Laminate, composite lens, display device, and virtual reality display device

Abstract

The present invention provides a laminate, a composite lens, a display device, and a virtual reality display device that, when applied to a display device (in particular, a virtual reality display device) and used for viewing, are less prone to color unevenness. The laminate according to the present invention includes a light-absorbing anisotropic film and an adhesive layer disposed adjacent to the light-absorbing anisotropic film, wherein the light-absorbing anisotropic film contains an organic dichroic dye, and the sum of the surface free energy E1 of the surface on the adhesive layer side of the light-absorbing anisotropic film and the surface free energy E2 of the surface on the light-absorbing anisotropic film side of the adhesive layer is 54.0 mN / m-1 or more.

Description

Laminate, composite lens, display device, virtual reality display device

[0001] The present invention relates to a laminate, a composite lens, a display device, and a virtual reality display device.

[0002] Optically absorptive anisotropic films containing organic dichroic dyes are used in a variety of applications. For example, a circular polarizer is formed by combining an optically absorptive anisotropic film with a retardation layer, and the film is used to prevent reflection of external light. The film is also used as a component of a virtual reality display device. Patent Document 1 discloses an optically absorptive anisotropic film containing a dichroic azo dye compound. Patent Document 1 also discloses an embodiment in which a barrier layer is disposed between the optically absorptive anisotropic film and a pressure-sensitive adhesive layer.

[0003] Japanese Patent Application Laid-Open No. 2022-153544

[0004] On the other hand, from the viewpoint of thinning, it is desirable not to use such a barrier layer. The present inventors have found that when a laminate obtained by directly laminating an optically absorbing anisotropic film and an adhesive layer without using a barrier layer is applied to a display device, problems arise in that color unevenness occurs and display performance deteriorates. In particular, they have found that the above problem occurs significantly when the laminate is applied to a virtual reality display device.

[0005] In view of the above circumstances, an object of the present invention is to provide a laminate that is less likely to cause color unevenness when applied to a display device (particularly a virtual reality display device) and viewed. Another object of the present invention is to provide a composite lens, a display device, and a virtual reality display device.

[0006] The present inventors have conducted extensive research into the above-mentioned problems and have found that the above problems can be solved by the following configuration.

[0007] (1) A laminate comprising an optically absorbing anisotropic film and an adhesive layer disposed adjacent to the optically absorbing anisotropic film, wherein the optically absorbing anisotropic film contains an organic dichroic dye, and the sum of the surface free energy E1 of the surface of the optically absorbing anisotropic film on the adhesive layer side and the surface free energy E2 of the surface of the adhesive layer on the optically absorbing anisotropic film side is 54.0 mNm －１or more. (2) The laminate according to (1), wherein the thickness of the optically absorptive anisotropic film is 10.0 μm or less. (3) The laminate according to (1) or (2), wherein the optically absorptive anisotropic film contains four or more organic dichroic dyes. (4) The laminate according to any one of (1) to (3), further comprising an alignment film disposed adjacent to the optically absorptive anisotropic film on the side opposite to the adhesive layer side of the optically absorptive anisotropic film. (5) The laminate according to any one of (1) to (4), wherein the thickness of the adhesive is 13.0 μm or less. (6) The laminate according to any one of (1) to (5), further comprising an adjacent layer disposed adjacent to the adhesive layer on the side opposite to the optically absorptive anisotropic film side of the adhesive layer, wherein the adjacent layer has an elastic modulus of 100 MPa or more. (7) The laminate according to any one of (1) to (6), wherein the optically absorptive anisotropic film contains a surfactant, and wherein the Log P value of the surfactant is 3.0 or less. (8) The laminate according to any one of (1) to (7), wherein a surface activation treatment has been performed on the surface of the adhesive layer side of the optically absorptive anisotropic film. (9) The laminate according to any one of (1) to (8), wherein the adhesive layer has a LogP value of 0.5 or less. (10) The laminate according to any one of (1) to (9), further comprising a retardation layer on the side of the adhesive layer opposite to the optically absorptive anisotropic film side. (11) The laminate according to any one of (1) to (10), further comprising a reflective polarizer and a retardation layer on the side of the adhesive layer opposite to the optically absorptive anisotropic film side. (12) A composite lens comprising, in this order, the laminate according to any one of (1) to (11), a lens, and a half mirror. (13) A display device comprising the laminate according to any one of (1) to (11). (14) A virtual reality display device comprising the laminate according to any one of (1) to (11).

[0008] According to the present invention, it is possible to provide a laminate that is less likely to cause color unevenness when applied to a display device (particularly a virtual reality display device) and viewed. Furthermore, according to the present invention, it is possible to provide a compound lens, a display device, and a virtual reality display device.

[0009] Fig. 1 is a diagram showing an example of a laminate of the present invention. Fig. 2 is a diagram showing another example of a laminate of the present invention. Fig. 3 is a diagram showing another example of a laminate of the present invention. Fig. 4 is a diagram showing an example of a composite lens of the present invention. Fig. 5 is a diagram showing an example of a virtual reality display device of the present invention.

[0010] The present invention will be described in detail below. The following description of the constituent elements may be based on representative embodiments and specific examples, but the present invention is not limited to such embodiments. In this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits.

[0011] In this specification, the term "absorption axis" refers to the polarization direction in which the absorbance is maximized in the plane when linearly polarized light is incident, and the term "in-plane slow axis" refers to the direction in which the refractive index is maximized in the plane.

[0012] In this specification, Re(λ) and Rth(λ) represent the in-plane retardation and the thickness retardation, respectively, at a wavelength λ. Unless otherwise specified, the wavelength λ is 550 nm. In the present invention, Re(λ) and Rth(λ) are values ​​measured at a wavelength λ using an AxoScan (manufactured by Axometrics). By inputting the average refractive index ((nx + ny + nz) / 3) and film thickness (d) into AxoScan, the following in-plane slow axis direction (°) is calculated: Re(λ) = R0(λ) Rth(λ) = ((nx + ny) / 2 - nz) × d. Note that R0(λ) is displayed as a numerical value calculated by AxoScan, but it means Re(λ).

[0013] In this specification, the refractive indices nx, ny, and nz are measured using an Abbe refractometer (NAR-4T, manufactured by Atago Co., Ltd.) with a sodium lamp (λ = 589 nm) as a light source. When measuring wavelength dependency, measurements can be made using a multi-wavelength Abbe refractometer DR-M2 (manufactured by Atago Co., Ltd.) in combination with an interference filter. Values ​​from the Polymer Handbook (John Wiley & Sons, Inc.) and catalogs of various optical films can also be used. Examples of average refractive index values ​​for major optical films are listed below: cellulose acylate (1.48), cycloolefin polymer (1.52), polycarbonate (1.59), polymethyl methacrylate (1.49), and polystyrene (1.59).

[0014] In this specification, A plates and C plates are defined as follows. There are two types of A plates: positive A plates (positive A plates) and negative A plates (negative A plates). When the refractive index in the in-plane slow axis direction of the film (the direction in which the in-plane refractive index is maximum) is nx, the refractive index in the direction perpendicular to the in-plane slow axis is ny, and the refractive index in the thickness direction is nz, the positive A plates satisfy the relationship of formula (A1), and the negative A plates satisfy the relationship of formula (A2). Note that the positive A plates have a positive Rth, and the negative A plates have a negative Rth. Formula (A1) nx>ny≒nz Formula (A2) ny<nx≒nz Note that the above "≒" encompasses not only the case where the two are completely identical, but also the case where the two are substantially identical. "Substantially the same" means, for example, that "ny ≒ nz" also includes cases where (ny - nz) x d (where d is the film thickness) is -10 to 10 nm, preferably -5 to 5 nm, and "nx ≒ nz" also includes cases where (nx - nz) x d is -10 to 10 nm, preferably -5 to 5 nm. There are two types of C plates: positive C plates (positive C plates) and negative C plates (negative C plates). Positive C plates satisfy the relationship of formula (C1), while negative C plates satisfy the relationship of formula (C2). Note that positive C plates have a negative Rth value, and negative C plates have a positive Rth value. Formula (C1) nz > nx ≒ ny Formula (C2) nz < nx ≒ ny Note that the above "≒" includes not only cases where the two are completely identical, but also cases where the two are substantially identical. The term "substantially the same" includes, for example, the case where (nx-ny) x d (where d is the thickness of the film) is 0 to 10 nm, preferably 0 to 5 nm, in "nx≈ny".

[0015] A characteristic feature of the laminate of the present invention is that the surface free energy of the optically absorbing anisotropic film and the surface free energy of the adhesive layer are adjusted so that the sum of the two is within a predetermined range. The inventors investigated the reasons for the aforementioned problem of color unevenness and poor display performance in display devices and found that the adhesion between the optically absorbing anisotropic film and the adhesive layer is an important factor. More specifically, they found that the cause of the color unevenness in display devices including a laminate comprising an optically absorbing anisotropic film and an adhesive layer is related to delamination between the optically absorbing anisotropic film and the adhesive layer. It is believed that delamination at the interface between the optically absorbing anisotropic film and the adhesive layer occurs when handling the laminate, such as during transportation or installation in a display device, resulting in worsening color unevenness in the display device. Therefore, in the present invention, the sum of the surface free energy of the optically absorbing anisotropic film and the surface free energy of the adhesive layer is adjusted to make the delamination less likely to occur, thereby suppressing the occurrence of color unevenness in the display device.

[0016] An example of a laminate of the present invention is shown in Figure 1. As shown in Figure 1, the laminate 10A includes an optically absorptive anisotropic film 12 and an adhesive layer 14. As will be described later, the laminate 10A may include other components in addition to the optically absorptive anisotropic film 12 and the adhesive layer 14. Below, first, the relationship between the surface free energy E1 of the surface 12S of the optically absorptive anisotropic film 12 facing the adhesive layer 14 and the surface free energy E2 of the surface 14S of the adhesive layer 14 facing the optically absorptive anisotropic film 12 will be described, and then each component will be described.

[0017] As shown in Figure 1, the surface free energy of the surface 12S of the optically absorptive anisotropic film 12 on the adhesive layer 14 side is defined as surface free energy E1, and the surface free energy of the surface 14S of the adhesive layer 14 on the optically absorptive anisotropic film 12 side is defined as surface free energy E2. The sum of the surface free energy E1 and the surface free energy E2 is 54.0 mNm －１Above all, when the laminate of the present invention is applied to a display device (particularly a virtual reality display device) and viewed, color unevenness is less likely to occur (hereinafter, also simply referred to as "the effect of the present invention is superior"), and the sum of the surface free energy E1 and the surface free energy E2 is 70.0 mNm －１ More than 80.0 mNm is preferable. －１ The upper limit of the sum of the surface free energy E1 and the surface free energy E2 is not particularly limited, and is 140.0 mNm or more. －１ In many cases, cracks are unlikely to occur in the laminate, and －１ Preferably, 110.0 mNm or less －１ The following is more preferable. The method for measuring the surface free energy is as follows. The surface free energy is measured with reference to D. K. Owens: J. Appl. Polym. Sci., 13, 1741 (1969) using pure water H ２ O and methylene iodide CH ２ I ２ and the respective contact angles θ Ｈ２Ｏ and θ ＣＨ２Ｉ２ From the above, it can be calculated by the following simultaneous equations (A) and (B). [Simultaneous equations] (A): 1 + cos θ Ｈ２Ｏ = 2(γ ｓ ｄ ) １／２ {(γ Ｈ２Ｏ ｄ ) １／２ / γ Ｈ２Ｏ ｖ}+2(γ ｓ ｈ ) １／２ {(γ Ｈ２Ｏ ｈ ) １／２ / γ Ｈ２Ｏ ｖ} (B):1+cosθ ＣＨ２Ｉ２ = 2(γ ｓ ｄ ) １／２ {(γ ＣＨ２Ｉ２ ｄ ) １／２ / γ ＣＨ２Ｉ２ ｖ}+2(γ ｓ ｈ ) １／２ {(γ ＣＨ２Ｉ２ｈ ) １／２ / γ ＣＨ２Ｉ２ ｖ γ Ｈ２Ｏ ｄ = 29.1, γ Ｈ２Ｏ ｈ = 43.7, γ Ｈ２Ｏ ｖ = 72.8, γ ＣＨ２Ｉ２ ｄ = 46.8, γ ＣＨ２Ｉ２ ｈ = 4.0, γ ＣＨ２Ｉ２ ｖ = 50.8 However, in the above simultaneous equations, γ ｓ ｄ is the dispersion force component of the surface free energy, and γ ｓ ｈ correspond to the hydrogen bond components of the surface free energy, and the sum of these is γ ｓ ｖ (=γ ｓ ｄ +γ ｓ ｈ The contact angle is measured using a contact angle meter (e.g., DropMaster 500 manufactured by Kyowa Interface Science Co., Ltd.) by conditioning the sample at 25°C and 60% humidity for 24 hours, and then dropping 10 μl of pure water and methylene iodide onto the sample surface under these conditions for 30 seconds.

[0018] The magnitude of the surface free energy E1 is not particularly limited as long as the sum of the surface free energy E1 and the surface free energy E2 is within a predetermined range, but is preferably 15.0 to 70.0 mNm －１ is preferred, and 20.0 to 60.0 mNm －１ The magnitude of the surface free energy E2 is not particularly limited as long as the sum of the surface free energy E1 and the surface free energy E2 is within a predetermined range, but is preferably 20.0 to 80.0 mNm －１ is preferred, and 30.0 to 70.0 mNm －１ is more preferred.

[0019] The method for adjusting the sum of the surface free energy E1 and the surface free energy E2 is not particularly limited, and known methods can be used. For example, a method of adjusting the properties of a surfactant contained in the optically absorbing anisotropic film can be used. Since the surfactant contained in the optically absorbing anisotropic film tends to be unevenly distributed on the surface of the optically absorbing anisotropic film, the surface free energy E1 can be adjusted by adjusting the properties of the surfactant (e.g., the Log P value of the surfactant), thereby adjusting the total magnitude of the surface free energy E1 and the surface free energy E2. Furthermore, the surface of the optically absorbing anisotropic film on the adhesive layer side can be subjected to a surface activation treatment (e.g., corona treatment, plasma treatment, etc.) to adjust the surface free energy E1, thereby adjusting the total magnitude of the surface free energy E1 and the surface free energy E2. In addition to the above, a method of adjusting the materials contained in the optically absorbing anisotropic film and the adhesive layer can be used.

[0020] Each member of the laminate will be described in detail below.

[0021] [Light-Absorption Anisotropic Film] The light-absorption anisotropic film can function as a linear polarizer that transmits linearly polarized light in a certain direction and absorbs linearly polarized light in a direction perpendicular to the linearly polarized light.

[0022] The optically absorptive anisotropic film contains an organic dichroic dye. The organic dichroic dye refers to an organic dye whose absorbance varies depending on the direction. The organic dichroic dye may be fixed in the optically absorptive anisotropic film. The optically absorptive anisotropic film may contain one type of organic dichroic dye alone or multiple types of organic dichroic dyes. In particular, it is preferable that the optically absorptive anisotropic film contains four or more types of organic dichroic dyes, as this provides better effects of the present invention. There is no particular upper limit on the number of organic dichroic dyes contained in the optically absorptive anisotropic film, and six or fewer types are preferred.

[0023] As the organic dichroic dye, a dichroic azo dye compound is preferred. A dichroic azo dye compound refers to an azo dye compound whose absorbance varies depending on the direction. A dichroic azo dye compound may or may not exhibit liquid crystallinity. When a dichroic azo dye compound exhibits liquid crystallinity, it may exhibit either nematic or smectic properties. The temperature range in which the liquid crystal phase is exhibited is preferably room temperature (approximately 20 to 28°C) to 300°C, and more preferably 50 to 200°C from the viewpoints of handleability and manufacturing suitability.

[0024] In the present invention, from the viewpoint of adjusting color hue, it is preferable to use at least one dye compound having a maximum absorption wavelength in the wavelength range of 560 to 700 nm (hereinafter also abbreviated as "first dichroic azo dye compound") and at least one dye compound having a maximum absorption wavelength in the wavelength range of 455 nm or more and less than 560 nm (hereinafter also abbreviated as "second dichroic azo dye compound").

[0025] In the present invention, three or more kinds of dichroic azo dye compounds may be used in combination. For example, from the viewpoint of making the absorptive polarizer closer to black, it is preferable to use a first dichroic azo dye compound, a second dichroic azo dye compound, and at least one dye compound having a maximum absorption wavelength in the wavelength range of 380 nm or more and less than 455 nm (hereinafter also abbreviated as "third dichroic azo dye compound") in combination. Among these, it is preferable to use at least one kind of the first dichroic azo dye compound, at least one kind of the second dichroic azo dye compound, and at least one kind of the third dichroic azo dye compound, and to use four or more kinds of the first dichroic azo dye compound, the second dichroic azo dye compound, and the third dichroic azo dye compound in total.

[0026] Examples of organic dichroic dyes that can be used in the present invention include those described in WO 2018 / 186503, WO 2019 / 189345, and WO 2018 / 124198.

[0027] The content of the organic dichroic dye is preferably 1% by mass or more, more preferably 5% by mass or more, and even more preferably 10% by mass or more, based on the total mass of the optical absorption anisotropic film. There is no upper limit, but the content is preferably 30% by mass or less, more preferably 25% by mass or less, and even more preferably 20% by mass or less.

[0028] The optically absorptive anisotropic film preferably contains a liquid crystal compound and an organic dichroic dye, and is preferably an optically absorptive anisotropic film that can be formed by coating a composition containing a liquid crystal compound and an organic dichroic dye.

[0029] As the liquid crystal compound, either a polymer liquid crystal compound or a low molecular weight liquid crystal compound can be used, with the polymer liquid crystal compound being preferred because it can increase the degree of orientation. Furthermore, as the liquid crystal compound, a polymer liquid crystal compound and a low molecular weight liquid crystal compound may be used in combination. The liquid crystal compound may be fixed in the light absorption anisotropic film. Here, "polymer liquid crystal compound" refers to a liquid crystal compound having a repeating unit in its chemical structure. Furthermore, "low molecular weight liquid crystal compound" refers to a liquid crystal compound not having a repeating unit in its chemical structure.

[0030] The low-molecular-weight liquid crystal compound is not particularly limited, but examples thereof include compounds exhibiting a nematic liquid crystal phase and compounds exhibiting a smectic liquid crystal phase, and from the viewpoint of increasing the degree of orientation, compounds exhibiting a smectic liquid crystal phase are preferred. For example, the liquid crystal compounds described in JP-A-2013-228706 can be mentioned.

[0031] Examples of the polymer liquid crystal compound include the thermotropic liquid crystalline polymer described in JP 2011-237513 A. When the light absorption anisotropic film contains a polymer liquid crystal compound, the polymer liquid crystal compound preferably forms a nematic liquid crystal phase. The temperature range in which the nematic liquid crystal phase is exhibited is preferably room temperature (23°C) to 450°C, and from the viewpoints of handling and manufacturing suitability, preferably 50 to 400°C.

[0032] The content of the liquid crystal compound in the optically absorptive anisotropic film is preferably 25 to 2,000 parts by mass, more preferably 100 to 1,300 parts by mass, and even more preferably 200 to 900 parts by mass, relative to 100 parts by mass of the organic dichroic dye. When the content of the liquid crystal compound is within the above range, the degree of orientation of the organic dichroic dye is further improved. The liquid crystal compound may be contained alone, or two or more types may be contained. When two or more types of liquid crystal compounds are contained, the content of the liquid crystal compounds refers to the total content of the liquid crystal compounds.

[0033] In addition to the above-mentioned components, the optically absorptive anisotropic film may contain surfactants, adhesion improvers, plasticizers, etc. The type of surfactant is not particularly limited, and known surfactants can be used. The Log P value of the surfactant is not particularly limited and is often 5.0 or less. In terms of better effects of the present invention, the Log P value of the surfactant is preferably 4.0 or less, more preferably 3.0 or less. The lower limit of the Log P value of the surfactant is not particularly limited, but 1.0 or more is preferred. Here, the Log P value is an index that expresses the hydrophilic and hydrophobic properties of a chemical structure and is sometimes called the hydrophilicity / hydrophobicity parameter. The Log P value can be calculated using software such as ChemBioDraw Ultra or HSPiP (Ver. 4.1.07). The OECD Guidelines for the Testing of Chemicals, Section 1, Test No. It can also be experimentally determined by the method of 117. In the present invention, unless otherwise specified, the LogP value is calculated by inputting the structural formula of the compound into HSPiP (Ver. 4.1.07).

[0034] Examples of surfactants include fluorine (meth)acrylate polymers described in paragraphs

[0018] to

[0043] of JP 2007-272185 A and silicon-containing polymers described in paragraphs

[0019] to

[0073] of WO 2023 / 054164 A. Compounds other than these may also be used as surfactants. One surfactant may be used alone, or two or more surfactants may be used in combination. When the optically absorptive anisotropic film contains a surfactant, the content of the surfactant is preferably 0.01 to 10% by mass, more preferably 0.02 to 5% by mass, based on the total solid mass of the optically absorptive anisotropic film.

[0035] Examples of adhesion improvers include the reactive additives listed in paragraphs

[0123] to

[0129] of JP 2019-091088 A and the boronic acid monomers listed in paragraphs

[0015] to

[0028] of WO 2015 / 053359 A.

[0036] In an optically absorptive anisotropic film, it is more preferable to align the organic dichroic dye by utilizing the orientation of the liquid crystal compound. That is, by utilizing the technology of a guest-host liquid crystal cell, the organic dichroic dye can be aligned as desired in association with the orientation of the host liquid crystal. Specifically, an optically absorptive anisotropic film can be produced by mixing the organic dichroic dye as a guest with a liquid crystal compound as a host liquid crystal, orienting the host liquid crystal, and aligning the organic dichroic dye along the orientation of the liquid crystal molecules, and then fixing the alignment state. Note that the orientation direction of the organic dichroic dye can be, for example, a direction parallel to the surface of the optically absorptive anisotropic film.

[0037] The thickness of the optically absorptive anisotropic film is not particularly limited, and is often 50.0 μm or less. In terms of the effects of the present invention being more excellent, the thickness is preferably 10.0 μm or less, and more preferably 5.0 μm or less. The lower limit is not particularly limited, but may be 0.1 μm or more.

[0038] [Adhesive Layer] Examples of adhesives constituting the adhesive layer include pressure-sensitive adhesives and adhesives. Examples of adhesives include rubber-based adhesives, acrylic-based adhesives, silicone-based adhesives, urethane-based adhesives, vinyl alkyl ether-based adhesives, polyvinyl alcohol-based adhesives, polyvinylpyrrolidone-based adhesives, polyacrylamide-based adhesives, and cellulose-based adhesives. Acrylic-based adhesives and polyvinyl alcohol-based adhesives are preferred, and polyvinyl alcohol-based adhesives are more preferred. Examples of adhesives include aqueous adhesives, solvent-based adhesives, emulsion-based adhesives, solventless adhesives, active energy ray-curable adhesives, and heat-curable adhesives. Examples of active energy ray-curable adhesives include electron beam-curable adhesives, ultraviolet-curable adhesives, and visible light-curable adhesives, with ultraviolet-curable adhesives being preferred.

[0039]

[0044] The Log P value of the adhesive layer is not particularly limited, and is often 1.5 or less, and is preferably 0.5 or less in terms of providing better effects of the present invention. The lower limit of the Log P value of the adhesive layer is not particularly limited, and is often -2.0 or more. The Log P value of the adhesive layer is calculated as the weight average value of the Log P values ​​of each component contained in the adhesive layer. For example, when the adhesive layer contains component A, which has a Log P value of X and is contained in an amount of 80 mass% relative to the total mass of the adhesive layer, and component B, which has a Log P value of Y and is contained in an amount of 20 mass% relative to the total mass of the adhesive layer, the Log P value of the adhesive layer is calculated as (X x 0.8) + (Y x 0.2).

[0040] The thickness of the adhesive layer is not particularly limited, but is often 20 μm or less, and is preferably 13.0 μm or less, more preferably 7.5 μm or less, in terms of achieving better effects of the present invention. The lower limit is not particularly limited, and is often 0.05 μm or more.

[0041] The laminate of the present invention may include other components in addition to the optically absorptive anisotropic film and adhesive layer described above. The laminate of the present invention may further include an adjacent layer disposed adjacent to the adhesive layer on the side of the adhesive layer opposite the optically absorptive anisotropic film side. The modulus of elasticity of the adjacent layer is not particularly limited, but is preferably 100 MPa or more, and more preferably 500 MPa or more, in terms of achieving superior effects of the present invention. The modulus of elasticity of the adjacent layer is not particularly limited, but is often 20 GPa or less, and more often 10 GPa or less. Examples of the adjacent layer include a retardation layer and a reflective polarizer, which will be described in detail later. The modulus of elasticity refers to the value obtained by measuring the indentation modulus of the surface of a test specimen using a microhardness evaluation device (e.g., a nanotriboindenter TI-950 manufactured by Bruker) under the following conditions: Indenter: triangular pyramidal diamond indenter (Berkovich indenter, interior angle of indenter: 142.35°, angle between center line and face: 65.35°) Maximum indentation depth of indenter: 500 nm Measurement temperature: 23°C

[0042] The laminate may further include an alignment film disposed adjacent to the optically absorptive anisotropic film on the side opposite to the adhesive layer side of the optically absorptive anisotropic film. When the optically absorptive anisotropic film contains a liquid crystal compound, the alignment film may be provided to control the alignment of the compound.

[0043] Alignment films can be formed by such means as rubbing an organic compound (preferably a polymer), oblique deposition of an inorganic compound, formation of a layer with microgrooves, or deposition of an organic compound (e.g., ω-tricosanoic acid, dioctadecylmethylammonium chloride, methyl stearate) by the Langmuir-Blodgett method (LB film). Furthermore, alignment films that exhibit alignment function upon application of an electric field, a magnetic field, or light irradiation (preferably polarized light) are also known.

[0044] The alignment film is preferably a photo-alignment film. The photo-alignment film is a film containing a compound having a photo-alignment group, and is a film that can be imparted with an alignment control force by exposure. Examples of the compound having a photo-alignment group include azo compounds, cinnamate compounds, chalcone compounds, and coumarin compounds.

[0045] The thickness of the alignment film is not particularly limited as long as it can exhibit the alignment function, but is preferably 0.01 to 5.0 μm, more preferably 0.05 to 2.0 μm.

[0046] Figure 2 shows another example of the laminate of the present invention. As shown in Figure 2, the laminate 10B includes an optically absorptive anisotropic film 12, an adhesive layer 14, and a retardation layer 16. Depending on the type of retardation layer 16, the laminate 10B can be used as a so-called circularly polarizing plate. The structures of the optically absorptive anisotropic film 12 and the adhesive layer 14 are as described above. The structure of the retardation layer will be described in detail below.

[0047] [Retardation Layer] The laminate of the present invention may include a retardation layer. The type of retardation layer is not particularly limited, but for example, the retardation layer may include a λ / 4 plate. A λ / 4 plate is a plate having a λ / 4 function, specifically, a plate having the function of converting linearly polarized light of a certain wavelength (preferably visible light) into circularly polarized light (or circularly polarized light into linearly polarized light). The in-plane retardation of the λ / 4 plate at a wavelength of 550 nm is not particularly limited, but is preferably 120 to 150 nm, more preferably 125 to 145 nm, and even more preferably 135 to 140 nm. In addition to λ / 4 plates, retardation layers whose in-plane retardation at a wavelength of 550 nm is 3 / 4 or 5 / 4 of the wavelength of any light in visible light are also preferred. The retardation layer may have reverse wavelength dispersion. Having reverse wavelength dispersion means that the value of retardation at that wavelength increases as the wavelength increases. The retardation layer may have a multi-layer structure, and a specific example of such a structure is a broadband λ / 4 plate formed by laminating a λ / 4 plate and a λ / 2 plate. The angle between the in-plane slow axis of the retardation layer and the absorption axis of the optically absorptive anisotropic film is not particularly limited, but is preferably within the range of 45°±10°.

[0048] The retardation layer may be a layer formed by fixing a liquid crystal compound that is twisted and aligned with the thickness direction as a helical axis. For example, as disclosed in Japanese Patent No. 5753922 and Japanese Patent No. 5960743, there may be mentioned a retardation layer having a layer formed by fixing a rod-shaped liquid crystal compound or a discotic liquid crystal compound that is twisted and aligned with the thickness direction as a helical axis.

[0049] The retardation layer may include a positive A plate. The in-plane retardation of the positive A plate at a wavelength of 550 nm is not particularly limited, but is preferably 120 to 150 nm, more preferably 125 to 145 nm, and even more preferably 135 to 140 nm. The positive A plate preferably functions as the above-mentioned λ / 4 plate.

[0050] The retardation layer may include a positive C plate. A positive C plate is a retardation layer having an in-plane retardation of substantially zero and a negative retardation in the thickness direction. The positive C plate functions as an optical compensation layer for increasing the degree of polarization of transmitted light with respect to obliquely incident light. The in-plane retardation of the positive C plate at a wavelength of 550 nm is preferably 10 nm or less. The retardation of the positive C plate in the thickness direction at a wavelength of 550 nm is preferably −600 to −40 nm.

[0051] The material constituting the retardation layer is not particularly limited, but it is preferably formed from a composition containing a liquid crystal compound. Such a retardation layer can typically be obtained by vertically aligning a rod-shaped polymerizable liquid crystal compound contained in a polymerizable liquid crystal composition and fixing the alignment state by polymerization. Alternatively, it can also be formed from a composition containing a side-chain polymer liquid crystal compound as the liquid crystal compound.

[0052] The thickness of the retardation layer is not particularly limited, but is preferably 0.1 to 8 μm, more preferably 0.3 to 5 μm.

[0053] Figure 3 shows another example of a laminate of the present invention. As shown in Figure 3, the laminate 10C includes an optically absorptive anisotropic film 12, an adhesive layer 14, a reflective polarizer 18, and a retardation layer 20. The retardation layer 20 includes a positive A plate 22 and a positive C plate 24. The laminate 10C can be used as a component of a virtual reality display device, which will be described later. The optically absorptive anisotropic film 12 and the adhesive layer 14 are configured as described above. Examples of the configurations of the positive A plate 22 and the positive C plate 24 included in the retardation layer 20 include the configurations described for the retardation layer included in the laminate 10B of Figure 2 above. The configuration of the reflective polarizer 18 will be described in detail below.

[0054] [Reflective Polarizer] A reflective polarizer (reflective linear polarizer) is a linear polarizer that transmits linearly polarized light in a certain direction and reflects linearly polarized light in a direction perpendicular to the linearly polarized light. Any known reflective polarizer (reflective linear polarizer) can be used as the reflective polarizer as long as it selectively transmits linearly polarized light in a certain direction in the wavelength range of visible light. Examples of reflective polarizers include a film obtained by stretching a dielectric multilayer film as described in JP 2011-053705 A and a wire grid polarizer. Commercially available reflective polarizers can also be suitably used. Examples of commercially available reflective polarizers include a reflective polarizer (product name APF) manufactured by 3M and a wire grid polarizer (product name WGF) manufactured by AGC.

[0055] [Other Members] The laminate of the present invention may contain other members in addition to the various members described above. The other members are not particularly limited, and examples thereof include an adhesive layer other than the adhesive layer disposed adjacent to the light absorption anisotropic film, a front-surface antireflection layer, and a support.

[0056] <Other adhesive layer> The laminate of the present invention may include an adhesive layer other than the adhesive layer arranged adjacent to the optically absorptive anisotropic film in order to enhance adhesion between the respective members. An example of the configuration of the other adhesive layer is the configuration of the adhesive layer arranged adjacent to the optically absorptive anisotropic film.

[0057] <Surface Antireflection Layer> The laminate of the present invention may include a surface antireflection layer. In the laminate of the present invention, the surface antireflection layer is preferably disposed on the surface-most side. The surface antireflection layer may be disposed on only one surface side of the laminate, or on both surfaces. The type of surface antireflection layer is not particularly limited, but from the viewpoint of further reducing the reflectance, moth-eye films and AR (anti-reflection) films are preferred. Furthermore, moth-eye films are preferred because they can maintain high antireflection performance even when the film thickness varies due to stretching and molding.

[0058] <Support> The laminate of the present invention may include a support. The type of support is not particularly limited, but it is preferably transparent. Examples include films of cellulose acylate, polycarbonate, polysulfone, polyethersulfone, polyacrylate, polymethacrylate, cyclic polyolefin, polyolefin, polyamide, polystyrene, and polyester. Among these, a cellulose acylate film, a cyclic polyolefin film, a polyacrylate film, or a polymethacrylate film is preferred as the support. Commercially available cellulose acetate films (e.g., "TD80U" or "Z-TAC" manufactured by Fujifilm Corporation) can also be used. Furthermore, it is preferable that the support have a small phase difference. Specifically, the in-plane retardation at a wavelength of 550 nm is preferably 10 nm or less, and the absolute value of the retardation in the thickness direction at a wavelength of 550 nm is preferably 50 nm or less.

[0059] The thickness of the support is not particularly limited, but is preferably from 5 to 300 μm, more preferably from 5 to 100 μm.

[0060] The laminate of the present invention may have a non-planar shape (for example, a curved structure) in part of its structure.

[0061] [Method for manufacturing the laminate] The method for manufacturing the laminate described above is not particularly limited, and known methods can be used. As described above, in order to adjust the surface free energy E1 and the surface free energy E2, the surface of the optically absorptive anisotropic film may be subjected to a surface activation treatment before providing an adhesive layer on the optically absorptive anisotropic film. Examples of surface activation treatments include corona treatment and plasma treatment. The treatment conditions are optimally selected depending on the materials used.

[0062]

[0023] Examples of methods for producing the laminate of the present invention include a method in which an optically absorbing anisotropic film is produced and then a pressure-sensitive adhesive layer is provided on the surface of the optically absorbing anisotropic film. The method for producing an optically absorbing anisotropic film includes the following steps 1 to 3: Step 1: Forming an alignment film on a support; Step 2: Applying a composition containing a liquid crystal compound and an organic dichroic dye to the alignment film obtained in step 1, thereby orienting the liquid crystal compound, thereby obtaining an optically absorbing anisotropic film; Step 3: Forming a pressure-sensitive adhesive layer on the surface of the optically absorbing anisotropic film, thereby obtaining a laminate. The procedures of the above steps are described in detail below.

[0063] Step 1 is a step of forming an alignment film on a support. The support and alignment film used are as described above. Among them, a photo-alignment film is preferable as the alignment film. The procedure for forming the photo-alignment film on a support is not particularly limited, and examples thereof include a method of applying a composition containing a photo-alignment material to a support to form a coating film, and irradiating the resulting coating film with polarized light.

[0064] Step 2 is a step of applying a composition containing a liquid crystal compound and an organic dichroic dye onto the alignment film obtained in step 1, thereby aligning the liquid crystal compound to obtain an optically absorptive anisotropic film. The liquid crystal compound and organic dichroic dye used in the composition are as described above. The composition may further contain a solvent. When at least one of the liquid crystal compound and the organic dichroic dye has a polymerizable group, the composition may further contain a polymerization initiator.

[0065] Examples of methods for applying the composition include known methods such as roll coating, gravure printing, spin coating, wire bar coating, extrusion coating, direct gravure coating, reverse gravure coating, die coating, spraying, and inkjet printing.

[0066] Next, a treatment for aligning the liquid crystal compound in the coating film is carried out. The alignment treatment may include a drying treatment. By the drying treatment, components such as the solvent can be removed from the coating film. The drying treatment may be carried out by leaving the coating film at room temperature for a predetermined time (for example, natural drying), or by heating and / or blowing air.

[0067] The alignment treatment preferably includes a heat treatment, which allows the liquid crystal compound contained in the coating film to be aligned. From the viewpoint of manufacturability, the heat treatment is preferably performed at 35 to 250°C, more preferably 45 to 190°C. The heating time is preferably 1 to 300 seconds, more preferably 1 to 60 seconds.

[0068] The alignment treatment may include a cooling treatment carried out after the heating treatment. The cooling treatment is a treatment for cooling the coating film after heating. This can fix the alignment of the liquid crystal compound contained in the coating film. The cooling method is not particularly limited and can be carried out by a known method. The optimal cooling temperature is selected depending on the liquid crystal compound used.

[0069] When the liquid crystal compound has a polymerizable group, it may be subjected to a curing treatment, such as a light irradiation treatment, if necessary.

[0070] Step 3 is a step of forming a tacky adhesive layer on the surface of the optically absorbing anisotropic film to obtain a laminate. The method of forming the tacky adhesive layer on the surface of the optically absorbing anisotropic film is not particularly limited, and examples thereof include a method of laminating a tacky adhesive layer on the surface of the optically absorbing anisotropic film, and a method of applying a tacky adhesive layer-forming composition on the surface of the optically absorbing anisotropic film to form a tacky adhesive layer.

[0071] In order to give the laminate a curved shape, the laminate may be subjected to various molding processes as necessary.

[0072] [Composite Lens] The composite lens of the present invention includes the above-described laminate, a lens, and a half mirror. Figure 4 shows an example of the composite lens of the present invention. The composite lens 30 includes, in this order, a laminate 10C, a lens 32, and a half mirror 34. The configuration of the laminate 10C is as described above. Below, the components included in the composite lens other than the laminate will be described in detail.

[0073] <Lens> A compound lens has a lens. Examples of lenses include convex lenses and concave lenses. Examples of convex lenses include biconvex lenses, plano-convex lenses, and convex meniscus lenses. Examples of concave lenses include biconcave lenses, plano-concave lenses, and concave meniscus lenses. As lenses used in virtual reality display devices, convex meniscus lenses or concave meniscus lenses are preferred in terms of expanding the viewing angle, and concave meniscus lenses are more preferred in terms of minimizing chromatic aberration. Lens materials that are transparent to visible light, such as glass, crystal, and plastic, can be used. Since birefringence in lenses can cause rainbow unevenness and light leakage, the smaller the birefringence, the more preferable, and materials with zero birefringence are more preferred.

[0074] <Half Mirror> The composite lens of the present invention has a half mirror. The half mirror is a conventionally known half mirror that transmits approximately half of incident light and reflects the remaining approximately half. The transmittance of the half mirror is preferably 50±30%, more preferably 50±10%. The type of half mirror is not particularly limited, but examples include a reflective layer made of a metal. Examples of metals include silver and aluminum. The thickness of the half mirror is preferably 1 to 20 nm, more preferably 2 to 10 nm, and even more preferably 3 to 6 nm.

[0075] [Display Device (Virtual Reality Display Device)] The laminate of the present invention is applicable to various display devices, and is preferably applied to a virtual reality display device. Fig. 5 is a schematic diagram showing an example of the configuration of a virtual reality display device. The virtual reality display device 40 shown in Fig. 5 includes, from the right side in the figure, an image display panel 42, a circular polarizer 44, and a composite lens 30. Note that the composite lens 30 used in Fig. 5 has the same configuration as the composite lens 30 shown in Fig. 4.

[0076] In the virtual reality display device 40 shown in FIG. 5 , light emitted from the image display panel 42 passes through a circular polarizer 44, becomes circularly polarized light, and then passes through the half mirror 34. It then passes through the positive A plate included in the laminate 10C, becomes linearly polarized light, and is incident on the reflective polarizer side included in the laminate 10C and reflected. The light reflected by the reflective polarizer passes through the positive A plate, becomes circularly polarized light, is reflected by the half mirror 34, passes through the positive A plate again, becomes linearly polarized light, and then re-enters the reflective polarizer. At this time, the polarization state of the light re-entering the reflective polarizer remains unchanged when reflected by the reflective polarizer. However, when reflected by the half mirror 34 and passes through the positive A plate, it changes to linearly polarized light that is orthogonal to the linearly polarized light that initially entered the reflective polarizer. Therefore, the light passes through the reflective polarizer and is visible to the user.

[0077] The image display panel 42 is a known image display panel (display panel) such as an organic electroluminescence display panel. In the illustrated example, the image display panel 42 emits an unpolarized image (image light). The unpolarized image emitted by the image display panel 42 passes through the circular polarizer 44 and is converted into circularly polarized light.

[0078] The features of the present invention will be explained in more detail below with reference to examples. Note that the materials, amounts used, ratios, processing details, and processing procedures shown below can be changed as appropriate without departing from the spirit of the present invention. Furthermore, configurations other than those shown below can also be used without departing from the spirit of the present invention.

[0079] [Preparation of Optically Absorbent Anisotropic Film C1] <Preparation of Support> The following composition was placed in a mixing tank, stirred, and 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 dope. The solids concentration of the dope was 23.5% by mass, the amount of plasticizer added was the ratio relative to the cellulose acylate, and the solvent for the dope was methylene chloride / methanol / butanol = 81 / 18 / 1 (mass ratio).

[0080] ------------------------------------------------ Cellulose acylate dope -------------------------------------------------- Cellulose acylate (acetyl substitution degree 2.86, viscosity average degree of polymerization 310) 100 parts by mass Sugar ester compound 1 (formula (S4) below) 6.0 parts by mass 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 part by mass Solvent (methylene chloride / methanol / butanol) 351.9 parts by mass --------------------------------------------------

[0081]

[0082]

[0083] The dope prepared above was cast using a drum film-forming machine. The dope was cast from a die onto a metal support cooled to 0°C, and the resulting web (film) was then peeled off from the drum. The drum was made of SUS (stainless steel).

[0084] The web (film) obtained by casting was peeled from the drum and then dried for 20 minutes in a tenter apparatus, in which both ends of the web were clipped with clips while the film was being transported at 30 to 40°C. Subsequently, the web was post-dried by zone heating while being transported with a roll. The obtained web was knurled and then wound up to give cellulose acylate film A1. The obtained cellulose acylate film A1 had a 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.

[0085] <Formation of Photo-Alignment Film B1> A composition B1 for forming a photo-alignment film, which will be described later, was continuously applied onto the cellulose acylate film A1 using a wire bar. The cellulose acylate film A1 on which the coating film was formed was dried with hot air at 140°C for 120 seconds, and then the coating film was irradiated with polarized ultraviolet light (10 mJ / cm ２ A photo-alignment film B1 was formed by irradiating the substrate with a TAC (triacetyl cellulose) film having a photo-alignment film B1. The photo-alignment film B1 had a thickness of 1.5 μm. ------------------------------------------------ Composition of composition B1 for forming a photo-alignment film------------------------------------------------ Photo-alignment compound PA-1 below: 100.00 parts by mass EPICLON N-695 (manufactured by DIC Corporation) 55.74 parts by mass jER YX7400 (manufactured by Mitsubishi Chemical Corporation) 18.75 parts by mass Polymerizable polymer PA-2 below: 8.01 parts by mass Thermal cationic polymerization initiator PAG-1 below: 16.75 parts by mass Stabilizer DIPEA below: 1.06 parts by mass Butyl acetate 1230.49 parts by mass

[0086] Photoalignment compound PA-1 (wherein the numerical value for each repeating unit represents the content (mass%) of each repeating unit relative to all repeating units; weight average molecular weight: 32,000)

[0087]

[0088] Polymerizable polymer PA-2 (wherein the numerical values ​​a, b, and c represent the content (mass%) of each repeating unit relative to the total repeating units; weight average molecular weight: 18,000)

[0089]

[0090] Thermal cationic polymerization initiator PAG-1

[0091]

[0092] Stabilizer DIPEA

[0093]

[0094] <Formation of Optically Absorbent Anisotropic Film C1> A composition for forming an optically absorbent anisotropic film C1 having the following composition was applied to the obtained photo-alignment film B1 using a wire bar to form a coating film. Next, the coating film was heated at 140°C for 15 seconds (first heating step), subsequently heat-treated at 80°C for 5 seconds, and then cooled to room temperature (25°C). Next, the coating film was heated at 75°C for 15 seconds (second heating step), and again cooled to room temperature. Thereafter, an LED (light emitting diode) lamp (center wavelength 365 nm) was used to heat the coating film at an illuminance of 200 mW / cm. ２ The optically absorptive anisotropic film C1 (polarizer) having a thickness of 1.0 μm was produced on the photo-alignment film B1 by irradiating the film with light for 2 seconds under the irradiation conditions of (1) above. The transmittance of the optically absorptive anisotropic film C1 in the wavelength range of 380 to 780 nm was measured using a spectrophotometer, and the average visible light transmittance was found to be 43%. The absorption axis of the optically absorptive anisotropic film C1 was in the plane of the optically absorptive anisotropic film C1 and was perpendicular to the width direction of the cellulose acylate film A1.

[0095] 0.08 parts by mass of organic dichroic dye Dye-C1 below; 0.25 parts by mass of organic dichroic dye Dye-C2 below; 1.43 parts by mass of liquid crystal compound L-1 below; 0.61 parts by mass of liquid crystal compound L-2 below; 0.04 parts by mass of adhesion improver A-1 below; 0.08 parts by mass of polymerization initiator IRGACUREOXE-02 (manufactured by BASF); 0.08 parts by mass of surfactant F-1 below; 94.96 parts by mass of cyclopentanone; Benzyl alcohol 2.43 parts by mass ――――――――――――――――――――――――――――――

[0096] Organic dichroic dye Dye-Y1

[0097]

[0098] Organic dichroic dye Dye-M1

[0099]

[0100] Organic dichroic dye Dye-C1

[0101]

[0102] Organic dichroic dye Dye-C2

[0103]

[0104] Liquid crystal compound L-1 (In the formula below, the numerical values ​​("59", "15", "26") shown for each repeating unit represent the content (% by mass) of each repeating unit relative to all repeating units. Weight average molecular weight: 18,000)

[0105]

[0106] Liquid crystal compound L-2

[0107]

[0108] Adhesion improver A-1

[0109]

[0110] Surfactant F-1 (wherein the numerical value for each repeating unit represents the content (% by mass) of each repeating unit relative to all repeating units; weight average molecular weight: 16,000)

[0111]

[0112] [Preparation of Optically Absorbent Anisotropic Film C2] Optically absorptive anisotropic film C2 was prepared in the same manner as in [Preparation of Optically Absorbent Anisotropic Film C1], except that the following optically absorptive anisotropic film-forming composition C2 was used instead of the optically absorptive anisotropic film-forming composition C1.

[0113] 0.08 parts by mass of the organic dichroic dye Dye-C1; 0.25 parts by mass of the organic dichroic dye Dye-C2; 1.43 parts by mass of the liquid crystal compound L-1; 0.61 parts by mass of the liquid crystal compound L-2; 0.04 parts by mass of the adhesion improver A-1; 0.08 parts by mass of polymerization initiator IRGACUREOXE-02 (manufactured by BASF); 0.08 parts by mass of surfactant F-2 (listed below); 94.96 parts by mass of cyclopentanone; 2.43 parts by mass ――――――――――――――――――――――――――――――

[0114] Surfactant F-2 (wherein the numerical value for each repeating unit represents the content (% by mass) of each repeating unit relative to all repeating units; weight average molecular weight: 15,000)

[0115]

[0116] [Preparation of Optically Absorbent Anisotropic Film C3] Optically absorptive anisotropic film C3 was prepared in the same manner as in [Preparation of Optically Absorbent Anisotropic Film C1], except that the following optically absorptive anisotropic film-forming composition C3 was used instead of the optically absorptive anisotropic film-forming composition C1.

[0117] 0.08 parts by mass of the organic dichroic dye Dye-C1; 0.25 parts by mass of the organic dichroic dye Dye-C2; 1.43 parts by mass of the liquid crystal compound L-1; 0.61 parts by mass of the liquid crystal compound L-2; 0.04 parts by mass of the adhesion improver A-1; 0.08 parts by mass of polymerization initiator IRGACUREOXE-02 (manufactured by BASF); 0.08 parts by mass of surfactant F-3 (listed below); 94.96 parts by mass of cyclopentanone; 2.43 parts by mass ――――――――――――――――――――――――――――――

[0118] Surfactant F-3 (wherein the numerical value for each repeating unit represents the content (% by mass) of each repeating unit relative to all repeating units; weight average molecular weight: 15,000)

[0119]

[0120] [Preparation of Optically Absorbent Anisotropic Film C4] Optically absorptive anisotropic film C4 was prepared in the same manner as in [Preparation of Optically Absorbent Anisotropic Film C1], except that the following optically absorptive anisotropic film-forming composition C4 was used instead of the optically absorptive anisotropic film-forming composition C1.

[0121] 0.04 parts by mass of the adhesion improver A-1; 0.08 parts by mass of the organic dichroic dye Dye-Y1; 0.013 parts by mass of the organic dichroic dye Dye-M1; 0.08 parts by mass of the organic dichroic dye Dye-C1; 1.43 parts by mass of the liquid crystal compound L-1; 0.61 parts by mass of the liquid crystal compound L-2; 0.04 parts by mass of the adhesion improver A-1; 0.08 parts by mass of polymerization initiator IRGACUREOXE-02 (manufactured by BASF); 0.007 parts by mass of the surfactant F-1; 94.96 parts by mass of cyclopentanone; 2.43 parts by mass of benzyl alcohol

[0122] [Preparation of Optically Absorbent Anisotropic Film C5] Optically absorptive anisotropic film C5 was prepared in the same manner as in [Preparation of Optically Absorbent Anisotropic Film C1], except that the following optically absorptive anisotropic film-forming composition C5 was used instead of the optically absorptive anisotropic film-forming composition C1.

[0123] 0.08 parts by mass of the organic dichroic dye Dye-C1; 0.25 parts by mass of the organic dichroic dye Dye-C2; 1.53 parts by mass of the following liquid crystal compound L-3; 0.51 parts by mass of the following liquid crystal compound L-4; 0.04 parts by mass of the above adhesion improver A-1; 0.08 parts by mass of polymerization initiator IRGACUREOXE-02 (manufactured by BASF); 0.08 parts by mass of the above surfactant F-1; 94.96 parts by mass of cyclopentanone; 2.43 parts by mass ――――――――――――――――――――――――――――――

[0124] Liquid crystal compound L-3

[0125]

[0126] Liquid crystal compound L-4

[0127]

[0128] [Preparation of Optically Absorbent Anisotropic Film C6] An integrated absorption-reflection polarizer corresponding to optically absorptive anisotropic film C6 was prepared according to the description in paragraphs 0031 to 0032 of JP-A No. 2018-521349.

[0129] [Example 1 (Preparation of Laminate and Composite Lens)] <Preparation of Retardation Layer Film 1 Having Positive A Plate> A coating solution E1 for forming a photo-alignment film having the following composition was continuously coated on the above-mentioned cellulose acylate film A1 using a wire bar. The cellulose acylate film A1 on which the coating film was formed was dried with hot air at 140°C for 120 seconds, and then the coating film was irradiated with polarized ultraviolet light (10 mJ / cm ２, using an ultra-high pressure mercury lamp) to form a photo-alignment film E1 having a thickness of 0.2 μm, thereby obtaining a TAC film with a photo-alignment film.

[0130] -------------------------------------------------- Coating liquid E1 for forming photoalignment film -------------------------------------------------- - 100.00 parts by mass of the polymer PA-3 described below - 5.00 parts by mass of the thermal cationic polymerization initiator PAG-1 described above - 0.005 parts by mass of the acid generator CPI-110TF described below - 16.50 parts by mass of isopropyl alcohol - 1072.00 parts by mass of butyl acetate - 268.00 parts by mass of methyl ethyl ketone --------------------------------------------------

[0131] Polymer PA-3 (In the formula below, the numerical value for each repeating unit represents the content (% by mass) of each repeating unit relative to all repeating units; weight average molecular weight: 45,000)

[0132]

[0133] Acid generator CPI-110TF

[0134]

[0135] Composition F1 having the following composition was applied onto the photo-alignment film E1 using a bar coater. The coating film formed on the photo-alignment film E1 was heated to 120°C with hot air, then cooled to 60°C, and then irradiated with 100 mJ / cm2 at a wavelength of 365 nm using a high-pressure mercury lamp under a nitrogen atmosphere. ２ The coating film was irradiated with ultraviolet light of 500 mJ / cm 2 while being heated to 120°C. ２The coating film was irradiated with ultraviolet light of 1000 nm, thereby fixing the alignment of the liquid crystal compound, and a retardation layer film 1 having a positive A plate F1 was produced. The thickness of the positive A plate F1 was 2.5 μm, and Re(550) was 144 nm. The positive A plate also satisfied the relationship Re(450)≦Re(550)≦Re(650). Re(450) / Re(550) was 0.82. The positive A plate corresponds to a so-called λ / 4 plate.

[0136] ------------------------------------------------- Composition F1 ------------------------------------------------- 43.50 parts by mass of polymerizable liquid crystal compound LA-1 described below 43.50 parts by mass of polymerizable liquid crystal compound LA-2 described below 8.00 parts by mass of polymerizable liquid crystal compound LA-3 described below 5.00 parts by mass of polymerizable liquid crystal compound LA-4 described below 0.55 parts by mass of polymerization initiator PI-1 described below 0.20 parts by mass of leveling agent T-1 described below 235.00 parts by mass of cyclopentanone ------------------------------------------------

[0137] Polymerizable liquid crystal compound LA-1 (tBu represents a tertiary butyl group)

[0138]

[0139] Polymerizable liquid crystal compound LA-2

[0140]

[0141] Polymerizable liquid crystal compound LA-3

[0142]

[0143] Polymerizable liquid crystal compound LA-4 (Me represents a methyl group)

[0144]

[0145] Polymerization initiator PI-1

[0146]

[0147] Leveling agent T-1 (in the formula below, the numerical value for each repeating unit represents the content (mass %) of each repeating unit relative to all repeating units; weight average molecular weight: 25,000)

[0148]

[0149] <Preparation of Retardation Layer Film 2 Having Positive C Plate> The above-described cellulose acylate film A1 was used as a temporary support. The cellulose acylate film A1 was passed through a dielectric heating roll at a temperature of 60°C to raise the surface temperature of the film to 40°C, and then an alkaline solution having the composition shown below was applied to one side of the film using a bar coater in an amount of 14 ml / m. ２ The film was heated to 110°C and transported for 10 seconds under a steam-type far-infrared heater manufactured by Noritake Co., Ltd. Next, pure water was applied to the film at a rate of 3 ml / m using the same bar coater. ２ Next, after repeating washing with water using a fountain coater and draining with an air knife three times, the film was transported to a drying zone at 70° C. for 10 seconds and dried to prepare an alkali-saponified cellulose acylate film A1.

[0150] ---------------------------------------------------------------- (Alkaline solution) ---------------------------------------------------------------- Potassium hydroxide 4.7 parts by mass Water 15.8 parts by mass Isopropanol 63.7 parts by mass Fluorine-containing surfactant SF-1 (C １４ H ２９ O (CH ２ CH ２ O) ２０ H) 1.0 part by mass Propylene glycol 14.8 parts by mass

[0151] An alignment film-forming coating solution G1 having the following composition was continuously applied onto the above-mentioned alkali-saponified cellulose acylate film A1 using a #8 wire bar, and the resulting film was dried with hot air at 60°C for 60 seconds and then with hot air at 100°C for 120 seconds to form an alignment film G1.

[0152] ------------------------------------------------------------------ Coating liquid G1 for forming alignment film -------------------------------------------------- Polyvinyl alcohol (PVA103, manufactured by Kuraray) 2.4 parts by mass Isopropyl alcohol 1.6 parts by mass Methanol 36 parts by mass Water 60 parts by mass ------------------------------------------------------------------

[0153] A coating solution H1 for forming a positive C plate having the following composition was applied onto the alignment film G1, and the resulting coating film was aged at 60° C. for 60 seconds, and then irradiated with 70 mW / cm 2 ２ An air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) was used, and the light output was 1000 mJ / cm ２ The liquid crystal compound was vertically aligned by irradiating the film with ultraviolet light of 1000 nm to fix the alignment state, thereby producing a retardation layer film 2 having a positive C plate H1 with a thickness of 0.5 μm. The Rth(550) of the obtained positive C plate was −60 nm.

[0154] -------------------------------- Coating liquid H1 for forming positive C-plate -------------------------------- 80 parts by mass of the following liquid crystal compound LC-1 20 parts by mass of the following liquid crystal compound LC-2 1 part by mass of the following vertical alignment liquid crystal compound promoter S01 8 parts by mass of ethylene oxide-modified trimethylolpropane triacrylate (V#360, manufactured by Osaka Organic Chemical Co., Ltd.) 3 parts by mass of Irgacure 907 (manufactured by BASF) 1 part by mass of Kayacure DETX (manufactured by Nippon Kayaku Co., Ltd.) 0.4 parts by mass of the following compound B03 170 parts by mass of methyl ethyl ketone 30 parts by mass of cyclohexanone --------------------------------

[0155] Liquid crystal compound LC-1

[0156]

[0157] Liquid crystal compound LC-2

[0158]

[0159] Vertical alignment liquid crystal compound promoter S01

[0160]

[0161] Compound B03 (In the formula below, the numerical value for each repeating unit represents the content (% by mass) of each repeating unit relative to all repeating units; weight average molecular weight: 15,000)

[0162]

[0163] <Preparation of Laminate B1> The laminate B1 was prepared according to the following procedure. A broadband dielectric multilayer film (3M trademark APF) was used as a reflective polarizer (linear polarization type reflective polarizer). The positive A plate side of the obtained retardation layer film 1 was attached to one surface of the APF, and the alignment film and support were peeled off. The alignment film was then peeled off, and the positive C plate side of the obtained retardation layer film 2 was attached to the exposed liquid crystal surface with an adhesive, and the support and alignment film were peeled off. Furthermore, an optically absorbing anisotropic film C1 was laminated on the other surface of the APF using the following lamination method A. This produced a laminate B1 (corresponding to the laminate of the present invention) consisting of an optically absorbing anisotropic film C1 / adhesive layer / reflective polarizer / adhesive layer / positive A plate / positive C plate. The elastic modulus of the APF was 4277 MPa.

[0164] (Lamination method A) A discharge amount of 150 W·min / m was applied to the surface of the optically absorptive anisotropic film C1. ２ The corona-treated surface was then bonded to the other surface of the APF using an adhesive. The adhesive used was NCF-D692 (manufactured by Lintec Corporation, thickness 5 μm).

[0165] <Formation of Half Mirror Lens> Aluminum was vapor-deposited on the convex side of a lens (a convex meniscus lens LE1076-A (diameter 2 inches) manufactured by Thorlab) so that the reflectance was 40%, thereby forming a half mirror lens.

[0166] <Preparation of Laminate B1K Molded to a Curved Surface> The laminate B1 was placed in a molding device. At this time, it was positioned so that the positive C-plate side was on the bottom. The molding space in the molding device consisted of box 1 and box 2, separated by the laminate B1. Mold 1 (a convex lens with a diameter of 2 inches and a curvature radius of 84 mm) was placed in box 1 below the laminate B1, with the convex surface (molding surface) facing up. Furthermore, a transparent window was installed on the top of box 2 above the laminate B1, and an IR light source for heating the laminate B1 was installed outside this window. Next, a vacuum pump was used to evacuate box 1 and box 2 to a pressure of 0.1 atmospheres or less. Next, as a heating step for the laminate B1, infrared rays were irradiated and the laminate B1 was heated until its temperature reached 108°C. Next, in a process of pressing the laminate B1 against the mold 1 and deforming it to conform to the shape of the mold 1, gas was flowed into box 2 from a gas cylinder to pressurize it to 300 kPa, and the laminate B1 was pressed against the mold 1. Finally, the laminate B1 was removed from the lens, which was mold 1. This resulted in a laminate B1 molded into a non-planar shape. Next, the non-planar laminate B1 was placed upside down from the initial molding, with the positive C-plate side facing upward. At this time, the non-planar region of the laminate B1 from the initial molding protruded downward. A meniscus lens (diameter 2 inches, radius of curvature of the concave side 70 mm) was placed as mold 2 directly below the non-planar region of the laminate B1, with the concave surface facing upward. Next, a vacuum pump was used to evacuate box 1 and box 2 to a pressure of 0.1 atmospheres or less. Next, in the step of heating the laminate B1, infrared rays were irradiated and the laminate B1 was heated until its temperature reached 108°C. Next, in the step of pressing the laminate B1 against the mold 2 and deforming it to conform to the shape of the mold 2, gas was flowed into the box 2 from a gas cylinder to pressurize it to 300 kPa, and the laminate B1 was pressure-bonded to the mold 2. Finally, the laminate B1 was removed from the lens, which was the mold 2. This resulted in a laminate B1K formed into a curved surface.

[0167] <Preparation of Compound Lens> For the half mirror lens prepared above, the laminate B1K was attached to the concave surface side of the half mirror lens with an adhesive, thereby obtaining a compound lens 1.

[0168] Example 2 A laminate B2 and a composite lens 2 were obtained in the same manner as in Example 1, except that Lamination Method A was changed to Lamination Method C.

[0169] <Lamination Method C> A discharge amount of 150 W·min / m was applied to the surface of the optically absorptive anisotropic film C1. ２ The corona-treated surface was then bonded to the other surface of the APF using a pressure-sensitive adhesive. The pressure-sensitive adhesive used was the composition described in paragraph 0153 of JP-A No. 2018-127610, and the bonding was carried out by the method described in paragraph 0161.

[0170] Example 3 A laminate B3 and a composite lens 3 were obtained in the same manner as in Example 1, except that lamination method A was changed to lamination method F. <Lamination method F> The surface of the optically absorptive anisotropic film C1 was bonded to the other surface of the APF using an adhesive. The adhesive used was a 3% aqueous solution of PVA (PVA-117H, manufactured by Kuraray Co., Ltd.).

[0171] Example 4 A laminate B4 and a composite lens 4 were obtained in the same manner as in Example 1, except that the optically absorptive anisotropic film C2 was used instead of the optically absorptive anisotropic film C1 and the lamination method A was changed to the lamination method E.

[0172] <Lamination Method E> The surface of the optically absorptive anisotropic film C2 was bonded to the other surface of the APF using an adhesive, such as NCF-D692 (manufactured by Lintec Corporation, thickness 5 μm).

[0173] Example 5 A laminate B5 and a composite lens 5 were obtained in the same manner as in Example 1, except that the optically absorptive anisotropic film C2 was used instead of the optically absorptive anisotropic film C1.

[0174] Example 6 A laminate B6 and a composite lens 6 were obtained in the same manner as in Example 1, except that the optically absorptive anisotropic film C3 was used instead of the optically absorptive anisotropic film C1.

[0175] Example 7 A laminate B7 and a composite lens 7 were obtained in the same manner as in Example 1, except that Lamination Method A was changed to Lamination Method D.

[0176] <Lamination Method D> A discharge amount of 150 W·min / m was applied to the surface of the optically absorptive anisotropic film C1. ２ The corona-treated surface was then bonded to the other surface of the APF using a pressure-sensitive adhesive. The pressure-sensitive adhesive used was a 3% aqueous solution of PVA (PVA-117H, manufactured by Kuraray Co., Ltd.).

[0177] Example 8 A laminate B8 and a composite lens 8 were obtained in the same manner as in Example 1, except that Lamination Method A was changed to Lamination Method B.

[0178] <Lamination Method B> A discharge amount of 150 W·min / m was applied to the surface of the optically absorptive anisotropic film C1. ２ The corona-treated surface was then bonded to the other surface of the APF using an adhesive. The adhesive used was NCF-D692 (manufactured by Lintec Corporation, thickness 15 μm).

[0179] Example 9 A laminate B9 and a composite lens 9 were obtained in the same manner as in Example 3, except that the optically absorptive anisotropic film C4 was used instead of the optically absorptive anisotropic film C1.

[0180] Example 10 A laminate B10 and a composite lens 10 were obtained in the same manner as in Example 3, except that the optically absorptive anisotropic film C5 was used instead of the optically absorptive anisotropic film C1.

[0181] Example 11 A laminate B11 and a composite lens 11 were obtained in the same manner as in Example 3, except that the optically absorptive anisotropic film C6 was used instead of the optically absorptive anisotropic film C1.

[0182] Comparative Example 1 A laminate B12 and a composite lens 12 were obtained in the same manner as in Example 1, except that Lamination Method A was changed to Lamination Method E.

[0183] [Evaluation] <Preparation of Virtual Reality Display Device> A virtual reality display device "Huawei VR Glass" manufactured by Huawei, which is a virtual reality display device employing a reciprocating optical system, was disassembled, and all of the compound lenses were removed. The compound lenses prepared in the above examples and comparative examples were incorporated into the main body in place of the removed compound lenses, and a virtual reality display device was fabricated by placing the compound lenses so that the light-absorbing anisotropic film side of the compound lenses was facing the eye. A black and white checkered pattern was displayed on the image display panel of the fabricated virtual reality display device, and color unevenness was visually evaluated using the following three-point scale. The results are shown in Table 1 below. (Evaluation of Color Unevenness) A: Very slightly visible, but not noticeable. B: Slightly visible, but not noticeable. C: Color unevenness is visible.

[0184] <Crack Evaluation> Twenty composite lenses were produced in the examples and comparative examples, and cracks in the laminate on the concave surface of the composite lens were visually evaluated using the following three levels. The results are shown in Table 1 below. (Crack Evaluation) A: 0 to 1 crack occurred in the number of lenses B: 2 to 10 crack occurred in the number of lenses C: 11 to 20 crack occurred in the number of lenses

[0185] In Table 1, the column "Surfactant Log P value" in the column "Lightly absorptive anisotropic film" indicates the Log P value of the surfactant contained in the lightly absorptive anisotropic film. In Table 1, the column "Log P value" in the column "Adhesive layer" indicates the Log P value of the adhesive layer.

[0186]

[0187] As shown in Table 1, the laminate of the present invention exhibited the desired effects. In particular, a comparison of Example 11 with other Examples confirmed that the effect was better when the thickness of the optically absorptive anisotropic film was 10.0 μm or less. Furthermore, a comparison of Example 9 with other Examples confirmed that the effect was better when the number of organic dichroic dyes was 4 or more. Furthermore, a comparison of Example 8 with other Examples confirmed that the effect was better when the thickness of the adhesive layer was 13.0 μm or less. Furthermore, a comparison of Example 7 with other Examples confirmed that the effect was better when E1 + E2 was 120 mNm or less. －１ It has been confirmed that the effect is more excellent in the following cases:

[0188] 10A, 10B, 10C Laminate 12 Light absorption anisotropic film 14 Adhesive layer 16, 20 Retardation layer 18 Reflective polarizer 22 Positive A plate 24 Positive C plate 30 Compound lens 32 Lens 34 Half mirror 40 Virtual reality display device 42 Image display device 44 Circular polarizer

Claims

1. A laminate comprising a light absorption anisotropic film and an adhesive layer disposed adjacent to the light absorption anisotropic film, wherein the light absorption anisotropic film contains an organic dichroic dye, and the sum of the surface free energy E1 of the surface of the light absorption anisotropic film on the adhesive layer side and the surface free energy E2 of the surface of the adhesive layer on the light absorption anisotropic film side is 54.0 mNm －１ or more. The laminate.

2. The laminate according to claim 1, wherein the thickness of the light absorption anisotropic film is 10.0 μm or less.

3. The laminate according to claim 1, wherein the light absorption anisotropic film contains four or more of the organic dichroic dyes.

4. The laminate according to claim 1, further comprising an alignment film disposed adjacent to the light absorption anisotropic film on the side opposite to the adhesive layer side of the light absorption anisotropic film.

5. The laminate according to claim 1, wherein the thickness of the adhesive is 13.0 μm or less.

6. The laminate according to claim 1, further having an adjacent layer disposed adjacent to the adhesive layer on the side opposite to the light absorption anisotropic film side of the adhesive layer, and the elastic modulus of the adjacent layer is 100 MPa or more.

7. The laminate according to claim 1, wherein the light absorption anisotropic film contains a surfactant, and the LogP value of the surfactant is 3.0 or less.

8. The laminate according to claim 1, wherein the surface of the light absorption anisotropic film on the adhesive layer side is subjected to a surface activation treatment.

9. The laminate according to claim 1, wherein the LogP value of the adhesive layer is 0.5 or less.

10. The laminate according to claim 1, further comprising a retardation layer on the side opposite to the light absorption anisotropic film side of the adhesive layer.

11. The laminate according to claim 1, further comprising a reflective polarizer and a retardation layer on the side opposite to the light absorption anisotropic film side of the adhesive layer.

12. A composite lens including the laminate according to any one of claims 1 to 11, a lens, and a half mirror in this order.

13. A display device including the laminate according to any one of claims 1 to 11.

14. A virtual reality display device including the laminate according to any one of claims 1 to 11.

Images