Bonded reflective polarizing element lens, head-mounted display, and method for manufacturing bonded reflective polarizing element lens

Abstract

The purpose of the present invention is to provide a reflective polarizer-bonded lens, a method for manufacturing the reflective polarizer-bonded lens, and a head-mounted display provided with the reflective polarizer-bonded lens. Even after a reliability test in a harsh high-temperature and humidified environment, at least one of peeling and cracking of a reflective polarizing element is suppressed. [Solution] A reflective polarizing element bonded lens provided with a resin lens having a first surface and a second surface opposite to each other, in which a reflective polarizing element is bonded to at least one of the first surface and the second surface, and in which a resin composition constituting the resin lens has a glass transition temperature (Tg) of 115-160 DEG C, an adhesive layer is provided between the resin lens and the reflective polarizing element, and a silane coupling agent layer is provided between the resin lens and the adhesive layer and / or between the adhesive layer and the reflective polarizing element.

Description

TECHNICAL FIELD

[0001] The present application relates to a reflection-type polarizing element attached lens, a head-mounted display provided with the reflection-type polarizing element attached lens, and a manufacturing method of the reflection-type polarizing element attached lens. BACKGROUND

[0002] In recent years, development of devices for Virtual Reality (hereinafter referred to as VR) and Augmented Reality (hereinafter referred to as AR) is now being actively conducted. For a VR head-mounted display, specifically, a device can be cited in which an image produced by a computer, an image taken by a stereo camera is displayed by an eye-use display disposed near an eye, an amplifying optical system disposed between the display and the eye is used, and the image is amplified from a perspective close to a human eye to a larger perspective, so that a user feels as if he or she exists in the image space. Also, similarly, for an AR head-mounted display, a device can be cited in which an image is made incident to a transparent waveguide body by a mirror, a diffraction grating, and a holographic element, the image light is outputted to a direction of an eye of a user by a mirror, a diffraction grating, and a holographic element disposed in a form of destroying total reflection after waveguiding by total reflection, so that the real world can be observed in a see-through manner from the transparent waveguide, and the image light is also overlapped in the real world and observed by the above optical system.

[0003] For these devices, it is required that an observer can wear the device without discomfort, and the image can be displayed without discomfort when the image is observed, it is required that the entire device is lightened, downsized, and thinned, and it is required that the image with a high sense of immersion is displayed.

[0004] In particular, in order to improve the sense of immersion, in particular in a VR head-mounted display, the perspective of the image is valued, and it is required that the amplifying optical system is thin and has a strong magnification to amplify the image up to a perspective close to a human eye and the device does not become a structure with a large volume.

[0005] As such an optical system, for example, as shown in Patent Documents 1 to 3, an eyepiece optical system using a polarizing folding light path is proposed.

[0006] Figure 1 Fig. 1 shows a basic configuration of such an eyepiece optical system as a conceptual diagram. In the eyepiece optical system, there are a first light path from an image display to a first mirror, a second light path from the first mirror to a second mirror, and a third light path from the second mirror to an eye of a user. Figure 1The left side in FIG. 1 is a configuration in which the image display device 11, a circularly polarizing element 12 (for example, a 1 / 4λ element attached to a linear polarizing plate), a half mirror 13, a lens 14, a 1 / 4λ element 15, and a reflective polarizing element 16 having a function of separating polarized light (for example, an optical element that reflects S waves perpendicular to the incident plane and transmits P waves parallel to the incident plane) are combined. Here, the light emitted from the image display device 11 is converted to circularly polarized light (for example, circularly polarized light in the counterclockwise direction when viewed from the advancing direction of the light) by the circularly polarizing element 12 and is transmitted through the half mirror 13. Then, the light is transmitted inside the lens 14 and is converted to linearly polarized light by the 1 / 4λ element 15 that imparts a 1 / 4λ phase difference. At this time, by making the transmission axis of the reflective polarizing element 16 orthogonal to the linearly polarized light axis, the light is reflected by the reflective polarizing element 16 and the optical path is folded back, and the light is converted to circularly polarized light (for example, circularly polarized light in the counterclockwise direction when viewed from the advancing direction of the light) again by the 1 / 4λ element 15. The light is transmitted inside the lens, is folded back by the half mirror again (for example, converted to circularly polarized light in the clockwise direction when viewed from the advancing direction of the light), is transmitted through the lens a third time, is converted to linearly polarized light by the 1 / 4λ element, becomes the polarized light axis of the transmission reflective optical element, is transmitted through the reflective polarizing element 16, and the user visually recognizes the image as a virtual image. By becoming such a structure (hereinafter referred to as a pancake lens structure), an optical system in which light is folded is obtained, the magnification of the lens can be increased, and a thin optical system can be applied to a head-mounted display.

[0007] Prior Art Documents

[0008] Patent Documents

[0009] Patent Document 1: U.S. Patent No. 6563638

[0010] Patent Document 2: Japanese Patent No. 6386210

[0011] Patent Document 3: Japanese Patent Application Publication No. 2020-85956

[0012] Patent Document 4: U.S. Patent No. 10409067

[0013] Patent Document 5: Japanese Patent Application Publication No. 2021-92767

[0014] Patent Document 6: Japanese Patent Application Publication No. Hei 10-10465

[0015] Patent Document 7: Japanese Patent Application Publication No. 2020-95205

[0016] Patent Document 8: Japanese Patent Application Publication No. 2024-4491 SUMMARY

[0017] However, in the above optical system, since light is transmitted 3 times in the lens, the contribution of birefringence of the lens is also 3 times, and it is easy to become a state in which the polarizing axis cannot be strictly controlled. In this case, light that should be linearly polarized receives a phase difference and becomes elliptically polarized, and thus, for example, an image that should be reflected by a reflective polarizing element is transmitted to cause ghosting and / or a flare. Furthermore, after being reflected twice, light that should have been transmitted is reflected again to cause a decrease in contrast and the like. Thus, these undesirable situations become a problem.

[0018] In particular, when a resin lens is used instead of glass to make a head-mounted display lightweight, the polarizing axis of image light rotates due to orientation birefringence caused by orientation of a main chain generated when the resin is injection molded, and the effects of photoelasticity caused by stress remaining inside and stress applied from the outside, and the aforementioned generation of ghosting, flares, and a decrease in contrast and the like become a large problem (for example, Patent Literature 3, Patent Literature 5).

[0019] Therefore, in order to suppress such problems, development of a low-birefringence resin is required, and in Patent Literatures 4 to 6, a low-birefringence resin in which the monomer composition ratio is strictly controlled so that both the orientation birefringence and the photoelasticity of the resin are extremely small is reported to be suitable for a lens for a head-mounted display.

[0020] If such a resin is used, the generation of ghosting and flares and a decrease in contrast and the like can be suppressed, and by combining a plurality of lenses, correction of monochromatic aberration and chromatic aberration of a virtual image can be performed. In particular, a non-spherical lens that is difficult to make using glass can efficiently correct monochromatic aberration of a virtual image. For example, in Patent Literature 7, it is exemplified that a non-spherical lens is effective for aberration correction.

[0021] In addition, in order to increase the magnification of the optical system and suppress the generation of ghosting or a decrease in contrast caused by reflection at the air interface, it is effective to adhere both the aforementioned phase difference plate and the reflective optical element to the lens surface.

[0022] When a reflective polarizing element adhered lens is made using a resin, the resin substrate and the polarizing separation film are often adhered and made using an adhesive. A reflective polarizing element adhered lens is superior to a glass-made lens in terms of weight reduction of an image display device, but a problem arises in that the optical performance (polarization separation ability, transmittance, and the like) significantly decreases due to the fact that the reflective polarizing element adhered lens has high water absorption and the resin substrate and the polarizing separation film are deformed due to moisture absorption in a high-temperature and high-humidity environment, and a difference in dimensional change during moisture absorption causes peeling at the adhesive layer interface. The reflective polarizing element adhered lens in which this peeling occurs has a problem in that the optical performance (polarization separation ability, transmittance, and the like) significantly decreases.

[0023] In addition, in order to improve the magnification as an optical system and suppress the contrast reduction and the generation of ghost caused by reflection at the air interface, it is effective to adhere both the phase difference plate and the reflective optical element to the lens surface.

[0024] In Patent Literature 8, it is reported that using a resin lens composed of a thermoplastic resin having a sufficiently high heat resistance, a small photoelastic coefficient, and a main chain or a side chain having an aromatic group (a functional group or a substituent derived from an aromatic hydrocarbon) or an alicyclic group, controlling the ratio Tp530 / Tc530 of the transmittance (Tp530) when a reflective optical element is adhered to a lens having a flat surface or a convex shape in a region including the optical axis of the lens satisfies Tp530 / Tc530≥150 when a polarized light parallel to the transmission axis of the reflective polarizing element is incident as a light parallel to the optical axis of the lens and the transmittance (Tc530) when a polarized light perpendicular to the transmission axis is incident in reverse, and thereby the problems of the generation of a light spot and ghost and the reduction of contrast can also be solved in a thin pancake lens structure. However, it is reported that in the adhesion to a lens having a high curvature, peeling of the reflective polarizing element, whitening of the peeled portion, wrinkles, and bubbles occur after a reliability test (500 hours under an environment of 60°C, 90% RH) and a cold and hot cycle test.

[0025] The present application was completed in view of the above problems, and an object of the present application is to provide a reflective polarizing element-adhered lens and a head-mounted display provided with the same, which suppress at least either one of peeling and the generation of cracks of a reflective polarizing element after a reliability test under a severe high-temperature and humidification environment.

[0026] In addition, an object of the present application is to provide a manufacturing method of a reflective polarizing element-adhered lens, which can manufacture a reflective polarizing element-adhered lens that suppresses at least either one of peeling and the generation of cracks of a reflective polarizing element after a reliability test under a severe high-temperature and humidification environment.

[0027] The present inventors have made intensive studies repeatedly, and completed the application shown below.

[0028] That is, the present application is as follows.

[0029] [1] A reflective polarizing element-adhered lens, wherein the reflective polarizing element-adhered lens is provided with a resin lens having a first surface and a second surface on opposite sides of each other, a reflective polarizing element is adhered to at least one of the first surface and the second surface, an adhesive layer is provided between the resin lens and the reflective polarizing element, a silane coupling agent layer is provided in at least one of between the resin lens and the adhesive layer and between the adhesive layer and the reflective polarizing element, and the glass transition temperature Tg of a resin composition constituting the resin lens is 115°C to 160°C.

[0030] [2] The reflective polarizing element attached lens according to [1], wherein an absolute value of an optical elastic coefficient of the resin lens is 10 x 10 -12 Pa -1 The following.

[0031] [3] The reflective polarizing element attached lens according to [1] or [2], wherein the resin lens is composed of a thermoplastic resin composition having an aromatic group or an alicyclic group in a main chain or a side chain.

[0032] [4] The reflective polarizing element attached lens according to any one of [1] to [3], wherein a surface of the resin lens to which the reflective polarizing element is attached is a convex or concave surface in a region including an optical axis, and an absolute value of a curvature radius R as a reference is 10 mm or more and 500 mm or less.

[0033] [5] The reflective polarizing element attached lens according to any one of [1] to [4], wherein the resin composition contains a methacrylic resin.

[0034] [6] The reflective polarizing element attached lens according to [5], wherein the methacrylic resin contains a methacrylic resin having a structural unit having a ring structure.

[0035] [7] The reflective polarizing element attached lens according to [6], wherein the structural unit contains at least one structural unit selected from the group consisting of a structural unit from an N-substituted maleimide monomer, a glutarimide-based structural unit, an aromatic vinyl structural unit, an alicyclic vinyl structural unit, and a lactone ring structural unit.

[0036] [8] The reflective polarizing element attached lens according to [7], wherein the structural unit contains a structural unit from an N-substituted maleimide monomer.

[0037] [9] The reflective polarizing element attached lens according to any one of [1] to [4], wherein the resin lens is composed of a resin composition containing a cyclic olefin copolymer, the cyclic olefin copolymer being a copolymer of ethylene and a cyclic olefin, or a copolymer of an a-olefin and a cyclic olefin.

[0038]

[10] The reflective polarizing element attached lens according to [9], wherein a proportion of a ring skeleton structural unit from a main chain of the cyclic olefin in the cyclic olefin copolymer is 36 mol% or more and 50 mol% or less.

[0039]

[11] The reflective polarizing element attached lens according to [9] or

[10] , wherein the structural unit from the cyclic olefin in the cyclic olefin copolymer is a structural unit from at least one compound selected from bicyclo[2.2.1]-2-heptene and tetracyclo[4.4.0.1 2，5 .1 7 ，10 .2.2.0]3-dodecene.

[0040]

[12] The reflective polarizing element attached lens according to any one of [1] to [4], wherein the resin lens is composed of a resin composition containing a ring-opening polymer hydride of a norbornene-based monomer.

[0041]

[13] The reflective polarizing element attached lens according to

[12] , wherein the resin composition containing the ring-opening polymer hydride of the norbornene-based monomer contains 20 to 100 mol% of a structural unit from the norbornene-based monomer and 0 to 80 mol% of a structural unit from another monomer copolymerizable with the norbornene-based monomer.

[0042]

[14] The reflective polarizing element attached lens according to

[13] , wherein the structural unit from the norbornene-based monomer contains 15 to 50% by weight of a structural unit from a tetracyclododecene-based monomer, 50 to 90% by weight of a structural unit from a methano-tetrahydrofluorene-based monomer, and 1 to 15% by weight of a structural unit from a norbornene monomer, and the total amount of the structural units from the respective monomers is 100% by weight or less.

[0043]

[15] The reflective polarizing element attached lens according to any one of [1] to

[14] , wherein the resin composition constituting the resin lens has a flexural strength of 65 MPa or more.

[0044]

[16] The reflective polarizing element attached lens according to any one of [1] to

[15] , wherein the reflective polarizing element has only one reflection surface related to polarization separation.

[0045]

[17] The reflective polarizing element attached lens according to any one of [1] to

[16] , wherein the adhesive layer is an adhesive layer composed of an adhesive not containing a silane coupling agent.

[0046]

[18] A head-mounted display provided with the reflective polarizing element attached lens according to any one of [1] to

[17] .

[0047]

[19] A manufacturing method of a reflective polarizing element attached lens, which is a manufacturing method of a reflective polarizing element attached lens in which a reflective polarizing element is attached to a resin lens, wherein the lens is a resin lens composed of a resin composition having a glass transition temperature Tg of 115°C to 160°C, the resin lens has a first surface and a second surface on opposite sides of each other, the manufacturing method of the reflective polarizing element attached lens includes a step of forming a silane coupling agent layer on at least one of the resin lens and the reflective polarizing element; a step of imparting an adhesive layer to at least one of the resin lens and the reflective polarizing element; and a step of attaching the reflective polarizing element to the resin lens.

[0048]

[20] The manufacturing method of a reflective polarizing element attached lens according to

[19] , wherein the resin lens is manufactured by injection molding.

[0049]

[21] The manufacturing method of a reflective polarizing element attached lens according to

[19] or

[20] , wherein the step of attaching the reflective polarizing element to the resin lens is performed under conditions in which the glass transition temperature Tg of a base material film constituting the reflective polarizing element is 膜 Tg 膜 -40°C to Tg 膜 +120°C.

[0050] According to the present application, it is possible to provide a reflective polarizing element attached lens and a head-mounted display provided with the same, which suppress at least either one of peeling and generation of cracks of a reflective polarizing element after a reliability test under a severe high-temperature and high-humidity environment.

[0051] According to the present application, it is possible to provide a manufacturing method of a reflective polarizing element attached lens, which can manufacture a reflective polarizing element attached lens that suppresses at least either one of peeling and generation of cracks of a reflective polarizing element after a reliability test under a severe high-temperature and high-humidity environment. BRIEF DESCRIPTION OF DRAWINGS

[0052] Figure 1 is a conceptual view of an optical system of a pancake lens structure.

[0053] Figure 2 is a schematic view of a reflective polarizing element attached lens.

[0054] Figure 3 is a partial cross-sectional conceptual view of a wire grid polarizing plate as a reflective polarizing element.

[0055] Figure 4is a conceptual diagram of an experimental apparatus for evaluating generation of double images, generation of light spots of an optical system using a pancake lens structure of a reflection-type polarizing element attached lens according to the present application.

[0056] Figure 5 is a diagram illustrating a display method of an image at the time of evaluation of image contrast as a modification example of the experiment of Figure 4

[0057] Explanation of reference numerals

[0058] 11: image display device.

[0059] 12: circular polarizing element.

[0060] 13: half mirror.

[0061] 14: lens.

[0062] 15: 1 / 4λ element.

[0063] 16: reflection-type polarizing element.

[0064] 21: reflection-type polarizing element attached lens.

[0065] 22: resin lens.

[0066] 23: reflection-type polarizing element.

[0067] 24: adhesive layer.

[0068] 25: silane coupling agent layer.

[0069] 30: wire grid reflection-type polarizing element.

[0070] 31: holding base material.

[0071] 32: resin base material.

[0072] 33: lattice-shaped convex portion.

[0073] 34: base material layer.

[0074] 36: dielectric layer.

[0075] 37: metal wire.

[0076] 39: bonding layer.

[0077] 40: smartphone.

[0078] 41: resin lens.

[0079] 42: reflection-type polarizing element.

[0080] 43: circular polarizing element.​

[0081] 44: Semi-reflective mirror element.

[0082] 45: 1 / 4 wave plate.

[0083] 46: Reflective polarizing element bonded lens.

[0084] 47: Circular polarizing element.

[0085] 48: Digital Single Lens Camera.

[0086] 49: Light shielding part. Detailed Implementation

[0087] Hereinafter, a method for implementing the present invention (hereinafter referred to as "this embodiment") will be described in detail. The present invention is not limited to the following description and can be implemented in various modifications within the scope of its spirit.

[0088] <Reflective polarizing element bonded lens>

[0089] The reflective polarizing element bonding lens of this embodiment is characterized in that the reflective polarizing element bonding lens comprises a resin lens having a first surface and a second surface having opposite sides, a reflective polarizing element is bonded to at least one of the first surface and the second surface, an adhesive layer is provided between the resin lens and the reflective polarizing element, at least one of the spaces between the resin lens and the adhesive layer and between the adhesive layer and the reflective polarizing element is provided with a silane coupling agent layer, and the glass transition temperature Tg of the resin composition constituting the resin lens is 115°C to 160°C.

[0090] The aforementioned reflective polarizing element bonding lens, after reliability testing under harsh high-temperature and humid conditions, also suppressed at least one of the following: peeling and cracking of the reflective polarizing element.

[0091] For the reflective polarizing element bonding lens 21 of this embodiment, refer to... Figure 2 Explanation will be provided. In Figure 2 In this embodiment, a reflective polarizing element bonding lens 21 has a reflective polarizing element 23 bonded to the first surface 22a of a resin lens 22, which has a first surface 22a and a second surface 22b on opposite sides. An adhesive layer 24 is provided between the resin lens 22 and the reflective polarizing element 23. Furthermore, silane coupling agent layers 25 are provided between the resin lens 22 and the adhesive layer 24, and between the adhesive layer 24 and the reflective polarizing element 23.

[0092] It should be noted that, in Figure 2In the present embodiment, the reflective polarizing element 23 is attached to the first surface 22a of the resin lens 22, but the reflective polarizing element 23 can be attached to the second surface 22b of the resin lens 22. In addition, in the present embodiment, the silane coupling agent layer 25 is provided between the resin lens 22 and the adhesive layer 24 and between the adhesive layer 24 and the reflective polarizing element 23, but the silane coupling agent layer 25 can be provided only between the resin lens 22 and the adhesive layer 24 or only between the adhesive layer 24 and the reflective polarizing element 23. Further, the shape of the surface of the resin lens 22 is a flat surface in the present embodiment for simplicity, but the shape of the surface of the resin lens 22 can be a convex surface or a concave surface. Figure 2 In the present embodiment, the reflective polarizing element 23 is attached to the first surface 22a of the resin lens 22, but the reflective polarizing element 23 can be attached to the second surface 22b of the resin lens 22. In addition, in the present embodiment, the silane coupling agent layer 25 is provided between the resin lens 22 and the adhesive layer 24 and between the adhesive layer 24 and the reflective polarizing element 23, but the silane coupling agent layer 25 can be provided only between the resin lens 22 and the adhesive layer 24 or only between the adhesive layer 24 and the reflective polarizing element 23. Further, the shape of the surface of the resin lens 22 is a flat surface in the present embodiment for simplicity, but the shape of the surface of the resin lens 22 can be a convex surface or a concave surface.

[0093] The reflective polarizing element attached lens of the present embodiment can be a reflective polarizing element attached lens including other components (for example, a wave plate, a phase difference coating, a half mirror, a functional coating such as an anti-reflection coating, and the like) in addition to the above-described reflective polarizing element and the resin lens. The above-described other components can be one or a plurality.

[0094] In the reflective polarizing element attached lens of the present embodiment, one or more transparent layers can be disposed between the resin lens and the silane coupling agent layer and / or between the adhesive layer and the silane coupling agent layer. That is, the structure of resin lens / transparent layer / silane coupling agent layer and / or the structure of adhesive layer / transparent layer / silane coupling agent layer can be provided.

[0095] As the transparent layer, for example, a hard coat layer, an anchor coat layer, and the like can be given. The thickness of these transparent layers is not particularly limited, and for example, can be in the range of 0.01 to 10 μm.

[0096] In the reflective polarizing element attached lens of the present embodiment, in the case where the reflective polarizing element is attached to only one surface of the resin lens, a functional layer (a hard coat layer, an anti-glare layer, an anti-reflection layer, and the like) can be provided by further subjecting the surface of the resin lens opposite to the surface to which the reflective polarizing element is attached to a surface functionalization treatment such as a hard coat treatment, an anti-reflection treatment, a transparent conductive treatment, an electromagnetic wave shielding treatment, a gas shielding treatment, and the like. The thickness of these functional layers is not particularly limited, and for example, can be in the range of 0.01 to 10 μm.

[0097] A hard coat layer imparted to the surface of the reflective polarizing element attached lens is formed, for example, by coating a coating solution in which a silicone-based curable resin, a curable resin containing an organic polymer composite inorganic microparticle, an urethane acrylate, an epoxy acrylate, a polyfunctional acrylate, or the like, and a photopolymerization initiator are dissolved or dispersed in an organic solvent, using a coating method known in the art, drying the same, and photocuring, and thus can be formed.

[0098] In addition, before the hard coat layer is applied, in order to improve adhesion, for example, a method in which an easily adhering layer, a primer layer, an anchor layer, or the like, which contains inorganic microparticles, is provided in advance, and then the hard coat layer is formed, can also be used.

[0099] The anti-glare layer imparted to the surface of the reflection-type polarizing element attached lens can be formed by jetting microparticles of silica, melamine resin, acrylic resin, or the like, and applying the same to other functional layers using a coating method known in the art, and then thermally or photo-curing the same.

[0100] As the anti-reflection layer imparted to the surface of the reflection-type polarizing element attached lens, a layer composed of a thin film of inorganic substances such as metal oxides, fluorides, silicides, borides, nitrides, sulfides, and the like can be exemplified; a layer in which resin layers having different refractive indexes such as acrylic resin, fluororesin, and the like are stacked in a single layer or multiple layers; and the like, and in addition, a layer in which a thin layer composed of composite microparticles containing inorganic compounds and organic compounds is stacked can also be used.

[0101] A mirror or a half mirror (a semi-transmissive reflective surface in which the ratio of the reflectance to the transmittance is not 50:50, but for example, the transmittance is 15% and the reflectance is 85%) can be imparted to the surface of the resin lens. Any suitable material can be used, and for example, the mirror can be constructed by applying a thin layer of a metal (for example, silver or aluminum) to the surface of the resin lens. When a thin layer of a metal is applied, since the metal absorbs light, as another method, the mirror can also be formed by stacking a thin film dielectric coating on the surface of the resin lens. In addition, the method of applying a metal and the method of applying a dielectric can be combined.

[0102] Depending on the thickness and / or the number of layers applied, the reflectance and the transmittance of light can be controlled, and in the method of stacking a dielectric, a design in which only light of an arbitrary wavelength is reflected can also be made.

[0103] The reflection-type polarizing element attached lens of the present embodiment is not limited, and is preferably used for an image display device having an ocular optical system that guides light from an image display element to the eyeball of an observer.

[0104] - Appearance -

[0105] It is preferable that the reflection-type polarizing element attached lens in the present embodiment not have wrinkles observed in appearance, and that there be no bubbles and peeling sites at the attached interface (for example, the interface between the reflection-type polarizing element and the lens). If such a defect is present, it sometimes becomes a defect in image visual recognition.

[0106] - Appearance after reliability test -

[0107] It is preferable that no wrinkles are observed in appearance after the reliability test for the reflection-type polarizing element attached lens in the present embodiment, and no adverse conditions such as air bubbles being trapped, peeling whitening, and the like occur at the interface between the reflection-type polarizing element and the resin lens. The appearance after the reliability test can be evaluated by the method described in the examples below.

[0108] [Resin lens]

[0109] The reflection-type polarizing element attached lens of the present embodiment is provided with a resin lens having a first surface and a second surface on opposite sides of each other.

[0110] The resin lens (hereinafter, sometimes simply referred to as "resin lens") used for the reflection-type polarizing element attached lens of the present embodiment is composed of a thermoplastic resin composition having an aromatic group or an alicyclic group in the main chain or side chain.

[0111] Resin composition

[0112] An appropriate embodiment of the resin composition constituting the resin lens will be described later, and it is preferable that the resin composition contains a resin containing at least one polar group belonging to the group consisting of a carbonyl group, a sulfonyl group, an amino group, and a hydroxyl group. By the resin composition containing a resin containing such a polar group, peeling is less likely to occur when the reflection-type polarizing element is attached, and firm adhesion can be ensured.

[0113] Shape

[0114] The shape of the resin lens is not particularly limited. The reflection-type polarizing element attachment surface of the resin lens is preferably a flat surface within the effective diameter, or the region including the optical axis of the lens is a convexly curved surface or a concavely curved surface. In a range in which the reflection-type polarizing element can be attached without wrinkles and air bubbles and in good condition, a convex portion or a concave portion for fixing to a frame can also be provided.

[0115] Note that the shape of the lens can be a spherical shape, a non-spherical shape, or a free-form surface shape within the effective diameter. In addition, the shape of the lens can also be a cylindrical shape in which a curved surface is formed only on one axis.

[0116] Size

[0117] The size of the resin lens is not particularly limited. However, from the viewpoint of ease of handling in the attachment process, the size of the resin lens is preferably Φ 10 mm or more and Φ 100 mm or less. The size of the resin lens is more preferably Φ 20 mm or more and Φ 80 mm or less, and further preferably Φ 25 mm or more and Φ 60 mm or less.

[0118] Curvature radius

[0119] The shape within the effective diameter of the attachment surface of the reflective polarizing element of the resin lens can be expressed using a radius of curvature R (unit: mm). There are a first surface and a second surface on opposite sides of each other in the resin lens, and the radius of curvature R is defined for each. A portion of the circumference of a circle drawn from the center of curvature of the lens, which is outside the lens, defines the lens surface shape. At this time, the line connecting the center of curvature of the first surface and the center of curvature of the second surface of the resin lens is the optical axis of the lens. For the radius of curvature of the lens, if the first surface side of the optical axis is negative and the second surface side is positive, the radius of curvature is expressed by a positive number when the first surface has a convex surface on the first surface side or the second surface has a concave surface on the second surface side, and on the other hand, the radius of curvature is expressed by a negative number when the first surface has a concave surface on the first surface side or the second surface has a convex surface on the second surface side. In the present application, the radius of curvature R that defines the lens shape is not particularly limited. If the case where the attachment surface is a flat surface (absolute value of the radius of curvature R = ∞) is excluded, the absolute value of the radius of curvature R is preferably 10 mm or more and 500 mm or less. The absolute value of the radius of curvature R is more preferably 20 mm or more and 300 mm or less, particularly preferably 30 mm or more and 200 mm or less, and most preferably 40 mm or more and 100 mm or less. By setting the shape to this range, the reflective polarizing element can be attached without wrinkles and bubbles and the like with a high yield.

[0120] The reflective polarizing element attachment lens of the present embodiment is a lens in which the surface to which the reflective polarizing element is attached is a convex or concave surface in a region including the optical axis, and the absolute value of the radius of curvature R as a reference is particularly preferably 10 mm or more and 500 mm or less.

[0121] It is preferable to use a lens whose shape does not include, as much as possible, a region that is not represented by the radius of curvature of the lens, i.e., a region of the outer peripheral flange of the lens, a region of a vent hole, or a region of a molded product for a handle. If there is a region where the curvature changes extremely (a point where the value is 0 when the curve representing the shape of the lens is twice differentiated), bubbles are easily trapped when the reflective polarizing element is attached, and in addition, since it is likely to become a region where peeling occurs at the time of reliability testing, it is preferable to avoid.

[0122] In addition, in the case where the use of a pancake lens assumed in the present embodiment is taken into consideration, it is preferable to reduce the absolute value of the radius of curvature of the reflective polarizing element attachment surface of the resin lens to increase the magnification. The absolute value of the radius of curvature is, for example, 100 mm or less. However, if the absolute value of the radius of curvature is too small, the attachment of the reflective polarizing element becomes difficult, and in addition, the aberration of the optical system is also difficult to correct, and therefore, it is preferable to appropriately design while considering the balance.

[0123] In the case where the reflection-type polarizing element bonding surface of the resin lens is flat, in the case where a reflection-type polarizing element bonded to the resin lens, such as a 1 / 4 wave plate (1 / 4 wavelength film) imparting a 1 / 4 phase difference to a prescribed wavelength, and a coating imparting a 1 / 4 phase difference are used together, it is effective for avoiding application of an undesirable stress to these elements.

[0124] When the reflection-type polarizing element bonding surface of the resin lens is aspherical, the surface shape can be set as a rotationally symmetrical asphere in which the sag amount z of the surface follows the following Equation I.

[0125] Mathematical Equation 1

[0126]

[0127] In Equation I, c, k, D, E, F, G, H, and I are constants, z (unit: mm) is the distance from the vertex of the surface (in the direction parallel to the optical axis), and r (unit: mm) represents the radial distance from the vertex. The parameter k is called the conic constant. In addition, c is the reciprocal 1 / R (unit: mm) of the curvature radius R serving as the reference. -1

[0128] Phase difference within effective diameter

[0129] For the resin lens, the average value of the absolute value of the phase difference within the effective diameter is preferably 10 nm or less, more preferably 7 nm or less, and still more preferably 5 nm or less, as a resin lens monomer. By bonding a resin lens in the range as described above to a reflection-type polarizing element, ghosting (image overlapping), light spots, and a decrease in contrast, and the like do not occur, and a clear and high-resolution image can be visually recognized.

[0130] Here, the effective diameter of the resin lens represents the range in which an image can be visually recognized when the lens is assembled into the frame of a head-mounted display, and is represented as the diameter of a circle with the optical axis of the lens as the center. Therefore, the product with a flange or the like for assembly into the frame is to be excluded from this part. In the case where the range in which an image can be visually recognized is not a perfect circle, the minor axis is set as the effective diameter. When there is no clear effective diameter, the region including 80% or more of the projected area of the lens is considered, excluding the region of the flange or the like that does not belong to the surface of the lens. The projected area refers to the area of the shape of the entire or partial region of the resin lens projected onto the horizontal plane when the resin lens is placed on the horizontal plane, and parallel light rays parallel to the direction of gravity are irradiated from a point vertically above the infinite distance (i.e., the parallel projection area). The phase difference within the effective diameter of the resin lens can be specifically measured by the method described in the Examples below.

[0131] ​As for the method of obtaining such a resin lens, the resin lens in the above range can be obtained by applying the preferred resin composition and preferred molding conditions described later. In addition to this, methods such as cutting the peripheral region of the gate where the birefringence of the resin lens is large, and methods of manufacturing using a molded body in which the monomer that flowed into the mold is cured by a photocuring reaction or a thermal curing reaction can also be exemplified. However, for the method of cutting the peripheral region of the gate, since the adjustment range at the time of optical system assembly becomes small, it is not preferred. For example, the attachment to the lens needs to be performed under strict control so that the polarizing transmission axis of the reflective polarizing element is disposed at a prescribed position, and thus adjustment becomes difficult. In addition, the method of manufacturing the lens by a curing reaction makes it difficult to improve the shape accuracy, and in addition, when considered from an economic viewpoint, there is a problem in the length of the cycle time required to obtain one lens.

[0132] - glass transition temperature -

[0133] The glass transition temperature (Tg) of the resin lens is preferably 115°C or higher and 160°C or lower.

[0134] By the glass transition temperature of the resin lens being 115°C or higher, in addition to ensuring the heat resistance to the heat from electronic device classes of head-mounted displays, even if the process of heating at the time of attachment of the reflective polarizing element is performed, the dimensions do not change, and from the viewpoint of being able to obtain good adhesion, it is preferred. In addition, if the heat resistance temperature is low, the amount of dimensional change in a high-temperature environment becomes large, and thus, from the viewpoint of suppressing the photoelastic birefringence that occurs due to the tension at the attachment interface and the like, due to the difference in the dimensional change of the attached optical element film and the resin lens, it is also preferred. The glass transition temperature (Tg) is more preferably 120°C or higher, further preferably 125°C or higher, and most preferably 130°C or higher.

[0135] On the other hand, in the case where the glass transition temperature (Tg) is 160°C or lower, melting processing under extremely high-temperature conditions can be avoided, and thermal decomposition of the resin and the like is suppressed, and a good product can be obtained. From the viewpoint of further obtaining the above effects, the glass transition temperature (Tg) is more preferably 155°C or lower, still more preferably 150°C or lower, and further preferably 140°C or lower.

[0136] Note that the glass transition temperature (Tg) can be determined by measurement in accordance with JIS-K7121. Specifically, it can be found by the method described in the Examples described later.

[0137] The glass transition temperature of the above-described resin lens can be adjusted to the above range, for example, by manufacturing a molded body from the resin composition preferred in the present application described later, and by the main chain in the resin composition having a ring structure, the glass transition temperature can be increased.

[0138] - photoelastic coefficient CR

[0139] The absolute value of the photoelastic coefficient CR of the resin lens |CR| is preferably 10.0 x 10 -12 Pa -1 More preferably, the absolute value of the photoelastic coefficient CR of the resin lens |CR| is 5.0 x 10 -12 Pa -1 Further preferably, the absolute value of the photoelastic coefficient CR of the resin lens |CR| is 3.0 x 10 -12 Pa -1 Particularly preferably, the absolute value of the photoelastic coefficient CR of the resin lens |CR| is 1.0 x 10 -12 Pa -1 or less.

[0140] Regarding the photoelastic coefficient, it is described in various literatures (for example, refer to "Chemistry Zokuhou" (No. 39, 1998, published by Gakkai Center) and is defined by the following equations (i-a) and (i-b). It is known that the closer the value of the photoelastic coefficient CR is to zero, the smaller the change in birefringence caused by external force.

[0141] |CR| = |Δn| / σR (i-a)

[0142] |Δn| = |nx - ny| (i-b)

[0143] (In the equations, CR represents the photoelastic coefficient, σR represents the tensile stress, |Δn| represents the absolute value of birefringence, nx represents the refractive index in the stretching direction, and ny represents the refractive index in the direction perpendicular to the stretching direction in the plane.)

[0144] If the absolute value of the photoelastic coefficient CR of the resin lens |CR| is 10.0 x 10 -12 Pa -1 or less, the photoelastic birefringence caused by the dimensional change accompanying the change in size due to the stress or temperature or the like of the environment at the time of fixing the lens is sufficiently small, and a resin lens from which a clear image can be obtained can be obtained. In addition, if the absolute value of the photoelastic coefficient CR |CR| is large, when a reflective polarizing element is used as the bonded lens, a difference in dimensional change due to expansion and contraction between the resin lens and the reflective polarizing element occurs due to environmental changes such as temperature and humidity, and thus internal deformation occurs, causing birefringence. Birefringence causes the occurrence of ghost images and deterioration of contrast as described above, and thus is not preferable.

[0145] Note that the measurement of the photoelastic coefficient CR is performed by forming a press film using a vacuum compression molding machine after the resin lens is cut into pieces. Specifically, it can be obtained by the method described in the Examples described later.

[0146] The absolute value of the photoelastic coefficient of the above-mentioned molded body can be adjusted to the above-mentioned range, for example, by forming a molded body from the preferred resin composition in the present application described later, and the copolymerization composition ratio of the monomer having a positive photoelastic coefficient and the monomer having a negative photoelastic coefficient when forming a homopolymer is preferably adjusted to an appropriate range. In addition, stress deformation can be relaxed by annealing, but heat treatment is required from the glass transition temperature of the resin -25°C to the vicinity of the glass transition temperature to sufficiently relax the stress, and in this process, the surface shape changes to cause focal point deviation and the like, and thus is not preferred. Therefore, it is preferred that the lens is formed from a resin composition having a small photoelastic coefficient.

[0147] Difference in saturated water absorption between resin lens and reflective polarizing element

[0148] In addition, when the saturated water absorption of the transparent substrate constituting the reflective polarizing element is high, it is preferred to use a material having a high saturated water absorption for the resin composition constituting the resin lens, and when the saturated water absorption of the resin composition constituting the resin lens is denoted as water absorption (resin lens) and the saturated water absorption of the transparent substrate constituting the reflective polarizing element is denoted as water absorption (reflective polarizing element), the absolute value of the difference between the water absorption (resin lens) and the water absorption (reflective polarizing element) is preferably in the range of 0.1 to 3.0%, more preferably in the range of 0.1 to 2.0%, further preferably in the range of 0.1 to 1.5%, and particularly preferably in the range of 0.1 to 1.0%. By combining the ranges to form the reflective polarizing element bonded lens of the present application, it is possible to suppress adverse conditions such as peeling of the bonded surface due to the difference in expansion rate caused by water absorption in the high temperature and high humidity test.

[0149] [Reflective polarizing element]

[0150] As the reflective polarizing element to be attached to the attached lens of the present embodiment, an element having a polarizing beam splitter (PBS) function of performing polarization division can be used. As the reflective polarizing element in the present embodiment, for example, a polarizing element in which thin films having different birefringences are laminated, a wire grid polarizing element of a structural birefringence type using a subwavelength structure, or an element composed of a cholesteric liquid crystal that separates right circularly polarized light and left circularly polarized light can be used. In industry, as the polarizing element in which thin films having different birefringences are laminated (hereinafter, sometimes referred to as a laminated reflective polarizing element), a multilayer birefringent film APF, IQP-S, IQP-E, DBEF, or the like manufactured by 3M Company can be used. In addition, as the wire grid polarizing element, a wire grid reflective polarizing element (WGF: registered trademark) manufactured by Asahi Kasei Corporation, ProFlux PPL02 (manufactured by Moxtek, Inc.), or the like can be used. In addition, as the element composed of a cholesteric liquid crystal, NIPOCS APCF (manufactured by Nitto Electric Industrial Co., Ltd.), or the like can be used.

[0151] As the reflective polarizing element, a wire grid reflective polarizing element (manufactured by Asahi Kasei Corporation, WGF: registered trademark) or IQP-E (manufactured by 3M Company) is preferable. In addition, the attaching process to the curved surface will be described later, and in order to have a function of polarization separation characteristics independent of extension, WGF is particularly preferable. Even if a tension is applied to the base film with the attachment to the lens, the polarization characteristics are difficult to be broken. In addition, in the case of the laminated reflective polarizing element, before being attached to the base material having a curved surface, the difference in the shrinkage ratio of the straight biaxial needs to be considered, and a process of being deformed into a rotationally asymmetric shape in advance with a mold before being attached to the lens, but in the wire grid film, it can be directly attached to the base material without such a pretreatment. Further, since the reflection surface related to the polarization separation is one surface, unlike the polarization separation based on multilayer reflection, the resolution performance at the time of back projection image is excellent, and thus it can be appropriately used in the present embodiment.

[0152] The wire grid reflective polarizing element adopts a structure in which a metal wire (for example, aluminum) is held by a resin protrusion arranged at a pitch of 100 nm or so on the surface of a holding base material (for example, a film (base material film) used as a base) as described later. With the wire grid reflective polarizing element, light vibrating in a direction parallel to the metal wire is reflected, and light vibrating in a perpendicular direction has a transmission characteristic. Thus, it has a feature that the polarization direction can be selected to be reflected / transmitted according to the direction of the metal wire.

[0153] The wire grid polarizing element will be described. Figure 3 is a cross-sectional view of the wire grid polarizing element.

[0154] The wire grid reflective polarizing element is configured to have a holding substrate (base film) 31 and a resin substrate 32 provided on the surface 31a of the holding substrate 31 via a bonding layer 39. In other words, the surface 31a of the holding substrate 31 and the surface 32a of the resin substrate 32 are bonded via the bonding layer 39.

[0155] As shown in FIG. 1, a plurality of lattice-shaped protrusions 33 are provided on the resin substrate 32. In addition, as shown in FIG. 2, for the resin substrate 32, a substrate layer 34 having a prescribed thickness is formed integrally with the lattice-shaped protrusions 33. Figure 3 Figure 3 As shown in FIG. 1, a plurality of lattice-shaped protrusions 33 are provided on the resin substrate 32. In addition, as shown in FIG. 2, for the resin substrate 32, a substrate layer 34 having a prescribed thickness is formed integrally with the lattice-shaped protrusions 33.

[0156] As long as the holding substrate 31 is substantially transparent in the target wavelength region, for example, an inorganic material such as glass, a resin material can also be used, and as a manufacturing method, a roll process can be used, and since the following property of a curved surface is high, a film (resin material) is preferably used.

[0157] As a resin that can be used for the holding substrate 31, there are polymethyl methacrylate resin, polycarbonate resin, polystyrene resin, cyclic olefin resin (COP), cross-linked polyethylene resin, polyvinyl chloride resin, polyarylate resin, polyphenylene ether resin, modified polyphenylene ether resin, polyetherimide resin, polyethersulfone resin, polysulfone resin, polyether ketone resin, and other amorphous thermoplastic resins, polyethylene terephthalate (PET) resin, polyethylene naphthalate resin, polyethylene resin, polypropylene resin, polybutylene terephthalate resin, aromatic polyester resin, polyacetal resin, polyamide resin, and other crystalline thermoplastic resins, and triacetate resin (TAC), and the like. As the holding substrate 31, specifically, TD80UL, ZRD60SL manufactured by FUJIFILM Corporation, KC6UA manufactured by Konica Minolta, Inc., and the like can be appropriately used.

[0158] As the resin substrate 32, for example, in addition to the same thermoplastic resins as the holding substrate 31, ultraviolet (UV) curable resins and thermosetting resins such as acrylic, epoxy, urethane, and the like can be used. In addition, the UV curable resins or thermosetting resins can be combined with the above-described thermoplastic resins or triacetate resins, or used alone to constitute the substrate. Note that, as a method of applying the UV curable resins, in addition to a gravure method using a gravure roll, a slit die method, and a doctor blade method, an inkjet method or a spray method using a potential difference, and the like can be exemplified. In addition, in order to cure it, a light source that emits UV light, visible light of about 405 nm taking into account the absorption of an ultraviolet absorber added, or a light source that emits electron rays can also be used.

[0159] ​The lattice-shaped protrusions 33 formed on the surface of the resin substrate 32 are preferably rectangular in cross-section perpendicular to the extending direction of the lattice-shaped structure. The rectangular shape is composed of repeated concave and convex portions, including trapezoidal, rectangular, and square shapes. Furthermore, when the outline of the lattice-shaped structure in cross-section is considered as a function, it can also have a curve with a gradual change in curvature like a parabola before and after the inflection point, and can also include shapes where the protrusions have narrowing portions. Depending on the shape of the lattice-shaped structure, metal lines of a shape that are separated and continuous in the vertical direction can be easily formed on the sides of the protrusions and the bottom of the concave portions of the lattice-shaped structure on the substrate surface using the tilting vapor deposition method described later. It should be noted that when forming metal lines by the tilting vapor deposition method, the metal lines 37 are provided biased towards one side of the lattice-shaped protrusions 33. Therefore, the period of the lattice-shaped structure and the period (pitch P) of the metal lines 37 are approximately the same.

[0160] The period of the concave-convex structure (the spacing P between the 33 lattice-shaped protrusions) (refer to) Figure 3 There is no particular limitation on the period, but it is preferable to set it to a period that can exert the polarization separation characteristics. Generally, the smaller the period of the metal line 37, the better the polarization separation characteristics of the wire grid polarizer in a wide frequency band. When the metal line 37 is in contact with air (refractive index 1.0), sufficient polarization separation characteristics are practically achieved by setting the period of the metal line 37 to less than 1 / 3 to 1 / 4 of the wavelength of the light being targeted. Therefore, when considering the utilization of light in the visible light region, it is preferable to set the period of the metal line 37 and the period of the uneven structure of the resin substrate 32 to 150 nm or less, more preferably 130 nm or less, even more preferably 120 nm or less, and most preferably 100 nm or less. There is no particular limitation on the lower limit of the period of the metal line 37 and the period of the uneven structure of the resin substrate 32, but from the viewpoint of ease of manufacture, it is preferable to be 50 nm or more, more preferably 60 nm or more, and even more preferably 80 nm or more.

[0161] It should be noted that, for this wire grid reflective polarizing element, the metal line 37 is preferably arranged on one side of the grid-like protrusion 33 of the concave-convex structure. Therefore, the extending direction of the concave-convex structure is substantially parallel to the extending direction of the metal line 37. In addition, the concave-convex structure and the metal line 37 can extend substantially in a predetermined direction, and the concave, convex and metal lines of the concave-convex structure do not need to extend strictly parallel to each other.

[0162] like Figure 3 As shown, a metal layer (metal line 37) is formed on at least a portion of the surface of each lattice-shaped protrusion 33 via a dielectric layer 36. Alternatively, the dielectric layer 36 may not be formed. In this case, the metal layer (metal line 37) is formed directly on the surface of the lattice-shaped protrusion 33.

[0163] To improve the adhesion of the resin base 32 to the metal wire 37, a dielectric layer 36 having high adhesion to both can be provided therebetween. Thus, by improving the adhesion of the resin base 32 to the metal wire 37, peeling of the metal wire 37 can be prevented. The dielectric layer 36 need only be substantially transparent in the visible light region. As a dielectric that can be suitably used, for example, a single body of an oxide, nitride, halide, or carbide of silicon (Si), or a composite thereof (a dielectric in which other elements, single bodies, or compounds are mixed in a dielectric single body), or a single body of an oxide, nitride, halide, or carbide of aluminum (Al), chromium (Cr), yttrium (Y), zirconium (Zr), tantalum (Ta), titanium (Ti), barium (Ba), indium (In), tin (Sn), zinc (Zn), magnesium (Mg), calcium (Ca), cerium (Ce), copper (Cu), or the like metal, or a composite thereof can be used. The method of layering the dielectric material is not particularly limited, and for example, a physical vapor deposition method such as vacuum evaporation, sputtering, ion plating, or the like can be suitably used.

[0164] The metal constituting the metal layer (metal wire 37) is preferably a metal having high reflectivity of light in the visible light region and high adhesion to the material constituting the dielectric layer 36. The metal wire 37 can be formed using a conductive material such as aluminum, silver, copper, platinum, gold, or an alloy in which each of these metals is a main component. The metal wire 37 is preferably constituted by aluminum, silver, or an alloy thereof. From the viewpoint of cost, the metal wire 37 is further preferably constituted by aluminum or an alloy thereof. In particular, aluminum can reduce absorption loss in the visible light region, and is thus preferred. The method of producing the metal wire 37 is not limited. As the method of producing the metal wire 37, for example, electron beam lithography, a method of forming using mask patterning by an interference exposure method and dry etching, and a method of producing by oblique evaporation, or the like can be exemplified. From the viewpoint of productivity, as the method of producing the metal wire 37, an oblique evaporation method is preferred.

[0165] The tilted vapor deposition method refers to a method in which the vapor deposition source exists in a direction tilted relative to the surface of the substrate in a cross-section (hereinafter referred to as "section view") perpendicular to the extension direction of the uneven structure, and metal is deposited onto the substrate at a predetermined angle to form a layer. For the vapor deposition angle, a preferred range is determined based on the convex part of the uneven structure and the cross-sectional shape of the fabricated metal line 37. Generally, 5 degrees to 45 degrees is preferred, and more preferably 5 degrees to 35 degrees. Furthermore, in controlling the height and other cross-sectional shapes of the metal line 37, it is preferable to gradually decrease or increase the vapor deposition angle while taking into account the projection effect of the layered metal during vapor deposition. It should be noted that, while maintaining the curvature of the substrate 31 surface, vapor deposition can also be performed in a direction tilted relative to the normal direction of the surface of the resin substrate 32. In addition, the shape of the vapor deposition source is not limited as long as it can sufficiently vaporize the area to be vaporized; discontinuous dots or continuous lines can be selected. When the vapor deposition source is dot-shaped, vapor deposition can also be performed from a direction inclined relative to the extension direction of the concave and convex structure. Appearingly, the spacing between the concave and convex structures is expanded, and vapor deposition can be performed up to the bottom of the concave portion, which is therefore preferred.

[0166] Specifically, a center of the vapor deposition source is positioned at an angle of 5 degrees or more but less than 45 degrees relative to the center of the vapor deposition area on the surface of the resin substrate 32, which has a surface texture extending approximately parallel to each other in a specific direction at predetermined intervals. Metal lines 37 are formed on the texture. More preferably, the center of the vapor deposition source is positioned at an angle of 5 degrees or more but less than 35 degrees relative to the center of the vapor deposition area on the surface of the resin substrate 32. This allows for selective placement of metal lines 37 on any one side of the lattice-like protrusions 33 of the surface texture on the resin substrate 32. It should be noted that when vapor deposition is performed while the substrate is being transported, vapor deposition can also be performed with the center of the vapor deposition area and the center of the vapor deposition source meeting the above conditions at a given moment.

[0167] The metal deposition amount (average thickness) is preferably around 50 nm to 300 nm. It should be noted that the average thickness mentioned here refers to the thickness of the deposited material when the material is deposited on a smooth glass substrate in a direction perpendicular to the glass surface, and is used as a reference for the metal deposition amount.

[0168] like Figure 3 As shown, the adhesion between the retaining substrate 31 and the resin substrate 32 can be improved and the refractive index adjusted via the target adhesive layer and the bonding layer 39 of the adhesive layer. For example, a dielectric layer such as silicon dioxide or aluminum oxide can be formed between the retaining substrate 31 and the resin substrate 32 with a thin film thickness. Alternatively, a modified layer that imparts functional groups or micro-textured shapes can be formed by performing corona discharge treatment, atmospheric pressure plasma treatment, vacuum plasma treatment, or ultraviolet treatment on the surface 31a of the retaining substrate 31.

[0169] The thickness of the wire grid reflective polarizing element 30 is not particularly limited, and is, for example, about 50 μm to 200 μm. The thinner the thickness, the higher the followability to the lens surface, and the yield in the process of attaching the resin lens to the surface can be dramatically improved. Specifically, the thickness of the wire grid reflective polarizing element 30 is preferably 50 to 150 μm, and more preferably 50 to 130 μm. In addition, the wire grid reflective polarizing element 30 is configured by the resin substrate 32 and the metal layer (metal wire 37) from the holding substrate 31, and thus the thickness of the wire grid reflective polarizing element 30 can be reduced to about 0.5 μm to 50 μm.

[0170] Before the adhesion process, surface treatment such as corona treatment is performed on the surface of the holding substrate 31 of the wire grid reflective polarizing element 30, which does not have the metal wire 37, and is exposed. This is effective in improving the adhesion strength. In the case where the lattice-shaped convex portion 33 is a COP, in order to prevent the metal wire 37 from being detached from the concave-convex structure, the treatment conditions are preferably adjusted so that the discharge amount calculated from the discharge electrode length, the substrate film conveying speed, and the discharge power corresponds to 10 to 120 W-min / m2. 2 .

[0171] The reflective polarizing element in the reflective polarizing element-attached lens of the present embodiment can have a plurality of reflection surfaces related to polarization separation, but, as with the wire grid polarizing plate shown in FIG. 1, it is preferable that the reflective polarizing element have only one reflection surface related to polarization separation. Figure 3

[0172] [Adhesion Layer]

[0173] The reflective polarizing element-attached lens of the present embodiment has an adhesion layer between the resin lens and the reflective polarizing element.

[0174] The size and shape of the adhesion layer are not particularly limited, and, from the viewpoint of obtaining a uniform in-plane thickness and sufficient adhesion strength, for example, the average thickness is preferably 0.01 to 500 μm, more preferably 0.5 to 100 μm, and further preferably 1.0 to 10 μm.

[0175] The adhesion layer can cover the entire adhesion surface (the surface opposite to the reflective polarizing element) of the resin lens, or can cover only a part thereof. In addition, the adhesion layer can cover the entire adhesion surface (the surface opposite to the resin lens substrate) of the reflective polarizing element, or can cover only a part thereof.

[0176] ​The peeling area ratio of the adhesive layer of the reflective polarizing element attached lens in this embodiment is preferably 15% or less, more preferably 10% or less, and further preferably 5% or less when exposed to an environment of 85°C and 85% relative humidity for 500 hours. If the peeling area ratio of the adhesive layer when exposed to an environment of 85°C and 85% relative humidity for 500 hours is within the above range, there is a tendency to further suppress the deterioration of optical performance in a high-temperature and high-humidity environment and to obtain a further clear image.

[0177] Note that, specifically, the method for measuring the peeling area can be measured by the method described in the examples described later.

[0178] In the reflective polarizing element attached lens of this embodiment, the adhesive layer is preferably an adhesive layer composed of an adhesive not containing a silane coupling agent.

[0179] - Adhesive and adhesive agent -

[0180] As the material used in the adhesion and bonding process in the adhesive layer, various adhesive agents and adhesives can be used, but from the viewpoint of processability, a solid sheet material is preferred, and an adhesive is preferably used. Here, the adhesive refers to a material having the characteristic of having adhesiveness in a semi-solid form without solidifying the liquid, so that it can be bonded to the adherend surface by applying only a small pressure.

[0181] As a material in the adhesive layer, a double-sided tape covered with a release paper on both sides can be used. As long as a material having transparency to transmit light of a target wavelength is used, it can be used without any problem, and, for example, CS9861US, CS9862UA, HJ-9150W manufactured by NITTO ELECTRIC CO., LTD., MO-T015, MO-3005, MO-3006, MO-3014 manufactured by LINTEC Corporation, 5405X-75 manufactured by MJS, and the like can be suitably used. Note that when the alignment film-attached polarizing plate is a wire grid polarizing plate in which a film is attached to a substrate, expansion and contraction of the film due to changes in the ambient temperature need to be taken into consideration. In order to follow the tension applied to the attachment surface due to the difference in the shrinkage and expansion of the substrate (e.g., a lens) on the one side and the wire grid polarizing plate, an adhesive material having flexibility is effective, and an adhesive material composed of an acrylic resin as described above and an adhesive material composed of a silicone resin are preferable. In consideration of heat resistance, an adhesive in which a silicone resin is a main component (hereinafter referred to as "silicone-based adhesive") is preferable. In addition, in consideration of transparency, adhesive force, and procurement cost, an adhesive in which an acrylic resin is a main component (hereinafter referred to as "acrylic-based adhesive") is preferable, and further, from the viewpoint of suppressing a decrease in the polarizing properties, it is more preferable that a hydroxyl group is included in the resin structure of the adhesive.

[0182] In addition, from the viewpoint of maintaining the handleability and flexibility, the thickness of the material in the adhesive layer is preferably 50 μm or more. On the other hand, if the adhesive material is too thick, it is difficult to ensure the specular property (or surface accuracy as indicated by the design shape), and thus it is preferably 100 μm or less.

[0183] In addition, the adhesive preferably uses a material having a strong adhesive force. By using a material having a strong adhesive force, peeling can be suppressed even in a high-temperature high-humidity environment or the like. As a material having a strong adhesive force, a material having an adhesive force to glass of 1.5 N / 25 mm or more can be used, and a material having an adhesive force to glass of 5.0 N / 25 mm or more is preferable.

[0184] Note that an additive can be added to the adhesive. The additive refers to a refractive index adjusting agent, a tackifier, a filler, a pigment, a diluent, and the like, and ultraviolet absorbers, antioxidants, light stabilizers, antistatic agents, and the like that improve the stability of the adhesive can be mentioned.

[0185] [SILANE COUPLING AGENT LAYER]

[0186] The reflection-type polarizing element-attached lens of the present embodiment is characterized in that a silane coupling agent layer is included in at least one of between the resin lens and the adhesive layer and between the adhesive layer and the reflection-type polarizing element.

[0187] When a plurality of silane coupling agent layers are provided, the silane coupling agent layers can be formed of the same material or different materials.

[0188] The reflection-type polarizing element attached lens of the present embodiment has at least one silane coupling agent layer described above, thereby enabling the resin substrate and the adhesive layer to be firmly bonded, enabling the degradation of optical performance in a high-temperature, humidified environment to be suppressed, and enabling a clear image to be obtained.

[0189] The silane coupling agent layer can be formed by chemical vapor deposition of a silane coupling agent on at least one of the resin lens, the adhesive layer, and the reflection-type polarizing element. For example, by using a vacuum plasma device, water, oxygen, or the like is supplied into a reaction chamber, at least one surface of the lens, the adhesive layer, and the reflection-type polarizing element can be hydrophilized, and then reacted with a silane coupling agent to form a silane coupling agent layer.

[0190] A silane coupling agent is a compound having an organic functional group that reacts with an organic material and a hydrolyzable group (e.g., an alkoxy group or the like) that reacts with an inorganic material in the molecule, and is used at the interface of organic and inorganic materials with the aim of improving the interaction of the two materials. On the other hand, when a silane coupling agent is used to improve the interface interaction of organic materials with each other, it is necessary to react the organic material with the hydrolyzable group of the silane coupling agent, and therefore the treatment conditions are mostly limited. For example, in Japanese Patent No. 4065962 and Japanese Patent No. 5733392, treatment examples are described in which an epoxy resin or a cyclic olefin resin is treated with a silane coupling agent, but include a process of heating the resin substrate at a high temperature, a process of irradiating vacuum ultraviolet light of a short wavelength, and the range of resins that can be applied is limited. In particular, methacrylic resin compositions are generally low in heat resistance and are decomposed by ultraviolet light, and therefore it is preferable that the treatment of the methacrylic resin composition with a silane coupling agent be performed under mild conditions.

[0191] As the silane coupling agent that forms the silane coupling agent layer, a known silane coupling agent can be used, but an alkoxy silane having at least one alkoxy group is preferable. As the number of alkoxy groups, 2 or 3 (i.e., a dialkoxy silane or a trialkoxy silane) is preferable, and a silane having 3 alkoxy groups is particularly preferable. The number of carbon atoms of the alkoxy group is preferably 1 to 4, and more preferably 1 to 3.

[0192] As specific examples of the silane coupling agent which forms the silane coupling agent layer, there are mentioned 3-(trimethoxysilyl)propyl methacrylate, 3-[tris(trimethylsilyloxy)silyl]propyl methacrylate, 3-[diethoxy(methyl)silyl]propyl methacrylate, 3-[dimethoxy(methyl)silyl]propyl methacrylate, (triethoxysilyl)methyl methacrylate, 3-[dimethoxy(methyl)silyl]propyl acrylate, 3-(methoxydimethylsilyl)propyl acrylate, 3-(trimethoxysilyl)propyl acrylate, [dimethoxy(methyl)silyl]methyl methacrylate, vinyltrimethoxysilane, vinyltriethoxysilane, dimethylethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, dimethoxymethylvinylsilane, trimethoxy(7-octen-1-yl)silane, 3-aminopropyltriethoxysilane, trimethoxy[3-(phenylamino)propyl]silane, 3-(2-aminoethylamino)propyltrimethoxysilane, 3-(2-aminoethylamino)propyldimethoxymethylsilane, 3-aminopropyldimethoxymethylsilane, 3-(ethoxydimethylsilyl)propane-1-amine, [3-(6-aminohexylamino)propyl]trimethoxysilane, 3-aminopropyldiethoxymethylsilane, 3-(methylamino)propyltriethoxysilane, 3-aminopropyltrimethoxysilane, trimethoxy[3-(methylamino)propyl]silane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyl(dimethoxy)methylsilane, triethoxy(3-glycidyloxypropyl)silane, diethoxy(3-glycidyloxypropyl)methylsilane, and the like. They can be used singly or in combination of two or more. From the viewpoint of good reactivity with the acrylic adhesive, it is preferable to use a silane coupling agent having a (meth)acryloyl group.

[0193] As the method for forming the silane coupling agent layer, it is possible to form by the liquid phase method and the gas phase method which have been known conventionally. For example, in the liquid phase method, it is a method for forming the silane coupling agent layer by contacting the substrate with an organic solution containing the silane coupling agent for a prescribed time. On the other hand, the gas phase method is a method for forming the silane coupling agent layer by contacting the substrate with a vapor containing the silane coupling agent without using a solvent for a prescribed time. For example, by using a vacuum plasma device, water, oxygen, or the like is supplied into the reaction chamber, thereby introducing a hydrophilic functional group to the surface of the substrate, and then it is allowed to react with the silane coupling agent, whereby it is possible to form the silane coupling agent layer. The gas phase method is different from the liquid phase method in that it does not use a solvent, and therefore it is possible to suppress damage to the substrate due to dissolution of the solvent or the like. In addition, from the viewpoint that it is possible to reduce the amount of waste liquid and the environmental load is small, it is preferable to form the silane coupling agent layer by the gas phase method.

[0194] For the plasma treatment at the time of forming the silane coupling agent layer, a conventionally known treatment method can be used. For example, an atmospheric pressure plasma treatment in which plasma is generated by applying a voltage between metal electrodes facing each other via a dielectric and a space, and a process gas such as oxygen or nitrogen is irradiated with the generated plasma, and the substrate is irradiated with the plasma can be used. Alternatively, a vacuum plasma treatment in which the substrate is directly exposed to plasma by placing the substrate in metal electrodes facing each other via a dielectric in a closed chamber can be used.

[0195] A resin whose molecular chain is easily cleaved by plasma irradiation, like the methacrylic resin composition, can be treated by using a remote plasma method in which a process gas containing plasma is irradiated with the substrate, like the atmospheric pressure plasma treatment, to reduce damage to the substrate. On the other hand, a direct plasma method like the vacuum plasma treatment in which the substrate is directly exposed to plasma has high treatment efficiency and can be performed in a closed environment, and thus the risk of impurities being mixed in at the time of treatment can be reduced. Further, in order to be able to continuously perform the hydrophilization process of the substrate and the formation of the silane coupling agent layer in one reactor, it is preferable to form the silane coupling agent layer using the vacuum plasma method.

[0196] The gas used for the plasma treatment is not particularly limited as long as it is a gas that can introduce a hydroxyl group to the surface of the substrate to be treated, and a conventionally known gas such as nitrogen, argon, oxygen, or water vapor can be used.

[0197] The electric power amount of the discharge treatment at the time of plasma treatment is preferably 60 W min to 1500 W min, more preferably 100 W min to 1000 W min, and further preferably 120 W min to 800 W min. If the electric power amount at the time of discharge treatment is 60 W min or more, the hydrophilization treatment of the substrate is sufficiently performed, and there is a tendency that the silane coupling agent layer can be formed efficiently. As a result, there is a tendency that the durability of the adhesive layer of the reflection-type polarizing element-bonded lens is good in a high-temperature and high-humidity environment. On the other hand, if the electric power amount at the time of discharge treatment is 1500 W min or less, the formation of a brittle layer near the surface of the resin lens due to degradation of the resin lens by the plasma treatment is reduced, and there is a tendency that the durability of the adhesive layer of the reflection-type polarizing element-bonded lens is good in a high-temperature and high-humidity environment. Therefore, it is preferable that the electric power amount at the time of discharge treatment be within the above range.

[0198] Various conditions at the time of forming the silane coupling agent layer (for example, the pressure and the flow rate of the gas at the time of vacuum plasma treatment) can be appropriately set and are not particularly limited.

[0199] As a method of confirming the formation of the silane coupling agent layer, known methods such as measurement of the contact angle of water before and after the formation of the silane coupling agent layer, X-ray photoelectron spectroscopy (XPS), secondary ion mass spectrometry (TOF-SIMS), and infrared spectroscopy can be used. Note that when confirming the presence or absence of the silane coupling agent layer after the formation of the adhesive layer thereon, the adhesive interface is exposed by a method such as mechanical peeling using polishing, etching, chemical peeling using a solvent, physical peeling using heating or cooling to deteriorate the adhesive, and the like, and thus surface analysis can be performed.

[0200] (resin composition)

[0201] Hereinafter, a resin composition included in a resin lens of a reflective polarizing element attached lens according to the present embodiment will be described.

[0202] The resin lens of the reflective polarizing element attached lens according to the present embodiment is composed of a resin composition. The resin included in the resin lens is not particularly limited as long as it has both low birefringence characteristics and heat resistance characteristics that do not impair the function of the reflective polarizing element, but as a resin that can highly achieve low birefringence characteristics, it is preferable to include a methacrylic resin. In other words, it is preferable that the resin lens be composed of a resin composition including a methacrylic resin, that is, a methacrylic resin composition.

[0203] In addition, it is also preferable that the resin lens be composed of a cyclic polyolefin-based resin composition. More preferably, the resin lens is composed of a resin composition including a cyclic olefin copolymer that is a copolymer of ethylene or an a-olefin and a cyclic olefin.

[0204] (methacrylic resin composition)

[0205] The methacrylic resin composition contains a methacrylic resin. In addition, the methacrylic resin composition can optionally include an additive other than the methacrylic resin, and can also include another thermoplastic resin, a rubbery polymer, or the like other than the methacrylic resin.

[0206] -methacrylic resin-

[0207] Hereinafter, the methacrylic resin included in the methacrylic resin composition will be described.

[0208] As the methacrylic resin, there is no particular limitation, and for example, a resin in which a structural unit derived from methyl methacrylate is the main body can be cited. Among them, a homopolymer of methyl methacrylate or a copolymer of methyl methacrylate and any one or more of monomers copolymerizable with methyl methacrylate such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, butyl acrylate, propylene nitrile, acrylic acid, methacrylic acid, vinyl pyridine, vinyl morpholine, vinyl pyrrolidone, tetrahydrofurfuryl acrylate, N,N-dimethylaminoethyl acrylate, N,N-dimethyl acrylamide, 2-hydroxy acrylate, 2-(hydroxymethyl)ethyl acrylate, ethylene glycol monoacrylate, glycerol monoacrylate, maleic anhydride, N-cyclohexyl maleimide, N-phenyl maleimide, styrene, or α-methyl styrene, and the like can be cited. In addition to these, as the methacrylic resin, a heat-resistant methacrylic resin including a structural unit derived from methyl methacrylate and a lactone ring or glutarimide in the main chain, a methyl methacrylate, and a low-hygroscopic methacrylic resin, and the like can be cited. They can be used alone or two or more of them can be used in combination.

[0209] As the methacrylic resin constituting the resin lens of the reflection-type polarizing element attached lens of the present embodiment, by appropriately adjusting the ratio of the structural unit (X) having a ring structure in the main chain to the structural unit derived from a methacrylic ester monomer, a head-mounted display resin lens in which the average value of the absolute value of the phase difference in the effective diameter, which is reduced due to orientation and residual stress at the time of molding, is 10 nm or less can be obtained. In addition, by appropriately adjusting the above ratio, the methacrylic resin can be sufficiently imparted with heat resistance. From these viewpoints, as the content of the structural unit derived from a methacrylic ester monomer, the methacrylic resin is set to 100% by mass, and is preferably 50 to 97% by mass, more preferably 55 to 97% by mass, further preferably 55 to 95% by mass, still further preferably 60 to 93% by mass, and particularly preferably 60 to 90% by mass.

[0210] Note that the content of the structural unit derived from a methacrylic ester monomer can be calculated by 1 H-NMR measurement and 13 C-NMR measurement. For 1 H-NMR measurement and 13 C-NMR measurement, for example, deuterated chloroform (CDCI3) or deuterated dimethyl sulfoxide (DMSO-d6) can be used as the measurement solvent, and measurement can be performed at a measurement temperature of 40°C.

[0211] From the viewpoints of transparency and heat resistance, it is preferable that the methacrylic resin in the present embodiment include a methacrylic resin having a structural unit having a ring structure.

[0212] As the aforementioned structural unit having a ring structure, at least one structural unit selected from the group consisting of a structural unit derived from an N-substituted maleimide monomer, a glutarimide-based structural unit, an aromatic vinyl-based structural unit, an alicyclic vinyl-based structural unit, and a lactone ring structural unit is preferably contained. In the case of a methacrylic acid resin into which a ring structure is introduced via a ring-formation step, a carboxylic acid side chain can remain, which is a main cause of the water absorption becoming extremely high, and adversely affects the adhesion to an antireflection coating and a mirror coating and the adhesion to a reflective polarizing element, and thus a methacrylic acid-based resin having a structural unit derived from an N-substituted maleimide monomer or a structural unit having an aromatic ring hydrogenation structure is more preferable. In addition, from the viewpoint of easily highly controlling optical properties such as intrinsic birefringence and photoelastic coefficient without mixing other thermoplastic resins, it is particularly preferable that the structural unit having a ring structure contain a structural unit derived from an N-substituted maleimide monomer.

[0213] --Structural Unit Derived from N-Substituted Maleimide Monomer--

[0214] Then, the structural unit derived from an N-substituted maleimide monomer will be described.

[0215] The structural unit derived from an N-substituted maleimide monomer can be at least one structural unit selected from the group consisting of a structural unit represented by the following General Formula (1) and a structural unit represented by the following General Formula (2), and is preferably formed of both the structural unit represented by the following General Formula (1) and the structural unit represented by the following General Formula (2).

[0216]

[0217] In General Formula (1), R 1 represents any one of an arylalkyl group having 7 to 14 carbon atoms and an aryl group having 6 to 14 carbon atoms, and R 2 and R 3 each independently represent any one of a hydrogen atom, an oxygen atom, a sulfur atom, an alkyl group having 1 to 12 carbon atoms, and an aryl group having 6 to 14 carbon atoms.

[0218] In addition, in the case where R 2 or R 3 is an aryl group, R 2 or R 3 may contain a halogen atom as a substituent.

[0219] In addition, R 1 may be substituted with a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a benzyl group, or the like.

[0220]

[0221] In General Formula (2), R 4 represents any one of a hydrogen atom, a cycloalkyl group having 3 to 12 carbon atoms, and an alkyl group having 1 to 12 carbon atoms, R 5 and R 6 each independently represents any one of a hydrogen atom, an oxygen atom, a sulfur atom, an alkyl group having 1 to 12 carbon atoms, and an aryl group having 6 to 14 carbon atoms.

[0222] In General Formula (1), as the arylalkyl group having 7 to 14 carbon atoms, for example, a benzyl group, a phenylethyl group, a phenylpropyl group, a naphthylmethyl group, a naphthylethyl group, a naphthylpropyl group, or the like can be given.

[0223] In General Formula (1) and General Formula (2), as the aryl group having 6 to 14 carbon atoms, for example, a phenyl group, a tolyl group, a xylyl group, a naphthyl group, a biphenyl group, an anthryl group, a phenanthryl group, or the like can be given.

[0224] In General Formula (1) and General Formula (2), as the alkyl group having 1 to 12 carbon atoms, it can be linear or branched, and is not particularly limited, and for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a t-butyl group, a 2-methylbutyl group, an n-pentyl group, a 2-pentyl group, a 3-pentyl group, a 2,2-dimethylpropyl group, an n-hexyl group, a heptyl group, an n-octyl group, a 1,1,3,3-tetramethylbutyl group, a 2-ethylhexyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, or the like can be given.

[0225] In General Formula (1), as the halogen atom, for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or the like can be given.

[0226] In General Formula (1), as the alkoxy group having 1 to 6 carbon atoms, for example, a methoxy group, an ethoxy group, an n-butoxy group, a methoxyethoxy group, or the like can be given.

[0227] In General Formula (2), as the cycloalkyl group having 3 to 12 carbon atoms, for example, a cyclopropyl group, a cyclopropylmethyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclohexylmethyl group, a trimethylcyclohexyl group, a Thujyl group, a norbornyl group, a borneol group, a norcaryl group, a caryl group, a menthyl group, a norpinyl group, a pinyl group, a 1-adamantyl group, a 2-adamantyl group, or the like can be given.

[0228] Hereinafter, specific examples of monomers forming the structural units represented by General Formula (1) and General Formula (2) will be shown.

[0229] As the monomer (N-aryl maleimide, N-aromatic-substituted maleimide, etc.) forming the structural unit represented by General Formula (1), for example, N-phenyl maleimide, N-benzyl maleimide, N-(2-chlorophenyl) maleimide, N-(4-chlorophenyl) maleimide, N-(4-bromophenyl) maleimide, N-(2-methylphenyl) maleimide, N-(2,6-dimethylphenyl) maleimide, N-(2-ethylphenyl) maleimide, N-(2-methoxyphenyl) maleimide, N-(2-nitrophenyl) maleimide, N-(2,4,6-trimethylphenyl) maleimide, N-(4-benzylphenyl) maleimide, N-(2,4,6-tribromophenyl) maleimide, N-naphthyl maleimide, N-anthryl maleimide, 3-methyl-l-phenyl-lH-pyrrole-2,5-dione, 3,4-dimethyl-l-phenyl-lH-pyrrole-2,5-dione, l,3-diphenyl-lH-pyrrole-2,5-dione, l,3,4-triphenyl-lH-pyrrole-2,5-dione, and the like can be given.

[0230] Among these monomers, from the viewpoint of heat resistance and optical properties such as birefringence, N-phenyl maleimide and N-benzyl maleimide are preferred.

[0231] These monomers are sometimes used alone, and sometimes two or more are used in combination.

[0232] As the monomer forming the structural unit represented by General Formula (2), for example, N-methyl maleimide, N-ethyl maleimide, N-n-propyl maleimide, N-isopropyl maleimide, N-n-butyl maleimide, N-isobutyl maleimide, N-sec-butyl maleimide, N-t-butyl maleimide, N-n-pentyl maleimide, N-n-hexyl maleimide, N-n-heptyl maleimide, N-n-octyl maleimide, N-lauryl maleimide, N-cyclopentyl maleimide, N-cyclohexyl maleimide, l-cyclohexyl-3-methyl-lH-pyrrole-2,5-dione, l-cyclohexyl-3,4-dimethyl-lH-pyrrole-2,5-dione, l-cyclohexyl-3-phenyl-lH-pyrrole-2,5-dione, l-cyclohexyl-3,4-diphenyl-lH-pyrrole-2,5-dione, and the like can be given.

[0233] Among these monomers, from the viewpoint of excellent weather resistance of the methacrylic resin, N-methyl maleimide, N-ethyl maleimide, N-isopropyl maleimide, and N-cyclohexyl maleimide are preferred, and N-cyclohexyl maleimide is particularly preferred because of the recent demand for excellent low moisture absorption of optical materials.

[0234] These monomers can be used alone, and two or more can be used in combination.

[0235] In the methacrylic resin in the methacrylic resin composition, from the aspect of being able to exhibit highly controlled birefringence characteristics, it is particularly preferable to use both the structural unit represented by General Formula (1) and the structural unit represented by General Formula (2).

[0236] The molar ratio (X1 / X2) of the content (X1) of the structural unit represented by General Formula (1) to the content (X2) of the structural unit represented by General Formula (2) is preferably greater than 0 and 15 or less, and more preferably greater than 0 and 10 or less. When the above molar ratio (X1 / X2) is within this range, the reflective polarizing element-adhered lens of the present embodiment maintains transparency, does not yellow, and does not impair environmental resistance, exhibiting good heat resistance and good photoelasticity characteristics.

[0237] The content of the structural unit from the N-substituted maleimide monomer is preferably in the range of 5 to 40 mass% and more preferably in the range of 5 to 35 mass% with respect to 100 mass% of the methacrylic resin. When the content of the structural unit from the N-substituted maleimide monomer is within this range, the methacrylic resin is able to achieve more sufficient improvement effects in heat resistance, and in addition, more preferable improvement effects in weather resistance, low water absorption, and optical characteristics. Note that setting the content of the structural unit from the N-substituted maleimide monomer to 40 mass% or less is effective in preventing a decrease in the reactivity of monomer components during polymerization, and a decrease in the properties of the methacrylic resin due to an increase in the amount of monomers that remain unreacted.

[0238] In addition, by appropriately adjusting the content of the structural unit from the N-substituted maleimide monomer within this range, the birefringence due to orientation and residual stress during molding is reduced, and a reflective polarizing element-adhered lens in which the average value of the absolute values of the in-plane retardation is 10 nm or less can be obtained. The most suitable content of the structural unit from the N-substituted maleimide monomer varies depending on the type of N-substituted maleimide, and for example, in the case where methyl methacrylate is used as the methacrylic ester monomer and N-phenylmaleimide and N-cyclohexylmaleimide are used as the N-substituted maleimide monomer, it is preferable to adjust the content within the range where the structural unit from methyl methacrylate is 79 to 83 mass%, the structural unit from N-phenylmaleimide is 6 to 8 mass%, and the structural unit from N-cyclohexylmaleimide is 11 to 13 mass%.

[0239] Within a range that does not impair the object of the present application, the methacrylic resin having the structural unit from the N-substituted maleimide monomer can contain a structural unit from another monomer that is copolymerizable with the methacrylic ester monomer and the N-substituted maleimide monomer.

[0240] For example, as the other monomer copolymerizable as described above, aromatic vinyl monomers; unsaturated nitrile monomers; cyclohexyl monomers, benzyl monomers, acrylates having an alkyl group having 1 to 18 carbon atoms; glycidyl compounds; unsaturated carboxylic acids; and the like can be exemplified.

[0241] As the aromatic vinyl monomers as described above, styrene, a-methylstyrene, divinylbenzene, and the like can be exemplified.

[0242] As the unsaturated nitrile as described above, acrylonitrile, methacrylonitrile, ethyl acrylonitrile, and the like can be exemplified.

[0243] As the acrylates as described above, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, and the like can be exemplified.

[0244] As the glycidyl compounds as described above, glycidyl (meth)acrylate, and the like can be exemplified.

[0245] As the unsaturated carboxylic acids as described above, acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, and semi-esters or anhydrides thereof, and the like can be exemplified.

[0246] The structural units from the other monomers copolymerizable as described above can be only one, or two or more.

[0247] As the content of these structural units from the other monomers copolymerizable, the methacrylic acid-based resin is taken as 100% by mass, it is preferably 0 to 10% by mass, more preferably 0 to 9% by mass, and further preferably 0 to 8% by mass.

[0248] If the content of the structural units from the other monomers is within the range, the molding processability and mechanical properties of the resin can be improved without impairing the original effects of introducing the ring structure, and thus is preferred.

[0249] Note that the content of the structural units from the N-substituted maleimide monomers and the content of the structural units from the other monomers copolymerizable can be determined by 1 H-NMR measurement and 13 C-NMR measurement. For the 1 H-NMR measurement and 13 C-NMR measurement, CDCl3or DMSO-d6, for example, can be used as the measurement solvent, and the measurement can be performed at a measurement temperature of 40°C.

[0250] -- glutarimide-based structural units

[0251] As the methacrylic resin having a glutarimide-based structural unit, for example, the methacrylic resin having a glutarimide-based structural unit described in Japanese Patent Application Publication No. 2006-249202, Japanese Patent Application Publication No. 2007-009182, Japanese Patent Application Publication No. 2007-009191, Japanese Patent Application Publication No. 2011-186482, Japanese Laid-Open Patent Publication No. 2012 / 114718, and the like can be cited, and can be formed by the method described in the publications.

[0252] The glutarimide-based structural unit constituting the methacrylic resin can be formed after polymerization of the resin.

[0253] Specifically, the glutarimide-based structural unit can be represented by the following general formula (3).

[0254]

[0255] In the above general formula (3), it is preferable that R 7 and R 8 are each independently a hydrogen atom or a methyl group, R 9 is any one of a hydrogen atom, a methyl group, a butyl group, and a cyclohexyl group, more preferably, R 7 is a methyl group, R 8 is a hydrogen atom, and R 9 is a methyl group.

[0256] The glutarimide-based structural unit can contain only a single kind, or can contain a plurality of kinds.

[0257] In the methacrylic resin having a glutarimide-based structural unit, with respect to the content of the glutarimide-based structural unit, it is preferable that the methacrylic resin is in the range of 3 to 70 mass%, more preferably in the range of 3 to 60 mass%, based on 100 mass% of the methacrylic resin.

[0258] If the content of the glutarimide-based structural unit is in the above range, a resin having good moldability, heat resistance, and optical properties can be obtained, and thus it is preferable.

[0259] In addition, by appropriately adjusting the content of the glutarimide-based structural unit in the range, birefringence due to orientation and residual stress at the time of molding can be reduced, and a reflection-type polarizing element attached lens in which the average value of the absolute value of the in-plane retardation is 5 nm or less can be obtained. The content of the glutarimide-based structural unit differs depending on the kind of the substituent of R 7 to R 9 of the general formula (3), for example, when R 7 and R 8 are hydrogen atoms and R 9When the content of the glutarimide-based structural unit is in the range of 3 to 10% by mass, the birefringence due to orientation and residual stress at the time of molding can be reduced, and a reflection-type polarizing element attached lens in which the average of the absolute values of the in-plane retardation is 10 nm or less can be obtained.

[0260] Note that the content of the glutarimide-based structural unit in the methacrylic resin can be determined using the method described in the aforementioned patent document.

[0261] The methacrylic resin having a glutarimide-based structural unit can further include an aromatic vinyl monomer unit, as necessary.

[0262] There is no particular limitation on the aromatic vinyl monomer, and styrene, α-methylstyrene, and the like can be given, with styrene being preferred.

[0263] There is no particular limitation on the content of the aromatic vinyl unit in the methacrylic resin having a glutarimide-based structural unit, and the content is preferably in the range of 0 to 20% by mass, based on 100% by mass of the methacrylic resin having a glutarimide-based structural unit.

[0264] The content of the aromatic vinyl unit is preferably in the above range in order to achieve both heat resistance and excellent photoelastic properties.

[0265] For example, when a methacrylate-styrene copolymer obtained by copolymerizing methyl methacrylate as a methacrylate monomer and styrene as an aromatic vinyl monomer is glutarimidized to obtain a resin, by adjusting the content of the structural unit derived from methyl methacrylate to be in the range of 65 to 90% by mass, the content of the structural unit derived from styrene to be in the range of 5 to 15% by mass, and the content of the glutarimide-based structural unit to be in the range of 5 to 20% by mass, the birefringence due to orientation and residual stress at the time of molding can be reduced, and a reflection-type polarizing element attached lens in which the average of the absolute values of the in-plane retardation is 10 nm or less can be obtained.

[0266] -- Aromatic vinyl structural unit --

[0267] There is no particular limitation on the aromatic vinyl structural unit, and for example, the structural unit derived from styrene, the structural unit derived from α-methylstyrene, and the like can be given, with the structural unit derived from styrene being preferred.

[0268] -- Aromatic vinyl structural unit --

[0269] As the alicyclic vinyl structural unit, for example, it is possible to form by the method described in Japanese Patent Application Publication No. 2006-291184, Japanese Patent Application Publication No. 2014-77043, and Japanese Patent Application Publication No. 2014-77044, and the like.

[0270] -- Lactone ring structural unit

[0271] The methacrylic resin having a lactone ring structural unit can be formed, for example, by the method described in Japanese Patent Application Publication No. 2001-151814, Japanese Patent Application Publication No. 2004-168882, Japanese Patent Application Publication No. 2005-146084, Japanese Patent Application Publication No. 2006-96960, Japanese Patent Application Publication No. 2006-171464, Japanese Patent Application Publication No. 2007-63541, Japanese Patent Application Publication No. 2007-297620, and Japanese Patent Application Publication No. 2010-180305, and the like.

[0272] The lactone ring structural unit constituting the methacrylic resin can be formed after polymerization of the resin.

[0273] As the lactone ring structural unit in the present embodiment, since the stability of the ring structure is excellent, it is preferably a six-membered ring.

[0274] As the six-membered ring lactone ring structural unit, for example, a structure represented by the following general formula (4) is particularly preferable.

[0275]

[0276] In the above general formula (4), R 10 , R 11 , and R 12 are each independently a hydrogen atom or an organic residue having 1 to 20 carbon atoms.

[0277] As the organic residue, for example, there are mentioned a saturated aliphatic hydrocarbon group (alkyl group, etc.) having 1 to 20 carbon atoms such as a methyl group, an ethyl group, a propyl group, and the like; an unsaturated aliphatic hydrocarbon group (alkenyl group, etc.) having 2 to 20 carbon atoms such as a vinyl group, a propenyl group, and the like; an aromatic hydrocarbon group (aryl group, etc.) having 6 to 20 carbon atoms such as a phenyl group, a naphthyl group, and the like; a group in which one or more hydrogen atoms in these saturated aliphatic hydrocarbon groups, unsaturated aliphatic hydrocarbon groups, and aromatic hydrocarbon groups are substituted with at least one selected from the group consisting of a hydroxyl group, a carboxyl group, an ether group, and an ester group; and the like.

[0278] The lactone ring structure unit can be introduced into the molecular chain by, for example, copolymerizing an acrylic monomer having a hydroxyl group with a methacrylic ester monomer such as methyl methacrylate, or by introducing a hydroxyl group and an ester group or a hydroxyl group and a carboxyl group, and then causing dealcoholization (esterification) or dehydration condensation (hereinafter, also referred to as "cyclization condensation reaction") between the hydroxyl group and the ester group or between the hydroxyl group and the carboxyl group.

[0279] As the acrylic monomer having a hydroxyl group used in the polymerization, for example, 2-(hydroxymethyl)acrylic acid, 2-(hydroxyethyl)acrylic acid, 2-(hydroxymethyl)acrylic acid alkyl ester (for example, 2-(hydroxymethyl)acrylic acid methyl ester, 2-(hydroxymethyl)acrylic acid ethyl ester, 2-(hydroxymethyl)acrylic acid isopropyl ester, 2-(hydroxymethyl)acrylic acid n-butyl ester, 2-(hydroxymethyl)acrylic acid t-butyl ester), 2-(hydroxyethyl)acrylic acid alkyl ester, and the like can be given, and 2-(hydroxymethyl)acrylic acid, 2-(hydroxymethyl)acrylic acid alkyl ester as a monomer having a hydroxyl alkyl moiety are preferable, and 2-(hydroxymethyl)acrylic acid methyl ester, 2-(hydroxymethyl)acrylic acid ethyl ester are particularly preferable.

[0280] The content of the lactone ring structure unit in the methacrylic resin having a lactone ring structure unit is preferably 5 to 40% by mass, more preferably 5 to 35% by mass, with respect to 100% by mass of the methacrylic resin.

[0281] If the content of the lactone ring structure unit is within this range, it is possible to exhibit the effects of introducing a ring structure, such as an improvement in solvent resistance and an improvement in surface hardness, while maintaining moldability. In addition, by appropriately adjusting the content of the lactone ring structure unit within this range, it is possible to reduce birefringence due to orientation and residual stress at the time of molding, and it is possible to obtain a reflection-type polarizing element bonded lens in which the average of the absolute values of the in-plane phase difference is 10 nm or less.

[0282] Note that the content of the lactone ring structure in the methacrylic resin can be determined using the method described in the aforementioned patent literature.

[0283] The methacrylic resin having a lactone ring structure unit can also have a structural unit from another monomer that can be copolymerized with the aforementioned methacrylic ester monomer and the acrylic monomer having a hydroxyl group.

[0284] As such another monomer that can be copolymerized, for example, monomers having a polymerizable double bond such as styrene, vinyltoluene, α-methylstyrene, α-hydroxymethylstyrene, α-hydroxyethylstyrene, acrylonitrile, methacrylonitrile, methallyl alcohol, ethylene, propylene, 4-methyl-1-pentene, vinyl acetate, 2-hydroxymethyl-1-butene, methyl vinyl ketone, N-vinylpyrrolidone, N-vinylcarbazole, and the like can be given.

[0285] These other monomers (structural units) can be only one or two or more.

[0286] As the content of these structural units from other monomers copolymerizable with the methyl methacrylate monomer, it is preferably 0 to 20 mass% relative to 100 mass% of the methyl methacrylate resin, more preferably less than 10 mass% from the viewpoint of weather resistance, and further preferably less than 7 mass%.

[0287] The methyl methacrylate resin in the present embodiment can have only one of the above-described structural units from other monomers copolymerizable with the methyl methacrylate monomer, or two or more.

[0288] --Methyl methacrylate resin containing aromatic ring hydrogenated structural units--

[0289] In addition to the methyl methacrylate resin having a structural unit having a ring structure in the main chain and a structural unit from a methyl methacrylate monomer, as the methyl methacrylate resin having a low birefringence satisfying the present embodiment, as an example, a methyl methacrylate resin having an aromatic ring hydrogenated structural unit is given.

[0290] As a method of producing the methyl methacrylate resin having an aromatic ring hydrogenated structural unit, a method of producing a core hydrogenated polymer by hydrogenating a copolymer of an aromatic vinyl compound and a (meth)acrylate in the presence of a hydrogenation catalyst and a reaction solvent is used.

[0291] The method of polymerizing monomers containing an aromatic vinyl compound and a (meth)acrylate can use a publicly known method, as long as it is industrially simple using a method of radical polymerization. Radical polymerization can appropriately select a publicly known method such as bulk polymerization, solution polymerization, emulsion polymerization, suspension polymerization, and the like, but in order to avoid moisture content at the time of hydrogenation reaction, production by a bulk polymerization method or a solution polymerization method is preferable. In the production method in the present embodiment, as the polymerization form, for example, any one of a batch polymerization method, a semi-batch method, and a continuous polymerization method can be used.

[0292] As a method of producing the methyl methacrylate resin containing an aromatic ring hydrogenated structural unit, for example, it can be formed by the method described in Japanese Patent Application Publication No. 2006-291184, Japanese Patent Application Publication No. 2014-77043, Japanese Patent Application Publication No. 2014-77044, and the like.

[0293] Hereinafter, one example of the production method of the methyl methacrylate resin containing an aromatic ring hydrogenated structural unit obtained by hydrogenating a copolymer of an aromatic vinyl compound and a (meth)acrylate will be specifically described.

[0294] As the aromatic vinyl compound used in the polymerization, specifically, styrene, α-methylstyrene, vinyltoluene, α-hydroxymethylstyrene, α-hydroxyethylstyrene, p-hydroxystyrene, alkoxy styrene, chlorostyrene, and the like can be mentioned, but styrene is preferred. In addition, two or more kinds of aromatic vinyl compounds can be copolymerized. In particular, by using styrene having a substituent at the α-position, the heat resistance of the resin can be improved, and thus it is preferred.

[0295] As the solvent used in the polymerization, it is also necessary to consider that the solvent itself is stable under the reaction conditions, and that the solubility of the copolymer before and after the hydrogenation reaction (the copolymer of the aromatic vinyl compound and the (meth)acrylate and the core hydrogenated polymer obtained by hydrogenating the aromatic ring) and the solubility of hydrogen are good, and that the reaction proceeds rapidly. In addition, when devolatilization of the solvent component after the reaction is assumed, it is also important that the solvent has a high ignition point. As the solvent satisfying these conditions, hydrocarbon compounds such as n-pentane, n-hexane, n-octane, cyclohexane; ether compounds such as 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether; amide compounds such as dimethylformamide, dimethylacetamide; ester compounds; and the like are mentioned, and ether compounds and ester compounds are particularly preferred. As the ether compound, tetrahydrofuran is particularly preferred. These solvents can be used alone or in combination of two or more kinds.

[0296] As the ester compound, a carboxylic acid ester compound is preferred. The carboxylic acid ester compound uses an aliphatic ester compound, and preferably a compound represented by the following general formula (5). In the following general formula (5), R1is an alkyl group having 1 to 6 carbon atoms, and R2is an alkyl group having 1 to 6 carbon atoms. As R1and R2, as examples, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, hexyl, and cyclohexyl are mentioned. As the ester compound, methyl acetate, ethyl acetate, n-butyl acetate, pentyl acetate, methyl propionate, ethyl propionate, n-propyl propionate, n-butyl propionate, methyl n-butyrate, methyl isobutyrate, n-butyl n-butyrate, methyl n-pentanoate, methyl n-hexanoate, and the like are used, and in particular, methyl acetate, ethyl acetate, methyl propionate, methyl isobutyrate, and methyl n-butyrate are further preferred.

[0297] R1-COO-R2(5)

[0298] The concentration of the copolymer (the copolymer of the aromatic vinyl compound and the (meth)acrylate and the core hydrogenated polymer obtained by hydrogenating the aromatic ring) in the solution at the time of the hydrogenation reaction is usually 1 to 50% by weight, preferably 3 to 30% by weight, and further preferably 5 to 25% by weight. If the concentration of the copolymer is too high, it is not preferred in terms of the handling inconvenience due to the decrease in the reaction rate and the increase in the viscosity of the solution, and if the concentration is low, it is not preferred in terms of the productivity and the economy.

[0299] The moisture concentration in the polymer solution before the hydrogenation reaction is 0.5% by weight or less, preferably 0.2% by weight or less, and further preferably 0.05% by weight or less. If the moisture amount is greater than 0.5% by weight, the manufactured core hydrogenated polymer (pellets, powder) sometimes becomes colored, which is not preferable as an optical material.

[0300] During the polymerization reaction, a polymerization initiator and a chain transfer agent can be added as needed, but sulfur components hinder the hydrogenation reaction, and thus it is preferable to contain as little sulfur as possible.

[0301] As the polymerization initiator, any polymerization initiator other than those having a sulfur functional group can be used without particular limitation, and for example, the polymerization initiators disclosed in the production method of the methacrylic resin having the structural unit from the N-substituted maleimide monomer described above can be used.

[0302] These polymerization initiators can be used alone or in combination with two or more.

[0303] These polymerization initiators can be added at any stage as long as the polymerization reaction is performed.

[0304] The amount of the polymerization initiator to be added is not particularly limited as long as it is appropriately set according to the combination of monomers and the reaction conditions, and can be 0.05 to 1% by mass when the total amount of the monomers used in the polymerization is 100% by mass.

[0305] The preferred method of adding the polymerization initiator and the chain transfer agent in the polymerization step can be, for example, the method described in the production method of the methacrylic resin having the structural unit from the N-substituted maleimide monomer described above.

[0306] The concentration of dissolved oxygen in the polymerization solution can be, for example, the value disclosed in the production method of the methacrylic resin having the structural unit from the N-substituted maleimide monomer described above.

[0307] The chain transfer agent is not necessarily required. In addition, when used, it is preferable to use, for example, a tetrachlorocarbon such as carbon tetrachloride, tetrabromocarbon, tetracarbon iodide, or a dimer of a styrene such as 2,4-diphenyl-4-methyl-1-pentene. A thiol compound, which is a chain transfer agent commonly used, introduces a sulfur functional group to the end of the polymer, which hinders the hydrogenation reaction of the aromatic ring, and thus is not preferable.

[0308] They can be used alone or in combination with two or more.

[0309] These chain transfer agents can be added at any stage as long as the polymerization reaction is performed, and are not particularly limited.

[0310] The amount of the chain transfer agent to be added is not particularly limited as long as a desired polymerization degree is obtained under the polymerization conditions used, and is preferably 0.05 to 1 mass% when the total amount of the monomers used in the polymerization is taken as 100 mass%.

[0311] Note that when a thiol compound-based chain transfer agent is not generally used, the thermal decomposition properties of the raw polymer decrease, but for a methyl methacrylate resin including an aromatic ring hydrogenated structural unit, the decomposition temperature and the like are determined only by the hydrogenation rate, and if the hydrogenation rate is the same, the use of a sulfur-based chain transfer agent does not affect the decomposition temperature.

[0312] As the catalyst used in the hydrogenation reaction (hydrogenation catalyst), there is no particular limitation as long as it has hydrogenation activity. Specifically, nickel, ruthenium, rhodium, palladium, platinum, and the like can be given. Among them, as a substance in which the reaction rate is high and the solvent does not undergo a side reaction and is maintained before and after the reaction, a substance in which palladium is supported on a carrier is particularly preferable. Generally, as the catalyst carrier, activated carbon, alumina (AI2O3), silica (SiO2), silica-alumina (SiO2-AI2O3), diatomaceous earth, zirconia, and the like are used. As the carrier of the catalyst in the present application, there is no limitation, and activated carbon or alumina or zirconia is preferably used.

[0313] The loading amount of palladium metal on the carrier is generally in the range of 0.01 to 50% by weight, preferably 0.05 to 20% by weight, and further preferably 0.1 to 10% by weight. Economically, it is preferable that the amount of use of expensive palladium be as small as possible, but when activated carbon or zirconia is used as the carrier, palladium can be highly dispersedly supported, and in addition, the reaction rate per unit of palladium is very large, and thus, in the case where the loading amount of palladium is set to 0.1 to 1.0% by weight, a sufficient reaction rate can also be maintained. Note that when measuring the dispersion degree of palladium, a known method such as a carbon monoxide pulse adsorption method is used.

[0314] As the precursor of palladium, known salts or complexes such as palladium chloride, palladium nitrate, and palladium acetate can be used. When impregnated and supported on a carrier, the precursor is made into a solution, and as examples of the combination (precursor / solvent) of the precursor solution, there are palladium chloride / hydrochloric acid water, palladium chloride / sodium chloride water, palladium nitrate / water, palladium nitrate / hydrochloric acid water, palladium acetate / hydrochloric acid water, palladium acetate / organic solvent, and the like.

[0315] As preferable conditions for the hydrogenation reaction, a temperature of 60 to 250°C, a hydrogen pressure of 3 to 30 MPa, and a reaction time of 3 to 20 hr are exemplified. If the reaction temperature is too low, the reaction rate becomes slow, and if the reaction temperature is too high, side reactions such as decomposition of the polymer and hydrogenation decomposition of the solvent occur, and thus are not preferable. Further, in the case where the hydrogen pressure is low, the reaction rate is slow, and on the contrary, if the hydrogen pressure is further increased, a high-pressure resistant reactor is required, and thus is not preferable in terms of economy.

[0316] By separating the hydrogenation catalyst and the volatile components (solvent, etc.) from the polymer solution after the hydrogenation reaction, a core-hydrogenated polymer can be obtained.

[0317] The separation of the catalyst can be performed by a known method such as filtration or centrifugal separation. The residual catalyst metal concentration in the polymer needs to be as low as possible in view of coloring, influence on mechanical properties, etc., and is preferably 10 ppm or less, and further preferably 1 ppm or less.

[0318] After the separation of the catalyst, as a method for purifying the polymer by separating the volatile components such as the solvent from the obtained core-hydrogenated polymer solution, a devolatilization method after the devolatilization by the devolatilization method described in the production method of the methacrylic resin having a structural unit derived from an N-substituted maleimide monomer is preferable from the viewpoint of reduction of the fluorescence intensity.

[0319] In the case of the copolymer of the aromatic vinyl compound and the (meth)acrylate, the composition of the structural unit of the copolymer does not necessarily coincide with the composition of the input monomers, but is determined by the amount of the monomers actually entering the copolymer by the polymerization reaction. If the polymerization rate is 100%, the ratio of the structural unit of the copolymer coincides with the input monomer composition ratio, but in fact, the production is mostly performed at a polymerization rate of 50 to 80%, and the higher the reactivity, the more the monomer enters the copolymer, and thus, the input composition of the monomers and the composition of the structural unit of the copolymer can deviate, and thus, the input monomer composition ratio needs to be appropriately adjusted.

[0320] In the structural unit of the copolymer of the aromatic vinyl compound and the (meth)acrylate used in the hydrogenation reaction in the present application, the molar ratio (A / B) of the structural unit derived from the (meth)acrylate monomer (A mol) to the structural unit of the aromatic vinyl compound monomer (B mol) is preferably 0.25 or more and 4.0 or less. If the molar ratio (A / B) is less than 0.25, the mechanical strength is poor, and sometimes cannot withstand practical use. If the molar ratio (A / B) is more than 4.0, the number of hydrogenated aromatic rings is small, and thus, the effect of improving the properties such as the glass transition temperature caused by the hydrogenation reaction is sometimes insufficient.

[0321] The content of these structural units derived from other monomers copolymerizable therewith is preferably 0 to 20% by mass, more preferably less than 10% by mass, and even more preferably less than 7% by mass, relative to 100% by mass of the methacrylic resin, from the viewpoint of weather resistance.

[0322] The methacrylic resin in the present embodiment can have only one of the above structural units derived from other monomers copolymerizable therewith, or can have two or more.

[0323] Method for producing methacrylic resin

[0324] Hereinafter, the method for producing the methacrylic resin of the present embodiment will be described.

[0325] In the method for producing the methacrylic resin, as the polymerization form, batch, semi-batch, or continuous type can be used. Here, the batch type means a process in which the reaction is started after the total amount of raw materials is charged into the reactor and is continued until the end, and the product is recovered after the end. The semi-batch type means a process in which either the raw material charging or the product recovery is performed while the reaction is in progress. Further, the continuous type means a process in which both the raw material charging and the product recovery are performed while the reaction is in progress. As the method for producing the methacrylic resin, from the viewpoint of precisely controlling the composition of the copolymer, the semi-batch type in which a part of the raw material charging is performed after the start of the reaction is preferred.

[0326] In addition, the continuous type can be used, but as the method for producing the methacrylic resin, the continuous type is preferably not used for the following reasons. When the polymerization is performed using one complete-mixing reactor, there is an advantage that the difference in the monomer composition between the components having different molecular weights in the methacrylic resin can be reduced, but since a large amount of unreacted monomers remains after the polymerization, there is a tendency to adversely affect the color tone. On the other hand, in the case of using a plug flow reactor, the amount of unreacted monomers can be reduced, but there is a tendency that the difference in the monomer composition between the components having different molecular weights in the methacrylic resin becomes large. In the case of combining a plurality of complete-mixing reactors or a complete-mixing reactor and a plug flow reactor in series, the amount of unreacted monomers can be reduced, but there is a tendency that the difference in the monomer composition between the components described above becomes large.

[0327] As the polymerization method of the methacrylic resin, there is no particular limitation, and for example, emulsion polymerization, solution polymerization, radical polymerization, anionic polymerization, cationic polymerization, and the like can be mentioned.

[0328] As the polymerization solvent, there is no particular limitation, and for example, aromatic hydrocarbons such as toluene, xylene, ethylbenzene, cumene, and the like; esters such as methyl isobutyrate, and the like; ketones such as methyl isobutyl ketone, butyl cellosolve, methyl ethyl ketone, cyclohexanone, and the like; polar solvents such as dimethylformamide, 2-methylpyrrolidone, and the like can be used.

[0329] In addition, alcohols such as methanol, ethanol, isopropanol, and the like can also be used as the polymerization solvent, within a range that does not hinder the dissolution of the polymerization product.

[0330] As the amount of the solvent at the time of polymerization, any amount that allows the polymerization to proceed, does not cause the copolymer and the used monomers to precipitate, and can be easily removed is acceptable, and there is no particular limitation. For example, when the total amount of the used monomers is set to 100 parts by mass, it is preferably set to 10 to 200 parts by mass, more preferably 25 to 200 parts by mass, further preferably 50 to 200 parts by mass, and more further preferably 50 to 150 parts by mass.

[0331] As the polymerization initiator, any of the initiators generally used in radical polymerization can be used, and for example, organic peroxides such as cumene hydroperoxide, diisopropylbenzene hydroperoxide, di-t-butyl peroxide, lauryl peroxide, benzoyl peroxide, t-butylperoxy isopropyl carbonate, t-amylperoxy-2-ethylhexanoate, t-amylperoxy isononanoate, 1,1-di(t-butylperoxy)cyclohexane, and the like; azo compounds such as 2,2'-azobis(isobutyronitrile), 1,1'-azobis(cyclohexanecarbonitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), dimethyl-2,2'-azobis(isobutyrate), and the like; and the like can be exemplified.

[0332] They can be used alone or in combination of two or more.

[0333] As to these polymerization initiators, they can be added at any stage as long as the polymerization reaction proceeds.

[0334] As the amount of the polymerization initiator to be added, when the total amount of the monomers used in the polymerization is set to 100 parts by mass, it can be 0.01 to 1 parts by mass, and is preferably 0.05 to 0.5 parts by mass.

[0335] As the chain transfer agent, the chain transfer agents generally used in radical polymerization can be used, and for example, thiol compounds such as n-butyl mercaptan, n-octyl mercaptan, n-decyl mercaptan, n-dodecyl mercaptan, 2-ethylhexyl mercaptoacetate, and the like; halogen compounds such as carbon tetrachloride, dichloromethane, tribromomethane, and the like; unsaturated hydrocarbon compounds such as α-methylstyrene dimer, α-terpinene, dipentene, terpinolene, and the like can be exemplified.

[0336] They can be used alone or in combination of two or more.

[0337] As for these chain transfer agents, they can be added at any stage as long as the polymerization is in progress, and there is no particular limitation.

[0338] As the amount of addition of the chain transfer agent, when the total amount of the monomers used in the polymerization is taken as 100 parts by mass, it can be 0.01 to 1 parts by mass, and preferably 0.05 to 0.5 parts by mass.

[0339] As the method for recovering the polymer from the polymerization solution obtained by solution polymerization, there is no particular limitation, and for example, a method in which, after the polymerization solution is added in the presence of an excess of a poor solvent such as a hydrocarbon-based solvent, an alcohol-based solvent, or the like in which the polymerization product obtained by polymerization is not dissolved, the solution is treated (emulsified and dispersed) using a homogenizer, and the unreacted monomer is subjected to a pretreatment such as liquid-liquid extraction, solid-liquid extraction, or the like to be separated from the polymerization solution; or a method in which the polymerization solvent and the unreacted monomer are separated via a process called a devolatilization process, and the polymerization product is recovered; and the like can be given.

[0340] Here, the devolatilization process refers to a process in which volatile components such as the polymerization solvent, the residual monomer, and the reaction byproduct are removed under heating and reduced pressure.

[0341] As the device used in the devolatilization process, for example, a devolatilization device composed of a tubular heat exchanger and a devolatilization tank; a thin film evaporator such as Wiprene and Exeva manufactured by Gensco Environmental Solutions Corporation, KONTRO and Tilt Wing KONTRO manufactured by Hitachi, Ltd., and the like; an extruder having a residence time and a surface area sufficient to exhibit devolatilization performance with a vent hole; and the like can be given.

[0342] A devolatilization process using a devolatilization device in which any two or more of these devices are combined, and the like can also be used.

[0343] From the viewpoint of improving the color tone, it is preferable to use a devolatilization device in which a heat exchanger and a reduced pressure vessel are the main structures and which does not have a rotating part as its structure.

[0344] Specifically, a devolatilization device composed of a devolatilization tank and a discharge device can be used, in which the devolatilization tank is configured to have a heat exchanger disposed at the upper portion thereof and a reduced pressure unit attached to a reduced pressure vessel having a size that enables devolatilization, and the discharge device is a gear pump or the like for discharging the polymer after devolatilization.

[0345] As the devolatilizer, a heat exchanger such as a multi-tube heat exchanger, a fin-type heat exchanger, a flat-plate heat exchanger having a flat-plate flow path and a heater, or the like can be used. By using the devolatilizer without a rotating portion as described above, a methacrylic resin having a good color tone can be obtained, and thus it is preferable.

[0346] The treatment temperature in the devolatilizer is preferably 150 to 350°C, more preferably 170 to 300°C, and further preferably 200 to 280°C. By setting the treatment temperature to be higher than the lower limit, the residual volatile components can be suppressed, and by setting the treatment temperature to be lower than the upper limit, the coloring and decomposition of the obtained methacrylic resin can be suppressed.

[0347] - Additives -

[0348] The resin composition of the resin lens of the reflective polarizing element-attached lens of the present embodiment can contain various additives, within a range that does not significantly impair the effects of the present application.

[0349] As the additives, there are no particular limitations, and examples include antioxidants, light stabilizers such as hindered amine-based light stabilizers, ultraviolet absorbers, release agents, other thermoplastic resins than methacrylic resins, paraffin-based processing oils, naphthenic-based processing oils, aromatic-based processing oils, paraffin, organic polysiloxanes, mineral oils, and other softening agents / plasticizers, flame retardants, antistatic agents, organic fibers, pigments such as iron oxides, inorganic fillers, glass fibers, carbon fibers, metal whiskers, colorants, phosphite-based compounds, phosphonite-based compounds, phosphate-based compounds, and mixtures thereof.

[0350] -- Antioxidants --

[0351] It is preferable that the resin composition of the resin lens of the reflective polarizing element-attached lens of the present embodiment contain an antioxidant that suppresses deterioration or coloring during molding or use.

[0352] As the aforementioned antioxidant, there are no limitations, and examples include hindered phenol-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, and the like. For the resin composition of the present embodiment, in order to highly control the deformation and warping of the surface of the molded product, it is important to maintain the resin at a high temperature within the mold cavity and to set a moderate cooling time. When a long heat history is experienced, in order to obtain the desired heat stability, it is necessary to increase the amount of heat stabilizer added, but from the viewpoint of inhibiting the bleeding of the heat stabilizer and preventing adhesion to the mold, it is preferable to use a plurality of heat stabilizers in combination, for example, it is preferable to use at least one selected from phosphorus-based antioxidants and sulfur-based antioxidants in combination with a hindered phenol-based antioxidant.

[0353] These antioxidants can be used singly or in combination of two or more.

[0354] As the hindered phenol-based antioxidant, there are no limitations, and examples include pentaerythritol tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], thiodiethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 3,3',3",5,5',5"-hexa-tert-butyl-a,a',a"-(m-terphenyl-2,4,6-triyl)tri-p-cresol, 4,6-bis(octylthiomethyl)-o-cresol, 4,6-bis(dodecylthiomethyl)-o-cresol, ethylene bis(oxiranylyl)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate], hexamethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 1,3,5-tris[(4-tert-butyl-3-hydroxy-2,6-dimethylphenyl)methyl]-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2,6-di-tert-butyl-4-(4,6-bis(octylthio)-1,3,5-triazin-2-ylamino)phenol, 2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl acrylate, 2-tert-butyl-4-methyl-6-(2-hydroxy-3-tert-butyl-5-methylbenzyl)phenyl acrylate, and the like.

[0355] Among these, pentaerythritol tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl acrylate are particularly preferable.

[0356] In addition, as the hindered phenol-based antioxidant, a commercially available phenol-based antioxidant can also be used. As such commercially available phenol-based antioxidants, there are no limitations, and for example, Irganox 1010 (Irganox 1010: pentaerythritol tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], manufactured by BASF), Irganox 1076 (Irganox 1076: octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, manufactured by BASF), Irganox 1330 (Irganox 1330: 3,3',3",5,5',5"-hexa-tert-butyl-a,a',a"-(m-phenylene-2,4,6-triyl) tri-p-cresol, manufactured by BASF), Irganox 3114 (Irganox 3114: 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, manufactured by BASF), Irganox 3125 (Irganox 3125, manufactured by BASF), ADK STAB AO-60 (pentaerythritol tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], manufactured by ADEKA company), ADK STAB AO-80 (3,9-bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl}-2,4,8,10-tetraoxaspiro[5.5]undecane, manufactured by ADEKA company), Sumilizer BHT (Sumilizer BHT, manufactured by Sumitomo Chemical Co., Ltd.), Cyanox 1790 (Cyanox 1790, manufactured by Cytec Industries Inc.), Sumilizer GA-80 (Sumilizer GA-80, manufactured by Sumitomo Chemical Co., Ltd.), Sumilizer GS (Sumilizer GS: 2-[1-(2-hydroxy-3,5-di-tert-amylphenyl)ethyl]-4,6-di-tert-amylphenyl acrylate, manufactured by Sumitomo Chemical Co., Ltd.), Sumilizer GM (Sumilizer GM: 2-tert-butyl-4-methyl-6-(2-hydroxy-3-tert-butyl-5-methylbenzyl)phenyl acrylate, manufactured by Sumitomo Chemical Co., Ltd.), vitamin E (manufactured by Eisai Co., Ltd.), and the like can be mentioned.

[0357] Among these commercially available phenol-based antioxidants, from the viewpoint of imparting the effect of heat stability with the resin, Irganox 1010, ADK STAB AO-60, ADK STAB AO-80, Irganox 1076, Sumilizer GS, and the like are preferred.

[0358] They can be used singly with only one, or two or more in combination.

[0359] In addition, as the aforementioned phosphorus-based antioxidant, there are no limitations, and examples include tris(2,4-di-tert-butylphenyl) phosphite, bis(2,4-bis(l,l-dimethylethyl)-6-methylphenyl)ethyl phosphite, tetra(2,4-di-tert-butylphenyl)(l,l-biphenyl)-4,4'-diyl bisphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis(2,4-dicumylphenyl) pentaerythritol diphosphite, tetra(2,4-di-tert-butylphenyl)(l,l-biphenyl)-4,4'-diyl bisphosphite, di-tert-butyl-m-tolyl-phosphite, 4-[3-[(2,4,8,10-tetra-tert-butyldibenzo[d,f][l,3,2]dioxaphosphepin)-6-yloxy]propyl]-2-methyl-6-tert-butylphenol, and the like.

[0360] Further, as the phosphorus-based antioxidant, a commercially available phosphorus-based antioxidant can also be used. As such commercially available phosphorus-based antioxidant, there are no limitations, and for example, Irgafos 168 (Irgafos 168: tris(2,4-di-tert-butylphenyl) phosphite, manufactured by BASF), Irgafos 12 (Irgafos 12: tris[2-[[2,4,8,10-tetra-tert-butyldibenz[d,f][1,3,2]dioxaphosphepin-6-yl]oxy]ethyl]amine, manufactured by BASF), Irgafos 38 (Irgafos 38: bis(2,4-bis(1,1-dimethylethyl)-6-methylphenyl)ethyl phosphite, manufactured by BASF), ADK STAB 329K (ADK STAB-229K, manufactured by ADEKA company), ADK STAB PEP-36 (ADK STAB PEP-36, manufactured by ADEKA company), ADK STAB PEP-36A (ADK STAB PEP-36A, manufactured by ADEKA company), ADK STAB PEP-8 (ADK STAB PEP-8, manufactured by ADEKA company), ADK STAB HP-10 (ADK STAB HP-10, manufactured by ADEKA company), ADK STAB 2112 (ADK STAB 2112, manufactured by ADEKA company), ADK STAB 1178 (ADK STAB 1178, manufactured by ADEKA company), ADK STAB 1500 (ADK STAB 1500, manufactured by ADEKA company), Sandstab P-EPQ (manufactured by Clariant company), Weston 618 (Weston 618, manufactured by GE), Weston 619G (Weston 619G, manufactured by GE), Ultranox 626 (Ultranox 626, manufactured by GE), Sumilizer GP (Sumilizer GP: 4-[3-[(2,4,8,10-tetra-tert-butyldibenz[d,f][1,3,2]dioxaphosphepin)-6- yloxy]propyl]-2-methyl-6-tert-butylphenol, manufactured by Sumitomo Chemical Company), HCA (9,10-dihydro-9-oxo-10-phosphorylphenanthrene-10-oxide, manufactured by San-Ei Chemical Industry, Co., Ltd.), and the like can be mentioned.

[0361] Among these commercially available phosphorus-based antioxidants, from the viewpoint of the effect of imparting heat stability to the resin, the effect of combination with various antioxidants, ADK STAB PEP-36, ADK STAB PEP-36A, ADK STAB HP-10, and ADK STAB 1178 are preferred, and ADK STAB PEP-36A and ADK STAB PEP-36 are particularly preferred.

[0362] These phosphorus-based antioxidants can be used singly or in combination of two or more.

[0363] In addition, as the aforementioned sulfur-based antioxidant, there are no limitations, and examples include 2,4-bis(dodecylthiomethyl)-6-methylphenol (Irganox 1726, manufactured by BASF), 2,4-bis(octylthiomethyl)-6-methylphenol (Irganox 1520L, manufactured by BASF), 2,2-bis{〔3-(dodecylthio)-1-oxopropoxy〕methyl}propane-1,3-diyl bis〔3-dodecylthio〕propanoate (ADK STAB AO-412S, manufactured by ADEKA company), 2,2-bis{〔3-(dodecylthio)-1-oxopropoxy〕methyl}propane-1,3-diyl bis〔3-dodecylthio〕propanoate (KEMINOX PLS, manufactured by CHEMIPRO KASEI KAISHA, LTD.), and di(tridecyl) 3,3'-thiodipropionate (AO-503, manufactured by ADEKA company), and the like.

[0364] Among these commercially available sulfur-based antioxidants, from the viewpoint of the effect of imparting heat stability to the resin, the effect of combination with various antioxidants, and the viewpoint of workability, ADK STAB AO-412S and KEMINOX PLS are preferred.

[0365] These sulfur-based antioxidants can be used singly or in combination of two or more.

[0366] The content of the antioxidant is an amount that can obtain the effect of improving heat stability, and since there are concerns that bleeding and the like can occur during processing when the content is excessive, it is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, further preferably 1 part by mass or less, more further preferably 0.8 parts by mass or less, more further preferably 0.01 to 0.8 parts by mass, and particularly preferably 0.01 to 0.5 parts by mass, with respect to 100 parts by mass of the methacrylic resin.

[0367] -- hindered amine-based light stabilizer

[0368] The resin composition constituting the resin lens of the reflection type polarizing element attached lens of the present embodiment can contain a hindered amine-based light stabilizer.

[0369] The hindered amine-based light stabilizer is not particularly limited, and is preferably a compound containing three or more ring structures. Here, the ring structure is preferably at least one selected from the group consisting of an aromatic ring, an aliphatic ring, an aromatic heterocycle, and a non-aromatic heterocycle, and when a compound has two or more ring structures, the ring structures can be the same as or different from each other.

[0370] As the hindered amine-based light stabilizer, there are no particular limitations, and, for example, specifically, mention can be made of bis(l,2,2,6,6-pentamethyl-4-piperidyl)[[3,5-bis(l,l-dimethylethyl)-4-hydroxyphenyl]methyl]butyl malonate, a mixture of bis(l,2,2,6,6-pentamethyl-4-piperidyl)sebacate and methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-N,N'-dicarboxyhexanediamine, a polycondensate of dibutylamine-1,3,5-triazine-N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,6-hexanediamine and N-(2,2,6,6-tetramethyl-4-piperidyl)butylamine, poly[{6-(l,l,3,3-tetramethylbutyl)amino-l,3,5-triazine-2,4-diyl}{(2,2,6,6-tetramethyl-4-piperidyl)imino}hexamethylene{(2,2,6,6-tetramethyl-4-piperidyl)imino}], tetra(l,2,2,6,6-pentamethyl-4-piperidyl)butane-l,2,3,4-tetracarboxylic acid ester, tetra(2,2,6,6-tetramethyl-4-piperidyl)butane-l,2,3,4-tetracarboxylic acid ester, a reaction product of 1,2,2,6,6-pentamethyl-4-piperidinediol and β,β,β',β'-tetramethyl-2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diethanol, a reaction product of 2,2,6,6-tetramethyl-4-piperidinediol and β,β,β',β'-tetramethyl-2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diethanol, bis(l-undecyloxy-2,2,6,6-tetramethylpiperidin-4-yl) carbonate, 1,2,2,6,6-pentamethyl-4-piperidylmethyl acrylate, 2,2,6,6-tetramethyl-4-piperidylmethyl acrylate, and the like.

[0371] Among them, preferred are bis (1, 2, 2, 6, 6-pentamethyl-4-piperidyl) [[3, 5-bis (1, 1-dimethylethyl)-4-hydroxyphenyl] methyl] butylmalonate, a condensate of dibutylamine-1, 3, 5-triazine-N, N'-bis (2, 2, 6, 6-tetramethyl-4-piperidyl)-1, 6-hexanediamine and N- (2, 2, 6, 6-tetramethyl-4-piperidyl) butylamine, poly [ {6- (1, 1, 3, 3-tetramethylbutyl) amino-1, 3, 5-triazine-2, 4-diyl} (2, 2, 6, 6-tetramethyl-4-piperidyl) imino] hexamethylene { (2, 2, 6, 6-tetramethyl-4-piperidyl) imino}, a reaction product of 1, 2, 2, 6, 6-pentamethyl-4-piperidinediol and β, β, β', β'-tetramethyl-2, 4, 8, 10-tetraoxaspiro [5.5] undecane-3, 9-diethanol, and a reaction product of 2, 2, 6, 6-tetramethyl-4-piperidinediol and β, β, β', β'-tetramethyl-2, 4, 8, 10-tetraoxaspiro [5.5] undecane-3, 9-diethanol.

[0372] The content of the hindered amine-based light stabilizer is preferably an amount that provides an effect of improving light stability, and is preferably 5% by mass or less, more preferably 3% by mass or less, further preferably 1% by mass or less, still further preferably 0.8% by mass or less, still further preferably 0.01 to 0.8% by mass, and particularly preferably 0.01 to 0.5% by mass, relative to 100% by mass of the methacrylic resin.

[0373] -- ultraviolet absorber --

[0374] The resin composition constituting the resin lens of the reflection-type polarizing element attached lens of the present embodiment can contain an ultraviolet absorber.

[0375] The ultraviolet absorber is not particularly limited, and is preferably an ultraviolet absorber having a maximum absorption wavelength in the range of 280 to 380 nm, and examples thereof include benzotriazole-based compounds, benzotriazine-based compounds, benzophenone-based compounds, oxobenzophenone-based compounds, benzoate-based compounds, phenol-based compounds, oxazole-based compounds, cyanoacrylate-based compounds, benzoxazinone-based compounds, and the like.

[0376] These ultraviolet absorbers can be used singly or in combination of two or more.

[0377] As the ultraviolet absorber, particularly, from the viewpoints of compatibility with the resin, volatility upon heating, a benzotriazole-based compound, a benzotriazine-based compound having a molecular weight of 400 or more are preferred, and further, from the viewpoint of inhibiting decomposition of the ultraviolet absorber itself due to heating during extrusion processing, a benzotriazine-based compound is particularly preferred.

[0378] The content of the ultraviolet absorber is not particularly limited as long as it does not hinder heat resistance, humidity resistance, heat stability, and molding processability and is an amount in which the effects of the present application can be exerted, and is preferably 0.1 to 5 parts by mass, preferably 0.2 to 4 parts by mass, more preferably 0.25 to 3 parts by mass, and further preferably 0.3 to 3 parts by mass, with respect to 100 parts by mass of the methacrylic acid-based resin. If it is within this range, the balance of ultraviolet absorption performance, moldability, and the like is excellent.

[0379] -- Release Agent --

[0380] The resin composition constituting the resin lens of the reflection-type polarizing element attached lens of the present embodiment can contain a release agent. As the aforementioned release agent, there are no particular limitations, and for example, fatty acid esters, fatty acid amides, fatty acid metal salts, hydrocarbon-based lubricants, alcohol-based lubricants, polyalkylene glycols, carboxylic acid esters, paraffin-based mineral oils of hydrocarbons, and the like can be exemplified.

[0381] These release agents can be used singly or in combination of two or more.

[0382] As the fatty acid ester that can be used as the aforementioned release agent, there are no particular limitations, and conventionally known substances can be used.

[0383] As the fatty acid ester, for example, ester compounds of fatty acids having 12 to 32 carbon atoms such as lauric acid, palmitic acid, margaric acid, stearic acid, oleic acid, arachidic acid, and behenic acid, and monohydric aliphatic alcohols such as palmityl alcohol, stearyl alcohol, and behenyl alcohol, polyhydric aliphatic alcohols such as glycerol, pentaerythritol, dipentaerythritol, and sorbitan; complex ester compounds of fatty acids and polyhydric organic acids and monohydric aliphatic alcohols or polyhydric aliphatic alcohols; and the like can be exemplified.

[0384] As such fatty acid esters, for example, cetyl palmitate, butyl stearate, stearyl stearate, stearyl citrate, glycerol mono-octanoate, glycerol mono-decanoate, glycerol mono-laurate, glycerol mono-palmitate, glycerol di-palmitate, glycerol mono-stearate, glycerol di-stearate, glycerol tri-stearate, glycerol mono-oleate, glycerol di-oleate, glycerol tri-oleate, glycerol mono-linoleate, glycerol mono-behenate, glycerol mono-12-hydroxystearate, glycerol di-12-hydroxystearate, glycerol tri-12-hydroxystearate, glycerol diacetyl mono-stearate, glycerol citrate fatty acid ester, pentaerythritol adipate stearate, partially saponified ester of montanic acid, pentaerythritol tetra-stearate, dipentaerythritol hexa-stearate, sorbitan tri-stearate, and the like can be exemplified.

[0385] These fatty acid esters can be used singly only, or two or more in combination.

[0386] As commercially available products, for example, RIKEMAL series, POEM series, RIKESTER series, RIKEMASTER series manufactured by RIKEN VITAMIN CO., LTD.; EXCEL series, RHEODOL series, EXCEPARL series, COCONARD series manufactured by KAWABATA CO., LTD. can be exemplified, and more specifically, RIKEMAL S-100, RIKEMAL H-100, POEM V-100, RIKEMAL B-100, RIKEMAL HC-100, RIKEMAL S-200, POEM B-200, RIKESTER EW-200, RIKESTER EW-400, EXCEL S-95, RHEODOL MS-50, and the like can be exemplified.

[0387] The content of the release agent is only required to be an amount to obtain the effect as a release agent, and since there is a concern that in the case of an excessive content, there are problems such as poor extrusion due to bleeding and screw sliding during processing, the content of the release agent is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, further preferably 1 part by mass or less, more further preferably 0.8 parts by mass or less, more further preferably 0.01 to 0.8 parts by mass, and particularly preferably 0.01 to 0.5 parts by mass, with respect to 100 parts by mass of the methacrylic acid-based resin. If added in the above range, there is a tendency to suppress the lowering of transparency due to the addition of the release agent, and to suppress the release failure during injection molding.

[0388] --Other thermoplastic resins--

[0389] The resin composition of the present embodiment can also contain other thermoplastic resins (hereinafter, also referred to simply as "other thermoplastic resins") other than the aforementioned methacrylic resins, within the scope of the object of the present application, for the purpose of adjusting birefringence and improving flexibility.

[0390] As the other thermoplastic resins, for example, polyacrylates such as polybutyl acrylate; styrene-based polymers such as polystyrene, styrene-methyl methacrylate copolymer, styrene-butyl acrylate copolymer, styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene block copolymer; and the like can be given. Further, for example, 3-4 layer structured acrylic rubber particles described in Japanese Patent Application Publication No. 59-202213, Japanese Patent Application Publication No. 63-27516, Japanese Patent Application Publication No. 51-129449, Japanese Patent Application Publication No. 52-56150, and the like; rubbery polymers disclosed in Japanese Patent No. 60-17406, Japanese Patent Application Publication No. 8-245854; graft copolymer particles containing methacrylic rubber obtained by multistage polymerization described in International Publication No. 2014-002491; and the like can be given.

[0391] Among them, from the viewpoint of obtaining good optical and mechanical properties, a rubber-containing graft copolymer particle of a styrene-acrylonitrile copolymer having a graft portion on the surface layer, the graft portion being composed of a component that is compatible with the methacrylic resin containing a structural unit (X) having a ring structure, is preferable.

[0392] As the average particle diameter of the aforementioned acrylic rubber particles, graft copolymer particles containing methacrylic rubber, and rubbery polymers, from the viewpoint of improving the impact strength and optical properties and the like of the molded article obtained from the composition of the present embodiment, 0.03 to 1 μm is preferable, and 0.05 to 0.5 μm is more preferable.

[0393] As the content of the other thermoplastic resins, when the methacrylic resin is 100 parts by mass, 0 to 50 parts by mass is preferable, and 0 to 25 parts by mass is more preferable.

[0394] ((Cyclic olefin resin composition)

[0395] As the resin composition of the resin lens of the reflective polarizing element attached lens of the present embodiment, a cyclic olefin resin composition is also preferable. Note that the cyclic polyolefin resin composition refers to a resin composition containing a cyclic olefin, such as a resin composition containing a cyclic olefin monomer, a copolymer or a terpolymer as a copolymer of a cyclic olefin and other monomers copolymerizable with the cyclic olefin.

[0396] As the cyclic olefin monomer, any cyclic hydrocarbon having an ethylenically unsaturated bond and a bicyclo ring can be used, but a substance having a bicyclo[2.2.1]-2-heptene (norbornene) skeleton is particularly preferable. As the cyclic olefin, specifically, bicyclo[2.2.1]-2-heptene (norbornene) and derivatives thereof, tricyclo[4.3.0.1 2，5 ]-3-decene and derivatives thereof, tricyclo[4.4.0.1 2，5 ]-3-undecene and derivatives thereof, tetracyclo[4.4.0.1 2，5 .1 7，10 ]-3-dodecene (tetracyclododecene) and derivatives thereof, pentacyclo[6.5.1.1 3，6 .0 2，7 .0 9，13 ]-4-pentadecene and derivatives thereof, pentacyclo[7.4.0.1 2，5 .1 9，12 .0 8 ，13 ]-3-pentadecene and derivatives thereof, pentacyclo[6.5.1.1 3，6 .0 2，7 .0 9，13 ]-4,10-pentadecadiene and derivatives thereof, pentacyclo[8.4.0.1 2，5 .1 9，12 .0 8，13 ]-3-hexadecene and derivatives thereof, tetracyclo[9.2.1.0 2，10 .0 3，8 ]tetradeca-3,5,7,12-tetraene (methylene tetracyclone) and derivatives thereof, and the like can be used, but are not limited thereto. As the cyclic olefin, as the substituent, a polar group such as an ester group, a carboxyl group, and a carboxylic anhydride group can be present. Among them, the cyclic olefin is preferably at least one selected from bicyclo[2.2.1]-2-heptene and tetracyclo[4.4.0.1 2，5 .1 7，10 ]-3-dodecene.

[0397] Note that, in the present application, the "norbornene-based monomer" refers to a monomer having a norbornene skeleton, such as norbornene and derivatives thereof, tetracyclododecene-based monomer, and methylene tetracyclone-based monomer, and the like. Here, the "tetracyclododecene-based monomer" refers to tetracyclododecene and derivatives thereof. In addition, the "methylene tetracyclone-based monomer" refers to methylene tetracyclone and derivatives thereof.

[0398] As the other monomer copolymerizable with the cyclic olefin, an α-olefin such as ethylene, propylene, 1-butene, 1-pentene, 3-methyl-l-butene, 1-hexene, 4-methyl-l-pentene, and the like, a non-conjugated diene such as 1,4-hexadiene, 4-methyl-l,4-hexadiene, 5-methyl-l,4-hexadiene, and 1,7-octadiene, and the like can be exemplified. Among them, as the other monomer copolymerizable with the cyclic olefin, an α-olefin is preferable.

[0399] Preferably, the resin lens is composed of a resin composition containing a cyclic olefin copolymer. Further, more preferably, the resin lens is composed of a resin composition containing a cyclic olefin copolymer which is a copolymer of ethylene and a cyclic olefin, or a copolymer of an α-olefin and a cyclic olefin.

[0400] As the α-olefin, propylene, 1-butene, 1-pentene, 4-methyl-l-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, and the like can be exemplified.

[0401] As the cyclic olefin, a cyclic olefin such as the above-described bicyclo[2.2.1]-2-heptene, and the like can be exemplified.

[0402] In the resin composition containing the cyclic olefin copolymer, the proportion of the ring skeleton structure unit from the main chain of the cyclic polyolefin in the cyclic olefin copolymer is preferably 36 mol% or more and 50 mol% or less.

[0403] In the resin composition containing the cyclic olefin copolymer, the structure unit from the cyclic olefin in the cyclic polyolefin copolymer is preferably a structure unit from at least one compound selected from the group consisting of bicyclo[2.2.1]-2-heptene and 2，5 .1 7，10 ]-3-dodecene.

[0404] Further, it is also preferable that the resin lens be composed of a resin composition containing a ring-opening polymer hydrogenate of a norbornene-based monomer.

[0405] In the case where the resin lens is composed of a resin composition containing a ring-opening polymer hydrogenate of a norbornene-based monomer, more preferably, the resin composition contains 20 to 100 mol% of a structure unit from the norbornene-based monomer, and 0 to 80 mol% of a structure unit from another monomer copolymerizable with the norbornene-based monomer.

[0406] In addition, in the case where the resin lens is composed of a resin composition including a ring-opening polymer hydride of a norbornene-based monomer, it is preferable that the structural units from the norbornene-based monomer include 15 to 50% by mass of structural units from a tetralindene-based monomer, 50 to 90% by mass of structural units from a methano-tetrahydrofluorene-based monomer, and 1 to 15% by mass of structural units from a norbornene monomer (where the structural units from each monomer total 100% by mass or less).

[0407] (Properties of the resin composition, etc.)

[0408] In the resin composition that constitutes the resin lens of the reflective polarizing element attached lens of the present embodiment, the amount of the residual solvent (residual solvent amount) is preferably less than 1000 mass ppm, more preferably less than 800 mass ppm, and further preferably less than 700 mass ppm.

[0409] Here, the residual solvent refers to a polymerization solvent used at the time of polymerization (excluding alcohol), and a solvent used at the time of re-dissolving the resin obtained by polymerization to perform solutionization, and specifically, as the polymerization solvent, aromatic hydrocarbons such as toluene, xylene, ethylbenzene, cumene, etc.; ketones such as methyl isobutyl ketone, butyl cellosolve, methyl ethyl ketone, cyclohexanone, etc.; polar solvents such as dimethylformamide, 2-methylpyrrolidone, etc. can be exemplified, and as the solvent used for re-dissolution, toluene, methyl ethyl ketone, dichloromethane, etc. can be exemplified.

[0410] The resin composition that constitutes the resin lens of the reflective polarizing element attached lens of the present embodiment has a residual alcohol amount (residual alcohol amount) of preferably less than 500 mass ppm, more preferably less than 400 mass ppm, and further preferably less than 350 mass ppm. Here, the residual alcohol refers to alcohol produced as a byproduct of a cyclization condensation reaction, and specifically, aliphatic alcohols such as methanol, ethanol, isopropyl alcohol, etc. can be exemplified.

[0411] The above residual solvent amount and the above residual alcohol amount can be measured by gas chromatography.

[0412] -Glass transition temperature-

[0413] The resin composition that constitutes the resin lens of the reflective polarizing element attached lens of the present embodiment has a glass transition temperature (Tg) of preferably 115°C to 160°C. The glass transition temperature (Tg) is further preferably 115 to 155°C, more further preferably 115 to 150°C, and most preferably 120 to 150°C.

[0414] Note that the glass transition temperature can be measured according to JIS-K7121 and by the midpoint method. The glass transition temperature of the above-described resin composition is 115°C or higher, and heat resistance can be ensured even under heat generation from electronic devices of the head-mounted display type and high-temperature environments in some outdoor and vehicle-mounted environments, and in addition, the size does not change in a process in which heat is applied when the reflective polarizing element is attached, and good adhesion can be obtained, and this is preferable from this aspect. In addition, by suppressing deformation, the photoelastic birefringence generated at the interface of the reflective polarizing element and the resin lens can also be suppressed, and this is preferable. The glass transition temperature (Tg) of the resin composition is more preferably 120°C or higher, further preferably 125°C or higher, and most preferably 130°C or higher.

[0415] On the other hand, in the case where the glass transition temperature (Tg) of the resin composition is 160°C or lower, melting processing under extremely high-temperature conditions is avoided, and thermal decomposition of the resin and the like is suppressed, and a good product can be obtained. From the viewpoint of further obtaining the above-described effects, the glass transition temperature (Tg) is preferably 155°C or lower, more preferably 150°C or lower, and further preferably 140°C or lower.

[0416] In addition, when the glass transition temperature is greater than 160°C, in the injection molding process described later, the mold temperature needs to be kept high to reduce the birefringence of the resin lens, and when the resin lens is removed, the cooling time needs to be lengthened to suppress deformation of the grooves and the like, and the cycle time becomes long, and in addition, due to the temperature difference from room temperature, rapid cooling makes it easy for deformation to remain inside the resin lens, and from the viewpoint of sufficiently reducing the birefringence of the resin lens, this is not preferable.

[0417] - Flexural strength -

[0418] For the resin composition that constitutes the resin lens, the resin lens and the reflective polarizing element respectively expand or shrink with heat and water absorption, but the difference in the size change at this time causes a flexural stress. Due to this, the resin lens of the reflective polarizing element attached lens sometimes cracks or breaks. In order to prevent such a defect, it is preferable that the flexural strength be large. The flexural strength of the resin composition is preferably 65 MPa or higher. The flexural strength is more preferably 75 MPa or higher, and further preferably 85 MPa or higher. By the flexural strength being in this range, when the reflective polarizing element attached lens is placed in a reliability test, it is difficult for the resin lens to break and the like.

[0419] Note that the flexural strength is a value measured in accordance with ISO 178, and specifically, it can be measured by the method described in the Examples described later.

[0420] - Flexural modulus -

[0421] For the resin composition used in the present embodiment, the resin lens and the reflective polarizing element each expand or shrink with heat, water absorption, but the difference in the dimensional change at this time causes a bending stress. Due to this, the resin lens to which the reflective polarizing element is attached to the lens sometimes deforms from the shape of the optical design. In order to prevent such a defect, it is preferable that the bending elastic modulus be large. The bending elastic modulus is preferably 2500 MPa or greater. The bending elastic modulus is more preferably 3000 MPa or greater, and further preferably 3300 MPa or greater. By the bending elastic modulus being in this range, the face shape of the resin lens caused by the bending stress is also less likely to be damaged when the reflective polarizing element attached lens is placed in a reliability test.

[0422] Note that the bending elastic modulus is a value measured in accordance with ISO 178, and specifically, can be measured by the method described in the Examples described later.

[0423] [Method for manufacturing resin lens of reflective polarizing element attached lens]

[0424] The resin lens of the reflective polarizing element attached lens of the present embodiment is formed by molding the above-described resin composition. As the method for manufacturing the resin lens of the present embodiment, a molding method such as injection molding, compression molding, or extrusion molding can be used. Among these, from the viewpoint of productivity, injection molding is preferable.

[0425] Generally, the injection molding method is composed of the following processes: (1) an injection process of melting the resin and filling the molten resin into the cavity of a mold whose temperature is controlled; (2) a holding pressure process of applying pressure to the cavity until the gate is sealed, and injecting resin in an amount corresponding to the amount of the molten resin filled in the injection process that comes into contact with the mold and shrinks due to cooling; (3) a cooling process of keeping the molded product until the resin is cooled after the holding pressure is released; and (4) a process of opening the mold and taking out the cooled molded product.

[0426] In the method for manufacturing the resin lens, as the temperature setting from the tip of the nozzle of the injection molding machine barrel to the center, the glass transition temperature (Tg) of the methacrylic resin composition used is used as a reference, and it is set to Tg + 100°C to Tg + 180°C, preferably in the range of Tg + 110°C to Tg + 160°C, and more preferably in the range of Tg + 120°C to Tg + 150°C.

[0427] Here, the molding temperature refers to the control temperature of the band heater wound around the injection nozzle. By setting to the above temperature range, the molten resin sufficiently flows, and molding can be performed in a state where deterioration due to thermal decomposition of the resin is suppressed. The higher the molding temperature, the higher the flowability of the resin, and it is more difficult to generate an oriented birefringence, but under high temperature conditions, in addition to the fact that thermal decomposition of the resin causes adverse effects on the color tone, transmittance, and haze (Haze), gas is generated at the time of injection molding, and thus the generated gas fills the mold, the gas that is pressed into the concave-convex portion at the time of filling of the resin cannot be discharged, the filling of the resin is suppressed, and thus the mold transfer rate deteriorates. The molding temperature should be appropriately selected while observing the state of the resin lens.

[0428] As the mold temperature, it is preferable to be in the range of Tg - 70°C to Tg, and more preferable to be in the range of Tg - 50°C to Tg - 20°C, based on the glass transition temperature (Tg) of the resin composition.

[0429] By increasing the mold temperature to a temperature around Tg, it is possible to reduce the birefringence of the resin lens, but on the other hand, since it is easy to adhere to the mold, there is a possibility that deterioration of the lens surface precision, a gap in the resin accompanying the adhesion, and a delay in the process due to the breakage of the gate portion will occur, and thus it should be appropriately selected.

[0430] In addition, as the injection speed, it can be appropriately selected depending on the thickness and size of the resin lens to be obtained, and for example, it can be appropriately selected from the range of 2 to 1000 mm / sec. In addition, as the pressure for pressure retention, it can be appropriately selected depending on the shape of the resin lens to be obtained, and for example, it can be appropriately selected in the range of 30 to 120 MPa.

[0431] Here, the pressure for pressure retention refers to the pressure maintained by the screw for further sending out the molten resin from the gate after the molten resin is filled.

[0432] In addition, in order to relax the residual stress generated by injection molding and reduce the phase difference of the resin lens, an annealing process can be performed. Based on the glass transition temperature (Tg) of the resin composition, the temperature at the time of annealing is preferably in the range of Tg - 50°C to Tg, and more preferably in the range of Tg - 30°C to Tg - 10°C.

[0433] - Imparting a phase difference layer to the resin lens -

[0434] A phase difference layer can be imparted to the surface of the resin lens. For example, a phase difference layer for any wavelength can be imparted by coating a liquid crystal polymer. As a preferred coating for forming a phase difference layer, a linear photopolymerizable polymer (LPP) material described in U.S. Patent Application Publication No. 2002 / 0180916, U.S. Patent Application Publication No. 2003 / 028048, Patent Application Publication No. 2005 / 0072959, and a liquid crystal polymer (LCP) material can be cited.

[0435] (Method for producing resin composition)

[0436] The method for producing the resin composition constituting the resin lens is not particularly limited as long as a composition satisfying the requirements of the present application can be obtained. For example, a method in which a kneader such as an extruder, a heating roll, a kneader, a roll mixer, a Banbury mixer, or the like is used for kneading can be cited. Among them, from the viewpoint of productivity, it is preferable to perform the kneading using an extruder. The kneading temperature is not particularly limited as long as it is set in accordance with the preferred processing temperature of the polymer constituting the methacrylic resin and the other resins mixed, and as a guideline, it is in the range of 140 to 300°C, and preferably in the range of 180 to 280°C. In addition, in order to reduce the volatile components, it is preferable to provide an exhaust port on the extruder.

[0437] Regardless of which method is selected, it is preferable to produce the composition while reducing oxygen and water as much as possible.

[0438] For example, as the concentration of dissolved oxygen in the polymerization solution in the solution polymerization, it is preferable to be less than 300 ppm in the polymerization step, and in addition, as the oxygen concentration in the extruder or the like in the production method using an extruder or the like, it is preferable to be set to be less than 1 vol%, and further preferably to be set to be less than 0.8 vol%. As the amount of moisture of the methacrylic resin, it is preferable to adjust it to be 1000 mass ppm or less, and more preferably to be 500 mass ppm or less.

[0439] If it is within these ranges, it becomes easier to produce a composition satisfying the requirements of the present application, which is advantageous.

[0440] <Method for producing reflection type polarizing element attached lens>

[0441] The manufacturing method of the reflective polarizing element attached lens of the present embodiment is a manufacturing method of a reflective polarizing element attached lens in which a reflective polarizing element is attached to a resin lens, characterized in that the resin lens is a resin lens composed of a resin composition having a glass transition temperature (Tg) of 115°C to 160°C, the resin lens has a first surface and a second surface on opposite sides of each other, the manufacturing method has: a step of forming a silane coupling agent layer on at least one of the resin lens and the reflective polarizing element; a step of imparting an adhesive layer to at least one of the resin lens and the reflective polarizing element; and a step of attaching the reflective polarizing element to the resin lens.

[0442] According to the above manufacturing method of the reflective polarizing element attached lens, it is possible to manufacture a reflective polarizing element attached lens in which at least either one of peeling of the reflective polarizing element and generation of cracks is suppressed after reliability tests in a severe high-temperature and high-humidity environment.

[0443] In the above manufacturing method, for the step of attaching the reflective polarizing element to the resin lens, the temperature of the base material film is set to a temperature range of -40°C to Tg 膜 Tg 膜 -40°C to Tg 膜 +120°C. By setting the temperature of the step of attaching the reflective polarizing element to the resin lens to this range, it is possible to favorably maintain the adhesion of the reflective polarizing element to the resin lens, and further, it is difficult for adverse conditions such as generation of wrinkles or entry of air bubbles into the attached surface with the resin lens to occur. Further, by attaching in the above temperature range, the adhesion of the resin lens and / or the silane coupling agent layer to the adhesive layer is improved.

[0444] Note that the glass transition temperature Tg 膜 It is possible to measure using a dynamic viscoelasticity device.

[0445] Note that the explanations regarding the resin lens, the reflective polarizing element attached lens, the silane coupling agent layer, and the adhesive layer in the manufacturing method of the reflective polarizing element attached lens can be applied to the descriptions regarding these in the explanations regarding the reflective polarizing element attached lens.

[0446] In the step of forming the silane coupling agent layer on at least one of the resin lens and the reflective polarizing element, it is possible to form the silane coupling agent layer on both the resin lens and the reflective polarizing element.

[0447] In the manufacturing method of the reflection-type polarizing element attached lens according to the present embodiment, as a method of attaching the reflection-type polarizing element to the resin lens, for example, a method obtained by injection molding the lens on a film using a film insert molding process, a method obtained by using attachment using a vacuum attachment device, or the like can be given. Among these, from the viewpoint that a wrinkle or the like is not generated in the reflection-type polarizing element, the reflection-type polarizing element can be attached in a good appearance, and a lens having excellent surface precision can be used, the attachment method using the vacuum attachment device is preferable. In the case of the film insert molding process, it is necessary to balance the molding conditions favorable for attachment and surface precision, a method favorable for reducing birefringence, and set, and the range of the molding conditions is narrow, so it is difficult to make the surface precision and the birefringence characteristics of the lens good.

[0448] In order to easily attach the reflection-type polarizing element to the resin lens, the reflection-type polarizing element can be processed into a prescribed shape by molding using heat before the attachment process and used in the attachment process after the processing.

[0449] Specifically, by overlapping the reflection-type polarizing element in a softened state obtained by heating the reflection-type polarizing element with a mold of a desired shape, a reflection-type polarizing element of the desired shape can be obtained. At this time, in order to ensure the precision of the shape, molding can be performed by sandwiching with a male mold and a female mold.

[0450] Then, the reflection-type polarizing element in an unprocessed state or the reflection-type polarizing element processed into the aforementioned desired shape can be attached to the resin lens by attachment using a vacuum attachment device or a film insert molding process.

[0451] In the manufacturing method of the reflection-type polarizing element attached lens according to the present embodiment, it is preferable that the resin lens used be produced by injection molding.

[0452] The processing temperature of the vacuum attachment device is preferably set in accordance with the glass transition temperature (Tg 膜 ) of the base film of the reflection-type polarizing element attached to the resin lens. The processing temperature of the vacuum attachment device can be set, for example, in the range of Tg 膜 - 40°C to Tg 膜 + 120°C. The processing temperature of the vacuum attachment device is more preferably set in the range of Tg 膜 - 20°C to Tg 膜 + 100°C, further preferably in the range of Tg 膜 - 10°C to Tg 膜 + 95°C, and still further preferably in the range of Tg 膜 to Tg 膜+90°C. By setting the processing temperature of the vacuum lamination device within this range, the adhesion of the reflective polarizing element to the resin lens can be favorably maintained, and further, adverse conditions such as the generation of wrinkles or bubbles on the reflective polarizing element into the lamination surface with the resin lens are difficult to occur. Further, by lamination with the above temperature range, the adhesion of the resin lens and / or the silane coupling agent layer to the adhesive layer is improved.

[0453] Preferably, when laminating the reflective polarizing element using a vacuum lamination device, the lamination surface of the reflective polarizing element with the resin lens is subjected to an adhesive treatment.

[0454] As the adhesive, one having a high followability to deformation such as shrinkage / expansion of the resin lens due to heat, water absorption, and the like is preferred, and a relatively soft adhesive is preferred.

[0455] As the base material constituting the reflective polarizing element, with respect to the water absorption rates of the resin composition constituting the resin lens and the reflective polarizing element that enable lamination following deformation of the resin lens due to water absorption, when laminating the reflective polarizing element to the resin lens using a vacuum lamination device, it is preferred to reduce the absolute value of the difference between the saturated water absorption rate of the reflective polarizing element and the saturated water absorption rate of the resin lens.

[0456] The specific range of the difference is described in the item "- Difference in saturated water absorption rate between resin lens and reflective polarizing element -".

[0457] The reflective polarizing element and the resin lens can be processed to have a phase difference by laminating or applying a phase difference film in a manner having a prescribed phase difference (for example, a phase difference of a quarter of a specific wavelength) before lamination. Note that, for imparting a phase difference by application, the content described in the item "- Imparting a phase difference layer to the resin lens -" can be utilized.

[0458] However, from the viewpoint of maintaining the mirror surface properties (flatness), surface precision of the reflective surface in addition to ensuring good adhesion of the reflective polarizing element to the resin lens, it is preferred to laminate the reflective polarizing element directly to the resin lens.

[0459] < Polarization Conversion Element >

[0460] The polarization conversion element of the present embodiment is characterized by comprising the reflective polarizing element lamination lens of the present embodiment.

[0461] The polarization conversion element of the present embodiment comprises the reflective polarizing element lamination lens of the present embodiment, and thus deterioration of optical properties under a high-temperature, high-humidity environment is suppressed, and a clear image can be obtained when used as a component of an image display device.

[0462] The polarizing conversion element of the present embodiment can be manufactured by a publicly known method, for example, by the method described in Japanese Patent Application Publication No. 2012-118430.

[0463] <Head-mounted display>

[0464] The head-mounted display of the present embodiment is characterized by being provided with the reflective polarizing element attached lens of the present embodiment.

[0465] The head-mounted display of the present embodiment is provided with the reflective polarizing element attached lens of the present embodiment, and therefore, deterioration of optical performance under a high-temperature and high-humidity environment is suppressed, and furthermore, the reflective polarizing element does not peel off after environmental testing under a severe high-temperature and high-humidity environment (under an environment of 85°C, 85% RH, for 500 hours), and the performance and durability are excellent.

[0466] The head-mounted display of the present embodiment can be manufactured by a publicly known method, for example, by the method described in Japanese Patent Application Publication No. 2023-184603.

[0467] Examples

[0468] Hereinafter, specific examples and comparative examples will be described, but the present application is not limited to these.

[0469] (Evaluation of properties of resin composition)

[0470] Hereinafter, the method for measuring the properties of the resin composition will be described.

[0471] (Measurement of bending strength and bending elastic modulus)

[0472] A resin composition pellet manufactured in the manufacturing example described later was dried at 80 to 100°C for 24 hours, and injection molding was performed using an injection molding machine (Toshiba Machine Co., Ltd., EX-100SX) in accordance with JIS-K6717, thereby manufacturing an ISO 3167 type dumbbell-shaped test piece having a thickness of 4.0 mm. The central portion of the test piece was cut out, and a molded piece having a length of 80 mm, a width of 10 mm, and a thickness of 4.0 mm was prepared. Tensile testing was performed using a low load universal material testing machine (Instron Corporation) at a measurement temperature of 23°C, a test speed of 2 mm / minute, and a span distance of 64 mm in accordance with ISO 178. Six measurements were performed, and the bending strength (MPa) and the bending elastic modulus (MPa) were calculated as the average values thereof, respectively.

[0473] (Measurement of resin lens and reflective polarizing element attached lens and evaluation of properties)

[0474] Hereinafter, a method for measuring the characteristics of the resin lens and the reflective polarizing element attached lens composed of the resin composition will be described.

[0475] <Analysis of Structural Units>

[0476] In the reflective polarizing element attached lens manufactured in the examples and comparative examples described later, unless otherwise specified, for each structural unit after cutting a part of the resin lens, the amount of each structural unit was identified by 1 H-NMR measurement and 13 C-NMR measurement for the resin and the resin composition. 1 H-NMR measurement and 13 The measurement conditions of H-NMR measurement and

[0477] Measurement device: JNM-ECZ400S manufactured by JEOL Ltd.

[0478] Measurement solvent: CDC13, DMSO-d6, or o-C6D4Cl2.

[0479] Measurement temperature: 40°C.

[0480] Note that in the case where the ring structure included in the main chain of the methacrylic resin is a lactone ring structure, it was confirmed by the method described in Japanese Patent Application Publication No. 2001-151814 and Japanese Patent Application Publication No. 2007-297620. From the ratio of the integral values of CH and CH2, it was confirmed that a prescribed amount of olefin was copolymerized with the ring tetra-cyclo[4.4.0.1 2，5 .1 7，10 ]-3-dodecene.

[0481] <Measurement of Glass Transition Temperature of Resin Composition Constituting Resin Lens>

[0482] The glass transition temperature (Tg) (°C) of the resin composition constituting the resin lens was determined according to JIS-K7121. First, in the reflective polarizing element bonding lenses manufactured in the examples and comparative examples described later, after being conditioned under standard conditions (23°C, 50% RH) (placed at 23°C for 1 week), four points (four sites) were cut from the portion cut from the resin lens as test pieces, each containing approximately 10 mg. Then, using a differential scanning calorimeter (Perkin Elmer Japan, Diamond DSC) at a nitrogen flow rate of 25 mL / min, the sample was heated from room temperature (23°C) to 200°C at a rate of 10°C / min (first heating), held at 200°C for 5 minutes to allow complete melting, and then cooled from 200°C to 40°C at a rate of 10°C / min, held at 40°C for 5 minutes. Furthermore, in the DSC curve plotted during the second heating under the above heating conditions (second heating), the intersection point (glass transition temperature of the methacrylic resin composition) of the step-like change curve during the second heating and the straight line equidistant from the extension of each baseline in the vertical direction was determined according to JIS-K7121. A differential scanning calorimeter (PerkinElmer, DSC8000) was used under a nitrogen flow rate of 25 mL / min. The sample was heated from room temperature (23°C) to 200°C at a rate of 10°C / min (single heating), held at 200°C for 5 minutes to allow complete melting, and then cooled from 200°C to 40°C at a rate of 10°C / min, held at 40°C for 5 minutes. The glass transition temperature (Tg) (°C) was determined by intersecting the step-like change portion of the differential scanning calorimeter (DSC) curve during the second heating under the above heating conditions with the straight line equidistant from the extensions of each baseline in the vertical direction (midpoint glass transition temperature). Four measurements were taken for each sample, and the arithmetic mean of the four measurements (rounded to the nearest decimal) was taken as the measured value.

[0483] <Glass transition temperature (Tg) of the substrate film constituting the reflective polarizing element 膜 The determination of ) >

[0484] The glass transition temperature (Tg) of the substrate film constituting the reflective polarizing element was determined using a dynamic viscoelastic apparatus (EPLEXOR II 500N; Netzsch company) under ISO 6721-1 conditions. 膜 It should be noted that the Tg of the substrate film constituting the reflective polarizing element was measured. 膜 At that time, about 10 mg was cut from the substrate film and used as a sample for testing.

[0485] Note that when confirming the Tg of the plurality of base material films constituting the reflective polarizing element, the lower Tg 膜 as a reference.

[0486] Measurement of absolute value of photoelastic coefficient

[0487] The portion of the lens to which the portion of the resin lens cut out was compression-molded using a vacuum compression molding machine as a measurement sample.

[0488] As the specific sample preparation conditions, the portion of the lens to which the portion of the resin lens cut out was compression-molded using a vacuum compression molding machine (manufactured by Jinushi Metal Industry, SFV-30 type) at 260°C under reduced pressure (about 10 kPa) for 10 minutes, and then at 260°C and about 10 MPa for 5 minutes. After the pressure was reduced and released, the sample was moved to a compression molding machine for cooling and allowed to cool and solidify. After the obtained compression-molded sample was allowed to mature for 24 hours or more in a constant temperature and humidity chamber adjusted to 23°C and 60% humidity, a measurement test piece (about 150 μm thick and 6 mm wide) was cut out. The photoelastic coefficient CR (Pa -1 ) was measured using a birefringence measuring device described in detail in Polymer Engineering and Science (1999, 39, 2349-2357).

[0489] The test piece in the form of a film was arranged in a film stretching device (manufactured by Yugen Seizo) also provided in the constant temperature and humidity chamber so that the distance between the jaws was 50 mm. Then, the device was arranged so that the laser path of the birefringence measuring device (manufactured by Otsuka Electronics, RETS-100) was located at the center of the film, and the birefringence of the test piece was measured while a tensile stress was applied at a strain rate of 50% / minute (distance between jaws: 50 mm, jaw moving speed: 5 mm / minute).

[0490] From the relationship between the birefringence (Δn) and the tensile stress (σR) obtained by the measurement, the slope of the line was calculated by least square approximation, and the photoelastic coefficient (CR) (Pa -1 ) was calculated. The data of the tensile stress between 2.5 MPa ≤ σR ≤ 10 MPa were used for the calculation.

[0491] CR = Δn / σR

[0492] Here, the birefringence (Δn) is the value shown below.

[0493] Δn = nx-ny

[0494] (nx: refractive index in the stretching direction, ny: refractive index in the direction perpendicular to the stretching direction in the plane.)

[0495] <Phase difference within the effective diameter of the resin lens>

[0496] For the resin lenses obtained through the examples and comparative examples, the surface distribution of the phase difference of the lens was measured from the optical axis direction using a birefringence evaluation system PA-300-L manufactured by PhotonicLattice Inc. at a wavelength of 520 nm. The area was specified within the effective diameter (Φ41 mm) of the lens, and the average value (nm) of the absolute value of the phase difference was calculated.

[0497] <Transmittance (total light transmittance) within the effective diameter of the resin lens>

[0498] For the resin lenses obtained through the examples and comparative examples, a spectrophotometer / haze meter (manufactured by Nippon Denshoku Kogyo Co., Ltd., COH7700) was used. The light source was passed through the optical axis of the lens, and the transmittance (%) was measured every 10 nm within the wavelength range of 400–700 nm using a D65 light source and a 2° field of view. The measured value of the total light transmittance (%) was obtained. The average value of the three resin lenses molded under the same conditions was taken as the total light transmittance (%).

[0499] <Evaluation of contrast and observed image of pancake lens>

[0500] Referring to the contents of Japanese Patent Application Publication No. 2024-4491, a lens was prepared by attaching a wire grid polarizing element or a stacked reflective polarizing element to a convex surface. Using this lens, the contrast of the pancake lens structure was evaluated.

[0501] Made and used in a dark room Figure 4 This is a simulation device illustrating the principle of a head-mounted display with a pancake lens structure. Furthermore, the optical data used as the substrate during the fabrication of this device are shown in Tables 1-4. Figure 4 Refer to Table 1 for the composition; when referring to Tables 2-4, adjust the distance between each component. The type column in the table refers to the surface shape, n d It refers to the refractive index of the d-line, ν d This refers to the Abbe number based on the d-line, and the thickness refers to the distance between the surfaces. For the type column, SPH indicates that the surface shape is spherical, and ASP indicates that the surface shape is aspherical. The surface shape is represented by the radius of curvature R, conic constant k, and even-order aspherical coefficients D, E, F, and G, using the aspherical calculation formula in Equation I. When the radius of curvature is infinite, it refers to a plane. The surface number is used for backray tracing of the image from the virtual image position to the image display element surface, with the exit pupil position as surface 1.

[0502] In this simulation device, the smartphone 40 (manufactured by Sharp Corporation, AQUOS sense6, SH-M19) is arranged and an image is output. Also, the image is displayed as a grid pattern in which a black portion of a quadrangle is surrounded by a white line as shown in Figure 5 At this time, the smartphone 40 is arranged (the diameter of the circumscribed circle of the region displayed as being composed of 9 black portions and the white line surrounding it coincides with the effective diameter of the image display region, or the diameter of the circumscribed circle is 9 times or more the effective diameter of the image display region) and an image is output.

[0503] Then, the image light is transmitted through a member in which the circularly polarizing element 43 (an element in which an absorbing type linearly polarizing element and a 1 / 4 wave plate are attached, manufactured by Kenko Tokina Co., Ltd., 49S ZX C-PL) is arranged so that the linearly polarizing element side faces the smartphone 40 and is converted into circularly polarized light (for example, circularly polarized light in the counterclockwise direction when viewed from the advancing direction). Then, the semi-reflecting mirror element 44 (the incident surface has an anti-reflection coating, the emission surface is a dielectric multilayer film semi-reflecting mirror, the transmittance: reflectance = 50%: 50%) is transmitted. Then, the 1 / 4 wave plate 45 (manufactured by Nippon Sheet Glass Co., Ltd., an element in which a glass plate having a thickness of 0.7 mm after single-side AR coating is sandwiched by WA140T of 40 mmφ with the AR coating facing the outside) is transmitted and is converted into linearly polarized light (first linearly polarized light). At this time, whether the combination of the aforementioned circularly polarizing element 43 and the 1 / 4 wave plate 45 can form linearly polarized light can be confirmed separately by whether the linearly polarizing element can block light. In addition, an optical shielding portion 49 is provided further outside than the 1 / 4 wave plate 45, and extraneous light such as stray light caused by reflection is shielded.

[0504] Then, the semi-reflecting mirror element 44 is transmitted, and the 1 / 4 wave plate 45 is transmitted and is converted into circularly polarized light (for example, circularly polarized light in the counterclockwise direction when viewed from the advancing direction), and is reflected by the semi-reflecting mirror element 44 and is converted into circularly polarized light (for example, circularly polarized light in the clockwise direction when viewed from the advancing direction), and when the 1 / 4 wave plate 45 is transmitted, the first linearly polarized light is converted into second linearly polarized light in which the axis is rotated by 90 degrees, and the resin lens 41 is transmitted, and then, in the reflecting type polarizing element 42, the polarization direction becomes coincident with the transmission axis, so it is transmitted. Further, the face of the circularly polarizing element 47 (in which an absorbing type linearly polarizing element (not shown) and a 1 / 4 wave plate (not shown) are attached) in which the linearly polarizing element is attached is arranged so as to face the reflecting type polarizing element attached lens 46 side to transmit the aforementioned second linearly polarized light.

[0505] As a photographing camera, a digital single-lens reflex camera, abbreviated as 48, was used, and the EOS RP manufactured by Canon Inc. (using a standard zoom lens RF24-105mm F4-F7.1 IS STM) was used for photographing. When the image focus was not aligned, the position of the smartphone 40 was adjusted within a range of 1 to 3 mm. The photographing conditions were set to ISO-8000, focal length 31 mm, exposure time 1 / 250 seconds, and aperture value f / 5.6.

[0506] In the image, for the image in which a black portion of a quadrangle was photographed in the center, the brightness of the black portion of the quadrangle and the brightness of the adjacent white line were introduced into the following Formula II, and the contrast was calculated. The contrast values between the black portion of the quadrangle and the adjacent white line were averaged for nine quadrangles, and were used as the image contrast in the evaluation of the present application. In addition, the brightness values of the aforementioned images were calculated using image software (ImageJ).

[0507] Formula II: Image contrast = (average brightness of the white line adjacent to the black portion of the quadrangle - average brightness of the black portion of the quadrangle) / (average brightness of the white line adjacent to the black portion of the quadrangle + average brightness of the black portion of the quadrangle)

[0508] In addition, for the photographed images, the evaluation related to the presence or absence of double images and light spots caused by ghosting was performed according to the following criteria.

[0509] No influence of double images and light spots: A.

[0510] Slight influence of double images and light spots: B.

[0511] Ghost images caused by double images could be observed, and white images were formed due to light spots: C.

[0512] Double images were clearly observed, and white images were formed due to light spots: D.

[0513] Table 1

[0514]

[0515] Table 2

[0516]

[0517] Table 3

[0518]

[0519] Table 4

[0520]

[0521] Evaluation of appearance (presence or absence of peeling and presence or absence of cracks) after reliability test

[0522] The durability in a constant temperature and humidity environment was evaluated using five of the reflective polarizing elements attached lenses obtained in the examples and comparative examples. The reflective polarizing elements attached lenses were put in a constant temperature and humidity chamber (manufactured by ESPEC company, PL-4KP) maintained at 85°C, 85% RH. After 500 hours under the environment of 85°C, 85% RH, the reflective polarizing elements attached lenses were taken out, and the appearance of the five reflective polarizing elements attached lenses was evaluated in terms of two items, presence or absence of peeling and presence or absence of cracks on the lenses.

[0523] The evaluation results are shown in Tables 5 to 8. In the tables, the number of lenses in which peeling was present and the number of lenses in which cracks were present are described.

[0524] Evaluation of appearance after cold and heat cycle test

[0525] The cold and heat cycle test was set to one cycle: -30°C x 1 hour, 85°C x 1 hour, using a constant temperature and humidity tank (low temperature constant temperature and humidity chamber PL-2J manufactured by ESPEC company), for 20 cycles, for 10 of the reflective polarizing elements attached lenses obtained in the examples and comparative examples, and the appearance of the reflective polarizing elements attached lenses was evaluated according to the following criteria, and the number of lenses corresponding to defective products was counted. The measurement results are shown in Tables 5 to 8. Note that the number of lenses corresponding to defective products was evaluated according to the following criteria, and the number corresponding to defective products is described.

[0526] Good product: no wrinkles, bubbles, peeling, and the like, and the appearance was good.

[0527] Defective product: cracks, wrinkles, bubbles, or peeling of the reflective polarizing element were observed on the lenses.

[0528] [Raw materials]

[0529] The raw materials used in the examples and comparative examples described below are shown below.

[0530] [[Monomers constituting the methacrylic resin]]

[0531] Methyl methacrylate (MMA): manufactured by Asahi Kasei Corporation.

[0532] N-phenylmaleimide (PMI): manufactured by Japan Catalyst Co., Ltd.

[0533] N-cyclohexylmaleimide (CMI): manufactured by Japan Catalyst Co., Ltd.

[0534] Styrene: manufactured by FUJIFILM Wako Pure Chemical Corporation.

[0535] 2-(hydroxymethyl) methyl acrylate (MHMA): manufactured by Combi-Blocks company.

[0536] [[Organic solvent]]

[0537] m-xylene (mXy): manufactured by Mitsubishi Gas Chemical Company, Inc.

[0538] Methyl isobutyrate: manufactured by Kanto Chemical Co., Inc.

[0539] Toluene: manufactured by FUJIFILM Wako Pure Chemical Corporation.

[0540] [[Polymerization initiator]]

[0541] 1,1-di(tert-butylperoxy)cyclohexane: manufactured by NOF Corporation.

[0542] Tert-amylperoxy-2-ethylhexanoate: manufactured by ARKEMA Yoshitomi, Ltd., "Luperox 575".

[0543] Tert-amylperoxy isononanoate: manufactured by ARKEMA Yoshitomi, Ltd.

[0544] [[Chain transfer agent]]

[0545] n-Octyl mercaptan: manufactured by Chevron Phillips Chemical Company.

[0546] n-Dodecyl mercaptan: manufactured by FUJIFILM Wako Pure Chemical Corporation.

[0547] N-phenylmaleimide and N-cyclohexylmaleimide among the aforementioned raw materials were stored in a cabinet in which the temperature was adjusted to a range of 20 to 30°C from the time of delivery, and raw materials within 3 months from the delivery date were used.

[0548] Before use, the raw materials were dissolved in m-xylene, liquid-liquid extraction was performed using pure water, and then the water layer was used to quantify the acid components. A large amount of maleic acid was confirmed from N-phenylmaleimide, and a total of 950 ppm of acid components was confirmed. On the other hand, a total of 110 ppm of acid components was confirmed from N-cyclohexylmaleimide. When the amount of maleic acid is greater than 1000 ppm, the maleimide is washed with water and dehydrated by the method described in Japanese Patent No. 2021-92767, and after purification, it is supplied to the production of a methacrylic resin.

[0549] (Preparation of resin composition)

[0550] Synthesis Example 1 (Methacrylic Resin Composition A)

[0551] Methacrylic acid methyl ester (hereinafter, referred to as MMA) 318.7 kg, N-phenylmaleimide (hereinafter, referred to as PMI) 35.5 g, N-cyclohexylmaleimide (hereinafter, referred to as CMI) 63.7 kg, n-octyl mercaptan as a chain transfer agent 0.341 kg, m-xylene (hereinafter, referred to as mXy) 225.1 kg were measured and added to a 1.25 m 3 The reactor was stirred to obtain a mixed monomer solution.

[0552] Then, 116.9 kg of mXy was measured and added to tank 1, and a replenishing solvent was prepared.

[0553] Further, 104.5 kg of MMA and 85.5 kg of mXy were measured and placed in tank 2, and stirring was performed to obtain a replenishing MMA solution.

[0554] Nitrogen-based bubbling was performed on the inside liquid of the reactor at a rate of 30 L / min for 1 hour, and nitrogen-based bubbling was performed on tank 1 and tank 2 at a rate of 10 L / min for 30 minutes, respectively, to remove dissolved oxygen.

[0555] Then, steam was blown into the jacket to raise the temperature of the solution in the reactor to 125°C, and a polymerization initiator solution in which 1,1-di(tert-butylperoxy)cyclohexane 0.457 kg was dissolved in 2.67 kg of mXy was added at a rate of 1 kg / hour while stirring at 50 rpm, and the polymerization was started. Note that, in the polymerization, the temperature of the solution in the reactor was controlled to 125 ± 2°C by jacket-based temperature adjustment. After 30 minutes from the start of the polymerization, the addition rate of the polymerization initiator solution was reduced to 0.25 kg / hour, and mXy was added from tank 1 at a rate of 29.24 kg / hour for 3.5 hours.

[0556] Then, 4 hours after the start of the polymerization, the addition rate of the polymerization initiator solution was increased to 0.75 kg / hour, and the replenishing MMA solution was added from tank 2 at a rate of 95 kg / hour for 2 hours.

[0557] Further, 6 hours after the start of the polymerization, the addition rate of the polymerization initiator solution was reduced to 0.25 kg / hour, and 7 hours after the start of the polymerization, the addition was stopped.

[0558] After 8 hours from the start of polymerization, a polymerization solution containing a methacrylic resin was obtained. To this, 0.261 kg of Irganox 1010, 0.784 kg of Irgafos 168, 0.784 kg of RIKEMAL H-100 as a release agent were added as antioxidants.

[0559] Then, the obtained polymerization solution was supplied to a concentration device composed of a tubular heat exchanger and a gasification tank, which were previously heated to 250°C, to perform devolatilization. The degree of vacuum of the gasification tank was set to 10 to 15 Torr. The resin flowing from the gasification tank was discharged with a screw pump, extruded from a die, and water-cooled, and then pelletized to obtain a methacrylic resin composition A having an N-substituted maleimide structural unit.

[0560] The Tg of the obtained methacrylic resin composition A was 133°C, the flexural strength was 66 MPa, and the flexural modulus of elasticity was 3400 MPa. Other properties are collectively described in Tables 5 to 8.

[0561] - Synthesis Example 2 [Methacrylic Resin Composition B] -

[0562] A monomer composition composed of 75.000 mole% of MMA, 24.998 mole% of styrene, and 0.002 mole% of t-amylperoxy-2-ethylhexanoate as a polymerization initiator was continuously supplied at 1 kg / h to a 10 L full-mixing tank equipped with a spiral ribbon blade, and continuous polymerization was performed at an average residence time of 2.5 hours and a polymerization temperature of 150°C. It was continuously withdrawn from the bottom at a constant liquid level of the polymerization tank, supplied to a concentration device composed of a tubular heat exchanger and a gasification tank to perform devolatilization. The degree of vacuum of the gasification tank was set to 10 to 15 Torr. The resin flowing from the gasification tank was discharged with a screw pump, extruded from a die, and water-cooled, and then pelletized to obtain a methacrylic resin composition A having an N-substituted maleimide structural unit.

[0563] The copolymer was dissolved in methyl isobutyrate to prepare a 10 mass% methyl isobutyrate solution. Into a 1000 mL autoclave device, 500 parts by mass of the 10 mass% methyl isobutyrate solution of the copolymer, 1 part by mass of 10 mass% Pd / C (manufactured by N.E. CHEMCAT CORPORATION) as a hydrogenation catalyst were charged, and the aromatic double bonds in the styrene sites of the copolymer were hydrogenated at 9 MPa of hydrogen pressure, 200°C for 15 hours. The hydrogenation catalyst was removed with a filter, and after 0.04 parts by mass of RIKEMAL H-100 was added to the polymer solution, the solution was supplied to a concentration device composed of a tubular heat exchanger and a vaporization tank to be devolatilized. The degree of vacuum of the vaporization tank was set to 10 to 15 Torr. The resin flowing from the vaporization tank was discharged with a gear pump, extruded from a die, and water-cooled, and then pelletized to obtain the particles of the methacrylic resin composition B.

[0564] The Tg of the obtained particles was 118°C, the flexural strength was 95 MPa, and the flexural modulus of elasticity was 3170 MPa. Other characteristics are collectively described in Tables 5 to 8.

[0565] Synthesis Example 3 [Methacrylic Resin Composition C]

[0566] Into a 30 L reaction kettle having a stirring device equipped with a paddle wing, a temperature sensor, a cooling tube, and a nitrogen introduction tube, 2.25 kg of methyl methacrylate, 0.32 kg of 2-(hydroxymethyl) methyl acrylate, 0.024 kg of styrene, 0.025 parts by mass of n-dodecyl mercaptan as a chain transfer agent with respect to 100 parts by mass of the total amount of all the monomers finally charged into the reaction kettle, 0.025 parts of ADK STAB 2112, and 5.39 kg of toluene were charged, nitrogen was introduced thereto, and the temperature was raised to 105°C while stirring.

[0567] As an initial initiator, a solution composed of 0.20 kg of toluene and 0.014 kg of t-amyl peroxy isononanoate was dropped into the polymerization tank for 10 minutes while polymerization was performed at 105°C to 110°C. Further, 10 minutes later, a solution composed of 0.26 kg of toluene and 0.017 kg of t-amyl peroxy isononanoate was dropped for 3 hours, and, at the same time as the dropping of the initiator solution, a solution composed of 2.75 kg of methyl methacrylate, 0.40 kg of 2-(hydroxymethyl) methyl acrylate, and 0.24 kg of styrene was dropped for 3 hours while polymerization was performed at a polymerization temperature of 105 to 110°C, and, further, aging was performed for 2 hours. To the obtained polymer solution, a mixed solution of 4.5 g of a phosphoric acid stearyl ester / distearyl phosphoric acid ester mixture and 72 g of toluene was added, and a cyclization condensation reaction was performed at 90 to 110°C for 1.5 hours. Then, 0.10 parts by mass of RIKEMAL H-100 was added with respect to 100 parts by mass of the total amount of the monomers finally charged into the reaction tank, and stirring was performed to effect mixing.

[0568] A φ 42 mm devolatilization extruder having four front exhaust ports and one rear exhaust port was used to perform a cyclization condensation reaction and devolatilization treatment on the obtained polymer solution at a cylinder temperature of 220°C and 120 rpm at a rate of 5 kg / hour in terms of the resin amount, to obtain a particulate methyl methacrylate resin composition C.

[0569] The Tg of the obtained particulate was 127°C, the flexural strength was 98 MPa, and the flexural modulus of elasticity was 3600 MPa.

[0570] - Synthesis Example 4 [Methyl Methacrylate Resin Composition D] -

[0571] A MS resin (copolymer of MMA and α-methylstyrene) was polymerized according to the method for producing the copolymer (A) described in [Example] of Japanese Patent Application Publication No. 2003-231785. The mass ratio of MMA and styrene charged into the autoclave was changed, and, when the total monomer weight at the time of polymerization was set to 100 parts by mass, 0.15 parts by mass of RIKEMAL H-100 was added, and polymerization was performed to obtain a precursor resin (MMA: α-methylstyrene = 88 mass%: 12 mass%). A co-rotating twin-screw extruder having a screw diameter of 40 mm was used, the extruder cylinder temperature was set to 275°C, the screw rotation number was set to 150 rpm, the MS resin obtained by the above polymerization was fed from a hopper at 20 kg / hour, and nitrogen was introduced into the extruder at a flow rate of 200 mL / min. The resin was melted by the kneading blocks, and, after being filled, 2.2 parts by mass of monomethylamine with respect to 100 parts by mass of the raw material resin was injected from a nozzle to perform an imidization reaction.

[0572] At the end of the reaction zone (just before the exhaust port), a reverse thread was installed, and the resin was filled. The pressure of the exhaust port was reduced to 30 Torr to remove the by-products and excess monomethylamine after the reaction. The resin coming out of the die provided at the outlet of the extruder as a strand was cooled in a water tank, and then pelletized using a pelletizer, thereby obtaining the imide resin.

[0573] Then, using a co-rotating twin-screw extruder with a screw diameter of 40 mm, the extruder cylinder temperature was set to 255°C, the screw rotation number was set to 150 rpm, and the obtained imide resin was supplied at 20 kg / hr, and the resin was melted by the kneading blocks, and after being filled, a mixed solution of dimethyl carbonate and triethylamine as an esterification agent was injected from the nozzle, and the carboxylic acid group in the resin was reduced. With respect to 100 parts by mass of the imide resin, 2.6 parts by mass of dimethyl carbonate and 0.2 parts by mass of triethylamine were used. The pressure of the exhaust port was reduced to 30 Torr to remove the by-products and excess dimethyl carbonate after the reaction. The resin coming out of the die provided at the outlet of the extruder as a strand was cooled in a water tank, and then pelletized using a pelletizer, thereby obtaining the particles of the methacrylic resin composition D having a glutarimide structure.

[0574] The Tg of the obtained particles was 134°C, the flexural strength was 117 MPa, and the flexural modulus of elasticity was 3500 MPa.

[0575] - Synthesis Example 5 [Methacrylic Resin Composition E] -

[0576] 270.1 kg of MMA, 83.8 kg of PMI, 167.5 kg of CMI, 0.11 kg of n-octyl mercaptan as a chain transfer agent, and 247.0 kg of mXy were measured, and added to a 1.25 m 3 The reactor was stirred, and a mixed monomer solution was obtained.

[0577] Then, 123.0 kg of mXy was measured, and added to Tank 1. Further, 110.0 kg of MMA and 80.0 kg of mXy were measured, and placed in Tank 2, and stirred, and a supplemental monomer solution was obtained. The internal liquid of the reactor was subjected to nitrogen-based bubbling at a rate of 30 L / min for 1 hour, and Tank 1 and Tank 2 were subjected to nitrogen-based bubbling at a rate of 10 L / min for 30 minutes, respectively, and dissolved oxygen was removed.

[0578] Then, steam was blown into the jacket to raise the solution temperature in the reactor to 124°C. While stirring at 50 rpm, a polymerization initiator solution consisting of 0.35 kg of 1,1-di(tert-butylperoxide)cyclohexane dissolved in 4.652 kg of mXy was added at a rate of 1 kg / h to initiate polymerization. mXy was also added from tank 1 at a rate of 30.75 kg / h for 4 hours. It should be noted that during polymerization, the solution temperature in the reactor was controlled at 124 ± 2°C by temperature regulation based on the jacket.

[0579] Then, from 4 hours to 6 hours later, a monomer solution containing MMA is added from tank 2 at a rate of 95 kg / h.

[0580] Furthermore, for the polymerization initiator solution, the addition rate is reduced to 0.25 kg / h after 0.5 hours of polymerization, to 0.75 kg / h after 4 hours, to 0.5 kg / h after 6 hours, and the addition of the polymerization initiator solution is stopped after 7 hours of polymerization. Then, polymerization continues for another 3 hours to obtain a polymerization solution containing methacrylic resin with ring structure units in the main chain.

[0581] 0.83 kg of ADK STAB PEP-36, 0.28 kg of Irgafos168, 0.44 kg of Irganox 1076, and 1.10 kg of RIKEMAL H-100 were added to the polymerization solution under stirring.

[0582] The obtained polymerization solution is then fed to a concentration device consisting of a tubular heat exchanger preheated to 260°C and a vaporization tank for devolatilization. The vacuum level of the vaporization tank is set to 10–15 Torr. The resin flowing from the vaporization tank is discharged by a screw pump, extruded from a drawing die, and water-cooled before granulation to obtain granules of methacrylic resin E having N-substituted maleimide structural units.

[0583] The obtained particles have a Tg of 154℃, a flexural strength of 59MPa, and a flexural modulus of 3500MPa.

[0584] -Synthesis Example 6 [Methacrylic Acid Resin Composition F]-

[0585] To a 1.25m [unclear - possibly referring to a specific location or system] equipped with a stirring device with paddle-shaped blades, a temperature sensor, a cooling pipe, and a nitrogen inlet pipe. 3 432.3 kg of methyl methacrylate (MMA), 25.4 kg of N-cyclohexylmaleimide (CMI), 450.0 kg of m-xylene, and 0.28 kg of n-octylthiol were added to a reactor and dissolved to prepare a raw material solution. Nitrogen was then introduced into the solution, and the temperature was raised to 125°C while stirring.

[0586] In addition, an initiator feed solution in which 0.23 kg of Perhexa C-75 and 1.82 kg of m-xylene were mixed was prepared. When the raw material solution reached 127°C, the supply (addition) of the initiator feed solution (polymerization initiator mixture) was started in accordance with the procedures of (1) to (6).

[0587] (1) 0.0 to 0.5 hours: supply rate 1.00 kg / hour.

[0588] (2) 0.5 to 1.0 hours: supply rate 0.50 kg / hour.

[0589] (3) 1.0 to 2.0 hours: supply rate 0.42 kg / hour.

[0590] (4) 2.0 to 3.0 hours: supply rate 0.35 kg / hour.

[0591] (5) 3.0 to 4.0 hours: supply rate 0.14 kg / hour.

[0592] (6) 4.0 to 7.0 hours: supply rate 0.13 kg / hour.

[0593] After the initiator was supplied for a total of 7 hours (B time = 7 hours), the reaction was continued for 1 hour, and the polymerization reaction was performed for 8 hours from the start of the addition of the initiator.

[0594] In the polymerization reaction, the internal temperature was controlled at 127 ± 2°C. The polymerization solution obtained above was subjected to devolatilization treatment using a φ 42 mm devolatilization extruder having four front vents and one rear vent at 140 rpm, which was converted to 10 kg / hour in terms of the amount of resin, and a granular methacrylic resin composition F was obtained.

[0595] The Tg of the obtained granules was 118°C, and the flexural strength was 103 MPa and the flexural modulus of elasticity was 3200 MPa.

[0596] - Synthesis Example 7 [Methacrylic Resin Composition G] -

[0597] A 1.25 m 3A reaction vessel was charged with 430.8 kg of methyl methacrylate (MMA), 33.4 kg of N-phenylmaleimide (N-PMI), 41.5 kg of N-cyclohexylmaleimide (N-CMI), 5.4 kg of acrylonitrile (AN), 450.0 kg of m-xylene, and 0.055 kg of n-octyl mercaptan, dissolved, to prepare a raw material solution. Nitrogen was introduced thereto, and the temperature was raised to 120°C while stirring. Separately, an initiator feed solution A prepared by mixing 0.18 kg of Perhexa 25B and 0.73 kg of m-xylene, and an initiator feed solution B prepared by mixing 0.061 kg of Perhexa 25B and 0.24 kg of m-xylene were prepared. When the temperature of the raw material solution reached 130°C, the initiator feed solution A was supplied at a rate of 5.5 kg / hour for 10 minutes. After 2 hours, the temperature in the reaction vessel was lowered to 115°C over 0.5 hour, and after the temperature reached 115°C, the initiator feed solution B was supplied at a rate of 1.8 kg / hour for 10 minutes (B time = 2.83 hours), and the reaction was continued directly, and a polymerization reaction was carried out for a total of 13 hours, and the reaction was terminated. The polymerization solution obtained was subjected to devolatilization treatment using a φ 42 mm twin-screw devolatilization extruder having four front vents and one rear vent at 140 rpm at a rate of 10 kg / hour based on the amount of resin, to obtain a particulate of a methacrylic resin composition G.

[0598] The Tg of the obtained particulate was 125°C, the flexural strength was 110 MPa, and the flexural modulus of elasticity was 3200 MPa.

[0599] Synthesis Example 8 [Methacrylic Resin Composition H]

[0600] A co-rotating twin-screw extruder having a screw diameter of 40 mm was used, the temperature of the extruder cylinder was set to 275°C, the screw rotation number was set to 150 rpm, and a poly(methyl methacrylate) having a weight average molecular weight of 108,000 containing 0.1 parts by mass of RIKEMAL H-100 when the total amount of the polymer was 100 parts by mass was supplied from a hopper at a rate of 20 kg / hour, and nitrogen was introduced into the extruder at a flow rate of 200 mL / min. The resin was melted by a kneading block, and after being filled, 1.8 parts by mass of monomethylamine with respect to 100 parts by mass of the raw resin was injected from a nozzle to perform an imidization reaction. A reverse thread was provided at the end of the reaction zone (just before the vent) so as to be filled with the resin. The pressure of the vent was reduced to 50 Torr to remove the by-product after the reaction and excess monomethylamine. The resin coming out from the die provided at the outlet of the extruder in a strand was cooled in a water tank, and then pelletized using a pelletizer, to obtain an imide resin.

[0601] Then, using a co-rotating twin-screw extruder with a screw diameter of 40 mm, the extruder cylinder temperature was set to 255°C, the screw rotation number was set to 150 rpm, and the obtained imide resin was supplied at 20 kg / hr to melt the resin with the kneading blocks, and after filling, a mixed solution of dimethyl carbonate and triethylamine as an esterification agent was injected from the nozzle to reduce the carboxylic acid group in the resin. With respect to 100 parts by mass of the imide resin, 3.2 parts by mass of dimethyl carbonate and 0.8 parts by mass of triethylamine. The pressure at the exhaust port was reduced to 50 Torr to remove the by-products and excess dimethyl carbonate after the reaction. The resin coming out as a strand from the die provided at the outlet of the extruder was cooled in a water tank, and then granulated using a granulator to obtain granules of the methacrylic resin composition H having a glutarimide structure.

[0602] The obtained granules had a Tg of 123°C, a flexural strength of 127 MPa, and a flexural modulus of 3570 MPa.

[0603] - Synthesis Example 9 [Methacrylic Resin Composition I] -

[0604] Into a 30-L reaction kettle having a stirring device with paddle wings installed, a temperature sensor, a cooling tube, and a nitrogen introduction tube, 2.25 kg of methyl methacrylate, 1.25 kg of 2-(hydroxymethyl) methyl acrylate, 0.025 parts by mass of n-dodecyl mercaptan as a chain transfer agent with respect to 100 parts by mass of the total amount of all monomers, 0.025 parts of ADK STAB 2112, and 6.25 kg of toluene were charged, nitrogen was introduced thereinto, and the temperature was raised to 105°C while stirring. While refluxing, 0.05 parts by mass of t-amyl peroxynonanoate with respect to 100 parts by mass of the total amount of all monomers was added to the polymerization tank, and polymerization was performed at a polymerization temperature of 105 to 110°C for 6 hours while dropping 0.1 parts by mass of t-amyl peroxynonanoate over 2 hours.

[0605] To the obtained polymer solution, 6.3 g of a phosphoric acid stearyl ester / distearyl phosphoric acid ester mixture was added, and a cyclization condensation reaction was performed at 90 to 110°C for 5 hours. Then, 0.15 parts by mass of RIKEMAL H-100 with respect to 100 parts by mass of the total amount of all monomers was added, and stirring was performed to perform mixing. Using a φ 42-mm devolatilization extruder with four front exhaust ports and one rear exhaust port, the obtained polymer solution was subjected to a cyclization condensation reaction and devolatilization treatment at 120 rpm at 2.2 kg / hr converted from the amount of resin to obtain granules of the methacrylic resin composition I.

[0606] The obtained granules had a Tg of 133°C, a flexural strength of 71 MPa, and a flexural modulus of 3600 MPa.

[0607] Synthesis Example 10 [Resin composition J of cyclic olefin copolymer]

[0608] First, a vanadium catalyst having a vanadium concentration of 6.7 mmol / L-cyclohexane was prepared by diluting VO(OC2H5)Cl2with cyclohexane. An organoaluminum compound catalyst having an aluminum concentration of 107 mmol / L-hexane was prepared by diluting ethylaluminum sesquichloride (Al(C2H5)Cl2.5) with hexane. Then, a continuous copolymerization reaction of ethylene and tetra[4.4.0.1 1.5 .1 1.5 .1 2，5 .1 7，10 ]-3-dodecene (tetracyclododecene) was performed using a stirred polymerizer (inner diameter 500 mm, reaction volume 100 L). Here, ethylene was supplied to the polymerizer together with hydrogen. When the copolymerization reaction was performed, the vanadium catalyst prepared by the above method was supplied to the polymerizer in an amount such that the vanadium catalyst concentration in the cyclohexane in the polymerizer used as a polymerization solvent became 0.6 mmol / L. In addition, ethylaluminum sesquichloride as an organoaluminum compound was supplied to the polymerizer in an amount such that Al / V = 18.0. The polymerization temperature was set to 8°C, and the polymerization pressure was set to 1.8 kg / cm 2 G, and the copolymerization reaction was continuously performed.

[0609] To the copolymer solution of ethylene and tetra[4.4.0.1 2，5 .1 7，10 ]-3-dodecene drawn from the polymerizer, water and a 25 mass% sodium hydroxide aqueous solution as a pH adjuster were added to stop the polymerization reaction. In addition, the catalyst residue present in the copolymer was removed (deashed) from the copolymer solution. After the above deashing treatment, Irganox 1010 as a stabilizer was added to the cyclohexane solution of the copolymer of ethylene and tetra[4.4.0.1 2，5 .1 7，10 ]-3-dodecene (polymer concentration 7.7 mass%) in an amount of 0.4 parts by mass with respect to 100 parts by mass of the copolymer. Then, the mixture was temporarily mixed for 1 hour using a stirred tank having an effective volume of 1.0 m 3 before entering the flash drying process.

[0610] To a double-tube heater (outer tube diameter 2B, inner tube diameter 3 / 4B, length 21 m) using water vapor at 20 kg / cm 2 G as a heat source, the above cyclohexane solution of the copolymer having a concentration of 5 mass% of the copolymer in cyclohexane was supplied in an amount of 150 kg / h, and heated to 180°C.

[0611] A double-tube heater (outer tube diameter 2B, inner tube diameter 3 / 4B, length 21 m) using water vapor at 20 kg / cm2 A double-pipe flash dryer (outer pipe diameter 2B, inner pipe diameter 3 / 4B, length 27 m) and a flash hopper (volume 200 L) of G for water vapor, which removes cyclohexane as a polymerization solvent and most of the unreacted monomers from the cyclohexane solution of the above-described copolymer via the above-described heating process, thereby obtaining a random copolymer of ethylene and tetra[4.4.0.1 2，5 .1 7，10 ]-3-dodecene (cycloolefin copolymer) in a molten state after flash drying.

[0612] Pentaerythritol distearate (UNISTER H-476D manufactured by NIKKOL CORPORATION) as a fatty acid ester was directly charged into a twin-screw extruder with a vent in a molten state heated at 100°C for 4 hours in an amount of 2.1 parts by mass relative to 100 parts by mass of the cycloolefin-based copolymer (A-1), and was kneaded with the aforementioned cycloolefin copolymer charged from a resin charging portion of the extruder, pelletized using an underwater pelletizer installed at an outlet of the extruder, and the obtained pellets were dried with hot air at a temperature of 100°C for 4 hours to obtain a resin composition J of a cycloolefin copolymer. In this resin composition, the proportion of the ring skeleton structure unit was 38 mol%.

[0613] The Tg of the obtained pellets was 137°C, the flexural strength was 77 MPa, and the flexural modulus of elasticity was 3350 MPa.

[0614] - Synthesis Example 11 [Cycloolefin Resin Composition K] -

[0615] Drying was performed, and a cycloolefin-based copolymer solution was charged into a nitrogen-substituted polymerization reactor. The cycloolefin-based copolymer solution was prepared by dissolving 65 mol% of tetra[4.4.0.1 2，10 .0 3，8A monomer mixture consisting of 7 parts of tetradeca-3,5,7,12-tetraene (methyl bridged tetrahydrofluorene), 30 mole% of tetracyclododecene, and 5 mole% of bicyclo(2.2.1)hept-2-ene (norbornene), 1% relative to the total amount of monomers used in polymerization, 1600 parts of dehydrated cyclohexane, 1.5 parts of 1-docosene as a molecular weight modifier, 1.3 parts of diisopropyl ether, 0.33 parts of isobutyl alcohol, 0.84 parts of triisobutylaluminum, and 30 parts of a cyclohexane solution of tungsten hexachloride at 0.66%, was stirred at 55°C for 10 minutes. Then, the reaction system was maintained at 55°C while stirring, and 693 parts of a monomer mixture of the same composition as described above and 72 parts of a cyclohexane solution of tungsten hexachloride at 0.66% were continuously dropped into the above polymerization reactor over 150 minutes, respectively, and after the dropping was completed, stirring was performed for 30 minutes. Then, 1.0 part of isopropyl alcohol was added to stop the polymerization reaction. The polymerization reaction solution was analyzed by gas chromatography, and the result was that the monomer conversion was 100%. Then, 300 parts of the above polymerization reaction solution was transferred to a high-pressure autoclave with a stirrer, 100 parts of cyclohexane and 2.0 parts of a diatomite-supported nickel catalyst (product name "T8400RL" manufactured by Nitobo Chemical Co., nickel loading rate 58%) were added. After the inside of the autoclave was replaced with hydrogen, a hydrogenation reaction was performed at 180°C under a hydrogen pressure of 4.5 MPa for 6 hours.

[0616] The reaction solution obtained in the hydrogenation reaction was subjected to pressure filtration treatment using a pressure filter (product name "Funda filter" manufactured by Ishikawajima-Harima Heavy Industries Co.) at a pressure of 0.25 MPa using diatomite (product name "Radiolite (registered trademark) #500" manufactured by Showa Chemical Industry Co.) as a filter bed, and a colorless transparent solution was obtained. Then, 0.5 part of an antioxidant (pentaerythritol-tetra[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] (product name "Irganox (registered trademark) 1010" manufactured by CIBA SPECIALTY CHEMICALS INC.) was added to 100 parts of the obtained solution, and dissolved. The solution was filtered using a filter (product name "Zeta Plus (registered trademark) 30H" manufactured by Cunofilter company, pore size 0.5 to 1 μm), and the filtrate was filtered using a metal fiber filter (product name "Nikafilter (registered trademark) 0.4 μm" manufactured by Nichidai company) to remove foreign matter.

[0617] Then, the filtrate obtained above was subjected to removal of cyclohexane and other volatile components as a solvent from the solution under conditions of a temperature of 260°C and a pressure of 1 kPa or less using a cylinder-type concentration dryer (product name "Kontro", manufactured by Hitachi Ltd.), and was extruded in a strand shape in a molten state from a die directly connected to the concentration dryer, and was water-cooled and then cut using a pelletizer (manufactured by Nagata Mfg. Co., Ltd., product name "OSP-2") to obtain pellets of the cyclic olefin resin composition K.

[0618] The Tg of the obtained pellets was 143°C, the flexural strength was 115 MPa, and the flexural modulus of elasticity was 2410 MPa.

[0619] (Example 1)

[0620] [Resin lens molding]

[0621] Using the methacrylic resin composition A obtained in Synthesis Example 1, injection molding was performed using an injection molding machine (S-2000i50B, manufactured by FANUC company). The mold used was a biconvex lens having a thickness of 7.0 mm and a diameter of 41 mm. As the finished product, the first surface, which includes the optical axis, was a convex surface having a non-spherical shape with a radius of curvature R = 95 mm, a conic constant k = -1.125, and no even-order constant set. The second surface, which includes the optical axis, was a convex surface having a radius of curvature R = 68 mm and a conic constant of -2.916, with no even-order constant set (if the second surface side is considered positive, it behaves as a spherical surface with a radius of curvature R = -68 mm). In addition, a flange for protrusion was provided outside the lens surface, and the entire lens had a diameter of 45 mm. The barrel temperature was set to Tg + 135°C of the resin composition used, and the mold temperature was set to Tg - 15°C of the resin composition used, and molding was performed. The holding pressure was set to 100 MPa for 5 seconds in the first stage, and then, in order to relieve the stress deformation inside the molded product, the pressure-holding second stage was set to 80 MPa for 4 seconds. In addition, the injection speed was set to 20 mm / s to perform molding, and a resin lens of Example 1 was obtained.

[0622] [Silane coupling agent layer forming step]

[0623] According to Japanese Patent Application Publication No. 2022-151518, in the silane coupling agent layer forming step, a silane coupling agent layer was formed on the bonding surface of the resin lens, and the silane coupling agent layer was present between the adhesive layer of the resin lens and the wire grid reflection type polarizing element WGF (manufactured by Asahi Kasei Corporation).

[0624] For the formation of a silane coupling agent layer on the resin lens, a capacitively coupled high-frequency plasma device was used to perform plasma treatment, resulting in the formation of the silane coupling agent layer. First, the reaction chamber was depressurized to 5–10 Pa using a depressurization unit. Then, water vapor was introduced into the chamber to bring the pressure inside to 100 Pa. Plasma was generated by irradiating the chamber with water vapor plasma at a high frequency of 13.56 MHz and a power of 50 W for 3 minutes. Then, vapor of 3-(trimethoxysilyl)propyl methacrylate was introduced into the chamber, causing the bonding surface of the resin lens to react with 3-(trimethoxysilyl)propyl methacrylate, thereby forming the silane coupling agent layer. The contact angle of water before and after the formation of the silane coupling agent layer on the resin lens was measured using a contact angle meter DMs-401 (manufactured by Kyowa Interface Chemicals Co., Ltd.). The results showed that the water contact angle changed before and after the formation of the silane coupling agent layer, thus confirming the formation of a silane coupling agent layer on the bonding surface of the resin lens.

[0625] [Fabrication of a resin substrate with lattice-shaped protrusions for making a master mold for a reflective polarizing element]

[0626] A nickel die was prepared with a 230 nm pitch and a 230 nm height lattice pattern on its surface. This lattice was patterned using laser interferometry, and its cross-sectional shape was sinusoidal, appearing as a striped lattice pattern when viewed from above. The planar dimensions were 500 mm in both length and width. Using this nickel die, the lattice pattern was transferred onto the surface of a 0.5 mm thick cycloolefin resin (hereinafter referred to as "COP") board with dimensions of 520 mm in both length and width using a hot-pressing method, thus creating a COP board with the transferred lattice pattern.

[0627] Then, the COP board with the embossed grid pattern transferred on it is cut into a rectangle of 520mm × 460mm to serve as the extension COP board for the extended part. At this time, it is cut out in a manner in which the length direction (520mm) of the 520mm × 460mm is approximately parallel to the extension direction of the embossed grid.

[0628] Then, the surface of the COP sheet for stretching was coated with silicone oil by spraying, and the sheet was left in a circulating air oven at about 80°C for 30 minutes. Then, the COP sheet for stretching was fixed with the chuck of the stretching machine at both ends of 10 mm in the longitudinal direction, and the sheet was left in a circulating air oven at a temperature of 113 ± 1°C for 10 minutes. Then, the distance between the chucks was stretched 2.7 times at a speed of 250 mm / min, and the stretching was completed. After 20 seconds, the stretched COP sheet was taken out to a room temperature environment and cooled while maintaining the distance between the chucks. About 40% of the central portion of the stretched COP sheet was uniformly narrowed, and the portion where the width was most reduced was 280 mm. The surface and cross section of the stretched COP sheet were observed by field emission scanning electron microscope (FE-SEM), and as a result, the pitch and height of the fine concave-convex lattice were 140 nm / 130 nm (pitch / height), respectively. The cross section was in a sinusoidal shape, and the shape in plan view was a striped lattice shape, which was similar to the shape of the concave-convex lattice before the stretching.

[0629] (Making of nickel stamper)

[0630] On the surface of the stretched COP sheet with a pitch of 140 nm obtained, a nickel stamper having a fine concave-convex lattice with a thickness of 0.2 mm, a length of 270 mm, and a width of 220 mm was made by sputtering 30 nm of gold as a conductive treatment, and then electroplating nickel, respectively. Note that the nickel stamper was made so that the longitudinal direction of the stamper was substantially perpendicular to the direction of stretching of the fine concave-convex lattice.

[0631] (Making of roll stamper)

[0632] The nickel stamper was processed into a cylindrical shape with the fine concave-convex lattice on the outer circumferential side, and then, was welded to serve as a roll stamper. At this time, the joining was performed in a direction in which the longitudinal direction of the nickel stamper became the circumferential direction of the roll stamper. Then, an adhesive tape (NITOFLON manufactured by Nitto Electric Industrial Co., Ltd.) with a width of 13 mm and a thickness of 80 μm was attached to the substantially central portion of the roll stamper in the circumferential direction.

[0633] (Preparation of base film roll)

[0634] A roll (film length 300 m) of triacetyl cellulose film (hereinafter referred to as TAC film; oxygen weight ratio 50% by weight; Tg film = 130°C) with a width of 250 mm and a thickness of 80 μm was knurled in a range of 1 to 15 mm at the ends in the width direction using a disc-shaped mold having a convex shape so that the average height from the surface of the base film became 50 μm.

[0635] (Making of fine concave-convex lattice transfer film roll)

[0636] For the TAC film roll on which the knurling was performed as described above, in addition to the position of the NITOFLON tape described above, about 2 μm of the ultraviolet-curable resin was continuously applied on the inside in the width direction of the portion on which the knurling was performed, the coated surface was contacted with the fine concave-convex grid of the roll die on which the fine concave-convex grid having the above-described 140 nm pitch was formed in such a manner that the extending direction of the fine concave-convex grid was parallel to the width direction of the TAC film, and using an ultraviolet lamp having a center wavelength of 365 nm, ultraviolet rays were irradiated from the film side at 1000 mJ / cm2. 2 After the ultraviolet rays were irradiated and the fine concave-convex grid of the roll die was continuously transferred, it was wound into a roll shape. Hereinafter, this roll is referred to as a roll stock. The fine concave-convex grid transfer film obtained by FE-SEM observation was confirmed to have a sine wave-like cross-sectional shape and a stripe-like lattice shape in plan view.

[0637] (Drying of the roll stock)

[0638] In order to dry the moisture contained in the roll stock obtained as described above, the roll stock was transferred to a vacuum tank provided with three 200 W infrared heaters, and while the film was unwound, it was caused to travel at 2 m / minute in a vacuum. After heating, it was wound into a roll shape. The degree of vacuum at the time when the film travel was stopped was 0.03 Pa, and the degree of vacuum during the film travel (during drying) was 0.15 Pa. In addition, in order to know the surface temperature of the TAC film after passing through the heater, a thermolabel (registered trademark) was preliminarily attached to the TAC film. The surface temperature of the TAC film after passing through the heater was between 60°C and 70°C.

[0639] (Formation of metal nanowires)

[0640] The dried roll stock was left in the vacuum tank of the drying machine for 12 hours, as a result of which the temperature of the film decreased to 23°C. Then, the roll stock was transferred to a vacuum chamber for metal wire formation. Then, a silicon nitride layer was provided on the fine concave-convex grid surface by a reactive AC magnetron sputtering method. Specifically, two silicon targets each having a size of 127 mm x 750 mm x 10 mm were arranged side by side, while the roll stock was unwound at a distance of 80 mm between the substrate and the target, the argon gas flow rate was 200 sccm, the nitrogen gas flow rate was 300 sccm, the output was 11 kW, the frequency was 37.5 kHz, the travel speed was 5 m / minute, it was transported to the winding roll side using a film transport roll, and the process was performed, and then it was wound into a roll shape. The tension at the time of sputtering was 30 N, the main roll temperature was 30°C, the degree of vacuum of the background before the start of sputtering was 0.005 Pa, and the degree of vacuum during sputtering was 0.38 Pa. A silicon nitride film was formed on a Si chip under the same conditions, and the thickness of the silicon nitride layer was calculated using an ellipsometer, and the result was 3 nm.

[0641] After the sputtering, the temperature of the roll was measured by an infrared thermometer, and the result was 24°C. After forming a thin film layer of silicon nitride on the lattice-shaped convex portion transfer surface of the roll by the sputtering method, the roll was transported in the opposite direction to that during the sputtering by the main roll, and a metal nanowire was formed by the resistance heating evaporation method, and the roll was wound. Note that aluminum (Al) was used as the metal. At this time, the Al evaporation was performed using the oblique evaporation method, and the mask was arranged in a plane perpendicular to the length direction of the lattice at an angle of 32° to 15° from the normal line of the substrate surface to the evaporation source. The opening width of the mask was 60 mm, and the distance from the center of the mask opening to the evaporation boat was 400 mm. The degree of vacuum before heating of the evaporation boat was 0.005 Pa. The tension was 30 N, and the temperature of the main roll was 30°C. Under the above conditions, the lattice-shaped convex portion transfer film was transported at a film transport speed of 3.5 m / min, and an aluminum wire having a purity of 99.9% or more and a wire diameter of 1.7 mm was supplied to the heated boat at a transport speed of 200 mm / min, and the aluminum was evaporated. The degree of vacuum during the evaporation was 0.007 Pa.

[0642] (Measurement of film thickness of aluminum)

[0643] The film portion in the later stage of the evaporation was cut out from the wire grid polarizing plate obtained by the evaporation, and the film thickness of the aluminum was converted from the emission intensity of fluorescent X-rays, and the result was 130 nm.

[0644] (Etching of aluminum)

[0645] The lattice-shaped convex portion transfer film roll on which the metal nanowire of Al was formed was transported in a 0.5% by weight NaOH water tank at a temperature of 23°C for 65 seconds while the film was unwound, and then, the film was washed with water and dried with air to obtain a roll of a wire grid polarizing plate having desired optical properties.

[0646] (Collection of wire grid polarizing element for attachment)

[0647] After the wire grid polarizing plate roll on which the etching was performed was left to stand for a predetermined time in the environment described later, a piece having a length of 270 mm was cut out to obtain a wire grid polarizing element for attachment. The appearance was visually observed on a white backlight. The appearance was uniform, and peeling and the like were not observed in the shadow and the metal wire portion.

[0648] A product in which a two-sided adhesive sheet was attached to the holding substrate 21 side of the wire grid reflective polarizing element (TAC substrate) having a thickness of 80 μm obtained in the above process was prepared.

[0649] On the attachment side base (lower chamber) of the vacuum attachment device, a flat convex resin lens obtained by the aforementioned injection molding was arranged with the use of a jig that holds the lens in a manner that the spherical surface (R = 68 mm) of the lens is on the upper surface and the aspherical surface (R = 95 mm) is on the lower surface as the attached surface.

[0650] In the vacuum molding machine having the upper and lower chambers, the upper and lower chambers were set to a vacuum state in a manner that the grid was fixed. At this time, the surface of the grid polarizing element having the fine uneven structure was fixed toward the upper chamber side. Then, the grid polarizing element was heated by the heater in the device while measuring the temperature by the infrared monitor, and heating was performed until reaching about 210°C, and then the aforementioned resin lens fixed in the lower chamber was brought into contact with the grid polarizing element. Then, the air was slowly leaked from the upper chamber side, and then the lower chamber side was depressurized. The grid polarizing element having the curved surface shape was obtained by the above. The portion having the desired curved surface shape was cut out by laser cutting, and thus the reflective polarizing element attachment lens of Example 1 was obtained. The evaluation results are shown in Table 5.

[0651] (Example 2)

[0652] In Example 1, when the grid polarizing element was attached to the obtained resin lens, a product in which the grid-shaped convex portion 23 side of the grid polarizing element was attached with an adhesive sheet was prepared and used, and otherwise, the molding and attachment of the grid polarizing element were performed under the same conditions as in Example 1. The evaluation results are shown in Table 5.

[0653] (Example 3)

[0654] Using the methacrylic resin composition A obtained in Synthesis Example 1, injection molding was performed using an injection molding machine (S-2000i50B manufactured by FANUC Corporation). As the mold, a meniscus lens having an optical axis thickness of 3.2 mm was used. As the finished product, the first surface, which is the surface including the optical axis, was a convex surface, and was an aspherical surface shape having a curvature radius R = 92.5 mm, a conic constant k = -1.259, and even-order aspherical constants of D = 2.316 x 10 -7 , E = -2.959 x 10 -10 , and F = -9.218 x 10 -14 , and the second surface was a flat surface.

[0655] The barrel temperature was set to Tg + 125°C of the resin composition used, and the mold temperature was set to Tg - 20°C of the resin composition used, and molding was performed. The holding pressure was set to 90 MPa for 5 seconds in the first stage, and then, in order to relax the stress deformation inside the molded product, the holding pressure in the second stage was set to 70 MPa for 4 seconds. In addition, molding was performed with the injection speed set to 6 m / s, and the same resin lens as that of Example 1 was obtained. The shape of the lens was measured by NH-3SPs (manufactured by San-Ei Gen F.F.I., Inc.), and the molding conditions were appropriately adjusted to obtain a lens of a prescribed shape, and a lens of a prescribed shape was obtained.

[0656] When the wire grid polarizing element was attached to the same resin lens as that obtained in Example 1, the surface to be attached was set to a spherical surface (R = 92.5 mm), and otherwise, molding and attachment of the wire grid polarizing element were performed under the same conditions as in Example 1. The evaluation results are shown in Table 5.

[0657] (Example 4)

[0658] Using the methacrylic resin composition A obtained in Synthesis Example 1, injection molding was performed using an injection molding machine (S-2000i50B manufactured by FANUC Corporation). A meniscus lens having an optical axis thickness of 5 mm was used for the mold. As the finished product, the first surface, which is the surface including the optical axis, was a convex surface, and was a non-spherical surface shape having a curvature radius R = 43.1 mm, a conic constant k = -1.387, and non-spherical surface constants of even order of D = -1.32 x 10 -6 , E = 1.02 x 10 -8 , F = -3.73 x 10 -11 , G = 6.15 x 10 -14 , H = -3.37 x 10 -17 , and the second surface was a flat surface.

[0659] The barrel temperature was set to Tg + 125°C of the resin composition used, and the mold temperature was set to Tg - 20°C of the resin composition used, and molding was performed. The holding pressure was set to 90 MPa for 5 seconds in the first stage, and then, in order to relax the stress deformation inside the molded product, the holding pressure in the second stage was set to 70 MPa for 4 seconds. In addition, molding was performed with the injection speed set to 6 m / s, and the same resin lens as that of Example 1 was obtained. The shape of the lens was measured by NH-3SPs (manufactured by San-Ei Gen F.F.I., Inc.), and the molding conditions were appropriately adjusted to obtain a lens of a prescribed shape, and a lens of a prescribed shape was obtained.

[0660] When the wire grid polarizing element was attached to the same resin lens as the resin lens obtained in Example 1, the surface to be attached was set to a spherical surface (R = 43.1 mm), and molding and attachment of the wire grid polarizing element were performed under the same conditions as in Example 1, except for this. The evaluation results are shown in Table 5.

[0661] (Example 5)

[0662] Using the methacrylic resin composition A obtained in Synthesis Example 1, injection molding was performed using an injection molding machine (S-2000i50B manufactured by FANUC Corporation). As the mold, a meniscus lens having an optical axis thickness of 4.2 mm was used. As the finished product, the first surface, which is the surface including the optical axis, was a convex surface, and was a non-spherical surface shape having a curvature radius R = 66.9 mm and a conic constant k = -1.608, and the second surface was a flat surface.

[0663] The barrel temperature was set to Tg + 125°C of the resin composition used, and the mold temperature was set to Tg - 20°C of the resin composition used, and molding was performed. The holding pressure was set to 90 MPa for 5 seconds in the first stage, and then, in order to relax the stress deformation inside the molded product, the holding pressure in the second stage was set to 70 MPa for 4 seconds. In addition, the injection speed was set to 6 m / s to perform molding, and the same resin lens as the resin lens of Example 1 was obtained. The shape of the lens was measured by NH-3SPs (manufactured by San-Ei Gen F.F.I., Inc.), and the molding conditions were appropriately adjusted to obtain a lens having a prescribed shape, and a lens having a prescribed shape was obtained.

[0664] When the wire grid polarizing element was attached to the same resin lens as the resin lens obtained in Example 1, the surface to be attached was set to a spherical surface (R = 66.9 mm), and molding and attachment of the wire grid polarizing element were performed under the same conditions as in Example 1, except for this. The evaluation results are shown in Table 5.

[0665] (Example 6)

[0666] Using the methacrylic resin composition B obtained in Synthesis Example 2, molding and attachment of the wire grid polarizing element were performed under the same conditions as in Example 5, except for this. The evaluation results are shown in Table 5.

[0667] (Example 7)

[0668] Using the methacrylic resin composition C obtained in Synthesis Example 3, molding and attachment of the wire grid polarizing element were performed under the same conditions as in Example 5, except for this. The evaluation results are shown in Table 5.

[0669] (Example 8)

[0670] Using the methacrylic resin composition D obtained in Synthesis Example 4, molding and attachment of the wire grid polarizing element were performed under the same conditions as in Example 5 except for this. The evaluation results are shown in Table 5.

[0671] (Example 9)

[0672] Using the thermoplastic resin composition E obtained in Synthesis Example 5, molding and attachment of the wire grid polarizing element were performed under the same conditions as in Example 5 except for this. The evaluation results are shown in Table 6.

[0673] (Example 10)

[0674] Using the methacrylic resin composition F obtained in Synthesis Example 6, molding and attachment of the wire grid polarizing element were performed under the same conditions as in Example 5 except for this. The evaluation results are shown in Table 6.

[0675] (Example 11)

[0676] Using the methacrylic resin composition G obtained in Synthesis Example 7, molding and attachment of the wire grid polarizing element were performed under the same conditions as in Example 5 except for this. The evaluation results are shown in Table 6.

[0677] (Example 12)

[0678] Using the methacrylic resin composition H obtained in Synthesis Example 8, molding and attachment of the wire grid polarizing element were performed under the same conditions as in Example 5 except for this. The evaluation results are shown in Table 6.

[0679] (Example 13)

[0680] Using the methacrylic resin composition I obtained in Synthesis Example 9, molding and attachment of the wire grid polarizing element were performed under the same conditions as in Example 5 except for this. The evaluation results are shown in Table 6.

[0681] (Example 14)

[0682] Using the cyclic olefin copolymer resin composition J obtained in Synthesis Example 10, molding and attachment of the wire grid polarizing element were performed under the same conditions as in Example 5 except for this. The evaluation results are shown in Table 6.

[0683] (Example 15)

[0684] Using the cyclic olefin resin composition K obtained in Synthesis Example 11, molding and attachment of the wire grid polarizing element were performed under the same conditions as in Example 5 except for this. The evaluation results are shown in Table 6.

[0685] (Example 16)

[0686] A product in which the double-coated tape was attached to the holding substrate 21 side of the wire grid reflective polarizing element WGF (TAC substrate) formed by forming the silane coupling agent layer by the same method as the resin lens was prepared, so that the silane coupling agent layer was provided between the resin lens and the adhesive layer and between the adhesive layer and the wire grid reflective polarizing element, and in addition to this, molding and attachment of the wire grid polarizing element were performed under the same conditions as in Example 1. The evaluation results are shown in Table 6.

[0687] (Example 17)

[0688] [Manufacture of laminated reflective polarizing element]

[0689] The two multilayer optical packets were coextruded with packets of 325 alternating layers of polyethylene naphthalate (PEN) and a low refractive index isotropic layer having a refractive index of about 1.57, manufactured using a mixture of polycarbonate and co-polyester (PC:coPET) in a molar ratio of about 42.5 mol% PC and 57.5 mol% coPET, and having a Tg of 105 degrees Celsius, such that the isotropic material substantially maintains isotropy in the uniaxial direction. The isotropic material was chosen such that the refractive index in the two non-stretch directions, after stretching, remains substantially matched to the refractive index of the birefringent material in the non-stretch directions, while on the other hand, in the stretch direction, there is a substantial mismatch in refractive index between the birefringent layer and the non-birefringent layer. The PEN and PC / coPET polymers were fed from separate extruders to a multilayer co-extrusion feedblock, for a total of 652 layers, with PC / coPET thicker protective boundary layers applied on the outside of the stacked optical packets, which were assembled into packets of 325 alternating optical layers (respectively "Packet 1" and "Packet 2"). The film was substantially uniaxially stretched using a parabolic tenter as described in U.S. Patent No. 6,916,440 (Jackson et al.). The film was stretched at a temperature of about 150 degrees Celsius until a stretch ratio of about 6.

[0690] A product in which the double-coated tape was attached to the 68-μm laminated reflective polarizing element obtained in the above process was prepared.

[0691] On the attachment side base (lower chamber) of the vacuum attachment device, a plano-convex resin lens after formation of the aforementioned silane coupling agent layer was disposed using a jig that held the lens in a manner such that the spherical surface (R = 68 mm) was on the upper surface and the aspherical surface (R = 95 mm) was on the lower surface as the attached surface.

[0692] A vacuum forming machine having a chamber above and below was used to fix the layered reflective polarizing element in a state of being stacked with a separation layer. The chambers above and below in the device were both set to a vacuum state. At this time, the layered reflective polarizing element was fixed with the surface having the fine concave-convex structure facing the upper chamber side. Then, the layered reflective polarizing element was heated by a heater in the device while measuring the temperature thereof by an infrared monitor, and heating was performed until reaching about 160°C. After that, the aforementioned resin lens fixed in the lower chamber was brought into contact with the layered reflective polarizing element. Then, air was slowly leaked from the upper chamber side, and then the lower chamber side was depressurized. The layered reflective polarizing element having a curved shape was obtained by the above. The portion to which the desired curved shape was imparted was cut out by laser cutting, and thus the reflective polarizing element attached lens of Example 17 was obtained. The evaluation results are shown in Table 6.

[0693] (Comparative Example 1)

[0694] In addition to not performing the [silane coupling agent layer forming step] on the basis of the method of Example 1, molding and attachment of the wire grid polarizing element were performed under the same conditions as Example 1. The evaluation results are shown in Table 7.

[0695] (Comparative Example 2)

[0696] In addition to not performing the [silane coupling agent layer forming step] on the basis of the method of Example 2, molding and attachment of the wire grid polarizing element were performed under the same conditions as Example 2. The evaluation results are shown in Table 7.

[0697] (Comparative Example 3)

[0698] In addition to not performing the [silane coupling agent layer forming step] on the basis of the method of Example 3, molding and attachment of the wire grid polarizing element were performed under the same conditions as Example 3. The evaluation results are shown in Table 7.

[0699] (Comparative Example 4)

[0700] In addition to not performing the [silane coupling agent layer forming step] on the basis of the method of Example 4, molding and attachment of the wire grid polarizing element were performed under the same conditions as Example 4. The evaluation results are shown in Table 7.

[0701] (Comparative Example 5)

[0702] In addition to using a methacrylic resin L (Delpet LP-1; manufactured by Asahi Kasei Corporation), molding and attachment of the wire grid polarizing element were performed under the same conditions as Example 1. The evaluation results are shown in Table 7.

[0703] (Comparative Example 6)

[0704] The molding and the attachment of the wire grid polarizing element were performed under the same conditions as in Example 6 except that the [silane coupling agent layer forming step] was not performed on the basis of the method of Example 6. The evaluation results are shown in Table 7.

[0705] (Comparative Example 7)

[0706] The molding and the attachment of the wire grid polarizing element were performed under the same conditions as in Example 7 except that the [silane coupling agent layer forming step] was not performed on the basis of the method of Example 7. The evaluation results are shown in Table 7.

[0707] (Comparative Example 8)

[0708] The molding and the attachment of the wire grid polarizing element were performed under the same conditions as in Example 8 except that the [silane coupling agent layer forming step] was not performed on the basis of the method of Example 8. The evaluation results are shown in Table 8.

[0709] (Comparative Example 9)

[0710] The molding and the attachment of the wire grid polarizing element were performed under the same conditions as in Example 9 except that the [silane coupling agent layer forming step] was not performed on the basis of the method of Example 9. The evaluation results are shown in Table 8.

[0711] (Comparative Example 10)

[0712] The molding and the attachment of the wire grid polarizing element were performed under the same conditions as in Example 10 except that the [silane coupling agent layer forming step] was not performed on the basis of the method of Example 10. The evaluation results are shown in Table 8.

[0713] (Comparative Example 11)

[0714] The molding and the attachment of the wire grid polarizing element were performed under the same conditions as in Example 11 except that the [silane coupling agent layer forming step] was not performed on the basis of the method of Example 11. The evaluation results are shown in Table 8.

[0715] (Comparative Example 12)

[0716] The molding and the attachment of the wire grid polarizing element were performed under the same conditions as in Example 12 except that the [silane coupling agent layer forming step] was not performed on the basis of the method of Example 12. The evaluation results are shown in Table 8.

[0717] (Comparative Example 13)

[0718] The molding and the attachment of the wire grid polarizing element were performed under the same conditions as in Example 13 except that the [silane coupling agent layer forming step] was not performed on the basis of the method of Example 13. The evaluation results are shown in Table 8.

[0719] (Comparative Example 14)

[0720] In addition to not performing the [silane coupling agent layer forming step] on the basis of the method of Example 14, molding and attachment of the wire grid polarizing element were performed under the same conditions as Example 14. The evaluation results are shown in Table 8.

[0721] (Comparative Example 15)

[0722] In addition to not performing the [silane coupling agent layer forming step] on the basis of the method of Example 15, molding and attachment of the wire grid polarizing element were performed under the same conditions as Example 15. The evaluation results are shown in Table 8.

[0723] (Comparative Example 16)

[0724] In addition to not performing the [silane coupling agent layer forming step] on the basis of the method of Example 17, molding and attachment of the laminated reflective polarizing element were performed under the same conditions as Example 17. The evaluation results are shown in Table 8.

[0725] Table 5

[0726]

[0727] Table 6

[0728]

[0729] Table 7

[0730]

[0731] Table 8

[0732]

[0733] From Tables 5 to 8, it was found that if the reflective polarizing element attached lens satisfies the requirements of the present application, at least either one of peeling and crack generation of the reflective polarizing element is suppressed after the reliability test under a severe high-temperature and humid environment.

[0734] The reflective polarizing element attached lens of the present application is suitably used as an ocular optical system for a head-mounted display, a microscope, an electronic viewfinder, and the like.

Claims

1. A reflective polarizing element bonding lens, wherein, The reflective polarizing element bonding lens comprises a resin lens having a first surface and a second surface that are opposite to each other. A reflective polarizing element is attached to at least one of the first and second surfaces. An adhesive layer is provided between the resin lens and the reflective polarizing element. A silane coupling agent layer is provided in at least one of the spaces between the resin lens and the adhesive layer, and between the adhesive layer and the reflective polarizing element. The glass transition temperature (Tg) of the resin composition constituting the resin lens is 115°C to 160°C.

2. The reflective polarizing element bonding lens as described in claim 1, wherein, The absolute value of the photoelastic coefficient of the resin lens is 10 × 10⁻⁶. -12 Pa -1 the following.

3. The reflective polarizing element bonding lens as described in claim 1 or 2, wherein, The resin lens is composed of a thermoplastic resin composition having aryl or alicyclic groups in the main chain or side chain.

4. The reflective polarizing element bonding lens as described in claim 1 or 2, wherein, The surface of the resin lens that is bonded to the reflective polarizing element is convex or concave in the region containing the optical axis, and the absolute value of the radius of curvature R used as a reference is more than 10 mm and less than 500 mm.

5. The reflective polarizing element bonding lens as described in claim 1 or 2, wherein, The resin composition comprises a methacrylic resin.

6. The reflective polarizing element bonding lens as described in claim 5, wherein, The methacrylic resin comprises a methacrylic resin having structural units with a ring structure.

7. The reflective polarizing element bonding lens as described in claim 6, wherein, The structural unit comprises at least one structural unit selected from the group consisting of structural units derived from N-substituted maleimide monomers, glutarimide structural units, aromatic vinyl structural units, alicyclic vinyl structural units, and lactone ring structural units.

8. The reflective polarizing element bonding lens as described in claim 7, wherein, The structural unit comprises a structural unit derived from an N-substituted maleimide monomer.

9. The reflective polarizing element bonding lens as described in claim 1 or 2, wherein, The resin lens is composed of a resin composition comprising a cyclic olefin copolymer, wherein the cyclic olefin copolymer is a copolymer of ethylene and a cyclic olefin, or a copolymer of α-olefin and a cyclic olefin.

10. The reflective polarizing element bonding lens as described in claim 9, wherein, The proportion of cyclic skeleton structural units from the main chain of the cyclic olefin in the cyclic olefin copolymer is more than 36 mol% and less than 50 mol%.

11. The reflective polarizing element bonding lens as described in claim 10, wherein, The structural units derived from the cyclic olefins in the cyclic olefin copolymer are derived from bicyclic [2.2.1]-2-heptene and tetracyclic [4.4.0.1]. 2，5 .1 7，10 The structural unit of at least one compound selected from ]-3-dodecene.

12. The reflective polarizing element bonding lens as described in claim 1 or 2, wherein, The resin lens is composed of a resin composition containing an open-ring polymer hydride of norbornene monomers.

13. The reflective polarizing element bonding lens as described in claim 12, wherein, The resin composition comprising the ring-opening polymer hydride of norbornene monomer contains 20 to 100 mol% of structural units derived from the norbornene monomer and 0 to 80 mol% of structural units derived from other monomers capable of copolymerizing with the norbornene monomer.

14. The reflective polarizing element bonding lens as described in claim 13, wherein, The structural units derived from norbornene monomers comprise 15-50 wt% structural units derived from tetracyclododecene monomers, 50-90 wt% structural units derived from methyl-bridged tetrahydrofluorene monomers, and 1-15 wt% structural units derived from norbornene monomers, and the total amount of structural units from each monomer is 100 wt%.

15. The reflective polarizing element bonding lens as described in claim 1 or 2, wherein, The flexural strength of the resin composition constituting the resin lens is 65 MPa or higher.

16. The reflective polarizing element bonding lens as described in claim 1 or 2, wherein, The reflective polarizing element has only one reflective surface related to polarization separation.

17. The reflective polarizing element bonding lens as described in claim 1 or 2, wherein, The adhesive layer is an adhesive layer composed of an adhesive that does not contain a silane coupling agent.

18. A head-mounted display, wherein, The head-mounted display has a reflective polarizing element bonded lens as described in claim 1 or 2.

19. A method for manufacturing a reflective polarizing element-bonded lens, comprising bonding a reflective polarizing element to a resin lens to form a reflective polarizing element-bonded lens, wherein... The resin lens is a resin lens composed of a resin composition with a glass transition temperature (Tg) of 115℃ to 160℃. The resin lens has a first surface and a second surface that are opposite to each other. The manufacturing method of the reflective polarizing element-bonded lens includes: The process of forming a silane coupling agent layer in at least one of the resin lens and the reflective polarizing element; The process of applying an adhesive layer to at least one of the resin lens and the reflective polarizing element; and The process of attaching the reflective polarizing element to the resin lens.

20. The method for manufacturing a reflective polarizing element-bonded lens as described in claim 19, wherein, The resin lens is manufactured by injection molding.

21. The method for manufacturing a reflective polarizing element-bonded lens as described in claim 19, wherein, The process of attaching the reflective polarizing element to the resin lens is based on the glass transition temperature Tg of the substrate film constituting the reflective polarizing element. 膜 As a benchmark at Tg 膜 -40℃~Tg 膜 The bonding process is carried out at +120℃.

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