Stacked body and display device

Abstract

The objective of this invention is to provide a laminate and display device that exhibits improved crack resistance, adhesion, and durability. The laminate of this invention is a laminate having a light-absorbing anisotropic layer and an adhesive layer disposed adjacent to at least one surface of the light-absorbing anisotropic layer. The light-absorbing anisotropic layer contains a dichroic substance with a molecular weight of 1000 or less, and the adhesive layer has an indentation modulus of 0.4 to 6.0 MPa. Regarding the low-molecular-weight component with a molecular weight of 1000 or less, the adhesive layer satisfies either condition 1 or 2 below: Condition 1: Does not contain low-molecular-weight components. Condition 2: When low-molecular-weight components are present, the content of the low-molecular-weight component whose Hansen solubility parameter satisfies a specified relationship is 1.0% by mass or less relative to the mass of the adhesive layer.

Description

Technical Field

[0001] This invention relates to a laminate and a display device. Background Technology

[0002] Previously, when functions such as attenuation, polarization, scattering, or light blocking of laser beams or natural light were required, devices were used that operated on different principles for each function. Therefore, products corresponding to these functions were manufactured using different processes for each functional category. For example, in image display devices (e.g., liquid crystal displays), linear polarizers or circular polarizers are used to control optical rotation or birefringence in the display. Furthermore, in organic light-emitting diodes (OLEDs), circular polarizers are also used to prevent reflection of external light.

[0003] Previously, iodine was widely used as a dichroic material in these polarizers (hereinafter also referred to as "light absorption anisotropic layers"). However, research is underway to use organic pigments as dichroic materials to replace iodine. Furthermore, it is known that when a laminate having an anisotropic light-absorbing layer is bonded to other components using an adhesive, from the viewpoint of ensuring the durability of the anisotropic light-absorbing layer, an oxygen barrier layer (barrier layer) is provided between the anisotropic light-absorbing layer and the adhesive layer (for example, see Patent Documents 1 and 2). Previous technical documents Patent documents

[0004] Patent Document 1: International Publication No. 2022 / 059662 Patent Document 2: International Publication No. 2020 / 203028 Summary of the Invention The technical problem to be solved by the invention

[0005] Based on the laminates with anisotropic light-absorbing layers described in Patent Documents 1 and 2, and considering manufacturing suitability and thinning, the inventors conducted research on a method without an oxygen barrier layer (i.e., a method where the anisotropic light-absorbing layer is adjacent to the adhesive layer). The results showed that, depending on the physical properties or composition of the adhesive layer adjacent to the anisotropic light-absorbing layer, sometimes one or more of the following are poor: crack resistance, adhesion, and durability.

[0006] Therefore, the objective of this invention is to provide a laminate and a display device that exhibit improved crack resistance, adhesion, and durability. means for solving technical problems

[0007] The inventors conducted in-depth research to solve the above-mentioned problems and discovered that by setting an adhesive layer with an indentation elastic modulus within a specified range and satisfying specified conditions regarding low molecular weight components with a molecular weight of less than 1000, and then setting the adhesive layer adjacent to at least one surface of the light absorption anisotropic layer, a laminate with good crack resistance, adhesion and durability is formed, thereby completing the present invention. That is, the inventors have discovered a structure that can solve the above-mentioned problems.

[0008] [1] A laminate having a light-absorbing anisotropic layer and an adhesive layer disposed adjacent to at least one surface of the light-absorbing anisotropic layer, wherein, The light-absorbing anisotropic layer contains dichroic substances with a molecular weight of less than 1000. The indentation elastic modulus of the adhesive layer is 0.4–6.0 MPa. For low molecular weight components with a molecular weight of less than 1000, the adhesive layer shall meet either condition 1 or 2 below. Condition 1: It does not contain low molecular weight components. Condition 2: When low molecular weight components are present, the content of the low molecular weight components satisfying the following formula (I) is less than 1.0% by mass relative to the mass of the adhesive layer. A < B (I) In Equation (I), A represents the distance between the Hansen solubility parameter of the matrix component in the light absorption anisotropic layer and the Hansen solubility parameter of the low molecular weight component in the adhesive layer, and B represents the distance between the Hansen solubility parameter of the matrix component in the adhesive layer and the Hansen solubility parameter of the low molecular weight component in the adhesive layer. [2] According to the laminate described in [1], the matrix component of the light-absorbing anisotropic layer is a liquid crystal compound. [3] According to the laminate described in [1] or [2], wherein the Hansen solubility parameter of the matrix component of the light-absorbing anisotropic layer is 18 or higher. [4] The laminate according to any one of [1] to [3], wherein the matrix component of the adhesive layer is an acrylic or methacrylic polymer. [5] The laminate according to any one of [1] to [4], wherein the Hansen solubility parameter of the matrix component of the adhesive layer is 18 or less. [6] The laminate according to any one of [1] to [5], wherein the ratio of the indentation elastic modulus of the light-absorbing anisotropic layer to the indentation elastic modulus of the adhesive layer is 7000 or less. [7] A display device having a laminate as described in any one of [1] to [6]. Invention Effects

[0009] According to the present invention, a laminate and a display device with improved crack resistance, adhesion and durability can be provided. Attached Figure Description

[0010] Figure 1 This is a diagram illustrating an embodiment of a virtual reality display device, showing an example of the display device of the present invention, and illustrating an example of the light rays of the main image. Detailed Implementation

[0011] The present invention will now be described in detail. The following description of the constituent elements is sometimes based on representative embodiments of the present invention, but the present invention is not limited to such embodiments. In addition, in this specification, the numerical range represented by “~” indicates the range including the values ​​recorded before and after “~” as the lower limit and upper limit. Furthermore, in this specification, the upper or lower limit value recorded within a certain numerical range can be replaced with the upper or lower limit value of other numerical ranges recorded in stages. Also, the upper or lower limit value recorded within a certain numerical range in this specification can be replaced with the values ​​shown in the embodiments. Furthermore, in this specification, each component may be used individually with one corresponding substance, or two or more substances may be used simultaneously. Where two or more substances are used simultaneously for each component, unless otherwise specified, the content of that component refers to the total content of the substances used simultaneously. Furthermore, in this specification, "(meth)acrylate" is the expression for "acrylate" or "methacrylate", "(meth)acrylic acid" is the expression for "acrylic acid" or "methacrylic acid", and "(meth)acryloyl" is the expression for "acryloyl" or "methacryloyl".

[0012] In this specification, Re(λ) and Rth(λ) represent the in-plane retardation and the thickness-direction retardation at wavelength λ, respectively. Unless otherwise specified, wavelength λ is set to 550 nm. Furthermore, in this specification, Re(λ) and Rth(λ) are values ​​obtained by measurement at wavelength λ in an AxoScan OPMF-1 (manufactured by OPT Science Inc.). Specifically, the following can be calculated by inputting the average refractive index ((nx+ny+nz) / 3) and film thickness (d(μm)) into AxoScan OPMF-1: Slow axis direction (°) Re(λ) = R0(λ) Rth(λ)=((nx+ny) / 2-nz)×d. Additionally, R0(λ) is displayed as a value calculated by AxoScan OPMF-1, but it represents Re(λ).

[0013] In this specification, as a substituent (a monovalent substituent), for example, the substituents described in substituent group A below can be listed. Furthermore, in this specification, "may have substituents" includes not only the form without substituents, but also the form with one or more substituents. <Substituent group A> As substituents, examples include: Halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, preferably chlorine atom, fluorine atom, more preferably fluorine atom); Alkyl groups (preferably straight-chain, branched, or cyclic alkyl groups having 1 to 48 carbon atoms, more preferably straight-chain, branched, or cyclic alkyl groups having 1 to 24 carbon atoms, especially preferably straight-chain, branched, or cyclic alkyl groups having 1 to 8 carbon atoms, for example, straight-chain alkyl groups having 1 to 6 carbon atoms (e.g., methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl), branched alkyl groups having 3 to 6 carbon atoms (e.g., isopropyl, isobutyl, tert-butyl, sec-butyl, neopentyl, isohexyl, 3-methylpentyl), and cyclic alkyl groups having 3 to 12 carbon atoms (e.g., cyclopropyl, cyclopentyl, cyclohexyl, 1-norbornyl, 1-adamantyl)). Alkenyl (preferably an alkenyl group with 2 to 48 carbon atoms, more preferably an alkenyl group with 2 to 18 carbon atoms, for example, vinyl, allyl, 1-butenyl, 2-butenyl); Alkynyl (preferably an alkynyl group with 2 to 6 carbon atoms, more preferably an alkynyl group with 2 to 4 carbon atoms, for example, ethynyl, 1-propynyl, propynyl, 1-butynyl, 2-butynyl); Aryl (preferably aryl with 6 to 48 carbon atoms, more preferably aryl with 6 to 24 carbon atoms, for example, phenyl, oligoaryl (naphthyl, anthracene, phenanthrene, fluorenyl, pyrene, triphenylene, biphenyl); Heteroaryl (preferably a heterocyclic group with 1 to 32 carbon atoms, more preferably a heterocyclic group with 1 to 18 carbon atoms, for example, 2-thienyl, 4-pyridyl, 2-furanyl, 2-pyrimidinyl, 1-pyridyl, 2-benzothiazolyl, 1-imidazolyl, 1-pyrazolyl, benzotriazol-1-yl); Arylalkyl group (preferably arylalkyl group with 7 to 15 carbon atoms, for example, benzyl, phenethyl, methylbenzyl, phenylpropyl, 1-methylphenylethyl, phenylbutyl, 2-methylphenylpropyl, tetrahydronaphthyl, naphthylmethyl, naphthylethyl, indene, fluorenyl, anthrylmethyl, phenanthrylmethyl)); Silyl group (preferably a silyl group with 3 to 38 carbon atoms, more preferably a silyl group with 3 to 18 carbon atoms, for example, trimethylsilyl, triethylsilyl, tributylsilyl, tert-butyldimethylsilyl, tert-hexyldimethylsilyl); Hydroxyl; cyano; nitro; morpholino; Alkoxy groups (preferably alkoxy groups with 1 to 48 carbon atoms, more preferably alkoxy groups with 1 to 24 carbon atoms, such as methoxy, ethoxy, 1-butoxy, 2-butoxy, isopropoxy, tert-butoxy, dodecyloxy, cycloalkoxy (e.g., cyclopentoxy, cyclohexyloxy)). Aryloxy group (preferably an aryloxy group with 6 to 48 carbon atoms, more preferably an aryloxy group with 6 to 24 carbon atoms, for example, phenoxy group, 1-naphthoxy group); Alkenyloxy group (preferably an alkenyloxy group having 2 to 6 carbon atoms, for example, ethyleneoxy, 1-propenoxy, 2-n-propenoxy (allyloxy), 1-n-butenoxy, isopentenoxy). Heterocyclic oxides (preferably heterocyclic oxides with 1 to 32 carbon atoms, more preferably heterocyclic oxides with 1 to 18 carbon atoms, for example, 1-phenyltetrazol-5-oxy, 2-tetrahydropyranoxy); Silyoxy group (preferably a siloxy group with 1 to 32 carbon atoms, more preferably a siloxy group with 1 to 18 carbon atoms, for example, trimethylsiloxy, tert-butyldimethylsiloxy, diphenylmethylsiloxy). Acyloxy group (preferably an acyloxy group with 2 to 48 carbon atoms, more preferably an acyloxy group with 2 to 24 carbon atoms, for example, acetoxy, pivaloyloxy, benzoyloxy, dodecyloxy, acryloyloxy, methacryloyloxy); Hydroxyalkoxide (preferably a hydroxyalkoxide with 2 to 10 carbon atoms, for example, a hydroxyethoxy group); Alkoxycarbonyloxy (preferably alkoxycarbonyloxy with 2 to 48 carbon atoms, more preferably alkoxycarbonyloxy with 2 to 24 carbon atoms, such as ethoxycarbonyloxy, tert-butoxycarbonyloxy, cycloalkoxycarbonyloxy (e.g., cyclohexyloxycarbonyloxy)). Aryloxycarbonyloxy (preferably aryloxycarbonyloxy with 7 to 32 carbon atoms, more preferably aryloxycarbonyloxy with 7 to 24 carbon atoms, for example, phenoxycarbonyloxy); Carbamoyloxy (preferably carbamoyloxy with 1 to 48 carbon atoms, more preferably carbamoyloxy with 1 to 24 carbon atoms, for example, N,N-dimethylcarbamoyloxy, N-butylcarbamoyloxy, N-phenylcarbamoyloxy, N-ethyl-N-phenylcarbamoyloxy). Aminosulfonyloxy group (preferably an aminosulfonyloxy group with 1 to 32 carbon atoms, more preferably an aminosulfonyloxy group with 1 to 24 carbon atoms, for example, N,N-diethylaminosulfonyloxy group, N-propylaminosulfonyloxy group). Alkylsulfonyloxy (preferably an alkylsulfonyloxy with 1 to 38 carbon atoms, more preferably an alkylsulfonyloxy with 1 to 24 carbon atoms, for example, methylsulfonyloxy, hexadecylsulfonyloxy, cyclohexylsulfonyloxy). Arylsulfonyloxy (preferably an arylsulfonyloxy with 6 to 32 carbon atoms, more preferably an arylsulfonyloxy with 6 to 24 carbon atoms, for example, phenylsulfonyloxy); Acyl group (preferably an acyl group with 1 to 48 carbon atoms, more preferably an acyl group with 1 to 24 carbon atoms, for example, formyl, acetyl, acryloyl, methacryloyl, pivaloyl, benzoyl, tetradecanoyl, cyclohexyl); Alkoxycarbonyl (preferably an alkoxycarbonyl with 2 to 48 carbon atoms, more preferably an alkoxycarbonyl with 2 to 24 carbon atoms, for example, methoxycarbonyl, ethoxycarbonyl, octadecyloxycarbonyl, cyclohexyloxycarbonyl, 2,6-di-tert-butyl-4-methylcyclohexyloxycarbonyl); Aryloxycarbonyl (preferably an aryloxycarbonyl with 7 to 32 carbon atoms, more preferably an aryloxycarbonyl with 7 to 24 carbon atoms, for example, phenoxycarbonyl); Carbamoyl group (preferably a carbamoyl group with 1 to 48 carbon atoms, more preferably a carbamoyl group with 1 to 24 carbon atoms, for example, carbamoyl group, N,N-diethylcarbamoyl group, N-ethyl-N-octylcarbamoyl group, N,N-dibutylcarbamoyl group, N-propylcarbamoyl group, N-phenylcarbamoyl group, N-methyl-N-phenylcarbamoyl group, N,N-dicyclohexylcarbamoyl group); Amino group (preferably an amino group with 32 or fewer carbon atoms, more preferably an amino group with 24 or fewer carbon atoms, for example, amino, methylamino, N,N-dimethylamino, N,N-dibutylamino, tetradecylamino, 2-ethylhexylamino, cyclohexylamino). Aniline (preferably an aniline with 6 to 32 carbon atoms, more preferably an aniline with 6 to 24 carbon atoms, for example, aniline or N-methylaniline); Heterocyclic amino group (preferably a heterocyclic amino group with 1 to 32 carbon atoms, more preferably a heterocyclic amino group with 1 to 18 carbon atoms, for example, 4-pyridylamino group). Carbonamide (preferably a carbonamide group with 2 to 48 carbon atoms, more preferably a carbonamide group with 2 to 24 carbon atoms, such as acetamide, benzamide, tetradecanoamide, pivaloylamide, cyclohexaneamide); Urea group (preferably a urea group with 1 to 32 carbon atoms, more preferably a urea group with 1 to 24 carbon atoms, for example, urea group, N,N-dimethylurea group, N-phenylurea group); Imide group (preferably an imide group with 36 or fewer carbon atoms, more preferably an imide group with 24 or fewer carbon atoms, for example, N-succinimide group, N-phthalimide group); Alkoxycarbonylamino (preferably an alkoxycarbonylamino with 2 to 48 carbon atoms, more preferably an alkoxycarbonylamino with 2 to 24 carbon atoms, for example, methoxycarbonylamino, ethoxycarbonylamino, tert-butoxycarbonylamino, octadecyloxycarbonylamino, cyclohexyloxycarbonylamino). Aryloxycarbonylamino (preferably aryloxycarbonylamino with 7 to 32 carbon atoms, more preferably aryloxycarbonylamino with 7 to 24 carbon atoms, for example, phenoxycarbonylamino); Sulfonamide group (preferably a sulfonamide group with 1 to 48 carbon atoms, more preferably a sulfonamide group with 1 to 24 carbon atoms, for example, methanesulfonamide group, butanesulfonamide group, benzenesulfonamide group, hexadecylsulfonamide group, cyclohexanesulfonamide group); Aminosulfonylamino (preferably an aminosulfonylamino with 1 to 48 carbon atoms, more preferably an aminosulfonylamino with 1 to 24 carbon atoms, for example, N,N-dipropylaminosulfonylamino, N-ethyl-N-dodecylaminosulfonylamino). Azo group (preferably an azo group with 1 to 32 carbon atoms, more preferably an azo group with 1 to 24 carbon atoms, for example, phenyl azo group, 3-pyrazolyl azo group); Alkylthio (preferably an alkylthio group with 1 to 48 carbon atoms, more preferably an alkylthio group with 1 to 24 carbon atoms, for example, methylthio, ethylthio, octylthio, cyclohexylthio); Arylthio (preferably an arylthio group with 6 to 48 carbon atoms, more preferably an arylthio group with 6 to 24 carbon atoms, for example, a phenylthio group); Heterocyclic thio groups (preferably heterocyclic thio groups with 1 to 32 carbon atoms, more preferably heterocyclic thio groups with 1 to 18 carbon atoms, for example, 2-benzothiazolyl thio group, 2-pyridyl thio group, 1-phenyltetrazole thio group); Alkyl sulfinyl group (preferably an alkyl sulfinyl group with 1 to 32 carbon atoms, more preferably an alkyl sulfinyl group with 1 to 24 carbon atoms, for example, a dodecyl sulfinyl group); Arylsulfinyl group (preferably an arylsulfinyl group with 6 to 32 carbon atoms, more preferably an arylsulfinyl group with 6 to 24 carbon atoms, for example, a phenylsulfinyl group); Alkyl sulfonyl group (preferably an alkyl sulfonyl group with 1 to 48 carbon atoms, more preferably an alkyl sulfonyl group with 1 to 24 carbon atoms, for example, methyl sulfonyl, ethyl sulfonyl, propyl sulfonyl, butyl sulfonyl, isopropyl sulfonyl, 2-ethylhexyl sulfonyl, hexadecyl sulfonyl, octyl sulfonyl, cyclohexyl sulfonyl); Arylsulfonyl group (preferably an arylsulfonyl group with 6 to 48 carbon atoms, more preferably an arylsulfonyl group with 6 to 24 carbon atoms, for example, phenylsulfonyl group, 1-naphthylsulfonyl group); Aminosulfonyl group (preferably an aminosulfonyl group with 32 or fewer carbon atoms, more preferably an aminosulfonyl group with 24 or fewer carbon atoms, for example, aminosulfonyl group, N,N-dipropylaminosulfonyl group, N-ethyl-N-dodecylaminosulfonyl group, N-ethyl-N-phenylaminosulfonyl group, N-cyclohexylaminosulfonyl group, N-(2-ethylhexyl)aminosulfonyl group); Phosphonoyl group (preferably a phosphonoyl group with 1 to 32 carbon atoms, more preferably a phosphonoyl group with 1 to 24 carbon atoms, for example, phenoxyphosphonoyl, octoxyphosphonoyl, phenylphosphonoyl). Phosphonoamino (preferably a phosphonoamino with 1 to 32 carbon atoms, more preferably a phosphonoamino with 1 to 24 carbon atoms, for example, diethoxyphosphonoamino, dioctyloxyphosphonoamino). Epoxy groups; -NHCOCH3; -SO2NHC2H4OCH3; -NHSO2CH3; And so on, and more than two of these can be combined. These substituents can be further replaced by these substituents. Furthermore, when there are two or more substituents, they can be the same or different. And, where possible, they can also bond together to form a ring.

[0014] [Layered Body] The laminate of the present invention is a laminate having a light-absorbing anisotropic layer and an adhesive layer disposed adjacent to at least one surface of the light-absorbing anisotropic layer. Furthermore, the light-absorbing anisotropic layer of the laminate of the present invention contains a dichroic substance with a molecular weight of 1000 or less. Furthermore, the adhesive layer of the laminate of the present invention has the following properties: the indentation elastic modulus is 0.4 to 6.0 MPa, and with respect to the low molecular weight component with a molecular weight of 1000 or less, it satisfies either condition 1 or 2 below. Condition 1: Does not contain the aforementioned low molecular weight components. Condition 2: When the above-mentioned low molecular weight components are present, the content of the low molecular weight components that satisfy the following formula (I) is 1.0% by mass or less relative to the mass of the adhesive layer. A < B (I) In the above formula (I), A represents the distance between the Hansen solubility parameter of the matrix component in the light absorption anisotropic layer and the Hansen solubility parameter of the low molecular weight component in the adhesive layer, and B represents the distance between the Hansen solubility parameter of the matrix component in the adhesive layer and the Hansen solubility parameter of the low molecular weight component in the adhesive layer.

[0015] In this invention, the molecular weights (both below 1000) of the dichroic substances and low molecular weight components can be determined using the following methods. <Dichromatic substances> The molecular weight of dichroic substances can be obtained by measuring the solution obtained by dissolving the light-absorbing anisotropic layer or the extract obtained by immersing the light-absorbing anisotropic layer in a solvent using liquid chromatography-mass spectrometry (LC / MS), but is not limited to the above methods. <Low molecular weight components> The molecular weight of the low molecular weight component is obtained by measuring the solution obtained by dissolving the adhesive layer or the extract obtained by immersing the adhesive layer in a solvent under the following conditions using gas chromatography-mass spectrometry (GC / MS). Furthermore, the low molecular weight component contained in the adhesive layer can be quantified by using a standard sample, but is not limited to the above methods. GC / MS determination conditions String: DB-5MS (0.25mm) ×30m, film thickness 0.25μm) Column temperature: 50℃ (0~2min) -10℃ / min -320℃ (29~40min) Carrier gas: He (1.0 mL / min) Sample injection volume: 0.5 μL Detection: EI-MS

[0016] Furthermore, in this invention, the indentation elastic modulus of the adhesive layer refers to the value obtained by measuring the indentation elastic modulus of the surface of the test specimen (the surface of the adhesive layer opposite to the light-absorbing anisotropic layer) under the following conditions using a microhardness evaluation device (such as a Burker Nanoindenter TI-950). Additionally, the indentation elastic modulus of the light-absorbing anisotropic layer, as described later, refers to the value obtained by measuring the indentation elastic modulus of the surface of the test specimen (the surface of the light-absorbing anisotropic layer on the adhesive layer side) under the same conditions. Indenter: Triangular pyramidal diamond indenter (Berkovich indenter, indenter interior angle: 142.35°, angle between center line and surface: 65.35°) Maximum indentation depth of the indenter: 500nm Measurement temperature: 23℃

[0017] Furthermore, the Hansen solubility parameters (HSP) (hereinafter also referred to as "HSP values") divide the solubility of a substance into three components (dispersion term δd, polar term δp, and hydrogen bonding term δh) and represent them in three-dimensional space. The dispersion term δd represents the effect based on dispersion forces, the polar term δp represents the effect based on dipole-dipole interactions, and the hydrogen bonding term δh represents the effect based on hydrogen bonding forces. Furthermore, in this invention, the Hansen solubility parameter is a value calculated by inputting the structural formula of the compound into HSP (Ver. 5.1.08). Additionally, in copolymers, δd, δp, and δh are calculated using structural formulas that replace the bonding portions of each repeating unit with hydrogen atoms, and the values ​​are averaged over the mass ratio of the copolymer components. Furthermore, in the case of a three-dimensional crosslinked matrix of (meth)acrylate, δd, δp, and δh are calculated using the structural formulas of each monomer; moreover, when multiple monomers are mixed, the values ​​are averaged over the mass ratio. Furthermore, in this invention, the distances represented by A and B in the above formula (I) can be calculated as Ra by substituting δd, δp, and δh calculated for each component into the following formula. Additionally, δd1, δp1, and δh1 in the following formula are values ​​calculated based on the low molecular weight components in the adhesive layer; δd2, δp2, and δh2 are values ​​calculated based on the matrix components in the light absorption anisotropic layer when calculating A; and values ​​calculated based on the matrix components in the adhesive layer when calculating B. [Formula 1]

[0018] In this invention, as described above, by setting an adhesive layer with an indentation elastic modulus in the range of 0.4 to 6.0 MPa and satisfying condition 1 or 2 above with respect to low molecular weight components with a molecular weight of less than 1000, an adhesive layer is provided adjacent to at least one surface of the light absorption anisotropic layer, thereby creating a laminate with good crack resistance, adhesion and durability. While the exact reasons for this effect are not clear, the inventors speculate as follows. First, it is known that from the viewpoint of ensuring adhesion, a high elastic modulus of the adhesive layer is preferable. However, as shown in Comparative Examples 3 and 4 described later, cracks occur when the indentation elastic modulus exceeds 6.0 MPa. Furthermore, as shown in Comparative Example 1 described later, adhesion is poor when the indentation elastic modulus is less than 0.4 MPa. Furthermore, as shown in Comparative Example 2 described later, for low molecular weight components with a molecular weight of 1000 or less, the durability is poor when conditions 1 and 2 above are not met. This is thought to be because the dichroic substance contained in the light-absorbing anisotropic layer migrates (flows out) to the adjacent adhesive layer. However, the inventors speculate that the reason for the flow out of the dichroic substance is that before the dichroic substance flows out, the low molecular weight compound in the adhesive layer migrates (flows out) to the light-absorbing anisotropic layer, and the fluidity of the light-absorbing anisotropic layer becomes higher. Therefore, it is believed that in this invention, by setting the indentation elastic modulus of the adhesive layer in the range of 0.4 to 6.0 MPa, the crack resistance and adhesion become good. Furthermore, it is believed that the low molecular weight components in the adhesive layer with a molecular weight of less than 1000 satisfy either condition 1 or 2 above, thereby suppressing the outflow of low molecular weight compounds into the light-absorbing anisotropic layer. As a result, the outflow of dichroic substances into the adhesive layer is suppressed, thus improving durability. The light absorption anisotropic layer and the adhesive layer of the laminate of the present invention will be described in detail below.

[0019] [Light Absorption Anisotropic Layer] <Dichromatic substances> As described above, the light-absorbing anisotropic layer of the laminate of the present invention contains a dichroic substance with a molecular weight of 1000 or less. Dichroism refers to pigments whose absorbance varies depending on the direction. Furthermore, dichroic materials may or may not exhibit liquid crystal properties.

[0020] There are no particular limitations on dichroic substances, and examples include visible light absorbing substances (dichroic organic pigments, iodine), luminescent substances (fluorescent substances, phosphorescent substances), ultraviolet light absorbing substances, infrared light absorbing substances, nonlinear optical substances, carbon nanotubes, and inorganic substances (e.g., quantum rods), etc. Conventionally known dichroic substances (dichroic pigments) can be used. Preferably, the visible light absorbing substance is one that has the maximum absorption wavelength in the visible light region. Specifically, examples include paragraphs

[0067] to

[0071] of Japanese Patent Application Publication No. 2013-228706, paragraphs

[0008] to

[0026] of Japanese Patent Application Publication No. 2013-227532, paragraphs

[0008] to

[0015] of Japanese Patent Application Publication No. 2013-209367, paragraphs

[0045] to

[0058] of Japanese Patent Application Publication No. 2013-14883, paragraphs

[0012] to

[0029] of Japanese Patent Application Publication No. 2013-101328, paragraphs

[0009] to

[0017] of Japanese Patent Application Publication No. 2013-37353, and paragraphs

[0051] to

[0065] of Japanese Patent Application Publication No. 2013-37353. Paragraphs

[0049] to

[0073] of Japanese Patent Application Publication No. 2012-63387, paragraphs

[0016] to

[0018] of Japanese Patent Application Publication No. Hei 11-305036, paragraphs

[0009] to

[0011] of Japanese Patent Application Publication No. 2001-133630, paragraphs

[0030] to

[0169] of Japanese Patent Application Publication No. 2011-215337, paragraphs

[0021] to

[0075] of Japanese Patent Application Publication No. 2010-106242, paragraphs

[0011] to

[0025] of Japanese Patent Application Publication No. 2010-215846, paragraphs

[0017] to

[0069] of Japanese Patent Application Publication No. 2011- Paragraphs

[0013] to

[0133] of Japanese Patent Application Publication No. 213610, paragraphs

[0074] to

[0246] of Japanese Patent Application Publication No. 2011-237513, paragraphs

[0005] to

[0051] of Japanese Patent Application Publication No. 2016-006502, paragraphs

[0014] to

[0032] of Japanese Patent Application Publication No. 2018-053167, paragraphs

[0014] to

[0033] of Japanese Patent Application Publication No. 2020-11716, paragraphs

[0005] to

[0041] of International Publication No. 2016 / 060173, paragraphs

[0008] to

[0062] of International Publication No. 2016 / 136561, and International Publication No. 2017 / 154835. Paragraphs

[0014] to

[0033] of International Publication No. 2017 / 154695, paragraphs

[0013] to

[0037] of International Publication No. 2017 / 195833, paragraphs

[0014] to

[0034] of International Publication No. 2018 / 164252, paragraphs

[0021] to

[0030] of International Publication No. 2018 / 186503, paragraphs

[0043] to

[0063] of International Publication No. 2019 / 189345, paragraphs

[0043] to

[0085] of International Publication No. 2019 / 225468, and paragraphs

[0050] to

[0074] of International Publication No. 2020 / 004106.The contents described in paragraphs

[0015] to

[0038] of International Publication No. 2021 / 044843, etc.

[0021] As a dichroic substance, a dichroic azo dye compound is preferred. Dichroic azo dye compounds refer to azo dye compounds whose absorbance varies depending on the direction. Dichroic azo dye compounds may or may not exhibit liquid crystal properties. When a dichroic azo dye compound exhibits liquid crystal properties, it can display either a nematic or smectic form. The preferred temperature range for displaying the liquid crystal phase is room temperature (approximately 20–28°C) to 300°C, and more preferably 50–200°C from the viewpoint of operability and manufacturing suitability.

[0022] In this invention, from the viewpoint of hue adjustment, it is preferable to use at least one pigment compound (first dichroic azo pigment compound) having a maximum absorption wavelength in the wavelength range of 560 to 700 nm and at least one pigment compound (second dichroic azo pigment compound) having a maximum absorption wavelength in the wavelength range of 455 nm or more and less than 560 nm.

[0023] In this invention, three or more dichroic azo pigment compounds may be used simultaneously. For example, from the viewpoint of making the light absorption anisotropic layer close to black, it is preferable to use a first dichroic azo pigment compound, a second dichroic azo pigment compound, and at least one pigment compound (a third dichroic azo pigment compound) that has a maximum absorption wavelength in the range of 380 nm or more and less than 455 nm. In this invention, from the viewpoint of excellent light resistance of the light-absorbing anisotropic layer, it is preferable to contain two or more first dichroic azo dye compounds.

[0024] In this invention, the dichroic azo dye compound preferably has crosslinking groups. Examples of crosslinking groups include (meth)acryloyl, epoxy, oxetyl, and styryl, with (meth)acryloyl being preferred.

[0025] The content of the dichroic substance is preferably 3 to 90% by mass, more preferably 5 to 70% by mass, and even more preferably 10 to 60% by mass, relative to the mass of the light-absorbing anisotropic layer. Furthermore, when multiple dichroic substances are used simultaneously, the total amount of the multiple dichroic substances is preferably within the above-mentioned range.

[0026] <Liquid Crystal Compounds> The light-absorbing anisotropic layer of the laminate of the present invention preferably contains a liquid crystal compound. This suppresses the precipitation of the dichroic material and allows the dichroic material to be oriented with a higher degree of orientation. As a liquid crystal compound, either a high molecular weight liquid crystal compound or a low molecular weight liquid crystal compound can be used, but from the viewpoint of improving the degree of orientation, a high molecular weight liquid crystal compound is preferred. Furthermore, the liquid crystal compound can contain only one type, or two or more types, or both high-molecular-weight liquid crystal compounds and low-molecular-weight liquid crystal compounds can be used simultaneously. "Polymer liquid crystal compounds" refer to liquid crystal compounds with repeating units in their chemical structure. Furthermore, liquid crystal compounds with repeating units in their chemical structure are also called side-chain type polymer liquid crystal compounds. Furthermore, "low molecular weight liquid crystal compounds" refers to liquid crystal compounds that do not have repeating units in their chemical structure. Examples of polymeric liquid crystal compounds include, for example, the thermotropic liquid crystal polymer described in Japanese Patent Application Publication No. 2011-237513, and the polymeric liquid crystal compounds described in paragraphs

[0012] to

[0042] of International Publication No. 2018 / 199096. As a low-molecular-weight liquid crystal compound, examples include the liquid crystal compounds described in paragraphs

[0072] to

[0088] of Japanese Patent Application Publication No. 2013-228706, among which liquid crystal compounds exhibiting smectic form are preferred. Examples of such liquid crystal compounds include those described in paragraphs

[0019] to

[0140] of International Publication No. 2022 / 014340, which are incorporated herein by reference. Furthermore, the liquid crystal compound is preferably a liquid crystal compound that does not exhibit dichroism in the visible light region.

[0027] The weight-average molecular weight (Mw) of the polymeric liquid crystal compound is preferably 2,000 to 300,000, more preferably 2,000 to 100,000. If the Mw of the polymeric liquid crystal compound is within the above range, the processing of the polymeric liquid crystal compound becomes easier. The weight-average molecular weight (Mw) and number-average molecular weight (Mn) of the polymeric liquid crystal compounds were obtained by gel permeation chromatography (GPC). • Solvent (eluent): N-methylpyrrolidone • Device Name: TOSOH HLC-8220GPC • String: Connect 3 TOSOH TSKgel Super HZM-H (4.6mm × 15cm) tubes for use. • Column temperature: 25℃ • Sample concentration: 0.1% by mass • Flow rate: 0.35 ml / min • Calibration curves: Calibration curves for seven samples of TSK standard polystyrene manufactured based on TOSOH CORPORATION, in the range of Mw = 2,800,000 to 1,050 (Mw / Mn = 1.03 to 1.06).

[0028] Relative to the content of the dichroic material (100 parts by mass), the content of the liquid crystal compound is preferably 25 to 2000 parts by mass, more preferably 100 to 1300 parts by mass, and even more preferably 200 to 900 parts by mass. By keeping the content of the liquid crystal compound within the above range, the orientation degree of the dichroic material is further improved. Furthermore, when using multiple liquid crystal compounds simultaneously, it is preferable that the total amount of the multiple liquid crystal compounds is within the above range.

[0029] In this invention, the matrix component of the light-absorbing anisotropic layer is preferably a liquid crystal compound. Among them, the matrix component of the light-absorbing anisotropic layer refers to the component whose complexation amount is the largest among the components other than the dichroic substances contained in the light-absorbing anisotropic layer. Therefore, relative to the mass of the light-absorbing anisotropic layer, the content of the liquid crystal compound is preferably more than 50% by mass and less than 90% by mass, more preferably 55% to 85% by mass, and even more preferably 60% to 80% by mass. Furthermore, when multiple liquid crystal compounds are used simultaneously, the total amount of the multiple liquid crystal compounds is preferably within the above-mentioned range.

[0030] Furthermore, in this invention, from the perspective of promoting appropriate phase separation from hydrophobic dichroic materials and improving orientation, it is preferable that the HSP value of the matrix component of the light-absorbing anisotropic layer is 18 or more, more preferably 18 to 26.

[0031] The light absorption anisotropic layer of the laminate of the present invention is preferably a layer formed by fixing the orientation state of the above-mentioned dichroic material and liquid crystal compound, and more preferably a layer formed by using a light absorption anisotropic layer forming composition comprising the above-mentioned dichroic material and liquid crystal compound. In addition to the dichroic substances and liquid crystal compounds mentioned above, the composition for forming anisotropic light-absorbing layers preferably contains surfactants, orientation agents, polymerization initiators, and solvents, as described later.

[0032] <surfactants> As a surfactant, fluoro(meth)acrylate polymers described in paragraphs

[0018] to

[0043] of Japanese Patent Application Publication No. 2007-272185, or silicon-containing polymers described in paragraphs

[0019] to

[0073] of International Patent Publication No. 2023 / 054164, can be used. Other compounds besides these can also be used as surfactants. A single surfactant can be used, or two or more surfactants can be used simultaneously. When the composition for forming anisotropic light-absorbing layers contains a surfactant, the surfactant content is preferably 0.01 to 10% by mass, more preferably 0.02 to 5% by mass, relative to the total solid content of the composition for forming anisotropic light-absorbing layers.

[0033] <Orientation Agent> Boric acid compounds and onium salts can be used as orientation agents. Boric acid compounds function as either horizontal or vertical orientation agents. Onium salts function as vertical orientation agents. An orientation agent can be used alone or in combination with two or more agents.

[0034] As a boric acid compound, the preferred compound is one represented by formula (30).

[0035] Equation (30) [Chemical Formula 1]

[0036] In equation (30), R 1 and R 2 Each of these can be independently represented by a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. R 3 This indicates a substituent containing a (meth)acryloyl group. As a specific example of boric acid compounds, the boric acid compounds represented by general formula (I) described in paragraphs 0023 to 0032 of Japanese Patent Application Publication No. 2008-225281 can be cited. The compounds exemplified below are also preferred as boric acid compounds.

[0037] [Chemical Formula 2]

[0038] Specific examples of onium salts include those described in paragraphs 0052 to 0058 of Japanese Patent Application Publication No. 2012-208397, those described in paragraphs 0024 to 0055 of Japanese Patent Application Publication No. 2008-026730, and those described in Japanese Patent Application Publication No. 2002-37777.

[0039] When the composition for forming anisotropic light-absorbing layers contains an orientation agent, the content of the orientation agent is preferably 0.01 to 30% by mass, more preferably 0.1 to 10% by mass, relative to the total solid content of the composition for forming anisotropic light-absorbing layers.

[0040] <Polymerization Initiator> There are no particular restrictions on the type of polymerization initiator, but photosensitive compounds, i.e., photopolymerization initiators, are preferred. As photopolymerization initiators, a wide variety of compounds can be used without particular limitations. Examples of photopolymerization initiators include α-carbonyl compounds (as described in U.S. Patent Nos. 2,367,661 and 2,367,670), acyl-acid ethers (as described in U.S. Patent No. 2,448,828), α-hydrocarbon-substituted aromatic acyl-acid compounds (as described in U.S. Patent No. 2,722,512), polynuclear quinone compounds (as described in U.S. Patent Nos. 3,046,127 and 2,951,758), and combinations of triarylimidazolium dimers and p-aminobenzophenone (as described in U.S. Patent No. 3,549,367). The list includes compounds such as acridine and phenazine compounds (Japanese Patent Application Publication No. 60-105667 and US Patent No. 4239850), oxadiazole compounds (US Patent No. 4212970), o-acyl oxime compounds (Japanese Patent Application Publication No. 2016-27384

[0065] ), and acylphosphine oxide compounds (Japanese Patent Application Publication No. 63-40799, Japanese Patent Application Publication No. 5-29234, Japanese Patent Application Publication No. 10-95788, and Japanese Patent Application Publication No. 10-29997). Commercially available products can also be used as photopolymerization initiators, such as Irgacure 184, Irgacure 907, Irgacure 369, Irgacure 651, Irgacure 819, Irgacure OXE-01 and Irgacure OXE-02 manufactured by BASF. Polymerization initiators can be used alone or in combination with two or more.

[0041] When the composition for forming anisotropic light-absorbing layers contains a polymerization initiator, the content of the polymerization initiator is preferably 0.01 to 30% by mass, more preferably 0.1 to 15% by mass, relative to the total solid content of the composition for forming anisotropic light-absorbing layers.

[0042] <Solvent> As solvents, examples include ketones (e.g., acetone, 2-butanone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone), ethers (e.g., dioxane, tetrahydrofuran, tetrahydropyran, dioxolane, tetrahydrofurfuryl alcohol, and cyclopentyl methyl ether), aliphatic hydrocarbons (e.g., hexane), alicyclic hydrocarbons (e.g., cyclohexane), aromatic hydrocarbons (e.g., benzene, toluene, xylene, and trimethylbenzene), halogenated hydrocarbons (e.g., dichloromethane, chloroform, dichloroethane, dichlorobenzene, and chlorotoluene), and esters (e.g., Organic solvents such as methyl acetate, ethyl acetate, butyl acetate, diethyl carbonate, etc., alcohols (e.g., ethanol, isopropanol, butanol, cyclohexanol, etc.), cellosols (e.g., methyl cellosol, ethyl cellosol, and 1,2-dimethoxyethane, etc.), cellosol acetates, sulfoxides (e.g., dimethyl sulfoxide, etc.), amides (e.g., dimethylformamide and dimethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone, 1,3-dimethyl-2-imidazolium ketone, etc.), and heterocyclic compounds (e.g., pyridine, etc.) and water are permitted. These solvents may be used individually or in combination. Of these solvents, organic solvents are preferred for reasons of superior performance of the present invention, and more preferably carbon halogens or ketones.

[0043] When the composition for forming anisotropic light-absorbing layers contains a solvent, the solvent content is preferably 70 to 99% by mass, more preferably 83 to 97% by mass, and even more preferably 85 to 95% by mass, relative to the total mass of the composition for forming anisotropic light-absorbing layers.

[0044] <Production Method> The method for fabricating the light-absorbing anisotropic layer is not particularly limited, but a preferred method is one that sequentially comprises the following steps (hereinafter also referred to as "this manufacturing method"): a step of forming a coated film by coating the above-mentioned light-absorbing anisotropic layer forming composition onto an alignment film (hereinafter also referred to as "coating film forming step"); and a step of aligning the liquid crystal components contained in the above-mentioned coated film (hereinafter also referred to as "alignment step"). In addition, liquid crystal components refer to components that not only contain the aforementioned liquid crystal compounds, but also dichroic substances with liquid crystal properties. The following is a description of each process.

[0045] The coating film forming process is a process of forming a coating film by coating the above-mentioned light-absorbing anisotropic layer composition onto an alignment film. By using a light-absorbing anisotropic layer forming composition containing the above-mentioned solvent, or by using a liquid such as a melt prepared by heating or the like, the light-absorbing anisotropic layer forming composition can be easily coated onto an alignment film. Coating methods for compositions used to form anisotropic light-absorbing layers include known methods such as roller coating, gravure printing, spin coating, wire rod coating, extrusion coating, direct gravure coating, reverse gravure coating, die coating, spray coating, and inkjet coating.

[0046] The alignment film can be any film as long as it is a film in which the liquid crystal components contained in the composition for forming anisotropic light absorption layers are oriented. The alignment film can be formed by methods such as triboelectric treatment of the film surface of organic compounds (preferably polymers), tilted evaporation of inorganic compounds, formation of layers with microgrooves, or accumulation of organic compounds (e.g., ω-trisanoic acid, octadecylmethylammonium chloride, methyl stearate) based on the Langmuir-Blodgett process (LB film). Furthermore, an alignment film that generates an alignment function by applying an electric field, a magnetic field, or light irradiation is known. In this invention, from the viewpoint of easily controlling the pretilt angle of the alignment film, an alignment film formed by triboelectric treatment is preferred; from the viewpoint of uniform alignment, a photo-aligned film formed by light irradiation is also preferred.

[0047] As a photoalignment film, a photoalignment film containing azo dyes or polyvinyl cinnamate can be used. When ultraviolet light is irradiated from a direction that is tilted at a certain angle relative to the normal direction of the light-alignment layer, anisotropy is generated that is tilted relative to the normal direction of the light-alignment layer, and the light-absorbing anisotropic layer is oriented thereon, thereby enabling the dichroic substances in the light-absorbing anisotropic layer to be oriented. Furthermore, the liquid crystal layer that enables the mixing and orientation of liquid crystal compounds can also be used as an alignment film.

[0048] The alignment process is the process of aligning the liquid crystal components (especially dichroic substances) contained in the coating film. It is understood that in the alignment process, the dichroic substances are aligned along the liquid crystal compound oriented through the alignment film. The orientation process may include a drying process. This drying process removes components such as solvents from the coated film. The drying process can be performed by placing the coated film at room temperature for a specified time (e.g., natural drying), or by heating and / or air supply.

[0049] The orientation process preferably includes heat treatment. This further orients the dichroic material contained in the coated film, thereby further improving the degree of orientation of the dichroic material. From the viewpoint of manufacturing suitability, the heat treatment is preferably 10–250°C, more preferably 25–190°C. Furthermore, the heating time is preferably 1–300 seconds, more preferably 1–60 seconds.

[0050] The orientation process can include a cooling treatment performed after heat treatment. The cooling treatment involves cooling the heated coating film to room temperature (20–25°C). This further fixes the orientation of the dichroic material contained in the coating film, and further improves the degree of orientation of the dichroic material. There are no particular limitations on the cooling method; it can be implemented using known methods. Through the above processes, the light absorption anisotropic layer of the present invention can be obtained.

[0051] This manufacturing method may include a step (hereinafter also referred to as the "curing step") after the above-mentioned orientation step, in which the light-absorbing anisotropic layer is cured. The curing process is carried out, for example, by heating and / or light irradiation (exposure). Preferably, the curing process is carried out by light irradiation. The light source used for curing can be various types of light sources such as infrared, visible light, or ultraviolet light, but ultraviolet light is preferred. Furthermore, during curing, ultraviolet light can be irradiated while heating is being performed, or ultraviolet light can be irradiated through a filter that allows only specific wavelengths to pass through. Furthermore, the exposure can be performed under a nitrogen atmosphere. When curing the light-absorbing anisotropic layer via free radical polymerization, it is preferable to perform the exposure under a nitrogen atmosphere since the hindrance of oxygen to polymerization can be reduced.

[0052] The thickness of the light-absorbing anisotropic layer is not particularly limited, but from the viewpoint of achieving better results in this invention, it is preferably 0.5 to 7 μm, and more preferably 1.0 to 3 μm.

[0053] [Adhesive layer] As described above, the laminate of the present invention has an adhesive layer disposed adjacent to at least one surface of the light-absorbing anisotropic layer. Furthermore, as described above, the adhesive layer of the laminate of the present invention is an adhesive layer with an indentation elastic modulus of 0.4 to 6.0 MPa, and with respect to low molecular weight components with a molecular weight of 1000 or less, it satisfies either condition 1 or 2 below. Condition 1: Does not contain the aforementioned low molecular weight components. Condition 2: When the above-mentioned low molecular weight components are present, the content of the low molecular weight components that satisfy the following formula (I) is 1.0% by mass or less relative to the mass of the adhesive layer. A < B (I) In the above formula (I), A represents the distance between the Hansen solubility parameter of the matrix component in the light absorption anisotropic layer and the Hansen solubility parameter of the low molecular weight component in the adhesive layer, and B represents the distance between the Hansen solubility parameter of the matrix component in the adhesive layer and the Hansen solubility parameter of the low molecular weight component in the adhesive layer. In addition, regarding low molecular weight components with a molecular weight of 1000 or less, if condition 2 above is met, that is, if the content of the low molecular weight component satisfying formula (I) above is 1.0% by mass or less relative to the mass of the adhesive layer, the content of the low molecular weight component satisfying "A≥B" is not particularly limited, but it is usually more common to be 10% by mass or less.

[0054] In this invention, the indentation elastic modulus of the adhesive layer is 0.4 to 6.0 MPa, but the lower limit of the indentation elastic modulus is preferably 0.5 MPa or more, more preferably more than 0.5 MPa, and even more preferably 0.6 MPa or more. Furthermore, the upper limit of the indentation elastic modulus is preferably 5.5 MPa or less, more preferably 5.0 MPa or less. There are no particular limitations on the method for adjusting the indentation elastic modulus of the adhesive layer. For example, the elastic modulus can be increased by performing heat treatment.

[0055] The adhesive layer of the laminate of the present invention is preferably an adhesive layer that satisfies condition 1 above. On the other hand, when the adhesive layer of the laminate of the present invention is an adhesive layer that satisfies condition 2 above, the low molecular weight component included in the adhesive layer with a molecular weight of 1000 or less can be, for example, uncured polymer initiator or adhesive (monomer component) used in forming the adhesive layer. Furthermore, the low molecular weight component is preferably one that does not have a maximum absorption wavelength in the visible light region.

[0056] <Polymer> The adhesive layer of the laminate of the present invention is preferably a polymer of (meth)acrylic, silicone, urethane, vinyl alkyl ether, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide or cellulose, wherein a polymer of (meth)acrylic is preferred.

[0057] In this invention, from the perspective of improving adhesion, it is preferable that the matrix component of the adhesive layer is a (meth)acrylic polymer. The matrix component of the adhesive layer refers to the component with the largest proportion among the components contained in the adhesive layer. Therefore, the content of (meth)acrylic polymer is preferably more than 50% by mass, more preferably more than 70%, relative to the mass of the adhesive layer. The upper limit can be determined by taking into account other components, and it is usually less than 100% by mass, less than 99% by mass, or less than 95% by mass.

[0058] As polymers based on (meth)acrylic acid, examples include (meth)acrylic ester copolymers, etc. As a (meth)acrylate copolymer, a copolymer having crosslinking points capable of crosslinking by various crosslinking methods is used. There are no particular limitations on (meth)acrylate copolymers having such crosslinking points, and any copolymer can be appropriately selected from (meth)acrylate copolymers that are conventionally used as resin components of conventionally known adhesives.

[0059] As copolymers of (meth)acrylates having such crosslinking points, preferred examples include (meth)acrylates with 1 to 20 carbon atoms in the alkyl group of the ester moiety, monomers having crosslinking functional groups in the molecule, and copolymers of other monomers used as needed.

[0060] Among them, (meth)acrylates in which the alkyl group of the ester part has 1 to 20 carbon atoms include, for example, (meth)acrylate methyl acrylate, (meth)acrylate ethyl acrylate, (meth)acrylate propyl acrylate, (meth)acrylate butyl acrylate, (meth)acrylate pentyl acrylate, (meth)acrylate hexyl acrylate, (meth)acrylate cyclohexyl acrylate, (meth)acrylate 2-ethylhexyl acrylate, (meth)acrylate isooctyl acrylate, (meth)acrylate decyl acrylate, (meth)acrylate dodecyl acrylate, (meth)acrylate myristyl acrylate, (meth)acrylate palmitate, (meth)acrylate stearate, etc., and one or more can be used at the same time.

[0061] On the other hand, monomers having cross-linking functional groups within the molecule are preferably monomers having at least one functional group selected from the group consisting of hydroxyl, carboxyl, amino, and amide groups. Specifically, examples include hydroxyalkyl methacrylates such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl methacrylate, and 4-hydroxybutyl methacrylate; methacrylamides such as methacrylamide, N-methyl(meth)acrylamide, and N-hydroxymethyl(meth)acrylamide; monomethylaminoethyl methacrylate, monoethylaminoethyl methacrylate, monomethylaminopropyl methacrylate, and monoethylaminopropyl methacrylate; and olefinic unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, and citraconic acid. These monomers can be used individually or in combination with two or more.

[0062] In (meth)acrylate copolymers, there are no particular restrictions on the copolymerization method; it can be any of random, block, and graft copolymers. Furthermore, the weight-average molecular weight of the (meth)acrylate copolymer is preferably 500,000 or more, preferably 600,000 to 3,000,000, and even more preferably 1,900,000 to 2,500,000.

[0063] Furthermore, in this invention, considering the small change in adhesion corresponding to humidity, the HSP value of the matrix component of the adhesive layer is preferably 18 or less, and more preferably 15 to 18.

[0064] The adhesive layer of the laminate of the present invention is more preferably a layer formed using an adhesive layer forming composition comprising the polymer described above. The adhesive layer forming composition may contain, in addition to the polymer described above, the adhesive, polymerization initiator and solvent described later, provided that the formed adhesive layer meets condition 1 or 2 above.

[0065] <Adhesive> As adhesives, polyfunctional (meth)acrylate monomers are preferably listed, for example. As multifunctional (meth)acrylate monomers, specific examples include, for instance, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, polyethylene glycol dimethacrylate, neopentyl glycol adipate dimethacrylate, pivalic acid neopentyl glycol dimethacrylate, dicyclopentyl dimethacrylate, caprolactone-modified dicyclopentenyl dimethacrylate, ethylene oxide-modified dimethacrylate, di(acryloyloxyethyl) isocyanurate, allylated cyclohexyl dimethacrylate, and other difunctional monomers; trimethylolpropane trimethacrylate, dipentaerythritol trimethacrylate, propionic acid-modified dipentaerythritol trimethacrylate, etc. Trifunctional types include esters, pentaerythritol tri(meth)acrylate, propylene oxide-modified trimethylolpropane tri(meth)acrylate, and tri(acryloyloxyethyl)isocyanurate; quadrufunctional types include diglycerol tetra(meth)acrylate and pentaerythritol tetra(meth)acrylate; quintuple functional types include propionic acid-modified dipentaerythritol penta(meth)acrylate; and hexafunctional types include dipentaerythritol hexa(meth)acrylate and caprolactone-modified dipentaerythritol hexa(meth)acrylate.

[0066] <Polymerization Initiator> As a polymerization initiator, for example, the same polymerization initiator described as any component of a composition for forming anisotropic light-absorbing layers can be listed.

[0067] <Solvent> As a solvent, for example, the same solvents described as any component of the composition for forming anisotropic light-absorbing layers can be listed.

[0068] The thickness of the adhesive layer is not particularly limited, but from the viewpoint of thinness, it is preferably 25 μm or less, more preferably 15 μm or less, and even more preferably 5 μm or less. The lower limit is not particularly limited and is usually 0.1 μm or more.

[0069] In this invention, considering the improved crack resistance, the ratio (elastic modulus P / elastic modulus N) of the indentation elastic modulus P of the light-absorbing anisotropic layer to the indentation elastic modulus N of the adhesive layer is preferably 7000 or less, more preferably 6000 or less, and even more preferably 5000 or less. Furthermore, the aforementioned ratio (elastic modulus P / elastic modulus N) is preferably 300 or more, more preferably 400 or more, and even more preferably 500 or more.

[0070] [Other components] In addition to the light-absorbing anisotropic layer and the adhesive layer described above, the laminate of the present invention may also have other components. Other components include, for example, a phase retardation layer, a reflective polarizer layer (e.g., a cholesteric liquid crystal layer, a linearly polarized reflective polarizer, etc.), a surface antireflective layer, a support (substrate), and an alignment film.

[0071] A phase difference layer (hereinafter also referred to as a "specific phase difference layer") that has the function of converting linearly polarized light into circularly polarized light is a type of phase difference layer. A specific phase difference layer is not particularly limited as long as it has the function of converting linearly polarized light into circularly polarized light; for example, the λ / 4 plate can be cited. A λ / 4 plate is a plate with λ / 4 functionality, specifically a plate that has the function of converting linearly polarized light of a specific wavelength (preferably visible light) into circularly polarized light (or converting circularly polarized light into linearly polarized light). The in-plane delay of the λ / 4 plate at a wavelength of 550 nm is not particularly limited, but it is preferably 120-150 nm, more preferably 125-145 nm, and even more preferably 135-140 nm. In addition to the λ / 4 plate, a phase retardation layer that is in-plane delayed to 3 / 4 or 5 / 4 of the wavelength of any type of visible light at a wavelength of 550 nm is also preferred.

[0072] A specific phase difference layer can exhibit inverse wavelength dispersion. Inverse wavelength dispersion means that the phase difference at a given wavelength increases as the wavelength increases. Furthermore, a specific phase difference layer can be a multi-layer structure. As an example of such a case, a broadband λ / 4 plate formed by stacking λ / 4 and λ / 2 plates can be cited. The angle between the slow axis of the specific phase difference layer and the absorption axis of the light absorption anisotropy layer is not particularly limited, but is preferably in the range of 45°±10°.

[0073] A specific retardation layer can be a layer formed by immobilizing a liquid crystal compound, wherein the liquid crystal compound is twisted and oriented with the thickness direction as the twist axis. For example, as disclosed in Japanese Patent No. 05753922 and Japanese Patent No. 05960743, a retardation layer having a layer formed by immobilizing a rod-shaped liquid crystal compound or a disk-shaped liquid crystal compound, wherein the liquid crystal compound is twisted and oriented with the thickness direction as the twist axis, can be listed.

[0074] The thickness of the specific phase difference layer is not particularly limited, but it is preferably 0.1 to 8 μm, more preferably 0.3 to 5 μm.

[0075] <Positive C Board> The positive C-plate is a type of phase retardation layer. The positive C-plate is a phase difference layer with essentially zero in-plane retardation and negative retardation in the thickness direction. It functions as an optical compensation layer to improve the polarization of transmitted light for obliquely incident light. The in-plane delay of the positive C plate at a wavelength of 550 nm is preferably less than 10 nm. The thickness retardation of the positive C plate at a wavelength of 550 nm is preferably -600 to -40 nm.

[0076] The material constituting the positive C-plate is not particularly limited, but it is preferably formed from a composition containing a liquid crystal compound. Such a positive C-plate typically allows the rod-shaped polymeric liquid crystal compound contained in the polymeric liquid crystal composition to be vertically oriented, and the orientation state to be fixed by polymerization. Furthermore, it can also be formed from a composition containing a side-chain type polymeric liquid crystal compound as the liquid crystal compound.

[0077] The thickness of the positive C plate is not particularly limited, but from the viewpoint of thinning, it is preferably 0.5 to 10 μm, and more preferably 0.5 to 5 μm.

[0078] <Cholesterol-type liquid crystal layer> Cholesterol-type liquid crystal layers are optical components that separate incident light into right-handed and left-handed circularly polarized light, and cause one type of circularly polarized light to be positively reflected while allowing the other type of circularly polarized light to pass through. Cholesterol-type liquid crystal layers can be exemplified by cholesterol-type liquid crystal layers formed by immobilizing a cholesterol-type liquid crystal phase. When stretched or shaped into three-dimensional forms, cholesterol-type liquid crystal layers are preferred as optical films for curved surface forming from the viewpoint of suppressing the decrease in polarization degree and polarization axis distortion. Furthermore, the decrease in polarization degree due to polarization axis distortion is less likely to occur.

[0079] The cholesterol-type liquid crystal layer preferably has at least a blue light reflective layer with a reflectance of 40% or more at a wavelength of 460 nm, a green light reflective layer with a reflectance of 40% or more at a wavelength of 550 nm, a yellow light reflective layer with a reflectance of 40% or more at a wavelength of 600 nm, and a red light reflective layer with a reflectance of 40% or more at a wavelength of 650 nm. This structure exhibits high reflectance characteristics over a wide wavelength range in the visible light region, and is therefore preferred. Furthermore, the aforementioned reflectance values ​​refer to the reflectance when unpolarized light is incident on the cholesterol-type liquid crystal layer at each wavelength. Furthermore, the cholesterol-type liquid crystal layer can have a pitch gradient structure that allows the helical pitch of the cholesterol-type liquid crystal phase to vary continuously in the thickness direction.

[0080] Furthermore, as a cholesteric liquid crystal layer, it is preferable to simultaneously use a cholesteric liquid crystal layer formed by immobilizing a cholesteric liquid crystal phase containing rod-shaped liquid crystal compounds and a cholesteric liquid crystal phase formed by immobilizing a cholesteric liquid crystal phase containing disc-shaped liquid crystal compounds. With this type of structure, the cholesteric liquid crystal phase containing rod-shaped liquid crystal compounds has a positive RtH, while the cholesteric liquid crystal phase containing disc-shaped liquid crystal compounds has a negative RtH. Therefore, their Rth values ​​cancel each other out, and ghosting can be suppressed even for incident light from an oblique direction, which is therefore preferable.

[0081] The thickness of the cholesteric liquid crystal layer is not particularly limited, but from the viewpoint of thinning, it is preferably 30 μm or less, and more preferably 15 μm or less. The lower limit is not particularly limited and is usually 1 μm or more.

[0082] <Linearly polarized light type reflective polarizer> A linearly polarized reflective polarizer is a polarizer that has the following function: it reflects one type of linearly polarized light from mutually orthogonal linearly polarized light, while allowing the other type of linearly polarized light to pass through. Examples of linearly polarized reflective polarizers include films with stretched dielectric multilayers and wire grid polarizers. Commercially available examples include reflective polarizers (trade name APF) manufactured by 3M Company and wire grid polarizers (trade name WGF) manufactured by Asahi Kasei Corporation.

[0083] <Surface Anti-reflective Layer> The laminate of the present invention may have a surface anti-reflective layer. In the laminate of the present invention, the surface antireflective layer is preferably disposed on the outermost surface. The surface antireflective layer may be disposed on only one surface of the laminate, or it may be disposed on both surfaces. The type of surface anti-reflective layer is not particularly limited, but from the viewpoint of further reducing reflectivity, moth-eye film and AR (Anti-Reflection) film are preferred. Furthermore, even if the film thickness varies due to stretching and forming, high anti-reflective performance can be maintained, therefore moth-eye film is preferred. In addition, the angle between the transmission axis of the linearly polarized reflective polarizer and the transmission axis of the light-absorbing anisotropic layer is preferably in the range of 0 to 10°.

[0084] <Support (Substrate)> The laminate of the present invention may have a support. The support can be placed at any location. For example, in the case where the cholesteric liquid crystal layer and the retardation layer are films transferred from a temporary support, the support can be used as their transfer destination. The type of support is not particularly limited, but transparency is preferred. Examples include films made of cellulose acylates, polycarbonate, polysulfone, polyethersulfone, polyacrylate, polymethacrylate, cyclic polyolefins, polyolefins, polyamides, polystyrene, and polyesters. Among these, cellulose acylate films, cyclic polyolefin films, polyacrylate films, or polymethacrylate films are preferred as supports. Furthermore, commercially available cellulose acetate films (e.g., "TD80U" and "Z-TAC" manufactured by FUJIFILMCorporation) can also be used. Furthermore, the support body is preferably small in phase difference. Specifically, the in-plane delay at a wavelength of 550 nm is preferably less than 10 nm, and the absolute value of the delay in the thickness direction at a wavelength of 550 nm is preferably less than 50 nm.

[0085] From the viewpoint of stretching and forming, the support body preferably has a peak temperature of tanδ of 170°C or less. From the viewpoint of being able to form at low temperatures, the peak temperature of tanδ is preferably 150°C or less, and more preferably 130°C or less.

[0086] The method for determining tanδ is described below. Using a dynamic viscoelasticity measuring device (ITKDVA-200), the film samples that had been conditioned for more than 2 hours in a Rh atmosphere at 25°C and 60% humidity were tested for E” (loss modulus) and E’ (storage modulus) under the following conditions, and tanδ (=E” / E’) was used as the obtained value. Device: DVA-200 manufactured by ITKDVA Sample size: 5mm, length 50mm (gap 20mm) Measurement conditions: Tensile mode Measurement temperature: -150~220℃ Heating conditions: 5℃ / minute Frequency: 1Hz

[0087] The thickness of the support is not particularly limited, but it is preferably 5 to 300 μm, more preferably 5 to 100 μm, and even more preferably 5 to 30 μm.

[0088] [Display device] The display device of the present invention is a display device having the above-described laminate of the present invention. Examples of such display devices include liquid crystal displays, organic EL displays, and virtual reality displays. Display devices can be thin and shaped into curved surfaces. The laminate used in this invention is thin and easily bent because it lacks an oxygen barrier layer (barrier layer), making it preferably suitable for display devices with curved display surfaces. Examples of such curved surfaces include those with a radius of curvature of 20 mm or more and 300 mm or less for the portion with the smallest curvature.

[0089] Virtual reality display device Figure 1 This is a schematic diagram illustrating an example of the structure of a virtual reality display device. Figure 1 The virtual reality display device 80 shown in the figure has an image display panel 82, a circularly polarizing plate 84, a semi-reflective mirror 86, a lens 88, and the laminate 90 of the present invention from the right side of the figure. Depend on Figure 1 The laminate 90, lens 88 and semi-reflective mirror 86 shown constitute a composite lens. exist Figure 1In the virtual reality display device 80 shown, light 92 emitted from the image display panel 82 becomes circularly polarized light after passing through a circularly polarizing plate 84, and then passes through a semi-reflective mirror 86. Next, it is reflected from the side of the reflective polarizing layer (e.g., a cholesteric liquid crystal layer) included in the laminate 90 of the present invention through a lens 88, and after passing through the lens 88 again, it is reflected again by the semi-reflective mirror 86, and then passes through the lens 88 again before entering the laminate 90. At this time, the circularly polarized state of light 92 does not change when reflected by the laminate 90, but becomes circularly polarized light with the opposite direction of rotation when reflected by the semi-reflective mirror 86. Therefore, light 92 passes through the laminate 90, and the user can visually recognize it. Furthermore, when light 92 is reflected by the semi-reflective mirror 86, since the semi-reflective mirror is concave, the image is magnified, and the user can visually recognize the magnified virtual image. The above-described mechanism is called a reciprocating optical system or a refracting optical system, etc. In addition, the light-absorbing anisotropic layer included in the laminate 90 functions as a so-called linear polarizer to block light that unnecessarily passes through the cholesteric liquid crystal layer and prevent it from becoming light leakage (ghosting) that can be observed by users of virtual reality display devices.

[0090] The image display panel 82 is, for example, a known image display panel such as an organic electroluminescent display panel. In the example shown, the image display panel 82 emits an image of unpolarized light (image light). The image of unpolarized light emitted by the image display panel 82 is converted into circularly polarized light by the circularly polarized light plate 84. Example

[0091] The present invention will now be described in further detail with reference to embodiments. The materials, amounts, proportions, processing contents, and processing order shown in the following embodiments can be appropriately modified without departing from the spirit of the invention. Therefore, the scope of the present invention should not be interpreted limitedly by the embodiments shown below.

[0092] [Synthesis of the polymer (matrix) contained in the adhesive layer] A copolymer with a weight-average molecular weight of 2 million and a molecular weight distribution (Mw / Mn) of 3.0 was synthesized by conventional methods using butyl acrylate and butyl methacrylate in a mass ratio of 95:5. The copolymer was then purified to remove components with a molecular weight of 1000 or less below the detection limit before being used as a matrix. This copolymer is labeled "butyl acrylate / butyl methacrylate" in Table 1 below.

[0093] [Example 1] [Preparation of substrate A1] The following composition was added to a mixing vessel and stirred, and then heated at 90°C for 10 minutes. The resulting composition was then filtered through filter paper with an average pore size of 34 μm and a sintered metal filter with an average pore size of 10 μm to prepare a coating. The coating had a solids content of 23.5% by mass, the amount of plasticizer added was relative to the cellulose acylate, and the solvent for the coating was dichloromethane / methanol / butanol = 81 / 18 / 1 (mass ratio).

[0094] ―――――――――――――――――――――――――――――――― Cellulose acylated coatings ―――――――――――――――――――――――――――――――― Cellulose acylates (Acetyl substitution degree 2.86, average viscosity degree of polymerization 310) 100 parts by weight • 6.0 parts by mass of sugar ester compound 1 (formula (S4) below) • Sugar ester compound 2 (formula (S5) below) 2.0 parts by mass • Silica particle dispersion (AEROSIL R972, manufactured by NIPPON AEROSIL CO., LTD.) 0.1 parts by weight • Solvent (dichloromethane / methanol / butanol) 351.9 parts by weight ――――――――――――――――――――――――――――――――

[0095] Glycoester compound 1 [Chemical Formula 3]

[0096] Glycoester compound 2 [Chemical Formula 4]

[0097] The coating produced above was cast using a roller film casting machine. The coating was cast from the mold and brought into contact with a metal support cooled to 0°C. Then, the resulting web (film) was peeled off from the roller. The roller was made of SUS (stainless steel).

[0098] The film was dried for 20 minutes using a tenter frame as follows: after the cast web (film) was peeled from the rollers, it was conveyed at 30-40°C by clamping both ends of the web. Then, the web was post-dried by zone heating while being conveyed by rollers. The resulting web was then knurled, wound, and used to form substrate A1. The obtained substrate 1 has a film thickness of 60 μm, an in-plane retardation Re(550) of 1 nm at a wavelength of 550 nm, and a thickness direction retardation Rth(550) of 35 nm at a wavelength of 550 nm.

[0099] [Fabrication of photoalignment film B1] The photo-alignment film forming composition B1 (described later) is continuously coated onto the substrate 1 using a wire rod. The support with the coating is dried in hot air at 140°C and a wind speed of 1 m / s for 120 seconds, followed by irradiation of the coating with polarized ultraviolet light (10 mJ / cm²). 2 Using an ultra-high pressure mercury lamp, a photo-alignment film B1 was fabricated, thus obtaining a substrate 1 with the photo-alignment film. The thickness of the photo-alignment film B1 is 1.5 μm. In addition, the solid content concentration of the composition B1 for photo-aligned film formation is 20%, and the viscosity is 3.5 mPa·s.

[0100] ―――――――――――――――――――――――――――――――― Composition of composition B1 for photo-alignment film formation ―――――――――――――――――――――――――――――――― • 100.00 parts by weight of the following polymer PA-1 (photo-oriented compound) • EPICLON N-695 (manufactured by DIC Corporation) 55.74 parts by weight ·jER YX7400 (manufactured by Mitsubishi Chemical Corporation) 18.75 parts by weight • 8.01 parts by weight of the following polymer compound PB-1 • 16.75 parts by weight of the following thermal cationic polymerization initiator PAG-1 • 1.06 parts by weight of the following stabilizer DIPEA • 0.50 parts by weight of the following acid-degrading surfactant SA-1 ·Butyl acetate 803 parts by weight ――――――――――――――――――――――――――――――――

[0101] Polymer PA-1 (photooriented compound) [weight average molecular weight: 32000, where the values ​​listed in each repeating unit in the following formula represent the content (mass%) of each repeating unit relative to all repeating units.] [Chemical Formula 5]

[0102] PAG-1 thermal cationic polymerization initiator [Chemical Formula 6]

[0103] stabilizer DIPEA [Chemical Formula 7]

[0104] Polymer compound PB-1 (weight average molecular weight: 18000) [Chemical Formula 8]

[0105] Acid-degrading surfactant SA-1 [weight average molecular weight: 78000] [Chemical Formula 9]

[0106] [Formation of the light-absorbing anisotropic layer C1] A light-absorbing anisotropic layer forming composition C1, consisting of the following components, is continuously coated onto the obtained light-alignment film B1 using a wire rod, thereby forming a coating film. Next, the coating was heated at 140°C for 15 seconds, then heated at 80°C for 5 seconds, and then cooled to room temperature (23°C). Next, the coating was heated at 75°C for 60 seconds, and then cooled to room temperature again. Then, by irradiating the light-aligning film B1 with an LED (light-emitting diode) lamp (center wavelength 365nm) at 300mJ, a light-absorbing anisotropic layer C1 (polarizer) (thickness: 1.8μm) was formed. Furthermore, the total content of the first dichroic substance Dye-C1, the second dichroic substance Dye-M1, and the third dichroic substance Dye-Y1 contained in the light-absorbing anisotropic layer C1 is 220 mg / cm³. 3 . The transmittance of the light-absorbing anisotropic layer C1 in the wavelength region of 280–780 nm was measured using a spectrophotometer, and the average transmittance of visible light was 42%. The absorption axis of the light-absorbing anisotropic layer C1 lies in the plane of the light-absorbing anisotropic layer C1 and is orthogonal to the width direction of the substrate A1.

[0107] ―――――――――――――――――――――――――――――――― Composition of composition C1 for forming anisotropic light-absorbing layers ―――――――――――――――――――――――――――――――― • 0.65 parts by mass of the first dichroic substance Dye-Cl • 0.15 parts by mass of the second dichroic substance Dye-M1 described below • 0.52 parts by mass of the third dichroic substance Dye-Y1 • 2.69 parts by mass of the following liquid crystal compound L-1 • 1.15 parts by weight of the following liquid crystal compound L-2 • 0.17 parts by weight of the following adhesion improver A-1 Polymerization initiators IRGACUREOXE-02 (manufactured by BASF) 0.17 parts by weight • 0.013 parts by weight of the following surfactant F-1 · Cyclopentanone 92.14 parts by weight · Benzyl alcohol 2.36 parts by weight ――――――――――――――――――――――――――――――――

[0108] Dichroic substance Dye-C1 [Chemical Formula 10]

[0109] Dichroic substance Dye-M1 [Chemical Formula 11]

[0110] Dichroic substance Dye-Y1 [Chemical Formula 12]

[0111] Liquid crystal compound L-1 [weight-average molecular weight: 18000, where the values ​​("59", "15", "26") in each repeating unit below represent the content (mass%) of each repeating unit relative to all repeating units.] [Chemical Formula 13]

[0112] Liquid crystal compound L-2 [a mixture of the following liquid crystal compounds (RA), (RB), and (RC) in a mass ratio of 84:14:2] [Chemical Formula 14]

[0113] Adhesion improver A-1 [Chemical Formula 15]

[0114] Surfactant F-1 [weight-average molecular weight: 15000, where the values ​​recorded in each repeating unit represent the content (mass%) of each repeating unit relative to all repeating units.] [Chemical Formula 16]

[0115] [Preparation (bonding) of adhesive layer D1] The adhesive layer D1 was formed by applying the adhesive layer forming composition prepared with the composition shown in Table 1 below to the release layer of a 38 μm thick polyethylene terephthalate release film (SP-PET3811 manufactured by LINTEC Corporation) as a release film using a blade-type coating machine and then drying it at 90°C for 1 minute. Next, the adhesive layer D1 is bonded to the surface of the pre-fabricated light-absorbing anisotropic layer C1 in such a way that they come into contact. Next, after 30 seconds of lamination, the substrate is irradiated with ultraviolet (UV) light from the release film side under the following conditions, followed by a 2-hour heat treatment at 50°C to obtain the laminated precursor (layer structure: substrate A1 / photo-aligned film B1 / light-absorbing anisotropic layer C1 / adhesive layer D1 / release film). Next, after peeling off the release film and bonding TG40 (manufactured by FUJIFILM Corporation), the substrate A1 is peeled off to obtain laminate 1 (layer structure: photo-alignment film B1 / photo-absorption anisotropic layer C1 / adhesive layer D1 / TG40). In addition, as shown in Table 1 below, the adhesive layer D1 of the laminate 1 does not contain low molecular weight components with a molecular weight of less than 1000. <UV Irradiation Conditions> • Use electrodeless lamps and H-tube lamps manufactured by Fusion. Illuminance 600mW / cm 2 Light intensity 150 mJ / cm 2 In addition, the UV illuminance and photometer used was the "UVPF-36" manufactured by Aigggraphics Inc.

[0116] [Example 2] Except for changing the composition of the adhesive layer forming composition to the composition shown in Table 1 below, the laminate 2 was prepared using the same method as in Example 1. In addition, as shown in Table 1 below, the adhesive layer of the laminate 2 contains a low molecular weight component with a molecular weight of 1000 or less, but the content of the low molecular weight component that satisfies “A < B” as expressed in the above formula (I) is 1.0% by mass or less.

[0117] [Example 3] In place of the light-absorbing anisotropic layer C1, the following light-absorbing anisotropic layer C2 was formed. Otherwise, the laminate 3 was fabricated using the same method as in Example 1. In addition, as shown in Table 1 below, the adhesive layer D1 of the laminate 3 does not contain low molecular weight components with a molecular weight of less than 1000.

[0118] [Formation of the light-absorbing anisotropic layer C2] Composition C2 for forming anisotropic light-absorbing layers was prepared with the following composition, and was heated at 80°C for 2 hours while stirring, and then filtered through a 0.45 μm filter. ―――――――――――――――――――――――――――――――― Composition C2 for forming anisotropic light-absorbing layers ―――――――――――――――――――――――――――――――― • 0.8 parts by mass of the following dichroic substance D1 • 2.6 parts by mass of the following dichroic substance D2 • 2.2 parts by mass of the following dichroic substance D3 • 1.8 parts by mass of the following dichroic substance D4 • 100.0 parts by weight of the following liquid crystal compound M-1 • Polymerization initiator IRGACURE 369 (manufactured by BASF) 5.0 parts by weight • BYK361N (manufactured by BYK Chemie Japan Co., Ltd.) 0.9 parts by weight · Cyclopentanone 925.0 parts by weight ――――――――――――――――――――――――――――――――

[0119] Dichroic substance D1 [Chemical Formula 17]

[0120] Dichroic substance D2 [Chemical Formula 18]

[0121] Dichroic substance D3 [Chemical Formula 19]

[0122] Dichroic substance D4 [Chemical Formula 20]

[0123] Liquid crystal compound M1 (a mixture of compound A and compound B in a ratio of 75 / 25)

[0124] (Compound A) [Chemical Formula 21]

[0125] (Compound B) [Chemical Formula 22]

[0126] The light-absorbing anisotropic layer forming composition C2 described above was applied using a wire rod onto the light-aligned film B1 of a TAC (triacetyl cellulose) film with a light-aligned film, which was prepared using the same method as in Example 1. The resulting coating was then heated at 120°C for 60 seconds and cooled to room temperature. Then, the exposure was 2000 mJ / cm by using a high-pressure mercury lamp. 2 The ultraviolet light formed a light-absorbing anisotropic layer C2 with a thickness of 2.5 μm. In addition, it was confirmed that the liquid crystal in the light-absorbing anisotropic layer C2 is a smectic B phase.

[0127] [Example 4] As a thermoplastic resin substrate, a single side of the resin substrate was corona treated with a strip-shaped amorphous polyethylene terephthalate copolymer film (thickness: 100 μm) with a glass transition temperature of 75 °C. A PVA aqueous solution (coating solution) was prepared by adding 13 parts by mass of potassium iodide to 100 parts by mass of a PVA-based resin, which was prepared by mixing polyvinyl alcohol (degree of polymerization 4200, degree of saponification 99.2 mol%) and acetoacetyl modified PVA (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., product name "Gohsefimer") in a 9:1 ratio, and dissolving it in water. A PVA-based resin layer with a thickness of 13 μm was formed by coating the corona-treated surface of a resin substrate with the above-mentioned PVA aqueous solution and drying it at 60°C, thereby creating a laminate. The obtained laminate was stretched uniaxially by 2.4 times along the longitudinal (long side) direction in an oven at 130°C (assisted stretching treatment in air). Next, the laminate was immersed in an insoluble bath (an aqueous solution of boric acid mixed with 4 parts by mass relative to 100 parts by mass of water) at a liquid temperature of 40°C for 30 seconds (insoluble treatment). Next, the solution was immersed for 60 seconds in a staining bath at 30°C (an iodine aqueous solution obtained by mixing iodine and potassium iodide in a mass ratio of 1:7 relative to 100 parts by mass of water), while adjusting the concentration (staining treatment). Next, it was immersed for 30 seconds in a crosslinking bath at a liquid temperature of 40°C (an aqueous solution of boric acid, mixed with 3 parts by mass of potassium iodide and 5 parts by mass of boric acid relative to 100 parts by mass of water) (crosslinking treatment). Then, while immersing the laminate in a boric acid aqueous solution (boric acid concentration 4% by mass, potassium iodide concentration 5% by mass) at a liquid temperature of 70°C, uniaxial stretching (underwater stretching treatment) was performed between rollers with different circumferential speeds along the longitudinal direction (long side direction) to make the total stretching ratio 5.5 times. Then, the laminate was immersed in a cleaning bath at a liquid temperature of 20°C (an aqueous solution of 3 parts by mass of potassium iodide mixed with 100 parts by mass of water) (cleaning treatment). Then, while drying in an oven at approximately 90°C, it is brought into contact with SUS heating rollers at a surface temperature of approximately 75°C (drying shrinkage treatment). In this way, an anisotropic light-absorbing layer C4 is formed on a resin substrate, thereby obtaining a laminate with a layer structure of a resin substrate and an anisotropic light-absorbing layer C4. Next, using the same method as in Example 1, an adhesive layer was bonded to the surface of the light-absorbing anisotropic layer C4 of the obtained laminate. After bonding, 30 seconds later, ultraviolet (UV) light was irradiated from the release film side under the same conditions as in Example 1, followed by heat treatment at 50°C for 2 hours to obtain the laminate precursor (layer structure: resin substrate / light-absorbing anisotropic layer C4 / adhesive layer D1 / release film). Next, the release film is peeled off and TG40 (manufactured by FUJIFILM Corporation) is bonded to obtain laminate 4 (layer structure: resin substrate / light absorption anisotropic layer C4 / adhesive layer D1 / TG40). In addition, as shown in Table 1 below, the adhesive layer D1 of the laminate 4 does not contain low molecular weight components with a molecular weight of less than 1000.

[0128] [Comparative Example 1] Except for the absence of heat treatment after bonding the adhesive layer, the laminate H1 was fabricated using the same method as in Example 1. In addition, as shown in Table 1 below, the adhesive layer D1 of the laminate H1 does not contain low molecular weight components with a molecular weight of less than 1000, but the indentation elastic modulus of the adhesive layer D1 is less than 0.4 MPa.

[0129] [Comparative Example 2] Except for changing the composition of the adhesive layer forming composition to the composition shown in Table 1 below, the laminate H2 was prepared using the same method as in Example 1. In addition, as shown in Table 1 below, the adhesive layer of laminate H2 contains more than 1.0% by mass of low molecular weight components with a molecular weight of less than 1000.

[0130] [Comparative Example 3] Except for changing the composition of the adhesive layer forming composition to the composition shown in Table 1 below, the laminate H3 was prepared using the same method as in Example 1. In addition, as shown in Table 1 below, the adhesive layer of laminate H3 contains more than 1.0% by mass of low molecular weight components with a molecular weight of less than 1000.

[0131] [Comparative Example 4] Except that the adhesive layer forming composition was changed to a commercially available product (NCF-D692, manufactured by LINTEC Corporation), the laminate H4 was prepared using the same method as in Example 1. In addition, as shown in Table 1 below, the adhesive layer (NCF-D692) of laminate H4 contains more than 1.0% by mass of low molecular weight components with a molecular weight of less than 1000.

[0132] [Comparative Example 5] Except that the adhesive layer forming composition was changed to a commercially available product (NCF-D692, manufactured by LINTEC Corporation), the laminate H5 was prepared using the same method as in Example 3. In addition, as shown in Table 1 below, the adhesive layer (NCF-D692) of laminate H5 contains more than 1.0% by mass of low molecular weight components with a molecular weight of less than 1000.

[0133] [Comparative Example 6] The following adhesive layer forming composition H6 was prepared. ──────────────────────────────── Adhesive layer forming composition H6 ―――――――――――――――――――――――――――――――― • 70 parts by weight of CEL2021P (manufactured by Daicel Corporation) · 20 parts by weight of 1,4-Butanediol diglycidyl ether 10 parts by weight of 2-ethylhexyl glycidyl ether • The following CPI-100P 2.25 parts by weight ────────────────────────────────

[0134] CEL2021P [Chemical Formula 23]

[0135] CPI-100P [Chemical Formula 24]

[0136] <Creating the H6 Layer> A laminate consisting of substrate 1, photo-alignment film B1, and light-absorbing anisotropic layer C1 was fabricated using the same method as in Example 1. Next, the light-absorbing anisotropic layer C1 side of the laminate was bonded to TG40 (manufactured by FUJIFILM Corporation) using an adhesive layer forming composition H6, and the UV irradiation conditions were adjusted and cured to an indentation elastic modulus of 6000 MPa. Next, substrate A1 was peeled off to obtain laminate H6 (layer structure: photo-aligned film B1 / photo-absorbing anisotropic layer C1 / adhesive layer H6 / TG40).

[0137] [evaluate] [Crack resistance] Crack resistance was evaluated according to the general test method for coatings - flexural resistance (cylindrical mandrel method) as described in JIS-K-5600-5-1 (1999), and the following method was used. Specifically, under conditions of 25°C and 55% relative humidity, the prepared laminates 1-4 and H1-H6 were conditioned for 16 hours, and then wound onto mandrels with diameters (Φ) of 2, 3, 4, 5, 6, 8, 10, 12, 16, 20, 25, and 32 mm, with TG40 on the outer side. The occurrence of cracks was observed, and the crack resistance was evaluated based on the smallest mandrel diameter that did not produce cracks. Cracks occurring with a larger mandrel diameter indicate weaker crack resistance. <Evaluation Criteria> A: Even a 2mm mandrel will not crack. B: Cracks appear on the 3-4mm mandrel. C: Cracks occur in mandrels with a diameter greater than 5mm.

[0138] [Adhesiveness] The laminates 1 to 4 and laminates H1 to H6 were subjected to a cross-cut test (checkerboard tape peel test) according to JIS D0202-1988. One hundred squares were formed by cutting a lattice pattern from the TG40 side to the light-absorbing anisotropic layer. Among the 100 squares formed, the number of squares peeled off was counted by applying and peeling off cellophane tape (“CT24”, manufactured by NICHIBAN CO.,LTD.), and evaluated according to the following criteria. <Evaluation Criteria> A: The number of squares that were peeled off is 0. B: The number of squares to be removed is 1 to 30. C: The number of squares that have been removed is 31 or more.

[0139] [Durability] Laminates 1-4 and laminates H1-H6 were subjected to 500 hours in an environment of 80°C and relative humidity less than 10%. The smaller the change in transmittance before and after the time, the better the durability. Transmittance was measured using a spectrophotometer (VAP-7070, manufactured by JASCO Corporation) and calculated based on the average of orthogonal and parallel transmittance in the wavelength region of 380-780 nm. <Evaluation Criteria> A: Transmittance change is less than 2%. B: Transmittance change is greater than 2%.

[0140] [Table 1]

[0141] As shown in Table 1, even when the adhesive layer adjacent to the light-absorbing anisotropic layer does not contain low molecular weight components with a molecular weight of less than 1000, the adhesion is poor if the indentation elastic modulus is less than 0.4 MPa (Comparative Example 1), and the crack resistance is poor if the indentation elastic modulus exceeds 6.0 MPa (Comparative Example 6). Furthermore, it is known that if the adhesive layer adjacent to the light absorption anisotropic layer is an adhesive layer containing more than 1.0% by mass of a low molecular weight component with a molecular weight of less than 1000, the durability is poor (Comparative Examples 2 to 5). Among them, it is known that if the indentation elastic modulus exceeds 6.0 MPa, the crack resistance is poor (Comparative Examples 3 to 5).

[0142] In contrast, it can be seen that if the adhesive layer adjacent to the light-absorbing anisotropic layer is an adhesive layer with an indentation elastic modulus of 0.4 to 6.0 MPa and a molecular weight of less than 1000 that satisfies condition 1 or 2 above, then the crack resistance, adhesion and durability all become good (Examples 1 to 4). In particular, a comparison between Examples 1-3 and Example 4 shows that if the ratio of the indentation elastic modulus P of the light-absorbing anisotropic layer to the indentation elastic modulus N of the adhesive layer (elastic modulus P / elastic modulus N) is 7000 or less, the crack resistance becomes better. Symbol Explanation

[0143] 80-Virtual reality display device, 82-Image display device, 84-Circularly polarized light plate, 86-Semi-reflective mirror, 88-Lens, 90-Layered body, 92-Light ray.

Claims

1. A laminate comprising a light-absorbing anisotropic layer and an adhesive layer disposed adjacent to at least one surface of the light-absorbing anisotropic layer, wherein, The light-absorbing anisotropic layer contains a dichroic substance with a molecular weight of less than 1000. The indentation elastic modulus of the adhesive layer is 0.4–6.0 MPa. For low molecular weight components with a molecular weight of less than 1000, the adhesive layer satisfies either condition 1 or 2 below. Condition 1: Does not contain the aforementioned low molecular weight components. Condition 2: When the low molecular weight component is present, the content of the low molecular weight component satisfying the following formula (I) relative to the mass of the adhesive layer is 1.0% by mass or less. A < B (I) In formula (I), A represents the distance between the Hansen solubility parameter of the matrix component in the light-absorbing anisotropic layer and the Hansen solubility parameter of the low molecular weight component in the adhesive layer, and B represents the distance between the Hansen solubility parameter of the matrix component in the adhesive layer and the Hansen solubility parameter of the low molecular weight component in the adhesive layer.

2. The laminated body according to claim 1, wherein, The matrix component of the light-absorbing anisotropic layer is a liquid crystal compound.

3. The laminated body according to claim 2, wherein, The Hansen solubility parameter of the matrix component of the light-absorbing anisotropic layer is 18 or higher.

4. The laminated body according to claim 1, wherein, The matrix component of the adhesive layer is an acrylic or methacrylic polymer.

5. The laminated body according to claim 4, wherein, The Hansen solubility parameter of the matrix component of the adhesive layer is below 18.

6. The laminate according to claim 1, wherein, The ratio of the indentation elastic modulus of the light-absorbing anisotropic layer to the indentation elastic modulus of the adhesive layer is less than 7000.

7. A display device having a laminate according to any one of claims 1 to 6.

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