Laminate, optical component, imprinting method, and production method for optical component

Abstract

A laminate comprising a glass layer and a resin layer positioned on at least one surface of the glass layer, wherein the ratio (resin layer / glass layer) of the average thickness of the resin layer to the average thickness of the glass layer is less than 0.9.

Description

Laminate, optical component, imprinting method, and method for manufacturing optical component

[0001] The present invention relates to a laminate, an optical component, an imprint method, and a method for manufacturing an optical component.

[0002] In recent years, display elements such as flat panel displays (FPDs; for example, liquid crystal display elements, organic EL display elements, etc.) and solar cells have become lighter and thinner from the viewpoints of transportability, storability, design, etc., and there is also a demand for improved flexibility. Conventionally, glass substrates have often been used for transparent laminates used in display elements and solar cells. Glass substrates are excellent in transparency, solvent resistance, gas barrier properties, and heat resistance. However, when the glass material constituting the glass substrate is made lighter and thinner, the flexibility is not sufficient to a certain extent, and the impact resistance is insufficient, resulting in problems such as difficulty in handling.

[0003] In order to improve the handleability of thin glass substrates, substrates in which a resin layer is formed on the glass surface have been disclosed (see, for example, Patent Document 1). However, even with these techniques, laminates exhibiting sufficient dimensional stability and flexibility have not yet been obtained.

[0004] Meanwhile, nanoimprinting technology, which is used in display elements such as flat panel displays (FPDs; for example, liquid crystal display elements, organic EL display elements, etc.) and solar cells, is a method of transferring nanometer- to micrometer-sized components, which are impossible to achieve by injection molding, onto a substrate using a mold, and there are two types of nanoimprinting: UV (Ultra-Violet) nanoimprinting and thermal nanoimprinting. UV nanoimprinting is a method in which UV-curable resin poured into a mold is irradiated with UV light to harden the UV-curable resin, thereby forming a molded product. Thermal nanoimprinting is a method in which thermoplastic resin poured into a mold is molded by applying heat and pressure. UV nanoimprinting has a short curing time of just a few seconds, making it a highly productive method.

[0005] For example, when manufacturing optical components by the UV nanoimprint method, a method has been proposed in which a photosensitive resin layer such as a UV-curable resin is formed on a resin substrate such as a polyethylene terephthalate (PET) film, and the photosensitive resin layer is exposed to light through a mask pattern to be cured, thereby forming a molded body on the resin substrate (see Patent Document 2).

[0006] Japanese Patent Application Laid-Open No. 11-329715 International Publication No. 01 / 22165

[0007] The optical members described in Patent Documents 1 and 2 have problems in that the molded product warps due to, for example, cure shrinkage that occurs when a UV-curable resin on a resin substrate such as a PET film is cured, and expansion and shrinkage of the resin substrate due to application of heat during use.

[0008] An object of the embodiments of the present invention is to provide a laminate that can solve the above-mentioned problems in the prior art and can suppress warpage.

[0009] One embodiment of the present invention is a laminate comprising a glass layer and a resin layer disposed on at least one surface of the glass layer, wherein the ratio of the average thickness of the resin layer to the average thickness of the glass layer (resin layer / glass layer) is less than 0.9.

[0010] The embodiments of the present invention can provide a laminate that can suppress warpage.

[0011] FIG. 1 is a cross-sectional schematic diagram showing an example of a laminate according to an embodiment of the present invention. FIG. 2 is a cross-sectional schematic diagram showing another example of a laminate according to an embodiment of the present invention. FIG. 3 is a cross-sectional schematic diagram showing another example of a laminate according to an embodiment of the present invention. FIG. 4 is a cross-sectional schematic diagram showing another example of a laminate according to an embodiment of the present invention. FIG. 5 is a cross-sectional schematic diagram showing another example of a laminate according to an embodiment of the present invention. FIG. 6 is a schematic top view for explaining a measurement method when measuring distortion of a laminate according to an embodiment of the present invention by digital image correlation analysis (DIC analysis). FIG. 7A is an explanatory diagram showing an example of a speckle pattern on the exposed surface (upper surface) of the resin layer of the laminate before heating when measuring distortion of the laminate according to an embodiment of the present invention by digital image correlation analysis (DIC analysis). FIG. 7B is an explanatory diagram showing an example of a speckle pattern on the exposed surface (upper surface) of the resin layer of the laminate after heating when measuring distortion of the laminate according to an embodiment of the present invention by digital image correlation analysis (DIC analysis). FIG. 8 is a photograph showing the distortion of the laminates of Examples 1 to 5 and Comparative Example 1 after heating, measured by a digital image correlation method (DIC analysis), using a color meter.

[0012] Hereinafter, embodiments of the present invention will be described in detail. Note that the embodiments are not limited by the following description and can be modified as appropriate within the scope of the present invention. Furthermore, in this specification, unless otherwise specified, the term "to" indicating a range of values ​​means that the values ​​before and after it are included as the lower and upper limits.

[0013] Furthermore, when describing embodiments of the present invention with reference to the drawings, the same components in each drawing may be designated by the same reference numerals, and duplicated explanations may be omitted. Furthermore, the number, position, size, shape, etc. of components are not limited to the embodiments of the present invention, and may be any number, position, size, shape, etc. that is preferable for implementing the present invention.

[0014] (Laminate) The laminate according to an embodiment of the present invention comprises a glass layer and a resin layer disposed on at least one surface of the glass layer, and further comprises other layers as necessary. In the laminate according to an embodiment of the present invention, the ratio of the average thickness of the resin layer to the average thickness of the glass layer (resin layer / glass layer) is less than 0.9. This allows the laminate according to an embodiment of the present invention to suppress warpage, particularly warpage due to heating.

[0015] [Average Thickness Ratio (Resin Layer / Glass Layer)] In the laminate according to the embodiment of the present invention, the ratio of the average thickness of the resin layer to the average thickness of the glass layer (resin layer / glass layer) is less than 0.9, preferably 0.5 or less, more preferably 0.4 or less, and even more preferably 0.3 or less. When the average thickness ratio (resin layer / glass layer) is 0.9 or more, warping occurs in the laminate. On the other hand, when the average thickness ratio (resin layer / glass layer) is less than 0.9, warping of the laminate can be suppressed, and further suitable flexibility can be obtained.

[0016] In the embodiments of the present invention, the "average thickness of the glass layer" and the "average thickness of the resin layer" refer to the sum of the average thicknesses of the glass layer and the resin layer (total thickness) when the glass layer and the resin layer are multilayered.

[0017] In this embodiment, the term "average thickness" refers to the average value of thicknesses at three points arbitrarily selected from the target layer. The thickness of each layer can be measured using a known film thickness measuring device (for example, R1-205, PEACOCK (registered trademark) manufactured by Ozaki Seisakusho Co., Ltd.).

[0018] [Warp Suppression] The warp suppression of the laminate in an embodiment of the present invention is measured by digital image correlation (DIC analysis). Specifically, a spray paint commonly used in DIC analysis (e.g., a water-based lacquer spray, manufactured by Sunday Paint Co., Ltd.) is spray-coated onto the exposed surface of the resin layer of the laminate in an embodiment of the present invention, and a random granular pattern (hereinafter sometimes referred to as a "speckle pattern") is applied to the exposed surface of the resin layer of the laminate. The z-direction strain of the laminate is calculated from the change in the speckle pattern before and after heating the laminate at 60°C.

[0019] 7A is an explanatory diagram showing an example of a speckle pattern on the exposed surface (upper surface) of the resin layer of a laminate before heating when measuring the distortion of the laminate by DIC analysis in an embodiment of the present invention. FIG. 7B is an explanatory diagram showing an example of a speckle pattern on the exposed surface (upper surface) of the resin layer of a laminate after heating when measuring the distortion of the laminate by DIC analysis in an embodiment of the present invention. Points A and B in FIG. 7A represent adjacent points on the speckle pattern. The distance between points A and B is defined as D. Points A and B' in FIG. 7B represent adjacent points on the speckle pattern after heating, and indicate that, when point A in FIG. 7A is the starting point, point B has moved to the position of point B' in FIG. 7B due to the expansion of the resin layer. The distance between points A and B' is defined as D'. If distortion occurs in the resin layer of the laminate after heating, expansion or contraction occurs in the x and y directions on the exposed surface (upper surface) of the resin layer. When the resin layer of the laminate expands due to heating (i.e., distance D < distance D'), the resin layer of the laminate warps, and the position of point B in FIG. 7A moves to the position of point B' in FIG. 7B. Therefore, the distance D before heating will move away from the distance D' after heating. Thus, the distortion of the laminate in an embodiment of the present invention can be calculated based on the following formula (1), where ΔD is the difference between the distance D and the distance D'. Note that when the resin layer of the laminate shrinks due to heating (i.e., distance D > distance D'), the direction of movement of point B' will move toward point A on D, which is represented by a straight line. In this case, too, the distortion of the laminate in an embodiment of the present invention can be calculated based on the following formula (1). Furthermore, the x direction and the y direction both indicate directions perpendicular to the thickness direction of the laminate. The x direction and the y direction may be the machine direction (also referred to as the "flow direction" or "MD direction") of the resin of the resin layer, or may be a direction perpendicular to the MD direction (also referred to as the "width direction" or "TD direction"). Distortion (%) = ΔD / D × 100 Equation (1)

[0020] Next, the amount of deformation in the z direction is calculated from the strain calculated based on formula (1). In an embodiment of the present invention, the z direction refers to the direction perpendicular to the plane consisting of the x direction and the y direction, i.e., the thickness direction of the laminate in an embodiment of the present invention. FIG. 6 is a schematic top view illustrating a measurement method for measuring the strain of a laminate in an embodiment of the present invention by DIC analysis. As shown in FIG. 6, the surface of the laminate on which a speckle pattern is applied (the region indicated by the solid line in FIG. 6) is divided into nine parts as shown by the dotted lines in FIG. 6, and the maximum value of the z-direction deformation amount in each of the nine divided parts is calculated at nine points. Furthermore, the maximum value of the z-direction deformation amount at the nine points is defined as the maximum z-direction deformation amount of the measurement sample at 60°C. The "maximum z deformation amount" calculated in this manner is defined as the "maximum thermal warpage amount" in an embodiment of the present invention. The larger the maximum thermal warpage amount, the greater the thermal warpage of the laminate. The strains in the x and y directions and the displacement in the z direction can be measured using a known deformation measurement / strain analysis device (for example, StalinMaster, manufactured by LaVision).

[0021] The absolute value of the maximum thermal warpage in the thickness direction of the laminate according to the embodiment of the present invention at 60°C as measured by a digital image correlation method is not particularly limited and can be appropriately selected depending on the purpose, but is preferably less than 2 mm, more preferably 0.5 mm or less, even more preferably 0.3 mm or less, and particularly preferably 0.1 mm or less. When the absolute value of the maximum thermal warpage in the thickness direction of the laminate is less than 2 mm, the laminate according to the embodiment of the present invention can be suitably used as a substrate for imprints.

[0022] [Thickness] The average thickness of the laminate according to the embodiment of the present invention is not particularly limited and can be appropriately selected depending on the purpose. However, it is preferably 450 μm or less, more preferably 380 μm or less, even more preferably 300 μm or less, even more preferably 200 μm or less, particularly preferably 150 μm or less, and most preferably 80 μm to 130 μm. In the embodiment of the present invention, the average thickness of the laminate refers to the sum of the average thicknesses of all layers contained in the laminate according to the embodiment of the present invention (total thickness). By including a resin layer in the laminate according to the embodiment of the present invention, the thickness of the glass layer can be made significantly thinner than that of conventional glass substrates. That is, even a thin resin layer can contribute to improved impact resistance and toughness, so that the laminate according to the embodiment of the present invention having a resin layer is lightweight, thin, has excellent impact resistance, and can suppress warpage.

[0023] [Light Transmittance] The light transmittance at a wavelength of 550 nm of the laminate according to the embodiment of the present invention is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 80% or more, more preferably 85% or more, and even more preferably 90% or more. The light transmittance at a wavelength of 550 nm of the laminate can be measured using a spectrophotometer (for example, U-4100, manufactured by Hitachi, Ltd.).

[0024] Furthermore, the laminate according to the embodiment of the present invention preferably exhibits a decrease in light transmittance of 5% or less after being subjected to a heat treatment for 2 hours at 180° C. With such a decrease, it is possible to preferably ensure a practically acceptable light transmittance even when subjected to a heat treatment required in the imprint process.

[0025] [Surface roughness Ra] The surface roughness Ra of the laminate in an embodiment of the present invention (substantially, the surface roughness Ra of the resin layer or other layer) is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 50 nm or less, more preferably 30 nm or less, and even more preferably 10 nm or less.

[0026] [Linear expansion coefficient] The linear expansion coefficient of the laminate in an embodiment of the present invention is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 15 ppm / °C or less, more preferably 10 ppm / °C or less, and even more preferably 1 ppm / °C to 10 ppm / °C. Due to the presence of a glass layer, the laminate in an embodiment of the present invention exhibits excellent dimensional stability (for example, a linear expansion coefficient in the above-mentioned range). More specifically, in addition to the rigidity of the glass layer itself, the resin layer is restrained by the glass layer, which can also suppress dimensional fluctuations of the resin layer. As a result, the laminate as a whole exhibits excellent dimensional stability and suppresses warpage.

[0027] <Glass Layer> The material constituting the glass layer in the laminate according to the embodiment of the present invention is not particularly limited, but is preferably inorganic glass.

[0028] The classification of inorganic glass according to its composition is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include soda-lime glass, borate glass, aluminosilicate glass, quartz glass, etc. These may be used alone or in combination of two or more.

[0029] Furthermore, the classification of inorganic glass according to the alkali component is not particularly limited and can be appropriately selected depending on the purpose. For example, alkali-free glass, low-alkali glass, etc. can be mentioned.

[0030] Examples of alkali metal components in inorganic glass include Na ２ O.K. ２ O, Li ２ The content of the alkali metal component in the inorganic glass is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 15 mass % or less, and more preferably 10 mass % or less, based on the total mass of the inorganic glass.

[0031] The shape of the glass layer is not particularly limited and can be appropriately selected from any shape, but a plate shape is preferred.

[0032] In the laminate according to the embodiment of the present invention, the glass layer may be a single layer or a multilayer body, but is preferably a single layer.

[0033] The average thickness of the glass layer is not particularly limited and can be appropriately selected depending on the purpose as long as the average thickness ratio (resin layer / glass layer) is less than 0.9, but is preferably 200 μm or less, more preferably 20 μm to 200 μm, and even more preferably 50 μm to 100 μm. Since the laminate in the embodiment of the present invention has a resin layer on at least one surface of the glass layer, a thickness of the glass layer of 200 μm or less can impart suitable flexibility to the laminate, and a thickness of 20 μm or more can impart suitable impact resistance to the laminate.

[0034] The light transmittance of the glass layer at a wavelength of 550 nm is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 85% or more, more preferably 90% or more, and even more preferably 95% or more. The light transmittance of the glass layer at a wavelength of 550 nm can be measured using a spectrophotometer (for example, U-4100, manufactured by Hitachi, Ltd.).

[0035] The method for forming the glass layer is not particularly limited and can be selected appropriately depending on the purpose. For example, a glass layer made of inorganic glass can be formed by melting a mixture containing a main raw material such as silica or alumina, an antifoaming agent such as mirabilite or antimony oxide, and a reducing agent such as carbon at a temperature of 1,400°C to 1,600°C, forming it into a thin plate, and then cooling and forming it. The method for forming the glass layer into a thin plate (e.g., 200 μm or less) is not particularly limited and can be selected appropriately depending on the purpose. Examples include the slot downdraw method, the fusion method, and the float method. The glass layer formed into a plate shape by these methods may be chemically polished with a solvent such as hydrofluoric acid, as necessary, to thin the plate or improve its smoothness. The glass layer may also be surface-treated.

[0036] The glass layer may be a commercially available glass as is, or may be a commercially available inorganic glass that has been polished to a desired thickness. Examples of commercially available inorganic glass include 7059, 1737, and EAGLE 2000 (all manufactured by Corning Incorporated), AN100 (manufactured by Asahi Glass Co., Ltd.), NA-35 (manufactured by NH Technoglass Co., Ltd.), OA-10G (manufactured by Nippon Electric Glass Co., Ltd.), D263 (registered trademark), and AF45 (registered trademark) (all manufactured by Schott Corporation).

[0037] <Resin Layer> The material constituting the resin layer in the laminate according to the embodiment of the present invention is not particularly limited as long as it contains a resin, and can be appropriately selected depending on the purpose. If necessary, the material may further contain other components.

[0038] <<Resin>> The resin contained in the resin layer is not particularly limited and can be appropriately selected depending on the purpose. Examples include thermoplastic resins and curable resins that are cured by heat or active energy rays. These may be used alone or in combination of two or more. Among these, it is preferable that the resin layer contains a thermoplastic resin.

[0039] Specific examples of resins contained in the resin layer include polyethersulfone-based resins; polycarbonate-based resins; epoxy-based resins; acrylic-based resins; polyester-based resins such as polyethylene terephthalate and polyethylene naphthalate; polyolefin-based resins; cycloolefin-based resins such as norbornene-based resins; polyimide-based resins; polyamide-based resins; polyimideamide-based resins; polyarylate-based resins; polysulfone-based resins; and polyetherimide-based resins.

[0040] Among these, it is preferable that the resin layer contains at least one selected from the group consisting of a thermoplastic resin (A) having at least one repeating unit selected from the group consisting of a repeating unit represented by the following general formula (1) and a repeating unit represented by the following general formula (2), a thermoplastic resin (B) having one or more repeating units represented by the following general formula (3), and a thermoplastic resin (C) having a hydroxyl group at a terminal.

[0041] -Thermoplastic Resin (A)- The thermoplastic resin (A) is a thermoplastic resin having at least one repeating unit selected from the group consisting of a repeating unit represented by the following general formula (1) and a repeating unit represented by the following general formula (2). By containing the thermoplastic resin (A), it is possible to obtain a resin layer that has excellent adhesion to other layers (e.g., coupling agent layers, adhesive layers, etc.) in contact with the glass layer or the resin layer and also has excellent toughness. As a result, it is possible to obtain a laminate that is less susceptible to crack propagation when cut. Furthermore, the thermoplastic resin (A) having such excellent adhesion to other layers in contact with the glass layer or the resin layer is strongly constrained by the glass layer, thereby reducing dimensional fluctuations. As a result, a laminate having a resin layer containing the thermoplastic resin (A) exhibits excellent dimensional stability and more suitably suppresses warpage.

[0042] In general formula (1), R １ represents a substituted or unsubstituted aromatic hydrocarbon group having 6 to 24 carbon atoms, an alicyclic hydrocarbon group having 4 to 14 carbon atoms, or a linear or branched aliphatic hydrocarbon group having 1 to 8 carbon atoms; R ２ represents a substituted or unsubstituted aromatic hydrocarbon group having 6 to 24 carbon atoms, a linear or branched aliphatic hydrocarbon group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 5 to 12 carbon atoms, or a hydrogen atom.

[0043] In general formula (1), R １ is preferably a substituted or unsubstituted aromatic hydrocarbon group having 6 to 20 carbon atoms, an alicyclic hydrocarbon group having 4 to 12 carbon atoms, or a linear or branched aliphatic hydrocarbon group having 1 to 6 carbon atoms, and more preferably a substituted or unsubstituted aromatic hydrocarbon group having 6 to 18 carbon atoms, an alicyclic hydrocarbon group having 5 to 10 carbon atoms, or a linear or branched aliphatic hydrocarbon group having 1 to 4 carbon atoms.

[0044] In general formula (1), R ２ is preferably a substituted or unsubstituted aromatic hydrocarbon group having 6 to 20 carbon atoms, a linear or branched aliphatic hydrocarbon group having 1 to 6 carbon atoms, an alicyclic hydrocarbon group having 5 to 10 carbon atoms, or a hydrogen atom.

[0045]

[0046] In general formula (2), R ３ and R ４ are each independently a linear or branched aliphatic hydrocarbon group having 1 to 8 carbon atoms, a hydrogen atom, or an alicyclic hydrocarbon group having 5 to 12 carbon atoms, A is a carbonyl group or a linear or branched aliphatic hydrocarbon group having 1 to 8 carbon atoms, m is an integer of 0 to 8, and n is an integer of 0 to 4. Here, "each independently" means that R ３ and R ４ may be the same as or different from each other.

[0047] In general formula (2), R ３ and R ４ are each independently preferably a linear or branched aliphatic hydrocarbon group having 1 to 5 carbon atoms, a hydrogen atom, or an alicyclic hydrocarbon group having 5 to 10 carbon atoms, and more preferably a linear or branched aliphatic hydrocarbon group having 1 to 4 carbon atoms, a hydrogen atom, or an alicyclic hydrocarbon group having 5 to 8 carbon atoms.

[0048] In general formula (2), A is preferably a carbonyl group or a linear or branched aliphatic hydrocarbon group having 1 to 6 carbon atoms, and more preferably a carbonyl group or a linear or branched aliphatic hydrocarbon group having 1 to 4 carbon atoms.

[0049] In formula (2), m is preferably an integer of 0 to 6, and more preferably an integer of 0 to 3.

[0050] In the general formula (2), n is preferably an integer of 0 to 2.

[0051] The degree of polymerization of the thermoplastic resin (A) is not particularly limited and can be appropriately selected depending on the purpose, but is preferably from 10 to 6,000, more preferably from 20 to 5,000, and even more preferably from 50 to 4,000.

[0052] Specific examples of the thermoplastic resin (A) include styrene-maleic anhydride copolymer, ester group-containing cycloolefin polymer, etc. These may be used alone or in combination of two or more.

[0053] -Thermoplastic Resin (B)- The thermoplastic resin (B) is a thermoplastic resin having one or more repeating units represented by the following general formula (3). By containing the thermoplastic resin (B) in the resin layer, it is possible to obtain a resin layer that has excellent adhesion to the glass layer or other layers in contact with the resin layer (e.g., a coupling agent layer, an adhesive layer, etc.) and also has excellent toughness. As a result, it is possible to obtain a laminate that is less susceptible to crack propagation when cut. Furthermore, the thermoplastic resin (B) having such excellent adhesion to the glass layer or other layers in contact with the resin layer is strongly constrained by the glass layer, thereby reducing dimensional fluctuations. As a result, a laminate having a resin layer containing the thermoplastic resin (B) exhibits excellent dimensional stability and more suitably suppresses warpage.

[0054] In general formula (3), R ５ represents a substituted or unsubstituted aromatic hydrocarbon group having 6 to 24 carbon atoms, a linear or branched aliphatic hydrocarbon group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 4 to 14 carbon atoms, or an oxygen atom; R ６ represents a substituted or unsubstituted aromatic hydrocarbon group having 6 to 24 carbon atoms, a linear or branched aliphatic hydrocarbon group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 5 to 12 carbon atoms, or a hydrogen atom.

[0055] In general formula (3), R ５ is preferably a substituted or unsubstituted aromatic hydrocarbon group having 6 to 20 carbon atoms, a linear or branched aliphatic hydrocarbon group having 1 to 6 carbon atoms, an alicyclic hydrocarbon group having 4 to 12 carbon atoms, or an oxygen atom, and more preferably a substituted or unsubstituted aromatic hydrocarbon group having 6 to 18 carbon atoms, a linear or branched aliphatic hydrocarbon group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 5 to 10 carbon atoms, or an oxygen atom.

[0056] In general formula (3), R ６ is preferably a substituted or unsubstituted aromatic hydrocarbon group having 6 to 20 carbon atoms, a linear or branched aliphatic hydrocarbon group having 1 to 6 carbon atoms, an alicyclic hydrocarbon group having 5 to 10 carbon atoms, or a hydrogen atom.

[0057] The degree of polymerization of the thermoplastic resin (B) is not particularly limited and can be appropriately selected depending on the purpose, but is preferably from 10 to 6,000, more preferably from 20 to 5,000, and even more preferably from 50 to 4,000.

[0058] Specific examples of the thermoplastic resin (B) include polyarylates, polyesters, polycarbonates, etc. These may be used alone or in combination of two or more.

[0059] Thermoplastic resin (C) is a thermoplastic resin having a terminal hydroxyl group. Thermoplastic resin (C) is suitably used when the laminate has a coupling agent layer formed with an epoxy group-terminated coupling agent.

[0060] Specific examples of the thermoplastic resin (C) include thermoplastic resins obtained by modifying terminal hydroxyl groups such as polyimide, polyimideamide, polyethersulfone, polyetherimide, polysulfone, polyarylate, and polycarbonate. These may be used alone or in combination of two or more. Use of such thermoplastic resin (C) can provide a resin layer that exhibits excellent adhesion to a coupling agent layer formed with an epoxy-terminated coupling agent and also exhibits excellent toughness. As a result, a laminate can be obtained that is less susceptible to crack propagation upon cutting. Furthermore, such thermoplastic resin (C) that exhibits excellent adhesion to a coupling agent layer formed with an epoxy-terminated coupling agent is strongly bound to the glass layer, resulting in reduced dimensional fluctuation. As a result, a laminate having a resin layer containing thermoplastic resin (C) exhibits excellent dimensional stability and more favorably suppresses warpage. Any appropriate method can be used for the terminal hydroxyl group modification. Details of the epoxy-terminated coupling agent will be described later.

[0061] The degree of polymerization of the thermoplastic resin (C) is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 90 to 6,200, more preferably 130 to 4,900, and even more preferably 150 to 3,700.

[0062] The weight average molecular weight of the thermoplastic resin (C) is not particularly limited and can be appropriately selected depending on the purpose. However, it is preferred that the weight average molecular weight of the thermoplastic resin (C) is 2.0×10 in terms of polyethylene oxide. ４ ~150 x 10 ４ is preferred, and 3 × 10 ４ ~120 x 10 ４ More preferably, 3.5 × 10 ４ ~90 x 10 ４ The weight average molecular weight of the thermoplastic resin (C) is more preferably 2.0×10 ４ When the thickness is more than 150×10, the toughness of the resin layer can be obtained and the glass layer can be reinforced. ４ If the viscosity is not more than 100%, the viscosity will not be too high and the handling properties will be good.

[0063] The terminal hydroxyl group of the thermoplastic resin (C) is not particularly limited and can be appropriately selected depending on the purpose, but a phenolic hydroxyl group is preferred. When the thermoplastic resin (C) contains a phenolic hydroxyl group, the resin layer and the coupling agent layer formed by the epoxy group-terminated coupling agent can be firmly adhered to each other.

[0064] The content of terminal hydroxyl groups in the thermoplastic resin (C) is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 0.3 or more, more preferably 0.5 to 2.0, per 100 degrees of polymerization of the thermoplastic resin (C). When the content of terminal hydroxyl groups in the thermoplastic resin (C) is 0.3 or more per 100 degrees of polymerization of the thermoplastic resin (C), a thermoplastic resin having excellent reactivity with an epoxy group-terminated coupling agent can be obtained.

[0065] <<Other Components>> The other components in the resin layer are not particularly limited and can be selected appropriately depending on the purpose, and examples thereof include various additives such as diluents, antioxidants, modifiers, surfactants, dyes, pigments, anti-discoloration agents, UV absorbers, softeners, stabilizers, plasticizers, antifoaming agents, reinforcing agents, etc. The type, number, and amount of additives contained in the resin layer are not particularly limited and can be selected appropriately depending on the purpose.

[0066] Furthermore, when the resin layer contains the thermoplastic resin (C), it is preferable that the resin layer further contains at least one selected from the group consisting of imidazoles, epoxies, and oxetanes. When the resin layer contains at least one selected from the group consisting of imidazoles, epoxies, and oxetanes, the resin layer and the glass layer having the epoxy group-terminated coupling agent layer can be stably adhered to each other, and therefore the laminate can be obtained with a high yield.

[0067] -Imidazoles- Examples of imidazoles include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, epoxyimidazole adduct, and 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazo. methylimidazolium chloride, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, etc. These may be used alone or in combination of two or more.

[0068] The content of the imidazoles is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 0.5% by mass to 5% by mass, and more preferably 1% by mass to 4% by mass, relative to the total mass of the thermoplastic resin (C).

[0069] -Epoxies- Epoxies are not particularly limited as long as they have an epoxy group in the molecule, and examples thereof include bisphenol-type epoxy resins such as bisphenol A, bisphenol F, bisphenol S, or water additives thereof; novolac-type epoxy resins such as phenol novolac and cresol novolac; nitrogen-containing ring-type epoxy resins such as triglycidyl isocyanurate and hydantoin; alicyclic epoxy resins; aliphatic epoxy resins; aromatic epoxy resins such as naphthalene and biphenyl; glycidyl-type epoxy resins such as glycidyl ether, glycidyl amine, and glycidyl ester; dicyclo-type epoxy resins such as dicyclopentadiene; ester epoxy resins; ether ester epoxy resins; and modified versions thereof. These may be used alone or in combination of two or more. Among these, preferred epoxies are bisphenol A epoxy resins, alicyclic epoxy resins, nitrogen-containing ring-type epoxy resins, and glycidyl epoxy resins.

[0070] The content of the epoxy compounds is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 1% by mass to 15% by mass, more preferably 3% by mass to 10% by mass, based on the total mass of the thermoplastic resin (C).

[0071] -Oxetanes- The oxetanes are not particularly limited and can be appropriately selected depending on the purpose. However, at least one selected from the group consisting of compounds represented by the following general formula (4), compounds represented by the following general formula (5), and compounds represented by the following general formula (6) is preferred.

[0072] In general formula (4), R ７ represents a hydrogen atom, an alicyclic hydrocarbon group, a phenyl group, a naphthyl group, or an aliphatic hydrocarbon group having 1 to 10 carbon atoms.

[0073]

[0074]

[0075] In general formula (6), R ８represents an alicyclic hydrocarbon group, a phenyl group, a naphthyl group, or an aliphatic hydrocarbon group having 1 to 10 carbon atoms; and p represents an integer of 1 to 5.

[0076] Specific examples of oxetanes include 3-ethyl-3-hydroxymethyloxetane (oxetane alcohol), 2-ethylhexyloxetane, xylylene bisoxetane, 3-ethyl-3(((3-ethyloxetan-3-yl)methoxy)methyl)oxetane, and the like. These may be used alone or in combination of two or more.

[0077] The content of the oxetanes is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 0.5% by mass to 10% by mass, more preferably 1% by mass to 5% by mass, based on the total mass of the thermoplastic resin (C).

[0078] The resin layer may be a single layer or a multilayer. In one embodiment, the resin layer is a multilayer having a layer containing a thermoplastic resin (A) and a layer containing a thermoplastic resin that does not have the repeating units represented by general formula (1) and general formula (2). In another embodiment, the resin layer is a multilayer having a layer containing a thermoplastic resin (B) and a layer containing a thermoplastic resin that does not have the repeating unit represented by general formula (3). When the resin layer is such a multilayer, a laminate having better mechanical strength and heat resistance can be obtained.

[0079] The glass transition temperature (Tg) of the resin contained in the resin layer is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 150° C. to 350° C., more preferably 180° C. to 320° C., and even more preferably 210° C. to 290° C. When the glass transition temperature (Tg) of the resin contained in the resin layer is 150° C. to 350° C., a laminate having excellent heat resistance can be obtained.

[0080] The resin layer preferably also has chemical resistance. Specifically, it is preferable that the resin layer has chemical resistance to solvents used in the cleaning step, resist stripping step, etc. in the imprinting process. Examples of solvents used in the cleaning step, etc. in the imprinting process include isopropyl alcohol, acetone, dimethyl sulfoxide (DMSO), and N-methylpyrrolidone (NMP).

[0081] The average thickness of the resin layer is not particularly limited as long as the average thickness ratio (resin layer / glass layer) is less than 0.9, and can be appropriately selected depending on the purpose. However, it is preferably less than 180 μm, more preferably 5 μm to 100 μm, even more preferably 5 μm to 40 μm, and particularly preferably 5 μm to 30 μm. When the average thickness of the resin layer is less than 180 μm, warping of the laminate can be suitably suppressed. When resin layers are disposed on both sides of the glass layer or when the laminate is composed of multiple layers, the thicknesses of the respective resin layers may be the same or different, but it is preferable that the thicknesses of the respective resin layers are the same. Furthermore, when resin layers are disposed on both sides of the glass layer or when the laminate is composed of multiple layers, the respective resin layers may be composed of the same resin or resins having the same properties, or may be composed of different resins, but it is preferable that the respective resin layers are composed of the same resin. Therefore, it is particularly preferable that the respective resin layers are composed of the same resin and have the same thickness. With such a configuration, even when heat-treated, thermal stress is evenly applied to both sides of the glass layer, making warping extremely unlikely to occur.

[0082] The elastic modulus of the resin layer at 25°C is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 1.5 GPa to 10 GPa, more preferably 1.7 GPa to 8 GPa, and even more preferably 1.9 GPa to 6 GPa. When the elastic modulus of the resin layer at 25°C is 1.5 GPa to 10 GPa, even if the glass layer is made thin, the resin layer relieves local stress in the tearing direction at defects during deformation, making it less likely for cracks or breakage to occur in the glass layer.

[0083] The light transmittance of the resin layer at a wavelength of 550 nm is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 80% or more, more preferably 85% or more, and even more preferably 90% or more. The light transmittance of the resin layer at a wavelength of 550 nm can be measured using a spectrophotometer (for example, U-4100, manufactured by Hitachi, Ltd.).

[0084] <Other Layers> In addition to the glass layer and the resin layer, the laminate may further include other layers as necessary. Examples of the other layers in the laminate include a coupling agent layer, an adhesive layer, a transparent conductive layer, and a hard coat layer.

[0085] <<Coupling Agent Layer>> The coupling agent layer is preferably a layer disposed between the glass layer and the resin layer, and more preferably a layer in contact with the glass layer. The coupling agent layer can be formed, for example, by curing a coupling agent on the glass layer.

[0086] The coupling agent constituting the coupling agent layer is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include amino group-containing coupling agents, epoxy group-containing coupling agents, epoxy group-terminated coupling agents, isocyanate group-containing coupling agents, vinyl group-containing coupling agents, mercapto group-containing coupling agents, (meth)acryloxy group-containing coupling agents, etc. These may be used alone or in combination of two or more.

[0087] In the embodiment of the present invention, the term "(meth)acryloxy group" means an "acryloxy group" or a "methacryloxy group".

[0088] When the resin layer contains a thermoplastic resin having an ester bond (e.g., at least one of thermoplastic resin (A) and thermoplastic resin (B)), the coupling agent constituting the coupling agent layer is preferably an amino group-containing coupling agent, an epoxy group-containing coupling agent, or an isocyanate group-containing coupling agent. The substitution position of the substituent possessed by these coupling agents may or may not be at the terminal of the molecule. When a resin layer containing a thermoplastic resin having an ester bond and a glass layer are arranged only via a coupling agent layer formed with such a coupling agent (i.e., without an adhesive layer), the resin layer containing a thermoplastic resin having an ester bond can be firmly adhered to the glass layer via the coupling agent layer. It is presumed that the amino group, epoxy group, or isocyanate group in the coupling agent chemically bonds or interacts with the resin layer, and the silyl group in the coupling agent can chemically bond (typically, covalently) with a substituent (e.g., a hydroxyl group) possessed by the glass layer. As a result, it is believed that the above-mentioned strong adhesion can be obtained.

[0089] When the resin layer contains a thermoplastic resin having hydroxyl groups (e.g., thermoplastic resin (C)), the coupling agent constituting the coupling agent layer is preferably an epoxy group-terminated coupling agent. When a resin layer containing a thermoplastic resin having hydroxyl groups and a glass layer are arranged only via a coupling agent layer formed with such a coupling agent (i.e., without an adhesive layer), the resin layer containing a thermoplastic resin having hydroxyl groups can be firmly adhered to the glass layer via the coupling agent layer. It is presumed that the epoxy group in the coupling agent chemically bonds or interacts with the resin layer, and the silyl group in the coupling agent can chemically bond with a substituent (e.g., a hydroxyl group) in the glass layer. As a result, it is believed that the above-mentioned strong adhesion can be obtained.

[0090] Examples of the amino group-containing coupling agent include alkoxysilanes having an amino group and halogenated silanes having an amino group, with alkoxysilanes having an amino group being preferred.

[0091] Specific examples of alkoxysilanes having an amino group include 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropyldimethylmethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropylmethyldimethoxysilane, 6-aminohexyltrimethoxysilane, 6-aminohexyltriethoxysilane, 11-aminoundecyltrimethoxysilane, 11-aminoundecyltriethoxysilane, and 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine.

[0092] Specific examples of halogenated silanes having an amino group include 3-aminopropyltrichlorosilane, 3-aminopropylmethyldichlorosilane, 3-aminopropyldimethylchlorosilane, 6-aminohexyltrichlorosilane, and 11-aminoundecyltrichlorosilane.

[0093] Specific examples of epoxy group-containing coupling agents and epoxy group-terminated coupling agents include 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane.

[0094] A specific example of an isocyanate group-containing coupling agent is 3-isocyanatepropyltriethoxysilane.

[0095] Specific examples of vinyl group-containing coupling agents include vinyltrichlorosilane, vinyltris(β-methoxyethoxy)silane, vinyltriethoxysilane, vinylmethoxysilane, and γ-methacryloxypropyltrimethoxysilane.

[0096] Specific examples of mercapto group-containing coupling agents include mercaptomethyldimethylethoxysilane, (mercaptomethyl)methyldiethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, and γ-mercaptopropyltriethoxysilane.

[0097] Specific examples of the (meth)acryloxy group-containing coupling agent include γ-(meth)acryloxypropyltrimethoxysilane, γ-(meth)acryloxypropyltriethoxysilane, γ-(meth)acryloxypropylmethyldimethoxysilane, and γ-(meth)acryloxypropylmethyldiethoxysilane.

[0098] The coupling agent may be synthesized by a known method, or a commercially available product may be used.

[0099] Examples of commercially available amino group-containing coupling agents include those manufactured by Shin-Etsu Chemical Co., Ltd. under the trade names "KBM-602" (N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane), "KBM-603" (N-2-(aminoethyl)-3-aminopropyltrimethoxysilane), "KBE-603" (N-2-(aminoethyl)-3-aminopropyltriethoxysilane), "KBM-903" (3-aminopropyltrimethoxysilane), "KBE-903" (3-aminopropyltriethoxysilane), "KBM-573" (N-phenyl-3-aminopropyltrimethoxysilane), and "KBE-9103" (3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine).

[0100] Examples of commercially available epoxy group-containing coupling agents (and epoxy group-terminated coupling agents) include those manufactured by Shin-Etsu Chemical Co., Ltd., under the trade name "KBM-303" (2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane), the trade name "KBM-403" (3-glycidoxypropyltrimethoxysilane), the trade name "KBE-402" (3-glycidoxypropylmethyldiethoxysilane), and the trade name "KBE-403" (3-glycidoxypropyltriethoxysilane).

[0101] An example of a commercially available isocyanate group-containing coupling agent is the product name "KBE-9007" (3-isocyanatepropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd.

[0102] The average thickness of the coupling agent layer is not particularly limited as long as it does not impair the effects of the present invention and can be appropriately selected depending on the purpose, but is preferably 0.001 μm to 10 μm, more preferably 0.001 μm to 2 μm.

[0103] <<Adhesive Layer>> The adhesive layer is preferably a layer for bonding between the glass layer and the resin layer. Furthermore, the laminate according to the embodiment of the present invention may have a coupling agent layer between the glass layer and the adhesive layer or between the adhesive layer and the resin layer.

[0104] The material constituting the adhesive layer is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include curable resins that are cured by heat or active energy rays. Specific examples of such resins include cyclic ethers having an epoxy group, a glycidyl group, an oxetanyl group, or the like, silicone resins, acrylic resins, and mixtures thereof.

[0105] The adhesive layer may also contain a coupling agent. When the adhesive layer contains a coupling agent, the adhesiveness to the glass layer and / or the resin layer (when the laminate has a coupling agent layer, the adhesiveness to the coupling agent layer and / or the resin layer) can be improved.

[0106] The average thickness of the adhesive layer is not particularly limited as long as it does not impair the effects of the present invention and can be appropriately selected depending on the purpose, but is preferably 10 μm or less, more preferably 0.01 μm to 10 μm, and even more preferably 0.1 μm to 7 μm. When the average thickness of the adhesive layer is 10 μm or less, excellent adhesion between the glass layer and the resin layer can be achieved without impairing the flexibility of the laminate.

[0107] <<Transparent Conductive Layer>> The transparent conductive layer is preferably disposed on the resin layer on the side opposite to the side on which the glass layer is disposed. The transparent conductive layer can function as an electrode or an electromagnetic wave shield when the laminate according to the embodiment of the present invention is used as a substrate for a display element or a solar cell.

[0108] The material constituting the transparent conductive layer is not particularly limited as long as it has conductivity and can be appropriately selected depending on the purpose, and examples thereof include metals such as copper and silver; metal oxides such as indium tin oxide (ITO) and indium zinc oxide (IZO); conductive polymers such as polythiophene and polyaniline; compositions containing carbon nanotubes, etc. These may be used alone or in combination of two or more.

[0109] The average thickness of the transparent conductive layer is not particularly limited as long as it does not impair the effects of the present invention, and can be appropriately selected depending on the purpose.

[0110] <<Hard Coat Layer>> The hard coat layer is preferably disposed on the resin layer on the side opposite to the side on which the glass layer is disposed. The hard coat layer has the function of imparting chemical resistance, scratch resistance, and surface smoothness to the laminate according to the embodiment of the present invention.

[0111] The material constituting the hard coat layer is not particularly limited and can be appropriately selected depending on the purpose. Examples include epoxy resins, acrylic resins, silicone resins, and mixtures thereof. These may be used alone or in combination of two or more. Among these, epoxy resins, which have excellent heat resistance, are preferred. The hard coat layer can be obtained by curing these resins with heat or active energy rays.

[0112] <Manufacturing Method> The method for manufacturing the laminate in an embodiment of the present invention is not particularly limited and can be appropriately selected depending on the purpose. Examples include a method of forming a resin layer on a glass layer by solution coating to obtain a laminate (hereinafter, sometimes referred to as "Manufacturing Method Example 1"), and a method of forming a resin layer by attaching a resin film on a glass layer to obtain a laminate (hereinafter, sometimes referred to as "Manufacturing Method Example 2").

[0113] <<Manufacturing Method Example 1>> A method for forming a resin layer on a glass layer by solution coating to obtain a laminate preferably includes a coating step of applying a solution containing materials that constitute the resin layer to one or both surfaces of the glass layer to form a coating layer, a drying step of drying the coating layer, and a heat treatment step of heat-treating the dried coating layer to form a resin layer, and more preferably includes a coupling treatment step of coupling-treating the surface of the glass layer. The materials that constitute the resin layer used here are as described in the <Resin Layer> section above.

[0114] -Coating Step- The coating solvent used in the coating step is not particularly limited and can be appropriately selected depending on the purpose. Examples include halogenated solvents such as methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, and trichloroethane; aromatic solvents such as toluene, benzene, and phenol; cellosolve-based solvents such as methyl cellosolve and ethyl cellosolve; ether-based solvents such as propylene glycol monomethyl ether and ethylene glycol monoisopropyl ether; and ketone-based solvents such as methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone. These solvents may be used alone or in combination of two or more. Among these, halogenated solvents, aromatic solvents, cellosolve-based solvents, and ether-based solvents are preferred as coating solvents used in the coating step, as they can sufficiently maintain adhesion between the resin layer and the glass layer even under high temperature and high humidity conditions, and can produce a laminate with excellent durability and reliability.

[0115] The method for applying the solution containing the material that constitutes the resin layer is not particularly limited and can be appropriately selected depending on the purpose. Examples include coating methods such as air doctor coating, blade coating, knife coating, reverse coating, transfer roll coating, gravure roll coating, kiss coating, cast coating, spray coating, slot orifice coating, calendar coating, electrodeposition coating, dip coating, and die coating; and printing methods such as relief printing methods such as flexographic printing, intaglio printing methods such as direct gravure printing and offset gravure printing, lithographic printing methods such as offset printing, and stencil printing methods such as screen printing.

[0116] - Drying Step - Any appropriate drying method (for example, natural drying, air drying, or heat drying) can be used for the drying step. In the case of heat drying, the drying temperature is preferably 100°C to 200°C, and the drying time is preferably 1 minute to 10 minutes.

[0117] -Heat Treatment Step- Any appropriate heat treatment method can be adopted for the heat treatment step, but the heat treatment temperature is preferably 100°C to 300°C, and the heat treatment time is preferably 5 minutes to 45 minutes. When the laminate according to the embodiment of the present invention has a coupling agent layer, the heat treatment step can chemically bond or interact with the resin contained in the resin layer.

[0118] - Coupling Treatment Step - It is more preferable to include a coupling treatment step in which the surface of the glass layer is subjected to a coupling treatment prior to the coating step. By performing the coupling treatment to form a coupling agent layer on the surface of the glass layer, the resin layer can be firmly adhered to the glass layer via the coupling agent layer. The materials constituting the coupling agent layer used here are as described above in the section <Coupling Agent Layer>.

[0119] Any appropriate method may be employed for the coupling treatment, and specifically, for example, a method may be used in which a solution containing a coupling agent is applied to the surface of the glass layer, followed by heat treatment.

[0120] The solvent used when preparing a solution containing a coupling agent is not particularly limited as long as it is a solvent that does not react with the coupling agent, and any appropriate solvent can be used. Specific examples of solvents used when preparing a solution containing a coupling agent include aliphatic hydrocarbon solvents such as hexane and hexadecane; aromatic solvents such as benzene, toluene, and xylene; halogenated hydrocarbon solvents such as methylene chloride and 1,1,2-trichloroethane; ether solvents such as tetrahydrofuran and 1,4-dioxane; alcohol solvents such as methanol and propanol; ketone solvents such as acetone and 2-butanone; and water. These solvents may be used alone or in combination of two or more.

[0121] Any appropriate heat treatment method can be adopted for the coupling treatment, but the heat treatment temperature is preferably 50° C. to 150° C. and the heat treatment time is preferably 1 minute to 10 minutes. The heat treatment can chemically bond the coupling agent to the surface of the glass layer.

[0122] <<Manufacturing Method Example 2>> In a method of obtaining a laminate by forming a resin layer by adhering a resin film onto a glass layer, the resin layer may be formed by adhering a commercially available resin film to the surface of the glass layer, or the resin layer may be formed by applying a resin solution to any appropriate substrate to form a resin film, and then transferring the resin film to the surface of the glass layer to adhere the glass layer and the resin film to each other.

[0123] Furthermore, before the resin film is attached, the surface of the glass layer may be subjected to a surface modification treatment such as corona treatment, plasma treatment, excimer treatment, or flame treatment, or the glass layer may be subjected to a coupling treatment. The above-mentioned methods can be used as the coupling treatment method. Among these, corona treatment is preferred for the surface of the glass layer, since it generates reactive functional groups on the surface of the glass layer, improving adhesion to the resin layer, and also removes foreign matter from the surface of the glass layer through an ashing effect, reducing surface irregularities, thereby enabling the production of a laminate with excellent appearance characteristics.

[0124] The resin film may be subjected to an annealing treatment before or after being attached to the glass layer. By performing the annealing treatment, impurities such as residual solvent and unreacted monomer components can be efficiently removed. The temperature and time of the annealing treatment are not particularly limited and can be appropriately selected depending on the purpose, but the temperature is preferably 100°C to 200°C, and the time is preferably 5 minutes to 20 minutes.

[0125] The resin film may be attached to the surface of the glass layer via an adhesive layer. The adhesive layer may be formed on the resin film and then attached to the surface of the glass layer, or the adhesive layer may be formed on the glass layer and then the resin film may be attached.

[0126] Examples of methods for forming the adhesive layer include a method in which a thermosetting resin or an active energy ray-curable resin is applied to the surface of a glass layer or a resin film, the glass layer and the resin film are then attached, and the thermosetting resin or the active energy ray-curable resin is then cured by ultraviolet light irradiation or heat treatment. The irradiation conditions for ultraviolet light irradiation are not particularly limited, but the cumulative irradiation light amount is preferably 100 mJ / cm. ２ ~2,000mJ / cm ２ The irradiation time is preferably 5 to 30 minutes. There are no particular restrictions on the conditions for the heat treatment, but it is preferable that the heating temperature is 100°C to 200°C and the heating time is 5 to 30 minutes. After the thermosetting resin or active energy ray curable resin is applied to the surface of the glass layer or the resin film, the thermosetting resin or active energy ray curable resin may be semi-cured before the glass layer and the resin film are attached. There are no particular restrictions on the conditions for semi-curing, but it is preferable that the irradiation time is 1 mJ / cm or less. ２ ~1,000mJ / cm ２ This can be done by irradiating the surface with ultraviolet light for 1 to 60 seconds.

[0127] Hereinafter, examples of the configuration of the laminate according to the embodiment of the present invention will be specifically described with reference to the drawings.

[0128] 1 is a schematic cross-sectional view showing an example of a laminate according to an embodiment of the present invention. The laminate 100a includes a glass layer 10 and a resin layer 11 disposed on one or both surfaces, preferably both surfaces, of the glass layer 10.

[0129] 2 is a cross-sectional schematic diagram showing another example of a laminate according to an embodiment of the present invention. The laminate 100b differs from the first embodiment in that it further includes a coupling agent layer 12 between the glass layer 10 and the resin layer 11.

[0130] 3 is a schematic cross-sectional view showing another example of a laminate according to an embodiment of the present invention. The laminate 100c differs from the first embodiment in that it further includes an adhesive layer 13 between the glass layer 10 and the resin layer 11.

[0131] 4 is a cross-sectional schematic diagram showing another example of a laminate according to an embodiment of the present invention. The laminate 100d includes a glass layer 10, and a coupling agent layer 12, an adhesive layer 13, and a resin layer 11 disposed in this order on one or both surfaces, preferably both surfaces, of the glass layer 10.

[0132] In the laminate according to an embodiment of the present invention, the glass layer 10 and the resin layer 11 may be arranged with a coupling agent layer 12 interposed therebetween (glass layer 10 / coupling agent layer 12 / resin layer 11) as shown in FIG. 2 , or may be arranged with an adhesive layer 13 interposed therebetween (glass layer 10 / adhesive layer 13 / resin layer 11) as shown in FIG. 3 . Alternatively, the laminate according to the present invention may have a coupling agent layer 12 and an adhesive layer 13 as shown in FIG. 4 , with the glass layer 10, coupling agent layer 12, adhesive layer 13, and resin layer 11 arranged in this order. Preferably, the coupling agent layer 12 is formed directly on the glass layer 10. More preferably, the glass layer 10 and the resin layer 11 are arranged with only the coupling agent layer 12 interposed therebetween (glass layer 10 / coupling agent layer 12 / resin layer 11). Such a configuration allows the glass layer 10 and the resin layer 11 to be firmly adhered to each other, resulting in a laminate with excellent dimensional stability, suppressed warpage, and resistance to crack propagation.

[0133] The coupling agent layer is preferably chemically bonded (typically covalently bonded) to the glass layer, so that a laminate having excellent adhesion between the glass layer and the coupling agent layer can be obtained.

[0134] The resin layer or adhesive layer is preferably bonded to or interacts with the coupling agent layer by a chemical bond (typically, a covalent bond), resulting in a laminate having excellent adhesion between the coupling agent layer and the resin layer or adhesive layer.

[0135] <Uses> The laminate according to the embodiment of the present invention can be suitably used as a substrate for nanoimprinting.

[0136] (Optical component) The optical component according to the embodiment of the present invention includes the laminate according to the embodiment of the present invention, and further includes other members as necessary. The laminate according to the embodiment of the present invention is as described in the section (Laminate).

[0137] <Other Components> There are no particular limitations on the other components in the optical component according to the embodiment of the present invention, as long as they do not impair the effects of the present invention, and examples include well-known components that are commonly used in optical components.

[0138] <Manufacturing Method> There are no particular limitations on the method for manufacturing an optical component according to an embodiment of the present invention, as long as the laminate according to an embodiment of the present invention is used, but the optical component is preferably manufactured by the method for manufacturing an optical component according to an embodiment of the present invention described below.

[0139] <Applications> The optical component according to the embodiment of the present invention can be suitably used in display devices or solar cells. Examples of display devices include liquid crystal displays, plasma displays, and organic EL displays.

[0140] (Imprinting Method) The imprinting method in an embodiment of the present invention includes a transfer step of pressing a concave-convex portion of an imprinting mold structure having the concave-convex portion against a surface of a resin layer of a laminate in an embodiment of the present invention opposite to a surface on which a glass layer is disposed, and transferring a concave-convex pattern based on the concave-convex portion of the imprinting mold structure to the resin layer, and may further include other steps such as a curing step and a demolding step, as necessary.

[0141] <Transfer Step> The transfer step is a step of pressing the concave-convex portions of an imprint mold structure having the concave-convex portions against the surface of the resin layer of the laminate in an embodiment of the present invention opposite to the surface on which the glass layer is disposed, thereby transferring a concave-convex pattern based on the concave-convex portions of the imprint mold structure to the resin layer.

[0142] The imprinting mold structure having concave and convex portions is not particularly limited, and any known imprinting mold structure can be used, such as a master for bit patterned media (BPM) having fine concave and convex portions.

[0143] There are no particular restrictions on the width or diameter and depth of the recesses and protrusions in the imprint mold structure having recesses and projections, and these can be selected appropriately depending on the type of optical component to be manufactured.

[0144] When the material constituting the resin layer is a thermoplastic resin, in the transfer step, heat is applied at a temperature suited to the thermoplastic resin, and the imprinting mold structure having concave-convex portions is pressed against the softened resin, thereby allowing the concave-convex pattern based on the concave-convex portions of the imprinting mold structure to be suitably transferred to the resin layer. Furthermore, when the material constituting the resin layer is a curable resin that is cured by heat or active energy rays, the imprinting mold structure having concave-convex portions can be pressed against the uncured resin before application of heat or active energy rays, allowing the concave-convex pattern based on the concave-convex portions of the imprinting mold structure to be suitably transferred to the resin layer.

[0145] <Curing Step> The curing step is a step of curing the resin constituting the resin layer in a state in which the imprint mold structure having the concave and convex portions is pressed against the resin layer of the laminate according to an embodiment of the present invention.

[0146] The curing method is not particularly limited and can be appropriately selected depending on the type of resin constituting the resin layer. For example, a method of curing by heat or active energy rays can be mentioned.

[0147] <Mold Release Step> The mold release step is a step of separating the imprint mold structure having the concave-convex portions from the resin layer after the curing step (mold release). This separates the resin layer from the imprint mold structure having the concave-convex portions, thereby obtaining a resin layer to which a concave-convex pattern based on the concave-convex portions of the imprint mold structure having the concave-convex portions has been transferred.

[0148] (Method for manufacturing optical component) A method for manufacturing an optical component in an embodiment of the present invention includes a transfer step of pressing the concave-convex portion of an imprint mold structure having the concave-convex portion against the surface of the resin layer of the laminate in an embodiment of the present invention opposite to the surface on which the glass layer is disposed, and transferring a concave-convex pattern based on the concave-convex portion of the imprint mold structure to the resin layer, and may further include other steps such as a curing step and a demolding step, as necessary.

[0149] The imprinting method according to the embodiment of the present invention can be suitably applied to the method for manufacturing an optical component according to the embodiment of the present invention. Therefore, the transfer step, curing step, and demolding step in the method for manufacturing an optical component according to the embodiment of the present invention can be performed in the same manner as the transfer step, curing step, and demolding step in the method for manufacturing an optical component using the imprinting method according to the embodiment of the present invention.

[0150] The optical component manufactured by the optical component manufacturing method according to the embodiment of the present invention can be suitably used in a display element or a solar cell. Examples of the display element include a liquid crystal display, a plasma display, and an organic EL display. The laminate according to the embodiment of the present invention has reduced warpage, and therefore, an optical component having excellent properties can be obtained.

[0151] The present invention will be specifically explained below with reference to examples and comparative examples, but the present invention is not limited to these examples in any way.

[0152] Example 1 In Example 1, a laminate 100e having the cross-sectional structure shown in FIG. 5 was produced by the following method.

[0153] A square inorganic glass (OA-10G, manufactured by Nippon Electric Glass Co., Ltd.) having a thickness of 100 μm, a length of 6 cm, and a width of 6 cm was used as the glass layer, and one surface of the glass layer was washed with isopropyl alcohol and then subjected to a corona treatment.

[0154] An adhesive (epoxy resin (Celloxide 2021P, manufactured by Daicel Chemical Industries, Ltd.)) was applied to the entire surface of the glass layer 10 (the corona-treated surface) so that the average thickness after curing would be 3 μm. Next, a square polyimide (PI) film (Upilex (registered trademark) 25S, manufactured by UBE Corporation) 11 with an average thickness of 25 μm, length of 6 cm, and width of 6 cm was laminated on the adhesive-coated surface. Next, ultraviolet light (wavelength: 365 nm, intensity: 1,000 mJ / cm) was applied from a high-pressure mercury lamp. ２ The adhesive was cured by irradiating the adhesive with the above-mentioned light from the glass layer side, thereby forming an adhesive layer 13. In this way, a laminate 100e was formed in which the glass layer 10, the adhesive layer 13, and the resin layer 11 were laminated in this order.

[0155] Example 2 A laminate was formed in the same manner as in Example 1, except that the polyimide (PI) film (UPILEX (registered trademark) 25S, manufactured by UBE Corporation) having an average thickness of 25 μm and a square shape of 6 cm in length and 6 cm in width was replaced with a PET film (COSMOSHINE (registered trademark) A4360 38 μm, manufactured by TOYOBO CO., LTD.) having an average thickness of 38 μm and a square shape of 6 cm in length and 6 cm in width.

[0156] Example 3 A laminate was formed in the same manner as in Example 1, except that the polyimide (PI) film (Upilex (registered trademark) 25S, manufactured by UBE Corporation) having an average thickness of 25 μm and a square shape of 6 cm in length and 6 cm in width was replaced with a PET film (Lumirror (registered trademark) #16-F68, manufactured by Toray Industries, Inc.) having an average thickness of 16 μm and a square shape of 6 cm in length and 6 cm in width.

[0157] Example 4 A laminate was formed in the same manner as in Example 1, except that the polyimide (PI) film (Upilex (registered trademark) 25S, manufactured by UBE Corporation) having an average thickness of 25 μm and a square shape of 6 cm in length and 6 cm in width was replaced with a PET film (Lumirror (registered trademark) #25-F66, manufactured by Toray Industries, Inc.) having an average thickness of 25 μm and a square shape of 6 cm in length and 6 cm in width.

[0158] Example 5 A laminate was formed in the same manner as in Example 1, except that the polyimide (PI) film (Upilex (registered trademark) 25S, manufactured by UBE Corporation) having an average thickness of 25 μm and a square shape of 6 cm in length and 6 cm in width was replaced with a PET film (Lumirror (registered trademark) #6-F557, manufactured by Toray Industries, Inc.) having an average thickness of 6 μm and a square shape of 6 cm in length and 6 cm in width.

[0159] Comparative Example 1 A laminate was formed in the same manner as in Example 1, except that the polyimide (PI) film (UPILEX (registered trademark) 25S, manufactured by UBE Corporation) having an average thickness of 25 μm and a square shape of 6 cm in length and 6 cm in width was replaced with a PET film (COSMOSHINE (registered trademark) A4360 100 μm, manufactured by TOYOBO CO., LTD.) having an average thickness of 100 μm and a square shape of 6 cm in length and 6 cm in width.

[0160] <Warp Evaluation> The warp of each laminate formed in Examples 1 to 5 and Comparative Example 1 was evaluated using digital image correlation (DIC analysis). Specifically, a measurement sample was prepared by spraying a spray (water-based lacquer spray, manufactured by Sunday Paint Co., Ltd.) onto the exposed surface of the resin layer 11 of the laminate 100e shown in FIG. 5 to create a random granular pattern (speckle pattern) on the surface. This measurement sample was placed in an oven with an observation window. The surface of the laminate with the speckle pattern was positioned facing the observation window. A thermocouple was also installed near the measurement sample in the oven. Next, a twin-lens camera equipped with an LED lamp was used to photograph a subset of the entire surface of the laminate, measuring 6 cm in length and 6 cm in width, from outside the observation window. The entire region was illuminated with an LED and photographed, and this image was designated "Image 1" of the laminate before heating. Next, the oven was heated, and when the thermocouple indicated 60°C, a twin-lens camera equipped with the LED lamp was used to photograph the subset on the surface of the laminate from outside the observation window while irradiating the LED, and this was designated as "Image 2" of the laminate in its heated state.

[0161] The captured images 1 and 2 were analyzed for strain in the x and y directions, as well as the amount of deformation in the z direction, using a deformation measurement and strain analysis device (SterinMaster, manufactured by LaVision). During the analysis, as shown in FIG. 6, the surface of the laminate on which the speckle pattern was applied (the area indicated by the solid line in FIG. 6) was divided into nine parts as shown by the dotted lines in FIG. 6, and the maximum value of the z-direction deformation amount in each of the nine divided parts was calculated. Furthermore, the maximum value among the maximum z-direction deformation amounts at the nine points was determined as the maximum z deformation amount of the measurement sample at 60 ° C. The larger the maximum z deformation amount, the greater the thermal warpage of the laminate. The results of the maximum z deformation amount are shown in Table 1 below as "maximum thermal warpage amount." Furthermore, for image 2, a photograph showing the distortion based on a color meter is shown in FIG. 8.

[0162]

[0163] Comparing Examples 1 to 5 with Comparative Example 1, the laminates of Examples 1 to 5, which had an average thickness ratio (resin layer / glass layer) of less than 0.9, exhibited a suppressed maximum thermal warpage. Furthermore, the thinner the resin layer, the greater the suppression effect on the maximum thermal warpage.

[0164] Examples of aspects of the present invention include the following. <1> A laminate comprising a glass layer and a resin layer disposed on at least one surface of the glass layer, wherein the ratio of the average thickness of the resin layer to the average thickness of the glass layer (resin layer / glass layer) is less than 0.9. <2> The laminate according to <1>, wherein the absolute value of the maximum thermal warpage in the thickness direction of the laminate at 60°C as measured by a digital image correlation method is less than 2 mm. <3> The laminate according to <1> or <2>, wherein the average thickness of the glass layer is 200 μm or less. <4> The laminate according to any one of <1> to <3>, wherein the laminate is used as a substrate for imprinting. <5> An optical component comprising the laminate according to any one of <1> to <4>. <6> An imprinting method comprising: a transfer step of pressing a concave-convex portion of an imprinting mold structure having a concave-convex portion against a surface of a resin layer of the laminate according to any one of <1> to <4> opposite to a surface on which a glass layer is disposed, and transferring a concave-convex pattern based on the concave-convex portion of the imprinting mold structure to the resin layer. <7> A method for producing an optical component comprising: a transfer step of pressing a concave-convex portion of an imprinting mold structure having a concave-convex portion against a surface of a resin layer of the laminate according to any one of <1> to <4> opposite to a surface on which a glass layer is disposed, and transferring a concave-convex pattern based on the concave-convex portion of the imprinting mold structure to the resin layer.

[0165] As described above, the present invention has been described based on specific embodiments and examples, but these embodiments and examples are presented merely as examples, and the present invention is not limited to these embodiments and examples. The embodiments can be embodied in various other forms, and various combinations, omissions, substitutions, additions, modifications, etc. can be made without departing from the spirit of the invention. These embodiments and their modifications are included within the scope and spirit of the invention, and are also included in the inventions and their equivalents set forth in the claims.

[0166] This international application claims priority based on Japanese Patent Application No. 2023-168647, filed on September 28, 2023, the entire contents of which are incorporated herein by reference.

[0167] The laminate according to the embodiment of the present invention can be suitably used as a substrate for nanoimprinting. Furthermore, an optical component having the laminate according to the embodiment of the present invention can be widely used in display elements such as liquid crystal displays, organic EL displays, and plasma displays, as well as solar cells.

[0168] 100a, 100b, 100c, 100d, 100e ... laminate 10 ... glass layer 11 ... resin layer 12 ... coupling agent layer 13 ... adhesive layer

Claims

1. A laminate comprising a glass layer and a resin layer disposed on at least one surface of the glass layer, wherein the ratio of the average thickness of the resin layer to the average thickness of the glass layer (resin layer / glass layer) is less than 0.

9.

2. The laminate according to claim 1, wherein the absolute value of the maximum thermal warpage in the thickness direction of the laminate at 60°C as measured by a digital image correlation method is less than 2 mm.

3. The laminate according to claim 1 or 2, wherein the average thickness of the glass layer is 200 μm or less.

4. The laminate according to any one of claims 1 to 3, which is used as a substrate for imprinting.

5. An optical component comprising a laminate according to any one of claims 1 to 4.

6. An imprinting method comprising a transfer step of pressing an uneven portion of an imprinting mold structure having an uneven portion against a surface of a resin layer of a laminate according to any one of claims 1 to 4 opposite to a surface on which a glass layer is disposed, and transferring an uneven pattern based on the uneven portion of the imprinting mold structure to the resin layer.

7. A method for manufacturing an optical component, comprising a transfer step of pressing an uneven portion of an imprint mold structure having an uneven portion against a surface of a resin layer of a laminate described in any one of claims 1 to 4 opposite to a surface on which a glass layer is disposed, and transferring an uneven pattern based on the uneven portion of the imprint mold structure to the resin layer.

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