Laminate and method for manufacturing same

Abstract

The purpose of the present invention is to provide a laminate excellent in light resistance without being provided with a flattening layer, and a manufacturing method capable of efficiently manufacturing the laminate. The present invention relates to a laminate having a dye-containing resin layer and an inorganic compound layer on both surfaces of the dye-containing resin layer, wherein the arithmetic average roughness Ra1 of both surfaces of the dye-containing resin layer as measured with an atomic force microscope is 2.5 nm or less, or the arithmetic average roughness Ra2 of the surfaces of the two inorganic compound layers as measured with an atomic force microscope is 2.3 nm or less.

Description

Laminate and method for manufacturing the same

[0001] The present invention relates to a laminate and a method for manufacturing the same. More specifically, it relates to a laminate with excellent light resistance and a method for manufacturing the same.

[0002] Various optical components are used in display devices such as organic EL displays and liquid crystal displays, image sensors, solar cells, laser processing machines, and sensors for autonomous driving. Because these optical components are exposed to light such as sunlight, ultraviolet light, and laser light, high light resistance is required to ensure the practical lifespan of the product.

[0003] As an example of optical components, optical films and optical lenses that contain dyes and can selectively absorb or block light within a specific range of wavelengths are known. It is known that the dyes used in such optical components degrade when exposed to light and oxygen, leading to a decrease in their function. Therefore, to maintain the light resistance of the above-mentioned dyes, it is necessary to limit the supply of oxygen molecules to the dye molecules.

[0004] On the other hand, a method is known for imparting gas barrier properties to a resin film that can block gases such as oxygen, by laminating an inorganic layer onto a resin layer (Patent Documents 1-2). For example, Patent Document 1 describes a gas barrier film having excellent interlayer adhesion by providing a planarization layer on a resin base layer and then providing a gas barrier layer on top of it.

[0005] Japanese Patent Publication No. 2015-58687 Japanese Patent Publication No. 2015-196315

[0006] However, when the resin layer contains a dye, even if a planarization layer like the one in Patent Document 1 is provided, the dye deteriorates, leading to a problem of reduced light resistance. In particular, optical components require a high degree of light resistance to fully exhibit their performance, but conventional materials have not been able to adequately meet this requirement. Furthermore, providing a planarization layer reduces the dimensional accuracy of the molded product. While a decrease in dimensional accuracy is not a problem for films, it is fatal for precision molded products such as lenses. In addition, when a planarization layer is provided, coating processes such as solution-based spin coating or dipping are required to improve the surface accuracy of the planarization layer, which complicates the manufacturing process and raises concerns about warping, deformation, and even cracking caused by solvents.

[0007] The present invention has been made in view of the above problems, and aims to provide a laminate with excellent light resistance without providing a planarization layer, and a manufacturing method that can efficiently produce the above laminate.

[0008] Through various studies, the inventors have found that by forming inorganic compound layers on both sides of a dye-containing resin layer, and setting the surface roughness of either the dye-containing resin layer or the inorganic compound layer to a specific range, the interlayer adhesion between the dye-containing resin layer and the inorganic compound layer, as well as the density of the inorganic compound layer, can be improved without the need for a planarizing layer. This allows for a high degree of suppression of oxygen molecules contacting the dye-containing resin layer, thereby suppressing the degradation of the dye contained in the dye-containing resin layer and enabling the laminate to exhibit and maintain excellent light resistance. This led to the completion of the present invention.

[0009] In other words, the present invention includes the following embodiments: <1> A laminate having a dye-containing resin layer and inorganic compound layers on both sides of the dye-containing resin layer, characterized in that the arithmetic mean roughness Ra1 measured by atomic force microscopy on both sides of the dye-containing resin layer is 2.5 nm or less, or the arithmetic mean roughness Ra2 measured by atomic force microscopy on the surfaces of the two inorganic compound layers is 2.3 nm or less. <2> The laminate according to <1>, characterized in that the inorganic compound layer is formed by a vapor deposition method. <3> The laminate according to <1> or <2>, characterized in that the inorganic compound layer contains at least one inorganic compound selected from the group consisting of inorganic oxides, inorganic carbides, inorganic nitrides, inorganic fluorides, inorganic phosphides, and inorganic sulfides. <4> The laminate according to any one of <1> to <3>, characterized in that the thickness of the inorganic compound layer is 10 to 50,000 nm. <5> The laminate according to any one of <1> to <4> above, characterized in that the dye contained in the dye-containing resin layer includes at least one selected from the group consisting of squarylium-based dyes and cyanine-based dyes. <6> The laminate according to any one of <1> to <5> above, further characterized in having a multilayer dielectric film. <7> A method for manufacturing the laminate according to any one of <1> to <6> above, the manufacturing method comprising the steps of: (1) forming a dye-containing resin layer by molding a resin composition containing a dye and a resin; and (2) forming inorganic compound layers on both sides of the dye-containing resin layer. <8> The method for manufacturing the laminate according to <7> above, characterized in that the molding is performed by extruding the molten mixture of the resin composition. <9> The method for manufacturing the laminate according to <8> above, characterized in that the extruding is performed by pressing the extruded molten mixture between rolls. <10> The method for manufacturing the laminate according to <7> above, characterized in that the molding is performed by injection molding the molten mixture of the resin composition. <11> The method for manufacturing the laminate according to <7> above, characterized in that the molding is performed by a solution casting method using the resin composition. <12> The method for manufacturing a laminate according to any one of <7> to <11> above, characterized in that the inorganic compound layer is formed by a vapor phase film deposition method.

[0010] The laminate of the present invention exhibits excellent light resistance and can maintain desired optical properties. Furthermore, the method for manufacturing the laminate of the present invention can efficiently produce a laminate with excellent light resistance.

[0011] The present invention will be described in detail below. Furthermore, combinations of two or more of the individual preferred embodiments of the present invention described below are also preferred embodiments of the present invention.

[0012] 1. Laminate The present invention relates to a laminate having a dye-containing resin layer and inorganic compound layers on both sides of the dye-containing resin layer, characterized in that the arithmetic mean roughness Ra1 measured by atomic force microscopy on both sides of the dye-containing resin layer is 2.5 nm or less, or the arithmetic mean roughness Ra2 measured by atomic force microscopy on the surfaces of the two inorganic compound layers is 2.3 nm or less.

[0013] If the arithmetic mean roughness Ra1 of both sides of the above-mentioned dye-containing resin layer is 2.5 nm or less, the interlayer adhesion between the dye-containing resin layer and the inorganic compound layer and the density of the inorganic compound layer are improved, and contact between the dye and oxygen molecules in the dye-containing resin layer is highly suppressed, thereby suppressing the degradation of the dye and improving the light resistance of the laminate. Furthermore, if the arithmetic mean roughness Ra2 of the surfaces of the inorganic compound layers laminated on both sides of the above-mentioned dye-containing resin layer is 2.3 nm or less, in the laminate of the present invention, the occurrence of defects that impair the adhesion of the inorganic compound layer to the dye-containing resin layer and the density of the inorganic compound layer can be greatly suppressed. This means that in order to ensure the adhesion of the inorganic compound layer to the dye-containing resin layer and the density of the inorganic compound layer, the surface precision of the dye-containing resin layer is high, and as a result, the interlayer adhesion between the dye-containing resin layer and the inorganic compound layer and the density of the inorganic compound layer are improved, thereby suppressing the degradation of the dye and improving the light resistance of the laminate. In the laminate of the present invention, excellent light resistance can be obtained by satisfying at least one of the arithmetic mean roughness Ra1 of both sides of the dye-containing resin layer within the predetermined range described above, or the arithmetic mean roughness Ra2 of the surfaces of the two inorganic compound layers, but it is more preferable to satisfy both.

[0014] The arithmetic mean roughness Ra1 of both sides of the dye-containing resin layer is preferably 2.3 nm or less, and more preferably 2.0 nm or less, in order to further improve light resistance. The lower limit of the arithmetic mean roughness Ra1 is not particularly limited, but from the viewpoint of easy and inexpensive manufacturing, Ra1 is preferably 0.1 nm or more, more preferably 0.2 nm or more, and even more preferably 0.3 nm or more. Ra1 is preferably 0.1 to 2.5 nm, more preferably 0.2 to 2.3 nm, and even more preferably 0.3 to 2.0 nm.

[0015] Furthermore, the arithmetic mean roughness Ra2 of the surfaces of the two inorganic compound layers laminated on both sides of the dye-containing resin layer is preferably 2.2 nm or less, more preferably 2.1 nm or less, and even more preferably 2.0 nm or less, in order to further improve light resistance. The lower limit of the arithmetic mean roughness Ra2 is not particularly limited, but from the viewpoint of easy and inexpensive manufacturing, Ra2 is preferably 0.1 nm or more, more preferably 0.2 nm or more, and even more preferably 0.3 nm or more. Ra2 is preferably 0.1 to 2.3 nm, more preferably 0.2 to 2.2 nm, even more preferably 0.3 to 2.1 nm, and even more preferably 0.3 to 2.0 nm. Note that the surfaces of the two inorganic compound layers laminated on both sides of the dye-containing resin layer refer to the surfaces of each inorganic compound layer that are opposite to the surface on the dye-containing resin layer side. The inorganic compound layers are laminated in contact with the dye-containing resin layer.

[0016] The arithmetic mean roughnesses Ra1 and Ra2 mentioned above refer to the arithmetic mean roughness (Ra) as defined in ASME B46.12. The arithmetic mean roughnesses Ra1 and Ra2 are determined by measurement using an atomic force microscope (AFM). The method for determining the roughness by measurement using an atomic force microscope involves observing a 5 μm square area on the surface of the dye-containing resin layer or inorganic compound layer using an atomic force microscope, and is specifically the method described in the examples below.

[0017] Each layer constituting the laminate of the present invention will now be described. (Dye-containing resin layer) The dye-containing resin layer is a layer containing a dye and a resin. The dye may be an organic dye, an inorganic dye, or an organic-inorganic composite dye, but an organic dye is preferred because it has a narrow absorption wavelength range, making it easy to adjust the transmission and absorption of specific wavelengths, and it has high compatibility with organic resins. The effects of the present invention are particularly evident when an organic dye that is easily degraded by light and oxygen is used as the dye.

[0018] The maximum absorption wavelength of the above-mentioned dye is not particularly limited and may be appropriately selected depending on the application and purpose of the laminate. However, in order to improve the light resistance of the laminate, it is preferably in the range of 380 to 1200 nm, more preferably in the range of 400 to 1100 nm, and even more preferably in the range of 420 to 1050 nm.

[0019] Examples of the above dyes include squarylium dyes, cyanine dyes, crokonium dyes, cyclic tetrapyrrole dyes (porphyrins, chlorines, naphthalocyanines, cholines, etc.) which may have copper (e.g., Cu(II)) or zinc (e.g., Zn(II)) as the central metal ion, pyrrolopyrrole dyes, azo dyes, quinone dyes, xanthene dyes, indoline dyes, arylmethane dyes, quaterylene dyes, diimonium dyes, perylene dyes, quinacdrin dyes, oxazine dyes, dipyromethene dyes, nickel complex dyes, copper ion dyes (phosphones) Examples of visible light absorbing dyes and near-infrared absorbing dyes include copper oxides (copper phosphates), copper phosphate complexes (compounds of monophosphate and copper, complexes of diphosphate and copper)), dithiol metal complex dyes, azo dyes, polymethine dyes, phthalide dyes, quinone dyes (naphthoquinone dyes, anthraquinone dyes), indophenol dyes, pyryllium dyes, thiopyrillium dyes, crokonium dyes, tetradehydrocholine dyes, triphenylmethane dyes, aluminum dyes, and pyran dyes (pyrans, benzopyrans, chromones, coumarins, xanthenes). The dye-containing resin layer may contain only one of the above dyes or two or more. In particular, it is preferable to include at least one dye selected from the group consisting of squarylium dyes and cyanine dyes, as this has a narrow absorption wavelength range and makes it easy to adjust the transmission and absorption of specific wavelengths.

[0020] The above-mentioned squarylium-based dyes are not particularly limited, and examples include known squarylium-based dyes described in Japanese Patent Publication No. 2016-166320 (a squarylium dye molecularly designed so that when a nitrogen-containing five-membered ring is bonded to the squarylium skeleton via a carbon atom, the methine group bonding the nitrogen-containing five-membered ring and the squarylium skeleton forms a ring structure), Japanese Patent Publication No. 2014-148567 (a squarylium dye in which a nitrogen-containing ring such as an indole ring is bonded to an oxocarbon-based compound via a single methine group (which does not form a ring structure), thereby conjugating the nitrogen-containing ring and the squarylium skeleton), Japanese Patent Publication No. 2014-059550 (a squarylium dye in which an oxocarbon-based compound and a benzene ring are bonded without a single methine group (which does not form a ring structure)), Japanese Patent Publication No. 2016-74649, etc., but in terms of high heat resistance, those having multiple ring structures in the molecule are preferred.

[0021] The above-mentioned cyanine-based dyes are not particularly limited, and include known cyanine-based dyes described in International Publication No. 2006 / 082945 (polymethine and indolium cation having nitrogen-containing aromatic rings at each end of the polymethine), International Publication No. 2001 / 062853, International Publication No. 2012 / 063964 (indolium-based cation having a diphenylamino group bonded to the meso position of a heptamethine chain having a cyclopentene ring structure), International Publication No. 2005 / 007753 (indolium cation having multiple cyanine dye skeletons linked by divalent groups within the same molecule), International Publication No. 2021 / 145456, etc., but cyanine compounds having an acidic ion as a counteranion are preferred in terms of high heat resistance.

[0022] The content of the above-mentioned dye is not particularly limited and may be appropriately selected depending on the purpose and application of the laminate. However, in terms of good light transmittance and absorption, it is preferably 0.001 to 10% by mass, more preferably 0.005 to 5% by mass, and even more preferably 0.01 to 3% by mass, in 100% by mass of the dye-containing resin layer.

[0023] The above-mentioned resins are not particularly limited and may be appropriately selected according to the purpose and application of the laminate. Examples include thermoplastic resins such as polyolefin resins, cycloolefin resins, acrylic resins, styrene resins, vinyl halogenated resins, polyvinyl alcohol resins, polyester resins, polyacetal resins, polycarbonate resins, polyester polycarbonate resins, polyamide resins, polyimide resins, polysulfone resins, polyphenylene ether resins, polyphenylene sulfide resins, fluororesins, cellulose derivatives, and polyurethane resins, as well as thermosetting resins such as epoxy resins, phenolic resins, cyanate ester resins, melamine resins, polyimide resins, bismaleimide resins, urea resins, alkyd resins, silicone resins, vinyl ester resins, urethane resins, and unsaturated polyester resins. These may be used individually or in combination of two or more. In particular, the above resin preferably contains thermoplastic resins and epoxy resins, and more preferably contains at least one selected from the group consisting of cycloolefin resins, polycarbonate resins, polyester polycarbonate resins, polyphenylene sulfide resins, and epoxy resins, in terms of good moldability and adhesion to inorganic compound layers.

[0024] The resin content is not particularly limited and can be appropriately selected depending on the purpose and application of the laminate. However, in terms of good transparency and heat resistance, it is preferably 40 to 99.999% by mass, more preferably 50 to 99.99% by mass, and even more preferably 60 to 99.8% by mass, of 100% by mass of the dye-containing resin layer.

[0025] The above-mentioned pigment-containing resin layer may contain other components in addition to the pigment and resin described above. Examples of these other components include ultraviolet absorbers, heat stabilizers, antioxidants, antistatic agents, hydrolysis inhibitors, leveling agents, defoamers, photoradical generators, photoacid generators, and thermal acid generators.

[0026] The above ultraviolet absorber is not particularly limited. For example, organic ultraviolet absorbers such as triazine-based, benzotriazole-based, benzophenone-based, benzoxazine-based, malonic ester-based, cyanoacrylate-based, and ethylene compounds described in JP-A-2019-14707, and known ultraviolet absorbers such as inorganic ultraviolet absorbers like titanium oxide, zinc oxide, and cerium oxide can be mentioned. Among them, organic ultraviolet absorbers are preferred in terms of good compatibility and heat resistance, and triazine-based, benzotriazole-based, and ethylene compounds described in JP-A-2019-14707 are more preferred.

[0027] The content of the above ultraviolet absorber is not particularly limited, but it may be appropriately selected according to the purpose and application. From the viewpoints of heat resistance and compatibility, it is preferably 0.1 to 20% by mass, more preferably 0.2 to 15% by mass, and still more preferably 0.3 to 10% by mass in 100% by mass of the dye-containing resin layer.

[0028] The thickness of the above dye-containing resin layer is not particularly limited, but it is preferably 0.5 to 2000 μm, more preferably 0.7 to 1000 μm, and still more preferably 1 to 500 μm in terms of preventing the intrusion of oxygen from the cross-section and increasing the design freedom of the laminate.

[0029] The above dye-containing resin layer can be formed by preparing a resin composition containing the above-described dye and resin and then molding the resin composition. The specific formation of the dye-containing resin layer will be described in detail in the section on the method for producing the laminate described later.

[0030] (Inorganic compound layer) The inorganic compound layer is a layer made of an inorganic compound. Examples of the inorganic compound include compounds containing elements of Groups 1 to 14 of the periodic table. The elements contained in the above inorganic compound preferably include silicon, titanium, zinc, aluminum, lanthanum, magnesium, zirconium, lithium, tantalum, etc. Among them, at least one element selected from the group consisting of silicon, titanium, zinc, zirconium, and tantalum is more preferred, and silicon and titanium are still more preferred in terms of good adhesion to the above dye-containing resin layer.

[0031] The above inorganic compound preferably contains at least one inorganic compound selected from the group consisting of inorganic oxides, inorganic carbides, inorganic nitrides, inorganic fluorides, inorganic phosphides, and inorganic sulfides, in terms of good transparency and adhesion to the above dye-containing resin layer. Among these, inorganic oxides, inorganic nitrides, and inorganic sulfides are more preferred, and inorganic oxides are even more preferred, in terms of good adhesion to the above dye-containing resin layer.

[0032] Examples of the inorganic oxides mentioned above include silicon monoxide, silicon dioxide, aluminum oxide, titanium oxide, tantalum oxide, magnesium oxide, and zirconium oxide. Examples of the inorganic carbides mentioned above include silicon carbide, titanium carbide, zirconium carbide, and tantalum carbide. Examples of the inorganic nitrides mentioned above include silicon nitride, titanium nitride, aluminum nitride, lithium nitride, and zirconium nitride. Examples of the inorganic fluorides mentioned above include magnesium fluoride, titanium fluoride, zinc fluoride, aluminum fluoride, magnesium fluoride, zirconium fluoride, and lithium fluoride. Examples of the inorganic phosphides mentioned above include aluminum phosphate. Examples of the inorganic sulfides mentioned above include zinc sulfide.

[0033] In particular, the inorganic compound preferably contains at least one selected from the group consisting of silicon monoxide, silicon dioxide, aluminum oxide, titanium oxide, and tantalum oxide, and more preferably contains at least one selected from the group consisting of silicon monoxide, silicon dioxide, and titanium oxide, in terms of good transparency and adhesion to the dye-containing resin layer. The inorganic compound may also be a glass containing silicon dioxide. The inorganic compound may consist of only one type or two or more types.

[0034] The above inorganic compound layer may be a single layer or may be composed of a plurality of layers. When it is composed of a plurality of layers, layers of the same or different types of inorganic compounds may be continuously laminated. When the above inorganic compound layer is composed of a plurality of layers, the arithmetic mean roughness Ra2 of the surface of the inorganic compound layer described above means the arithmetic mean roughness of the surface of the inorganic compound layer on the side opposite to the surface that contacts the above dye-containing resin layer in the inorganic compound layer composed of a plurality of layers.

[0035] The above inorganic compound layer is not particularly limited as long as it is made of an inorganic compound. For example, it may be a glass substrate or a formation by a vapor deposition method. Among them, it is preferably a formation by a vapor deposition method. Examples of the vapor deposition method include a sputtering method, a vacuum evaporation method, an IAD vacuum evaporation method, a chemical vapor deposition method (CVD), an ion plating method, a laser ablation method, etc. These can be carried out by known methods.

[0036] The thickness of the above inorganic compound layer is preferably 10 to 50000 nm, more preferably 15 to 10000 nm, and still more preferably 20 to 5000 nm in terms of good adhesion to the above dye-containing resin layer and good denseness of the above inorganic compound layer. In addition, when the above inorganic compound layer is composed of a plurality of layers, the thickness of the inorganic compound layer means the total thickness of the plurality of continuously laminated inorganic compound layers.

[0037] When the above inorganic compound layer is composed of a plurality of layers, the thickness of each of the above plurality of layers is not particularly limited, but is preferably 10 to 1000 nm, more preferably 15 to 900 nm, and still more preferably 20 to 800 nm in terms of designing transmission and reflection in the visible light region and the infrared region.

[0038] (Multilayer dielectric film) The laminate may have a multilayer dielectric film. By having a multilayer dielectric film, it is possible to prevent the reflection of light incident on the laminate and improve transmittance, or to reflect light of a specific wavelength and adjust the incidence of light in a desired wavelength range on the laminate. The multilayer dielectric film may be laminated on one surface of the two inorganic compound layers laminated on both sides of the dye-containing resin layer, or on both surfaces, but it is preferable to laminate on both sides in order to suppress warping and deformation. Furthermore, as will be described later, if the multilayer dielectric film corresponds to the inorganic compound layer described above, the multilayer dielectric film may be laminated on the surface of the dye-containing resin layer.

[0039] A multilayer dielectric film is a dielectric layer formed by combining multiple layers, and a film having a configuration in which dielectric layers with different refractive indices are alternately stacked is preferred. Specifically, a multilayer dielectric film is preferred in which dielectric layer A and dielectric layer B having a refractive index higher than that of dielectric layer A are alternately stacked.

[0040] Examples of materials constituting the dielectric layer A include materials with a refractive index of 1.6 or less, specifically inorganic materials such as silica, alumina, lithium fluoride, lanthanum fluoride, magnesium fluoride, and sodium aluminum hexafluoride; silicate resins; silicone resins; and fluorine-containing organic materials (e.g., fluorinated methacrylate resins, fluorinated acrylate resins, fluorinated epoxy resins, and fluorine-containing silicone resins).

[0041] Examples of materials constituting dielectric layer B include materials with a refractive index of 1.7 or higher, specifically those mainly composed of titanium oxide, zirconium oxide, tantalum pentoxide, niobium pentoxide, lanthanum oxide, yttrium oxide, zinc oxide, zinc sulfide, indium oxide, etc., with small amounts of titanium oxide, tin oxide, cerium oxide, etc. (for example, tin-doped indium oxide (ITO)).

[0042] The lamination of each dielectric layer is not particularly limited. For example, a low refractive index dielectric film (dielectric layer A) and a high refractive index dielectric film (dielectric layer B) may be alternately laminated on the surface of the dye-containing resin layer or inorganic compound layer described above by known methods such as CVD, sputtering, vacuum deposition, IAD vacuum deposition, ion plating, or ion beam sputtering.

[0043] The thickness of each dielectric layer is preferably 30 to 500 nm, more preferably 40 to 400 nm, and even more preferably 50 to 300 nm, in terms of blocking light in the ultraviolet and infrared regions.

[0044] The total number of layers of low-refractive-index dielectric films and high-refractive-index dielectric films is preferably in the range of 2 to 200 layers, more preferably in the range of 3 to 150 layers, and even more preferably in the range of 5 to 100 layers.

[0045] The thickness of the above multilayer dielectric film is not particularly limited, but is preferably 0.06 to 25 μm, more preferably 0.08 to 20 μm, and even more preferably 0.1 to 15 μm, in terms of facilitating lens optical design.

[0046] Furthermore, when a multilayer dielectric film, formed from an inorganic compound as dielectric layer A and dielectric layer B, is laminated on the surface of the dye-containing resin layer, the multilayer dielectric film corresponds to the inorganic compound layer described above. Also, when a multilayer dielectric film is laminated on the surface of the dye-containing resin layer, and the multilayer dielectric film includes a dielectric layer made of an organic compound, the dielectric layer made of an inorganic compound between the dye-containing resin layer and the dielectric layer made of the organic compound corresponds to the inorganic compound layer described above.

[0047] Specific examples of the above-mentioned multilayer dielectric films include anti-reflective films and specific wavelength reflective films.

[0048] The laminate described above may further have other known layers such as an antistatic layer, a water-repellent layer, an oil-repellent layer, an anti-fogging layer, or an anti-drip layer. These layers are preferably provided on top of the inorganic compound layer or the multilayer dielectric film.

[0049] The shape of the laminate described above is not particularly limited and can be appropriately selected according to the purpose and application of the laminate. Examples include sheet-like, film-like, and lens-like shapes. Among these, film-like and lens-like shapes are preferred due to their processability and versatility.

[0050] 2. Method for Manufacturing Laminates The method for manufacturing the laminate of the present invention is not particularly limited, and it may be manufactured by known methods such as forming a dye-containing resin layer and laminating inorganic compound layers on both sides thereof, or sequentially laminating a dye-containing resin layer and an inorganic compound layer on an inorganic compound layer. However, in order to efficiently manufacture the above laminate, it is preferable to include a step (1) of forming a dye-containing resin layer by molding a resin composition containing a dye and a resin, and a step (2) of forming inorganic compound layers on both sides of the dye-containing resin layer. A method for manufacturing a laminate, wherein the manufacturing method includes a step (1) of forming a dye-containing resin layer by molding a resin composition containing a dye and a resin, and a step (2) of forming inorganic compound layers on both sides of the dye-containing resin layer, is also one of the present inventions.

[0051] Step (1) The method for manufacturing the laminate described above includes a step of forming a dye-containing resin layer by molding a resin composition containing a dye and a resin. Examples of the dye and resin are those described above. The resin composition described above can be prepared by mixing the dye, resin, and other components as needed using a known mixer, disperser, kneader, or the like.

[0052] The method for molding the above resin composition is not particularly limited, and can be appropriately selected from known molding methods such as extrusion molding, injection molding, blow molding, compression molding, vacuum molding, and solution casting, depending on the shape of the laminate to be obtained. In particular, since it is easy to form a dye-containing resin layer having the above-mentioned surface roughness (arithmetic mean roughness), the molding is preferably carried out by extrusion molding of the molten mixture of the above resin composition, injection molding, or by solution casting using the above resin composition.

[0053] The melting temperature when preparing the molten mixture of the above resin composition can be appropriately selected depending on the type of resin and pigment in the resin composition, but from the viewpoint of the heat resistance of the pigment and the heat distortion temperature of the molded product, it is preferably 200 to 300°C, more preferably 210 to 290°C, and even more preferably 220 to 280°C.

[0054] The above extrusion molding can be carried out by known methods such as the T-die method and the inflation method, but it is preferable to carry it out by pressing the molten mixture extruded from the T-die between rolls, as this facilitates the formation of a film or sheet.

[0055] The above extrusion can be carried out using a known extruder, such as an extruder using a T-type die. The discharge rate of the resin composition during extrusion is preferably 5 to 200 kg / hour, and more preferably 10 to 150 kg / hour, in terms of good productivity and quality stability.

[0056] Furthermore, a quantitative gear pump can be installed after the extruder to ensure stability of the extrusion amount (film thickness accuracy). To remove gel material and foreign matter generated during extrusion, which is necessary for optical components, it is also preferable to install a wire mesh screen, a sintered filter made of metal fibers such as stainless steel, or a polymer filter consisting of multiple sintered filters.

[0057] The surface roughness of the roll used in the above-mentioned clamping process is preferably such that the arithmetic mean roughness (Ra) of the roll surface is 10 nm or less, more preferably 8 nm or less, even more preferably 6 nm or less, even more preferably 3 nm or less, and particularly preferably 2.5 nm or less, in order to facilitate the formation of a dye-containing resin layer having the above-mentioned surface roughness. The lower limit of the arithmetic mean roughness (Ra) of the roll surface is not particularly limited, but from the viewpoint of easy and inexpensive manufacturing, the Ra is preferably 0.1 nm or more, more preferably 0.25 nm or more, and even more preferably 0.4 nm or more. The Ra is preferably 0.1 to 10 nm, more preferably 0.25 to 8 nm, even more preferably 0.4 to 6 nm, even more preferably 0.4 to 3 nm, and particularly preferably 0.4 to 2.5 nm. The arithmetic mean roughness (Ra) is a value obtained by measuring in the same manner as the arithmetic mean roughness Ra1 described above.

[0058] The material of the roll is not particularly limited, but metal rolls are preferred because they have high surface hardness and good smoothness. The metal roll may have a surface plated with a metal such as chromium or nickel. The thickness of the chromium plating layer is preferably 1 μm or less, more preferably 0.5 μm or less, and even more preferably 0.2 μm or less, in order to suppress surface cracks. When performing chromium plating, it is preferable to separately provide a different metal such as hard copper or nickel as a base for the chromium plating, as this can ensure surface smoothness. The thickness of the nickel plating layer is preferably 10 to 200 μm, and more preferably 30 to 100 μm, in order to facilitate surface polishing for smoothing.

[0059] The temperature of the roll can be appropriately selected depending on the components contained in the resin composition, but it is preferably 70 to 180°C, more preferably 80 to 160°C, and even more preferably 90 to 140°C.

[0060] The thickness of the dye-containing resin layer to be obtained can be adjusted by appropriately selecting the distance between the two rolls during pressing, the discharge amount, the molding width, and the line speed.

[0061] When the above molten mixture is compressed between rolls, a resin film may be used as an intermediary. The presence of a resin film between the molten mixture and the rolls facilitates the transfer of the film surface, resulting in a smoother surface for the molten mixture. The resin film may be present on one or both of the two surfaces of the molten mixture in contact with the rolls, but it is preferable for the film to be present on both surfaces for better smoothness and production stability.

[0062] As the resin film described above, it is preferable to use a thermoplastic resin film having a two-layer structure with two or more biaxially oriented layers and containing an anti-blocking agent on only one surface, in order to obtain a highly smooth surface and good film unwinding properties. When pressing, it is preferable to press the molten mixture using the side without the anti-blocking agent to form the dye-containing resin layer. As the resin component of the resin film described above, films made of polyethylene terephthalate (PET) resin, polyethylene naphthalate (PEN) resin, polyamide (PA) resin, polysulfide resin, etc., are preferred from the viewpoint of heat resistance and versatility. The lamination requirements can be the same resin or different resins.

[0063] The arithmetic mean roughness (Ra) of the surface of the resin film described above is preferably 10 nm or less, more preferably 6 nm or less, even more preferably 3 nm or less, and even more preferably 2.5 nm or less, in order to obtain a dye-containing resin layer with higher surface accuracy. The lower limit of the arithmetic mean roughness (Ra) of the surface of the resin film described above is not particularly limited, but from the viewpoint of easy and inexpensive manufacturing, Ra is preferably 0.2 nm or more, more preferably 0.3 nm or more, and even more preferably 0.5 nm or more. Ra is preferably 0.2 to 10 nm, more preferably 0.3 to 6 nm, even more preferably 0.5 to 3 nm, and even more preferably 0.5 to 2.5 nm. The arithmetic mean roughness of the surface of the resin film described above can be determined by measuring it in the same way as the arithmetic mean roughness (Ra1) described above.

[0064] As the resin film mentioned above, commercially available products may be used, for example, CosmoShine® A4160 (a polyester film manufactured by Toyobo Co., Ltd.).

[0065] The film-like dye-containing resin layer obtained by pressing the above molten mixture between rolls may be further subjected to biaxial stretching. By performing biaxial stretching, the strength, transparency, and surface smoothness of the film can be improved.

[0066] The above injection molding is not particularly limited and can be carried out by known methods of injecting the molten mixture into a mold for molding. The mold used for the above injection molding is not particularly limited as long as it can form a pigment-containing resin layer having the surface roughness described above, but a mold in which a nickel-plated machined surface is directly cut with a diamond tool or a mold in which the nickel plating is electroless nickel-phosphorus is preferred because it is easier to form a pigment-containing resin layer with higher surface accuracy.

[0067] The surface roughness of the mold used above is preferably such that the arithmetic mean roughness (Ra) of the mold surface is 10 nm or less, more preferably 8 nm or less, even more preferably 6 nm or less, even more preferably 3 nm or less, and particularly preferably 2.5 nm or less, in order to facilitate the formation of a dye-containing resin layer having the surface roughness described above. The lower limit of the arithmetic mean roughness (Ra) of the mold surface is not particularly limited, but from the viewpoint of easy and inexpensive manufacturing, Ra is preferably 0.1 nm or more, more preferably 0.25 nm or more, and even more preferably 0.4 nm or more. Ra is preferably 0.1 to 10 nm, more preferably 0.25 to 8 nm, even more preferably 0.4 to 6 nm, even more preferably 0.4 to 3 nm, and particularly preferably 0.4 to 2.5 nm. The arithmetic mean roughness (Ra) is a value obtained by measuring in the same way as the arithmetic mean roughness Ra1 described above. The cylinder temperature and mold temperature for injection molding can be set appropriately for each resin used. The mold temperature can be set within the range of -60°C to -5°C of the glass transition temperature (Tg) of the resin used in the dye-containing resin layer, and more preferably within the range of -50°C to -10°C of the glass transition temperature of the resin used in the dye-containing resin layer. The above glass transition temperature is determined in accordance with JIS K7121-1987.

[0068] Furthermore, if the laminate is in the form of a film or sheet, the molding may be carried out by a solution casting method using the resin composition. The resin composition used in the solution casting method preferably further contains a solvent, but if the resin composition contains a liquid thermosetting resin, it may not contain a solvent.

[0069] The above solvents are not particularly limited and can be appropriately selected depending on the components contained in the resin composition. Examples include alcohol-based solvents such as methanol, ethanol, isopropanol, and n-butanol; ketone-based solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ether-based solvents such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, anisole, and glyme-based solvents; ester-based solvents such as ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, and 3-methoxybutyl acetate; aromatic hydrocarbon-based solvents such as toluene, xylene, and ethylbenzene; nitrile-based solvents such as acetonitrile, propionitrile, butyronitrile, and benzonitrile; halogen-based solvents such as chloroform and dichloromethane; and N-methyl-2-pyrrolidone. Among these, ketone-based solvents, ether-based solvents, ester-based solvents, and N-methyl-2-pyrrolidone are preferred due to their high solubility and low environmental impact.

[0070] A resin composition containing the above solvent can be prepared by mixing the above-mentioned dye, resin, and other components as needed in the above solvent using the above-mentioned known mixing method.

[0071] The above solution casting method is not particularly limited and includes known methods. Specifically, examples include a method in which a resin composition is cast onto a resin film as a carrier film and then heated and dried to form a dye-containing resin layer, or a method in which the resin composition is cast onto a metal belt and then heated and dried, heat-cured, or cured with electromagnetic waves such as electron beams or light (ultraviolet rays) to form a dye-containing resin layer. The amount of resin composition cast should be adjusted as appropriate to obtain a dye-containing resin layer of the desired thickness.

[0072] Examples of resin films used in the above solution casting method include those similar to the resin films used in the extrusion molding described above.

[0073] The above metal belt is not particularly limited and includes known ones. The arithmetic mean roughness (Ra) of the surface of the above metal belt is preferably 10 nm or less, more preferably 8 nm or less, even more preferably 6 nm or less, even more preferably 3 nm or less, and particularly preferably 2.5 nm or less, in order to obtain a dye-containing resin layer with higher surface accuracy. The lower limit of the arithmetic mean roughness (Ra) of the surface of the above metal belt is not particularly limited, but from the viewpoint of easy and inexpensive manufacturing, Ra is preferably 0.2 nm or more, more preferably 0.3 nm or more, and even more preferably 0.5 nm or more. Ra is preferably 0.2 to 10 nm, more preferably 0.3 to 8 nm, even more preferably 0.5 to 6 nm, even more preferably 0.5 to 3 nm, and particularly preferably 0.5 to 2.5 nm. The arithmetic mean roughness of the surface of the above metal belt can be measured and determined by the same method as the arithmetic mean roughness (Ra1) described above.

[0074] The arithmetic mean roughness Ra1 of the surface of the dye-containing resin layer obtained by the above step (1) is as described above.

[0075] Step (2) The method for manufacturing the laminate further comprises step (2) of forming inorganic compound layers on both sides of the dye-containing resin layer formed in step (1). Examples of inorganic compounds constituting the inorganic compound layer include the inorganic compounds mentioned above. The formation of the inorganic compound layer is preferably carried out by a vapor deposition method. The vapor deposition method is as described above.

[0076] The arithmetic mean surface roughness Ra2 of the inorganic compound layer obtained by the above step (2) is as described above.

[0077] The method for manufacturing the laminate described above may include other steps in addition to those described above. Examples of these other steps include forming a multilayer dielectric film, forming an antistatic layer, and forming a functional layer such as hydrophilic, hydrophobic, oleophobic, antifouling, or anti-drip. These steps can be carried out by known methods.

[0078] 3. Applications The laminate of the present invention has excellent light resistance. Therefore, it can be suitably used in applications where light resistance is required. Examples of applications for the laminate of the present invention include optical components such as optical lenses such as imaging lenses for cameras, optical filters, transparent glass and cover glass for watch glass and display devices, sunglasses and laser-processed safety glasses, laser light-shielding sheets or films, and films or lenses for optical sensors for autonomous driving; display devices such as substrates for color filters, substrates for touch panels, display protective films, and anti-reflective films; and electrical or electronic components such as solar cell modules. Among these, optical component applications are preferred because they are used in unspecified environments and require long-term reliability.

[0079] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, "parts" means "parts by mass".

[0080] In this invention, each evaluation was performed by the following method. <Arithmetic Mean Roughness (Ra)> Surface roughness measurement by atomic force microscope (AFM) An AFM (DimensionIcon manufactured by Burker Corporation) was used to perform measurements under the following conditions. From the obtained images, PlaneFit processing and Flatten processing were performed using the attached analysis software "NanoScopeAnalysisV 1.40", and then the arithmetic mean roughness (Ra) of the image surface roughness was determined as follows using Roughness. That is, in one measurement sample, 20 regions (5 μm × 5 μm squares) were selected, and an image was obtained for each region. The 20 regions were selected so that adjacent regions were separated by at least 5 μm. For each of the 20 regions, the aforementioned analysis is performed on the obtained image, and the arithmetic mean roughness of each is calculated, and the 20 arithmetic mean roughnesses (Ra １ Ra ２ , , Ra １９ Ra ２０The arithmetic mean roughness (Ra) of the 12 samples was taken as the simple average of the 12 arithmetic mean roughness values, excluding the 4 highest and 4 lowest values ​​(a total of 8 samples). (Measurement equipment and conditions) Measurement equipment: Atomic force microscope (AFM) manufactured by Burker Corporation (model number DimensionIcon) Measurement mode: PeakForceQNM (force curve method) Cantilever: ScanAsist-Air manufactured by Bruker AXS Measurement atmosphere: 23°C, in air Measurement range: 5 (μm) square Resolution: 512 × 512 Measurement speed: 0.977 Hz Indentation load (Setpoint): 500 (pN)

[0081] <Lightfastness> The obtained laminate was subjected to 24-hour light irradiation at a color temperature of 5500K using an LED photographic light manufactured by Ulanzi (illuminance 100,000 Lux ± 5%). The absorbance of the laminate at λmax before and after light irradiation was determined using a spectrophotometer (Shimadzu Corporation; UV3600PC). The lightfastness was evaluated by comparing the remaining percentage (%) of the absorbance after light irradiation with the initial absorbance before light irradiation (set as 100%), according to the following criteria. Illuminance was measured directly above the sample using an illuminometer; ESCO pocket-type digital illuminometer (model number LX20). (Evaluation criteria) ○: Remaining percentage of 90% or more ×: Remaining percentage of less than 90%

[0082] (Example 1) A resin composition was prepared by dry blending 100 parts of polycarbonate resin (L-1225 WL, manufactured by Teijin Corporation), 3 parts of ultraviolet absorber (Chinubin 1577, manufactured by BASF Japan), and 0.05 parts of dye (A) in a tumbler. This composition was supplied from a hopper to a single-screw extruder (50 mmφ L / D42 with vacuum vent) equipped with a T-type die, and melt-extruded at a discharge rate of 20 kg / hr and a melting temperature of 250°C. This molten extruded material was pressed between an electroless nickel-phosphorus plated metal roll N-1 (plating thickness 50 μm, surface Ra (arithmetic mean roughness) 2.5 nm) and a mirror-finish chromium plated metal roll C-1 (plating thickness 30 μm, surface Ra 10.5 nm, 120°C) with an optical PET film (Cosmoshine A4160, surface Ra 0.95 nm, thickness 50 μm) in between, to obtain a resin plate (dye-containing resin layer) (1), which is a film-like molded product with a thickness of 100 μm. One side of the surface of the obtained resin plate (1) was designated as surface A and the other side as surface B, and the arithmetic mean roughness (Ra) of each side is shown in Table 1. SiO was deposited on both sides of the obtained resin plate (1) using an ion beam-assisted vacuum deposition apparatus (apparatus name OTFC-900, Optotran Co., Ltd.). ２ An inorganic compound layer (100 nm thick) was formed to obtain a laminate (1). The arithmetic mean roughness (Ra) of the A and B surfaces of the obtained laminate (1) is shown in Table 1.

[0083] (Example 2) A resin plate (2) was obtained in the same manner as in Example 1, except that dye (A) was changed to dye (B), and then a laminate (2) was obtained. The arithmetic mean roughness (Ra) of the surfaces of the obtained resin plate (2) and laminate (2) is shown in Table 1.

[0084] (Example 3) A resin plate (3) was obtained in the same manner as in Example 1, except that the polycarbonate resin was changed to a cycloolefin copolymer resin (K26R, manufactured by Mitsui Chemicals, Inc.) and the ultraviolet absorber was changed to ultraviolet absorber (A), and then a laminate (3) was obtained. The arithmetic mean roughness (Ra) of the surfaces of the obtained resin plate (3) and laminate (3) is shown in Table 1.

[0085] (Example 4) A resin plate (4) was obtained in the same manner as in Example 2, except that the polycarbonate resin was changed to a cycloolefin copolymer resin (K26R, manufactured by Mitsui Chemicals, Inc.), and the ultraviolet absorber was changed to an ultraviolet absorber (A). Then, a laminate (4) was obtained. The arithmetic mean roughness (Ra) of the surfaces of the obtained resin plate (4) and laminate (4) is shown in Table 1.

[0086] (Example 5) On both surfaces of the resin plate (1) prepared in Example 1, SiO ２ and TiO ２ were alternately deposited in five layers (SiO ２ / TiO ２ / SiO ２ / TiO ２ / SiO ２ , each with a thickness of 10 to 300 nm and a total thickness of 2000 nm) of a multilayer dielectric film (anti-reflection film: average visible light reflectance AVE. 0.5%) using an ion beam-assisted vacuum deposition apparatus (apparatus name OTF-C900, manufactured by Optran Co., Ltd.). A laminate (5) was obtained. The arithmetic mean roughness (Ra) of the surface of the obtained laminate (5) is shown in Table 1.

[0087] (Example 6) Instead of the electroless nickel-phosphorus plated metal roll N-1 of Example 1, a mirror-finish chromium plated metal roll C-2 (plating thickness 30 μm, surface Ra 9.8 nm) was used. A resin plate (6) was formed by sandwiching the resin extruded from a T-die on both sides through an optical PET film (Cosmo Shine A4160, surface Ra 0.95 nm, thickness 50 μm). A laminate (6) was obtained in the same manner as in Example 1, except for this. The arithmetic mean roughness (Ra) of the surfaces of the obtained resin plate (6) and laminate (6) is shown in Table 1.

[0088] (Example 7) A resin plate (7) was obtained in the same manner as in Example 5, except that the dye (A) was changed to a dye (B). Then, a laminate (7) was obtained. The arithmetic mean roughness (Ra) of the surfaces of the obtained resin plate (7) and laminate (7) is shown in Table 1.

[0089] (Example 8) A laminate (8) was obtained in the same manner as in Example 1, except that the mirror-finish chrome-plated metal roll C-1 of Example 1 was replaced with an electroless nickel-phosphorus plated metal roll N-2 (plating thickness 50 μm, surface Ra 1.8 nm), and the resin plate (8) was formed without using optical PET. The arithmetic mean roughness (Ra) of the surfaces of the obtained resin plate (8) and laminate (8) is shown in Table 1.

[0090] (Example 9) A resin plate (9) was obtained in the same manner as in Example 1, except that the amount of dye (A) was 0.025 parts and the thickness of the resin plate was 200 μm, and then a laminate (9) was obtained. The arithmetic mean roughness (Ra) of the surfaces of the obtained resin plate (9) and laminate (9) is shown in Table 1.

[0091] (Example 10) A resin composition was prepared by dry blending 100 parts of polycarbonate resin (L-1225 WL, manufactured by Teijin Corporation), 1 part of ultraviolet absorber (Chinubin 1577, manufactured by BASF Japan), and 0.005 parts of dye (A) in a tumbler. This composition was supplied to an injection molding machine (NS40, manufactured by Nissei Plastic Industrial Co., Ltd.) and injected into a 100 mm square, 1 mm thick mold at 240°C to obtain a resin plate (10) with a thickness of 1000 μm. The surface of the mold was electroless nickel-phosphorus plated (plating thickness 30 μm). For the fixed mold, the surface Ra was 2.6 nm and the mold temperature was 130°C, while for the mobile mold, the surface Ra was 2.8 nm and the mold temperature was 130°C. SiO was deposited on both sides of the resin plate (10) using an ion beam-assisted vacuum deposition apparatus (apparatus name OTFC-900, manufactured by Optolan). ２ An inorganic compound layer (100 nm thick) was formed to obtain a laminate (10). The arithmetic mean roughness (Ra) of the surfaces of the obtained resin plate (10) and laminate (10) is shown in Table 1.

[0092] (Example 11) A resin composition was prepared by dry blending 100 parts of cycloolefin copolymer resin (K26R, manufactured by Mitsui Chemicals, Inc.), 1 part of ultraviolet absorber (A), and 0.005 parts of dye (A) in a tumbler. This composition was supplied to an injection molding machine (NS40, manufactured by Nissei Plastic Industrial Co., Ltd.) and injected into a 100 mm square, 1 mm thick mold at 260°C to obtain a resin plate (11) with a thickness of 1000 μm. The surface of the mold was electroless nickel-phosphorus plated (plating thickness 30 μm). For the stationary mold, the surface Ra was 3.0 nm and the mold temperature was 110°C, while for the mobile mold, the surface Ra was 2.8 nm and the mold temperature was 110°C. SiO was deposited on both sides of the resin plate (11) using an ion beam-assisted vacuum deposition apparatus (apparatus name OTFC-900, manufactured by Optolan Inc.). ２ An inorganic compound layer (100 nm thick) was formed to obtain a laminate (11). The arithmetic mean roughness (Ra) of the surfaces of the obtained resin plate (11) and laminate (11) is shown in Table 1.

[0093] (Example 12) A resin composition was prepared by stirring and mixing 100 parts of bisphenol A type epoxy resin (jER® 825, manufactured by Mitsubishi Chemical Corporation), 3 parts of ultraviolet absorber (Chinubin 1577, manufactured by BASF Japan), 0.05 parts of dye (B), and 1 part of CPI®-200K (manufactured by Sunapro Co., Ltd.) as a photoacid generator. This resin composition was applied to a 3 mm thick iron plate with a mirror-finish chrome plating, onto which an optical PET film (Cosmoshine A4160, surface Ra 0.95 nm, thickness 50 μm) was attached. A gap was created using a 200 μm thick spacer, and another optical PET film (Cosmoshine A4160, surface Ra 0.95 nm, thickness 50 μm) was placed. After curing by irradiation with ultraviolet light (wavelength 365 nm), the mold was removed to obtain a 200 μm thick resin plate (12). On both sides of the obtained resin plate (12), SiO was deposited using an ion beam-assisted vacuum deposition apparatus (apparatus name OTFC-900, manufactured by Optolan). ２ An inorganic compound layer (100 nm thick) was formed to obtain a laminate (12). The arithmetic mean roughness (Ra) of the resin plate (12) and the laminate (12) is shown in Table 1.

[0094] (Example 13) A resin composition was prepared by stirring and mixing 100 parts of bisphenol A type epoxy resin (jER® 825, manufactured by Mitsubishi Chemical Corporation), 3 parts of ultraviolet absorber (Chinubin 1577, manufactured by BASF Japan), 0.05 parts of dye (B), and 1 part of CPI®-200K (manufactured by Sunapro Corporation) as a photoacid generator. This composition was applied to a nickel-phosphorus plated metal plate (surface Ra 2.6 nm), a gap was created with a 200 μm thick spacer, and an optical PET film (Cosmoshine A4160, surface Ra 0.95 nm, thickness 50 μm) was placed on top. After curing by irradiation with ultraviolet light (wavelength 365 nm), the plate was demolded to obtain a 200 μm thick resin plate (13). SiO₂ was then deposited on both sides of the obtained resin plate (13) using an ion beam-assisted vacuum deposition apparatus (apparatus name OTFC-900, manufactured by Optolan Corporation). ２ An inorganic compound layer (100 nm thick) was formed to obtain a laminate (13). The arithmetic mean roughness (Ra) of the resin plate (13) and the laminate (13) is shown in Table 1.

[0095] (Example 14) 15 parts of solvent-soluble polycarbonate resin (Yupizeta FPC-0330, manufactured by Mitsubishi Gas Chemical Co., Ltd.), 0.2 parts of ultraviolet absorber (Chinubin 1577, manufactured by BASF Japan Co., Ltd.), and 0.5 parts of dye (A) were dissolved in 85 parts of a mixed solvent of toluene / THF / PEGMEA = 50 / 25 / 25. This solution was spin-coated (at a rotation speed of 2500 rpm) onto a glass substrate (D236, manufactured by Shibuya Optical Co., Ltd., thickness 210 μm, 50 mm × 50 mm, surface Ra 0.18 nm), dried at 90°C, and a glass substrate (14) with a dye-containing resin layer was obtained. The thickness of the dye-containing resin layer on the glass substrate was 2 μm. On the resin layer surface of the obtained dye-containing resin-coated glass substrate (14), SiO was deposited using an ion beam-assisted vacuum deposition apparatus (apparatus name OTFC-900, manufactured by Optolan). ２ An inorganic compound layer (100 nm thick) was formed to obtain a laminate (14). The arithmetic mean roughness (Ra) of the surface of the dye-containing resin layer and the laminate (14) is shown in Table 1. In Table 1, the Ra and thickness of the dye-containing resin layer are shown in the columns for Ra and thickness of the resin plate. Also, the Ra of the B surface of the resin plate is the same as the Ra of the glass surface.

[0096] (Comparative Example 1) A resin composition was prepared by dry-blending 100 parts of polycarbonate resin (L-1225 WL, manufactured by Teijin Corporation), 3 parts of ultraviolet absorber (Chinubin 1577, manufactured by BASF Japan), and 0.05 parts of dye (A) in a tumbler. This composition was supplied from a hopper to a single-screw extruder (50 mmφ L / D42 with vacuum vent) equipped with a T-type die, and melt-extruded at a discharge rate of 20 kg / hr and a melting temperature of 250°C. This molten extruded material was sandwiched between a mirror-chrome plated metal roll C-2 (plating thickness 50 μm, surface Ra 9.5 nm) and a mirror-chrome plated metal roll C-1 (plating thickness 30 μm, surface Ra 10.5 nm, 120°C) with an optical PET film (Cosmoshine A4160, surface Ra 0.95 nm, thickness 50 μm) to obtain a 100 μm thick film-like molded product (resin plate (c1)). Both sides of the obtained resin plate (c1) were coated with SiO using an ion beam-assisted vacuum deposition apparatus (apparatus name OTFC-900, Optotran Co., Ltd.). ２ An inorganic compound layer (100 nm thick) was formed to obtain a laminate (c1). The arithmetic mean roughness (Ra) of the resin plate (c1) and the laminate (c1) is shown in Table 1.

[0097] (Comparative Example 2) On both sides of the resin plate (c1) prepared in Comparative Example 1, SiO was deposited using an ion beam-assisted vacuum deposition apparatus (apparatus name OTFC-900, manufactured by Optolan). ２ and TiO ２ Five layers alternately (SiO ２ / TiO ２ / SiO ２ / TiO ２ / SiO ２ A multilayer dielectric film (anti-reflective film: visible light reflectance AVE 0.5%) with each layer having a thickness of 10 to 300 nm and a total thickness of 2000 nm was formed to obtain a laminate (c2). The arithmetic mean roughness (Ra) of the surface of the laminate (c2) is shown in Table 1.

[0098] (Comparative Example 3) A resin composition was dry-blended in a tumbler using 100 parts of polycarbonate resin (L-1225 WL, manufactured by Teijin), 3 parts of ultraviolet absorber (Chinubin 1577, manufactured by BASF Japan), and 0.05 parts of dye (B). This composition was supplied from a hopper to a single-screw extruder (50 mmφ L / D42 with vacuum vent) equipped with a T-type die, and melt-extruded at a discharge rate of 20 kg / hr and a melting temperature of 250°C. This molten extruded material was pressed between mirror-plated chrome-plated metal roll C-2 (plating thickness 50 μm, surface Ra 9.5 nm) and mirror-plated chrome-plated metal roll C-1 (plating thickness 30 μm, surface Ra 10.5 nm, 120°C) to obtain a film-like molded product (resin plate (c3)) with a thickness of 100 μm. On both sides of the obtained resin plate (c3), SiO was deposited using an ion beam-assisted vacuum deposition apparatus (apparatus name OTFC-900, manufactured by Optolan). ２ An inorganic compound layer (100 nm thick) was formed to obtain a laminate (c3). The arithmetic mean roughness (Ra) of the resin plate (c3) and the laminate (c3) is shown in Table 1.

[0099] (Comparative Example 4) A resin composition was prepared by dry blending 100 parts of cycloolefin copolymer resin (K26R, manufactured by Mitsui Chemicals, Inc.), 1 part of ultraviolet absorber (A), and 0.005 parts of dye (A) in a tumbler. This composition was supplied to an injection molding machine (manufactured by Nissei Plastic Industrial Co., Ltd.; 40 tons) and injected into a 100 mm square, 1 mm thick mold at 260°C to obtain a resin plate (c4) with a thickness of 1000 μm. The surface of the mold was finished with mirror chrome plating. The fixed mold had a surface Ra of 15.6 nm and a mold temperature of 110°C, while the mobile mold had a surface Ra of 20.3 nm and a mold temperature of 110°C. SiO was deposited on both sides of the resin plate (c4) using an ion beam-assisted vacuum deposition apparatus (apparatus name OTFC-900, manufactured by Optolan Inc.). ２ An inorganic compound layer (100 nm thick) was formed to obtain a laminate (c4). The arithmetic mean roughness (Ra) of the resin plate (c4) and the laminate (c4) is shown in Table 1.

[0100] (Comparative Example 5) A resin composition was prepared by stirring and mixing 100 parts of bisphenol A type epoxy resin (jER® 825, manufactured by Mitsubishi Chemical Corporation), 3 parts of ultraviolet absorber (Chinubin 1577, manufactured by BASF Japan), 0.05 parts of dye (B), and 1 part of CPI®-200K (manufactured by Sunapro Corporation) as a photoacid generator. This composition was applied to a mirror-finished chrome-plated metal plate (surface Ra 8.3 nm), sandwiched between optical PET film (Cosmoshine A4160, surface Ra 0.95 nm, thickness 50 μm) via a 200 μm thick spacer, cured by irradiation with ultraviolet light (wavelength 365 nm), and then demolded to obtain a 200 μm thick resin plate (c5). SiO₂ was then deposited on both sides of the obtained resin plate (c5) using an ion beam-assisted vacuum deposition apparatus (apparatus name OTFC-900, manufactured by Optolan Corporation). ２ An inorganic compound layer (100 nm thick) was formed to obtain a laminate (c5). The arithmetic mean roughness (Ra) of the resin plate (c5) and the laminate (c5) is shown in Table 1.

[0101] The ultraviolet absorber used (Tinuvin 1577) is the following compound.

[0102]

[0103] The ultraviolet absorber (A) is the following compound.

[0104]

[0105] The pigment (A) is the following squarylium compound.

[0106]

[0107] The pigment (B) is the following cyanine compound.

[0108]

[0109] The light resistance of the obtained laminate was evaluated using the method described above. The results are shown in Table 1.

[0110]

[0111] In Table 1, "Chromium / PET" refers to the surface of a chromium-plated metal roll or chromium-plated sheet with a mirror finish via an optical PET film. From Table 1, it was found that by controlling the Ra on both sides of the dye-containing resin layer to 2.5 nm or less and forming inorganic compound layers on both sides, it is possible to significantly improve the light resistance of the dye contained in the dye-containing resin layer. It was also found that by setting the Ra on the surfaces of the two inorganic compound layers formed on both sides of the dye-containing resin layer to 2.3 nm or less, it is also possible to improve the light resistance.

Claims

1. A laminate comprising a dye-containing resin layer and inorganic compound layers on both sides of the dye-containing resin layer, characterized in that the arithmetic mean roughness Ra1 measured by atomic force microscopy on both sides of the dye-containing resin layer is 2.5 nm or less, or the arithmetic mean roughness Ra2 measured by atomic force microscopy on the surfaces of the two inorganic compound layers is 2.3 nm or less.

2. The laminate according to claim 1, characterized in that the inorganic compound layer is formed by a vapor deposition method.

3. The laminate according to claim 1 or 2, characterized in that the inorganic compound layer comprises at least one inorganic compound selected from the group consisting of inorganic oxides, inorganic carbides, inorganic nitrides, inorganic fluorides, inorganic phosphides, and inorganic sulfides.

4. The laminate according to any one of claims 1 to 3, characterized in that the thickness of the inorganic compound layer is 10 to 50,000 nm.

5. The laminate according to any one of claims 1 to 4, characterized in that the dye contained in the dye-containing resin layer includes at least one selected from the group consisting of squarylium-based dyes and cyanine-based dyes.

6. The laminate according to any one of claims 1 to 5, further characterized by having a multilayer dielectric film.

7. A method for manufacturing a laminate according to any one of claims 1 to 6, the method comprising: (1) forming a dye-containing resin layer by molding a resin composition containing a dye and a resin; and (2) forming inorganic compound layers on both sides of the dye-containing resin layer.

8. The method for manufacturing a laminate according to claim 7, characterized in that the molding is carried out by extruding the molten mixture of the resin composition.

9. The method for manufacturing a laminate according to claim 8, characterized in that the extrusion molding is carried out by pressing the extruded molten mixture between rolls.

10. The method for manufacturing a laminate according to claim 7, characterized in that the molding is carried out by injection molding of the molten mixture of the resin composition.

11. The method for manufacturing a laminate according to claim 7, characterized in that the molding is carried out by a solution casting method using the resin composition.

12. The method for manufacturing a laminate according to any one of 7 to 11, characterized in that the inorganic compound layer is formed by a vapor deposition method.

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