Optical laminates and image display devices

Abstract

To provide a novel optical laminate capable of suppressing color loss at edges of a polarizer under high temperature and high humidity.SOLUTION: An optical laminate provided herein comprises a polarizer, a selective light absorbing adhesive layer, and an intermediate layer laminated between the polarizer and the selective light absorbing adhesive layer in contact therewith. The intermediate layer comprises just one or more layers selected from a group consisting of a liquid crystal cured layer, alignment layer, and adhesive layer. The polarizer has iodine absorbed and aligned therein and contains 5.0 mass% or less boron. An adhesive composition forming the selective light absorbing adhesive layer contains a selective light absorbing polymer.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] This invention relates to an optical laminate and an image display device. [Background technology]

[0002] Polarizing plates, which are formed by laminating protective films onto one or both sides of a polarizer, are optical components widely used in image display devices such as liquid crystal displays (LCDs) and organic electroluminescent (OLED) displays, including mobile televisions, and especially in various mobile devices such as mobile phones, smartphones, and tablet terminals in recent years. Polarizing plates are often used by bonding them to image display elements (such as liquid crystal cells and organic EL display elements) via an adhesive layer (for example, Japanese Patent Application Publication No. 2010-229321 (Patent Document 1)). For this reason, polarizing plates are sometimes sold in the market in the form of polarizing plates with an adhesive layer already provided on one side.

[0003] Furthermore, mobile devices are often used in harsh environments with high temperature and humidity, so polarizers require high durability. Japanese Patent Publication No. 2013-105036 (Patent Document 2) describes that by increasing the boric acid content in the polarizer and generating many boric acid crosslinks, the I3 complex exists with high orientation and high stability, suppressing the occurrence of blue leaks and resulting in a polarizer with excellent low-temperature and high-humidity durability. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2010-229321 [Patent Document 2] Japanese Patent Publication No. 2013-105036 [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] In polarizing plates, there was a problem that color fading was likely to occur at the edges of the polarizer under high temperature and high humidity conditions. This problem was particularly pronounced in configurations where a protective film was laminated to only one side of the polarizer. Although a method of suppressing color fading of the polarizer by increasing the boron content in the polarizer is known, this method has the problem of being prone to shrinkage when heated.

[0006] The present invention aims to provide a novel optical laminate in which color fading at the edges of the polarizer is suppressed under high temperature and high humidity conditions. [Means for solving the problem]

[0007] The present invention provides an optical laminate and an image display device using the same, as illustrated below. [1] An optical laminate comprising a polarizer, a light-selective absorbing adhesive layer, and an intermediate layer laminated between the polarizer and the light-selective absorbing adhesive layer in contact with them, The intermediate layer comprises only one or more layers selected from the group consisting of a liquid crystal curing layer, an alignment layer, and a bonding layer. The polarizer has iodine adsorbed and oriented, and a boron content of 5.0% by mass or less. The adhesive composition forming the light-selective absorbing adhesive layer comprises a light-selective absorbing polymer, forming an optical laminate. [2] The optical laminate according to [1], further comprising a protective film laminated on the side of the polarizer opposite to the intermediate layer side. [3] The light-selective absorption polymer has the following chemical formula (1): >NC=CC=C< (1) [However, not all of the one N atom and four C atoms that make up chemical formula (1) constitute part or all of an aromatic heterocycle.] An optical laminate according to [1] or [2], comprising a resin having a structural unit having the structure shown in [1] or [2], and having a glass transition temperature of 40°C or less. [4] The optical laminate according to [3], wherein the light-selective absorbing polymer contains 0.01 parts by mass or more and 50 parts by mass or less of structural units having the structure shown in chemical formula (1) per 100 parts by mass of all structural units. [5] The optical laminate according to any one of claims [1] to [4], wherein the light-selective absorbing polymer has a weight-average molecular weight of 300,000 or more. [6] The optical laminate according to any one of [1] to [5], wherein the adhesive composition does not contain a light selective absorber, or the content of a light selective absorber is 0.5 parts by mass or less per 100 parts by mass of the total resin components. [7] The optical laminate according to any one of [1] to [6], wherein the intermediate layer has a λ / 4 phase difference layer which is the liquid crystal curing layer. [8] An optical laminate described in any one of items [1] to [7], which is an anti-reflective polarizing plate. [9] An image display device comprising an image display panel and the optical laminate described in [8] disposed in front of the image display panel.

[10] The image display device described in [9], which is an organic EL display device. [Effects of the Invention]

[0008] According to the present invention, it is possible to provide an optical laminate in which color loss at the edges of the polarizer is suppressed in a high-temperature, high-humidity environment, and an image display device including the same. [Brief explanation of the drawing]

[0009] [Figure 1] This is a schematic cross-sectional view showing an example of an optical laminate of the present invention. [Figure 2] This is a schematic cross-sectional view showing an example of an optical laminate of the present invention. [Figure 3] This is a schematic cross-sectional view showing an example of an optical laminate of the present invention. [Figure 4] This figure shows an example of an image observed with an optical microscope. [Figure 5] This figure shows an example of data obtained by converting an observed image into 256 grayscale levels. [Modes for carrying out the invention]

[0010] Embodiments of the present invention will be described below with reference to the drawings, but the present invention is not limited to the following embodiments. In all the following drawings, the scale has been adjusted as appropriate to make each component easier to understand, and the scale of each component shown in the drawings does not necessarily match the scale of the actual component.

[0011] <Optical laminate> The optical laminate of the present invention comprises a polarizer, a light-selective absorbing adhesive layer, and an intermediate layer laminated between the polarizer and the light-selective absorbing adhesive layer in contact with them. An example of the layer configuration of the optical laminate of the present invention is shown in Figures 1, 2, and 3. Figure 1 is a schematic cross-sectional view of an example of the optical laminate of the present invention. The optical laminate 100 shown in Figure 1 has, in this order, a protective film 11, a polarizer 10, an intermediate layer 300, and a light-selective absorbing adhesive layer (hereinafter also referred to as the "first adhesive layer") 20. The intermediate layer 300 has only one or more layers selected from the group consisting of a liquid crystal curing layer, an alignment layer, and a bonding layer.

[0012] Figure 2 is a schematic cross-sectional view of an example of the optical laminate of the present invention. The optical laminate 101 shown in Figure 2 has, in this order, a protective film 11, a polarizer 10, an intermediate layer 300, and a light-selective absorbing adhesive layer 20. The intermediate layer 300 has, in this order from the polarizer 10 side, a second adhesive layer 32, a first liquid crystal curing layer 30, an adhesive layer 33, and a second liquid crystal curing layer 31.

[0013] Figure 3 is a schematic cross-sectional view of an example of the optical laminate of the present invention. The optical laminate 102 shown in Figure 3 has, in this order, a protective film 11, a polarizer 10, an intermediate layer 300, and a light-selective absorbing adhesive layer 20. The intermediate layer 300 consists of a second adhesive layer 32.

[0014] The thickness of the optical laminates 100, 101, and 102 is not particularly limited, as it varies depending on the functions required of the optical laminates and their applications, but for example, it may be 5 μm or more and 200 μm or less, or it may be 10 μm or more and 150 μm or less, or 120 μm or less.

[0015] The light-selective absorbing adhesive layer contains a light-selective absorbing polymer. The optical laminate of the present invention has light-selective absorbing properties as a whole, because at least the light-selective absorbing adhesive layer has light-selective absorbing properties. Light-selective absorbing properties refer to the property of easily absorbing light of a specific wavelength, and have at least one absorption maximum in the ultraviolet wavelength region to the visible light region. For example, if the light-selective absorbing adhesive layer has ultraviolet absorbing ability, the optical laminate placed on an image display element has the function of protecting the image display element from ultraviolet light.

[0016] The optical laminate of the present invention may include layers having light-selective absorption properties in addition to the light-selective absorption adhesive layer. Examples of other layers include a protective film 11 and an intermediate layer 300. In the present invention, the light-selective absorption adhesive layer has light-selective absorption properties and contributes to the expression of light-selective absorption properties of the entire optical laminate, thereby improving the design freedom of the light-selective absorption properties of other layers. For example, in order to improve the light-selective absorption properties of the protective film 11, it may be necessary to design it to be thicker, but the high degree of freedom in designing the light-selective absorption properties makes it easy to make the protective film 11 thinner. For example, the intermediate layer 300 preferably contains substantially no light-selective absorber from the viewpoint of suppressing color fading at the edges of the polarizer under high temperature and high humidity conditions, and even if it contains light-selective absorber, the content should be 0.5 g / m². 2 The following is preferable: If the intermediate layer 300 has a second adhesive layer, the second adhesive layer is also preferably substantially free of light-selective absorbers, and if it is included, the content should be 0.5 g / m². 2 The following is preferable:

[0017] The light-selective absorbing adhesive layer is configured such that the light-selective absorbing polymer has light-selective absorption properties, contributing to the manifestation of the light-selective absorption properties of the light-selective absorbing adhesive layer. This allows for a configuration in the light-selective absorbing adhesive layer that does not contain a light-selective absorber, or a configuration that reduces the content of a light-selective absorber, thereby suppressing color fading at the edges of the polarizer under high temperature and high humidity conditions.

[0018] The inventors have found a correlation between the amount of light-selective absorbent contained in the adhesive layer and the degree of color loss at the edges of the polarizer under high temperature and high humidity conditions. Based on this finding, it is believed that when a relatively low molecular weight light-selective absorbent is used, the light-selective absorbent in the adhesive layer tends to migrate to the polarizer side under high temperature and high humidity conditions, and that this migration is one of the factors causing color loss. The inventors have further diligently investigated and found that by imparting light-selective absorption performance to the adhesive layer not by adding a light-selective absorbent, but by incorporating a light-selective absorbing polymer, color loss at the edges of the polarizer under high temperature and high humidity conditions can be suppressed, leading to the present invention. Since the light-selective absorbing polymer has a relatively large molecular weight, it is believed that migration to the polarizer is suppressed, thereby suppressing color loss at the edges of the polarizer.

[0019] [polarizer] A polarizer has the property of absorbing linearly polarized light having a vibration plane parallel to its absorption axis and transmitting linearly polarized light having a vibration plane perpendicular to the absorption axis (parallel to the transmission axis). In the optical laminate of the present invention, the polarizer 10 has iodine adsorbed and oriented, and the boron content is 5.0 mass% or less. A configuration in which the boron content is 5.0 mass% or less, preferably 4.5 mass% or less, can suppress shrinkage caused by heating. The boron content is preferably 0.5 mass% or more, and more preferably 1 mass% or more. In the polarizer 10, the lower the boron content, the more likely color loss will occur at the edges of the polarizer under high temperature and high humidity conditions. The boron in the polarizer 10 improves the degree of crosslinking of the polarizer 10 and contributes to the stable retention of iodine in the polarizer 10. Therefore, it is thought that if the boron content decreases, it becomes impossible to stably retain iodine, causing color loss. In the present invention, even if the boron content of the polarizer 10 is 5.0% by mass or less, color fading under high temperature and high humidity conditions can be suppressed.

[0020] The polarizer 10 can be a stretched film or stretched layer on which a dichroic dye having absorption anisotropy is adsorbed, a cured polymerizable liquid crystal compound, or a liquid crystal cured layer containing a dichroic dye. A dichroic dye is a dye that has the property that its absorbance in the long axis direction of the molecule is different from its absorbance in the short axis direction, and iodine is preferably used as the dye.

[0021] Polarizers, which are stretched films on which anisotropic absorption dyes are adsorbed, can typically be manufactured by a process that involves uniaxial stretching of a polyvinyl alcohol-based resin film, a process that involves dyeing the polyvinyl alcohol-based resin film with a dichroic dye such as iodine to adsorb the dichroic dye, a process that involves treating the polyvinyl alcohol-based resin film on which the dichroic dye has been adsorbed with an aqueous boric acid solution, and a process that involves washing with water after treatment with the aqueous boric acid solution.

[0022] The thickness of the polarizer is usually 30 μm or less, preferably 15 μm or less, more preferably 13 μm or less, even more preferably 10 μm or less, and particularly preferably 8 μm or less. The thickness of the polarizer is usually 2 μm or more, preferably 3 μm or more, and may be, for example, 5 μm or more.

[0023] Polyvinyl alcohol-based resins are obtained by saponifying polyvinyl acetate-based resins. Polyvinyl acetate-based resins include polyvinyl acetate, which is a homopolymer of vinyl acetate, as well as copolymers of vinyl acetate with other monomers copolymerizable thereto. Examples of other monomers copolymerizable with vinyl acetate include unsaturated carboxylic acid compounds, olefin compounds, vinyl ether compounds, unsaturated sulfone compounds, and (meth)acrylamide compounds having an ammonium group.

[0024] The degree of saponification of the polyvinyl alcohol-based resin is usually around 85 mol% to 100 mol%, preferably 98 mol% or higher. The polyvinyl alcohol-based resin may be modified, and polyvinyl formal, polyvinyl acetal, etc., modified with aldehydes can also be used. The degree of polymerization of the polyvinyl alcohol-based resin is usually 1000 to 10000, preferably 1500 to 5000.

[0025] A polarizer, which is a stretched layer on which an absorption anisotropy dye is adsorbed, can usually be manufactured by the following steps: applying a coating solution containing the polyvinyl alcohol-based resin onto a base film; uniaxially stretching the resulting laminated film; staining the polyvinyl alcohol-based resin layer of the uniaxially stretched laminated film with a dichroic dye such as iodine to adsorb the dichroic dye and form a polarizer; treating the film on which the dichroic dye is adsorbed with an aqueous boric acid solution; and washing with water after treatment with the aqueous boric acid solution. The base film used to form the polarizer may also be used as a protective film 11. If necessary, the base film may be peeled off from the polarizer. The material and thickness of the base film may be the same as those of the protective film 11 described later.

[0026] [Protective film] The protective film 11 can be a coating layer or film made of one or more optically transparent thermoplastic resins, such as cyclic polyolefin resins; cellulose acetate resins made of resins such as triacetylcellulose and diacetylcellulose; polyester resins made of resins such as polyethylene terephthalate, polyethylene naphthalate, and polybutylene terephthalate; polycarbonate resins; (meth)acrylic resins; and polypropylene resins. The protective film 11 may also contain a light-selective absorber, as described later. Note that the light-selective absorber contained in the protective film 11 is retained within the protective film 11 and is therefore unlikely to transfer to the polarizer.

[0027] A hard coat layer may be formed on the protective film 11. The hard coat layer may be formed on one side of the protective film 11 or on both sides. By providing a hard coat layer, the protective film 11 can be made to have improved hardness and scratch resistance. The hard coat layer may be a cured layer of, for example, an acrylic resin, a silicone resin, a polyester resin, a urethane resin, an amide resin, or an epoxy resin. The hard coat layer may contain additives to improve its strength. The additives are not limited to inorganic fine particles, organic fine particles, or mixtures thereof. The hard coat layer may be a cured layer of, for example, an ultraviolet-curable resin. Examples of ultraviolet-curable resins include acrylic resins, silicone resins, polyester resins, urethane resins, amide resins, and epoxy resins.

[0028] The thickness of the protective film 11 is usually 1 μm or more and 100 μm or less, but from the viewpoint of strength and handling, it is preferably 5 μm or more and 80 μm or less, more preferably 8 μm or more and 60 μm or less, and even more preferably 12 μm or more and 45 μm or less.

[0029] The protective film 11, which is a resin film, is bonded to the polarizer 10, for example, via an adhesive layer. Examples of adhesives that can form the adhesive layer include water-based adhesives, active energy ray curable adhesives, and thermosetting adhesives, with water-based adhesives and active energy ray curable adhesives being preferred. The two opposing surfaces bonded via the adhesive layer may be subjected to prior corona treatment, plasma treatment, flame treatment, etc., and may have a primer layer or the like.

[0030] [Light-selective absorbing adhesive layer] The light-selective absorbing adhesive layer 20 can be formed by applying a diluted solution, obtained by dissolving or dispersing an adhesive composition containing a light-selective absorbing polymer in an organic solvent, onto a substrate and drying it. A plastic film is preferred as the substrate, and specifically, a release film that has been treated with a release agent is a good example. Examples of release films include those made of resins such as polyethylene terephthalate, polybutylene terephthalate, polycarbonate, and polyarylate, with one side treated with a release agent such as silicone.

[0031] The thickness of the light-selective absorbing adhesive layer is, for example, 0.1 μm to 150 μm. When laminated with an image display panel, the thickness of the light-selective absorbing adhesive layer is usually 8 μm to 60 μm, and in terms of thinning, it is preferable to have a thickness of 30 μm or less, more preferably 25 μm or less, and especially 20 μm or less. When laminated with other optical films, such as a λ / 4 phase difference layer, the thickness of the light-selective absorbing adhesive layer is usually 2 μm to 30 μm, preferably 25 μm or less, more preferably 20 μm or less, especially preferably 18 μm or less, preferably 3 μm or more, and may be, for example, 10 μm or more, but in terms of further thinning, 10 μm or less, and especially 7 μm or less is preferred.

[0032] The light-selective absorbing adhesive layer 20 preferably has an absorbance of 0.1 to 1.6 at a wavelength of 410 nm. This is because having such an absorbance in the light-selective absorbing adhesive layer 20 makes it easier to construct a thin optical laminate while exhibiting the desired light-selective absorption performance as a whole.

[0033] The light-selective absorbing adhesive layer typically has an absorbance of 5.0 or less at a wavelength of 390 nm, but may also have an absorbance of 4.5 or less. The light-selective absorbing adhesive layer typically has an absorbance of 5.0 or less at a wavelength of 400 nm, but may also have an absorbance of 4.5 or less. The light-selective absorbing adhesive layer typically has an absorbance of 1.00 or less, preferably 0.60 or less, more preferably 0.40 or less, and 0.00 or more at a wavelength of 420 nm. The light-selective absorbing adhesive layer typically has an absorbance at a wavelength of 430 nm of less than 0.20, preferably 0.18 or less, more preferably 0.10 or less, and particularly preferably 0.05 or less, and 0.00 or more. The light-selective absorbing adhesive layer typically has an absorbance of less than 0.10, preferably 0.05 or less, and 0.00 or more at a wavelength of 440 nm. Because the absorbance at each wavelength falls within the above range, it can sufficiently absorb light in the ultraviolet region while allowing visible light to pass through unaffected.

[0034] The light-selective absorbing adhesive layer is preferably an adhesive layer that satisfies the following formula (3), and more preferably an adhesive layer that satisfies formula (4). A(405)≧0.5 (3) [In equation (3), A(405) represents the absorbance at a wavelength of 405 nm.] A(405) / A(440)≧5 (4) [In equation (4), A(405) represents the absorbance at a wavelength of 405 nm, and A(440) represents the absorbance at a wavelength of 440 nm.]

[0035] A larger value of A(405) indicates higher absorption at a wavelength of 405 nm. If the value of A(405) is less than 0.5, absorption at a wavelength of 405 nm is low, and materials that are susceptible to degradation by light around 400 nm (e.g., display devices such as organic EL elements and liquid crystal phase difference films) are more prone to degradation. The value of A(405) is preferably 0.6 or higher, more preferably 0.8 or higher, and particularly preferably 1.0 or higher. There is no particular upper limit, but it is usually 10 or lower.

[0036] The value of A(405) / A(440) represents the magnitude of absorption at a wavelength of 405 nm relative to the magnitude of absorption at a wavelength of 440 nm. A larger value indicates a specific absorption in the wavelength range around 405 nm. The value of A(405) / A(440) is preferably 10 or greater, more preferably 30 or greater, even more preferably 75 or greater, and particularly preferably 100 or greater.

[0037] [Adhesive composition] (Photoselective absorption polymer) The adhesive composition contains a photoselective absorbing polymer. The photoselective absorbing polymer is a polymer that has photoselective absorption properties. The photoselective absorbing polymer can preferably absorb light with wavelengths in the range of 360 nm to 420 nm. The photoselective absorbing polymer contains a photoselective absorbing structural unit having a moiety that has photoselective absorption properties. The photoselective absorbing structural unit preferably has a moiety that has photoselective absorption properties in its side chain. Examples of moieties that have photoselective absorption properties include a benzophenone group, a benzotriazole group, and the structure shown in the following chemical formula (1).

[0038] The light-selective absorption polymer is preferably of the following chemical formula (1): >NC=CC=C< (1) [However, not all of the one N atom and four C atoms that make up chemical formula (1) constitute part or all of an aromatic heterocycle.] The resin (A) contains a structural unit having the structure shown (hereinafter referred to as the "merocyanine structure") as a light-selective absorbing structural unit, and has a glass transition temperature of 40°C or less. The resin (A) may have a merocyanine structure in its main chain or in its side chains. It is more preferable that the resin (A) contains structural units having a merocyanine structure in its side chains.

[0039] The glass transition temperature (Tg) of resin (A) is 40°C or lower, preferably 20°C or lower, more preferably 10°C or lower, and even more preferably 0°C or lower. Furthermore, the glass transition temperature of resin (A) is typically -80°C or higher, preferably -60°C or higher, more preferably -50°C or higher, even more preferably -45°C or higher, and particularly preferably -30°C or higher. A glass transition temperature of 40°C or lower is advantageous for improving the adhesion of the light-selective absorbing adhesive layer formed from the adhesive composition containing resin (A) to the substrate. Additionally, a glass transition temperature of -80°C or higher is advantageous for improving the durability (appearance defects during high-temperature testing: cohesive failure, etc.) of the light-selective absorbing adhesive layer formed from the adhesive composition containing resin (A). The glass transition temperature can be measured using a differential scanning calorimeter (DSC).

[0040] The structural unit having a merocyanine structure in its side chain is not particularly limited, but it is preferable that it is a structural unit derived from a compound having a polymerizable group and a merocyanine structure.

[0041] Compounds having a polymerizable group and a merocyanine structure preferably satisfy the following formula (1-a), and more preferably satisfy formula (2-a). ε(405)≧5 (1-a) [In formula (1-a), ε(405) represents the Gram extinction coefficient of a compound having a polymerizable group and a merocyanine structure at a wavelength of 405 nm. The unit of the Gram extinction coefficient is L / (g·cm).] ε(405) / ε(440)≧20 (2-a) [In formula (2-a), ε(405) represents the Gram extinction coefficient of a compound having a polymerizable group and a merocyanine structure at a wavelength of 405 nm, and ε(440) represents the Gram extinction coefficient of a compound having a polymerizable group and a merocyanine structure at a wavelength of 440 nm.]

[0042] Compounds having a polymerizable group and a merocyanine structure preferably have an ε(405) value of 5 L / (g·cm) or more, more preferably 10 L / (g·cm) or more, even more preferably 20 L / (g·cm) or more, and even more preferably 30 L / (g·cm) or more, and are usually 500 L / (g·cm) or less. Compounds with a larger ε(405) value tend to absorb light at a wavelength of 405 nm more easily and exhibit a function of suppressing degradation by ultraviolet light and short-wavelength visible light. Compounds having a polymerizable group and a merocyanine structure preferably have an ε(405) / ε(440) value of 20 or more, more preferably 40 or more, even more preferably 70 or more, and particularly preferably 80 or more. Resins containing compounds with a large ε(405) / ε(440) value can absorb light around 405 nm without hindering the color expression of the display device, thereby suppressing the photodegradation of display devices such as phase difference films and organic EL elements.

[0043] Examples of structural units having a merocyanine structure in the side chain include structural units derived from compounds represented by formula (I). [ka] [In formula (I), R 1 , R 2 , R 3 , R 4 and R 5 Each of these independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 25 carbon atoms which may have substituents, an aromatic hydrocarbon group having 6 to 15 carbon atoms which may have substituents, a heterocyclic group, or an ethylenically unsaturated group, and the -CH2- contained in the aliphatic hydrocarbon group or aromatic hydrocarbon group is -NR 1A-SO₂-, -CO-, -O- or S-. R 6 and R 7 each independently represent a hydrogen atom, an alkyl group having 1 to 25 carbon atoms, an electron-withdrawing group or an ethylenically unsaturated group. R 1A represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. R 1 and R 2 may be linked to each other to form a ring structure, R 2 and R 3 may be linked to each other to form a ring structure, R 2 and R 4 may be linked to each other to form a ring structure, R 3 and R 6 may be linked to each other to form a ring structure, R 5 and R 7 may be linked to each other to form a ring structure, R 6 and R 7 may be linked to each other to form a ring structure. provided that one of R 1 to R 7 is an ethylenically unsaturated group]

[0044] R 1 to R 5 Examples of the aliphatic hydrocarbon group having 1 to 25 carbon atoms represented by include linear or branched alkyl groups having 1 to 25 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, sec-butyl, n-pentyl, isopentyl, n-hexyl, isohexyl, n-octyl, isooctyl, n-nonyl, isononyl, n-decyl, isodecyl, n-dodecyl, isododecyl, undecyl, lauryl, myristyl, cetyl and stearyl groups; cycloalkyl groups having 3 to 25 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl groups; cycloalkylalkyl groups having 4 to 25 carbon atoms such as cyclohexylmethyl group, and an alkyl group having 4 to 25 carbon atoms is preferable. R1 ~R 5 Examples of substituents that the aliphatic hydrocarbon group having 1 to 25 carbon atoms represented by may have include hydroxyl groups, cyano groups, halogen atoms, mercapto groups, amino groups, and nitro groups. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine.

[0045] R 1 ~R 5 Examples of aromatic hydrocarbon groups having 6 to 15 carbon atoms, represented by , include aryl groups having 6 to 15 carbon atoms such as phenyl, naphthyl, anthracenyl, and biphenyl groups; and aralkyl groups having 7 to 15 carbon atoms such as benzyl, phenylethyl, naphthylmethyl, and phenyl. R 1 ~R 5 The substituents that the C6-C15 aromatic hydrocarbon group represented by may have include a hydroxyl group, a cyano group, a halogen atom, a mercapto group, an amino group, a nitro group, an alkoxy group, an alkylthio group, an alkoxycarbonyl group, an acyl group, an acyloxy group, and -C(NR 2A )R 2B ,-CONR 3A R 3B , -SO2R 4A (R 2A , R 2B , R 3A and R 3B Each of these independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R 4A represents an alkyl group having 1 to 6 carbon atoms. Examples include:

[0046] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine. Examples of alkoxy groups include methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, octyloxy, 2-ethylhexyloxy, nonyloxy, decyloxy, undecyloxy, and dodecyloxy groups, which have 1 to 12 carbon atoms. Examples of alkylthio groups include alkylthio groups having 1 to 12 carbon atoms, such as methylthio groups, ethylthio groups, propylthio groups, and butylthio groups. Examples of acyl groups include acetyl groups, propionyl groups, and butyryl groups, which have 2 to 13 carbon atoms. Examples of acyloxy groups include methyl carbonyloxy group, ethyl carbonyloxy group, n-propyl carbonyloxy group, isopropyl carbonyloxy group, n-butyl carbonyloxy group, sec-butyl carbonyloxy group, tert-butyl carbonyloxy group, pentyl carbonyloxy group, hexyl carbonyloxy group, octyl carbonyloxy group, and 2-ethylhexyl carbonyloxy group, which have 2 to 13 carbon atoms. Examples of alkoxycarbonyl groups include methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group, pentyloxycarbonyl group, hexyloxycarbonyl group, octyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, nonyloxycarbonyl group, decyloxycarbonyl group, undecyloxycarbonyl group, and dodecyloxycarbonyl group, all of which have 2 to 13 carbon atoms. -CONR 3A R 3B Examples include aminocarbonyl groups, methylaminocarbonyl groups, dimethylaminocarbonyl groups, ethylaminocarbonyl groups, and methylmethylaminocarbonyl groups. -C(NR 2A )R 2B Examples include methylimino groups, dimethylimino groups, and methylethylimino groups. -SO2R 4A Examples include methylsulfonyl groups and ethylsulfonyl groups.

[0047] R 1A and R 1B Examples of C1-C6 alkyl groups represented by include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, and sec-butyl group.

[0048] R 1 ~R 5 Examples of heterocyclic groups represented by this symbol include aliphatic heterocyclic groups having 4 to 20 carbon atoms, such as pyrrolidine rings, pyrroline rings, imidazolidine rings, imidazoline rings, oxazoline rings, thiazoline rings, piperidine rings, morpholine rings, piperazine rings, indole rings, isoindole rings, quinoline rings, thiophene rings, pyrrole rings, thiazoline rings, and furan rings, or aromatic heterocyclic groups having 3 to 20 carbon atoms.

[0049] R 6 and R 7 Examples of C1-C25 alkyl groups represented by include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, sec-butyl group, n-pentyl group, isopentyl group, n-hexyl group, isohexyl group, n-octyl group, isooctyl group, n-nonyl group, isononyl group, n-decyl group, isodecyl group, n-dodecyl group, isododecyl group, undecyl group, lauryl group, myristyl group, cetyl group, stearyl group, and other linear or branched alkyl groups having 1-25 carbon atoms.

[0050] R 6 and R 7 Examples of electron-withdrawing groups represented by this formula include cyano groups, nitro groups, halogen atoms, alkyl groups substituted with halogen atoms, and groups represented by formula (I-1). [ka] [In the formula, R 111 This represents a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms, and at least one of the methylene groups contained in the alkyl group may be substituted with an oxygen atom. X 1 is, -CO-* 1 、-COO-* 1 -CS-* 1 , -CSS-* 1 -CSNR 112 -* 1 ,-CONR113 -* 1 , -CNR 114 -* 1 or SO2-* 1 It represents. R 112 , R 113 and R 114 Each of these independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group. * 1 is R 111 This represents a combination of two things. * represents a bond with a carbon atom.

[0051] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine. Examples of alkyl groups substituted with halogen atoms include perfluoroalkyl groups such as trifluoromethyl, perfluoroethyl, perfluoropropyl, perfluoroisopropyl, perfluorobutyl, perfluorosec-butyl, perfluorotert-butyl, perfluoropentyl, and perfluorohexyl groups. The number of carbon atoms in halogen-substituted alkyl groups is usually between 1 and 25.

[0052] R 111Examples of hydrocarbon groups with 1 to 25 carbon atoms represented by methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, sec-butyl, n-pentyl, isopentyl, n-hexyl, isohexyl, n-octyl, isooctyl, n-nonyl, isononyl, n-decyl, isodecyl, n-dodecyl, isododecyl, undecyl, lauryl, myristyl, cetyl, stearyl, and other groups with 1 to 25 carbon atoms. Examples of linear or branched alkyl groups include: cycloalkyl groups with 3 to 25 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl groups; cycloalkylalkyl groups with 4 to 25 carbon atoms such as cyclopropylmethyl and cyclohexylmethyl groups; aryl groups with 6 to 25 carbon atoms such as phenyl, naphthyl, anthracenyl, and biphenyl groups; and aralkyl groups with 7 to 25 carbon atoms such as benzyl, phenylethyl, naphthylmethyl, and phenyl. R 112 , R 113 and R 114 A C1-C6 alkyl group represented by R is: 1A Examples include alkyl groups with 1 to 6 carbon atoms represented by .

[0053] R 111 It is preferably an alkyl group having 4 to 25 carbon atoms, and more preferably an alkyl group having 4 to 12 carbon atoms. X 1 is, -CO-* 1 and COO-* 1 It is preferable that this be the case.

[0054] R 6 and R 7 The electron-withdrawing groups represented by are preferably a cyano group and a group represented by formula (I-1), respectively.

[0055] R 1 and R 2 The ring structure formed by the bonding of these elements to each other is R 1 and R 2is a nitrogen-containing ring structure containing a bonded nitrogen atom, and examples thereof include 4- to 10-membered nitrogen-containing heterocycles. R 1 and R 2 the ring structure formed by connecting to each other may be a monocyclic ring or a polycyclic ring. Specific examples include a pyrrolidine ring, a pyrroline ring, an imidazolidine ring, an imidazoline ring, an oxazoline ring, a thiazoline ring, a piperidine ring, a morpholine ring, a piperazine ring, an indole ring, and an isoindole ring. R 1 and R 2 the ring formed by bonding to each other may have a substituent, and examples of the substituent include alkyl groups having 1 to 12 carbon atoms such as methyl group, ethyl group, propyl group, butyl group, and isobutyl group; and alkoxy groups having 1 to 12 carbon atoms such as methoxy group, ethoxy group, propoxy group, and butoxy group.

[0056] R 2 and R 3 as the ring structure formed by bonding to each other, R 2 is a nitrogen-containing ring structure containing a bonded nitrogen atom, and examples thereof include 4- to 10-membered nitrogen-containing heterocycles. R 2 and R 3 the ring structure formed by connecting to each other may be a monocyclic ring or a polycyclic ring. Specific examples include a pyrrolidine ring, a pyrroline ring, an imidazolidine ring, an imidazoline ring, an oxazoline ring, a thiazoline ring, a piperidine ring, a morpholine ring, a piperazine ring, an indole ring, an isoindole ring, and a ring structure represented by the following formula (I-3).

Chemical Formula

[0057] Ring W 1 is preferably a 5-membered ring or a 6-membered ring having a nitrogen atom and X as constituent elements. The following are specific examples of ring structures represented by equation (I-3). [ka]

[0058] R 2 and R 3 The ring structure formed by the bonding of these elements may have substituents, such as C1-C12 alkyl groups including methyl, ethyl, propyl, butyl, and isobutyl groups; and C1-C12 alkoxy groups including methoxy, ethoxy, propoxy, and butoxy groups.

[0059] R 2 and R 3 The ring structure formed by the bonding of these elements is preferably a ring structure represented by the following formula (I-4). [ka] [In formula (I-4), R 11 The above has the same meaning. m2 represents an integer from 1 to 7. R 11a , R 11b , R 11c and R 11d Each of these independently represents either a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. * represents a bond with a carbon atom. m2 is preferably 2 or 3, and more preferably 2.

[0060] R 2 and R 4 The ring structure formed by the bonding of these elements includes a 4-membered to 10-membered nitrogen-containing ring structure, with a 5-membered to 9-membered nitrogen-containing ring structure being preferred. 2 and R 4The ring structure formed by the bonding of these elements may be monocyclic or polycyclic. These rings may have substituents. Examples of such ring structures include pyrrole rings, indole rings, pyrimidine rings, and the rings described below. [ka]

[0061] R 2 and R 4 The ring structure formed by the bonding of these groups may have substituents, such as C1-C12 alkyl groups such as methyl, ethyl, propyl, butyl, and isobutyl groups; C1-C12 alkoxy groups such as methoxy, ethoxy, propoxy, and butoxy groups; and -NR groups such as amino, methylamino, and dimethylamino groups. 22A R 22B The group represented by (R 22A and R 22B Each of these independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; examples include alkylthio groups having 1 to 12 carbon atoms such as methylthio, ethylthio, propylthio, butylthio, and pentylthio; and heterocyclic groups having 4 to 9 carbon atoms such as pyrrolidinyl, piperidinyl, and morpholinyl.

[0062] R 3 and R 6 The ring structure formed by the interconnection of these elements is R 3 -C=CC=CR 6 This is a ring structure that forms the framework of the ring. For example, a phenyl group is one such example.

[0063] R 5 and R 7 The following are examples of ring structures formed by the interconnection of these elements. 5 and R 7The ring structure formed by the bonding of these elements may have substituents, such as C1-C12 alkyl groups such as methyl, ethyl, propyl, butyl, and isobutyl groups; and C1-C12 alkoxy groups such as methoxy, ethoxy, propoxy, and butoxy groups. [ka]

[0064] R 6 and R 7 Examples of ring structures formed by the interconnection of these elements include the ring structures described below. 6 and R 7 The ring structure formed by the bonding of these elements to each other is a substituent (R1~R in the formula below) 16 The substituents may include alkyl groups having 1 to 12 carbon atoms, such as methyl, ethyl, propyl, butyl, and isobutyl groups; alkoxy groups having 1 to 12 carbon atoms, such as methoxy, ethoxy, propoxy, and butoxy groups; and ethylenically unsaturated groups as described later. [ka] [In the formula, * represents a bond with a carbon atom.]

[0065] R 1 ~R 7 Examples of ethylenically unsaturated groups represented by this formula include vinyl groups, α-methylvinyl groups, acryloyl groups, methacryloyl groups, allyl groups, styryl groups, and groups represented by formula (I-2). [ka] [In formula (I-2), X 2 This represents a vinyl group, an acryloyl group, or a methacryloyl group. R 115 represents a divalent aliphatic hydrocarbon group having 1 to 18 carbon atoms, and the -CH2- contained in the aliphatic hydrocarbon group is -O-, -CO-, -CS-, or NR 116- may be replaced with this. R 116 This represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. * represents a bond with a carbon or nitrogen atom.

[0066] R 115 Examples of divalent aliphatic hydrocarbon groups having 1 to 18 carbon atoms, represented by , include alkanediyl groups having 1 to 18 carbon atoms such as methylene group, ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group and 2-methylbutane-1,4-diyl group; and cycloalkanediyl groups having 3 to 18 carbon atoms such as cyclopropanediyl group, cyclobutanediyl group, cyclopentanediyl group and cyclohexanediyl group. It is preferable that the group is a divalent aliphatic hydrocarbon group having 1 to 12 carbon atoms. R 116 A C1-C6 alkyl group represented by R is: 1A Examples include alkyl groups with 1 to 6 carbon atoms represented by .

[0067] R 1 ~R 7 The ethylenically unsaturated groups represented by are preferably, independently, a vinyl group, an acryloyl group, a methacryloyl group, and a group represented by formula (I-2).

[0068] R 6 and R 7 It is preferable that one of these groups is an electron-withdrawing group. R 6 and R 7 It is preferable that one of them is an ethylenically unsaturated group.

[0069] The structural units derived from the compound represented by formula (I) are preferably structural units derived from the compound represented by formula (II). [ka] [In formula (II), R 11 , R 12 , R 13 , R 14 and R 15 Each of these independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 25 carbon atoms which may have substituents, an aromatic hydrocarbon group having 6 to 15 carbon atoms which may have substituents, or a heterocyclic group, and the -CH2- contained in the aliphatic hydrocarbon group or aromatic hydrocarbon group is -NR 11A -, -SO2-, -CO-, -O-, or S- may be substituted. R 16 and R 17 Each of these independently represents a hydrogen atom, an alkyl group having 1 to 25 carbon atoms, an electron-withdrawing group, or an ethylenically unsaturated group. R 11A This represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. R 12 and R 13 They may be linked to each other to form a ring structure, R 12 and R 14 These elements may be linked together to form a ring structure. However, R 16 or R 17 One of these is an ethylenically unsaturated group.

[0070] R 11 ~R 15 A C1-C25 aliphatic hydrocarbon group which may have substituents represented by R 1 Examples include the same aliphatic hydrocarbon group having 1 to 25 carbon atoms that may have substituents represented by . R 11 ~R 15 A C6-C15 aromatic hydrocarbon group which may have substituents represented by R 1 Examples include the same as the aromatic hydrocarbon group having 6 to 15 carbon atoms that may have substituents represented by . R 11 ~R 15 The complex algebra represented by is R1 Examples include the same complex algebras represented by .

[0071] R 16 and R 17 The alkyl group having 1 to 25 carbon atoms represented by R is 6 Examples include alkyl groups with 1 to 25 carbon atoms represented by . R 16 and R 17 As an electron-withdrawing group represented by R, 6 Examples include the same electron-withdrawing groups represented by . R 11A and R 11B A C1-C6 alkyl group represented by R is: 1A Examples include alkyl groups with 1 to 6 carbon atoms represented by .

[0072] R 12 and R 13 The ring structure that can be formed by the interconnection of these elements is R 2 and R 3 Examples include ring structures that can be formed by the interconnection of these elements. 12 and R 13 The ring structure that can be formed by the interconnection of these elements is preferably a single ring structure.

[0073] R 12 and R 14 The ring structure that can be formed by the interconnection of these elements is R 2 and R 4 Examples include ring structures that can be formed by the interconnection of these elements. 12 and R 14 The ring structure that can be formed by the interconnection of these elements is preferably a single ring structure. 12 and R 14 The ring structure that can be formed by the linkage of these rings is preferably an aromatic ring, and more preferably a pyrimidine ring structure.

[0074] R 11 , R 13 and R 15Each of these is preferably an aliphatic hydrocarbon group having 1 to 25 carbon atoms, which may have substituents; more preferably an alkyl group having 1 to 25 carbon atoms, which may have substituents; and even more preferably an alkyl group having 1 to 12 carbon atoms, which may have substituents. Especially R 11 Preferably, it is an aliphatic hydrocarbon group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and even more preferably a methyl group. R 12 and R 14 Each of these is independently an aliphatic hydrocarbon group having 1 to 25 carbon atoms, which may have substituents, or R 12 and R 14 It is preferable that they are connected to each other to form a ring structure. R 12 and R 13 It is preferable that the elements are linked to each other to form a ring structure, and more preferably a ring structure represented by formula (I-4) described above. Among the ring structures represented by formula (I-4), it is preferable that the ring structure represented by formula (I-4-1) or formula (I-4-2) be formed, and particularly preferable that the ring structure represented by formula (I-4-1) be formed. [ka] R 16 and R 17 Preferably, one of them is an ethylenically unsaturated group and the other is an electron-withdrawing group. R 16 and R 17 The electron-withdrawing groups represented by are preferably, independently, a cyano group, a nitro group, a fluoro group, a trifluoromethyl group, and a group represented by formula (I-1). A cyano group is particularly preferred. R 16 and R 17 The ethylenically unsaturated groups represented by are preferably, independently, a vinyl group, an acryloyl group, a methacryloyl group, and a group represented by formula (I-2). More preferably, *-CO-O-(CH2)nX2 , (X 2 represents a vinyl group, an acryloyl group, or a methacryloyl group, and n represents an integer from 1 to 10 (preferably an integer from 2 to 6).

[0075] R 12 and R 13 The compound represented by formula (II), which is linked to each other to form a ring structure, is preferably the compound represented by formula (II-A-1) or the compound represented by formula (II-A-2). 12 and R 14 The compound represented by formula (II), which is linked to each other to form a ring structure, is preferably the compound represented by formula (II-B-1). [ka] [In equations (II-A-1), (II-A-2), and (II-B-1), R 11 , R 14 , R 15 , R 16 and R 17 These each represent the same meaning as above. R 11e , R 11f , R 11g , R 11h , R 11k , R 11m , R 11n Each of these independently represents either a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. R 11q and R 11p Each of these independently consists of a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, and -NR. 22A R 22B The group represented by (R 22A and R 22B Each of these independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, or a heterocycle.

[0076] For example, a compound represented by formula (II), in which the electron-withdrawing group is a cyano group, can be obtained by reacting a compound represented by formula (I') with a compound represented by formula (L). [ka] [In the formula, R 222 represents a divalent linking group, X 2 [This represents a polymerizable group.] The reaction between the compound represented by formula (I') and the compound represented by formula (L) can be carried out under any conditions commonly used for Knefenagel condensation. For example, it is preferable to carry out the reaction in the presence of a base or a carboxylic acid anhydride. Examples of bases include triethylamine, N,N-diisopropylethylamine, pyridine, piperidine, pyrrolidine, proline, N,N-dimethylaminopyridine, imidazole, sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, sodium bicarbonate, potassium bicarbonate, potassium tertsia leaf toxide, sodium tertsia leaf toxide, and sodium hydrogen. Examples of carboxylic acid anhydrides include acetic anhydride, succinic anhydride, phthalic anhydride, maleic anhydride, and benzoic anhydride. The amount of base used is preferably 0.1 to 10 moles per mole of the compound represented by formula (I'). The amount of acetic anhydride used is preferably 0.2 to 5 moles per mole of the compound represented by formula (I'). The reaction between the compound represented by formula (I') and the compound represented by formula (L) is preferably carried out in an organic solvent. Examples of organic solvents include toluene, acetonitrile, dichloromethane, and trichloromethane.

[0077] The reaction between the compound represented by formula (I') and the compound represented by formula (L) is carried out by mixing the compound represented by formula (I') and the compound represented by formula (L). The reaction temperature between the compound represented by formula (I') and the compound represented by formula (L) is preferably -40 to 130°C, and the reaction time is usually preferably 1 to 24 hours.

[0078] The compound represented by formula (I') can be synthesized, for example, by the method described in Japanese Patent Publication No. 2014-194508.

[0079] The compound represented by formula (L) can be obtained, for example, by reacting cyanoacetic acid with a hydroxyalkyl acrylate. The amount of cyanoacetic acid used is preferably 0.5 to 3 moles per mole of hydroxyalkyl acrylate. The reaction between cyanoacetic acid and hydroxyalkyl acrylate can be carried out using any esterification catalyst commonly used in esterification reactions, but it is preferable to carry out the reaction in the presence of a base and a carbodiimide coupling agent. Examples of bases include triethylamine, diisopropylethylamine, pyridine, piperidine, pyrrolidine, proline, N,N-dimethylaminopyridine, imidazole, sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, sodium bicarbonate, potassium bicarbonate, potassium tertsia leaf toxide, sodium tertsia leaf toxide, and sodium hydrogen. Examples of carbodiimide coupling agents include N,N-dicyclohexylcarbodiimide, N,N-diisopropylcarbodiimide, and 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride. The amount of base used is preferably 0.5 to 5 moles per mole of cyanoacetic acid. The reaction between cyanoacetic acid and hydroxyalkyl acrylate is preferably carried out in an organic solvent. Examples of organic solvents include acetonitrile, isopropanol, toluene, trichloromethane, and dichloromethane.

[0080] The reaction between cyanoacetic acid and hydroxyalkyl acrylate is carried out by mixing the cyanoacetic acid and hydroxyalkyl acrylate. The reaction temperature between cyanoacetic acid and hydroxyalkyl acrylate is preferably -40 to 130°C, and the reaction time is usually preferably 1 to 24 hours.

[0081] Examples of compounds having a polymerizable group and a merocyanine structure include the compounds listed below. [ka]

[0082] [ka]

[0083] [ka]

[0084] [ka]

[0085] [ka]

[0086] [ka]

[0087] [ka]

[0088] Resin (A) may be a homopolymer of structural units having a merocyanine structure in its side chain, or it may be a copolymer containing structural units having a merocyanine structure in its side chain and other structural units. Resin (A) is preferably a copolymer. Examples of structural units that resin (A) may contain in addition to structural units having a merocyanine structure in its side chain include the structural units described in group A below. Group A: Structural units derived from (meth)acrylic acid esters, structural units derived from styrene monomers, structural units derived from vinyl monomers, structural units represented by formula (a), structural units represented by formula (b), and structural units represented by formula (c) [ka] [In the formula, R a1 This represents a divalent hydrocarbon group. R b1 and R b2 Each of these independently represents either a hydrogen atom or a hydrocarbon group. R c1 and R c2 Each of these independently represents a divalent hydrocarbon group.

[0089] Examples of (meth)acrylic acid esters include linear alkyl esters of (meth)acrylic acid such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, n-nonyl (meth)acrylate, n-decyl (meth)acrylate, n-dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate; i-propyl (meth)acrylate, i-butyl (meth)acrylate, t-butyl (meth)acrylate, i-pentyl (meth)acrylate, i-hexyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate. Examples include branched alkyl esters of (meth)acrylic acid such as syl, i-octyl (meth)acrylate, i-nonyl (meth)acrylate, i-stearyl (meth)acrylate, and i-amyl (meth)acrylate; alkyl esters containing an alicyclic skeleton of (meth)acrylic acid such as cyclohexyl (meth)acrylate, isobolonyl (meth)acrylate, adamantyl (meth)acrylate, dicyclopentanyl (meth)acrylate, cyclododecyl (meth)acrylate, methylcyclohexyl (meth)acrylate, trimethylcyclohexyl (meth)acrylate, tert-butylcyclohexyl (meth)acrylate, and cyclohexyl α-ethoxyacrylate; and aromatic ring skeleton esters of (meth)acrylic acid such as phenyl (meth)acrylate.

[0090] Structural units derived from (meth)acrylic acid esters can also be exemplified by substituent-containing (meth)acrylic acid alkyl esters, in which substituents are introduced to the alkyl group in (meth)acrylic acid alkyl esters. The substituents in substituent-containing (meth)acrylic acid alkyl esters are groups that substitute for hydrogen atoms of the alkyl group, and specific examples include phenyl groups, alkoxy groups, and phenoxy groups. Specific examples of substituent-containing (meth)acrylic acid alkyl esters include 2-methoxyethyl (meth)acrylate, ethoxymethyl (meth)acrylate, phenoxyethyl (meth)acrylate, 2-(2-phenoxyethoxy)ethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, and phenoxypoly(ethylene glycol) (meth)acrylate.

[0091] These (meth)acrylic acid esters can be used individually or in combination.

[0092] The resin (A) of the present invention preferably contains constituent units derived from alkyl (meth)acrylate (a1) in which the glass transition temperature Tg of the homopolymer is less than 0°C, and constituent units derived from alkyl (meth)acrylate (a2) in which the Tg of the homopolymer is 0°C or higher. This is advantageous in improving the high-temperature durability of the adhesive layer. The Tg of the alkyl (meth)acrylate homopolymer can be determined from literature values ​​such as those in the POLYMER HANDBOOK (Wiley-Interscience).

[0093] Specific examples of (meth)acrylate alkyl esters (a1) include alkyl esters of (meth)acrylates with approximately 2 to 12 carbon atoms in the alkyl group, such as ethyl acrylate, n- and i-propyl acrylate, n- and i-butyl acrylate, n-pentyl acrylate, n- and i-hexyl acrylate, n-heptyl acrylate, n- and i-octyl acrylate, 2-ethylhexyl acrylate, n- and i-nonyl acrylate, n- and i-decyl acrylate, and n-dodecyl acrylate.

[0094] Alkyl methacrylate (a1) may be used alone or in combination of two or more. Among these, n-butyl acrylate, n-octyl acrylate, and 2-ethylhexyl acrylate are preferred from the viewpoint of conformability and reworkability when laminated onto an optical film.

[0095] Alkyl methacrylate (a2) is an alkyl methacrylate other than alkyl methacrylate (a1). Specific examples of alkyl methacrylate (a2) include methyl acrylate, cyclohexyl acrylate, isobolonyl acrylate, stearyl acrylate, t-butyl acrylate, etc.

[0096] Alkyl methacrylate (a2) may be used alone or in combination of two or more types. In particular, from the viewpoint of high-temperature durability, alkyl methacrylate (a2) preferably contains methyl acrylate, cyclohexyl acrylate, isobolonyl acrylate, etc., and more preferably contains methyl acrylate.

[0097] Furthermore, structural units derived from (meth)acrylic acid esters also include structural units derived from (meth)acrylic acid esters that have polar functional groups. Examples of (meth)acrylic acid ester monomers having polar functional groups include 1-hydroxymethyl (meth)acrylate, 1-hydroxyethyl (meth)acrylate, 1-hydroxyheptyl (meth)acrylate, 1-hydroxybutyl (meth)acrylate, 1-hydroxypentyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxypentyl (meth)acrylate, 2-hydroxyhexyl (meth)acrylate, and 3 (meth)acrylate. -Hydroxypropyl, 3-hydroxybutyl (meth)acrylate, 3-hydroxypentyl (meth)acrylate, 3-hydroxyhexyl (meth)acrylate, 3-hydroxyheptyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 4-hydroxypentyl (meth)acrylate, 4-hydroxyhexyl (meth)acrylate, 4-hydroxyheptyl (meth)acrylate, 4-hydroxyoctyl (meth)acrylate, 2-chloro-2-hydroxypropyl (meth)acrylate, 3-chloro-2-hydroxy (meth)acrylate Xyxypropyl, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 5-hydroxypentyl (meth)acrylate, 5-hydroxyhexyl (meth)acrylate, 5-hydroxyheptyl (meth)acrylate, 5-hydroxyoctyl (meth)acrylate, 5-hydroxynonyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 6-hydroxyheptyl (meth)acrylate, 6-hydroxyoctyl (meth)acrylate, 6-hydroxynonyl (meth)acrylate, 6-hydroxydecyl (meth)acrylate, (meth)acrylate (Meth) 7-hydroxyheptyl acrylate, (meth) 7-hydroxyoctyl acrylate, (meth) 7-hydroxynonyl acrylate, (meth) 7-hydroxydecyl acrylate, (meth) 7-hydroxyundecyl acrylate, (meth) 8-hydroxyoctyl acrylate, (meth) 8-hydroxynonyl acrylate, (meth) 8-hydroxydecyl acrylate, (meth) 8-hydroxyundecyl acrylate, (meth) 8-hydroxydodecyl acrylate, (meth) 9-hydroxynonyl acrylate, (meth) 9-hydroxydecyl acrylate,9-Hydroxyundecyl (meth)acrylate, 9-Hydroxydodecyl (meth)acrylate, 9-Hydroxytridecyl (meth)acrylate, 10-Hydroxydecyl (meth)acrylate, 10-Hydroxyundecyl (meth)acrylate, 10-Hydroxydodecyl (meth)acrylate, 10-Hydroxytridecyl (meth)acrylate, 10-Hydroxytetradecyl (meth)acrylate, 11-Hydroxyundecyl (meth)acrylate, 11-Hydroxydodecyl (meth)acrylate, 11-Hydroxytridecyl (meth)acrylate, 11-Hydroxytetradecyl (meth)acrylate, 11-Hydroxytamine (meth)acrylate Examples include alkyl esters of (meth)acrylates having hydroxyl groups, such as xypentadecyl, 12-hydroxydodecyl (meth)acrylate, 12-hydroxytridecyl (meth)acrylate, 12-hydroxytetradecyl (meth)acrylate, 13-hydroxypentadecyl (meth)acrylate, 13-hydroxytetradecyl (meth)acrylate, 13-hydroxypentadecyl (meth)acrylate, 14-hydroxytetradecyl (meth)acrylate, 14-hydroxypentadecyl (meth)acrylate, 15-hydroxypentadecyl (meth)acrylate, and 15-hydroxyheptadecyl (meth)acrylate.

[0098] Examples of styrene monomers include styrene; alkylstyrenes such as methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, triethylstyrene, propylstyrene, butylstyrene, hexylstyrene, heptylstyrene, and octylstyrene; halogenated styrenes such as fluorostyrene, chlorostyrene, bromostyrene, dibromostyrene, and iodostyrene; nitrostyrene; acetylstyrene; methoxystyrene; and divinylbenzene.

[0099] Examples of vinyl monomers include fatty acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, and vinyl laurate; vinyl halides such as vinyl chloride and vinyl bromide; vinylidenes such as vinylidene chloride; nitrogen-containing heteroaromatic vinyls such as vinylpyridine, vinylpyrrolidone, and vinylcarbazole; conjugated dienes such as butadiene, isoprene, and chloroprene; and unsaturated nitriles such as acrylonitrile and methacrylonitrile.

[0100] Compounds that derive the structural unit represented by formula (a) can be synthesized, for example, by the reaction of a diisocyanate compound with a polyol. Compounds that derive the structural unit represented by formula (b) can be synthesized, for example, by reacting silane halides or silanes containing a hydroxyl group. The compounds that derive the structural unit represented by formula (c) can be synthesized, for example, by the reaction of a polycarboxylic acid with a polyol.

[0101] The structural unit selected from the structural units described in Group A is preferably a structural unit derived from (meth)acrylic acid ester. The structural unit derived from (meth)acrylic acid ester is preferably an alkyl (meth)acrylate ester or an alkyl (meth)acrylate ester having a hydroxyl group.

[0102] The resin (A) of the present invention may further contain other structural units (sometimes referred to as structural unit (aa)). Specifically, these include structural units derived from (meth)acrylamide monomers, structural units derived from monomers having carboxyl groups, structural units derived from monomers having heterocyclic groups, structural units derived from monomers having substituted or unsubstituted amino groups, and the like.

[0103] Examples of (meth)acrylamide monomers include N-methylol(meth)acrylamide, N-(2-hydroxyethyl)(meth)acrylamide, N-(3-hydroxypropyl)(meth)acrylamide, N-(4-hydroxybutyl)(meth)acrylamide, N-(5-hydroxypentyl)(meth)acrylamide, N-(6-hydroxyhexyl)(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, N-(3-dimethylaminopropyl)(meth)acrylamide, N-(1,1-dimethyl-3-oxobutyl)(meth)acrylamide, N-[2-(2-oxo-1-imidazolidinyl)ethyl](meth)acrylamide, 2-acryloylamino-2-methyl-1-propanesulfonic acid, N-(methoxymethyl)acrylamide, N-(ethoxymethyl)(meth)acrylamide, N-(propoxymethyl)(meth)acrylamide, N-(1-methylethoxymethyl)(meth)acrylamide, N-(1-methylpropoxymethyl)(meth)acrylamide, N-(2-methylpropoxymethyl)(meth)acrylamide, N-(butoxymethyl)(meth)acrylamide, N-(1,1-dimethylethoxymethyl)(meth)acrylamide, N-(2-methoxyethyl)(meth)acrylamide, N-(2-ethoxyethyl)( Examples include meth)acrylamide, N-(2-propoxyethyl)(meth)acrylamide, N-[2-(1-methylethoxy)ethyl](meth)acrylamide, N-[2-(1-methylpropoxy)ethyl](meth)acrylamide, N-[2-(2-methylpropoxy)ethyl](meth)acrylamide, N-(2-butoxyethyl)(meth)acrylamide, and N-[2-(1,1-dimethylethoxy)ethyl](meth)acrylamide. Among these, N-(methoxymethyl)acrylamide, N-(ethoxymethyl)acrylamide, N-(propoxymethyl)acrylamide, N-(butoxymethyl)acrylamide, and N-(2-methylpropoxymethyl)acrylamide are preferred.

[0104] Examples of monomers having a carboxyl group include (meth)acrylic acid, carboxyalkyl (meth)acrylate (e.g., carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate), maleic acid, maleic anhydride, fumaric acid, crotonic acid, etc., with acrylic acid being preferred.

[0105] Examples of monomers having heterocyclic groups include acryloylmorpholine, vinylcaprolactam, N-vinyl-2-pyrrolidone, vinylpyridine, tetrahydrofurfuryl (meth)acrylate, caprolactone-modified tetrahydrofurfuryl acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, glycidyl (meth)acrylate, and 2,5-dihydrofuran.

[0106] Examples of monomers having substituted or unsubstituted amino groups include aminoethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, and dimethylaminopropyl (meth)acrylate.

[0107] The structural units (aa) other than those having a merocyanine structure and those selected from group A are preferably monomers having a carboxyl group.

[0108] The content of structural units having a merocyanine structure in the side chain is preferably 0.01 to 50 parts by mass, more preferably 0.1 to 20 parts by mass, and even more preferably 0.5 to 10 parts by mass, based on 100 parts by mass of all structural units contained in resin (A). The content of at least one structural unit selected from the structural units described in Group A is preferably 50 parts by mass or more, and more preferably 60 to 99.99 parts by mass, per 100 parts by mass of all structural units of resin (A).

[0109] When resin (A) contains structural units (aa), the amount of structural units is preferably 20 parts by mass or less, more preferably 0.5 parts by mass or more and 15 parts by mass or less, even more preferably 0.5 parts by mass or more and 10 parts by mass or less, and particularly preferably 1 part by mass or more and 7 parts by mass or less, per 100 parts by mass of all structural units of resin (A).

[0110] When resin (A) contains structural units derived from an alkyl (meth)acrylate having a hydroxyl group, the content of such structural units is preferably 20 parts by mass or less, more preferably 0.5 parts by mass or more and 15 parts by mass or less, even more preferably 0.5 parts by mass or more and 10 parts by mass or less, and particularly preferably 1 part by mass or more and 7 parts by mass or less, per 100 parts by mass of the total structural units of resin (A). From the viewpoint of preventing an increase in the peeling force of the separator film that can be laminated on the outer surface of the adhesive layer, it is preferable that the material substantially does not contain monomers having amino groups. Here, substantially does not contain means that the amount is 0.1 parts by mass or less per 100 parts by mass of all constituent units that make up the resin (A).

[0111] In terms of reactivity between resin (A) and the crosslinking agent (B) described later, resin (A) preferably contains structural units derived from alkyl (meth)acrylate having a hydroxyl group or structural units derived from monomers having a carboxyl group, and more preferably contains both structural units derived from alkyl (meth)acrylate having a hydroxyl group and structural units derived from monomers having a carboxyl group. Preferred alkyl (meth)acrylate having a hydroxyl group are 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 5-hydroxypentyl acrylate, and 6-hydroxyhexyl acrylate. In particular, good durability can be obtained by using 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, and 5-hydroxypentyl acrylate. As the monomer having a carboxyl group, acrylic acid is preferred.

[0112] The weight-average molecular weight (Mw) of resin (A) is preferably 300,000 to 2,500,000, more preferably 500,000 to 2,500,000. A weight-average molecular weight of 300,000 or more improves the durability of the adhesive layer in high-temperature environments and makes it easier to suppress problems such as peeling between the adherend and the light-selective absorption adhesive layer, and cohesive failure of the light-selective absorption adhesive layer. A weight-average molecular weight of 2,500,000 or less is advantageous in terms of coatability when processing the adhesive composition into a sheet, for example (coating it to a substrate). From the viewpoint of achieving both durability of the light-selective absorption adhesive layer and coatability of the adhesive composition, the weight-average molecular weight is preferably 600,000 to 1,800,000, more preferably 700,000 to 1,700,000, and particularly preferably 1,000,000 to 1,600,000. Furthermore, the molecular weight distribution (Mw / Mn), expressed as the ratio of weight-average molecular weight (Mw) to number-average molecular weight (Mn), is usually 2 to 10, preferably 3 to 8. The weight-average molecular weight can be analyzed by gel permeation chromatography and is expressed as a value on a standard polystyrene basis.

[0113] When resin (A) is dissolved in ethyl acetate to form a 20% by mass solution, its viscosity at 25°C is preferably 20 Pa·s or less, and more preferably 0.1 to 15 Pa·s. A viscosity within this range is advantageous from the viewpoint of coatability when applying the adhesive composition to a substrate. The viscosity can be measured using a Brookfield viscometer.

[0114] The resin (A) of the present invention can be produced by known methods such as solution polymerization, bulk polymerization, suspension polymerization, and emulsion polymerization, with solution polymerization being particularly preferred. Examples of solution polymerization include mixing monomers and an organic solvent, adding a thermal polymerization initiator under a nitrogen atmosphere, and stirring for 3 to 15 hours at a temperature of 40 to 90°C, preferably 50 to 80°C. For reaction control, monomers or thermal polymerization initiators may be added continuously or intermittently during polymerization. The monomers and thermal initiators may also be added to the organic solvent.

[0115] As polymerization initiators, thermal polymerization initiators and photopolymerization initiators are used. Examples of photopolymerization initiators include 4-(2-hydroxyethoxy)phenyl(2-hydroxy-2-propyl)ketone. Examples of thermal polymerization initiators include azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane-1-carbonnitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethyl-4-methoxyvaleronitrile), dimethyl-2,2'-azobis(2-methylpropionate), and 2,2'-azobis(2-hydroxymethylpropionitrile); lauryl Examples include organic peroxides such as peroxide, t-butyl hydroperoxide, benzoyl peroxide, t-butyl peroxybenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, dipropyl peroxydicarbonate, t-butyl peroxyneodecanoate, t-butyl peroxypivalate, and (3,5,5-trimethylhexanoyl)peroxide; and inorganic peroxides such as potassium persulfate, ammonium persulfate, and hydrogen peroxide. Redox initiators using peroxides in combination with reducing agents can also be used.

[0116] The proportion of the polymerization initiator is approximately 0.001 to 5 parts by mass per 100 parts by mass of the total amount of monomers constituting resin (A). Polymerization of resin (A) may be carried out using a polymerization method using active energy rays (e.g., ultraviolet light).

[0117] Examples of organic solvents include aromatic hydrocarbons such as toluene and xylene; esters such as ethyl acetate and butyl acetate; aliphatic alcohols such as propyl alcohol and isopropyl alcohol; and ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone.

[0118] Resin (A) is preferably a resin that satisfies the following formula (1), and more preferably a resin that satisfies the following formula (2). ε(405)≧0.02 (1) [In equation (1), ε(405) represents the Gram extinction coefficient of the resin at a wavelength of 405 nm. The unit of the Gram extinction coefficient is L / (g·cm).] ε(405) / ε(440)≧5 (2) [In equation (2), ε(405) represents the Gram extinction coefficient of the resin at a wavelength of 405 nm, and ε(440) represents the Gram extinction coefficient of the resin at a wavelength of 440 nm.] The gram absorbance coefficient of resin (A) can be measured by the method described in the examples.

[0119] The resin (A) absorbs light at a wavelength of 405 nm more readily as the value of ε(405) increases. The value of ε(405) is preferably 0.02 L / (g·cm) or higher, more preferably 0.1 L / (g·cm) or higher, even more preferably 0.2 L / (g·cm) or higher, and is usually 10 L / (g·cm) or lower. When an adhesive composition containing resin (A) is applied to a display device such as an organic electroluminescent display (organic EL display device) or a liquid crystal display device (FPD: flat panel display), if the ε(405) of resin (A) is 0.02 L / (g·cm) or higher, the absorption performance of visible light around 400 nm is good, and thus the degradation of phase difference films and organic EL light-emitting elements used in display devices such as organic EL display devices and liquid crystal displays due to visible light can be suppressed.

[0120] The resin (A) can selectively absorb light with a wavelength around 400 nm as the value of ε(405) / ε(440) increases. The value of ε(405) / ε(440) is preferably 5 or greater, more preferably 50 or greater, even more preferably 75 or greater, and particularly preferably 100 or greater. When the ε(405) / ε(440) of resin (A) is 5 or greater, an adhesive composition containing resin (A) can be applied to a display device (FPD: flat panel display) such as an organic EL display device or a liquid crystal display device, and it can absorb light around 405 nm without hindering the color expression of the display device, thereby suppressing photodegradation of phase difference films, organic EL elements, etc.

[0121] (Other components contained in the adhesive composition) The adhesive composition may further contain a crosslinking agent (B), a silane compound (D), an antistatic agent, a light selective absorber, a resin other than resin (A), etc. The content of resin (A) is typically 60% to 99.99% by mass, preferably 70% to 99.9% by mass, and more preferably 80% to 99.7% by mass, based on 100% by mass of the solid content of the adhesive composition.

[0122] The adhesive composition may contain a crosslinking agent (B). Examples of crosslinking agents (B) include isocyanate-based crosslinking agents, epoxy-based crosslinking agents, aziridine-based crosslinking agents, and metal chelate-based crosslinking agents. In particular, an isocyanate-based crosslinking agent is preferred from the viewpoint of the pot life of the adhesive composition, the durability of the adhesive layer, and the crosslinking rate.

[0123] Preferred isocyanate compounds are those having at least two isocyanate groups (-NCO) in the molecule. Examples include aliphatic isocyanate compounds (e.g., hexamethylene diisocyanate), alicyclic isocyanate compounds (e.g., isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate), and aromatic isocyanate compounds (e.g., tolylene diisocyanate, xylylene diisocyanate diphenylmethane diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate, etc.). Furthermore, the crosslinking agent (B) may be a derivative of the isocyanate compound obtained by an addition reaction with a polyhydric alcohol compound (adduct) of the isocyanate compound [for example, an adduct of glycerol, trimethylolpropane, etc.], an isocyanurate, a biuret-type compound, a polyether polyol, a polyester polyol, an acrylic polyol, a polybutadiene polyol, a polyisoprene polyol, etc., resulting in a urethane prepolymer-type isocyanate compound. The crosslinking agent (B) can be used alone or in combination of two or more types. Among these, typical examples include aromatic isocyanate compounds (for example, tolylene diisocyanate, xylylene diisocyanate), aliphatic isocyanate compounds (for example, hexamethylene diisocyanate), or adducts of these compounds with polyhydric alcohol compounds (for example, glycerol, trimethylolpropane), or isocyanurates. If the crosslinking agent (B) is an adduct of aromatic isocyanate compounds and / or polyhydric alcohol compounds thereof, or isocyanurate derivatives, it is advantageous for forming an optimal crosslink density (or crosslink structure), which can improve the durability of the adhesive layer. In particular, if the adduct is of tolylene diisocyanate compounds and / or polyhydric alcohol compounds thereof, durability can be improved even when the adhesive layer is applied to a polarizing plate, for example.

[0124] The crosslinking agent (B) content is usually 0.01 to 15 parts by weight, preferably 0.05 to 10 parts by weight, and more preferably 0.1 to 5 parts by weight, per 100 parts by weight of resin (A).

[0125] The adhesive composition may further contain a silane compound (D). Examples of silane compounds (D) include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylethoxydimethylsilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, and 3-mercaptopropyltrimethoxysilane. The silane compound (D) may also be a silicone oligomer. Specific examples of silicone oligomers, expressed as combinations of monomers, are as follows:

[0126] 3-mercaptopropyltrimethoxysilane-tetramethoxysilane oligomer, 3-mercaptopropyltrimethoxysilane-tetraethoxysilane oligomer, 3-mercaptopropyltriethoxysilane-tetramethoxysilane oligomer, 3-mercaptopropyltriethoxysilane-tetramethoxysilane oligomer, 3-mercaptopropyltriethoxysilane-tetraethoxysilane oligomer, etc.; mercaptomethyl group-containing oligomers such as mercaptomethyltrimethoxysilane-tetramethoxysilane oligomer, mercaptomethyltriethoxysilane-tetraethoxysilane oligomer, mercaptomethyltriethoxysilane-tetramethoxysilane oligomer, mercaptomethyltriethoxysilane-tetraethoxysilane oligomer, etc.; 3-Glyzidoxy Copolymers containing a 3-glycidoxypropyl group, such as 3-glycidoxypropyl trimethoxysilane-tetramethoxysilane copolymer, 3-glycidoxypropyl trimethoxysilane-tetraethoxysilane copolymer, 3-glycidoxypropyl triethoxysilane-tetramethoxysilane copolymer, 3-glycidoxypropyl triethoxysilane-tetraethoxysilane copolymer, 3-glycidoxypropyl methyldimethoxysilane-tetramethoxysilane copolymer, 3-glycidoxypropyl methyldimethoxysilane-tetraethoxysilane copolymer, 3-glycidoxypropyl methyldiethoxysilane-tetramethoxysilane copolymer, and 3-glycidoxypropyl methyldiethoxysilane-tetraethoxysilane copolymer;3-Methacryloyloxypropyltrimethoxysilane-tetramethoxysilane oligomer, 3-Methacryloyloxypropyltrimethoxysilane-tetraethoxysilane oligomer, 3-Methacryloyloxypropyltriethoxysilane-tetramethoxysilane oligomer, 3-Methacryloyloxypropyltriethoxysilane-tetraethoxysilane oligomer, 3-Methacryloyloxypropylmethyldimethoxysilane-tetramethoxysilane oligomer, 3-Methacryloyloxypropylmethyldimethoxysilane-tetraeth Methacryloyloxypropyl group-containing oligomers such as xysilane oligomer, 3-methacryloyloxypropylmethyldiethoxysilane-tetramethoxysilane oligomer, and 3-methacryloyloxypropylmethyldiethoxysilane-tetraethoxysilane oligomer; 3-acryloyloxypropyltrimethoxysilane-tetramethoxysilane oligomer, 3-acryloyloxypropyltrimethoxysilane-tetraethoxysilane oligomer, and 3-acryloyloxypropyltriethoxysilane-tetramethoxysilane oligomer. Acryloyloxypropyl group-containing oligomers such as 3-acryloyloxypropyltriethoxysilane-tetraethoxysilane oligomer, 3-acryloyloxypropylmethyldimethoxysilane-tetramethoxysilane oligomer, 3-acryloyloxypropylmethyldimethoxysilane-tetraethoxysilane oligomer, 3-acryloyloxypropylmethyldiethoxysilane-tetramethoxysilane oligomer, and 3-acryloyloxypropylmethyldiethoxysilane-tetraethoxysilane oligomer; vinyl trimethoxy Vinyl group-containing oligomers such as sisilane-tetramethoxysilane oligomer, vinyltrimethoxysilane-tetraethoxysilane oligomer, vinyltriethoxysilane-tetramethoxysilane oligomer, vinyltriethoxysilane-tetraethoxysilane oligomer, vinylmethyldimethoxysilane-tetramethoxysilane oligomer, vinylmethyldimethoxysilane-tetraethoxysilane oligomer, vinylmethyldiethoxysilane-tetramethoxysilane oligomer, and vinylmethyldiethoxysilane-tetraethoxysilane oligomer;3-aminopropyltrimethoxysilane-tetramethoxysilane copolymer, 3-aminopropyltrimethoxysilane-tetraethoxysilane copolymer, 3-aminopropyltriethoxysilane-tetramethoxysilane copolymer, 3-aminopropyltriethoxysilane-tetraethoxysilane copolymer, 3-aminopropylmethyldimethoxysilane-tetramethoxysilane copolymer, 3-aminopropylmethyldimethoxysilane-tetraethoxysilane copolymer, 3-aminopropylmethyldiethoxysilane-tetramethoxysilane copolymer, amino group-containing copolymers such as 3-aminopropylmethyldiethoxysilane-tetraethoxysilane copolymer, and the like.;

[0127] The silane compound (D) may be a silane compound represented by the following formula (d1). [Chemical formula] (wherein A represents an alkanediyl group having 1 to 20 carbon atoms or a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, and -CH2- constituting the alkanediyl group and the alicyclic hydrocarbon group may be replaced by -O- or -CO-, R 41 represents an alkyl group having 1 to 5 carbon atoms, R 42 , R 43 , R 44 , R 45 and R 46 each independently represent an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms.)

[0128] Examples of the alkanediyl group having 1 to 20 carbon atoms represented by A include a methylene group, 1,2-ethanediyl group, 1,3-propanediyl group, 1,4-butanediyl group, 1,5-pentanediyl group, 1,6-hexanediyl group, 1,7-heptanediyl group, 1,8-octanediyl group, 1,9-nonanediyl group, 1,10-decanediyl group, 1,12-dodecanediyl group, 1,14-tetradecanediyl group, 1,16-hexadecanediyl group, 1,18-octadecanediyl group and 1,20-icosanediyl group. Examples of the divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms include a 1,3-cyclopentanediyl group and a 1,4-cyclohexanediyl group. Examples of groups in which -CH₂- constituting said alkanediyl group or said alicyclic hydrocarbon group is replaced by -O- or -CO- include -CH₂CH₂-O-CH₂CH₂-, -CH₂CH₂-O-CH₂CH₂-O-CH₂CH₂-, -CH₂CH₂-O-CH₂CH₂-O-CH₂CH₂-O-CH₂CH₂-, -CH₂CH₂-CO-O-CH₂CH₂-, -CH₂CH₂-O-CH₂CH₂-CO-O-CH₂CH₂-, -CH₂CH₂CH₂CH₂-O-CH₂CH₂- and CH₂CH₂CH₂CH₂-O-CH₂CH₂CH₂CH₂-.

[0129] R 41 ~R 45 Examples of the alkyl group having 1 to 5 carbon atoms represented by include a methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group and pentyl group, and R 42 ~R 45 Examples of the alkoxy group having 1 to 5 carbon atoms represented by include a methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, tert-butoxy group and pentyloxy group.

[0130] Examples of silane compounds represented by formula (d1) include (trimethoxysilyl)methane, 1,2-bis(trimethoxysilyl)ethane, 1,2-bis(triethoxysilyl)ethane, 1,3-bis(trimethoxysilyl)propane, 1,3-bis(triethoxysilyl)propane, 1,4-bis(trimethoxysilyl)butane, 1,4-bis(triethoxysilyl)butane, 1,5-bis(trimethoxysilyl)pentane, 1,5-bis(triethoxysilyl)pentane, 1,6-bis(trimethoxysilyl)hexane, 1,6-bis(triethoxysilyl)hexane, 1,6-bis(tripropoxysilyl)hexane, 1,8-bis(trimethoxysilyl)octane, 1,8-bis(triethoxysilyl)octane, and bis(tri(C1-5)) Examples include bis(diC1-5alkoxyC1-5alkylsilyl)C1-10 alkanes such as bis(dimethoxymethylsilyl)methane, 1,2-bis(dimethoxymethylsilyl)ethane, 1,2-bis(dimethoxyethylsilyl)ethane, 1,4-bis(dimethoxymethylsilyl)butane, 1,4-bis(dimethoxyethylsilyl)butane, 1,6-bis(dimethoxymethylsilyl)hexane, 1,6-bis(dimethoxyethylsilyl)hexane, 1,8-bis(dimethoxymethylsilyl)octane, and 1,8-bis(dimethoxyethylsilyl)octane; and bis(monoC1-5alkoxy-diC1-5alkylsilyl)C1-10 alkanes such as 1,6-bis(methoxydimethylsilyl)hexane and 1,8-bis(methoxydimethylsilyl)octane. Of these, bis(triC1-3 alkoxysilyl)C1-10 alkanes such as 1,2-bis(trimethoxysilyl)ethane, 1,3-bis(trimethoxysilyl)propane, 1,4-bis(trimethoxysilyl)butane, 1,5-bis(trimethoxysilyl)pentane, 1,6-bis(trimethoxysilyl)hexane, and 1,8-bis(trimethoxysilyl)octane are preferred, and 1,6-bis(trimethoxysilyl)hexane and 1,8-bis(trimethoxysilyl)octane are particularly preferred.

[0131] The content of silane compound (D) is usually 0.01 to 10 parts by mass, preferably 0.03 to 5 parts by mass, more preferably 0.05 to 2 parts by mass, and even more preferably 0.1 to 1 part by mass, per 100 parts by mass of resin (A).

[0132] The adhesive composition may further contain an antistatic agent. Examples of antistatic agents include surfactants, siloxane compounds, conductive polymers, and ionic compounds, with ionic compounds being preferred. Conventional ionic compounds are examples. Cationic components constituting the ionic compound include organic cations and inorganic cations. Examples of organic cations include pyridinium cations, pyrrolidinium cations, piperidinium cations, imidazolium cations, ammonium cations, sulfonium cations, and phosphonium cations. Examples of inorganic cations include alkali metal cations such as lithium cations, potassium cations, sodium cations, and cesium cations, and alkaline earth metal cations such as magnesium cations and calcium cations. Particularly from the viewpoint of compatibility with (meth)acrylic resins, pyridinium cations, imidazolium cations, pyrrolidinium cations, lithium cations, and potassium cations are preferred. The anionic component constituting the ionic compound may be either an inorganic anion or an organic anion, but an anionic component containing a fluorine atom is preferred in terms of antistatic performance. Examples of anionic components containing a fluorine atom include hexafluorophosphate anion (PF6-), bis(trifluoromethanesulfonyl)imide anion [(CF3SO2)2N-], bis(fluorosulfonyl)imide anion [(FSO2)2N-], and tetra(pentafluorophenyl)borate anion [(C6F5)4B-]. These ionic compounds can be used individually or in combination of two or more. Bis(trifluoromethanesulfonyl)imide anion [(CF3SO2)2N-], bis(fluorosulfonyl)imide anion [(FSO2)2N-], and tetra(pentafluorophenyl)borate anion [(C6F5)4B-] are particularly preferred. In terms of the time-dependent stability of the antistatic performance of the light-selective absorbing adhesive layer formed from the adhesive composition, ionic compounds that are solid at room temperature are preferred.

[0133] The amount of antistatic agent is, for example, 0.01 to 20 parts by mass, preferably 0.1 to 10 parts by mass, and more preferably 1 to 7 parts by mass, per 100 parts by mass of resin (A).

[0134] The adhesive composition contains a resin (A) which is a light-selective absorbing polymer, and may or may not contain a light-selective absorber. It is preferable that the adhesive composition does not contain a light-selective absorber. The light-selective absorber selectively absorbs light of a specific wavelength and preferably contains a compound having at least one absorption maximum at a wavelength of 360 nm to 420 nm, and more preferably contains a compound having an absorption maximum at 380 nm to 410 nm. When a light-selective absorber is included, the content of the light-selective absorber is preferably 0.5 parts by mass or less per 100 parts by mass of the total resin components. Since there is a correlation between the content of the light-selective absorber and the degree of color fading at the edges of the polarizer under high temperature and high humidity conditions, it is preferable that the content of the light-selective absorber be 0.5 parts by mass or less from the viewpoint of suppressing color fading.

[0135] The photoselective absorber is not particularly limited, but examples include organic photoselective absorbers such as oxybenzophenone-based photoselective absorbers, benzotriazole-based photoselective absorbers, salicylate-based photoselective absorbers, benzophenone-based photoselective absorbers, cyanoacrylate-based photoselective absorbers, and triazine-based photoselective absorbers. More specifically, examples include 5-chloro-2-(3,5-di-sec-butyl-2-hydroxylphenyl)-2H-benzotriazole, (2-2H-benzotriazole-2-yl)-6-(linear and side-chain dodecyl)-4-methylphenol, 2-hydroxy-4-benzyloxybenzophenone, and 2,4-benzyloxybenzophenone. These organic photoselective absorbers may be used individually or in combination of two or more.

[0136] Commercially available light-selective absorbers may be used. Examples of triazine-based light-selective absorbers include "Kemisorb 102" from Chemipro Chemical Co., Ltd., "ADEKA Stab LA46" and "ADEKA Stab LAF70" from ADEKA Corporation, and "Chinubin 109," "Chinubin 171," "Chinubin 234," "Chinubin 326," "Chinubin 327," "Chinubin 328," "Chinubin 928," "Chinubin 400," "Chinubin 460," "Chinubin 405," and "Chinubin 477" from BASF Japan. Examples of benzotriazole-based photoselective absorbers include "ADEKA Stab LA31" and "ADEKA Stab LA36" from ADEKA Corporation, "Sumisorb 200," "Sumisorb 250," "Sumisorb 300," "Sumisorb 340," and "Sumisorb 350" from Sumika Chemtex Co., Ltd., "Kemisorb 74," "Kemisorb 79," and "Kemisorb 279" from Chemipro Kasei Co., Ltd., and "TINUVIN 99-2," "TINUVIN 900," and "TINUVIN 928" from BASF.

[0137] The light selective absorber may be an inorganic light selective absorber. Examples of inorganic light selective absorbers include titanium dioxide, zinc oxide, indium oxide, tin oxide, talc, kaolin, calcium carbonate, titanium dioxide-based composite oxides, zinc oxide-based composite oxides, ITO (tin-doped indium oxide), ATO (antimond-doped tin oxide), etc. Examples of titanium dioxide-based composite oxides include silica, alumina-doped zinc oxide, etc. These inorganic light selective absorbers can be used individually or in combination of two or more. Organic light selective absorbers and inorganic light selective absorbers may also be used in combination.

[0138] The adhesive composition may contain one or more additives such as solvents, crosslinking catalysts, tackifiers, plasticizers, softeners, pigments, rust inhibitors, inorganic fillers, and light-scattering fine particles.

[0139] [Middle class] The optical laminate of the present invention includes an intermediate layer 300. The intermediate layer 300 has only one or more layers selected from the group consisting of a liquid crystal curing layer, an alignment layer, and a bonding layer. The thickness of the intermediate layer 300 is not limited, but is preferably, for example, 1 μm or more and 200 μm or less, and 5 μm or more and 200 μm or less.

[0140] From the viewpoint of suppressing color loss in the polarizer 10, the intermediate layer 300 is preferably free of light-selective absorbers. If it contains a light-selective absorber, the content of the light-selective absorber per unit area should be 0.5 g / m². 2 The following is preferable:

[0141] [Liquid crystal hardening layer] The optical laminate of the present invention may include a liquid crystal curing layer as an intermediate layer. The liquid crystal curing layer may be one or two or more layers. The optical laminate 101 shown in Figure 2 includes a first liquid crystal curing layer 30 and a second liquid crystal curing layer 31.

[0142] The liquid crystal curing layer is a layer of cured polymerizable liquid crystal compound, for example, a phase difference layer. The phase difference layer, which is a cured product of a polymerizable liquid crystal compound, can be described as having five forms, from the first to the fifth. First form: A phase difference layer in which rod-shaped liquid crystal compounds are oriented horizontally with respect to a support substrate. Second form: A phase difference layer in which rod-shaped liquid crystal compounds are oriented perpendicular to the supporting substrate. Third form: A phase difference layer in which rod-shaped liquid crystal compounds change orientation direction in a helical manner within the plane. Fourth form: A phase difference layer in which disc-shaped liquid crystal compounds are tilted and oriented. Fifth form: A biaxial phase difference layer in which disc-shaped liquid crystal compounds are oriented perpendicular to the supporting substrate. For example, the first, second, and fifth forms are preferably used as optical films for organic electroluminescent displays. Alternatively, phase difference layers of these forms may be laminated and used.

[0143] The retardation layer preferably has reverse wavelength dispersion. Reverse wavelength dispersion is an optical property in which the in-plane retardation value of the liquid crystal alignment surface at a short wavelength is smaller than the in-plane retardation value of the liquid crystal alignment surface at a long wavelength, and preferably, the retardation layer satisfies the following formulas (7) and (8). Here, Re(λ) represents the in-plane retardation value for light with a wavelength of λ nm. Re(450) / Re(550)≦1 (7) 1≦Re(630) / Re(550) (8) In the optical layered body of the present invention, when the retardation layer is in the first embodiment and has reverse wavelength dispersion, it is preferable because coloration during black display in a display device is reduced, and it is more preferable that 0.82≦Re(450) / Re(550)≦0.93 in the above formula (7). Further, 120≦Re(550)≦150 is preferred.

[0144] Examples of the polymerizable liquid crystal compound used for forming the retardation layer include compounds having a polymerizable group among those described in "3.8.6 Network (completely crosslinked type)" and "6.5.1 Liquid Crystal Material b. Polymerizable Nematic Liquid Crystal Material" in the Handbook of Liquid Crystals (edited by the Editorial Committee of Handbook of Liquid Crystals, published by Maruzen Co., Ltd. on October 30, 2000), as well as the polymerizable liquid crystal compounds described in Japanese Patent Application Laid-Open No. 2010-31223, Japanese Patent Application Laid-Open No. 2010-270108, Japanese Patent Application Laid-Open No. 2011-6360, Japanese Patent Application Laid-Open No. 2011-207765, Japanese Patent Application Laid-Open No. 2011-162678, Japanese Patent Application Laid-Open No. 2016-81035, International Publication No. WO 2017 / 043438, and Japanese National Publication No. 2011-207765. Examples of the method for producing a retardation layer from a polymer in an aligned state of a polymerizable liquid crystal compound include the method described in Japanese Patent Application Laid-Open No. 2010-31223.

[0145] The thickness of the retardation layer, which is a cured liquid crystal layer formed by curing a polymerizable liquid crystal compound, is, for example, 0.1 μm or more and 10 μm or less, preferably 0.5 μm or more and 8 μm or less, more preferably 1 μm or more and 6 μm or less.

[0146] The phase difference layer can be a λ / 4 phase difference layer that imparts a phase difference of 1 / 4 wavelength to the transmitted light, a λ / 2 phase difference layer that imparts a phase difference of 1 / 2 wavelength to the transmitted light, a positive A plate, and a positive C plate. In the case of an optical laminate 101 shown in Figure 2, which includes a first liquid crystal curing layer 30 and a second liquid crystal curing layer 31, possible combinations of the first liquid crystal curing layer 30 and the second liquid crystal curing layer 31 include a combination of a λ / 2 phase difference layer and a λ / 4 phase difference layer, a combination of a λ / 4 phase difference layer and a positive C layer, and so on.

[0147] The optical laminate of the present invention may be configured as a circular polarizer having a λ / 4 phase difference layer. The circular polarizer can be used as an anti-reflective polarizer.

[0148] [Orientation layer] The alignment layer has an orientation-regulating force that causes the liquid crystal compound contained in the liquid crystal curing layer formed on the alignment layer to be liquid crystal oriented in a desired direction. Examples of alignment layers include an alignment polymer layer formed from an alignment polymer, a photo-alignment polymer layer formed from a photo-alignment polymer, and a groove alignment layer having an uneven pattern or multiple grooves on its surface. The thickness of the alignment layer is usually 0.01 to 10 μm, and preferably 0.01 to 5 μm.

[0149] An oriented polymer layer can be formed by applying a composition in which the oriented polymer is dissolved in a solvent to a substrate layer, removing the solvent, and performing a rubbing treatment as needed. In this case, the orientation restricting force in an oriented polymer layer formed from an oriented polymer can be arbitrarily adjusted depending on the surface condition of the oriented polymer and the rubbing conditions.

[0150] A photo-aligned polymer layer can be formed by applying a composition containing a polymer or monomer having photoreactive groups and a solvent to a substrate layer and irradiating it with polarized light. In this case, the orientation restricting force in the photo-aligned polymer layer can be arbitrarily adjusted by the polarized light irradiation conditions for the photo-aligned polymer, etc.

[0151] The groove orientation layer can be formed by, for example, a method of forming an uneven pattern by exposing and developing a photosensitive polyimide film surface through an exposure mask having patterned slits; a method of forming an uncured layer of active energy ray curable resin on a plate-shaped master disc having grooves on its surface, transferring this layer to a substrate layer, and curing it; or a method of forming an uncured layer of active energy ray curable resin on a substrate layer, and then forming an uneven surface on this layer by pressing a roll-shaped master disc with an uneven surface against it, and curing it.

[0152] The base layer is preferably a film formed from a resin material. As the resin material, for example, a resin material that is excellent in transparency, mechanical strength, thermal stability, stretchability, etc. can be used. Specifically, examples include polyolefin resins such as polyethylene and polypropylene; cyclic polyolefin resins such as norbornene polymers; polyester resins such as polyethylene terephthalate and polyethylene naphthalate; (meth)acrylic acid resins such as (meth)acrylic acid and poly(meth)acrylate; cellulose ester resins such as triacetylcellulose, diacetylcellulose, and cellulose acetate propionate; vinyl alcohol resins such as polyvinyl alcohol and polyvinyl acetate; polycarbonate resins; polystyrene resins; polyarylate resins; polysulfone resins; polyethersulfone resins; polyamide resins; polyimide resins; polyetherketone resins; polyphenylene sulfide resins; polyphenylene oxide resins, and mixtures and copolymers thereof. Of these resins, it is preferable to use any of the following: cyclic polyolefin resins, polyester resins, cellulose ester resins, and (meth)acrylic acid resins, or a mixture thereof. Note that "(meth)acrylic acid" above means "at least one of acrylic acid and methacrylic acid."

[0153] The base layer may be a single layer of one or more of the above-mentioned resins, or it may have a multilayer structure of two or more layers. If it has a multilayer structure, the resins forming each layer may be the same or different.

[0154] The resin material forming the resin film may contain any additives. Examples of additives include light-selective absorbers, antioxidants, lubricants, plasticizers, mold release agents, color inhibitors, flame retardants, nucleating agents, antistatic agents, pigments, and colorants.

[0155] The thickness of the base layer is not particularly limited, but is generally preferred to be 5 to 200 μm, more preferably 10 to 200 μm, and even more preferably 10 to 150 μm, from the viewpoint of strength and workability such as handling.

[0156] To improve the adhesion between the substrate layer and the alignment layer, corona treatment, plasma treatment, flame treatment, etc. may be performed on at least the surface of the substrate layer on which the alignment layer is formed, or a primer layer may be formed. From a layer configuration consisting of a substrate layer / alignment layer / liquid crystal curing layer, the substrate layer may be peeled off and the alignment layer / liquid crystal curing layer may be used as components of the intermediate layer of the present invention, or the substrate layer / alignment layer may be peeled off and the liquid crystal curing layer may be used as a component of the intermediate layer of the present invention.

[0157] [Bonding layer] The intermediate layer 300 may include a bonding layer for joining the two layers. Examples of bonding layers include an adhesive layer, a tack layer (hereinafter also referred to as the "second tack layer"), etc. The optical laminate 101 shown in Figure 2 includes an adhesive layer 33 interposed between the first liquid crystal curing layer 30 and the second liquid crystal curing layer 31 to bond them together, and a second tack layer 32 laminated on the surface of the first liquid crystal curing layer 30 opposite to the adhesive layer 33.

[0158] The adhesive layer can be a water-based adhesive, an active energy ray-curable adhesive, or a thermosetting adhesive. The thickness of the adhesive layer is, for example, 10 nm to 20 μm, preferably 100 nm to 10 μm, and more preferably 500 nm to 5 μm.

[0159] The second adhesive layer may be composed of an adhesive composition similar to the adhesive composition that forms the light-selective absorbing adhesive layer described above, or it may be composed of an adhesive composition mainly composed of a resin such as (meth)acrylic, rubber, urethane, ester, silicone, or polyvinyl ether (hereinafter also referred to as the "second adhesive composition"). As the second adhesive composition, an adhesive composition using a (meth)acrylic resin as the base polymer, which has excellent transparency, weather resistance, heat resistance, etc., is preferred. The second adhesive composition may be of the active energy ray curing type or thermosetting type. The thickness of the second adhesive layer is usually 0.1 μm to 150 μm, for example 8 μm to 60 μm, and from the viewpoint of thinning, it is preferably 30 μm or less, and more preferably 20 μm or less.

[0160] From the viewpoint of suppressing color loss in the polarizer 10, the second adhesive layer is preferably free of light-selective absorbers, and if it contains a light-selective absorber, it is preferably 0.5 parts by mass or less per 100 parts by mass of the total resin components per unit area of ​​the light-selective absorber.

[0161] <Method for manufacturing optical laminates> Optical laminates 100, 101, and 102 can be manufactured by a method that includes a step of bonding the constituent layers together via a bonding layer. The method may also include a step of peeling off layers that are not constituent layers. When bonding layers together via a bonding layer, it is preferable to apply a surface activation treatment, such as corona treatment, to one or both of the bonding surfaces to improve adhesion.

[0162] <Optical laminate> The optical laminate of the present invention is planar, and its area is, for example, 30 mm × 30 mm to 180 mm × 90 mm. The optical laminate of the present invention may be rectangular, square, or other rectangular shapes, or it may have a notched portion where a part of the side constituting the rectangle is cut out, or it may have a semicircular shape or a shape with through holes in the plane, so-called irregular shapes. The absorption axes of the polarizers constituting the optical laminate may be parallel to, perpendicular to, or at an angle, such as 45°, if the outer shape of the optical laminate has straight sides. If an optical laminate has a phase difference layer and this phase difference layer has a slow phase axis in its plane, then this slow phase axis and the absorption axis of the polarizer constituting the optical laminate may intersect at 45°, 15°, or 75°.

[0163] <Image display device> The optical laminates 100, 101, and 102 can be placed on the front (viewing side) of the image display panel and used as components of an image display device. The optical laminates, which are circular polarizers, can also be used as anti-reflective polarizers to provide an anti-reflective function in an image display device. The image display device is not particularly limited and examples include organic electroluminescent (organic EL) display devices, inorganic electroluminescent (inorganic EL) display devices, liquid crystal display devices, and electroluminescent display devices. [Examples]

[0164] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, "%" and "parts" in the examples and comparative examples refer to "mass%" and "parts by mass," respectively.

[0165] [Fabrication of single-sided protective polarizing plate] (Fabrication of polarizers) A polyvinyl alcohol film with a thickness of 20 μm, a degree of polymerization of 2400, and a degree of saponification of 99% or more was uniaxially stretched to a stretching ratio of 4.1 times on a hot roll, and while maintaining tension, was immersed for 60 seconds at 28°C in a staining bath containing 0.05 parts by weight of iodine and 5 parts by weight of potassium iodide per 100 parts by weight of water.

[0166] Next, the polarizer was immersed in aqueous boric acid solution 1, which contained 5.5 parts by weight of boric acid and 15 parts by weight of potassium iodide per 100 parts by weight of water, at 64°C for 110 seconds. Then, it was immersed in aqueous boric acid solution 2, which contained 5.5 parts by weight of boric acid and 15 parts by weight of potassium iodide per 100 parts by weight of water, at 67°C for 30 seconds. After that, it was washed with pure water at 10°C and dried to obtain a polarizer. The thickness of the obtained polarizer was 8 μm and the boron content was 4.3% by weight.

[0167] (Adjustment of water-based adhesive) A water-based adhesive was prepared by dissolving 3 parts by mass of carboxyl group-modified polyvinyl alcohol (Kuraray Co., Ltd., product name "KL-318") in 100 parts by mass of water, and then adding 1.5 parts by mass of a water-soluble epoxy resin, a polyamide epoxy additive (Taoka Chemical Industry Co., Ltd., product name "Sumire's Resin (registered trademark) 650 (30), aqueous solution with a solid content concentration of 30% by mass") to the aqueous solution.

[0168] (Protective film A and release film B) As protective film A, a film was used in which a 3 μm thick hard coat layer was formed on a stretched film made of norbornene-based resin with a thickness of 25 μm (manufactured by Nippon Paper Industries Ltd., product name "COP25ST-HC"). Triacetylcellulose film (Fujifilm Corporation, "TD80UL") was used as release film B. The thickness of the release film was 80 μm, and the moisture permeability was 502 g / m². 2 It was 24 hours.

[0169] (Fabrication of single-sided protective polarizing plate) The fabricated polarizers were continuously transported, protective film A was continuously unwound from a roll of protective film A, and release film B was continuously unwound from a roll of release film B. A water-based adhesive was injected between the polarizer and the corona-treated protective film A, and pure water was injected between the polarizer and release film B. The film was then passed through a lamination roll to obtain a laminated film consisting of protective film A / water-based adhesive / polarizer / pure water / release film B. The laminated film was transported and subjected to a heat treatment at 80°C for 300 seconds in a drying oven to dry the water-based adhesive and to volatilize and remove the pure water interposed between the polarizer and release film B, thereby obtaining a single-sided protective polarizer with release film. Release film B was peeled off from the single-sided protective polarizer with release film to obtain a single-sided protective polarizer.

[0170] [Fabrication of phase-contrast laminates] (Preparation of the "Orientation Layer / First Liquid Crystal Hardening Layer") A λ / 4 phase difference layer (first liquid crystal cured layer), which consists of an alignment layer and a nematic liquid crystal compound that has been cured, was prepared on a substrate film. The total thickness of the "alignment layer / first liquid crystal cured layer" was 2 μm.

[0171] (Fabrication of "Orientation Layer / Second Liquid Crystal Hardening Layer") As a composition for forming an orientation layer, 10.0 parts by mass of polyethylene glycol di(meth)acrylate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., A-600), 10.0 parts by mass of trimethylolpropane triacrylate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., A-TMPT), 10.0 parts by mass of 1,6-hexanediol di(meth)acrylate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., A-HD-N), and 1.50 parts by mass of Irgacure 907 (manufactured by BASF, Irg-907) as a photopolymerization initiator were dissolved in 70.0 parts by mass of methyl ethyl ketone to prepare a coating solution for forming an orientation layer.

[0172] A long, 20 μm thick cyclic olefin resin (COP) film (manufactured by Nippon Zeon Co., Ltd.) was prepared as the base film, and an orientation layer forming coating liquid was applied to one side of the base film using a bar coater.

[0173] After coating, the coated layer is subjected to heat treatment at 80°C for 60 seconds, followed by exposure to ultraviolet (UVB) light at 220 mJ / cm². 2 Irradiation was performed to polymerize the composition for forming the orientation layer, and then cured to form an orientation layer with a thickness of 2.3 μm on the substrate film.

[0174] As a composition for forming a phase difference layer, 20.0 parts by mass of a photopolymerizable nematic liquid crystal compound (Merck, RMM28B) and 1.0 part by mass of Irgacure 907 (BASF, Irg-907) as a photopolymerization initiator were dissolved in 80.0 parts by mass of the solvent propylene glycol monomethyl ether acetate to prepare a coating solution for forming a phase difference layer.

[0175] A coating solution for forming a phase difference layer was applied to the previously obtained orientation layer, and the coated layer was heat-treated at 80°C for 60 seconds. Subsequently, ultraviolet (UVB) light was applied at 220 mJ / cm². 2 Irradiation was performed to polymerize the composition for forming the phase difference layer, and then curing it to form a phase difference layer (second liquid crystal cured layer) with a thickness of 0.7 μm on the orientation layer. In this way, an "orientation layer / second liquid crystal cured layer" with a total thickness of 3 μm was obtained on the substrate film.

[0176] (Fabrication of phase-contrast laminates) An "orientation layer / first liquid crystal cured layer" laminated on a base film and an "orientation layer / second liquid crystal cured layer" laminated on a base film were bonded together using an ultraviolet-curable adhesive (1 μm thick) so that the liquid crystal cured layer surfaces (the surfaces opposite to the base film) of each layer were the bonding surfaces. Next, the ultraviolet-curable adhesive was cured by irradiation with ultraviolet light to produce a phase difference laminate containing two liquid crystal cured layers, the first and second liquid crystal cured layers.

[0177] [Fabrication of light-selective absorption adhesive layer] <Adhesive layer (1)> (Synthesis of photoselective absorption monomers) A 300 mL four-necked flask, equipped with a Liebig condenser and thermometer, was subjected to a nitrogen atmosphere. 10 parts 2-hydroxyethyl acrylate, 8.1 parts cyanoacetic acid, 1.1 parts N,N-dimethyl-4-aminopyridine, 0.95 parts dibutylhydroxytoluene, and 50 parts toluene were charged into the flask and stirred with a magnetic stirrer. After cooling in an ice bath and confirming that the internal temperature reached 10°C, 12 parts N,N-diisopropylcarbodiimide were added dropwise over 1 hour. After the addition was complete, the flask was kept warm at an internal temperature of 0-10°C for a further 2 hours. Subsequently, insoluble components were removed by vacuum filtration to obtain 70 parts of filtrate containing the compound represented by UVA-M-02. [ka]

[0178] A 300 mL four-necked flask equipped with a Liebig condenser and thermometer was placed under a nitrogen atmosphere. 20 parts of the compound represented by UVA-M-01 (synthesized according to Japanese Patent Publication No. 2014-194508), 7.1 parts of acetic anhydride, 70 parts of filtrate containing UVA-M-02, and 40 parts of acetonitrile were charged into the flask and stirred with a magnetic stirrer. At an internal temperature of 25°C, 9 parts of N,N-diisopropylethylamine were added dropwise to the resulting mixture over 1 hour. The resulting mixture was kept warm at an internal temperature of 25°C for 2 hours. 200 g of ice water was added to the resulting mixture and stirred. The precipitated components were removed by vacuum filtration. The obtained crude product was recrystallized with isopropanol to obtain 10 parts of the compound represented by UVA-01. The obtained compound represented by UVA-01 was analyzed by LC-MS and 1 Identified by 1H-NMR. [ka]

[0179] (Preparation of light-selective absorption polymer (A-1)) In a reaction vessel equipped with a condenser, nitrogen inlet tube, thermometer, and stirrer, 96 parts by mass of butyl acrylate (referred to as "BA" in Table 1), 3 parts by mass of 2-hydroxyethyl acrylate (referred to as "HEA" in Table 1), and 1 part by mass of a light-selective absorbent monomer represented by UVA-01 (total solids: 100 parts by mass) were mixed with 135 parts by mass of ethyl acetate as a solvent. The internal temperature was raised to 60°C while replacing the air in the apparatus with nitrogen gas to eliminate oxygen. To the resulting mixture, the entirety of a solution prepared by dissolving 0.4 parts of azobisisobutyronitrile (polymerization initiator) in 10 parts of ethyl acetate was added. The resulting mixture was maintained at 60°C for 1 hour, and then ethyl acetate was continuously added to the reaction vessel at an addition rate of 17.3 parts / hr while maintaining the internal temperature at 50-70°C. The addition of ethyl acetate was stopped when the concentration of the acrylic resin reached 35%, and the internal temperature was maintained at 50-70°C for 12 hours from the start of ethyl acetate addition. Ethyl acetate was added to the mixture of the obtained light-selective absorbing polymer (A-1) to adjust the concentration of the resin component to 20%, and an ethyl acetate solution of the light-selective absorbing polymer (A-1) was prepared. The weight-average molecular weight Mw of the light-selective absorbing polymer (A-1) in polystyrene equivalent, calculated by GPC, was 500,000, and the Mw / Mn ratio was 7.5. The glass transition temperature, calculated by DSC, was -48.4°C.

[0180] (Preparation of adhesive composition and adhesive layer) (a) Preparation of adhesive composition To an ethyl acetate solution (resin concentration: 20%) of a light-selective absorbing polymer (A-1), 0.5 parts of a crosslinking agent (Coronate L, solids content 75%: manufactured by Tosoh Corporation) and 0.5 parts of a silane compound (manufactured by Shin-Etsu Chemical Co., Ltd.: KBM-403) were mixed per 100 parts of the solids content of the solution. Further, 2-butanone was added to bring the solids content concentration to 14% to obtain adhesive composition (1). The amount of the crosslinking agent (Coronate L) is expressed as parts by mass as an active ingredient.

[0181] (b) Preparation of the adhesive layer The adhesive composition prepared in (a) above was applied to the release-treated surface of a polyethylene terephthalate film (SP-PLR382050, manufactured by Lintec Corporation, hereinafter abbreviated as "separator") that had been treated with a release agent, using an applicator so that the thickness of the adhesive layer after drying was 17 μm, and the adhesive layer was dried at 100°C for 1 minute to produce an adhesive layer. The obtained adhesive layer was referred to as adhesive layer (1).

[0182] <Adhesive layer (2)> (Adjustment of acrylic resin (A-2)) A reaction vessel equipped with a condenser, nitrogen inlet, thermometer, and stirrer was charged with a mixed solution of 61.9 parts butyl acrylate, 1.9 parts 2-hydroxyethyl acrylate, and 135 parts ethyl acetate as a solvent. The internal temperature was raised to 60°C while replacing the air in the apparatus with nitrogen gas to eliminate oxygen. Subsequently, the entirety of a solution of 0.4 parts azobisisobutyronitrile (polymerization initiator) dissolved in 10 parts ethyl acetate was added. The resulting mixture was maintained at 60°C for 1 hour, and then ethyl acetate was continuously added to the reaction vessel at an addition rate of 17.3 parts / hr while maintaining the internal temperature at 50-70°C. The addition of ethyl acetate was stopped when the acrylic resin concentration reached 35%, and the temperature was maintained at this level for another 12 hours from the start of ethyl acetate addition. Finally, ethyl acetate was added to adjust the acrylic resin concentration to 20%, and an ethyl acetate solution of acrylic resin was prepared. The obtained acrylic resin had a weight-average molecular weight (Mw) of 600,000 and an Mw / Mn ratio of 7.0, calculated using GPC in polystyrene equivalent. This is referred to as acrylic resin (A-2). The glass transition temperature determined by DSC was -52.9°C.

[0183] (Preparation of adhesive composition and adhesive layer) (a) Preparation of adhesive composition To an ethyl acetate solution of acrylic resin (A-2) (resin concentration: 20%), 0.5 parts of a crosslinking agent (Coronate L, solids content 75%: manufactured by Tosoh), 0.5 parts of a silane compound (manufactured by Shin-Etsu Chemical Co., Ltd.: KBM-403), and 2.5 parts of a compound represented by the following formula (aa2) (a light-selective absorber) described as a light-selective absorber compound (2) in Synthesis Example 2 described in paragraph

[0142] of Japanese Patent Application Publication No. 2019-007001 were mixed, and 2-butanone was added to bring the solids content concentration to 14%, thereby obtaining adhesive composition (2). Note that the amount of the crosslinking agent (Coronate L) is in parts by mass as an active ingredient. [ka]

[0184] (b) Preparation of the adhesive layer An adhesive layer (2) was prepared from an adhesive composition using the same method as for adhesive layer (1).

[0185] [Preparation of the second adhesive layer] An ethyl acetate solution (resin concentration: 20%) of the above acrylic resin (A-2) was mixed with 0.5 parts of a crosslinking agent (Coronate L, solids content 75%: manufactured by Tosoh) and 0.5 parts of a silane compound (manufactured by Shin-Etsu Chemical Co., Ltd.: KBM-403). Furthermore, 2-butanone was added to bring the solids content concentration to 14% to obtain an adhesive composition. The amount of the crosslinking agent (Coronate L) is expressed as parts by mass as an active ingredient.

[0186] The adhesive composition was applied using an applicator to the release surface of the separator used to prepare the light-selective absorbing adhesive layer, so that the thickness of the adhesive layer after drying would be 5 μm. The second adhesive layer was then prepared by drying at 100°C for 1 minute.

[0187] [Fabrication of optically laminated structures] (Example 1, Comparative Example 1) A second adhesive layer was bonded to the polarizer side of the fabricated single-sided protective polarizing plate, and the separator was peeled off. The fabricated phase difference laminate was bonded to the surface of the second adhesive layer from which the separator had been peeled off, with the surface exposed by peeling off the base film on the first liquid crystal curing layer side. Subsequently, the base film on the second liquid crystal curing layer side was peeled off, and the adhesive layer described in Table 1 was bonded to the orientation layer surface on the second liquid crystal curing layer side as a light-selective absorbing adhesive layer, obtaining an optical laminate with the layer configuration of "protective film A / water-based adhesive / polarizer / second adhesive layer / orientation layer / first liquid crystal curing layer / second liquid crystal curing layer / orientation layer / light-selective absorbing adhesive layer / separator". In this optical laminate, the intermediate layer had the layer configuration of "second adhesive layer / orientation layer / first liquid crystal curing layer / UV-curable adhesive layer / second liquid crystal curing layer / orientation layer", and the total thickness was 11 μm. The optical laminates of Example 1 and Comparative Example 1 had the configuration shown in Figure 2.

[0188] In the above procedure, the adhesive layer was applied using an applicator to a thickness of 5 μm, and the second adhesive layer was prepared by drying at 100°C for 1 minute. The total thickness of the "orientation layer / first liquid crystal curing layer" was 2 μm. The total thickness of the "orientation layer / second liquid crystal curing layer" was 3 μm. The UV-curing adhesive had a thickness of 1 μm.

[0189] (Example 2, Comparative Example 2) A second adhesive layer was bonded to the polarizer side of the fabricated single-sided protective polarizing plate, and the separator was peeled off. The adhesive layer described in Table 1 was bonded to the side of the second adhesive layer from which the separator had been peeled off, as a light-selective absorbing adhesive layer, to obtain an optical laminate with the layer configuration of "protective film A / water-based adhesive / polarizer / second adhesive layer / light-selective absorbing adhesive layer / separator". In this optical laminate, the intermediate layer consisted of the "second adhesive layer", and its thickness was 5 μm. The optical laminates of Example 2 and Comparative Example 2 had the configuration shown in Figure 3.

[0190] In the above procedure, the adhesive layer was applied using an applicator to a thickness of 5 μm, and dried at 100°C for 1 minute to prepare the second adhesive layer.

[0191] [Measurement of absorbance of the adhesive layer] Adhesive layers (1) and (2) were laminated to glass, respectively. After removing the separator, a cycloolefin polymer (COP) film (ZF-14, manufactured by Zeon Corporation) was laminated to the adhesive layer to create a laminate for adhesive layer evaluation. The laminate for adhesive layer evaluation was set in a UV-2450 spectrophotometer (manufactured by Shimadzu Corporation), and the absorbance was measured using the double-beam method in a wavelength range of 300 to 800 nm in 1 nm steps. Table 1 shows the absorbance of the fabricated adhesive layer at a wavelength of 410 nm. Note that the absorbance of both the glass and the COP film at a wavelength of 410 nm is 0.

[0192] [Measurement of weight-average molecular weight (Mw)] The weight-average molecular weight (Mw) of the light-selective absorption polymer (A-1) and acrylic resin (A-2) was determined as the number-average molecular weight (Mn) on a polystyrene basis by size exclusion chromatography (SEC) using tetrahydrofuran as the mobile phase, as described below. The (meth)acrylic polymer to be measured was dissolved in tetrahydrofuran at a concentration of approximately 0.05% by mass, and 10 μL was injected into the SEC. The mobile phase was flowed at a flow rate of 1.0 mL / min. A PLgel MIXED-B column (Polymer Laboratories) was used. A UV-VIS detector (product name: Agilent GPC) was used as the detector.

[0193] [Measurement of boron content] 0.2 g of polarizer was dissolved in 200 g of 1.9 wt% mannitol aqueous solution. The resulting aqueous solution was titrated with 1 mol / L NaOH aqueous solution, and the boron content of the polarizer was calculated by comparing the amount of NaOH solution required for neutralization with the calibration curve.

[0194] [Heat resistance test and observation of color fading] The separators of the optical laminates obtained in Examples 1 and 2 and Comparative Examples 1 and 2 were peeled off and bonded to alkali-free glass plates, and then left for 500 hours in an environment of 65°C and 90% RH humidity. After that, polarizing plates in a crossed nicol relationship were bonded to the alkali-free glass surface opposite to the tested optical laminate, and the observations were made using an optical microscope, and the observed images were saved. The optical microscope used was a "VHX-500" manufactured by Keyence Corporation. Figure 4 shows an example of an observation image taken with an optical microscope. In Figure 4, when observing along the straight line indicated by the arrow (a straight line extending perpendicularly from the end 50) from the end 50 of the optical laminate inward, it can be seen that there are areas of color loss 51 and areas where no color loss has occurred (non-color loss areas) 52.

[0195] [Measurement of color loss using image processing] Microscopic observation images were converted to 256 grayscale levels (0-255) using the image analysis software "ImageJ" (free software). The method used for conversion to 256 grayscale levels (0-255) was to average the RGB values. Figure 5 shows an example of the converted data. The midpoint between the color-deprived area 51 and the non-color-deprived area 52 in the grayscale profile perpendicular to the edge 50 of the optical laminate (arrow in Figure 4) (the midpoint of the color-deprived gradation) was defined as the color-deprived edge of the optical laminate (Figure 5), and the distance (μm) from the edge 50 of the optical laminate to the color-deprived edge was measured as the color-deprived distance. The color-deprived distances of the optical laminate are shown in Table 1. The smaller the color-deprived distance, the narrower the color-deprived area and the better the resistance to humidity and heat.

[0196] The color loss distances of optical laminates with the same layer configuration (Example 1 and Comparative Example 1, Example 2 and Comparative Example 2) were compared, and the difference and the improvement rate of the color loss distance ((absolute value of the difference / color loss distance of Comparative Examples 1 and 2) × 100) are shown in Table 1.

[0197] [Table 1] [Explanation of Symbols]

[0198] 10 Polarizer, 11 Protective film, 20 Light-selective absorbing adhesive layer, 30 First liquid crystal curing layer, 31 Second liquid crystal curing layer, 32 Second adhesive layer, 33 Adhesive layer, 50 Edge of optical laminate, 51 Colorless area, 52 Non-colorless area, 100, 101, 102 Optical laminate, 300 Intermediate layer.

Claims

1. An optical laminate comprising a polarizer, a light-selective absorbing adhesive layer, and an intermediate layer laminated between the polarizer and the light-selective absorbing adhesive layer in contact with them, The intermediate layer comprises only one or more layers selected from the group consisting of a liquid crystal curing layer, an alignment layer, and a bonding layer. The polarizer has iodine adsorbed and oriented, and a boron content of 5.0% by mass or less. The adhesive composition forming the aforementioned light-selective absorbing adhesive layer comprises a light-selective absorbing polymer, The adhesive composition contains 0.5 parts by mass or less of a light-selective absorber (excluding the light-selective absorbent polymer) per 100 parts by mass of the total resin components. An optical laminate in which the content of a light-selective absorbent (excluding the light-selective absorbent polymer) per unit area in the intermediate layer is 0.5 g / m² or less.

2. The optical laminate according to claim 1, further comprising a protective film laminated on the side of the polarizer opposite to the intermediate layer side.

3. The aforementioned light-selective absorbing polymer has the following chemical formula (1): >NC=CC=C< (1) [However, not all of the one N atom and four C atoms constituting chemical formula (1) constitute part or all of an aromatic heterocycle.] The optical laminate according to claim 1 or 2, comprising a resin having a structural unit having the structure shown by and having a glass transition temperature of 40°C or less.

4. The optical laminate according to claim 3, wherein the light-selective absorbing polymer contains 0.01 parts by mass or more and 50 parts by mass or less of structural units having the structure represented by chemical formula (1) per 100 parts by mass of all structural units.

5. The optical laminate according to any one of claims 1 to 4, wherein the light-selective absorbing polymer has a weight-average molecular weight of 300,000 or more.

6. The optical laminate according to any one of claims 1 to 5, wherein the adhesive composition does not contain a light-selective absorber (except the light-selective absorbent polymer).

7. The optical laminate according to any one of claims 1 to 6, wherein the intermediate layer has a λ / 4 phase difference layer which is the liquid crystal curing layer.

8. An optical laminate according to any one of claims 1 to 7, which is an anti-reflective polarizing plate.

9. An image display device comprising an image display panel and an optical laminate according to claim 8 disposed in front of the image display panel.

10. The image display device according to claim 9, which is an organic EL display device.

Images