materials are obtained through layering inorganic materials using methods such as plasma-enhanced chemical vapor deposition (CVD), sputtering, or evaporation. Therefore, compared to organic materials, which can be fabricated through coating or thin-film bonding, the preparation process is more complex and costly. Furthermore, production efficiency is lower. For example, when forming a barrier layer containing inorganic materials using sputtering, it takes approximately 100 to 1000 times longer to achieve the same thickness as a barrier layer made of organic materials obtained through coating, making it unsuitable for mass production.

[0014] Therefore, the objective of this invention is to provide a laminate and an organic electroluminescent display device including the laminate, wherein the laminate has a barrier layer on a wavelength selective absorption layer, and wherein the laminate exhibits excellent light resistance even when used as an anti-reflective mechanism in an OLED display device instead of a circular polarizer, and also exhibits excellent productivity.

[0015] means for solving technical problems In view of the above-mentioned issues, the inventors, through in-depth research, discovered that simply combining a wavelength-selective absorption layer containing dyes and dye-resistant anti-fading agents with a gas-barrier layer containing an organic material with gas-barrier properties does not necessarily guarantee the desired lightfastness. However, by setting the gas-barrier layer to a structure containing a crystalline resin and having a specific thickness, excellent lightfastness can be obtained. This invention was completed based on further repeated research based on this insight.

[0016] That is, the above-mentioned problem was solved in the following way.

[0017] <1> A laminate includes a wavelength-selective absorption layer and a gas barrier layer disposed directly on at least one side of the wavelength-selective absorption layer, wherein the wavelength-selective absorption layer contains a resin, a dye comprising at least one of dyes A to D, and an anti-fading agent for the dye; wherein... The aforementioned 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.

[0018] Dye A: A dye with a main absorption wavelength band in the range of 390–435 nm. Dye B: A dye with a main absorption wavelength band in the range of 480–520 nm. Dye C: A dye with a main absorption wavelength band in the wavelength range of 580–620 nm. Dye D: A dye with a main absorption wavelength band in the range of 680–780 nm. <2> According to the laminate described in <1>, the crystallinity of the crystalline resin contained in the gas barrier layer is 25% or more.

[0019] <3> According to the laminate described in <1> or <2>, the oxygen permeability of the aforementioned gas barrier layer is 0.001 cc / m 2 •day•atm or more and 60cc / m 2 •day•atm or less.

[0020] <4> The laminate according to any one of <1> to <3>, wherein at least one of the dyes B and C is a squaric acid cyanine pigment represented by the following general formula (1).

[0021] [Chemical Formula 1] In the above formula, A and B independently represent aryl groups that can have substituents, heterocyclic groups that can have substituents, or -CH=G. G represents heterocyclic groups that can have substituents.

[0022] <5> The laminate according to any one of <1> to <4>, wherein the dye A is a pigment represented by the following general formula (A1).

[0023] [Chemical Formula 2] In the above formula, R 1 and R 2 Each can independently represent an alkyl or aryl group, R 3 ~R 6 Each independently represents a hydrogen atom or a substituent, R 5 With R 6 They can bond together to form a 6-membered ring.

[0024] <6> The laminate according to any one of <1> to <5>, wherein the dye D is at least one of the pigment represented by the following general formula (D1) and the pigment represented by the following general formula (1).

[0025] [Chemical Formula 3] In the above formula, R 1A and R 2A Each can independently represent an alkyl, aryl, or heteroaryl group, R 4A and R 5A Each independently represents a heteroaryl group, R 3A and R 6A Each substituent is represented independently. X 1 and X 2 Each is represented independently -BR 21a R 22a R 21a and R 22a Substituents are represented independently, R 21a and R 22a They can bond together to form a ring.

[0026] [Chemical Formula 4] In the above formula, A and B independently represent aryl groups that can have substituents, heterocyclic groups that can have substituents, or -CH=G. G represents heterocyclic groups that can have substituents.

[0027] <7> The laminate according to any one of <1> to <6>, wherein the aforementioned anti-fading agent is represented by the following general formula (IV).

[0028] [Chemical Formula 5] In the above formula, R 10 Each can independently represent alkyl, alkenyl, aryl, heterocyclic, or R. 18 CO-, R 19 SO2- or R 20 The group represented by NHCO-, R 18 R 19 and R 20 Each can independently represent an alkyl, alkenyl, aryl, or heterocyclic group. R 11 and R 12 Each independently represents a hydrogen atom, halogen atom, alkyl group, alkenyl group, alkoxy group, or alkenyloxy group, R 13 ~R 17 Each can independently represent a hydrogen atom, alkyl group, alkenyl group, or aryl group.

[0029] <8> The laminate according to any one of <1> to <7>, wherein the resin in the wavelength selective absorption layer comprises polystyrene resin.

[0030] <9> The laminate according to any one of <1> to <8>, wherein the resin in the wavelength selective absorption layer comprises a cyclic polyolefin resin.

[0031] <10> The laminate according to any one of <1> to <9>, wherein the wavelength-selective absorption layer comprises all four dyes A to D.

[0032] <11> The laminate according to any one of <1> to <10>, wherein the laminate comprises an ultraviolet absorbing layer and at least one layer selected from an adhesive layer and a bonding agent layer, the ultraviolet absorbing layer being disposed on the side opposite to the wavelength selective absorbing layer relative to the gas barrier layer, and the refractive index difference between adjacent layers in the laminate is 0.05 or less.

[0033] <12> An organic electroluminescent display device comprising any one of the following layers: <1> to <11>.

[0034] In this invention, when multiple substituents or linking groups (hereinafter referred to as substituents, etc.) represented by specific symbols or formulas are present, or when multiple substituents, etc. are specified simultaneously, each substituent, etc., may be identical or different from each other unless otherwise specified. The same applies to the number of substituents, etc. Furthermore, when multiple substituents, etc., are close together (especially adjacent), they may link together to form a ring unless otherwise specified. Furthermore, unless otherwise specified, rings such as alicyclic rings, aromatic rings, and heterocyclic rings may further fuse to form fused rings.

[0035] In this invention, unless otherwise specified, the components constituting the wavelength-selective absorption layer (dyes, resins, anti-fading agents for dyes, and other components, etc.) may each contain one type or two or more types in the wavelength-selective absorption layer. Similarly, unless otherwise specified, the components constituting the gas barrier layer (crystalline resins, etc.) may each contain one type or two or more types in the gas barrier layer.

[0036] In this invention, unless otherwise specified, the double bond can be either E-type or Z-type in the presence of E-type or Z-type in the molecule, or a mixture thereof.

[0037] In this invention, the designation of a compound (including complexes) includes not only the compound itself but also its salts and ions. Furthermore, it refers to a substance obtained by modifying a portion of its structure without impairing the effects of this invention. Moreover, compounds without specified substitution or non-substitution refer to compounds that may have any substituents without impairing the effects of this invention. The same applies to substituents and linking groups.

[0038] Furthermore, the numerical range represented by “~” in this invention refers to the range including the values ​​recorded before and after “~” as the lower limit and upper limit values.

[0039] In this invention, the composition includes not only mixtures with constant component concentrations (where each component is uniformly dispersed), but also mixtures with component concentrations varying within a range that does not impair the target function.

[0040] In this invention, having a main absorption wavelength band in the wavelength range of XX to YY nm means that the wavelength exhibiting maximum absorption (i.e., the maximum absorption wavelength) exists in the wavelength range of XX to YY nm. Therefore, if the maximum absorption wavelength is within the aforementioned wavelength range, the entire absorption band including that wavelength can be within the aforementioned wavelength range or can extend outside of it. Furthermore, when multiple maximum absorption wavelengths exist, it is sufficient that the maximum absorption wavelength exhibiting the maximum absorbance is within the aforementioned wavelength range. That is, maximum absorption wavelengths other than the maximum absorption wavelength exhibiting the maximum absorbance can exist anywhere within or outside the aforementioned wavelength range of XX to YY nm.

[0041] Invention Effects The laminate of the present invention has a gas barrier layer on the wavelength selective absorption layer. In this laminate, even when used as an anti-reflection mechanism in an OLED display device to replace a circular polarizer, it can exhibit excellent light resistance and also has excellent productivity.

[0042] Furthermore, in the organic electroluminescent display device of the present invention, the anti-reflective mechanism of the OLED display device includes the above-mentioned laminate instead of the circular polarizer, and the wavelength selective absorption layer provided by the laminate can exhibit excellent light resistance. Attached Figure Description

[0043] Figure 1 This is a schematic cross-sectional view illustrating an example of the laminate of the present invention.

[0044] Figure 2 This is a schematic longitudinal cross-sectional view of the structure of an OLED display device assumed for conducting a simulation experiment of external light reflection in the reference example. Detailed Implementation

[0045] [Layered Body] The laminate of the present invention comprises a wavelength selective absorption layer containing resin, dye and dye anti-fading agent and a gas barrier layer disposed directly on at least one surface of the wavelength selective absorption layer.

[0046] In the laminate of the present invention, the dye contained in the wavelength selective absorption layer is at least one of dyes A to D described later, which have a main absorption wavelength band in different wavelength regions.

[0047] The gas barrier layer in the laminate of the present invention contains a crystalline resin, has a thickness of 0.1 μm to 10 μm, and has an oxygen permeability of 60 cc / m³. 2 •day•atm or less.

[0048] In this invention, the main absorption wavelength band of the dye refers to the main absorption wavelength band of the dye measured in a laminate including a wavelength-selective absorption layer and a gas barrier layer. Specifically, in the embodiments described later, the measurement is performed in a laminate including a wavelength-selective absorption layer and a gas barrier layer, according to the conditions described in the section on the maximum absorption value of lightfastness evaluation film.

[0049] By providing the aforementioned gas barrier layer, the laminate of the present invention can improve the lightfastness of the dye contained in the wavelength-selective absorption layer. Although this reason is inferred, it is considered as follows.

[0050] The dye contained in the wavelength-selective absorption layer of the laminate of the present invention sometimes experiences a decrease in absorbance upon light irradiation. The main reason for this phenomenon is the decomposition of dye molecules by singlet oxygen generated from the transfer of excitation energy from light irradiation to oxygen molecules. The laminate of the present invention, by containing a dye and an anti-fading agent for the dye in the wavelength-selective absorption layer, can suppress dye decomposition caused by singlet oxygen as described above. Furthermore, by providing the aforementioned gas barrier layer at least near the air interface in the wavelength-selective absorption layer, the permeation of oxygen molecules (oxygen) can be suppressed, thereby inhibiting the decomposition of the dye in the wavelength-selective absorption layer.

[0051] Furthermore, in addition to the structure described above, the laminate of the present invention also has a gas barrier layer directly on at least one surface of the wavelength-selective absorption layer. This gas barrier layer contains a crystalline resin and exhibits a specific oxygen permeability. The laminate of the present invention with this structure can suppress the permeation of oxygen molecules at a desired level and also has excellent productivity. However, if the gas barrier layer becomes too thick, the amount of the aforementioned anti-fading agent transferred to the amorphous portion of the crystalline resin increases. As a result, while the oxygen permeability of the gas barrier layer can be reduced by thickening it, the desired improvement in lightfastness cannot be obtained, or conversely, the improvement in lightfastness may be reduced. It is believed that the laminate of the present invention, by setting a gas barrier layer of a specific thickness, can achieve an excellent level of suppression of the reduction in lightfastness based on the anti-fading agent and the gas barrier layer.

[0052] <<Wavelength Selective Absorption Layer>> The wavelength selective absorption layer in the laminate of the present invention contains a resin, a dye comprising at least one of the following dyes A to D having a main absorption wavelength band in different wavelength regions, and an anti-fading agent for the dye.

[0053] Dye A: A dye with a main absorption wavelength band in the range of 390–435 nm. Dye B: A dye with a main absorption wavelength band in the range of 480–520 nm. Dye C: A dye with a main absorption wavelength band in the wavelength range of 580–620 nm. Dye D: A dye with a main absorption wavelength band in the range of 680–780 nm. In the aforementioned wavelength-selective absorption layer, the "dye" is dispersed (preferably dissolved) in the aforementioned resin, making the wavelength-selective absorption layer a layer that displays a specific absorption spectrum originating from the dye. Furthermore, the aforementioned "dye anti-fading agent" is dispersed (preferably dissolved) in the resin to capture free radicals such as singlet oxygen, or to replace the dye in oxidation, thereby effectively inhibiting the fading of the dye.

[0054] <Dyes> The wavelength-selective absorption layer is a layer containing at least one of the dyes A, B, C and D.

[0055] Furthermore, the wavelength-selective absorption layer may contain one or more dyes A. Similarly, the wavelength-selective absorption layer may contain one or more dyes B to D.

[0056] The wavelength-selective absorption layer described above can also contain dyes other than dyes A to D.

[0057] Regarding the morphology of the wavelength-selective absorption layer in the laminate of the present invention, it is acceptable as long as the dye in the wavelength-selective absorption layer can display an absorption spectrum. Preferably, it is acceptable as long as it can simultaneously suppress external light reflection and suppress brightness reduction, and more preferably, it is acceptable as long as it does not easily affect the original hue of the displayed image. As one morphology of the aforementioned wavelength-selective absorption layer, at least one of dyes A to D can be dispersed (preferably dissolved) in the resin. This dispersion can be random, regular, or any other type.

[0058] Regarding the dyes A to D, the wavelength-selective absorption layer has main absorption wavelength bands at 390–435 nm, 480–520 nm, 580–620 nm, and 680–780 nm, respectively, in wavelength regions other than B (Blue, 460 nm), G (Green, 520 nm), and R (Red, 620 nm), which are used as light sources in OLED display devices. Therefore, by containing at least one of these dyes A to D, the wavelength-selective absorption layer can suppress the reflection of external light without impairing the color reproduction region of the light emitted from the OLED.

[0059] In particular, as a wavelength selective absorption layer that displays an absorption spectrum that has a negative correlation with the emission spectrum of the light source, from the viewpoint of bringing out the original color tone of the image of the OLED display device, the wavelength selective absorption layer contains dyes A, B, C and D, preferably a combination of at least two, more preferably a combination of at least three, and even more preferably all four.

[0060] As described above, when the wavelength-selective absorption layer contains two or more dyes A to D, the lightfastness can sometimes decrease due to chain transfer of free radicals generated during dye decomposition. To address this problem, the laminate of the present invention, by providing the specific gas barrier layer described later, exhibits excellent lightfastness that exceeds the decrease in lightfastness associated with dye mixing.

[0061] From the viewpoint of better preserving the original color tone of the image in the OLED display device, the wavelength selective absorption layer preferably contains all four dyes A to D and satisfies the following relationships (I) to (VI). In addition to suppressing external light reflection and brightness reduction, the wavelength selective absorption layer with this structure can also maintain the original color tone of the image in the OLED display device at a superior level.

[0062] Relation (I) Ab(450) / Ab(430) < 1.0 Relation (II) Ab(450) / Ab(500) < 1.0 Relation (III) Ab(540) / Ab(500) < 1.0 The relation (IV) Ab(540) / Ab(600) < 1.0 The relation (V) Ab(630) / Ab(600) ≤ 0.5 Relationship (VI) Ab(630) / Ab(700) < 1.0 Furthermore, in the embodiments described later, the absorbance ratios recorded in the above formulas (I) to (VI) are values ​​calculated using the absorbance Ab(λ) at a wavelength of λnm, which is measured in a laminated state including a wavelength-selective absorption layer and a gas barrier layer according to the conditions described in the absorption maximum value of the lightfastness evaluation film.

[0063] Within the range defined by the above relations (I) to (VI), the preferred range is as follows.

[0064] The upper limit of Ab(450) / Ab(430) in relation (I) is preferably 0.90 or less, more preferably 0.85 or less, even more preferably 0.80 or less, and especially preferably 0.60 or less. There is no particular restriction on the lower limit, but it is actually 0.05 or more, preferably 0.10 or more, and more preferably 0.20 or more.

[0065] The upper limit of Ab(450) / Ab(500) in relation (II) is preferably 0.90 or less, more preferably 0.80 or less, further preferably 0.75 or less, especially preferably 0.65 or less, wherein 0.60 or less is preferred, and 0.50 or less is most preferred. There is no particular limitation on the lower limit, but in practice it is 0.05 or more, preferably 0.10 or more, and more preferably 0.20 or more.

[0066] The upper limit of Ab(540) / Ab(500) in relation (III) is preferably 0.90 or less, more preferably 0.80 or less, further preferably 0.75 or less, especially preferably 0.70 or less, and most preferably 0.50 or less, and most preferably 0.20 or less. There is no particular limitation on the lower limit, but in practice it is 0.01 or more, preferably 0.02 or more, and more preferably 0.05 or more.

[0067] The upper limit of Ab(540) / Ab(600) in relation (IV) is preferably 0.90 or less, more preferably 0.85 or less, even more preferably 0.80 or less, particularly preferably 0.70 or less, and most preferably 0.50 or less, and most preferably 0.25 or less. There is no particular limitation on the lower limit, but in practice it is 0.01 or more, preferably 0.02 or more, and more preferably 0.05 or more.

[0068] The upper limit of Ab(630) / Ab(600) in the relation (V) is preferably 0.40 or less, more preferably 0.30 or less, even more preferably 0.20 or less, and especially preferably 0.15 or less. There is no particular restriction on the lower limit, but in practice it is 0.01 or more, preferably 0.02 or more, and more preferably 0.05 or more.

[0069] The upper limit of Ab(630) / Ab(700) in relation (VI) is preferably 0.95 or less, more preferably 0.90 or less, even more preferably 0.80 or less, and especially preferably 0.75 or less. There is no particular limitation on the lower limit, but it is actually 0.01 or more, preferably 0.03 or more, more preferably 0.10 or more, even more preferably 0.40 or more, and especially preferably 0.50 or more.

[0070] By satisfying the above-mentioned preferred ranges through equations (I) to (VI), the color tone variation caused by the laminate of the present invention can be reduced, and the original color tone of the image in the OLED display device can be better utilized. Therefore, dyes A to D preferably have clear absorption waveforms in the main absorption wavelength band.

[0071] For example, when dye B is a squaric acid cyanine pigment represented by general formula (1) described later, in the laminate of the present invention, relations (II) and (III) can satisfy the above-mentioned preferred range, and can maintain the original color tone of the image of the OLED display device at a better level. This is believed to be because the absorbance is low at wavelengths near the maximum absorption (534 nm) of the green visual material of the human cone.

[0072] Furthermore, when dye C is a squaric acid cyanine pigment represented by the general formula (1) described later, in the laminate of the present invention, formulas (I) to (IV) can satisfy the above-mentioned preferred range, and the original color tone of the image of the OLED display device can be maintained at a better level. Similarly, this is believed to be because the absorbance at wavelengths near the maximum absorption (534 nm) of the green visual material of the human cone is low.

[0073] In particular, satisfying the relation (V) is important in that it does not affect the original color tone of the image on the OLED display device. It is believed that the relation (V) can suppress a The changes resulted in the ability to maintain the aforementioned hue at an excellent level.

[0074] (Dye A) Regarding dye A, there are no particular restrictions as long as it has a main absorption wavelength band in the wavelength range of 390–435 nm in the laminate, and various dyes can be used.

[0075] From the viewpoint that the absorption waveform in the main absorption wavelength band is clear, the dye A described above is preferably represented by the following general formula (A1).

[0076] [Chemical Formula 6] In formula (A1), R 1 and R 2 Each can independently represent an alkyl or aryl group, R 3 ~R 6 Each independently represents a hydrogen atom or a substituent, R 5 With R 6 They can bond together to form a 6-membered ring.

[0077] As can be used as R 1 and R 2The alkyl group can be any one of unsubstituted alkyl groups and substituted alkyl groups, and can be either straight-chain or branched, or can have a cyclic structure.

[0078] Examples of unsubstituted alkyl groups include methyl, ethyl, n-propyl, isopropyl, and cyclohexyl. The number of carbon atoms in the unsubstituted alkyl group is preferably 1 to 12, more preferably 1 to 6.

[0079] Substituents that can be used as the aforementioned substituted alkyl groups include, for example, those included in substituent group A below.

[0080] (Substituted base set A) Halogen atom, alkyl, cycloalkyl, aralkyl, alkenyl, alkynyl, aryl, heteroatom-containing cycloyl group, cyano, hydroxyl, nitro, carboxyl (can be in salt form), alkoxy, aryloxy, siloxy, heterocyclic, acyloxy, carbamoyloxy, sulfonyloxy, alkoxycarbonyloxy, alkoxycarbonyloxy, amino (besides -NH2, also includes -NR) a 2 represents the substituted amino group. R a Each of these groups independently represents a hydrogen atom, alkyl group, aryl group, or heteroaryl group. At least one R group is present. a It can be alkyl, aryl, or heteroaryl. Acylamino, aminocarbonylamino, alkylcarbonylamino, alkylcarbonylamino, aryloxycarbonylamino, aminosulfonylamino, alkylsulfonylamino, arylsulfonylamino, sulfonamide, mercapto, alkylthio, arylthio, heterocyclic thio, aminosulfonyl, sulfonyl (may be in salt form), alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, acyl, aryloxycarbonyl, alkoxycarbonyl, carbamoyl, imide, phosphinyl, oxophosphinyl, oxophosphinyloxy, oxophosphinylamino, and silyl, and at least two of these linked monovalent groups. Among the substituent groups A above, preferred examples of substituents that the substituted alkyl group may have include halogen atoms, aryl groups, alkoxy groups, acyl groups, and hydroxyl groups.

[0081] The total number of carbon atoms in the aforementioned substituted alkyl groups is preferably 1 to 12. Examples include benzyl, hydroxybenzyl, and methoxyethyl.

[0082] The total carbon number of a substituted alkyl group refers to the total number of carbon atoms in the substituted alkyl group as a whole, including all the substituents that the substituted alkyl group may have. The same meaning will be used for other groups below.

[0083] Additionally, in R 1 and R 2 When both refer to alkyl groups, the alkyl groups can be the same or different.

[0084] Can be used as R 1 and R2 The aryl group can be either an unsubstituted aryl group or a substituted aryl group with a substituent.

[0085] As the unsubstituted aryl group mentioned above, an aryl group having 6 to 12 carbon atoms is preferred; for example, phenyl can be cited.

[0086] As a substituent that can be used to replace the aryl group, examples include the substituents included in the substituent group A.

[0087] In the above substituent group A, preferred examples of substituents that may be present in the substituted aryl group include halogen atoms (e.g., chlorine, bromine, and iodine atoms), hydroxyl groups, carboxyl groups, sulfonamide groups, and amino groups (preferably composed of -NR). a 2 represents the substituted amino group. R a Each can independently represent a hydrogen atom or an alkyl group. At least one R... a It is an alkyl group. Preferably, it has 1 to 4 carbon atoms. alkyl (preferably an alkyl group with 1 to 4 carbon atoms; for example, methyl, ethyl, n-propyl and isopropyl), alkoxy (preferably an alkoxy group with 1 to 4 carbon atoms; for example, methoxy, ethoxy, n-propoxy and isopropoxy), alkoxycarbonyl (preferably an alkoxycarbonyl group with 2 to 5 carbon atoms; for example, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl and isopropoxycarbonyl), and sulfonyloxy, and at least two of these groups forming a monovalent group.

[0088] As the aforementioned substituted aryl group, an aryl group with a total carbon number of 6 to 18 is preferred.

[0089] Examples include 4-chlorophenyl, 2,5-dichlorophenyl, hydroxyphenyl, 4-carboxyphenyl, 3,5-dicarboxyphenyl, 4-methanesulfonamide phenyl, 4-methylphenyl, 4-methoxyphenyl, 4-(2-hydroxyethoxy)phenyl, N,N-dimethylaminophenyl, 4-(N-carboxymethyl-N-ethylamino)phenyl, 4-ethoxycarbonylphenyl, and 4-methanesulfonyloxyphenyl.

[0090] Additionally, in R 1 and R 2 When both groups represent aryl groups, the aryl groups can be the same or different.

[0091] As can be used as R 3 R 4 R 5 and R 6 Substituents, for example, can be listed as those included in the substituent group A above.

[0092] In the above substituent group A, R 3 R 5 and R 6Alkyl or aryl groups are preferred. That is, as R 3 R 5 and R 6 Each of them is preferably a hydrogen atom, alkyl group, or aryl group.

[0093] Furthermore, in the aforementioned substituent group A, R 4 Alkyl or aryl groups are preferred. That is, as R 4 Preferably, it is a hydrogen atom, alkyl group, or aryl group.

[0094] As can be used as R 3 R 5 and R 6 The alkyl group can be any one of unsubstituted alkyl groups and substituted alkyl groups, and can be either straight-chain or branched, or can have a cyclic structure.

[0095] As can be used as the above R 3 R 5 and R 6 Unsubstituted alkyl groups, for example, methyl, ethyl, n-propyl, and isopropyl, can be used as the aforementioned R. 3 R 5 and R 6 The number of carbon atoms in the unsubstituted alkyl group is preferably 1 to 8, more preferably 1 to 4.

[0096] As mentioned above, R 3 R 5 and R 6 The substituted alkyl group may have substituents, for example, the substituents included in the substituent group A above.

[0097] As mentioned above, R 3 R 5 and R 6 Preferred examples of substituents that the substituted alkyl group may have include aryl (preferably phenyl), carboxyl and hydroxyl groups.

[0098] Can be used as the above R 3 R 5 and R 6 The total number of carbon atoms in the substituted alkyl group is preferably 1 to 8. Examples include benzyl, carboxymethyl, and hydroxymethyl.

[0099] Additionally, in R 3 R 5 and R 6 When both refer to alkyl groups, the alkyl groups can be the same or different.

[0100] As can be used as the above R 3 R 5 and R 6The aryl group can be either an unsubstituted aryl group or a substituted aryl group.

[0101] As can be used as the above R 3 R 5 and R 6 The unsubstituted aryl group, preferably an aryl group with 6 to 10 carbon atoms, for example, phenyl.

[0102] As mentioned above, R 3 R 5 and R 6 The substituted aryl group may have substituents, for example, the substituents included in the above substituent group A can be cited.

[0103] As mentioned above, R 3 R 5 and R 6 Preferred examples of substituents that the substituted aryl group may have include halogen atoms (e.g., chlorine, bromine, and iodine), hydroxyl groups, carboxyl groups, and alkyl groups (preferably alkyl groups having 1 to 4 carbon atoms; for example, methyl, ethyl, n-propyl, and isopropyl).

[0104] As can be used as the above R 3 R 5 and R 6 The substituted aryl group is preferably an aryl group with a total carbon number of 6 to 10. Examples include 4-chlorophenyl, 2,5-dichlorophenyl, hydroxyphenyl, carboxyphenyl, 3,5-dicarboxyphenyl and 4-methylphenyl.

[0105] In R 5 and R 6 In the case where all are substituents, from the viewpoint of lightfastness and heat resistance, R 3 Hydrogen atoms are preferred.

[0106] Additionally, in R 3 R 5 and R 6 When all groups are aryl, the aryl groups can be the same or different.

[0107] Can be used as R 4 The alkyl group can be any one of unsubstituted alkyl groups and substituted alkyl groups, and can be either straight-chain or branched, or can have a cyclic structure.

[0108] As can be used as the above R 4 Unsubstituted alkyl groups, for example, methyl, ethyl, n-propyl, isopropyl, and cyclohexyl. These can be used as the aforementioned R. 4 The number of carbon atoms in the unsubstituted alkyl group is preferably 1 to 8, more preferably 1 to 4.

[0109] As mentioned above, R4 The substituted alkyl group may have substituents, for example, the substituents included in the substituent group A above.

[0110] As mentioned above, R 4 Preferred examples of substituents that may be present in the substituted alkyl group include aryl (preferably phenyl), heteroatom-containing cyclogroup, carboxyl, hydroxyl, alkyl (preferably alkyl with 1 to 4 carbon atoms; for example, methyl, ethyl, n-propyl and isopropyl), alkoxy (preferably alkoxy with 1 to 4 carbon atoms; for example, methoxy, ethoxy, n-propoxy and isopropoxy), aryloxy, alkoxycarbonyl (preferably alkoxycarbonyl with 2 to 5 carbon atoms; for example, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl and isopropoxycarbonyl), alkylamino (preferably alkylamino with 1 to 4 carbon atoms; for example, dimethylamino), alkylcarbonylamino (preferably alkylcarbonylamino with 1 to 4 carbon atoms; for example, methylcarbonylamino), cyano and acyl, and monovalent groups formed by linking at least two of them.

[0111] Can be used as the above R 4 The total number of carbon atoms in the substituted alkyl group is preferably 1 to 18.

[0112] Examples include benzyl, carboxybenzyl, hydroxybenzyl, methoxycarbonylethyl, ethoxycarbonylmethyl, 2-cyanoethyl, 2-propionylaminoethyl, dimethylaminomethyl, methylcarbonylaminopropyl, di(methoxycarbonylmethyl)aminopropyl, and phenacyl.

[0113] Can be used as the above R 4 The aryl group can be either an unsubstituted aryl group or a substituted aryl group with a substituent.

[0114] As can be used as the above R 4 The unsubstituted aryl group, preferably an aryl group having 6 to 12 carbon atoms, for example, phenyl.

[0115] As mentioned above, R 4 The substituted aryl group may have substituents, for example, the substituents included in the above substituent group A can be cited.

[0116] As mentioned above, R 4Preferred examples of substituents that may be present in the substituted aryl group include halogen atoms (e.g., chlorine, bromine, iodine), hydroxyl, carboxyl, sulfonamide, amino, alkyl (preferably alkyl with 1 to 4 carbon atoms; for example, methyl, ethyl, n-propyl, isopropyl), alkoxy (preferably alkoxy with 1 to 4 carbon atoms; for example, methoxy, ethoxy, n-propoxy, isopropoxy), alkoxycarbonyl (preferably alkoxycarbonyl with 2 to 5 carbon atoms; for example, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl), and sulfonyloxy, as well as monovalent groups formed by at least two of them.

[0117] The above R 4 The substituted aryl group can have an amino group that is either unsubstituted (-NH2) or substituted (substituent group A above, -NR) as the amino group. a Any one of 2).

[0118] The above R 4 The substituted aryl group may have an amino group (-NR) a In 2), as R a Can you give examples related to R mentioned above? 4 The same group as the substituted alkyl group.

[0119] As the aforementioned substituted amino group, preferably an alkylamino group obtained by substituting one or two hydrogen atoms of the amino group with an alkyl group.

[0120] Examples of alkylamino groups include methylamino, dimethylamino, diethylamino, and pyrrolidine. The number of carbon atoms in the alkylamino group is preferably 1 to 8, more preferably 1 to 4.

[0121] As can be used as the above R 4 The substituted aryl group is preferably an aryl group with a total carbon number of 6 to 22. Examples include 4-chlorophenyl, 2,5-dichlorophenyl, hydroxyphenyl, 2,5-methoxyphenyl, 2-methoxy-5-ethoxycarbonylphenyl, 4-ethoxycarbonylphenyl, 4-ethoxycarbonylphenyl, 4-butoxycarbonylphenyl, 4-octyloxycarbonylphenyl, 4-carboxyphenyl, 3,5-dicarboxyphenyl, 4-methanesulfonamide phenyl, 4-methylphenyl, 4-methoxyphenyl, 4-ethoxyphenyl, and 4-(2-hydroxyphenyl) 4-(N-carboxymethyl-N-ethylamino)phenyl, N,N-dimethylaminophenyl, N,N-diethylaminophenyl, 4-(N-carboxymethyl-N-ethylamino)phenyl, 4-{N,N-di(ethoxycarbonylmethyl)amino}phenyl, 4-{di(ethoxycarbonylmethyl)amino}carbonylphenyl, 4-ethoxycarbonylphenyl, 4-methanesulfonylphenyl, 4-acetylaminosulfonylphenyl, 4-propionylaminosulfonylphenyl and 4-methanesulfonamidephenyl.

[0122] R 5With R 6 They can bond together to form a 6-membered ring.

[0123] R 5 With R 6 The 6-membered rings formed by mutual bonding are preferably benzene rings.

[0124] In particular, from the viewpoint of lightfastness, R in formula (A1) is preferred. 1 and R 2 R in 1 It is an alkyl group, more preferably R 1 It is an alkyl group, and R 2 It is alkyl or aryl. Furthermore, from the same point of view, R is further preferred. 1 and R 2 Each of them is an alkyl group, and is particularly preferred to be an alkyl group having 1 to 8 carbon atoms.

[0125] Furthermore, from the viewpoint of heat resistance and light resistance, R in formula (A1) is preferred. 1 and R 2 All are aryl.

[0126] In R 1 and R 2 When each aryl group is represented independently, R is preferred. 3 R 5 and R 6 Each independently represents a hydrogen atom, alkyl group, or aryl group, and R 3 and R 6 At least one of them is a hydrogen atom. From the viewpoint of heat resistance and lightfastness, R is more preferred. 3 R represents a hydrogen atom. 5 and R 6 In cases where each is independently represented by an alkyl or aryl group, R is further preferred. 3 R represents a hydrogen atom. 5 and R 6 When each alkyl group is represented independently, R is particularly preferred. 3 R represents a hydrogen atom. 5 and R 6 Each independently represents an alkyl group, and R 5 and R 6 The pigments can bond together to form rings to fused into pyrrole rings, or together with pyrrole rings to form indole rings. That is, the pigments represented by the above general formula (A1) are particularly preferred to be the pigments represented by the following general formula (A2).

[0127] [Chemical Formula 7] In equation (A2), R 1 ~R 4Respectively with R in general formula (A1) 1 ~R 4 The meanings are the same, and the preferred selection methods are also the same.

[0128] In equation (A2), R 15 Indicates a substituent. As can be used as R 15 Substituents, and examples of substituents included in the above substituent group A. As R 15 Preferably, it is an alkyl, aryl, halogen atom, acyl or alkoxy carbonyl group.

[0129] Can be used as R 15 The alkyl and aryl groups are respectively used as R 3 R 5 and R 6 The alkyl and aryl groups have the same meaning, and their preferred methods are also the same.

[0130] As can be used as R 15 Halogen atoms, for example, include chlorine, bromine and iodine atoms.

[0131] As can be used as R 15 Acyl groups, for example, acetyl, propionyl and butyryl.

[0132] As can be used as R 15 The alkoxycarbonyl group is preferably an alkoxycarbonyl group with 2 to 5 carbon atoms, for example, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl and isopropoxycarbonyl.

[0133] n is an integer from 0 to 4. There is no particular restriction on n, but for example, 0 or 1 is preferred.

[0134] The following are specific examples of pigments represented by the general formula (A1). However, the present invention is not limited to these.

[0135] In the specific examples below, Me represents methyl.

[0136] [Chemical Formula 8] [Chemical Formula 9] [Chemical Formula 10] As dye A, in addition to the pigment represented by general formula (2), the compounds described in paragraphs 0012 to 0067 of Japanese Patent Application Publication No. 5-53241 and the compounds described in paragraphs 0011 to 0076 of Japanese Patent Application Publication No. 2707371 are preferred.

[0137] (Dye B, Dye C) Regarding dye B, there are no particular restrictions as long as it has a main absorption wavelength band in the wavelength range of 480–520 nm in the laminate, and various dyes can be used.

[0138] Furthermore, regarding dye C, there are no particular restrictions as long as it has a main absorption wavelength band in the wavelength range of 580–620 nm in the laminate, and various dyes can be used.

[0139] Specific examples of dye B include pigments (dyes) of the pyrrole methine (PM) series, rhodamine (RH) series, boron dipyrromethene (BODIPY) series, and squarine (SQ) series.

[0140] Specific examples of dye C include pigments (dyes) from the tetraaza porphyrin (TAP) series, squaric acid cyanide series, and cyanine (CY) series.

[0141] Among these, from the viewpoint of clear absorption waveforms in the main absorption wavelength band, squaric acid cyanine pigments are preferred as dyes B and C, and squaric acid cyanine pigments represented by the following general formula (1) are more preferred. As described above, by using pigments with clear absorption waveforms as dyes B and C, the above relationships (I) to (VI) can be satisfied at an optimal level, and the original color tone of the image in the OLED display device can be maintained at a superior level.

[0142] That is, in the wavelength-selective absorption layer described above, from the viewpoint of suppressing the above-mentioned hue changes, it is preferable that at least one of dye B and dye C is a squaric acid cyanine pigment (preferably a squaric acid cyanine pigment represented by the following general formula (1)), and more preferably that both dye B and dye C are squaric acid cyanine pigments (preferably a squaric acid cyanine pigment represented by the following general formula (1)).

[0143] In this invention, the cations in the pigments represented by the following general formulas exist in a delocalized manner, and multiple tautomer structures exist. Therefore, in this invention, when at least one tautomer structure of certain pigments is applicable to each general formula, a certain pigment is defined as a pigment represented by each general formula. Therefore, a pigment represented by a specific general formula can also be called a pigment capable of having at least one tautomer structure represented by that specific general formula. In this invention, for pigments represented by general formulas, any tautomer structure can be used as long as at least one of its tautomer structures is applicable to that general formula.

[0144] [Chemical Formula 11] In general formula (1), A and B independently represent aryl groups that can have substituents, heterocyclic groups that can have substituents, or -CH=G. G represents heterocyclic groups that can have substituents.

[0145] There are no particular limitations on the aryl group that can be used as A or B; it can be a group containing a monocyclic ring or a group containing a fused ring. The number of carbon atoms in the aryl group is preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 12. Examples of aryl groups include groups containing a benzene ring or a naphthalene ring, and more preferably groups containing a benzene ring.

[0146] There are no particular limitations on the heterocyclic group that can be used as A or B, including groups containing aliphatic or aromatic heterocycles, with a preference for groups containing aromatic heterocycles. For example, heteroaryl groups that can be used as substituent X, as described later, are examples of heteroaryl groups that can be used as aromatic heterocyclic groups. The aromatic heterocyclic group that can be used as A or B is preferably a 5-membered or 6-membered ring group, more preferably a nitrogen-containing 5-membered ring group. Specifically, groups comprising any one of the following rings are preferred: pyrrole ring, furan ring, thiophene ring, imidazole ring, pyrazole ring, thiazole ring, oxazole ring, triazole ring, indole ring, pseudoindole ring, indoline ring, pyridine ring, pyrimidine ring, quinoline ring, benzothiazole ring, benzoxazole ring, and pyrazolotriazole ring. Among these, groups comprising any one of the following rings are preferred: pyrrole ring, pyrazole ring, thiazole ring, pyridine ring, pyrimidine ring, and pyrazolotriazole ring. Pyrazolotriazole comprises a fused ring consisting of a pyrazole ring and a triazole ring, whichever is a fused ring formed by the fusion of at least one of these rings. For example, the fused rings in general formulas (4) and (5) described below can be cited.

[0147] A and B can be bonded at any site (ring-forming atom) relative to the squaric acid cyano site (a 4-membered ring represented by general formula (1)) without particular restriction, but are preferably bonded on carbon atoms.

[0148] The G in -CH=G used as A or B represents a heterocyclic group that can have substituents. For example, examples of heterocyclic groups shown in A or B above are preferred. Preferably, groups comprising any one of a benzoxazole ring, a benzothiazole ring, and an indoline ring are preferred.

[0149] At least one of A and B may have a hydrogen-bonding group that can form hydrogen bonds within the molecule.

[0150] A, B, and G can each have a substituent X. When substituent X is present, adjacent substituents can bond together to further form a ring structure. Furthermore, multiple substituents X can be present. In the case of adjacent substituents X bonding together to further form a ring structure, two substituents X can have a heteroatom, such as a boron atom, between them to form a ring. This boron atom can be further substituted by substituents, such as alkyl and aryl substituents. As an example of a ring formed by the bonding of two substituents X, two -NR substituents can be given, for example. 14 R 15 The bonded ring, 2 of the following -NR 14 R 15 A ring is formed by bonding boron atoms between them.

[0151] As a substituent X, for example, R can be used as a general formula (2) described later. 1 Substituents. Specifically, examples include halogen atoms, cyano groups, nitro groups, alkyl groups (including cycloalkyl groups), alkenyl groups, ynyl groups, aryl groups, heteroaryl groups, aralkyl groups, ferrocenyl groups, and -OR groups. 10 -C(=O)R 11 -C (=O) OR 12 -OC (=O)R 13 -NR 14 R 15 -NHCOR 16 -CONR 17 R 18 -NHCONR 19 R 20 -NHCOOR 21 -SR 22 -SO2R 23 -SO3R 24 -NHSO2R 25 and -SO2NR 26 R 27 Furthermore, in addition to the aforementioned ferrocene group, substituent X preferably also has the matting agent portion described later.

[0152] In general formula (1), R 10 ~R 27 Each can independently represent a hydrogen atom, an aliphatic group, an aromatic group, or a heteroatom-containing cyclic group. It can be used as an R... 10 ~R 27 There are no particular restrictions on the aliphatic and aromatic groups, and the R group can be appropriately derived from the general formula (2) described below. 1 The substituents are selected from alkyl, cycloalkyl, alkenyl, and ynyl groups classified as aliphatic groups, and aryl groups classified as aromatic groups. It can be used as R 10 ~R27 The heteroatom-containing cyclic group can be aliphatic or aromatic, for example, capable of being suitably derived from R, which can be used as general formula (2) described later. 1 It is selected from heteroaryl or heteroatom-containing cyclic groups.

[0153] Additionally, in -COOR 12 R 12 In the case of a hydrogen atom (i.e., a carboxyl group), the hydrogen atom can dissociate (i.e., a carbonate group) or remain in a salt state. Furthermore, in the -SO3R group... 24 R 24 In the case of hydrogen atoms (i.e., sulfonyl), hydrogen atoms can dissociate (i.e., sulfonate group) or be in a salt state.

[0154] Examples of halogen atoms that can be used as substituents X include fluorine, chlorine, bromine, and iodine atoms.

[0155] The alkyl group that can be used as substituent X preferably has 1 to 20 carbon atoms, more preferably 1 to 15, and even more preferably 1 to 8. The alkenyl group preferably has 2 to 20 carbon atoms, more preferably 2 to 12, and even more preferably 2 to 8. The alkynyl group preferably has 2 to 40 carbon atoms, more preferably 2 to 30, and particularly preferably 2 to 25. The alkyl, alkenyl, and alkynyl groups can be any of straight-chain, branched, or cyclic, preferably straight-chain or branched.

[0156] The aryl group that can be used as substituent X comprises a monocyclic or fused-ring group. The number of carbon atoms in the aryl group is preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 12.

[0157] The alkyl moiety of the aralkyl group that can be used as substituent X is the same as the alkyl group described above. The aryl moiety of the aralkyl group is the same as the aryl group described above. The number of carbon atoms in the aralkyl group is preferably 7 to 40, more preferably 7 to 30, and even more preferably 7 to 25.

[0158] The heteroaryl group that can be used as substituent X includes a group comprising a monocyclic or fused ring, preferably a group comprising a monocyclic or fused ring having 2 to 8 rings, more preferably a group comprising a monocyclic or fused ring having 2 to 4 rings. The number of heteroatoms constituting the ring of the heteroaryl group is preferably 1 to 3. Examples of heteroatoms constituting the ring of the heteroaryl group include nitrogen, oxygen, or sulfur atoms. The heteroaryl group preferably comprises a 5-membered or 6-membered ring. The number of carbon atoms constituting the ring of the heteroaryl group is preferably 3 to 30, more preferably 3 to 18, and even more preferably 3 to 12. Examples of heteroaryl groups include, for instance, groups comprising any one of the following: pyridine ring, piperidine ring, furan ring, furfuran ring, thiophene ring, pyrrole ring, quinoline ring, morpholine ring, indole ring, imidazole ring, pyrazole ring, carbazole ring, phenothiazine ring, phenotoxazine ring, indoleline ring, thiazole ring, pyrazine ring, thiadiazine ring, benzoquinoline ring, and thiadiazine ring.

[0159] Ferrocene-based compounds that can be used as substituent X are preferably represented by the general formula (2M).

[0160] [Chemical Formula 12] In general formula (2M), L represents a single bond or a divalent linking group that is not conjugated with A, B, or G in general formula (1). R 1m ~R 9m These represent hydrogen atoms or substituents, respectively. M is an atom that can form metallocene compounds and represents Fe, Co, Ni, Ti, Cu, Zn, Zr, Cr, Mo, Os, Mn, Ru, Sn, Pd, Rh, V, or Pt. Indicates the bonding portion with A, B, or G.

[0161] Furthermore, in this invention, when L in the general formula (2M) is a single bond, the cyclopentadiene ring directly bonded to A, B, or G (the ring with R in the general formula (2M)) 1m The ring is not included in the conjugate structure conjugated with A, B or G.

[0162] As a divalent linking group that can be used as L, there are no particular limitations as long as it is not conjugated with A, B, or G, and the above-mentioned conjugated structure can be included inside it or at the cyclopentadiene ring end in the general formula (2M). Examples of divalent linking groups include, for example, alkylene groups with 1 to 20 carbon atoms, aryl groups with 6 to 20 carbon atoms, divalent heterocyclic groups obtained by removing two hydrogens from a heterocycle, -CH=CH-, -CO-, -CS-, -NR- (R represents a hydrogen atom or a monovalent substituent), -O-, -S-, -SO2-, or -N=CH-, or divalent linking groups formed by combining multiple of them (preferably 2 to 6). Preferably, it is a divalent linking group selected from the group consisting of alkylene groups having 1 to 8 carbon atoms, aryl groups having 6 to 12 carbon atoms, -CH=CH-, -CO-, -NR- (R as described above), -O-, -S-, -SO2-, and -N=CH-, or a combination of two or more (preferably 2 to 6) groups selected from the group. It is particularly preferred to be a linking group selected from the group consisting of alkylene groups having 1 to 4 carbon atoms, phenylene groups, -CO-, -NH-, -O-, and -SO2-, or a combination of two or more (preferably 2 to 6) groups selected from the group. There are no particular limitations on the divalent linking groups used in the combination, but groups containing -CO-, -NH-, -O-, or -SO2- are preferred. Examples include linking groups formed by combining two or more of -CO-, -NH-, -O-, or -SO2-, or linking groups formed by combining at least one of -CO-, -NH-, -O-, and -SO2- with an alkylene or aryl group. Examples of linking groups formed by combining two or more of -CO-, -NH-, -O-, or -SO2- include -COO-, -OCO-, -CONH-, -NHCOO-, -NHCONH-, and -SO2NH-. Examples of linking groups formed by combining at least one of -CO-, -NH-, -O-, and -SO2- with an alkylene or aryl group include groups formed by combining -CO-, -COO-, or -CONH- with an alkylene or aryl group.

[0163] There are no particular restrictions on the substituents that can be used as R, which is the same as the meaning of the substituents X that A can have in general formula (2).

[0164] L is preferably a single bond, or a group selected from the group consisting of alkylene groups having 1 to 8 carbon atoms, aryl groups having 6 to 12 carbon atoms, -CH=CH-, -CO-, -NR- (R as described above), -O-, -S-, -SO2-, and -N=CH-, or a group composed of two or more groups selected from the group.

[0165] L can have one or more substituents. There are no particular restrictions on the substituents that L can have, for example, they have the same meaning as the substituent X mentioned above. When L has multiple substituents, the substituents bonded to adjacent atoms can bond with each other to further form a ring structure.

[0166] As for the alkylene group that can be used as L, as long as it is a group with 1 to 20 carbon atoms, it can be straight-chain, branched, or cyclic. Examples include methylene, ethylene, propylene, methyl ethylene, methyl methylene, dimethyl methylene, 1,1-dimethyl ethylene, butylene, 1-methyl propyleneene, 2-methyl propyleneene, 1,2-dimethyl propyleneene, 1,3-dimethyl propyleneene, 1-methyl butylene, 2-methyl butylene, 3-methyl butylene, 4-methyl butylene, 2,4-dimethyl butylene, etc. 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, etc.

[0167] When L is used as a linking group comprising at least one of -CO-, -CS-, -NR- (R as described above), -O-, -S-, -SO2- and -N=CH-, groups such as -CO- can be introduced into any position in the alkylene group, and there is no particular limitation on the number of groups introduced.

[0168] As for the aryl group that can be used as L, there are no particular restrictions as long as it is a group with 6 to 20 carbon atoms. For example, groups obtained by further removing one hydrogen atom from each of the groups that can be used as A in general formula (1) and have 6 to 20 carbon atoms are exemplified.

[0169] There are no particular limitations on the heterocyclic group that can be used as L. For example, groups obtained by further removing one hydrogen atom from each of the groups exemplified as heterocyclic groups that can be used as A as described above can be given examples.

[0170] In general formula (2M), the remaining structure after removing the linking group L is equivalent to the structure obtained by removing one hydrogen atom from a metallocene compound (metallocene structural part). In this invention, any known metallocene compound that conforms to the partial structure specified by the above general formula (2M) (a compound in which hydrogen atoms replace L bonds) can be used without particular restriction. Hereinafter, the metallocene structural part specified by general formula (2M) will be specifically described.

[0171] In the general formula (2M), R 1m ~R 9m These represent hydrogen atoms or substituents, respectively. As can be used as R... 1m ~R 9m The substituents are not particularly limited, but for example, they can be derived from R, which can be used as general formula (3). 1 Choose from the substituents. R 1m ~R 9m The preferred groups are hydrogen atoms, halogen atoms, alkyl groups, acyl groups, alkoxy groups, amino groups, or amide groups, more preferably hydrogen atoms, halogen atoms, alkyl groups, acyl groups, or alkoxy groups, even more preferably hydrogen atoms, halogen atoms, alkyl groups, or acyl groups, especially preferably hydrogen atoms, halogen atoms, or alkyl groups, and most preferably hydrogen atoms.

[0172] As can be used as R 1m ~R 9m Alkyl groups can be used as R 1 Among the alkyl groups, alkyl groups having 1 to 8 carbon atoms are preferred, for example, methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, isobutyl, pentyl, tert-pentyl, hexyl, octyl, and 2-ethylhexyl.

[0173] The alkyl group may have a halogen atom as a substituent. Examples of alkyl groups substituted with halogen atoms include chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, fluoromethyl, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, perfluoroethyl, perfluoropropyl, and perfluorobutyl.

[0174] Furthermore, it can be used as R 1mIn alkyl groups such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, dibutoxy, tributoxy, 2-methoxyethoxy, chloromethoxy, dichloromethoxy, trichloromethoxy, bromomethoxy, dibromomethoxy, tribromomethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, perfluoroethoxy, perfluoropropoxy, perfluorobutoxy, and alkyl groups in which the terminal methylene group of the carbon chain is substituted, as well as alkyl groups in which the internal methylene group of the carbon chain is substituted, such as 2-methoxyethyl. Alkyl groups in which the methylene group is substituted with -CO- include, for example, acetyl, propionyl, monochloroacetyl, dichloroacetyl, trichloroacetyl, trifluoroacetyl, propane-2-one-1-yl, butane-2-one-1-yl.

[0175] In the general formula (2M), M is an atom that can form a metallocene compound, and represents Fe, Co, Ni, Ti, Cu, Zn, Zr, Cr, Mo, Os, Mn, Ru, Sn, Pd, Rh, V, or Pt. Preferably, M is 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.

[0176] As groups represented by the general formula (2M), L and R are preferred. 1m ~R 9m Groups formed by combining the preferred forms of L and M, for example, include groups selected from the group consisting of alkylene groups having 2 to 8 carbon atoms, aryl groups having 6 to 12 carbon atoms, -CH=CH-, -CO-, -NR- (R as described above), -O-, -S-, -SO2-, and -N=CH-, or groups formed by combining two or more groups selected from this group, as R. 1m ~R 9m It is a group composed of hydrogen atoms, halogen atoms, alkyl groups, acyl groups or alkoxy groups and Fe as M.

[0177] Alkyl, alkenyl, ynyl, aralkyl, aryl, and heteroaryl groups that can be used as substituent X, and groups that can be used as R 10 ~R 27The aliphatic groups, aromatic groups, and heteroatom-containing cyclic groups may be further substituented or unsubstituted. There are no particular limitations on the substituents that may be further substituented, but substituents are preferably selected from alkyl, aryl, amino, alkoxy, aryloxy, aromatic heterocyclic oxy, acyl, alkoxycarbonyl, aryloxycarbonyl, acyloxy, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, alkylthio, arylthio, aromatic heterocyclic thio, sulfonyl, ferrocene, hydroxyl, mercapto, halogen atom, cyano, sulfonyl, and carboxyl groups. More preferably, substituents are selected from alkyl, aryl, alkoxy, aryloxy, aromatic heterocyclic oxy, acyl, alkoxycarbonyl, aryloxycarbonyl, acyloxy, alkoxythio, arylthio, aromatic heterocyclic thio, sulfonyl, ferrocene, hydroxyl, mercapto, halogen atom, cyano, sulfonyl, and carboxyl groups. These groups can be suitably derived from R, which can be used as the general formula (2) described below. 1 Choose from the substituents.

[0178] As a preferred embodiment of the pigment represented by the above general formula (1), a pigment represented by the following general formula (2) can be cited.

[0179] [Chemical Formula 13] In general formula (2), A 1 It is the same as A in general formula (1). Among them, a heterocyclic group containing a nitrogen-containing 5-membered ring is preferred.

[0180] In general formula (2), R 1 and R 2 Each can independently represent a hydrogen atom or a substituent. R 1 With R 2 They can be the same or different, and they can bond together to form a ring.

[0181] As can be used as R 1 and R 2The substituents are not particularly limited, but examples include alkyl groups (methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, isobutyl, pentyl, hexyl, octyl, dodecyl, trifluoromethyl, etc.), cycloalkyl groups (cyclopentyl, cyclohexyl, etc.), alkenyl groups (vinyl, allyl, etc.), alkynyl groups (ethynyl, propargyl, etc.), aryl groups (phenyl, naphthyl, etc.), heteroaryl groups (furanyl, thiophene, pyridinyl, pyrazinyl, pyrazinyl, triazinyl, imidazolyl, pyrazolyl, thiazolyl, benzimidazolyl, benzoxazolyl, quinazolinyl, phthalazinyl, etc.), and heteroatom-containing cyclic groups (also called heterocyclic groups, for example, ...).Pyrroloalkyl, imidazoalkyl, morpholinyl, oxazolidinyl, etc.), alkoxy (methoxy, ethoxy, propoxy, etc.), cycloalkoxy (cyclopentoxy, cyclohexyloxy, etc.), aryloxy (phenoxy, naphthoxy, etc.), heteroaryloxy (aromatic heterocyclic thiols), alkylthio (methylthio, ethylthio, propylthio, etc.), cycloalkoxy (cyclopentoxy, cyclohexylthio, etc.), arylthio (phenylthio, naphthio, etc.), heteroarylthio (aromatic heterocyclic thiols), alkoxycarbonyl (methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl, octoxycarbonyl, etc.), aryloxycarbonyl (phenoxycarbonyl, naphthoxycarbonyl, etc.), phosphoryl (dimethoxyphosphonyl, diphenylphosphonyl) ), aminosulfonyl (aminosulfonyl, methylaminosulfonyl, dimethylaminosulfonyl, butylaminosulfonyl, cyclohexylaminosulfonyl, octylaminosulfonyl, phenylaminosulfonyl, 2-pyridylaminosulfonyl, etc.), acyl (acetyl, ethylcarbonyl, propylcarbonyl, cyclohexylcarbonyl, octylcarbonyl, 2-ethylhexylcarbonyl, phenylcarbonyl, naphthylcarbonyl, pyridylcarbonyl, etc.), acyloxy (acetoxy, ethylcarbonyloxy, butylcarbonyloxy, octylcarbonyloxy, phenylcarbonyloxy, etc.), amide (methylcarbonylamino, ethylcarbonylamino, dimethylcarbonylamino, propylcarbonylamino, pentylcarbonylamino, cyclohexylcarbonylamino, etc.), (e.g., methyl, 2-ethylhexylcarbonylamino, octylcarbonylamino, dodecylcarbonylamino, phenylcarbonylamino, naphthylcarbonylamino), sulfonamide (methylsulfonylamino, octylsulfonylamino, 2-ethylhexylsulfonylamino, trifluoromethylsulfonylamino), carbamoyl (aminocarbonyl, methylaminocarbonyl, dimethylaminocarbonyl, propylaminocarbonyl, pentylaminocarbonyl, cyclohexylaminocarbonyl, octylaminocarbonyl, 2-ethylhexylaminocarbonyl, dodecylaminocarbonyl, phenylaminocarbonyl, naphthylaminocarbonyl, 2-pyridylaminocarbonyl), urea (methylurea, ethylurea, pentylurea, cyclohexylurea, octyl...) The group includes alkyl sulfonyl groups (such as methyl sulfonyl, dodecyl sulfonyl, phenyl sulfonyl, naphthyl sulfonyl, 2-pyridylamino sulfonyl, etc.), alkyl sulfonyl groups (such as methyl sulfonyl, ethyl sulfonyl, butyl sulfonyl, cyclohexyl sulfonyl, 2-ethylhexyl sulfonyl, etc.), aryl sulfonyl groups (such as phenyl sulfonyl, naphthyl sulfonyl, 2-pyridyl sulfonyl, etc.), amino groups (such as amino, ethyl amino, dimethyl amino, butyl amino, dibutyl amino, cyclopentyl amino, 2-ethylhexyl amino, dodecyl amino, phenyl amino, naphthyl amino, 2-pyridyl amino, etc.), alkyl sulfonyloxy groups (methane sulfonyloxy), cyano, nitro, halogen atoms (fluorine, chlorine, bromine, etc.), hydroxyl groups, etc.

[0182] Preferably, the compounds are alkyl, alkenyl, aryl or heteroaryl, more preferably alkyl, aryl or heteroaryl, and even more preferably alkyl.

[0183] Can be used as R 1 and R 2The substituents can further have substituents. Examples of substituents that can be further had, which can be used as R, are given. 1 and R 2 The aforementioned substituents and A, B, and G in the aforementioned general formula (1) may have a substituent X. Furthermore, R 1 With R 2 They can bond together to form a ring, R 1 or R 2 With B 2 Or B 3 The substituents can bond together to form a ring.

[0184] The ring formed at this time is preferably a heterocyclic or heteroaryl ring. The size of the formed ring is not particularly limited, but a 5-membered or 6-membered ring is preferred. Furthermore, the number of rings formed is not particularly limited; it can be one or more. For example, R... 1 With B 2 The substituents and R 2 With B 3 The substituents are bonded together to form two rings.

[0185] In general formula (2), B 1 B 2 B 3 and B 4 Each can independently represent a carbon atom or a nitrogen atom. Contains B. 1 B 2 B 3 and B 4 The ring is an aromatic ring. B is preferred. 1 ~B 4 It has at least two carbon atoms, preferably B. 1 ~B 4 It consists entirely of carbon atoms.

[0186] Can be used as B 1 ~B 4 The carbon atom has a hydrogen atom or a substituent. It can be used as B. 1 ~B 4 The number of substituent carbon atoms in the carbon atom is not particularly limited, but is preferably 0, 1, or 2, more preferably 1. In particular, B is preferred. 1 and B 4 It consists of carbon atoms, and at least one of them has a substituent.

[0187] As can be used as B 1 ~B 4 There are no particular restrictions on the substituents that can be present on the carbon atoms; examples of substituents that can be used as R are given. 1 and R 2The above-mentioned substituents are preferably alkyl, alkoxy, alkoxycarbonyl, aryl, acyl, amide, sulfonamide, carbamoyl, alkylsulfonyl, arylsulfonyl, amino, cyano, nitro, halogen atom or hydroxyl, more preferably alkyl, alkoxy, alkoxycarbonyl, aryl, acyl, amide, sulfonamide, carbamoyl, amino, cyano, nitro, halogen atom or hydroxyl.

[0188] Can be used as B 1 ~B 4 The carbon atom may have substituents that can be further substituents. As an example of such a substituent, R in the aforementioned general formula (2) can be cited. 1 and R 2 Substituents that may be further present and substituents X that A, B and G in the aforementioned general formula (1) may have.

[0189] As can be used as B 1 and B 4 The substituents present on the carbon atom are further preferably alkyl, alkoxy, hydroxy, amide, sulfonamide or carbamoyl, especially alkyl, alkoxy, hydroxy, amide or sulfonamide, and most preferably hydroxy, amide or sulfonamide.

[0190] As can be used as B 2 and B 3 The substituents on the carbon atom are more preferably alkyl, alkoxy, alkoxycarbonyl, acyl, amino, cyano, nitro or halogen atom, and especially preferably any one of the substituents is an electron-withdrawing group (e.g. alkoxycarbonyl, acyl, cyano, nitro or halogen atom).

[0191] The pigment represented by the above general formula (2) is preferably a pigment represented by any one of the following general formulas (3), (4) and (5).

[0192] [Chemical Formula 14] In general formula (3), R 1 and R 2 Each of them independently represents a hydrogen atom or a substituent, and is related to R in the general formula (2) above. 1 and R 2 They have the same meaning and the same preferred range.

[0193] In general formula (3), B 1 ~B 4 Each of them independently represents a carbon atom or a nitrogen atom, and is related to B in the general formula (2) above. 1 ~B 4 They have the same meaning and the same preferred range.

[0194] In general formula (3), R3 and R 4 Each can independently represent a hydrogen atom or a substituent. As can be used as R 3 and R 4 The substituents are not particularly limited, and examples of substituents that can be used as the aforementioned R can be given. 1 and R 2 The substituents are the same groups.

[0195] Among them, it can be used as R 3 The substituents are preferably alkyl, alkoxy, amino, amide, sulfonamide, cyano, nitro, aryl, heteroaryl, heteroatom-containing cyclogroup, alkoxycarbonyl, carbamoyl or halogen atom, more preferably alkyl, aryl or amino, and even more preferably alkyl.

[0196] As can be used as R 4 The substituents are preferably alkyl, aryl, heteroaryl, heteroatom-containing cyclogroup, alkoxy, alkoxycarbonyl, acyl, acyloxy, amide, carbamoyl, amino, or cyano, more preferably alkyl, alkoxycarbonyl, acyl, carbamoyl, or aryl, and even more preferably alkyl.

[0197] Can be used as R 3 and R 4 The alkyl group can be any of straight-chain, branched, or cyclic, but straight-chain or branched is preferred. The alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 8. Examples of alkyl groups are methyl, ethyl, n-propyl, isopropyl, tert-butyl, 2-ethylhexyl, and cyclohexyl, more preferably methyl and tert-butyl.

[0198] [Chemical Formula 15] In general formula (4), R 1 and R 2 Each of them independently represents a hydrogen atom or a substituent, and is related to R in the general formula (2) above. 1 and R 2 They have the same meaning and the same preferred range.

[0199] In general formula (4), B 1 ~B 4 Each of them independently represents a carbon atom or a nitrogen atom, and is related to B in the general formula (2) above. 1 ~B 4 They have the same meaning and the same preferred range.

[0200] In general formula (4), R 5 and R 6 Each can independently represent a hydrogen atom or a substituent. As can be used as R 5 and R 6 The substituents are not particularly limited, and examples of substituents that can be used as the aforementioned R can be given.1 and R 2 The substituents are the same groups.

[0201] Among them, it can be used as R 5 The substituents are preferably alkyl, alkoxy, aryloxy, amino, cyano, aryl, heteroaryl, heteroatom-containing cyclic group, acyl, acyloxy, amide, sulfonamide, urea or carbamoyl, more preferably alkyl, alkoxy, acyl, amide or amino, and even more preferably alkyl.

[0202] Can be used as R 5 alkyl groups and R that can be used in general formula (3) 3 The meanings of alkyl groups are the same, and the preferred ranges are also the same.

[0203] In general formula (4), it can be used as R 6 The substituents are preferably alkyl, alkenyl, aryl, heteroaryl, heteroatom-containing cyclogroup, alkoxy, cycloalkoxy, aryloxy, alkoxycarbonyl, acyl, acyloxy, amide, sulfonamide, alkylsulfonyl, arylsulfonyl, carbamoyl, amino, cyano, nitro or halogen atom, more preferably alkyl, aryl, heteroaryl or heteroatom-containing cyclogroup, and even more preferably alkyl or aryl.

[0204] Can be used as R 6 alkyl groups and R that can be used in general formula (3) 4 The meanings of alkyl groups are the same, and the preferred ranges are also the same.

[0205] 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. This aryl group may have substituents, and examples of such substituents include those listed in substituent group B, with alkyl, sulfonyl, amino, amide, and sulfonylamino groups having 1 to 10 carbon atoms being particularly preferred. These substituents may further have substituents. Specifically, alkylsulfonylamino groups are preferred.

[0206] -Substituent group B- Halogen, alkyl, alkenyl, alkynyl, aryl, heterocyclic, cyano, hydroxyl, nitro, carboxyl, alkoxy, aminooxy, aryloxy, silyloxy, heterocyclic, acyloxy, carbamoyloxy, amino, acylamino, aminocarbonylamino, alkoxycarbonylamino, aryloxycarbonylamino, aminosulfonylamino, sulfonylamino (including alkyl or arylsulfonylamino), mercapto, alkylthio, arylthio, heterocyclic thio, aminosulfonyl, sulfonyl, alkyl or arylsulfinyl, sulfonyl (including alkyl or arylsulfonyl), acyl, aryloxycarbonyl, alkoxycarbonyl, carbamoyl, aryl or heterocyclic azo, imide, phosphinyl, oxophosphinyl, oxophosphinyloxy, oxophosphinylamino, silylalkyl, etc.

[0207] [Chemical Formula 16] In general formula (5), R 1 and R 2 Each of them independently represents a hydrogen atom or a substituent, and is related to R in the general formula (2) above. 1 and R 2 They have the same meaning and the same preferred range.

[0208] In general formula (5), B 1 ~B 4 Each of them independently represents a carbon atom or a nitrogen atom, and is related to B in the general formula (2) above. 1 ~B 4 They have the same meaning and the same preferred range.

[0209] In general formula (5), R 7 and R 8 Each can independently represent a hydrogen atom or a substituent. As can be used as R 7 and R 8 The substituents are not particularly limited, and examples of substituents that can be used as the aforementioned R can be given. 1 and R 2 The substituents are the same groups.

[0210] Among them, it can be used as R 7 The substituents, preferred range, more preferred range and further preferred range are the same as those that can be used as R in general formula (4). 5 The substituents are the same. It can be used as R. 5 alkyl groups and those that can be used as the above R 3 The meanings of alkyl groups are the same, and the preferred ranges are also the same.

[0211] In general formula (5), it can be used as R 8 The substituents, preferred range, more preferred range and further preferred range are the same as those that can be used as R in general formula (4). 6 The substituents are the same. It can be used as R. 8 The preferred range of alkyl and aryl groups is the same as that of R used in the above general formula (4). 6 The alkyl and aryl groups have the same meaning and the same preferred range.

[0212] In this invention, when using a squaric acid cyanine pigment as dye A, any squaric acid cyanine pigment represented by any one of the general formulas (1) to (5) can be used without particular restriction. For example, compounds described in Japanese Patent Application Publication No. 2006-160618, International Publication No. 2004 / 005981, International Publication No. 2004 / 007447, Dyes and Pigment, 2001, 49, pp. 161-179, International Publication No. 2008 / 090757, International Publication No. 2005 / 121098, and Japanese Patent Application Publication No. 2008-275726 can be cited.

[0213] Hereinafter, specific examples of pigments represented by any one of general formulas (1) to (5) are shown. However, the present invention is not limited to these.

[0214] In the following specific examples, Me represents methyl, Et represents ethyl, Bu represents butyl, and Ph represents phenyl.

[0215] [Chemical Formula 17] [Chemical Formula 18] [Chemical Formula 19] In addition to the specific examples mentioned above, specific examples of pigments represented by any one of the general formulas (3) to (5) are given below. Substituent B in the table below represents the following structures. In the following structures and the table below, Me represents methyl, Et represents ethyl, i-Pr represents isopropyl, Bu represents n-butyl, t-Bu represents tert-butyl, and Ph represents phenyl. In the following structures, This represents the bonding portion with the carbon four-membered ring in each general formula.

[0216] [Chemical Formula 20] [Chemical Formula 21] [Chemical Formula 22] [Chemical Formula 23] [Chemical Formula 24] [Chemical Formula 25] [Chemical Formula 26] [Chemical Formula 27] [Chemical Formula 28] As a preferred embodiment of the pigment represented by the above general formula (1), a pigment represented by the following general formula (6) can be cited.

[0217] [Chemical Formula 29] In general formula (6), R 3 and R 4 Each of them independently represents a hydrogen atom or a substituent, and is related to R in the above general formula (3). 3 and R 4 They have the same meaning and the same preferred range.

[0218] In general formula (6), A 2 It is the same as A in general formula (1). Among them, a heterocyclic group containing a nitrogen-containing 5-membered ring is preferred.

[0219] The pigment represented by the above general formula (6) is preferably a pigment represented by any one of the following general formulas (7), (8) and (9).

[0220] [Chemical Formula 30] In general formula (7), R 3 and R 4 Each of them independently represents a hydrogen atom or a substituent, and is related to R in the above general formula (3). 3 and R 4 They have the same meaning and the same preferred range. (2 Rs) 3 and 2 Rs 4 They can be the same or different.

[0221] [Chemical Formula 31] In general formula (8), R 3 and R 4 Each of them independently represents a hydrogen atom or a substituent, and is related to R in the above general formula (3). 3 They have the same meaning and the same preferred range.

[0222] In general formula (8), R 5 and R 6 Each of them independently represents a hydrogen atom or a substituent, and is related to R in the above general formula (4). 5 and R 6They have the same meaning and the same preferred range.

[0223] [Chemical Formula 32] In general formula (9), R 3 and R 4 Each of them independently represents a hydrogen atom or a substituent, and is related to R in the above general formula (3). 3 They have the same meaning and the same preferred range.

[0224] In general formula (9), R 7 and R 8 Each of them independently represents a hydrogen atom or a substituent, and is related to R in the above general formula (5). 7 and R 8 They have the same meaning and the same preferred range.

[0225] In this invention, when using a squaric acid cyanine pigment as dye B, any squaric acid cyanine pigment represented by any one of the general formulas (6) to (9) can be used without particular restriction. For example, the compounds described in Japanese Patent Application Publication No. 2002-97383 and Japanese Patent Application Publication No. 2015-68945 can be cited.

[0226] Hereinafter, specific examples of pigments represented by any one of general formulas (6) to (9) are shown. However, the present invention is not limited to these.

[0227] In the following specific examples, Me represents methyl, Et represents ethyl, i-Pr represents isopropyl, t-Bu represents tert-butyl, and Ph represents phenyl. In the following structures, This represents the bonding portion with the carbon four-membered ring in each general formula.

[0228] [Chemical Formula 33] [Chemical Formula 34] [Chemical Formula 35] [Chemical Formula 36] (Matte agent with built-in pigment) The squaric acid cyanine pigment represented by the above general formula (1) can be a matting agent-integrated pigment formed by linking the matting agent portion to the pigment via a covalent bond through a linking group. The above-mentioned matting agent-integrated pigment can also preferably be used as at least one of dyes B and C. That is, the above-mentioned matting agent-integrated pigment is included in dye B or dye C according to the wavelength having the main absorption wavelength band.

[0229] As a matting agent component, for example, ferrocene-based substituent X can be cited. Furthermore, the matting agent component in the matting compound described in paragraphs

[0199] to

[0212] and

[0234] to

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

[0230] The following are specific examples of squaric acid cyanine pigments represented by general formula (1), which are equivalent to matting agent-integrated pigments. However, the present invention is not limited to these.

[0231] In the following specific examples, Me represents methyl, Et represents ethyl, and Bu represents butyl.

[0232] [Chemical Formula 37] [Chemical Formula 38] [Chemical Formula 39] [Chemical Formula 40] [Chemical Formula 41] [Chemical Formula 42] [Chemical Formula 43] [Chemical Formula 44] [Chemical Formula 45] [Chemical Formula 46] [Chemical Formula 47] [Chemical Formula 48] [Chemical Formula 49] [Chemical Formula 50] [Chemical Formula 51] [Chemical Formula 52] [Chemical Formula 53] (Dye D) Regarding dye D, there are no particular restrictions as long as it has a main absorption wavelength band in the wavelength range of 680 to 780 nm in the laminate, and various dyes can be used.

[0233] As specific examples of dye D, one can cite various pigments (dyes) of the porphyrin, squaric acid cyanine, and cyanine (CY) series.

[0234] Regarding the dye D mentioned above, from the viewpoint of clear absorption waveform, it is preferred to be at least one of the pigments represented by the following general formula (D1) and the pigments represented by the general formula (1).

[0235] (Pigments represented by the general formula (D1)) [Chemical Formula 54] In equation (D1), R 1A and R 2A Each can independently represent an alkyl, aryl, or heteroaryl group, R 4A and R 5A Each independently represents a heteroaryl group, R 3A and R 6A Each substituent is represented independently. X 1 and X 2 Each is represented independently -BR 21a R 22a R 21a and R 22a Substituents are represented independently, R 21a and R 22a They can bond together to form a ring.

[0236] R 1A and R 2A Each can be independently represented as alkyl, aryl, or heteroaryl.

[0237] The alkyl group preferably has 1 to 40 carbon atoms. The lower limit is more preferably 3 or more, further preferably 5 or more, even more preferably 8 or more, and particularly preferably 10 or more. The upper limit is more preferably 35 or less, and even more preferably 30 or less. The alkyl group can be straight-chain, branched, or cyclic, but straight-chain or branched is preferred, and branched is particularly preferred. The branched alkyl group preferably has 3 to 40 carbon atoms. The lower limit is, for example, more preferably 5 or more, further preferably 8 or more, and even more preferably 10 or more. The upper limit is more preferably 35 or less, and even more preferably 30 or less. The branched number of the branched alkyl group is preferably 2 to 10, more preferably 2 to 8. If the number of branches is within the above range, the solvent solubility is good.

[0238] The aryl group preferably has 6 to 30 carbon atoms, more preferably 6 to 20, and even more preferably 6 to 12. Phenyl is preferred.

[0239] The heteroaryl group is preferably a monocyclic or fused ring, more preferably a monocyclic or fused ring with 2 to 8 fusions, and even more preferably a monocyclic or fused ring with 2 to 4 fusions. The number of heteroatoms constituting the heteroaryl group is preferably 1 to 3. The heteroatoms constituting the heteroaryl group are preferably nitrogen, oxygen, or sulfur atoms. The number of carbon atoms in the heteroaryl group is preferably 3 to 30, more preferably 3 to 18, more preferably 3 to 12, and particularly preferably 3 to 5. The heteroaryl group is preferably a 5-membered or 6-membered ring. Specific examples of heteroaryl groups include imidazole, pyridinyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazolyl, quinolinyl, quinoxalinyl, isoquinolinyl, indolenyl, furanyl, thiophene, benzoxazolyl, benzimidazolyl, benzothiazolyl, naphthothiazolyl, m-carbazolyl, and acrylonitrile.

[0240] R 1A and R 2A The alkyl, aryl, and heteroaryl groups in the compound may have substituents or may not be substituted. Examples of substituents that may be present include hydrocarbon groups, heteroaryl groups, amino groups, amide groups, alkylcarbonylamino groups, aryloxycarbonylamino groups, sulfonylamino groups, aminosulfonyl groups, carbamoyl groups, alkylthio groups, arylthio groups, heteroarylthio groups, alkylsulfonyl groups, arylsulfonyl groups, thionyl groups, ureyl groups, phosphatamido groups, mercapto groups, sulfonyl groups, carboxyl groups, nitro groups, hydroxamic acid groups, sulfinyl groups, hydrazine groups, imino groups, silyl groups, hydroxyl groups, halogen atoms, and cyano groups, which may contain an oxygen atom.

[0241] As a heteroaryl group, the above-mentioned R can be preferentially applied. 1A and R 2A Records of heteroaryl compounds in the literature.

[0242] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine.

[0243] Examples of hydrocarbon groups include alkyl, alkenyl, and aryl groups.

[0244] As an alkyl group, the above-mentioned R can be preferably used. 1A and R 2A The alkyl group in the text is recorded.

[0245] The number of carbon atoms in the alkenyl group is preferably 2 to 40. The lower limit is more preferably 3 or more, further preferably 5 or more, even more preferably 8 or more, and particularly preferably 10 or more. The upper limit is more preferably 35 or less, and even more preferably 30 or less. The alkenyl group can be straight-chain, branched, or cyclic, but straight-chain or branched is preferred, and branched is particularly preferred. The number of carbon atoms in the branched alkenyl group is preferably 3 to 40. The lower limit is more preferably 5 or more, further preferably 8 or more, and even more preferably 10 or more. The upper limit is more preferably 35 or less, and even more preferably 30 or less. The number of branches in the branched alkenyl group is preferably 2 to 10, more preferably 2 to 8. If the number of branches is within the above range, the solvent solubility is good.

[0246] The aryl group preferably has 6 to 30 carbon atoms, more preferably 6 to 20, and even more preferably 6 to 12.

[0247] As a hydrocarbon group containing an oxygen atom, examples include -LR x1 The group indicated.

[0248] L represents -O-, -CO-, -COO-, -OCO-, - (OR x2 ) m -or- (R x2 O) m -. R x1 Indicates alkyl, alkenyl, or aryl. R x2 Indicates alkylene or arylene. m represents an integer greater than 2, with m R's. x2 They can be the same or different.

[0249] L is preferably -O-, -COO-, or -OCO-, with -O- being more preferred.

[0250] R x1 The alkyl, alkenyl, and aryl groups referred to have the same meaning as described above, and their preferred ranges are also the same. R x1 Alkyl or alkenyl groups are preferred, with alkyl groups being more preferred.

[0251] R x2 The alkylene group represented preferably has 1 to 20 carbon atoms, more preferably 1 to 10, and even more preferably 1 to 5. The alkylene group can be straight-chain, branched, or cyclic, but straight-chain or branched is preferred.

[0252] R x2 The arylene group represented preferably has 6 to 20 carbon atoms, more preferably 6 to 12.

[0253] m represents an integer greater than or equal to 2, preferably 2 to 20, and more preferably 2 to 10.

[0254] As R 1A and R 2AThe alkyl, aryl, and heteroaryl groups may have substituents, preferably hydrocarbon groups containing oxygen atoms, and more preferably hydrocarbon groups containing oxygen atoms.

[0255] Hydrocarbon groups containing oxygen atoms are preferably composed of -OR x1 The group indicated by R. x1 Alkyl or alkenyl groups are preferred, alkyl groups are more preferred, and branched alkyl groups are particularly preferred. That is, R 1A and R 2A The substituent represented is preferably an alkoxy group. (The rest of the text appears to be a fragmented list of substituents and their meanings, possibly related to R.) 1A and R 2A It is an alkoxy group, and as a near-infrared absorbing substance with excellent solvent solubility, lightfastness, and visible transmittance, it can be preferably used as dye D in this invention.

[0256] The number of carbon atoms in the alkoxy group is preferably 1 to 40. The lower limit is more preferably 3 or more, further preferably 5 or more, even more preferably 8 or more, and particularly preferably 10 or more. The upper limit is more preferably 35 or less, and even more preferably 30 or less. The alkoxy group can be straight-chain, branched, or cyclic, but straight-chain or branched is preferred, and branched is particularly preferred. The number of carbon atoms in a branched alkoxy group is preferably 3 to 40. The lower limit is more preferably 5 or more, further preferably 8 or more, and even more preferably 10 or more. The upper limit is more preferably 35 or less, and even more preferably 30 or less. The number of branches in a branched alkoxy group is preferably 2 to 10, more preferably 2 to 8.

[0257] As R 1A and R 2A Preferably, it is a heteroaryl or aryl group, more preferably an aryl group, and even more preferably a phenyl group having a substituent at the 3-position.

[0258] R 3A and R 6A Substituents are represented independently.

[0259] Examples of substituents include alkyl, alkenyl, alkynyl, aryl, heteroaryl, amino (including alkylamino, arylamino, heterocyclic amino), alkoxy, aryloxy, heteroaryloxy, acyl, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, acyloxy, acylamino, alkylcarbonylamino, aryloxycarbonylamino, sulfonylamino, aminosulfonyl, carbamoyl, alkylthio, arylthio, heteroarylthio, alkylsulfonyl, arylsulfonyl, thionyl, ureyl, phosphatamido, hydroxyl, mercapto, halogen, cyano, sulfonyl, carboxyl, nitro, hydroxamic acid, sulfinyl, hydrazyl, imino, silyl, etc.

[0260] R 3A and R 6A Preferably, it contains electron-withdrawing groups.

[0261] Hammett states that substituents with a positive σp value (para-substituent constant) function as electron-withdrawing groups.

[0262] In this invention, substituents with a Hammett σp value of 0.2 or higher can be used as electron-withdrawing groups. A σp value of 0.25 or higher is preferred, more preferably 0.3 or higher, and particularly preferably 0.35 or higher. There is no particular upper limit, but 0.80 is preferred.

[0263] Specific examples of electron-withdrawing groups include cyano (0.66), carboxyl (-COOH: 0.45), alkoxycarbonyl (-COOMe: 0.45), aryloxycarbonyl (-COOPh: 0.44), carbamoyl (-CONH2: 0.36), alkylcarbonyl (-COMe: 0.50), arylcarbonyl (-COPh: 0.43), alkylsulfonyl (-SO2Me: 0.72), and arylsulfonyl (-SO2Ph: 0.68). Cyanoyl is particularly preferred. Here, Me represents methyl and Ph represents phenyl.

[0264] Regarding the σp value of Hammett, for example, reference can be made to paragraphs 0024 to 0025 of Japanese Patent Application Publication No. 2009-263614, which is incorporated herein by reference.

[0265] R 4A and R 5A Each can be represented independently as a heteroaryl group.

[0266] The heteroaryl group is preferably monocyclic or fused-ring, more preferably monocyclic or fused-ring with 2 to 8 fusion numbers, and even more preferably monocyclic or fused-ring with 2 to 4 fusion numbers. The number of heteroatoms constituting the heteroaryl group is preferably 1 to 3. The heteroatoms constituting the heteroaryl group are preferably nitrogen, oxygen, or sulfur atoms. The number of carbon atoms in the heteroaryl group is preferably 3 to 30, more preferably 3 to 18, more preferably 3 to 12, and particularly preferably 3 to 5. The heteroaryl group is preferably a 5-membered or 6-membered ring. Specific examples of heteroaryl groups can be found in R... 1A and R 2A The examples described herein preferably contain pyridyl, pyrimidinyl, triazolyl, quinolinyl, quinoxalinyl, isoquinolinyl, indolenyl, benzoxazolyl, or benzothiazolyl.

[0267] The heteroaryl group may have substituents or be unsubstituted. Examples of substituents include alkyl, alkenyl, alkynyl, aryl, amino (including alkylamino, arylamino, and heterocyclic amino), alkoxy, aryloxy, acyl, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, acyloxy, acylamino, alkylcarbonylamino, aryloxycarbonylamino, sulfonylamino, aminosulfonyl, carbamoyl, alkylthio, arylthio, heteroarylthio, sulfonyl, alkylsulfonyl, arylsulfonyl, thionyl, ureyl, phosphoramidyl, hydroxyl, mercapto, halogen atom, cyano, sulfonyl, carboxyl, nitro, hydroxamic acid, sulfinyl, hydrazyl, imino, silyl, etc. Halogen atoms, alkyl, and alkoxy groups are preferred.

[0268] The preferred halogen atoms are fluorine, chlorine, bromine, and iodine atoms, with chlorine atoms being particularly preferred.

[0269] The alkyl group preferably has 1 to 40 carbon atoms, more preferably 1 to 30, and especially preferably 1 to 25. The alkyl group can be straight-chain, branched, or cyclic, but straight-chain or branched is preferred, and straight-chain is especially preferred.

[0270] The number of carbon atoms in the alkoxy group is preferably 1 to 40, more preferably 1 to 30, and especially preferably 1 to 25. The alkoxy group can be straight-chain, branched, or cyclic, but straight-chain or branched is preferred, and straight-chain is especially preferred.

[0271] R 3A With R 4A R 5A With R 6A They can be bonded separately to form rings.

[0272] In R 3A With R 4A R 5A With R 6A When rings are formed by mutual bonding, 5- to 7-membered rings (preferably 5- or 6-membered rings) are preferred. As the formed ring, it is preferable that the anthocyanin serves as the acidic core. Specific examples include the following.

[0273] (a) 1,3-Dicarbonyl ring: for example, 1,3-indanedione, 1,3-cyclohexanedione, 5,5-dimethyl-1,3-cyclohexanedione, 1,3-dioxane-4,6-dione, etc.

[0274] (b) Pyrazolinone ring: for example, 1-phenyl-2-pyrazolin-5-one, 3-methyl-1-phenyl-2-pyrazolin-5-one, 1-(2-benzothiazolyl)-3-methyl-2-pyrazolin-5-one, etc.

[0275] (c) Isoxazoline ring: for example, 3-phenyl-2-isooxazoline-5-one, 3-methyl-2-isooxazoline-5-one, etc.

[0276] (d) Hydroxyindole ring: for example, 1-alkyl-2,3-dihydro-2-hydroxyindole, etc.

[0277] (e) 2,4,6-Triketone hexahydropyrimidine ring: For example, barbituric acid or 2-thiobarbituric acid and their derivatives. Examples of derivatives include 1-alkyl forms such as 1-methyl and 1-ethyl, 1,3-dimethyl, 1,3-diethyl, 1,3-dibutyl, 1,3-dialkyl, 1,3-diphenyl, 1,3-di(p-chlorophenyl), 1,3-di(p-ethoxycarbonylphenyl), 1,3-diaryl, 1-alkyl-1-aryl, 1,3-di(2-pyridyl), and 1,3-di-heterocyclic substituted forms at the 1,3 position.

[0278] (f) 2-Thio-2,4-thiazolidinedione ring: For example, bortanin and its derivatives. Examples of derivatives include 3-methylbortanin, 3-ethylbortanin, 3-allylbortanin and other 3-alkylbortanin, 3-phenylbortanin and other 3-arylbortanin, 3-(2-pyridyl)bortanin and other 3-heterocyclic substituted bortanin.

[0279] (g) 2-Thio-2,4-oxazolidinedione (2-Thio-2,4-(3H,5H)-oxazolidinedione ring: e.g., 3-ethyl-2-thio-2,4-oxazolidinedione, etc.)

[0280] (h) Thioninone ring: for example, 3(2H)-thioninone-1,1-dioxide, etc.

[0281] (i) 2-Thio-2,5-thiazolidinedione ring: for example, 3-ethyl-2-thio-2,5-thiazolidinedione, etc.

[0282] (j) 2,4-Thiazolidinedione ring: for example, 2,4-thiazolidinedione, 3-ethyl-2,4-thiazolidinedione, 3-phenyl-2,4-thiazolidinedione, etc.

[0283] (k) Thiazolin-4-one ring: for example, 4-thiazolinone, 2-ethyl-4-thiazolinone, etc.

[0284] (l) 4-Thiazolidinone ring: for example, 2-ethylmercapto-5-thiazolin-4-one, 2-alkylphenylamino-5-thiazolin-4-one, etc.

[0285] (m) 2,4-Imidazolidinedione (hydantoin) ring: for example, 2,4-imidazolidinedione, 3-ethyl-2,4-imidazolidinedione, etc.

[0286] (n) 2-Thio-2,4-imidazolidinedione (2-thiohydantoin) ring: for example, 2-thio-2,4-imidazolidinedione, 3-ethyl-2-thio-2,4-imidazolidinedione, etc.

[0287] (o) Imidazolin-5-one ring: for example, 2-propylmercapto-2-imidazolin-5-one, etc.

[0288] (p) 3,5-pyrazolidinedione ring: for example, 1,2-diphenyl-3,5-pyrazolidinedione, 1,2-dimethyl-3,5-pyrazolidinedione, etc.

[0289] (q) Benzothiophene-3-one ring: for example, benzothiophene-3-one, oxybenzothiophene-3-one, dioxobenzothiophene-3-one, etc.

[0290] (r) Indane ring: for example, 1-indane, 3-phenyl-1-indane, 3-methyl-1-indane, 3,3-diphenyl-1-indane, 3,3-dimethyl-1-indane, etc.

[0291] As R 3A With R 4A R 5A With R 6A The rings formed by mutual bonding are preferably 1,3-dicarbonyl rings, pyrazolone rings, 2,4,6-trionehexahydropyrimidine rings (also including thionone forms), 2-thio-2,4-thiazolidinedione rings, 2-thio-2,4-oxazolidinedione rings, 2-thio-2,5-thiazolidinedione rings, 2,4-thiazolidinedione rings, 2,4-imidazolidinedione rings, 2-thio-2,4-imidazolidinedione rings, 2-imidazolin-5-one rings, 3,5-pyrazolidinedione rings, benzothiophene-3-one rings, or indanone rings, and more preferably 1,3-dicarbonyl rings, 2,4,6-trionehexahydropyrimidine rings (also including thionone forms), 3,5-pyrazolidinedione rings, benzothiophene-3-one rings, or indanone rings.

[0292] Additionally, in R 3A With R 4A R 5A With R 6A In the case of mutual bonding forming a ring, R cannot be specified. 3A ~R 6A The σp value, but in this invention, the partial structures considered as rings are respectively R 3A ~R 6A The σp value is replaced by the value used to define the ring formation. For example, in R... 3A With R 4A In the case of forming a 1,3-indendyne ring, it is assumed that the benzoyl group replaces R respectively. 3A and R 4A .

[0293] X 1 and X 2 Represent -BR independently 21 R 22 .

[0294] R 21 and R 22 Substituents are represented independently, R 21 With R 22 They can bond together to form a ring.

[0295] As R 21 and R 22 The substituents represented are preferably halogen atoms, alkyl groups, alkoxy groups, aryl groups, heteroaryl groups and groups represented by the following formulas (2-4), more preferably halogen atoms, aryl groups or heteroaryl groups, and even more preferably aryl groups.

[0296] The preferred halogen atoms are fluorine, chlorine, bromine, and iodine atoms, with fluorine atoms being particularly preferred.

[0297] The alkyl group preferably has 1 to 40 carbon atoms. The lower limit is more preferably 3 or more. The upper limit is more preferably 30 or less, and even more preferably 25 or less. The alkyl group can be straight-chain, branched, or cyclic, but straight-chain or branched is preferred, and straight-chain is especially preferred.

[0298] The number of carbon atoms in the alkoxy group is preferably 1 to 40. The lower limit is more preferably 3 or more. The upper limit is more preferably 30 or less, and even more preferably 25 or less. The alkoxy group can be straight-chain, branched, or cyclic, but straight-chain or branched is preferred, especially straight-chain.

[0299] The aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 12. Phenyl is preferred as the aryl group.

[0300] The heteroaryl group can be monocyclic or polycyclic, preferably monocyclic. The number of heteroatoms constituting the heteroaryl group is preferably 1 to 3. The heteroatoms constituting the heteroaryl group are preferably nitrogen, oxygen, or sulfur atoms. The number of carbon atoms in the heteroaryl group is preferably 3 to 30, more preferably 3 to 18, even more preferably 3 to 12, and particularly preferably 3 to 5. The heteroaryl group is preferably a 5-membered or 6-membered ring. Specific examples of heteroaryl groups include those in R... 1A and R 2A Examples are illustrated in the text.

[0301] [Chemical Formula 55] In equation (2-4), R a5 ~R a9 Each can be used to represent a hydrogen atom or a substituent independently. This indicates the connection key with equation (D1). Regarding R... a5 ~R a9Examples of substituents include alkyl, alkoxy, aryl, and heteroaryl groups, with alkyl being preferred.

[0302] R 21 and R 22 They can bond together to form a ring. As R 21 With R 22 The rings formed by bonding, for example, include the structures shown in (2-1) to (2-3) below. Hereinafter, R represents a substituent, R... a1 ~R a4 Each of these groups independently represents a hydrogen atom or a substituent, and m1 to m3 independently represent integers from 0 to 4. As R and R... a1 ~R a4 The substituents represented can be exemplified in R. 21 and R 22 The substituents described herein are preferably alkyl groups.

[0303] [Chemical Formula 56] The pigment represented by the above general formula (D1) is preferably the pigment represented by the following general formula (D2).

[0304] [Chemical Formula 57] In equation (D2), R 1a and R 2a Substituents are represented independently, R 3a and R 6a Substituents are represented independently, R 4a and R 5a Each can be used independently to represent a heteroaryl group. R 3a With R 4a R 5a With R 6a They can be bonded separately to form rings. X 1a and X 2a Represent -BR independently 21a R 22a R 21a and R 22a Substituents are represented independently, R 21a With R 22a They can bond together to form a ring.

[0305] In equation (D2), R 3a ~R 6a X 1a X 2a R 21a and R 22a Each of the above R 3A ~R 6A X1 X 2 R 21 and R 22 They have the same meaning and the same preferred range.

[0306] R 1a and R 2a The substituents in R 1A and R 2A The alkyl, aryl, and heteroaryl groups in the text can have the same meaning of substituents, and the preferred range is also the same.

[0307] The pigment represented by the above general formula (D1) is more preferably represented by the following general formula (D3).

[0308] [Chemical Formula 58] In formula (D3), R 1b and R 2b Each independently represents a branched alkyl group, R 3b and R 6b Substituents are represented independently, R 4b and R 5b Each can be used independently to represent a heteroaryl group. R 3b With R 4b R 5b With R 6b They can be bonded separately to form rings. R 21b and R 22b Substituents are represented independently, R 21b With R 22b They can bond together to form a ring.

[0309] R 1b and R 2b Each branched alkyl group is represented independently. The number of carbon atoms is preferably 3 to 40. The lower limit is, for example, more preferably 5 or more, further preferably 8 or more, and even more preferably 10 or more. The upper limit is more preferably 35 or less, and even more preferably 30 or less. The number of branches of the branched alkyl group is preferably 2 to 10, more preferably 2 to 8.

[0310] R 3b ~R 6b R 21b and R 22b Each of the above R 3A ~R 6A R 21 and R 22 They have the same meaning and the same preferred range.

[0311] That is, R 3b and R 6b Preferably, it contains an electron-withdrawing group, more preferably a cyano group.

[0312] Preferred R 21b and R 22b Each of the following is independently a halogen atom, alkyl, alkoxy, aryl or heteroaryl, more preferably a halogen atom, aryl or heteroaryl, and even more preferably an aryl.

[0313] The following are specific examples of dye D. The compounds D-1 to D-24 and D-28 to D-90 shown below are pigments represented by the general formula (D1).

[0314] Additionally, in the following structural formula, iC 10 H 21 The "i" in "etc." indicates branching. Furthermore, Bu represents butyl, and Ph represents phenyl.

[0315] [Chemical Formula 59] [Chemical Formula 60] [Chemical Formula 61] [Chemical Formula 62] [Chemical Formula 63] [Chemical Formula 64] [Chemical Formula 65] [Chemical Formula 66] [Chemical Formula 67] (The pigment represented by general formula (1)) [Chemical Formula 68] In general formula (1), the manner in which A and B can be adopted is as described in general formula (1) for A and B in the aforementioned dyes B and C.

[0316] When dye D is a pigment represented by general formula (1), it is preferably a pigment represented by the following general formula (14).

[0317] [Chemical Formula 69] In general formula (14), R 1 and R 2R in the aforementioned general formula (2) 1 and R 2 They have the same meaning. Furthermore, R 41 and R 42 Also, R in the aforementioned general formula (2) 1 and R 2 They have the same meaning.

[0318] Among them, R 1 R 2 R 41 and R 42 Preferably alkyl, alkenyl, aryl or heteroaryl, more preferably alkyl, aryl or heteroaryl, and even more preferably alkyl or aryl.

[0319] R 1 R 2 R 41 and R 42 It can further have substituents. As an example of a substituent that can be further formed, R in the aforementioned general formula (2) can be cited. 1 and R 2 Substituents that may be further present and substituents X that A, B and G in the aforementioned general formula (1) may have.

[0320] B in general formula (14) 1 B 2 B 3 and B 4 Each of the above general formulas (2) contains B. 1 B 2 B 3 and B 4 The meaning is the same. Furthermore, B in general formula (14) 5 B 6 B 7 and B 8 Each of the above general formulas (2) contains B. 1 B 2 B 3 and B 4 They have the same meaning.

[0321] Can be used as B 1 B 2 B 3 B 4 B 5 B 6 B 7 and B 8 The carbon atoms of the carbon atom may have substituents that can be further substituents. Examples of such substituents that can be further substituents include the substituent X that A, B and G in the aforementioned general formula (1) can have.

[0322] In general formula (14), R1 With R 2 They can bond together to form a ring, R 1 or R 2 With B 2 Or B 3 The substituents can bond together to form a ring. Furthermore, R 41 With R 42 They can bond together to form a ring, R 41 or R 42 With B 6 Or B 7 The substituents can bond together to form a ring.

[0323] In the above description, the formed ring is preferably a heterocyclic or heteroaryl ring, and the size of the formed ring is not particularly limited, but a 5-membered or 6-membered ring is preferred. Furthermore, the number of rings formed is not particularly limited; it can be one or more. For example, R... 1 With B 2 The substituents and R 2 With B 3 The substituents are bonded together to form two rings.

[0324] The following are specific examples of dye D. The following compounds F-1 to F-33 are pigments represented by general formula (1).

[0325] [Chemical Formula 70] [Chemical Formula 71] In the aforementioned wavelength-selective absorption layer, the total content of dyes A to D, relative to 100 parts by mass of the resin constituting the wavelength-selective absorption layer, is preferably 0.10 parts by mass or more, more preferably 0.15 parts by mass or more, even more preferably 0.20 parts by mass or more, particularly preferably 0.25 parts by mass or more, and especially preferably 0.30 parts by mass or more. If the total content of dyes A to D in the wavelength-selective absorption layer is at or above the aforementioned preferred lower limit, a good anti-reflective effect can be obtained.

[0326] Furthermore, in the wavelength selective absorption layer, the total content of the dyes A to D is typically 50 parts by mass or less, preferably 40 parts by mass or less, and more preferably 30 parts by mass or less, relative to 100 parts by mass of the resin constituting the wavelength selective absorption layer.

[0327] The preferred contents of dyes A to D that may be contained in the wavelength-selective absorption layer are as follows.

[0328] The content of dye A is preferably 0.01 to 45 parts by weight, more preferably 0.1 to 30 parts by weight, relative to 100 parts by weight of the resin constituting the wavelength selective absorption layer. The content of dye B is preferably 0.01 to 45 parts by weight, more preferably 0.1 to 30 parts by weight, relative to 100 parts by weight of the resin constituting the wavelength selective absorption layer. The content of dye C is preferably 0.01 to 30 parts by weight, more preferably 0.1 to 10 parts by weight, relative to 100 parts by weight of the resin constituting the wavelength selective absorption layer. The content of dye D is preferably 0.05 to 50 parts by weight, more preferably 0.2 to 40 parts by weight, relative to 100 parts by weight of the resin constituting the wavelength selective absorption layer.

[0329] When the wavelength selective absorption layer contains all four dyes A to D, the preferred mass ratio of each dye A to D in the wavelength selective absorption layer is dye A: dye B: dye C: dye D = 1:0.1 to 10: 0.05 to 5: 0.1 to 10, more preferably 1:0.2 to 5: 0.1 to 3: 0.2 to 5.

[0330] Furthermore, when at least one of dyes B and C is the aforementioned matting agent-integrated pigment, from the viewpoint of antireflective effect, the content of the aforementioned matting agent-integrated pigment is preferably 0.1 parts by mass or more relative to 100 parts by mass of the resin constituting the wavelength selective absorption layer. The upper limit is preferably 45 parts by mass or less.

[0331] <Resin> The resin (hereinafter also referred to as "matrix resin") contained in the wavelength-selective absorption layer described above is capable of dispersing (preferably dissolving) the dye and the anti-fading agent of the dye described later, and is not particularly limited as long as it can suppress the reduction of lightfastness of the dye caused by the anti-fading agent. Preferably, it can satisfy the suppression of external light reflection and the suppression of brightness reduction, and can maintain the original color tone of the image of the OLED display device at an excellent level.

[0332] When at least one of dyes B and C is a squaric acid cyanine pigment represented by general formula (1), the matrix resin is preferably a low-polarity matrix resin in which the squaric acid cyanine pigment can exhibit clearer absorption. The squaric acid cyanine pigment exhibits clearer absorption, thereby satisfying the above-described relationships (I) to (VI) at a preferred level, and maintaining the original color tone of the image in the OLED display device at a superior level. Here, low polarity means that the fd value defined by the following relationship I is preferably 0.50 or higher.

[0333] Relationship I: fd = δd / (δd + δp + δh) In Equation I, δd, δp, and δh represent the terms corresponding to the London dispersion force, the dipole-dipole force, and the hydrogen bond force, respectively, relative to the solubility parameter δt calculated by the Hoy method. The specific calculation method is described later. That is, fd represents the ratio of δd to the sum of δd, δp, and δh.

[0334] By setting the fd value to 0.50 or higher, it is easier to obtain a clearer absorption waveform.

[0335] Furthermore, when the wavelength-selective absorption layer contains two or more matrix resins, the fd value is calculated as follows.

[0336] fd=Σ(w i •fd i ) Here, w i fd represents the mass fraction of the i-th matrix resin. i This represents the fd value of the i-th matrix resin.

[0337] -The term δd corresponding to the London dispersion force- The term δd corresponding to the London dispersion force refers to the value in reference "Properties of Polymers 3". rd The δd was calculated using the method described in the “2) Method of Hoy (1985, 1989)” section on pages 214-220 of ELSEVIER (1990), and was also calculated based on the description in the aforementioned section of the literature.

[0338] -The term δp- corresponding to dipole-dipole force- The term δp corresponding to the dipole-dipole force refers to the term in reference "Properties of Polymers 3". rd The δp was calculated using the method described in the “2) Method of Hoy (1985, 1989)” section on pages 214-220 of ELSEVIER (1990), and was also calculated based on the description in the aforementioned section of the literature.

[0339] -The term δh corresponding to hydrogen bond force- The term δh corresponding to hydrogen bonding force refers to the value in reference "Properties of Polymers 3". rdThe δh calculated by Amorphous Polymers is described in the “2) Method of Hoy (1985, 1989)” section on pages 214-220 of “ELSEVIER, (1990)”, and is calculated based on the description in the above section of the aforementioned literature.

[0340] Furthermore, if the matrix resin is a resin exhibiting constant hydrophobicity, the moisture content of the wavelength selective absorption layer can be set to a low moisture content, for example, 0.5% or less, which is preferable from the viewpoint of improving the lightfastness of the laminate of the present invention including the wavelength selective absorption layer.

[0341] In addition to polymers, resins can also contain any conventional components. However, the fd of the matrix resin mentioned above is a calculated value for the polymers constituting the matrix resin. Preferred examples of the matrix resins described above include polystyrene resins and cyclic polyolefin resins, with polystyrene resins being more preferred. Typically, the fd value of polystyrene resins is 0.45 to 0.60, and the fd value of cyclic polystyrene resins is 0.45 to 0.70. As mentioned above, an fd value of 0.50 or higher is preferably used.

[0342] Furthermore, in addition to these preferred resins, it is also preferable to use resin components that impart functionality to the wavelength-selective absorption layer, such as the stretchable resin component and the peel control resin component described later. That is, in this invention, the matrix resin is used in the sense that it includes stretchable resin components and peel control resin components, in addition to the resins described above.

[0343] From the viewpoint of clarifying the absorption waveform of the pigment, it is preferable that the matrix resin includes polystyrene resin.

[0344] (Polystyrene resin) The polystyrene included in the aforementioned polystyrene resin refers to a polymer containing styrene. Preferably, the polystyrene contains 50% by mass or more of styrene. The wavelength-selective absorption layer may contain one type of polystyrene or two or more types. Here, styrene refers to a monomer-derived structural unit having a styrene backbone in its structure.

[0345] From the viewpoint of controlling the photoelasticity and hygroscopicity to values ​​within the preferred range for wavelength-selective absorption layers, polystyrene more preferably contains 70% by mass or more of styrene, and even more preferably 85% by mass or more. Furthermore, polystyrene is also preferably composed solely of styrene.

[0346] Polystyrene, which consists solely of styrene, can be exemplified by homopolymers of styrene compounds and copolymers of two or more styrene compounds. Here, styrene compounds refer to compounds that have a styrene backbone in their structure, and in addition to styrene, also include compounds in which substituents have been introduced within the range where the olefinic unsaturated bonds of styrene can function as reactive (polymerizing) groups.

[0347] Specific styrene compounds include, for example, styrene; alkyl styrene 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 styrene such as hydroxystyrene, tert-butoxystyrene, vinylbenzoic acid, o-chlorostyrene, and p-chlorostyrene, in which hydroxyl, tert-butoxy, carboxyl, and halogen atoms are introduced into the benzene ring. Among these, from the viewpoint of availability and material cost, homopolymers of styrene (i.e., polystyrene) are preferred.

[0348] Furthermore, there are no particular limitations on the structural components other than styrene that can be included in the aforementioned polystyrene. That is, the polystyrene can be a styrene-diene copolymer or a styrene-polymerizable unsaturated carboxylic acid ester copolymer, etc. Furthermore, mixtures of polystyrene and synthetic rubber (e.g., polybutadiene and polyisoprene) can also be used. Moreover, impact-resistant polystyrene (HIPS) obtained by graft polymerization of styrene with synthetic rubber is preferred. Furthermore, polystyrene obtained by dispersing a rubbery elastomer in a continuous phase of a polymer containing a styrene component (e.g., a copolymer of a styrene component and a (meth)acrylate component), and then graft polymerization of the copolymer with the rubbery elastomer (referred to as grafted impact-resistant polystyrene "grafted HIPS") is also suitable. Furthermore, so-called styrene-based elastomers can also be appropriately used.

[0349] Furthermore, the aforementioned polystyrene can be hydrogenated (it can be hydrogenated polystyrene). There are no particular limitations on the type of hydrogenated polystyrene, but hydrogenated styrene-diene copolymers such as SEBS (hydrogenated styrene-butadiene-styrene block copolymer obtained by adding hydrogen to SBS (styrene-butadiene-styrene block copolymer)) and SEPS (hydrogenated styrene-isoprene-styrene block copolymer obtained by adding hydrogen to SIS (styrene-isoprene-styrene block copolymer)) are preferred. Only one type of hydrogenated polystyrene may be used, or two or more types may be used.

[0350] Furthermore, the aforementioned polystyrene can be modified polystyrene. There are no particular limitations on the type of modified polystyrene, but examples include polystyrene incorporating reactive groups such as polar groups. Specifically, acid-modified polystyrene such as maleic acid-modified polystyrene and epoxy-modified polystyrene are preferred.

[0351] As polystyrene, it is possible to use various polystyrene types with different compositions and molecular weights.

[0352] Polystyrene resins can be obtained by conventional methods such as anionic, bulk, suspension, emulsification, or solution polymerization. Furthermore, in polystyrene, at least a portion of the unsaturated double bonds of the benzene ring in the conjugated diene and styrene monomer can be hydrogenated. The hydrogenation rate can be determined by nuclear magnetic resonance (NMR).

[0353] Commercially available polystyrene resins can be used, such as: "CLEAREN530L" and "CLEAREN730L" manufactured by Denka Company Limited; "TUFPRENE126S" and "ASAPRENET411" manufactured by Asahi Kasei Corporation; "ClaytonD1102A" and "ClaytonD1116A" manufactured by Kraton Corporation; "Styrolux S" and "Styrolux T" manufactured by Styrolution Corporation; "ASAFLEX840" and "ASAFLEX860" (all SBS) manufactured by Asahi Kasei Chemicals Corporation; "679", "HF77", and "SGP-10" manufactured by PS Japan Corporation; "DICSTYRENEXC-515" and "DICSTYRENEXC-535" (all GPPS) manufactured by DIC Corporation; "475D", "H0103", and "HT478" manufactured by PS Japan Corporation; and DIC... Examples of HIPS include "DICSTYRENEGH-8300-5" (the above are HIPS) manufactured by Asahi Kasei Chemicals Corporation. Examples of hydrogenated polystyrene resins include "TUFTEC H series" manufactured by Asahi Kasei Chemicals Corporation, "Clayton G series" (the above are SEBS) manufactured by Shell Japan Ltd., "DYNARON" (hydrogenated styrene-butadiene random copolymer) manufactured by JSR Corporation, and "SEPTON" (SEPS) manufactured by KURARAY CO.,LTD. Furthermore, examples of modified polystyrene resins include "TUFTEC M series" 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.

[0354] In addition to the polystyrene resin, the wavelength-selective absorption layer preferably also contains polyphenylene ether resin. By simultaneously containing both polystyrene resin and polyphenylene ether resin, the toughness of the wavelength-selective absorption layer is improved, and the generation of defects such as cracks can be suppressed even in harsh environments such as high temperature and high humidity.

[0355] As the aforementioned polyphenylene ether resin, ZYLONS201A, ZYLON 202A, and ZYLON S203A manufactured by Asahi Kasei Corporation are preferred. Furthermore, a resin obtained by pre-mixing polystyrene resin and polyphenylene ether resin can be used. As a mixed resin of polystyrene resin and polyphenylene ether resin, ZYLON 1002H, ZYLON 1000H, ZYLON 600H, ZYLON 500H, ZYLON 400H, ZYLON 300H, and ZYLON 200H manufactured by Asahi Kasei Corporation are preferred, for example.

[0356] In the aforementioned wavelength-selective absorption layer, when polystyrene resin and polyphenylene ether resin are contained, the mass ratio of the two, calculated as polystyrene resin / polyphenylene ether resin, is preferably 99 / 1 to 50 / 50, more preferably 98 / 2 to 60 / 40, and even more preferably 95 / 5 to 70 / 30. By setting the proportion of polyphenylene ether resin within the aforementioned preferred range, the wavelength-selective absorption layer possesses sufficient toughness and allows for appropriate solvent evaporation when solution film formation is performed.

[0357] (Cyclic polyolefin resin) As the cyclic olefin compound contained in the cyclic polyolefin resin (also known as polycyclic olefin resin), there are no particular limitations as long as it has a ring structure containing carbon-carbon double bonds. Examples include norbornene compounds, monocyclic cyclic olefin compounds other than norbornene compounds, cyclic conjugated diene compounds, and vinyl alicyclic hydrocarbon compounds.

[0358] Examples of cyclic polyolefins 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 hydrides of polymers containing structural units derived from each of (1) to (4).

[0359] In this invention, open-ring polymers comprising structural units derived from norbornene compounds and structural units derived from monocyclic cyclic olefin compounds are included.

[0360] There are no particular limitations on the type of cyclic polyolefin, but polymers having structural units derived from norbornene compounds represented by the following general formula (A-II) or (A-III) are preferred. Polymers having structural units represented by the following general formula (A-II) are addition polymers of norbornene compounds, and polymers having structural units represented by the following general formula (A-III) are ring-opening polymers of norbornene compounds.

[0361] [Chemical Formula 72] In general formulas (A-II) and (A-III), m is an integer from 0 to 4, preferably 0 or 1.

[0362] In general formulas (A-II) and (A-III), R 3 ~R 6 Each can independently represent a hydrocarbon group with 1 to 10 hydrogen or carbon atoms.

[0363] There are no particular restrictions on the hydrocarbon groups in general formulas (AI) to (A-III), as long as they contain carbon and hydrogen atoms. Examples include alkyl, alkenyl, alkynyl, and aryl (aromatic hydrocarbon groups). Among them, alkyl or aryl groups are preferred.

[0364] In general formulas (A-II) and (A-III), X 2 and X 3 Y 2 and Y 3 Each of these can be independently represented as a hydrogen atom, a hydrocarbon group with 1 to 10 carbon atoms, a halogen atom, a hydrocarbon group with 1 to 10 carbon atoms substituted by a halogen atom, or -(CH2)nCOOR. 11 -(CH2)nOCOR 12 , -(CH2)nNCO, -(CH2)nNO2, -(CH2)nCN, -(CH2)nCONR 13 R 14 -(CH2)nNR 13 R 14 -(CH2)nOZ or -(CH2)nW, or X 2 With Y 2 or X 3 With Y 3 (-CO)₂O or (-CO)₂NR formed by mutual bonding 15 .

[0365] Here, R 11 ~R 15 Each can independently represent a hydrogen atom or a hydrocarbon group with 1 to 20 carbon atoms; Z represents a hydrocarbon group or a hydrocarbon group substituted with a halogen; W represents Si(R) 16 ) pD （3-p） (R) 16 Represents hydrocarbon groups with 1 to 10 carbon atoms, D represents a halogen atom, -OCOR 17 or -OR 17 (R) 17 (The group consists of a hydrocarbon group with 1 to 10 carbon atoms). p is an integer from 0 to 3). n is an integer from 0 to 10, preferably 0 to 8, and more preferably 0 to 6.

[0366] In general formulas (A-II) and (A-III), R 3 ~R 6 Hydrogen atoms or -CH3 are preferred respectively, and from the viewpoint of moisture permeability, hydrogen atoms are more preferred.

[0367] X 2 and X 3 Hydrogen atoms, -CH3 or -C2H5 are preferred respectively, and hydrogen atoms are preferred from the viewpoint of moisture permeability.

[0368] Y 2 and Y 3 Preferred atoms are hydrogen atoms, halogen atoms (especially chlorine atoms), or -(CH2)nCOOR. 11 (In particular, -COOCH3), from the viewpoint of moisture permeability, hydrogen atoms are preferred.

[0369] Other groups may be selected appropriately.

[0370] Polymers having structural units represented by general formula (A-II) or (A-III) may also contain at least one or more structural units represented by the following general formula (AI).

[0371] [Chemical Formula 73] In the general formula (AI), R 1 and R 2 Each independently represents a hydrogen atom or a hydrocarbon group with 1 to 10 carbon atoms, X 1 and Y 1 Each of these can be independently represented as a hydrogen atom, a hydrocarbon group with 1 to 10 carbon atoms, a halogen atom, a hydrocarbon group with 1 to 10 carbon atoms substituted by a halogen atom, or -(CH2)nCOOR. 11 -(CH2)nOCOR 12 , -(CH2)nNCO, -(CH2)nNO2, -(CH2)nCN, -(CH2)nCONR 13 R 14 -(CH2)nNR 13 R 14 -(CH2)nOZ, -(CH2)nW, or X 1 With Y1 (-CO)₂O or (-CO)₂NR formed by mutual bonding 15 .

[0372] Here, R 11 ~R 15 Each can independently represent a hydrogen atom or a hydrocarbon group with 1 to 20 carbon atoms; Z represents a hydrocarbon group or a hydrocarbon group substituted with a halogen; W represents Si(R) 16 ) p D （3-p） (R) 16 Represents hydrocarbon groups with 1 to 10 carbon atoms, D represents a halogen atom, -OCOR 17 or -OR 17 (R) 17 (A hydrocarbon group with 1 to 10 carbon atoms). p is an integer from 0 to 3). n is an integer from 0 to 10.

[0373] From the viewpoint of ensuring a tight fit for the polarizer, the cyclic polyolefin having structural units represented by general formula (A-II) or (A-III) preferably contains 90% by mass or less of structural units derived from the aforementioned norbornene compound relative to the total mass of the cyclic polyolefin, more preferably 30-85% by mass, even more preferably 50-79% by mass, and most preferably 60-75% by mass. Here, the proportion of structural units derived from the norbornene compound represents the average value in the cyclic polyolefin.

[0374] Addition (co)polymers of norbornene compounds are described in Japanese Patent Application Publication No. 10-7732, Japanese Patent Application Publication No. 2002-504184, U.S. Patent Publication No. 2004 / 229157A1 and International Patent Publication No. 2004 / 070463, etc.

[0375] As polymers of norbornene compounds, they are obtained by addition polymerization of norbornene compounds (e.g., polycyclic unsaturated compounds of norbornene) with each other.

[0376] Furthermore, as a polymer of norbornene, copolymers can be obtained by addition polymerization of norbornene with olefins such as ethylene, propylene, and butylene, conjugated dienes such as butadiene and isoprene, non-conjugated dienes such as ethylene-imide norbornene, and olefinic unsaturated compounds such as acrylonitrile, acrylic acid, methacrylic acid, maleic anhydride, acrylates, methacrylates, maleimide, vinyl acetate, and vinyl chloride, as needed. Among these, copolymers of norbornene and propylene are preferred.

[0377] Examples of addition (co)polymers of this norbornene compound include APL8008T (Tg 70℃), APL6011T (Tg 105℃), APL6013T (Tg 125℃), and APL6015T (Tg 145℃), all sold by Mitsui Chemicals, Inc. under the trade name Apel, with varying glass transition temperatures (Tg). Furthermore, TOPAS8007, TOPAS6013, and TOPAS6015 granules are sold by Polyplastics Co., Ltd. Appear3000 is sold by Ferrania.

[0378] The polymers of the aforementioned norbornene compounds are commercially available. For example, they are commercially available by JSR under the trade names Arton G or Arton F, and by Zeon Corporation under the trade names Zeonor ZF14, ZF16, Zeonex 250, or Zeonex 280.

[0379] Hydrogenates of polymers of norbornene compounds can be synthesized by hydrogenation following addition polymerization or translocation ring-opening polymerization of norbornene compounds. Synthetic methods are described, for example, in Japanese Patent Application Publication Nos. 1-240517, 7-196736, 60-26024, 62-19801, 2003-159767, and 2004-309979.

[0380] The molecular weight of the aforementioned cyclic polyolefins can be appropriately selected according to the intended use, but it is the mass-average molecular weight converted from polyisoprene or polystyrene in a cyclohexane solution (or toluene solution if the polymer is not dissolved) determined by gel permeation chromatography. It is typically in the range of 5,000 to 500,000, preferably 8,000 to 200,000, and more preferably in the range of 10,000 to 100,000. Polymers with molecular weights within the above range can achieve a high level of balanced mechanical strength and processability of the molded articles.

[0381] The wavelength-selective absorption layer preferably contains 5% by mass or more of the matrix resin, more preferably 20% by mass or more, even more preferably 50% by mass or more, particularly preferably 70% by mass or more, and more preferably 80% by mass or more, and most preferably 90% by mass or more.

[0382] The content of the matrix resin in the wavelength selective absorption layer is typically 99.90% by mass or less, preferably 99.85% by mass or less.

[0383] The wavelength-selective absorption layer may contain two or more cyclic polystyrene polymers, which may be used together with polymers that differ in at least one of their composition ratio and molecular weight. In this case, the total content of each polymer is within the aforementioned range.

[0384] (Elongation resin component) The aforementioned wavelength-selective absorption layer can be appropriately selected to contain components exhibiting elongation (also referred to as elongation-promoting resin components) as resin components. Specifically, examples include acrylonitrile-butadiene-styrene resin (ABS resin), styrene-butadiene resin (SB resin), isoprene resin, butadiene resin, polyether-polyurethane resin, and silicone resin. Furthermore, these resins can be further appropriately hydrogenated.

[0385] As the elongation resin component mentioned above, ABS resin or SB resin is preferred, and SB resin is more preferred.

[0386] The aforementioned SB resin can be, for example, commercially available resins. Examples of such commercially available products include TR2000, TR2003, TR2250 (trade names, manufactured by JSR Corporation), CLEAREN210M, 220M, 730V (trade names, manufactured by Denka Company Limited.), ASAFLEX800S, 805, 810, 825, 830, 840 (trade names, manufactured by Asahi Kasei Corporation), Eporex SB2400, SB2610, SB2710 (trade names, manufactured by Sumitomo Chemical Co., Ltd.), etc.

[0387] The wavelength-selective absorption layer 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.

[0388] As the above-mentioned elongation resin component, when a specimen with a thickness of 30 μm and a width of 10 mm is prepared by using the elongation resin component alone, the elongation at break at 25°C is preferably 10% or more, and more preferably 20% or more, when measured according to JIS 7127.

[0389] (Resin composition for peelability control) Regarding the aforementioned wavelength-selective absorption layer, when it is manufactured using a method that includes a step of peeling the wavelength-selective absorption layer from a release film, as described later in the manufacturing method for the wavelength-selective absorption layer, it is preferable to include a component for controlling peelability (a peelability control resin component) as the resin component. By controlling the peelability of the wavelength-selective absorption layer from the release film, it is possible to prevent peeling marks from remaining on the wavelength-selective absorption layer after peeling, and it is possible to handle various processing speeds during the peeling process. As a result, superior effects can be achieved in terms of improving the quality and productivity of the wavelength-selective absorption layer.

[0390] There are no particular limitations on the aforementioned peelability control resin components, and they can be appropriately selected depending on the type of release film. As will be described later, when a polyester polymer film is used as the release film, a polyester resin (also referred to as a polyester additive) is preferably used as the peelability control resin component. Furthermore, as will be described later, when a cellulose polymer film is used as the release film, a hydrogenated styrene-based thermoplastic elastomer (also referred to as a hydrogenated styrene additive) is preferably used as the peelability control resin component, and the description of hydrogenated polystyrene in the polystyrene resin included in the aforementioned wavelength-selective absorption layer can be applied.

[0391] The aforementioned polyester additives can be obtained through conventional methods such as the dehydration and fusion reaction of polybasic acids and polyols, the addition of diacid anhydrides to polyols, and the dehydration and fusion reaction, and are preferably polyesters formed from diacids and diols.

[0392] The weight-average molecular weight (Mw) of the above-mentioned polyester additives is preferably 500 to 50,000, more preferably 750 to 40,000, and even more preferably 2,000 to 30,000.

[0393] If the mass-average molecular weight of the aforementioned polyester additive is above the lower limit of the above-mentioned preferred value, it is preferred from the viewpoint of brittleness and resistance to damp heat; if it is below the upper limit of the above-mentioned preferred value, it is preferred from the viewpoint of compatibility with the resin.

[0394] The mass-average molecular weight of the aforementioned polyester additives is the mass-average molecular weight (Mw) converted from standard polystyrene, measured under the following conditions. The molecular weight distribution (Mw / Mn) can also be measured under the same conditions. Furthermore, Mn is the number-average molecular weight converted from standard polystyrene.

[0395] GPC: Gel permeation chromatography apparatus (HLC-8220GPC manufactured by Tosoh Corporation) The tubing is connected in sequence to protective columns HXL-H manufactured by Tosoh Corporation, TSK gel G7000HXL, two TSK gel GMHXL, and TSK gel G2000HXL. Eluent; tetrahydrofuran, Flow rate: 1 mL / min Sample concentration: 0.7–0.8% by mass Sample injection volume: 70 μL Temperature measured: 40℃ Detector; Differential refractometer (RI) (40°C) Standard material; TSK standard polystyrene manufactured by Tosoh Corporation Dicarboxylic acid is a preferred choice among dicarboxylic acid components that constitute polyester additives.

[0396] Examples of dicarboxylic acids include aliphatic dicarboxylic acids and aromatic dicarboxylic acids, with aromatic dicarboxylic acids or mixtures of aromatic and aliphatic dicarboxylic acids being preferred.

[0397] Among aromatic dicarboxylic acids, those with 8 to 20 carbon atoms are preferred, and those with 8 to 14 carbon atoms are more preferred. Specifically, at least one of phthalic acid, isophthalic acid, and terephthalic acid is preferred.

[0398] Among aliphatic dicarboxylic acids, aliphatic dicarboxylic acids with 3 to 8 carbon atoms are preferred, and aliphatic dicarboxylic acids with 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.

[0399] Furthermore, examples of diols constituting polyester additives include aliphatic diols and aromatic diols, with aliphatic diols being preferred.

[0400] Among aliphatic diols, aliphatic diols with 2 to 4 carbon atoms are preferred, and aliphatic diols with 2 to 3 carbon atoms are more preferred.

[0401] Examples of aliphatic diols include ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, and 1,4-butanediol, which can be used alone or in combination with two or more.

[0402] Polyester additives are particularly preferred to be compounds obtained by fused at least one of phthalic acid, isophthalic acid and terephthalic acid with an aliphatic diol.

[0403] The ends of the polyester additive can react with a monocarboxylic acid to achieve a seal. Aliphatic monocarboxylic acids are preferred as the sealing agent, with acetic acid, propionic acid, butyric acid, benzoic acid and their derivatives being particularly preferred, acetic acid or propionic acid being more preferred, and acetic acid being even more preferred.

[0404] Commercially available polyester additives include ester resins such as Polyester (e.g., LP050, TP290, LP035, LP033, TP217, TP220) manufactured by The Nippon Synthetic Chemical Industry Co., Ltd., and ester resins such as BYRON (e.g., BYRON245, BYRONK890, BYRON103, BYRON200, BYRON550, GK880) manufactured by TOYOBO CO., LTD.

[0405] The content of the peelability control resin component in the wavelength selective absorption layer is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, in the matrix resin. Furthermore, the upper limit is preferably 25% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less. From the viewpoint of obtaining adequate adhesion, the above-mentioned preferred range is preferred.

[0406] Anti-fading agent The wavelength-selective absorption layer contains a dye anti-fading agent (also simply referred to as an anti-fading agent) to prevent fading of dyes containing at least one of dyes A to D.

[0407] As the aforementioned anti-fading agent, commonly used anti-fading agents such as the antioxidants described in paragraphs

[0143] to

[0165] of International Publication No. 2015 / 005398, the free radical scavengers described in paragraphs

[0166] to

[0199] of International Publication No. 2015 / 005398, and the degradation inhibitors described in paragraphs

[0205] to

[0206] of International Publication No. 2015 / 005398 can be used without particular limitation.

[0408] As the aforementioned anti-fading agent, a compound represented by the following general formula (IV) is preferably used.

[0409] [Chemical Formula 74] In equation (IV), R 10 Indicates alkyl, alkenyl, aryl, heteroatom-containing cyclic groups or those derived from R 18 CO-, R 19 SO2- or R 20 The group represented by NHCO-. Here, R 18 R19 and R 20 Each can independently represent an alkyl, alkenyl, aryl, or heteroatom-containing cyclic group. R 11 and R 12 Each independently represents a hydrogen atom, halogen atom, alkyl group, alkenyl group, alkoxy group, or alkenyloxy group, R 13 R 14 R 15 R 16 and R 17 Each can independently represent a hydrogen atom, alkyl group, alkenyl group, or aryl group.

[0410] Among them, R 10 ~R 20 The alkyl group in it includes aralkyl groups.

[0411] As in equation (IV) by R 10 Examples of alkyl groups include methyl, ethyl, propyl, and benzyl; examples of alkenyl groups include allyl; examples of aryl groups include phenyl; and examples of heteroatom-containing cyclic groups include tetrahydropyranyl and pyrimidinyl. Furthermore, R... 18 R 19 and R 20 Each can independently represent an alkyl group (e.g., methyl, ethyl, n-propyl, n-butyl, benzyl, etc.), an alkenyl group (e.g., allyl, etc.), an aryl group (e.g., phenyl, methoxyphenyl, etc.), or a heteroatom-containing cyclic group (e.g., pyridyl, pyrimidinyl, etc.).

[0412] As R in equation (IV) 11 or R 12 Examples of halogen atoms that can be represented include chlorine and bromine; examples of alkyl groups include methyl, ethyl, n-butyl, and benzyl; examples of alkenyl groups include allyl; examples of alkoxy groups include methoxy, ethoxy, and benzyloxy; and examples of alkenyloxy groups include 2-propenyloxy.

[0413] As R in equation (IV) 13 R 14 R 15 R 16 or R 17 Examples of alkyl groups include methyl, ethyl, n-butyl, and benzyl; examples of alkenyl groups include 2-propenyl; and examples of aryl groups include phenyl, methoxyphenyl, and chlorophenyl.

[0414] R 10 ~R 20 It can also have substituents. Examples of substituents include those derived from R. 10 ~R 20 The groups represented.

[0415] Specific examples of compounds represented by general formula (IV) are shown below. However, the invention is not limited to these.

[0416] [Chemical Formula 75] [Chemical Formula 76] As the aforementioned anti-fading agent, a compound represented by the following general formula [III] is also preferred.

[0417] [Chemical Formula 77] In general formula [III], R 31 The symbol represents an aliphatic or aromatic group, and Y represents the group of non-metallic atoms required to form a 5- to 7-membered ring with nitrogen atoms.

[0418] In general formula [III], R 31 It represents an aliphatic or aromatic group, preferably an alkyl, aryl, or heterocyclic group (preferably an aliphatic heterocyclic group), and more preferably an aryl group.

[0419] Examples of heterocycles formed by Y and nitrogen atoms include piperidine rings, piperazine rings, morpholine rings, thiomorpholine rings, thiomorpholine-1,1-dione rings, pyrrolidine rings, and imidazoline rings.

[0420] Furthermore, the aforementioned heterocycles may also have substituents, such as alkyl and alkoxy groups.

[0421] Specific examples of compounds represented by general formula [III] are shown below. However, the invention is not limited to these.

[0422] [Chemical Formula 78] In addition to the specific examples mentioned above, as specific examples of compounds represented by the above general formula [III], we can also cite the exemplary compounds B-1 to B-65 described on pages 8 to 11 of Japanese Patent Application Publication No. 2-167543 and the exemplary compounds (1) to (120) described on pages 4 to 7 of Japanese Patent Application Publication No. 63-95439.

[0423] The content of the anti-fading agent in the wavelength selective absorption layer is preferably 1 to 15% by mass in 100% by mass of the total mass of the wavelength selective absorption layer, more preferably 5 to 15% by mass, even more preferably 5 to 12.5% ​​by mass, especially preferably 8 to 12.5% ​​by mass, and preferably 10 to 12.5% ​​by mass.

[0424] By including an anti-fading agent within the above-mentioned preferred range, the laminate of the present invention will not cause side effects such as discoloration of the wavelength-selective absorption layer, but can improve the lightfastness of the dye (pigment).

[0425] <Other Ingredients> In addition to the aforementioned dyes, matrix resins, and dye anti-fading agents, the wavelength-selective absorption layer may also contain matting agents and leveling agents (surfactants).

[0426] (Matte agent) Preferably, microparticles are added to the surface of the wavelength-selective absorption layer to impart slipability and prevent adhesion. As these microparticles, silica (SiO2) with a surface coated with hydrophobic groups and in the form of secondary particles is preferred. Alternatively, titanium dioxide, alumina, zirconium oxide, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, magnesium silicate, and calcium phosphate can be used in conjunction with or in place of silica. Commercially available microparticles include R972 and NX90S (both manufactured by NIPPON AEROSIL CO.,LTD., trade names).

[0427] These microparticles function as a so-called matting agent. By adding these microparticles, tiny irregularities are formed on the surface of the wavelength selective absorption layer. Even if the wavelength selective absorption layers overlap each other or other thin films due to these irregularities, they will not stick to each other, thus ensuring slipability.

[0428] In the case where the wavelength-selective absorption layer contains an extinction agent as microparticles, if there are 10 microparticles in the tiny irregularities caused by the protrusions of the microparticles from the filter surface... 4 pcs / mm 2 For protrusions with a height of 30nm or more, the improvement in sliding and adhesion is particularly significant.

[0429] From the viewpoint of improving adhesion and slip properties, it is particularly preferable to apply matting agent microparticles to the surface layer. Methods for applying microparticles to the surface layer include those based on multilayer casting and coating.

[0430] The content of the matting agent in the wavelength-selective absorption layer can be adjusted appropriately according to the purpose.

[0431] However, in the laminate of the present invention, it is preferable to apply the above-mentioned matting agent particles to the surface of the wavelength selective absorption layer that is in contact with the gas barrier layer, without impairing the effect of the present invention.

[0432] (Leveling agent) A leveling agent (surfactant) can be appropriately mixed into the wavelength-selective absorption layer described above. Commonly used compounds can be used as leveling agents, and fluorinated surfactants are particularly preferred. Specifically, for example, the compounds described in paragraphs

[0028] to

[0056] of Japanese Patent Application Publication No. 2001-330725 can be cited.

[0433] The content of leveling agent in the wavelength-selective absorption layer can be adjusted appropriately according to the purpose.

[0434] In addition to the components mentioned above, the wavelength-selective absorption layer may also contain low-molecular-weight plasticizers, oligomer plasticizers, delay modifiers, ultraviolet absorbers, degradation inhibitors, peeling accelerators, infrared absorbers, antioxidants, fillers, and compatibilizers.

[0435] <Method for manufacturing wavelength-selective absorption layers> The wavelength-selective absorption layer described above can be fabricated using conventional methods such as solution film formation, melt extrusion, or any method to form a coating on a substrate film (release film), and can also be appropriately combined with stretching. The wavelength-selective absorption layer is preferably fabricated using the coating method.

[0436] (Solution film formation method) In solution-based film fabrication, a solution is prepared by dissolving the wavelength-selective absorption layer material in an organic solvent or water. After appropriate concentration and filtration processes, the solution is uniformly cast onto a support. Next, the semi-dry film is peeled off the support, and the ends of the film are held appropriately using clamps or similar means, while the solvent is dried in a drying zone. Furthermore, stretching can be performed separately during and after the film drying process.

[0437] (Melted extrusion method) In melt extrusion, the material of the wavelength-selective absorber layer is hot-melted, and after appropriate filtration processes, it is uniformly cast onto a support. Next, the film, which has solidified through cooling, is peeled off, allowing for appropriate stretching. When the main material of the wavelength-selective absorber layer is a thermoplastic polymer resin, and the main material of the release film is also a thermoplastic polymer resin, a film can be formed from the molten polymer resin using a known co-extrusion method. At this time, by adjusting the types of polymers in the wavelength-selective absorber layer and the release film, as well as the additives mixed in each layer, or by adjusting the stretching temperature, stretching speed, and stretch ratio of the co-extruded film, the adhesion between the wavelength-selective absorber layer and the release film can be controlled.

[0438] Examples of co-extrusion methods include co-extrusion T-die method, co-extrusion blow molding method, and co-extrusion lamination method. Among these, co-extrusion T-die method is preferred. Co-extrusion T-die method can be implemented using a feed block or a multi-branch tube method. From the viewpoint of reducing thickness deviation, the multi-branch tube method is particularly preferred.

[0439] When using the co-extrusion T-die method, the melt temperature of the resin in the extruder with the T-die is preferably set to a temperature 80°C or higher than the glass transition temperature (Tg) of each resin, more preferably 100°C or higher, and preferably 180°C or lower, more preferably 150°C or lower. By setting the melt temperature of the resin in the extruder to the lower limit of the above-mentioned preferred range or higher, the flowability of the resin can be sufficiently improved, and by setting it to the upper limit of the above-mentioned preferred range or lower, resin deterioration can be prevented.

[0440] Typically, the sheet-like molten resin extruded from the mold opening is sealed to the cooling roller. There are no particular limitations on the method of sealing the molten resin to the cooling roller; for example, air knife method, vacuum box method, electrostatic sealing method, etc.

[0441] There is no particular limitation on the number of cooling rollers, but usually there are two or more. Furthermore, examples of cooling roller configurations include straight lines, Z-shaped lines, and L-shaped lines, but there are no particular limitations. Also, there are no particular limitations on the method by which the molten resin extruded from the mold opening passes through the cooling rollers.

[0442] The adhesion between the extruded sheet resin and the cooling roller changes depending on the temperature of the cooling roller. Increasing the temperature improves adhesion, but excessively high temperatures may cause the sheet resin to remain wrapped around the roller instead of peeling off. Therefore, regarding the cooling roller temperature, if the glass transition temperature (Tg) of the layer of resin in contact with the roller from the extruded resin is set as Tg, it is preferably set to below (Tg+30)°C, and more preferably within the range of (Tg-5)°C to (Tg-45)°C. By setting the cooling roller temperature within this preferred range, defects such as slippage and scratches can be prevented.

[0443] Here, it is preferable to reduce the content of residual solvent in the film before stretching. Methods for achieving this include, for example: (1) reducing the residual solvent in the resin used as a raw material; (2) pre-drying the resin before forming the film before stretching; etc. Pre-drying is performed, for example, by setting the resin in granular form and using a hot air dryer. The drying temperature is preferably 100°C or higher, and the drying time is preferably 2 hours or higher. By performing pre-drying, the residual solvent in the film before stretching can be reduced, thereby preventing bubbling of the extruded sheet resin.

[0444] (Coating method) In the coating method, a solution of the material for the wavelength-selective absorption layer described above is applied to the release film to form a coating. To control the adhesion between the coating and the release film, a release agent or similar agent can be pre-applied to the surface of the release film. The coating can be used in a subsequent process after being laminated with other components via an adhesive layer and then the release film can be peeled off. Regarding the adhesive constituting the adhesive layer, any adhesive can be used appropriately. Furthermore, the release film can be stretched appropriately along with the release film, either in the state where the solution of the material for the wavelength-selective absorption layer described above is coated on it or in the state where the coating is laminated.

[0445] The solvent used in the solution of the wavelength-selective absorption layer material can be appropriately selected based on the following considerations: the ability to dissolve or disperse wavelength-selective absorption layer materials; the ease with which they can form a uniform surface during coating and drying processes; the ability to ensure liquid preservation; and the possession of a suitable saturated vapor pressure.

[0446] -Addition of dyes (pigments) and anti-fading agents- Regarding the timing of adding the aforementioned dyes and anti-fading agents to the wavelength-selective absorption layer material, there are no particular limitations as long as they are added during film formation. For example, they can be added during the synthesis of the aforementioned matrix resin, or they can be mixed with the wavelength-selective absorption layer material during the preparation of the coating solution.

[0447] -Peel-off film- The thickness of the release film used to form the wavelength selective absorption layer by coating or similar methods is preferably 5 to 100 μm, more preferably 10 to 75 μm, and even more preferably 15 to 55 μm. If the film thickness is above or below the aforementioned preferred lower limit, sufficient mechanical strength is easily ensured, and defects such as curling, wrinkling, and bending are less likely to occur. Furthermore, if the film thickness is below or below the aforementioned preferred upper limit, when storing the multilayer film containing the wavelength selective absorption layer and the release film, for example, in a long roll, the surface pressure applied to the multilayer film is easily adjusted within an appropriate range, and adhesion defects are less likely to occur.

[0448] There is no particular limitation on the surface energy of the release film, but by adjusting the correlation between the surface energy of the material of the wavelength selective absorption layer and the surface energy of the coating solution and the surface energy of the side of the release film on which the wavelength selective absorption layer is formed, the adhesion between the wavelength selective absorption layer and the release film can be adjusted. If the surface energy difference is reduced, the adhesion tends to increase; if the surface energy difference is increased, the adhesion tends to decrease. The surface energy difference can be set appropriately.

[0449] The surface energy of the release film can be calculated based on the contact angle values ​​of water and diiodomethane using Owens' method. For example, the contact angle can be measured using the DM901 (manufactured by Kyowa Interface Science Co., Ltd., a contact angle measuring instrument).

[0450] The surface energy of the side of the release film forming the wavelength selective absorption layer is preferably 41.0 to 48.0 mN / m, more preferably 42.0 to 48.0 mN / m. If the surface energy is above or above the lower limit of the above-mentioned preferred value, the uniformity of the thickness of the wavelength selective absorption layer can be improved. If it is below or above the upper limit of the above-mentioned preferred value, it is easy to control the peeling force between the wavelength selective absorption layer and the release film within an appropriate range.

[0451] Furthermore, the surface roughness of the release film is not particularly limited, but adjustments can be made based on the relationship between the surface energy and hardness of the wavelength selective absorption layer surface and the surface energy and hardness of the release film surface on the side opposite to the side forming the wavelength selective absorption layer. For example, adjustments can be made to prevent adhesion failures when storing the multilayer film of the wavelength selective absorption layer and the release film in a long roll. Increasing the surface roughness tends to suppress adhesion failures, while decreasing the surface roughness tends to reduce the surface roughness of the wavelength selective absorption layer and the haze of the wavelength selective absorption layer. These settings can be appropriately adjusted.

[0452] As such a release film, any material and film can be appropriately used. Specific materials include polyester polymers (including polyethylene terephthalate films), olefin polymers, cycloolefin polymers, (meth)acrylic acid polymers, cellulose polymers, polyamide polymers, etc. Furthermore, to adjust the surface properties of the release film, appropriate surface treatments can be performed. To reduce surface energy, for example, corona treatment, room temperature plasma treatment, saponification treatment, etc., can be performed; to increase surface energy, silicone treatment, fluorine treatment, olefin treatment, etc., can be performed.

[0453] -Wavelength selection of absorption layer and peeling film peeling force- When the wavelength-selective absorption layer is formed using a coating method, the peel force between the wavelength-selective absorption layer and the release film can be controlled by adjusting the material of the wavelength-selective absorption layer, the material of the release film, and the internal deformation of the wavelength-selective absorption layer. This peel force can be measured, for example, in a test peeling the release film at a 90° angle. When measured at a speed of 300 mm / min, the peel force is preferably 0.001 to 5 N / 25 mm, more preferably 0.01 to 3 N / 25 mm, and even more preferably 0.05 to 1 N / 25 mm. If the value is above the lower limit of the above-preferred values, peeling outside the release film peeling process can be prevented; if the value is below the upper limit of the above-preferred values, poor peeling during the peeling process (e.g., zipping or breakage of the wavelength-selective absorption layer) can be prevented.

[0454] <Wavelength-selective absorption layer thickness> The thickness of the wavelength-selective absorption layer is not particularly limited, but it is preferably 1–18 μm, more preferably 1–12 μm, and even more preferably 2–8 μm. If the thickness is below the upper limit of the above-mentioned preferences, the reduction in polarization caused by fluorescence emitted by the dye (pigment) can be suppressed by adding a high concentration of dye to the film. Furthermore, the effects of matting agents and anti-fading agents are readily apparent. On the other hand, if the thickness is above the lower limit of the above-mentioned preferences, it is easier to maintain the uniformity of in-plane absorbance.

[0455] In this invention, a film thickness of 1–18 μm means that the thickness of the wavelength-selective absorption layer is within the range of 1–18 μm regardless of the location at which the measurement is performed. The same applies to film thicknesses of 1–12 μm and 2–8 μm. The film thickness can be measured using an electronic micrometer manufactured by ANRITSU CORPORATION.

[0456] <Absorbance of Wavelength-Selective Absorption Layer> The absorbance of the wavelength-selective absorption layer at a wavelength of 450 nm is preferably 0.05 or more and 3.0 or less, more preferably 0.1 or more and 2.0 or less, and even more preferably 0.1 or more and 1.0 or less.

[0457] Furthermore, the absorbance at a wavelength of 590 nm is preferably 0.1 or higher and 3.0 or lower, more preferably 0.2 or higher and 2.0 or lower, and even more preferably 0.3 or higher and 1.5 or lower.

[0458] By embedding the wavelength-selective absorption layer with absorbance adjusted within the above range into the OLED display device, the original color tone of the image of the OLED display device can be maintained at an excellent level, and display performance with higher brightness and further suppression of external light reflection can be obtained.

[0459] The absorbance of the wavelength-selective absorption layer can be adjusted according to the type and amount of dye added.

[0460] <Water content of wavelength-selective absorption layer> Regarding the water content of the wavelength-selective absorption layer, from a durability point of view, regardless of the film thickness, under conditions of 25°C and 80% relative humidity, it is preferably 0.5% by mass or less, and more preferably 0.3% by mass or less.

[0461] In this specification, the moisture content of the wavelength-selective absorption layer can be determined using a sample with an increased film thickness as needed. After the sample has been conditioned for more than 24 hours, the moisture content is determined by the Karl Fischer method using a moisture meter and sample drying devices "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 moisture content).

[0462] <Glass transition temperature (Tg) of wavelength-selective absorption layer> The glass transition temperature of the wavelength-selective absorption layer is preferably 50°C or higher and 140°C or lower. More preferably, it is 60°C or higher and 130°C or lower, and even more preferably, it is 70°C or higher and 120°C or lower. If the glass transition temperature is above or above the lower limit of the above-mentioned preferred values, the deterioration of the polarizer when used at high temperatures can be suppressed. If the glass transition temperature is below or above the upper limit of the above-mentioned preferred values, the organic solvent used in the coating solution can be prevented from easily remaining in the wavelength-selective absorption layer.

[0463] The glass transition temperature of the wavelength-selective absorption layer can be determined by the following method.

[0464] Using a differential scanning calorimeter (X-DSC7000 (manufactured by IT Keisoku Seigyo Co., Ltd.)), 20 mg of the wavelength-selective absorption layer was placed in the measurement dish and heated from 30 °C to 120 °C at a rate of 10 °C / min in a nitrogen flow and held for 15 minutes. Then, it was cooled to 30 °C at a rate of -20 °C / min. Next, it was heated again from 30 °C to 250 °C at a rate of 10 °C / min. The temperature at which the baseline began to deviate from the low-temperature side was set as the glass transition temperature (Tg).

[0465] The glass transition temperature of the aforementioned wavelength-selective absorption layer can be adjusted by mixing two or more polymers with different glass transition temperatures, or by changing the amount of low-molecular-weight compounds such as anti-fading agents.

[0466] <Processing of Wavelength Selective Absorption Layer> The wavelength-selective absorption layer is preferably hydrophilized by any glow discharge treatment, corona discharge treatment, or alkaline saponification treatment, with corona discharge treatment being the most preferred. Methods disclosed in Japanese Patent Application Publication No. 6-94915 or Japanese Patent Application Publication No. 6-118232 are also preferred.

[0467] Furthermore, depending on the requirements, the obtained membrane can undergo heat treatment, superheated steam contact, or organic solvent contact processes. Additionally, surface treatment can be performed as appropriate.

[0468] Furthermore, as an adhesive layer, a layer made of an adhesive composition using (meth)acrylic resin, styrene resin, silicone resin, etc. as a base polymer and incorporating crosslinking agents such as isocyanate compounds, epoxy compounds, aziridine compounds, etc., can also be applied.

[0469] Preferably, the adhesive layer in the OLED display device described later can be applied.

[0470] <<Gas Barrier Layer>> In the laminate of the present invention, at least one surface of the wavelength-selective absorption layer has a gas barrier layer containing a crystalline resin, the layer having a thickness of 0.1 μm to 10 μm, and the layer having an oxygen permeability of 60 cc / m 2 •day•atm or less.

[0471] In the aforementioned gas barrier layer, the aforementioned "crystalline resin" is a resin that has a melting point that changes from a crystalline phase to a liquid phase when the temperature is increased, and is able to impart gas barrier properties related to oxygen to the aforementioned gas barrier layer.

[0472] The laminate of the present invention, by having at least one gas barrier layer on the surface of the wavelength selective absorption layer in contact with air when using the laminate of the present invention, can suppress the reduction of the absorption intensity of the dye in the wavelength selective absorption layer. As long as the gas barrier layer is provided at the interface of the wavelength selective absorption layer in contact with air, the gas barrier layer can be provided on only one surface of the wavelength selective absorption layer or on both surfaces.

[0473] (Crystall resin) As for the crystalline resin included in the aforementioned gas barrier layer, any crystalline resin that has gas barrier properties and can impart the desired oxygen permeability to the gas barrier layer can be used without particular restrictions.

[0474] Examples of crystalline resins include polyvinyl alcohol and polyvinylidene chloride. From the viewpoint that the crystalline portion can effectively suppress gas permeation, polyvinyl alcohol is preferred.

[0475] The aforementioned polyvinyl alcohol can be modified or left unmodified. Examples of modified polyvinyl alcohol include those with acetyl groups, carboxyl groups, etc.

[0476] From the viewpoint of further improving oxygen barrier properties, the degree of saponification of the aforementioned polyvinyl alcohol is preferably 80.0 mol% or more, more preferably 90.0 mol% or more, even more preferably 97.0 mol% or more, and particularly preferably 98.0 mol% or more. There is no particular limitation on the upper limit, but practically it is 99.99 mol% or less. The degree of saponification of the aforementioned polyvinyl alcohol is a value calculated according to the method described in JIS K 6726 1994.

[0477] Without impairing the effects of the present invention, the aforementioned gas barrier layer may generally contain any components found in gas barrier layers. For example, in addition to the aforementioned crystalline resin, it may also contain amorphous resin materials, organic-inorganic hybrid materials such as sol-gel materials, SiO2, SiO2, etc. x SiON, SiN x Inorganic materials such as Al2O3.

[0478] Furthermore, without compromising the effectiveness of the present invention, the aforementioned gas barrier layer may contain solvents such as water and organic solvents generated during the manufacturing process.

[0479] The content of crystalline resin in the aforementioned gas barrier layer is preferably 90% by mass or more, more preferably 95% by mass or more, out of 100% by mass of the total mass of the gas barrier layer. There is no particular limitation on the upper limit, but it can also be set to 100% by mass.

[0480] The oxygen permeability of the aforementioned gas barrier layer is 60 cc / m 2 •day•atm below, preferably 50cc / m 2 •day•atm or less, preferably 30cc / m 2 •day•atm or less, preferably 10cc / m 2 •day•atm and below, 5cc / m is especially preferred 2 •day•atm and below, the optimal value is 1cc / m 2 •day•atm below. The actual lower limit is 0.001cc / m 2 •day•atm or more, for example, preferably more than 0.05cc / m 2 •day•atm. By keeping the oxygen permeability within the above-mentioned preferred range, lightfastness can be further improved.

[0481] Furthermore, the oxygen permeability of the gas barrier layer is measured according to the gas permeability test method based on JIS K 7126-2 2006. As the measuring device, for example, an oxygen permeability meter manufactured by MOCON, OX-TRAN2 / 21 (trade name), can be used. The measuring conditions are set to a temperature of 25°C and a relative humidity of 50%.

[0482] Oxygen permeability can be expressed in SI units as (fm) / (s•Pa). It can pass through (1fm) / (s•Pa) = 8.752 (cc) / (m 2 •day•atm) to convert. fm is read as femtometer and means 1fm = 10 -15 m.

[0483] From the perspective of further improving light resistance, the thickness of the gas barrier layer is preferably 0.5μm to 5μm, and more preferably 1.0μm to 4.0μm.

[0484] The thickness of the aforementioned air barrier layer was determined using the method described in the embodiments described later.

[0485] The crystallinity of the crystalline resin contained in the aforementioned gas barrier layer is preferably 25% or more, more preferably 40% or more, and even more preferably 45% or more. There is no particular limitation on the upper limit, but in practice it is 55% or less, preferably 50% or less.

[0486] The crystallinity of the crystalline resin contained in the above-mentioned gas barrier layer is a value determined and calculated according to the method described in J. Appl. Pol. Sci., 81,762 (2001) by the following method.

[0487] For samples stripped from the gas barrier layer, the heat of fusion 1 was determined using a DSC (differential scanning calorimeter) with a heating rate of 10 °C / min within the range of 20 °C to 260 °C. The heat of fusion 2 for complete crystallization was determined using the value described in J. Appl. Pol. Sci., 81, 762 (2001). The degree of crystallinity was calculated using the obtained heats of fusion 1 and fusion 2 by the following formula.

[0488] [Crystallization (%)] = ([Heat of fusion 1] / [Heat of fusion 2]) × 100 Specifically, the crystallinity mentioned above is a value determined and calculated using the method described in the examples below. Furthermore, heat of fusion 1 and heat of fusion 2 can be in the same unit, typically J / g. -1 .

[0489] <Manufacturing Method of Gas Barrier Layer> There are no particular limitations on the method for forming the gas barrier layer, but conventional methods include casting by spin coating and slot coating. Furthermore, methods such as laminating a commercially available resin-based gas barrier film or a pre-fabricated resin-based gas barrier film onto the wavelength-selective absorption layer can also be cited.

[0490] <Optical film> In addition to the wavelength-selective absorption layer and the gas barrier layer described above, the laminate of the present invention may also appropriately have any optical film without compromising the effects of the present invention.

[0491] Regarding any of the aforementioned optical films, there are no particular restrictions on optical properties or materials, but films containing at least one of cellulose ester resin, acrylic resin, cyclic olefin resin, and polyethylene terephthalate resin (or as a main component) are preferred. Furthermore, optically isotropic films or optically anisotropic retardation films can be used.

[0492] Regarding any of the aforementioned optical films, as optical films containing cellulose ester resins, for example, FUJITAC D80UL, FUJITAC TG60UL, and FUJITAC TJ40UL (all manufactured by FUJIFILM Corporation) can be used.

[0493] Regarding any of the aforementioned optical films, as optical films containing acrylic resins, the optical films containing (meth)acrylic resins containing styrene-based resins as described in Japanese Patent No. 4570042, the optical films containing (meth)acrylic resins having a glutarimide ring structure on the main chain as described in Japanese Patent No. 5041532, the optical films containing (meth)acrylic resins having a lactone ring structure as described in Japanese Patent Application Publication No. 2009-122664, and the optical films containing (meth)acrylic resins having glutaric anhydride units as described in Japanese Patent Application Publication No. 2009-139754 are all suitable.

[0494] Furthermore, regarding any of the aforementioned optical films, as optical films containing cyclic olefin resins, cyclic olefin resin films described after paragraph

[0029] of Japanese Patent Application Publication No. 2009-237376, cyclic olefin resin films containing additives that reduce Rth as described in Japanese Patent Application Publication No. 4881827 and Japanese Patent Application Publication No. 2008-063536 can be used.

[0495] Furthermore, any of the aforementioned optical films may contain an ultraviolet absorber. In the laminate of the present invention, the layer or optical film containing the ultraviolet absorber will also be referred to as an ultraviolet absorbing layer. As an ultraviolet absorber, commonly used compounds can be used without particular limitation, such as hindered phenolic compounds, hydroxybenzophenone compounds, benzotriazole compounds, salicylate compounds, benzophenone compounds, cyanoacrylate compounds, nickel complex salt compounds, etc.

[0496] Examples of hindered phenolic compounds include 2,6-di-tert-butyl-p-cresol, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis(3,5-di-tert-butyl-4-hydroxycinnamoamide), 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.

[0497] Examples of benzotriazole compounds include 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2,2-methylenebis(4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazole-2-yl)phenol), (2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butylaniline)-1,3,5-triazine, triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis(3,5-di-tert-butyl-4-hydroxy-oxidation) Cinnamamide), 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-pentylphenyl)-5-chlorobenzotriazole, 2,6-di-tert-butyl-p-cresol, 2-[5-chloro-2H-benzotriazole-2-yl]-4-methyl-6-(tert-butyl)phenol, pentaerythritol ester-tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], etc.

[0498] The content of ultraviolet absorber in the ultraviolet absorption layer can be adjusted appropriately according to the purpose.

[0499] <<Methods for Manufacturing Laminated Materials>> The laminate of the present invention can be manufactured using the above-described methods for manufacturing wavelength-selective absorption layers and gas barrier layers.

[0500] For example, a method can be used to directly fabricate the aforementioned barrier layer on the wavelength-selective absorption layer produced by the above manufacturing method. In this case, it is also preferable to perform corona treatment on the surface of the wavelength-selective absorption layer where the barrier layer is disposed.

[0501] Furthermore, when any of the aforementioned optical films are provided, it is preferable to bond them via an adhesive layer. For example, it is also preferable to bond the optical film containing the ultraviolet absorber via an adhesive layer or bonding agent after providing a gas barrier layer on the wavelength selective absorption layer.

[0502] OLED display devices The OLED display device of the present invention includes the laminate of the present invention.

[0503] As an OLED display device of the present invention, as long as the laminate of the present invention is included in a structure such that the barrier layer is located at least on the outer light side compared to the wavelength selective absorption layer, other structures of commonly used OLED display devices can be used without particular limitation. There are no particular limitations on the structural examples of the OLED display device of the present invention, but examples can be given of display devices that, from opposite sides relative to the outer light, sequentially include glass, a layer including TFTs (thin-film transistors), an OLED display element, a barrier film, a color filter, glass, an adhesive layer, the laminate of the present invention, and a surface film.

[0504] The aforementioned OLED display element has a structure in which an anode electrode, a light-emitting layer, and a cathode electrode are sequentially stacked. Between the anode electrode and the cathode electrode, in addition to the light-emitting layer, there are also a Hall injection layer, a Hall transport layer, an electron transport layer, and an electron injection layer. Furthermore, for example, reference can be made to the description in Japanese Patent Application Publication No. 2014-132522.

[0505] Furthermore, in addition to conventional color filters, color filters with stacked quantum dots can also be used as the aforementioned color filters.

[0506] Resin films can also be used to replace the glass mentioned above.

[0507] Regarding the OLED display device of the present invention, even when the structure of the laminate of the present invention is provided as an anti-reflection mechanism instead of a circular polarizer, the absorbance of the dye contained in the wavelength selective absorption layer can be maintained at an excellent level.

[0508] Furthermore, as mentioned above, when the dyes contained in the wavelength-selective absorption layer are configured as a combination of four dyes A to D, excellent lightfastness is achieved, exceeding the reduction in lightfastness associated with dye mixing. In particular, by containing four dyes A to D in a manner that satisfies the aforementioned formulas (I) to (VI), both suppression of external light reflection and suppression of brightness reduction can be achieved to a sufficient level, and the original hue of the image formed by light emitted from the light-emitting layer (light source) can be maintained to an excellent level.

[0509] That is, when a circular polarizer with anti-reflective properties is typically used as the surface film described above, the OLED display device of the present invention can achieve the aforementioned excellent effects without using a circular polarizer by employing the laminate of the present invention. Furthermore, the structure of the OLED display device of the present invention does not impede the use of an anti-reflective film without compromising the effects of the present invention.

[0510] There are no particular limitations on the method for forming the color image of the OLED that can be applied to the OLED display device of the present invention. Any of the following methods can be used: a three-color coating method (R (red) G (green) B (blue)), a color conversion method, and a color filter method. The three-color coating method is preferred. Therefore, as the light source of the OLED display device of the present invention, each light-emitting layer corresponding to the above-described image formation method can also be applied.

[0511] <Adhesive layer> In the OLED display device of the present invention, the laminate of the present invention is preferably bonded to the glass (substrate) via an adhesive layer on the side located opposite to the external light.

[0512] The composition of the adhesive composition used in the formation of the adhesive layer is not particularly limited; for example, a composition containing a mass-average molecular weight (M...) can be used. w The adhesive composition is based on a base resin with a molecular weight average of 500,000 or higher. When the molecular weight average of the base resin is less than 500,000, bubbles or peeling may occur under at least one condition, such as high temperature and high humidity, due to reduced cohesiveness, thus reducing the durability and reliability of the adhesive. There is no particular upper limit to the molecular weight average of the base resin, but if the molecular weight average increases excessively, the coatability may decrease due to increased viscosity; therefore, a molecular weight average of 2,000,000 or lower is preferred.

[0513] There is no particular limitation on the specific type of base resin. For example, acrylic resins, silicone resins, rubber resins, and EVA (ethylene-vinyl acetate) resins can be mentioned. When used in optical devices such as liquid crystal displays, acrylic resins are mainly used due to their excellent transparency, oxidation resistance, and resistance to yellowing, but they are not limited to this.

[0514] Examples of acrylic resins include polymers comprising a monomer mixture containing 80 to 99.8 parts by weight of (meth)acrylate monomer and 0.02 to 20 parts by weight (preferably 0.2 to 20 parts by weight) of other crosslinking monomers.

[0515] There is no particular limitation on the type of (meth)acrylate monomer; for example, alkyl (meth)acrylates can be mentioned. However, if the alkyl group in the monomer becomes an excessively long chain, the cohesive strength of the binder decreases, and it can sometimes be difficult to regulate the glass transition temperature (T0).g Therefore, it is preferable to use (meth)acrylate monomers having alkyl groups having 1 to 14 carbon atoms, as these monomers have poor adhesion or adhesive properties. Examples of such monomers include 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, amyl (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. In this invention, the above monomers can be used alone or in combination of two or more. Regarding the (meth)acrylate monomers, it is preferable to include 80 to 99.8 parts by mass of a monomer mixture in a proportion of 100 parts by mass. When the content of (meth)acrylate monomer is less than 80 parts by weight, the initial adhesive strength may sometimes decrease. If it exceeds 99.8 parts by weight, the durability may sometimes decrease due to the decrease in cohesion.

[0516] Other crosslinking monomers included in the monomer mixture can react with the multifunctional crosslinking agents described later to impart cohesiveness to the adhesive and to the polymer with crosslinking functional groups that regulate adhesion and durability. Examples of such crosslinking monomers include hydroxyl-containing monomers, carboxyl-containing monomers, and nitrogen-containing monomers. Examples of hydroxyl-containing monomers include 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. Examples of carboxyl-containing monomers include acrylic acid, methacrylic acid, 2-(meth)acryloyloxyacetic acid, 3-(meth)acryloyloxypropionic acid, 4-(meth)acryloyloxybutyric acid, acrylic acid dimer, itaconic acid, maleic acid, and maleic anhydride. Examples of nitrogen-containing monomers include (meth)acrylamide, N-vinylpyrrolidone, or N-vinylcaprolactam. In this invention, these crosslinking monomers can be used alone or in combination of two or more.

[0517] Regarding other crosslinking monomers, 0.02 to 20 parts by weight of the monomer mixture may be included. When the content is less than 0.02 parts by weight, the durability and reliability of the adhesive may sometimes decrease; when it exceeds 20 parts by weight, at least one of the adhesion and peelability may sometimes decrease.

[0518] The monomer mixture may also contain monomers represented by the following general formula (10). Such monomers can be added for the purpose of adjusting the glass transition temperature of the binder and imparting other functionalities.

[0519] [Chemical Formula 79] In the formula, R1 to R3 independently represent hydrogen atoms or alkyl groups, and R4 represents cyano; alkyl-substituted or unsubstituted phenyl; acetoxy; or COR5 (here, R5 represents alkyl-substituted or unsubstituted amino or glycidoxy).

[0520] In the definitions of R1 to R5 in the above formulas, alkyl or alkoxy refers to alkyl or alkoxy with 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, and more preferably 1 to 12 carbon atoms. Specifically, it can be methyl, ethyl, methoxy, ethoxy, propoxy, or butoxy.

[0521] Examples of monomers represented by general formula (10) include 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 carboxylic acid esters such as vinyl acetate, etc., but are not limited thereto. Regarding the monomer represented by general formula (10), it may contain 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 sometimes decrease.

[0522] There are no particular limitations on the method for manufacturing polymers using monomer mixtures. For example, they can be manufactured by general polymerization methods such as solution polymerization, photopolymerization, bulk polymerization, suspension polymerization, or latex polymerization. In this invention, solution polymerization is particularly preferred. Solution polymerization is preferably carried out by mixing the initiator while uniformly mixing each monomer and at a polymerization temperature of 50°C to 140°C. Examples of initiators used include azo-based polymerization initiators such as azobisisobutyronitrile and azobiscyclohexanenitrile; and common initiators such as peroxides such as benzoyl peroxide and acetyl peroxide.

[0523] The adhesive composition described above may further contain 0.1 to 10 parts by weight of a crosslinking agent relative to 100 parts by weight of the base resin. This crosslinking agent imparts cohesive strength 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 weight, the cohesive strength of the adhesive may sometimes decrease. Furthermore, if it exceeds 10 parts by weight, interlayer delamination and warping may sometimes occur, resulting in reduced durability and reliability.

[0524] There are no particular limitations on the type of crosslinking agent. For example, any crosslinking agent such as isocyanate compounds, epoxy compounds, aziridine compounds, and metal chelate compounds can be used.

[0525] Examples of isocyanate compounds include, for example, toluene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, tetramethylxylene diisocyanate, and naphthalene diisocyanate, as well as the reaction product of any one of these compounds with a polyol (e.g., trimethylolpropane); examples of epoxy compounds include ethylene glycol diglycidyl ether, triglycidyl ether, trimethylolpropane triglycidyl ether, N,N,N',N'-tetraglycidyl ethylenediamine, and glyceryl diglycidyl ether; examples of aziridine compounds include N,N'-toluene-2,4-bis(1-aziridinecarboxamide), N,N'-diphenylmethane-4,4'-bis(1-aziridinecarboxamide), tratamine, bisprothaloyl-1-(2-methylaziridine), and tri-1-aziridine phosphine oxide. Furthermore, as metal chelating compounds, examples include compounds in which at least one multivalent metal, such as aluminum, iron, zinc, tin, titanium, antimony, magnesium, and vanadium, is coordinated to acetylacetone or ethyl acetoacetate.

[0526] The above-mentioned adhesive composition may further contain 0.01 to 10 parts by weight of a silane coupling agent relative to 100 parts by weight of the base resin. Regarding silane coupling agents, the adhesive can help improve bonding reliability when placed under high temperature or high humidity conditions for extended periods, especially improving bonding stability when bonding to glass substrates, and enhancing heat resistance and moisture resistance. Examples of silane coupling agents include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltriethoxysilane, γ-aminopropyltriethoxysilane, 3-isocyanate propyltriethoxysilane, and γ-acetoacetate propyltrimethoxysilane. These silane coupling agents can be used alone or in combination of two or more.

[0527] Regarding silane-based coupling agents, the amount is preferably 0.01 to 10 parts by weight relative to 100 parts by weight of the base resin, and more preferably 0.05 to 1 part by weight. When the content is less than 0.01 parts by weight, the effect of increasing adhesion may sometimes be insufficient, and if it exceeds 10 parts by weight, it may sometimes cause reduced durability and reliability, such as bubbles or peeling.

[0528] The aforementioned adhesive composition may also contain an antistatic agent. As an antistatic agent, any compound can be used, provided it exhibits excellent compatibility with other components contained in the adhesive composition, such as acrylic resin, does not adversely affect the transparency, workability, or durability of the adhesive, and imparts antistatic properties to the adhesive. Examples of antistatic agents include inorganic salts and organic salts.

[0529] Inorganic salts are salts containing alkali metal cations or alkaline earth metal cations as their cation components. Lithium ions (Li₂) are an example of cations. + Sodium ions (Na) + ), potassium ions (K) + ), rubidium ions (Rb + ), cesium ions (Cs) + beryllium ions (Be) 2+ ), magnesium ions (Mg 2+ ), calcium ions (Ca 2+ ), Strontium ion (Sr) 2+ ) and barium ions (Ba 2+ Among one or more of these, lithium ion (Li) is a preferred example. + Sodium ions (Na) + ), potassium ions (K) + ), cesium ions (Cs) + beryllium ions (Be) 2+ ), magnesium ions (Mg 2+ ), calcium ions (Ca 2+ ) and barium ions (Ba 2+ Inorganic salts can be used alone or in combination of two or more. From the perspectives of ionic safety and migration within the binder, lithium ions (Li₂O₃) are particularly preferred. + ).

[0530] Organic salts are salts containing onium cations as their cationic components. The term "onium cation" refers to a positively charged (+) ion in which at least a portion of the charge is unevenly distributed among one or more atoms of nitrogen (N), phosphorus (P), and sulfur (S). Onium cations can be cyclic or acyclic compounds; in the case of cyclic compounds, they can be non-aromatic or aromatic compounds. Furthermore, in the case of cyclic compounds, they can contain one or more heteroatoms other than nitrogen, phosphorus, or sulfur atoms (e.g., oxygen). Furthermore, cyclic or acyclic compounds can be substituted with substituents such as hydrogen atoms, halogen atoms, alkyl groups, or aryl groups. Furthermore, in the case of acyclic compounds, they can contain one or more, preferably four or more, substituents, which can be cyclic or acyclic, aromatic or non-aromatic.

[0531] 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.

[0532] Specifically, the quaternary ammonium ion is preferably a cation represented by the following general formula 11.

[0533] [Chemical Formula 80] In general 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.

[0534] As in the above general formula 11, alkyl or alkoxy groups represent alkyl or alkoxy groups with 1 to 12 carbon atoms, preferably 1 to 8, and alkenyl or alkynyl groups represent alkenyl or alkynyl groups with 2 to 12 carbon atoms, preferably 2 to 8.

[0535] In general formula 11, aryl, as a substituent derived from aromatic compounds, represents phenyl, biphenyl, naphthalene, or anthracene cyclic systems, etc., and heteroaryl represents a heterocyclic or aryl ring containing 5 to 12 heteroatoms including one or more of O, N, and S. Specifically, it represents furanyl, pyrrolidinyl, pyrrolidinyl, thiophenyl, pyridyl, piperidinyl, indolyl, quinolinyl, thiazolyl, benzothiazole, and triazole, etc.

[0536] In general formula 11, alkyl, alkoxy, alkenyl, alkynyl, aryl or heteroaryl groups may be substituted by one or more substituents. Examples of substituents include hydroxyl groups, halogen atoms or alkyl or alkoxy groups having 1 to 12 carbon atoms, preferably 1 to 8, and more preferably 1 to 4.

[0537] In this invention, quaternary ammonium cations are preferably used as cations represented by general formula 11, and in particular, cations in which R1 to R4 are each independently substituted or unsubstituted alkyl groups having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms.

[0538] Examples of quaternary ammonium ions represented by general formula 11 include 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.

[0539] Examples of aromatic ammonium ions include, for example, ions of one or more of pyridinium, pyridazinium, pyrimidinium, pyrazinium, imidazoline, pyrazolium, thiazoline, oxazolium, and triazolium. Preferably, N-alkylpyridinium ions are substituted with alkyl groups having 4 to 16 carbon atoms, 1,3-alkylmethylimidazoline ions are substituted with alkyl groups having 2 to 10 carbon atoms, and 1,2-dimethyl-3-alkylimidazoline ions are substituted with alkyl groups having 2 to 10 carbon atoms. These aromatic ammonium ions can be used alone or in combination of two or more.

[0540] Furthermore, the aromatic ammonium ion is a compound represented by the following general formula 12.

[0541] [Chemical Formula 81] In general formula 12, R 10 To R 15 Each of these can 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.

[0542] In general formula 12, the definitions of alkyl, alkoxy, alkenyl, alkynyl, aryl and heteroaryl and their substituted derivatives are the same as those in general formula 11 above.

[0543] As a compound of general formula 12, R is particularly preferred. 11 To R 15 Each is independently a hydrogen atom or an alkyl group, R 10 It is an alkyl group.

[0544] In the examples of antistatic agents described above, such as the anions contained in inorganic or organic salts containing cations, fluorides (F...) are preferably cited. - ), chloride (Cl) - ), bromide (Br - ), iodide (I - ), perchlorate (ClO4) - ), hydroxides (OH) - ), carbonates (CO3) 2- ), nitrate esters (NO3) - ) sulfonates (SO4) - ), methylbenzenesulfonate (CH3( C6H4 SO3 - p-Toluenesulfonate (CH3C6H4SO3) - ), carboxybenzenesulfonate (COOH(C6H4)SO3) - ), trifluoromethanesulfonate (CF3SO2) - ), benzoate (C6H5COO)- ), acetate (CH3COO) - ), trifluoroacetate (CF3COO) - ), tetrafluoroborate (BF4) - ), tetrabenzylboronic acid ester (B(C6H5)4) - ), hexafluorophosphate (PF6) - ), tris(C2F5)3F3 - ), bis(trifluoromethanesulfonyl)imide (N(SO2CF3)2) - ), bis(pentafluoroethanesulfonyl)imide (N(SOC2F5)2) - ), bis(pentafluoroethane) carbonyl imide (N(COC2F5)2) - ), bis(perfluorobutanesulfonyl)imide (N(SO2C4F9)2) - ), bis(perfluorobutane) carbonyl imide (N(COC4F9)2 - ), trifluoromethanesulfonyl methyl compound (C(SO2CF3)3) - ) and trifluoromethane carbonyl methylation (C(SO2CF3)3 - However, it is not limited to these. Among anions, imide anions that can perform electron-withdrawing functions and are highly stable due to being substituted with hydrophobic fluorine are preferred.

[0545] From the viewpoint of improving the durability of the dye contained in the wavelength-selective absorption layer, an antistatic agent having quaternary ammonium ions represented by general formula 11 is particularly preferred.

[0546] The adhesive composition described above contains, relative to 100 parts by weight of the base resin, 0.01 to 5 parts by weight, preferably 0.01 to 2 parts by weight, and more preferably 0.1 to 2 parts by weight of an antistatic agent. When the content is less than 0.01 parts by weight, the desired antistatic effect may not be achieved; if it exceeds 5 parts by weight, the compatibility with other components may be reduced, leading to decreased durability, reliability, or transparency of the adhesive.

[0547] The adhesive composition described above may also contain an antistatic agent, specifically a compound capable of forming a coordination bond with the cations contained in the antistatic agent (hereinafter referred to as a "coordination-bonded compound"). By appropriately including a coordination-bonded compound, the anion concentration within the adhesive layer can be increased, effectively imparting antistatic properties, even when using a relatively small amount of antistatic agent.

[0548] There are no particular limitations on the types of coordination-bonding compounds that can be used, as long as they have functional groups within the molecule that can coordinate and bond with the antistatic agent. For example, alkyl oxide compounds can be cited.

[0549] There are no particular limitations on the alkylene oxide compounds, but it is preferred to use alkylene oxide compounds containing alkylene oxide units with 2 or more carbon atoms, preferably 3 to 12, and more preferably 3 to 8.

[0550] The molecular weight of the alkyl oxide compound is preferably 5,000 or less. As used in this invention, the term "molecular weight" refers to the molecular weight or mass-average molecular weight of the compound. In this invention, if the molecular weight of the alkyl oxide compound exceeds 5,000, the viscosity may sometimes increase excessively, resulting in poor coatability, or the ability to form complexes with metals may decrease. On the other hand, there is no particular limitation on the lower limit of the molecular weight of the alkyl oxide compound, but it is preferably 500 or more, more preferably 4,000 or more.

[0551] As an epoxide compound, there are no particular limitations as long as it exhibits the above-mentioned properties; for example, a compound represented by the following general formula 13 can be used.

[0552] [Chemical Formula 82] In general formula 13, A represents an alkylene group with 2 or more carbon atoms, n represents 1 to 120, and R... 16 and R 17 Each independently represents a hydrogen atom, hydroxyl group, alkyl group, or C(=O)R 18 The above R 18 It represents a hydrogen atom or an alkyl group.

[0553] In general formula 13, alkylene refers to an alkylene with 3 to 12 carbon atoms, preferably 3 to 8, specifically ethylene, propyleneene, butylene or pentylene.

[0554] In general formula 13, alkyl means alkyl with 1 to 12 carbon atoms, preferably 1 to 8, more preferably 1 to 4, and n preferably means 1 to 80, more preferably 1 to 40.

[0555] Examples of compounds represented by general formula 13 include fatty acid alkyl esters of polyepoxides (e.g., polyethylene oxide, polypropylene oxide, polybutane, or polypentane), or carboxylic acid esters of polyepoxides (e.g., polyethylene oxide, polypropylene oxide, polybutane, or polypentane), but are not limited thereto.

[0556] In this invention, in addition to the above-mentioned alkylene oxide compounds, various coordination-bonding compounds can be appropriately selected as needed, such as ester compounds having one or more ether bonds disclosed in Korean Patent Publication No. 2006-0018495, or compounds containing oxalate groups, diamine groups, polyvalent carboxyl groups, or ketone groups disclosed in Korean Patent Publication No. 2006-0128659.

[0557] Regarding the coordination bonding compound, it is included in the adhesive composition at a ratio of 3 parts by weight or less relative to 100 parts by weight of the base resin, more preferably 0.1 parts by weight to 3 parts by weight, and even more preferably 0.5 parts by weight to 2 parts by weight. If the content exceeds 3 parts by weight, the adhesive properties such as peelability may sometimes decrease.

[0558] From the viewpoint of adjusting adhesive properties, the above-described adhesive composition may further include 1 to 100 parts by weight of an adhesive-improving resin relative to 100 parts by weight of the base resin. When the content of the adhesive-improving resin is less than 1 part by weight, the addition effect may sometimes be insufficient; if it exceeds 100 parts by weight, at least one of the effects of improving compatibility and cohesion may sometimes decrease. There are no particular limitations on such adhesive-improving resins, but examples include (hydrogenated) hydrocarbon resins, (hydrogenated) rosin resins, (hydrogenated) rosin ester resins, (hydrogenated) terpene resins, (hydrogenated) terpene phenolic resins, polymerized rosin resins, or polymerized rosin ester resins. These adhesive-improving resins may be used alone or in combination of two or more.

[0559] The above-mentioned adhesive composition may further include, to a extent that it will not affect the effect of the invention, one or more polymerization initiators such as thermal polymerization initiators and photopolymerization initiators; epoxy resin; curing agent; ultraviolet stabilizer; antioxidant; colorant; reinforcing agent; filler; defoamer; surfactant; photopolymerizable compounds such as polyfunctional acrylates; and additives such as plasticizers.

[0560] <Substrate> In the OLED display device of the present invention, the laminate of the present invention is preferably bonded to the glass (substrate) via an adhesive layer or bonding agent layer on the side opposite to the external light.

[0561] There are no particular limitations on the method for forming the adhesive layer. For example, the following methods can be used: applying the adhesive composition to the wavelength selective absorption layer using a conventional device such as a rod coater, and then drying and curing it; or first applying the adhesive composition to the surface of a release substrate, drying it, and then transferring the adhesive layer to the wavelength selective absorption layer using the release substrate, and then allowing it to mature and cure.

[0562] There are no particular limitations on the release substrate; any release substrate can be used, such as the release film in the above-described method for manufacturing the wavelength-selective absorption layer.

[0563] In addition, the conditions for coating, drying, curing and hardening can be appropriately adjusted according to conventional methods.

[0564] <Refractive index of each layer in a laminate> In the OLED display device of the present invention, from the viewpoint of reducing the reflection of external light, the laminate of the present invention preferably adjusts the difference in refractive index of each layer relative to adjacent layers within a constant range. Adjacent layers refer to layers that are in direct contact with each other. The refractive index difference between the aforementioned adjacent layers is preferably 0.15 or less, more preferably 0.10 or less, further preferably 0.06 or less, particularly preferably 0.05 or less, and most preferably 0.04 or less. That is, all layers constituting the laminate of the present invention preferably satisfy the aforementioned refractive index difference between adjacent layers.

[0565] As a laminate of the present invention that satisfies the refractive index difference between the adjacent layers, it is preferable to have an ultraviolet absorbing layer disposed on the side opposite to the wavelength selective absorption layer, in addition to the wavelength selective absorption layer and the gas barrier layer. Furthermore, it is also preferable to include at least one of an adhesive layer and a bonding agent layer. If the adhesive layer is not located between the wavelength selective absorption layer and the gas barrier layer, it can be used when any layers are laminated together. For example, the adhesive layer can be disposed between the gas barrier layer and the ultraviolet absorbing layer.

[0566] Furthermore, when the laminate of the present invention is embedded in an OLED display device, it is preferable that the refractive index difference between adjacent layers is also satisfied between the layers of the laminate of the present invention in contact with the OLED display device. When the side of the laminate of the present invention located opposite to external light (for example, the side opposite to the wavelength selective absorption layer and the gas barrier layer) is bonded to glass (substrate) via an adhesive layer or bonding agent layer, it is preferable that the side of the laminate of the present invention located opposite to external light, the adhesive layer or bonding agent layer, and the glass respectively satisfy the refractive index difference between adjacent layers.

[0567] Furthermore, the sum of the interfacial reflectivities of the laminates of the present invention is preferably 0.30% or less, more preferably 0.20% or less, even more preferably 0.10% or less, particularly preferably 0.06% or less, and most preferably 0.03% or less, and most preferably 0.02% or less. There are no particular limitations on the lower limit value.

[0568] The sum of the above-mentioned interface reflectivities was calculated using the refractive indices and film thicknesses of each layer, according to the method described in Chapter 5, pages 173-174 of "Applied Physics Engineering Series 3: Thin Films," 7th edition, edited by Yoshida Sadao, and rounded to the third decimal place. Furthermore, the refractive indices and film thicknesses of each layer can be measured using the methods described in the examples described later.

[0569] For example, when viewed from the perspective of a visual observer, in the case of a structure formed by sequentially stacking a surface anti-reflective layer / support / adhesive (bonding) layer / gas barrier layer / wavelength selective absorption layer / adhesive (bonding) layer / glass, it is preferable to adjust the refractive index of each layer from the support to the glass to be within the following range. However, in the laminate of the present invention, excellent anti-reflective effect can be achieved even without a surface anti-reflective layer.

[0570] Support structure: 1.45~1.55 Adhesive layer: 1.47~1.57 Gas barrier layer: 1.49~1.59 Wavelength-selective absorption layer: 1.51–1.61 Adhesive layer: 1.47~1.57 Glass: 1.45~1.55 The refractive index of each layer can be adjusted by the structure of the resin used in each layer (based on high refractive index based on aromatic ring groups or sulfur atoms, or low refractive index based on fluorine atoms), the addition of high refractive index microparticles or nanoparticles such as titanium oxide or zirconium oxide, the addition of high refractive index materials such as sulfur atoms or nitrogen atoms, and the addition of low refractive index materials such as fluorine atoms.

[0571] The refractive index of each layer can be determined by spectroscopic microscopy or elliptic polarization, for example, by using a reflective spectroscopic film thickness gauge FE3000 (trade name) manufactured by OTSUKA ELECTRONICS Co., LTD. Specifically, it can be determined by the method described in the examples described later.

[0572] As the aforementioned surface antireflective layer, surface films with antireflective functions used in OLED display devices can be used without particular restrictions; for example, circular polarizers can be cited.

[0573] The aforementioned optical film can be used as the support, wherein an ultraviolet absorbing layer is preferred.

[0574] The aforementioned adhesive (bonding) layer refers to an adhesive layer composed of adhesive or a bonding layer composed of bonding agent.

[0575] [Adhesive layer] The adhesive layer described above can be applied to the adhesive layer in the OLED display device.

[0576] Examples of high refractive index materials that increase the refractive index of the adhesive layer by adding them to the adhesive layer include benzodithiols and triazine compounds.

[0577] i) Benzodithiols As a benzodithiol compound, for example, a compound represented by the following general formula (A) is preferred.

[0578] [Chemical Formula 83] In the above formula, Y 41 and Y 42 V represents either a hydrogen atom or a monovalent substituent independently. 41 and V 42 Each can be used to independently represent a hydrogen atom or a monovalent substituent.

[0579] Regarding compounds represented by general formula (A), the same applies to paragraphs

[0037] to

[0062] of Japanese Patent Application Publication No. 2009-096972. In this invention, compounds represented by general formula (A) preferably do not have a straight-chain alkyl group having 8 or more carbon atoms.

[0580] In general formula (A), Y is preferred. 41 and Y 42 One of them is a cyano group, and the other is a substituted or unsubstituted alkyl carbonyl group, a substituted or unsubstituted aryl carbonyl group, a substituted or unsubstituted heterocyclic carbonyl group, a substituted or unsubstituted alkyl sulfonyl group, or a substituted or unsubstituted aryl sulfonyl group, more preferably Y. 41 and Y 42 One of them is a cyano group, and the other is a substituted or unsubstituted alkyl carbonyl group, a substituted or unsubstituted aryl carbonyl group, or a substituted or unsubstituted heterocyclic carbonyl group. More preferably, one of them is a cyano group, and the other is a substituted or unsubstituted alkyl carbonyl group or a substituted or unsubstituted aryl carbonyl group.

[0581] In general formula (A), in V 41 and V 42When a substituent is indicated as monovalent, the preferred substituents are halogen, mercapto, cyano, carboxyl, phosphate, sulfonyl, hydroxyl, carbamoyl, aminosulfonyl, nitro, alkoxy, aryloxy, acyl, acyloxy, amide, alkylaminocarbonyloxy, sulfonyl, sulfinyl, sulfonamide, amino, substituted amino, ammonium, hydrazine, urea, imide, alkyl or arylthio, unsubstituted or substituted alkoxycarbonyl, aryloxycarbonyl, alkoxycarbonyloxy, unsubstituted alkyl, substituted alkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heterocyclic groups; more preferably cyano, acyl, acyloxy, or alkylaminocarbonyloxy; and even more preferably acyloxy or alkylaminocarbonyloxy. 41 and Y 42 The number of carbon atoms is preferably 1 to 18, more preferably 1 to 10.

[0582] The following are specific examples of compounds represented by general formula (A). However, compounds represented by general formula (A) are not limited to the specific examples below.

[0583] [Chemical Formula 84] [Chemical Formula 85] ii) Triazine compounds As triazine compounds, compounds represented by the following general formula (I) are preferred examples.

[0584] [Chemical Formula 86] In the above formula, R 12 Each independently represents an aryl or heterocyclic group having at least one substituent in the ortho, meta, or para positions.

[0585] X 11 Each can be used independently to represent a single bond or -NR. 13 -. Here, R 13 Each can independently represent a hydrogen atom, a substituted or unsubstituted alkyl, alkenyl, aryl, or heterocyclic group.

[0586] Can be used as R 12 The aryl group is preferably phenyl or naphthyl, and more preferably phenyl.

[0587] As can be used as R 12Examples of substituents that an aryl group may have include halogen atoms, hydroxyl groups, cyano groups, nitro groups, carboxyl groups, alkyl groups, alkenyl groups, aryl groups, alkoxy groups, alkenyloxy groups, aryloxy groups, alkoxycarbonyl groups, alkenyloxycarbonyl groups, aryloxycarbonyl groups, aminosulfonyl groups, alkyl-substituted aminosulfonyl groups, alkenyl-substituted aminosulfonyl groups, aryl-substituted aminosulfonyl groups, sulfonamide groups, carbamoyl groups, alkyl-substituted carbamoyl groups, alkenyl-substituted carbamoyl groups, aryl-substituted carbamoyl groups, amide groups, alkylthio groups, alkenylthio groups, arylthio groups, and acyl groups.

[0588] Can be used as R 12 The heterocyclic group preferably has aromaticity. The heterocycle in the heterocyclic group is preferably a 5-membered, 6-membered, or 7-membered ring, more preferably a 5-membered or 6-membered ring, and most preferably a 6-membered ring. The heteroatom constituting the ring is preferably a nitrogen atom, a sulfur atom, or an oxygen atom, more preferably a nitrogen atom. As an aromatic heterocycle, a pyridine ring (as a heterocyclic group, it is 2-pyridinyl or 4-pyridinyl) is particularly preferred. The heterocyclic group may have substituents. As a group that can be used as R... 12 Examples of substituents in heterocyclic groups include the substituents in the aryl group described above.

[0589] In X 11 In the case of a single bond, it can be used as R 12 The heterocyclic group is preferably a heterocyclic group having a free valence atom in the nitrogen atom. The heterocycle in the heterocyclic group having a free valence atom in the nitrogen atom is preferably a 5-membered ring, a 6-membered ring, or a 7-membered ring, more preferably a 5-membered ring or a 6-membered ring, and most preferably a 5-membered ring. The heterocycle in the heterocyclic group may have multiple nitrogen atoms as ring-forming atoms. Furthermore, the ring-forming atoms in the heterocyclic group may have heteroatoms other than nitrogen atoms (e.g., oxygen atoms, sulfur atoms).

[0590] The following are examples of heterocyclic groups having a free atomic valence in the nitrogen atom. In the following structural formulas, This indicates the free valence atom.

[0591] [Chemical Formula 87] Can be used as R 13 The alkyl group can be cyclic or chain-like, but chain-like alkyl groups are preferred, and straight-chain alkyl groups without branches are more preferred. The number of carbon atoms in the alkyl group is preferably 1 to 30, more preferably 1 to 20, further preferably 1 to 10, particularly preferably 1 to 8, and most preferably 1 to 6. The alkyl group may have substituents. Examples of substituents include halogen atoms, alkoxy groups (e.g., methoxy, ethoxy), and acyloxy groups (e.g., acryloyloxy, methacryloyloxy).

[0592] Can be used as R 13The alkenyl group can be cyclic or chain-like, but chain-like alkenyl groups are preferred, and more preferably straight-chain alkenyl groups without branches. The alkenyl group preferably has 2 to 30 carbon atoms, more preferably 2 to 20, further preferably 2 to 10, particularly preferably 2 to 8, and most preferably 2 to 6. The alkenyl group may have substituents. Examples of substituents include those that the aforementioned alkyl groups may have.

[0593] Can be used as R 13 Aryl and heterocyclic groups and those that can be used as R 12 The meanings of aryl and heterocyclic groups are the same. Aryl and heterocyclic groups can further have substituents; examples of substituents include those that can be used as R... 12 Aryl and heterocyclic groups can have substituents.

[0594] The molecular weight of the compound represented by the above general formula (I) is preferably 300 to 800.

[0595] Furthermore, it can be used in conjunction with a UV absorber along with a compound represented by the above general formula (I). The amount of UV absorber used is preferably 10 parts by mass or less, more preferably 3 parts by mass or less, relative to 100 parts by mass of the compound represented by general formula (I).

[0596] As a specific example of a triazine compound represented by the above formula (I), for example, the compound described in Japanese Patent Application Publication No. 2008-239786, in sections 0084 to 0094, as a specific example of a delayed development agent represented by general formula (I) can be preferably cited.

[0597] When the adhesive layer contains a high refractive index material, its content can be appropriately adjusted. For example, it can be set to 0.1 to 40 parts by mass relative to 100 parts by mass of the solid components (excluding solvents) of the adhesive, preferably 0.5 to 30 parts by mass, and more preferably 1.0 to 25 parts by mass.

[0598] (Adhesive layer) Examples of adhesives used in the aforementioned adhesive layer include polyvinyl alcohol-based adhesives such as polyvinyl alcohol and polyvinyl butyral, and vinyl latexes such as butyl acrylate.

[0599] From the viewpoint of refractive index, the degree of saponification of the polyvinyl alcohol used in the adhesive layer is preferably 30 mol% or more, and more preferably 50 mol% or more. When the adhesive layer is composed of two or more types of polyvinyl alcohol, it is preferable that at least one type of polyvinyl alcohol satisfies the above-mentioned degree of saponification, and more preferably that any one type of polyvinyl alcohol satisfies the above-mentioned degree of saponification.

[0600] As the polyvinyl alcohol-based adhesive of the present invention, commercially available polyvinyl alcohol can be used. For example, Kuraray Poval5-98, 11-98, 28-98, 60-98, 5-88, 9-88, 2-88, CP-1220T10 manufactured by KURARAY CO.,LTD., and DENKA POVAL K-05, K-17C, K-17E, H-12, H-17, B-05, B-17, etc. manufactured by Denka Company Limited are preferred.

[0601] When the laminate of the present invention has a layer I that is further in contact with a gas barrier layer disposed on at least one surface of a wavelength selective absorption layer, and the layer I satisfies the above-mentioned requirements for the gas barrier layer in the laminate of the present invention (containing a crystalline resin and having an oxygen permeability of less than a specific value), the gas barrier layer in the laminate of the present invention refers to a layer composed of the above-mentioned gas barrier layer and the above-mentioned layer I.

[0602] Layer I, which is understood as the gas barrier layer in the laminate of the present invention, can be exemplified, for example, by the corresponding layer in the adhesive layer described above. In this case, the thickness of the gas barrier layer, the oxygen permeability of the layer, and the crystallinity of the crystalline resin contained in the layer are measured and calculated using the methods described in the embodiments described later.

[0603] In the laminate of the present invention, which is formed by sequentially layering a surface anti-reflective layer, an ultraviolet absorbing layer, an adhesive layer, a gas barrier layer, a wavelength selective absorption layer, an adhesive layer, and glass, from the viewpoint of reducing the refractive index difference between adjacent layers and reducing external light reflection, it is preferable to have a structure that satisfies at least one of the following: the layer disposed between the ultraviolet absorbing layer and the gas barrier layer is an adhesive layer; the resin in the wavelength selective absorption layer includes the aforementioned cyclic polyolefin resin; and the layer disposed between the wavelength selective absorption layer and the glass is an adhesive layer containing a high refractive index material. More preferably, it satisfies at least two of these structures, and even more preferably, it satisfies all of them. However, in the laminate of the present invention, excellent anti-reflective effects can be achieved even without a surface anti-reflective layer.

[0604] Example The present invention will now be described in further detail with reference to embodiments. Appropriate modifications can be made to the materials, amounts, proportions, processing contents, processing order, etc., shown in the following embodiments, as long as they do not depart from the spirit of the invention. Therefore, the scope of the present invention is not limited to the embodiments shown below.

[0605] Furthermore, in the following embodiments, unless otherwise specified, the terms "parts" and "%" indicating composition are based on mass. Also, in the determination of the absorbance of the lightfastness evaluation film described later, λ... maxIt refers to the maximum absorption wavelength, which displays the maximum absorbance, and is measured in nm.

[0606] Fabrication of a wavelength-selective absorption layer The following shows the materials used in the fabrication of the wavelength-selective absorption layer.

[0607] <Matrix Resin> (Resin 1) Polystyrene resin (manufactured by PS Japan Corporation, PSJ-polystyrene GPPS SGP-10 (trade name)) was used as resin 1.

[0608] (Resin 2) Polyphenylene ether resin (manufactured by Asahi Kasei Corporation, ZYLON S201A (trade name), poly(2,6-dimethyl-1,4-phenylene ether), Tg 210℃) (Resin component 1 for peelability control) BYRON550 (trade name, manufactured by TOYOBO CO., LTD., polyester additive) <Dyes> As dye A, the following E-13 or E-24 was used; as dye B, the following A-33 was used; as dye C, the following C-80 was used; and as dye D, the following D-35 or F-29 was used.

[0609] In the following text, Ph represents phenyl.

[0610] [Chemical Formula 88] <Additives> (Anti-fading agent 1) [Chemical Formula 89] (Leveling agent 1) A polymeric surfactant composed of the following components is used as leveling agent 1. In the following structural formula, the proportions of each component are molar ratios, and t-Bu refers to tert-butyl.

[0611] [Chemical Formula 90] (Substrate 1) A polyethylene terephthalate film, Lumirror XD-510P (trade name, 50 μm thick, manufactured by TORAYINDUSTRIES, INC.), was used as substrate 1.

[0612] Example 1 <Fabrication of Wavelength Selective Absorption Layer 1 with Substrate> (1) Preparation of wavelength-selective absorption layer forming liquid 1 The components were mixed in the manner shown below to prepare wavelength-selective absorption layer forming liquid 1.

[0613] ―――――――――――――――――――――――――――――― Composition of wavelength-selective absorption layer forming liquid 1 ―――――――――――――――――――――――――――――― Resin 1 66.7 parts by weight Resin 2 17.5 parts by weight 0.20 parts by weight of peel control resin component Leveling agent 1 0.08 parts by weight Dye E-13 0.86 parts by weight Dye D-35 2.23 parts by weight Anti-fading agent 1 12.4 parts by weight Toluene (solvent) 1710.0 parts by weight Cyclohexanone (solvent) 190.0 parts by weight ―――――――――――――――――――――――――――――― Next, the obtained wavelength selective absorption layer forming liquid 1 was filtered using a filter with an absolute filtration accuracy of 5 μm (trade name: Hydrohobic Fluorepore Membrane, manufactured by Millex).

[0614] (2) Fabrication of wavelength selective absorption layer 1 with substrate With a dried film thickness of 2.5 μm, the wavelength selective absorption layer forming liquid 1 after the above filtration treatment was applied to the substrate 1 using a bar coater, and dried at 120°C, thereby producing a wavelength selective absorption layer 1 with a substrate.

[0615] <Fabrication of wavelength selective absorption layers 2, 3, 4a1, 4a2, 4b, 4c, 4d1, 4d2, 5 and 6 with substrate> The types and amounts of dyes were changed to those described in Table 1 below. Otherwise, wavelength selective absorption layers 2, 3, 4a1, 4a2, 4b, 4c, 4d1, 4d2, 5 and 6 were fabricated in the same manner as the fabrication of wavelength selective absorption layer 1 with substrate.

[0616] [Fabrication of a laminate consisting of a gas barrier layer and a wavelength selective absorption layer] The following shows the materials used in the fabrication of the stack of the gas barrier layer and the wavelength selective absorption layer (hereinafter referred to as the stack).

[0617] <Resin> (1) Crystalline resin (Resin 3) PVA105 (manufactured by KURARAY CO., LTD., Kuraray Poval PVA-105 (trade name), polyvinyl alcohol, saponification degree of 98-99 mol%) (Resin 4) AQ-4104 (manufactured by KURARAY CO., LTD., Exceval AQ-4104 (trade name), modified polyvinyl alcohol, saponification degree of 98-99 mol%) (Resin 5) PVA403 (manufactured by KURARAY CO., LTD., Kuraray Poval PVA-403 (trade name), polyvinyl alcohol, saponification degree of 80 mol%) (Resin 6) PVA117H (manufactured by KURARAY CO., LTD., Kuraray Poval PVA-117H (trade name), polyvinyl alcohol, saponification degree of 99 mol%) (2) Amorphous resin (Resin 7): STYRENE AS-70 (manufactured by Nippon Steel & Sumitomo Metal Corporation, STYRENE AS-70 (trade name), acrylonitrile-styrene copolymer) (Substrate 2) Using a corona treatment device (trade name: Corona-Plus, manufactured by VETAPHONE), at a discharge rate of 1000 W•min / m 2 Corona treatment is performed on the wavelength selective absorption layer side of the wavelength selective absorption layer 1 with substrate at a processing speed of 3.2 m / min, so as to be used as substrate 2.

[0618] <Creation of Layer No. L101> (1) Preparation of resin solution The components were mixed according to the composition shown below and stirred in a constant temperature bath at 90°C for 1 hour to dissolve resin 3, thus preparing the gas barrier layer forming liquid 1.

[0619] ―――――――――――――――――――――――――――――― Composition of gas barrier layer forming liquid 1 ―――――――――――――――――――――――――――――― 3-4.0 parts by weight of resin 96.0 parts by weight of pure water ―――――――――――――――――――――――――――――― Next, the obtained barrier layer forming liquid 1 was filtered using a filter with an absolute filtration accuracy of 5 μm (trade name: Hydrohobic Fluorepore Membrane, manufactured by Millex).

[0620] (2) Fabrication of laminated bodies With a dried film thickness of 1.1 μm, the above-mentioned filtered barrier layer forming liquid 1 was applied to the corona-treated side of the substrate 2 using a bar coater, and dried at 120°C for 60 seconds to produce laminate No. L101.

[0621] The laminate No. L101 has a structure formed by sequentially stacking a substrate 1, a wavelength selective absorption layer and a gas barrier layer.

[0622] <Fabrication of laminates No. L102~L116, Lc001~Lc008 and Lc101~Lc111> As described in Table 2 below, the composition of the gas barrier layer forming liquid, the type of wavelength selective absorption layer with substrate, and the thickness of the gas barrier layer were changed. Otherwise, laminates No. L102 to L116, Lc001 to Lc008, and Lc101 to Lc111 were manufactured in the same manner as laminate No. L101.

[0623] Laminates No. L101 to L116 are laminates of the present invention, laminates No. Lc001 to Lc008 are comparative laminates, and laminates No. Lc101 to Lc111 are reference examples.

[0624] <Lightfastness> (Preparation of lightfastness evaluation film) On the gas barrier layer side of the laminate, a TAC film (triacetyl cellulose film) containing UV absorber 1 (trade name: TINUVIN328, manufactured by Ciba-Geigy (now Novartis Pharma KK), concentration relative to TAC: 0.98 phr) and UV absorber 2 (trade name: TINUVIN326, manufactured by Ciba-Geigy (now Novartis Pharma KK), concentration relative to TAC: 0.24 phr) is bonded via an adhesive 1 (trade name: TINUVIN326, manufactured by Ciba-Geigy (now Novartis Pharma KK), concentration relative to TAC: 0.24 phr) with a TAC concentration of approximately 20 μm is bonded. Next, substrate 1 is peeled off, and glass is bonded to the wavelength selective absorption layer side where substrate 1 is bonded via the aforementioned adhesive 1, thereby fabricating a lightfastness evaluation film.

[0625] (The maximum absorption value of the film for evaluating lightfastness) Using a SHIMADZU CORPORATION UV3150 spectrophotometer (trade name), the absorbance of the lightfastness evaluation film in the wavelength range of 200 nm to 1000 nm was measured at 1 nm intervals. The absorbance difference between the absorbance of the lightfastness evaluation film at each wavelength and the absorbance of a lightfastness evaluation film with the same structure except for the dye-free spots was calculated, and the maximum value of this absorbance difference was defined as the absorbance maximum.

[0626] (Lightfastness) Using the SX75 Super Xenon Lamp Weathering Tester (trade name) manufactured by Suga Test Instruments Co., Ltd., the lightfastness evaluation film was irradiated with light for 200 hours at 60°C and 50% relative humidity. The maximum absorption value before and after the irradiation was measured, and the lightfastness was calculated using the following formula.

[0627] [Lightfastness (%)] = ([Maximum Absorption after 200 hours of light exposure] / [Maximum Absorption before light exposure]) × 100 The results are shown in Table 3.

[0628] <Evaluation of the physical properties of the gas barrier layer> The crystallinity, oxygen permeability, and thickness of the gas barrier layer were evaluated using the following methods. The results are shown in Table 3.

[0629] (Crystallization) A gas barrier layer of 2-3 mg was peeled off from the above-prepared laminate, and the heat of fusion was determined by heating the material at 10 °C / min in the range of 20 °C to 260 °C using a DSC7000X (trade name) manufactured by Hitachi High-Tech Science Corporation.

[0630] The crystallinity of the barrier layer was calculated according to the method described in J. Appl. Pol. Sci., 81, 762 (2001). Specifically, the crystallinity was calculated using the above-mentioned heat of fusion 1 and the heat of fusion for complete crystallization 2 described in J. Appl. Pol. Sci., 81, 762 (2001) by the following formula.

[0631] [Crystallization (%)] = ([Heat of fusion 1] / [Heat of fusion 2]) × 100 (Oxygen permeability) In the fabrication of the aforementioned lightfastness evaluation film, corona treatment was not applied to the wavelength-selective absorption layer. Otherwise, the lightfastness evaluation film was fabricated in the same manner, and the substrate 1 (corresponding to substrate 2) and the wavelength-selective absorption layer were peeled off. This resulted in an oxygen permeability evaluation film formed by sequentially layering a TAC film containing a UV absorber, an adhesive 1, and a gas barrier layer. Furthermore, in Nos. Lc101 to Lc111, the TAC film containing a UV absorber used in the fabrication of the lightfastness evaluation film was used as the oxygen permeability evaluation film.

[0632] The oxygen permeability measuring device used was the MOCON OX-TRAN 2 / 21 (trade name), measured using the isobaric method (JIS K 7126-2) at 25°C, 50% relative humidity, 1 atm oxygen partial pressure, and a measuring area of ​​50 cm². 2 The oxygen permeability of the evaluation membrane was measured under certain conditions.

[0633] In addition, in this experiment, the oxygen permeability was considered to be 600cc / m 2 The difference near day•atm is within the error range based on the deviation of the measurement test.

[0634] (thickness) Cross-sectional photographs of the laminate were taken using a field emission scanning electron microscope S-4800 (trade name) manufactured by Hitachi High-Technologies Corporation, and the thickness was read.

[0635] [Table 3]

[0636] (Notes in Table 3) The "-" mark in the lightfastness evaluation column indicates that the dye is not present.

[0637] In the laminates No. Lc101~Lc111, the "-" mark in the crystallinity column indicates that no measurement was performed because there is no gas barrier layer.

[0638] In the laminates No. Lc101 to Lc111, oxygen permeability refers to the oxygen permeability of the TAC film containing the UV absorber.

[0639] The unit for oxygen permeability is cc / m 2 •day•atm.

[0640] As shown in Table 3, the comparative examples of laminates No. Lc006 to Lc008, which have a gas barrier layer containing an amorphous resin, show almost no or minimal improvement in lightfastness compared to the reference example of laminate No. Lc101, which does not have a gas barrier layer, resulting in poor lightfastness. Furthermore, laminates No. Lc001 to Lc004 have a gas barrier layer containing a crystalline resin and possess a gas barrier layer of a specific film thickness as specified in this invention; however, the oxygen permeability of the gas barrier layer is greater than the specific range specified in this invention. The comparative examples of laminates No. Lc001 to Lc004 show almost no improvement in lightfastness compared to the reference example of laminate No. Lc101, which does not have a gas barrier layer, resulting in poor lightfastness.

[0641] Furthermore, laminate No. Lc005 includes a gas barrier layer containing a crystalline resin. The oxygen permeability of the gas barrier layer is within a specific range specified in this invention. However, if the film thickness of the gas barrier layer is 40 μm, it is thicker than the specific range specified in this invention. The laminate No. Lc005 of this comparative example shows no difference in lightfastness improvement effect compared to laminate No. L104 of this invention, which has a gas barrier layer film thickness of 2.5 μm. It is known that even with a gas barrier layer containing a crystalline resin and having an oxygen permeability within a specific range, if the film thickness of the gas barrier layer is thicker than the specific range specified in this invention, even if the oxygen permeability of the gas barrier layer can be reduced by thickening the gas barrier layer, the desired lightfastness improvement effect cannot be obtained.

[0642] On the other hand, it is known that the laminates No. L101 to L116 of the present invention have a greater effect on improving lightfastness than the laminates No. Lc101 to Lc111 of the reference examples that do not have a gas barrier layer, and have excellent lightfastness. Specifically, it is known that for laminates containing two dyes A and B, compared with reference examples No. Lc101 and No. L101 to 104, for laminates containing three dyes A to C, compared with reference examples No. Lc102 and No. L105 or reference examples No. Lc110 and No. L115, and for laminates containing four dyes A to D, compared with reference examples No. Lc103 and No. L106 or reference examples No. Lc111 and No. L116, the improvement in lightfastness is obtained at an excellent level. Furthermore, it is known that for laminates containing any one of dyes A to D, comparisons were made between Reference Examples No. Lc104 and No. L107, Reference Examples No. Lc105 and No. L108, Reference Examples No. Lc106 and No. L109, Reference Examples No. Lc107 and No. L110, Reference Examples No. Lc108 and No. L111, and Reference Examples No. Lc109 and No. L114, and overall, they exhibited an excellent improvement in lightfastness.

[0643] [Reference Example: Wavelength Selective Absorption Filter Containing Four Dyes A to D] The following is a detailed explanation: An OLED display device equipped with a wavelength selective absorption filter (wavelength selective absorption layer) containing four dyes A to D with main absorption wavelength bands in different wavelength regions can both suppress external light reflection and suppress brightness reduction, and can fully display the original color tone of the displayed image.

[0644] [Fabrication of a Wavelength-Selective Absorption Filter] The following shows the materials used in the fabrication of the wavelength-selective absorption filter.

[0645] <Matrix Resin> (Resin 8) The polystyrene resin (manufactured by PS Japan Corporation, PSJ-polystyrene GPPS SGP-10 (trade name), Tg100℃, fd0.56) was heated at 110℃ and then naturally cooled to room temperature (23℃) as resin 8.

[0646] (Resin 2) Polyphenylene ether resin (manufactured by Asahi Kasei Corporation, ZYLON S201A (trade name), poly(2,6-dimethyl-1,4-phenylene ether), Tg 210℃) (Elongation resin component 1) ASAFLEX810 (trade name, manufactured by Asahi Kasei Corporation, styrene-butadiene resin) (Resin component 1 for peelability control) BYRON550 (trade name, manufactured by TOYOBO CO., LTD., polyester additive) <Dyes> [Chemical Formula 91] FDG007: Product name, manufactured by YAMADA CHEMICAL CO.,LTD., tetrazaporphyrin-based pigment, λ max 594nm The dye used in Example 3 of Japanese Patent Application Publication No. 2017-203810 [Chemical Formula 92] In addition, the λ described in the dye section above max It refers to the maximum absorption wavelength that displays the maximum absorbance, as determined under the following conditions.

[0647] That is, the above dye was dissolved in chloroform to prepare a solution with a concentration of 1×10⁻⁶. -6 The solution used for determination was in mol / L. The maximum absorption wavelength λmax of this solution was measured at 23°C using a unit with a 10mm optical path length and a UV-1800PC spectrophotometer (manufactured by SHIMADZU CORPORATION).

[0648] <Additives> (Anti-fading agent 1) Example compound IV-8 in the above-mentioned anti-fading agents (Leveling agent 1) A polymeric surfactant composed of the following components is used as leveling agent 1. In the following structural formula, the proportions of each component are molar ratios, and t-Bu refers to tert-butyl.

[0649] [Chemical Formula 93] (Substrate 1) A polyethylene terephthalate film, Lumirror XD-510P (trade name, 50 μm thick, manufactured by TORAYINDUSTRIES, INC.), was used as substrate 1.

[0650] <Fabrication of Wavelength Selective Absorption Filter No. 101 with Substrate> (1) Preparation of toluene solution of elongation resin component 1 2.75 parts by weight of elongation resin component 1 were dissolved in 89.0 parts by weight of toluene. Next, 8.26 parts by weight of KYOWAAD700SEN-S (trade name, manufactured by Kyowa Chemical Industry Co., Ltd.) were added to the obtained solution. After stirring at room temperature (23°C) for 1 hour, the solution was filtered through a sintered metal filter with an absolute filtration accuracy of 2.5 μm (trade name: PALL Filter PMF, Media Code: FH025, manufactured by NIHON PALL LTD.) to remove KYOWAAD700SEN-S, thus preparing a toluene solution of elongation resin component 1 with alkali removed.

[0651] (2) Preparation of resin solution The components were mixed in the manner shown below to prepare a wavelength selective absorption filter forming liquid (composition) Ba-1.

[0652] ―――――――――――――――――――――――――――――― Composition of Ba-1, the forming liquid of wavelength selective absorption filter ―――――――――――――――――――――――――――――― 8 parts by weight of resin Resin 2 17.5 parts by weight 667.3 parts by mass of toluene solution of the elongation resin component 1 prepared above. Peel resistance control resin component 1 0.20 parts by weight Leveling agent 1 0.16 parts by weight Pigment 7-21 0.50 parts by weight Dye C-80 0.44 parts by weight Pigment E-13 0.86 parts by weight Dye D-35 1.12 parts by weight Anti-fading agent 1 12.4 parts by weight Toluene (solvent) 872.7 parts by weight Cyclohexanone (solvent) 380.0 parts by weight ―――――――――――――――――――――――――――――― Next, the obtained wavelength selective 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.).

[0653] (3) Fabrication of a wavelength selective absorption filter with a substrate With a dried film thickness of 2.5 μm, the wavelength selective absorption filter forming liquid Ba-1 after the above filtration treatment was coated onto the substrate 1 using a rod coater, and dried at 120°C, thereby producing a wavelength selective absorption filter No.101 with a substrate.

[0654] <Fabrication of Wavelength Selective Absorption Filters No. 102-108 and c11-c15 with Substrate> The types and amounts of dyes were changed to those listed in Table 4. Otherwise, wavelength selective absorption filters No. 102 to 108 and c11 to c15 were manufactured in the same manner as the wavelength selective absorption filter No. 101 with substrate.

[0655] Here, No. 101 to 108 are wavelength selective absorption filters that satisfy the aforementioned relations (I) to (VI), and No. c11 to c15 are wavelength selective absorption filters that do not satisfy the aforementioned relations (I) to (VI) and are used for comparison.

[0656] <Absorption maxima of wavelength-selective absorption filters> The absorbance of a substrate-supported wavelength-selective absorption filter in the wavelength range of 380 nm to 800 nm was measured in 1 nm increments using a UV3150 spectrophotometer (trade name) manufactured by SHIMADZU CORPORATION. The absorbance Ab at each wavelength λ nm of the substrate-supported wavelength-selective absorption filter was calculated. x The absorbance difference between Ab0(λ) and the absorbance of the substrate-based wavelength-selective absorption filter (i.e., the wavelength-selective absorption filter of No. c11) without dye, Ab0(λ) x (λ)-Ab0(λ), and the maximum value of this absorbance difference is defined as the absorption maximum.

[0657] <Simulation Experiments on Brightness, Reflectivity, and Hue> For an OLED display device equipped with the wavelength-selective absorption filter described above, a simulation experiment of external light reflection was conducted to calculate the brightness, reflectivity, and hue (a). and b ).

[0658] (1) Structure of OLED display device As an OLED display device used for simulation experiments, the following assumptions were made. Figure 2 The device shown displays an image using a blue OLED element and a color filter containing quantum dots (QDs).

[0659] Right now, Figure 2 In the OLED display device 1 shown, a blue OLED element, an RG selective reflective layer 21, a color filter (CF) containing quantum dots (QD), a black matrix 71, and a wavelength selective absorption filter 82 fabricated as described above are sequentially provided on a TFT substrate. The wavelength selective absorption filter 82 is located on the external light side (visual recognition side).

[0660] The TFT substrate has a structure in which a TFT 12 is disposed on a substrate 11. The blue OLED element has a structure in which an anode 13, a blue OLED 14, and a cathode 15 are stacked from the side of the TFT substrate. A blocking film 16 is disposed between the blue OLED element and the RG selective reflective layer 21.

[0661] The color filter containing quantum dots incorporates quantum dots as the light-emitting part for both red and green light. The red color filter has a structure in which a layer 31 containing red quantum dots and a light diffuser, a B selective reflective layer 51, and a red color filter 32 are sequentially arranged on the RG selective reflective layer 21. The green color filter has a structure in which a layer 41 containing green quantum dots and a light diffuser, a B selective reflective layer 51, and a green color filter 42 are sequentially arranged on the RG selective reflective layer 21. The layer 31 containing red quantum dots and a light diffuser is a color conversion part that converts light in the blue wavelength band to light in the red wavelength band, and the layer 41 containing green quantum dots and a light diffuser is a color conversion part that converts light in the blue wavelength band to light in the green wavelength band. The blue color filter has a structure in which a blue color filter 62 is arranged on the RG selective reflective layer 21.

[0662] A glass 81 is disposed between a quantum dot-containing color filter and a black matrix 71 and a wavelength selective absorption filter 82, and a low-reflection surface film 83 is disposed on the wavelength selective absorption filter 82.

[0663] (2) Simulation test conditions Figure 2 In the OLED display device 1 shown, in the simulation test of reflectivity and reflectance hue related to external light AR irradiation, the reflectivity, transmission spectrum and reflection spectrum of each component are specified in the following manner.

[0664] (i) In the red-green selective reflective layer, the reflectivity of the region with wavelength less than 500nm is assumed to be 0%, and the reflectivity of the region with wavelength above 500nm and below 800nm ​​is assumed to be 100%.

[0665] (ii) Regarding the transmission spectrum of the color filter, the panel spectrum and backlight spectrum were measured, and calculations were performed based on the panel spectrum / backlight spectrum.

[0666] (iii) The transmission spectrum of the wavelength selective absorption filter was obtained by measuring the transmission spectrum of the wavelength selective absorption filter with substrate fabricated above and the substrate used in the above fabrication.

[0667] (iv) The reflectance spectrum of carbon black was used as the reflectance of the black matrix.

[0668] (v) As the reflectivity of the OLED substrate, the reflectance spectrum of the substrate was measured by decomposing a commercially available LG Electronics OLED55B7P television (trade name) and removing the circular polarizer.

[0669] (vi) The area ratios of the blue, green, red, and black matrices were calculated by setting the area ratios of the blue, green, and red pixels to 17% and the area ratio of the black matrix to 49%.

[0670] In addition, the transmission and reflection spectra mentioned above were measured using a UV3150 spectrophotometer (trade name) manufactured by SHIMADZU CORPORATION.

[0671] (3) Calculation of reflectance and reflected hue Reflectivity and reflectance hue are calculated by multiplying the reflectance spectra of the blue, green, red, and black pixels by their respective area ratios. Specifically, as follows.

[0672] First, the reflectance spectra of the blue, green, red, and black pixels are respectively used as R. 蓝 R 绿 R 红 and R 黑 And it was calculated according to the following formula.

[0673] B, as the reflection of external light on the blue pixel ref It is assumed that the reflection on the anode 13 in the blue OLED display element is the reflection of external light G on the green pixel. ref and the reflection of external light on the red pixel R ref Assuming that RG selects the reflection on the reflective layer 21 (reference) Figure 2 ).

[0674] In the following formula, the transmission spectrum of the wavelength-selective absorption filter represents T. dye The transmission spectra of each color filter represent CF 蓝 CF 绿 and CF 红 The reflectivity of the green and red selective reflective layer is represented by R. sel The reflectivity of an OLED substrate is represented by R. sub The reflectivity of the black matrix represents R. BM .

[0675] R 蓝 = (T dye ) 2 ×CF 蓝 ×R sub R 绿 = (T dye ) 2 ×CF 绿 ×R sel R 红 = (T dye ) 2 ×CF 红 ×R sel R 黑 = (T dye ) 2 ×R BM Next, the area ratios of the blue, green, red, and black matrices are respectively used as A. 蓝 A 绿 A 红 and A 黑 The reflectance spectrum of the OLED display device is calculated using the following formula.

[0676] OLED display device reflectance spectrum = R 蓝 ×A 蓝 +R 绿 ×A 绿 +R 红 ×A 红 +R 黑 ×A 黑 Based on the above calculations of the OLED display device's reflectance spectrum, the reflectance (visibility correction) and a are calculated. and b .

[0677] (4) Calculation of relative brightness The relative brightness when using the wavelength-selective absorption filter described above was calculated as follows.

[0678] The emission spectrum S(λ) of the display was calculated from the backlight spectrum of a 55” Q7F (a quantum dot type liquid crystal television, product name) manufactured by Samsung Electronics Co., Ltd. Also, the transmission spectrum of the wavelength selective absorption filter was taken as T(λ).

[0679] The brightness without using the wavelength selective absorption filter was calculated by performing visibility correction on the spectrum S(λ), and this brightness was taken as 100. The brightness of S(λ)×T(λ) when using the wavelength selective absorption filter was calculated as the relative brightness with respect to the brightness without using the above wavelength selective absorption filter.

[0680] <Evaluation of the effect of suppressing brightness reduction> Using the relative brightness values obtained in the above simulation test, the effect of suppressing brightness reduction was evaluated according to the following evaluation criteria. In this test, “A” and “B” are considered qualified.

[0681] - Evaluation criteria - A: 80 < relative brightness ≤ 100 B: 60 < relative brightness ≤ 80 C: 0 ≤ relative brightness ≤ 60 <Evaluation of the effect of suppressing external light reflection> Using the reflectance values obtained in the above simulation test, the reduction rate of reflectance was calculated by the following formula, and the effect of suppressing external light reflection was evaluated according to the following evaluation criteria. In this test, “A” and “B” are considered qualified.

[0682] Reduction rate of reflectance = (R0 - R1) / R0 × 100% R1: Reflectance when using the wavelength selective absorption filter containing a dye R0: Reflectance when using the substrate - attached wavelength selective absorption filter of No.c11 without a dye - Evaluation criteria - A: 50% < reduction rate of reflectance ≤ 80% B: 20% < reduction rate of reflectance ≤ 50% C: 0 ≤ reduction rate of reflectance ≤ 20% <Evaluation of hue> Using the a , b values calculated in the above simulation test, the color difference was obtained by the following formula.

[0683] (Color difference The meanings represented by the respective symbols in the above formula are as follows.

[0684] When using a wavelength-selective absorption filter with a substrate containing dye, a When using a substrate-based, dye-free wavelength-selective absorption filter of No. C11, type a b when using a wavelength-selective absorption filter with a substrate containing dye When using a substrate-based, dye-free wavelength-selective absorption filter (No. C11) Among the color differences calculated by the above formula, below 16.0 is the practical level, below 15.0 is the preferred level, and below 5.0 is the secondary preferred level.

[0685] The results are shown in Table 4.

[0686] (Notes in the table) Regarding the amount of dye incorporated, it is recorded as the parts by mass relative to 100 parts by mass of the matrix resin.

[0687] The "-" mark in the dye column indicates that no dye is present.

[0688] Regarding the absorbance ratio of No. c11 and the "-" marking in the dye column, No. c11 is a substrate-based wavelength selective absorption filter without dye, and is equivalent to the reference filter for each wavelength selective absorption filter, therefore no value is recorded.

[0689] λ in the dye column max It refers to the wavelength (maximum absorption wavelength) that shows the largest absorption maximum value among the absorption maxima obtained by measuring the above wavelength selective absorption filter.

[0690] The dyes used are referred to by the following abbreviations.

[0691] Y93: CI Solvent Yellow 93 G3: CI Solvent Green 3 R111: CI Solvent Red 111 V13: CI Solvent Violet 13 B36: CI Solvent Blue 36 As shown in Table 4, the wavelength selective absorption filters No. c12 to c14 used for comparison, which contain combinations of conventional dyes, do not satisfy the aforementioned relationships (II), (III), (V), and (VI). These wavelength selective absorption filters No. c12 to c14 used for comparison all exhibit color differences exceeding 20 compared to the wavelength selective absorption filter (No. c11) without dyes, resulting in hue variations. It is impossible to simultaneously suppress external light reflection and brightness reduction while also suppressing hue variations. Furthermore, the wavelength selective absorption filter No. c15 used for comparison, which does not contain dyes A and D specified in this invention, does not satisfy the aforementioned relationships (I) and (VI). Similarly, this wavelength selective absorption filter No. c15 used for comparison exhibits a color difference exceeding 19.9 compared to the wavelength selective absorption filter (No. c11) without dyes, resulting in hue variations. It is impossible to simultaneously suppress external light reflection and brightness reduction while also suppressing hue variations.

[0692] In contrast, the wavelength-selective absorption filters No. 101 to 108 of the reference examples, which satisfy the aforementioned relations (I) to (VI), suppress hue changes sufficiently while simultaneously suppressing external light reflection and brightness reduction, achieving a level that is practically usable. Although the suppression of external light reflection and brightness reduction is achieved at the same level as wavelength-selective absorption filters No. c12 to c14 containing conventional dye combinations, an excellent effect on suppressing hue changes is shown. Moreover, wavelength-selective absorption filters No. 101 to 107, which use squaric acid cyanine pigments represented by general formula (1) as at least one of dyes B and C, can suppress external light reflection and brightness reduction simultaneously, and can also achieve a superior level of hue change suppression.

[0693] Example 2 <Fabrication of Wavelength Selective Absorption Layer with Substrate> The following shows the materials used in the fabrication of the wavelength-selective absorption layer.

[0694] (Resin 9) APEL APL6011T (trade name, manufactured by Mitsui Chemicals, Inc., a copolymer of ethylene and norbornene, Tg of 105°C), a cyclic polyolefin resin, was used as resin 9.

[0695] (dye) E-24 was used as dye A, A-33 and 7-22 were used as dye B, C-73 and C-80 were used as dye C, and F-34 was used as dye D.

[0696] E-24, A-33, and C-80 are the same as E-24, A-33, and C-80 in Example 1, respectively. 7-22, C-73, and F-34 are as follows.

[0697] [Chemical Formula 94] (Anti-fading agent 1) Anti-fading agent 1 used in Example 1 (Substrate A) Cellulose acylated film (manufactured by Fujifilm Corporation, trade name: ZRD40SL) was used as substrate A.

[0698] (1) Preparation of wavelength-selective absorption layer forming liquid A The components were mixed in the manner shown below to prepare wavelength-selective absorption layer forming liquid A.

[0699] ―――――――――――――――――――――――――――――― Composition of wavelength-selective absorption layer forming liquid A ―――――――――――――――――――――――――――――― 95.5 parts by weight of resin Peel resistance control resin composition: TUFTEC H-1043 (trade name, manufactured by Asahi Kasei Corporation) 3.4 parts by weight Leveling agent: Megaface F-554 (manufactured by DIC Corporation, fluoropolymer) 0.16 parts by weight Dye E-24 0.39 parts by weight Dye A-33 0.14 parts by weight Dye C-80 0.15 parts by weight Dye F-34 0.23 parts by weight Anti-fading agent 1 10.4 parts by weight Cyclohexane (solvent) 770.0 parts by weight ―――――――――――――――――――――――――――――― Next, the obtained wavelength selective absorption layer forming liquid A was filtered using filter paper (#63, manufactured by TOYO ROSHI KAISHA, Ltd.) with an absolute filtration accuracy of 10 μm, and further filtered using a metal sintered filter (FH025, manufactured by NIHON PALL LTD.) with an absolute filtration accuracy of 2.5 μm.

[0700] (2) Fabrication of wavelength selective absorption layer A with substrate With a dried film thickness of 2.5 μm, the wavelength selective absorption layer forming liquid A after the above filtration treatment was applied to the substrate A using a rod coater, and then dried at 120°C to produce a wavelength selective absorption layer A with a substrate.

[0701] (3) Fabrication of wavelength selective absorption layers B to D with substrate The type and amount of dye added were changed to those recorded in Table A-1 below. Otherwise, wavelength selective absorption layers B to D with a substrate were made in the same manner as the wavelength selective absorption layer A with a substrate.

[0702] <Creation of Layered Bodies No. L502-511> The lightfastness evaluation film of the laminate No. L116 prepared in Example 1 above is used as laminate No. L501. From the visual recognition side, the following layers are arranged in sequence: a TAC film containing a UV absorber as the first layer, a layer containing adhesive 1 as the second layer, a gas barrier layer as the third layer, a wavelength selective absorption layer 6 as the fourth layer, a layer containing adhesive 1 as the fifth layer, and glass as the sixth layer.

[0703] As described in Table B below, the types of adhesives constituting the second and fifth layers and the wavelength selective absorption layer of the fourth layer in the above-mentioned laminate No. L501 were changed. Otherwise, laminates No. L502 to L511 were manufactured in the same manner as laminate No. L501.

[0704] <Lightfastness> For the laminates No. L502 to L511 prepared above, the lightfastness was evaluated in the same manner as the lightfastness evaluation described in Example 1. The results are shown in Table A-2 below. Furthermore, laminates No. L503, L504, and L508 to L511 are omitted from the table, but they show the same lightfastness as No. L502.

[0705] Thus, the laminates No. L502 to L511 of the present invention are known to have the same level of excellent lightfastness as the laminate No. L501 of the present invention.

[0706] In addition, dye F-29 in the table below is the same as dye F-29 in Example 1.

[0707] [Table A-2]

[0708] <Evaluation of the physical properties of the gas barrier layer> In laminates No. L501 and L502, the third layer of the gas barrier layer is equivalent to the gas barrier layer in the laminate of the present invention. In laminates No. L503 to L511, the layer containing the second layer of adhesive and the third layer of gas barrier layer are equivalent to the gas barrier layer in the laminate of the present invention.

[0709] For the gas barrier layers of the present invention, including the second and third layers in laminates No. L503 to L511, the crystallinity and oxygen permeability of the gas barrier layers were evaluated in the same manner as in Example 1. The results are shown in Table B.

[0710] In addition, regarding crystallinity, after coating an adhesive layer equivalent to the second layer onto the gas barrier layer of laminate No. L116, 2-3 mg of the adhesive layer and the barrier layer were peeled off together and DSC was performed and calculated.

[0711] Furthermore, the thickness of the layer composed of adhesive 1 or 2 in the second layer is approximately 50–250 nm.

[0712] <Refractive Index> The refractive index and thickness of each of the six layers constituting the laminate, as well as the sum of the interfacial reflectivities, were measured and calculated. The results are shown in Table B.

[0713] (Refractive index) The refractive indices of the first and sixth layers are calculated as follows.

[0714] To prevent interface reflection from the substrate side, a Coulomb film (trade name, black laminate) manufactured by TOMOEGAWA CO., LTD. was bonded to the side of each sample opposite to the measurement surface (hereinafter referred to as the substrate side surface). Then, the reflectivity R1 was measured in the range of 380 nm to 780 nm by illuminating the sample from the measurement surface side using a reflectance spectrophotometer FE3000 (trade name) manufactured by OTSUKA ELECTRONICS Co., LTD.

[0715] The reflectance R1 is expressed using the refractive index n1 of the sample by the following equation (1). Therefore, the refractive index n1 of the sample in the range of 380 nm to 780 nm is calculated based on the measured reflectance.

[0716] Equation (1): R1 = (1 - n1) 2 / (1+n1) 2 The refractive indices of the 2nd, 3rd, 4th, and 5th layers are calculated as follows.

[0717] The forming solutions (samples) for each layer were coated onto a support with a known refractive index to a thickness of 1–3 μm. A laminate including the support and the sample was fabricated under the same conditions (drying temperature, etc.) as when forming the laminate comprising layers 1 through 6. To prevent interface reflection from the substrate side, a Coulomb film (trade name, black laminate) manufactured by TOMOEGAWA CO.,LTD. was bonded to the support side of the laminate. The reflectivity R² was measured in the range of 380 nm to 780 nm by irradiating the measurement surface of the sample with light using a reflectance spectrophotometer FE3000 (trade name) manufactured by OTSUKA ELECTRONICS Co.,LTD.

[0718] The reflectivity R2 is expressed by the following equation (2) using the refractive index n2 of the sample and the refractive index n3 of the support. Therefore, the refractive index n2 of the sample in the range of 380 nm to 780 nm is calculated based on the measured reflectivity and the refractive index n3 of the support.

[0719] Equation (2): R2 = (n2 - n3) 2 / (n2+n3) 2 (film thickness) The film thicknesses of layers 1 through 6 are calculated as follows.

[0720] The cross-section of the laminate was cut using a LEICA RM2265 rotary slicer, and the thickness of each layer was determined using a Hitachi High-Technologies S-4800 scanning electron microscope.

[0721] <Sum of Interface Reflectivities> Using the refractive index and film thickness of each layer, the sum of interfacial reflections of the laminate was calculated in the same manner as in Chapter 5, pages 173-174 of the 7th edition of "Applied Physics Engineering Series 3 Thin Films" edited by Yoshida Sadao.

[0722] <Notes on Table B> As described above, the first layer is composed of a TAC film containing a UV absorber, the third layer is composed of Exceval AQ-4104 (trade name, manufactured by KURARAY CO.,LTD.), and the sixth layer is composed of glass.

[0723] The wavelength selective absorption layer 6 in the fourth layer is composed of polystyrene resin and polyphenylene ether resin, while wavelength selective absorption layers A to D are composed of cyclic polyolefin resin.

[0724] “n” refers to the refractive index, and “Δn” refers to the interlayer refractive index difference between the two layers on its left and right.

[0725] The adhesives and bonding agents listed in the table are as follows.

[0726] (Adhesive) Adhesive 1: SK-2057 (trade name, manufactured by Soken Chemical & Engineering Co., Ltd.) Binder 2: 10 parts by weight of the following triazine compound are added to binder 1 relative to 100 parts by weight of the solid components. Binder 3: 20 parts by weight of the following triazine compound are added to binder 1 relative to 100 parts by weight of the solid components. Binder 4: 2.6 parts by weight of the following benzodithiol compound are added to binder 1 relative to 100 parts by weight of the solid components. In the above-mentioned adhesives 2 to 4, the solid component refers to the components in adhesive 1 other than the solvent.

[0727] [Chemical Formula 95] (Adhesive) Adhesive 1: Kuraray Poval5-98 (trade name, manufactured by KURARAY CO.,LTD., saponification degree is 98.0~99.0mol%) Adhesive 2: Mix at a mass ratio of 1 / 2: Kuraray Poval 5-88 (trade name, manufactured by KURARAY CO.,LTD., saponification degree 86.5~89.0mol%) / Kuraray Poval CP-1220T10 (trade name, manufactured by KURARAY CO.,LTD.). As shown in Table B, laminates No. L501 to L511 can suppress the difference in interfacial reflectivity to below 0.30%. Among them, laminates No. L502 to L511, where the refractive index difference between adjacent layers is below 0.10, can suppress the difference in interfacial reflectivity to below 0.10%, which is superior from the viewpoint of suppressing external light reflection. In particular, laminates No. L504 to L511, where the refractive index difference between adjacent layers is below 0.05, can suppress the difference in interfacial reflectivity to below 0.03%, which is especially superior from the viewpoint of suppressing external light reflection.

[0728] The invention has been described together with its embodiments, but unless otherwise stated, we do not intend to limit our invention to any of the details described, and it should be interpreted broadly without departing from the spirit and scope of the invention as shown in the appended claims.

[0729] This application claims priority based on Japanese Patent Application No. 2019-178639 filed on September 30, 2019; Japanese Patent Application No. 2019-206018 filed on November 14, 2019; Japanese Patent Application No. 2020-078899 filed on April 28, 2020; Japanese Patent Application No. 2020-095784 filed on June 1, 2020; and Japanese Patent Application No. 2020-165766 filed on September 30, 2020, the contents of which are incorporated herein by reference.

[0730] Symbol Explanation 1-OLED display device, 11-substrate, 12-TFT (thin-film transistor), 13-anode, 14-BOLED (blue OLED), 15-cathode, 16-barrier film, 21-RG selective reflective layer (red and green selective reflective layer), 31-layer containing red QD (red quantum dot) and light diffuser, 32-red color filter, 41-layer containing green QD (green quantum dot) and light diffuser, 42-green color filter, 51-B selective reflective layer (blue selective reflective layer), 62-blue color filter, 71-black matrix, 81-glass, 82-wavelength selective absorption filter (wavelength selective absorption layer), 83-surface film, 91-wavelength selective absorption layer, 92-barrier layer, 93-laminated structure, AR-external light, BM in -Incident light from outside the black matrix, R in -Incident light from outside the red pixel, G in -Incident light from outside onto the green pixel, B in -Incident light from outside the blue pixel, BM ref - Reflection of external light on the black matrix, R ref - Reflection of external light on the red pixel, G ref - Reflection of external light on the green pixel, B ref - Reflection of external light on the blue pixels.

Claims

1. A laminate comprising a wavelength-selective absorption layer and a gas barrier layer disposed directly on at least one side of the wavelength-selective absorption layer, wherein the wavelength-selective absorption layer contains a resin, a dye comprising at least one of dyes A to D, and an anti-fading agent for the dye; 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, The sum of the interfacial reflectivities of this laminate is less than 0.30%. Dye A: A dye with a main absorption wavelength band in the range of 390–435 nm. Dye B: A dye with a main absorption wavelength band in the wavelength range of 480–520 nm. Dye C: A dye with a main absorption wavelength band in the wavelength range of 580–620 nm. Dye D: A dye that has a main absorption wavelength band in the wavelength range of 680-780 nm.

2. A laminate comprising a wavelength-selective absorption layer and a gas barrier layer disposed directly on at least one side of the wavelength-selective absorption layer, wherein the wavelength-selective absorption layer contains a resin, a dye comprising at least one of dyes A to D, and an anti-fading agent for the dye; 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, In this laminate, the refractive index difference between adjacent layers is all below 0.

15. Dye A: A dye with a main absorption wavelength band in the range of 390–435 nm. Dye B: A dye with a main absorption wavelength band in the wavelength range of 480–520 nm. Dye C: A dye with a main absorption wavelength band in the wavelength range of 580–620 nm. Dye D: A dye that has a main absorption wavelength band in the wavelength range of 680-780 nm.

3. The laminate according to claim 1 or 2, wherein, The resin in the wavelength-selective absorption layer is a thermoplastic polymer resin.

4. The laminate according to claim 1 or 2, wherein, The crystallinity of the crystalline resin contained in the gas barrier layer is 25% or more.

5. The laminate according to claim 1 or 2, wherein, The oxygen permeability of the gas barrier layer is 0.001cc / m 2 •day•atm or more and 60cc / m 2 •day•atm or less.

6. The laminate according to claim 1 or 2, wherein, At least one of the dyes B and C is a squaric acid cyanine pigment represented by the following general formula (1). In the above formula, A and B independently represent aryl groups that can have substituents, heterocyclic groups that can have substituents, or -CH=G, where G represents heterocyclic groups that can have substituents.

7. The laminate according to claim 1 or 2, wherein, The dye A is a pigment represented by the following general formula (A1). In the above formula, R 1 and R 2 Each can be independently represented as alkyl or aryl, R 3 ~R 6 Each independently represents a hydrogen atom or a substituent, R 5 With R 6 They can bond together to form a 6-membered ring.

8. The laminate according to claim 1 or 2, wherein, The dye D is at least one of the following: a pigment represented by the following general formula (D1) and a pigment represented by the following general formula (1). In the above formula, R 1A and R 2A Each can independently represent an alkyl, aryl, or heteroaryl group, R 4A and R 5A Each independently represents a heteroaryl group, R 3A and R 6A Each substituent is represented independently, X 1 and X 2 Each is represented independently -BR 21a R 22a R 21a and R 22a Substituents are represented independently, R 21a and R 22a They can bond together to form a ring. In the above formula, A and B independently represent aryl groups that can have substituents, heterocyclic groups that can have substituents, or -CH=G, where G represents heterocyclic groups that can have substituents.

9. The laminate according to claim 1 or 2, wherein, The anti-fading agent is represented by the following general formula (IV), In the above formula, R 10 Each can independently represent alkyl, alkenyl, aryl, heterocyclic, or R. 18 CO-, R 19 SO2- or R 20 The group represented by NHCO-, R 18 R 19 and R 20 Each can independently represent an alkyl, alkenyl, aryl, or heterocyclic group, R 11 and R 12 Each independently represents a hydrogen atom, halogen atom, alkyl group, alkenyl group, alkoxy group, or alkenyloxy group, R 13 ~R 17 Each can independently represent a hydrogen atom, alkyl group, alkenyl group, or aryl group.

10. The laminate according to claim 1 or 2, wherein, The resin in the wavelength-selective absorption layer comprises polystyrene resin.

11. The laminate according to claim 1 or 2, wherein, The resin in the wavelength-selective absorption layer comprises a cyclic polyolefin resin.

12. The laminate according to claim 1 or 2, wherein, The wavelength-selective absorption layer contains all four dyes A through D.

13. The laminate according to claim 1 or 2, wherein, The laminate includes an ultraviolet absorbing layer and at least one layer selected from an adhesive layer and a bonding agent layer, wherein the ultraviolet absorbing layer is disposed on the opposite side of the wavelength selective absorbing layer relative to the gas barrier layer, and the refractive index difference between adjacent layers in the laminate is less than 0.

05.

14. An organic electroluminescent display device comprising the laminate according to any one of claims 1 to 13.

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