Laminate, imprint substrate, replica mold, method for manufacturing same, and imprint device

Abstract

This laminate includes a protective layer, a glass layer, and an adhesive layer that bonds the protective layer and the glass layer. The elastic modulus of the protective layer at 25°C is 1.5 GPa-10 GPa inclusive, and the elastic modulus of the adhesive layer at 25°C is 1 GPa-10 GPa inclusive.

Description

Laminate, imprint substrate, replica mold and its manufacturing method, and imprint device

[0001] The present disclosure relates to a laminate, an imprinting substrate, a replica mold and a manufacturing method thereof, and an imprinting apparatus.

[0002] Imprinting is a technique in which a mold with a finely textured structure is pressed against a transfer material, such as a resin, coated on the surface of a substrate, and the textured structure is precisely transferred to the transfer material through mechanical deformation, forming a finely textured structure on the substrate. Once a mold is fabricated, fine textured structures, such as nanostructures, can be easily and repeatedly molded. This makes imprinting a nanofabrication technique economical, with high throughput, and produces little hazardous waste. In recent years, it has been applied to a wide range of fields, including biomedicine, micro- and nanofluidics, data storage, electronics, and microelectromechanical devices.

[0003] However, in imprinting methods, there are problems in that the master mold (metal mold) is expensive and becomes unusable if it is damaged. Therefore, an inexpensive imprinting method is known in which a replica (duplicate) onto which the concave-convex structure of the mold is transferred is produced and used as a substitute for the mold. For example, a second mold onto which the concave-convex pattern of a first mold is transferred has been proposed, the second mold having a substrate and a resin layer formed on the substrate and onto which the concave-convex pattern of the first mold is transferred, the second mold including a thin glass substrate (see Patent Document 1).

[0004] On the other hand, imprinting methods include a production method called roll-to-roll, in which a concave-convex structure is continuously transferred to a substrate, such as a rolled film, while rotating a rolled mold and feeding the substrate, which may be several hundred meters long, and then rewound into a roll. The roll-to-roll method has high productivity, but when the substrate to be imprinted includes a thin glass sheet, the thin glass sheet may break during or after imprinting. Therefore, as a method for reducing breakage of thin glass sheets, an imprinting method has been proposed, which includes a transfer step in which a layer of molding material is sandwiched between a glass sheet and a mold, the concave-convex pattern of the mold is transferred to the layer of molding material, and a resin layer is formed on the glass sheet, and in the transfer step, a support sheet is used to support the surface of the glass sheet opposite to the surface on which the resin layer is formed, and a protective portion is formed on the edge surface of the glass sheet using the molding material held by the portion of the support sheet that protrudes from the glass sheet (see Patent Document 2).

[0005] International Publication No. 2015 / 012161 Japanese Patent Application Laid-Open No. 2014-14996

[0006] The second mold described in Patent Document 1 has a problem of being easily broken when used in a roll-to-roll system. Furthermore, while the method described in Patent Document 2 can reduce breakage of the glass sheet, if the glass sheet does break, the glass will scatter, and the fragments may cause further breakage of the glass sheet or malfunction of the imprinting apparatus.

[0007] The present disclosure aims to solve the above-mentioned problems of the prior art and to provide a laminate that is less likely to shatter when the glass layer is broken.

[0008] The present disclosure relates to a laminate comprising a protective layer, a glass layer, and an adhesive layer that bonds the protective layer and the glass layer, wherein the protective layer has an elastic modulus of 1.5 GPa or more and 10 GPa or less at 25°C, and the adhesive layer has an elastic modulus of 1 GPa or more and 10 GPa or less at 25°C.

[0009] The present disclosure can provide a laminate that is less likely to shatter when the glass layer is broken.

[0010] FIG. 1 is a schematic cross-sectional view showing an example of a laminate according to an embodiment of the present disclosure. FIG. 2 is a schematic perspective view showing an example of a laminate roll formed by winding a laminate according to an embodiment of the present disclosure into a roll. FIG. 3 is a schematic cross-sectional view showing a modified example of a laminate according to an embodiment of the present disclosure. FIG. 4 is a schematic cross-sectional view showing an example of an imprinting substrate according to an embodiment of the present disclosure. FIG. 5 is a schematic cross-sectional view showing a modified example of an imprinting substrate according to an embodiment of the present disclosure. FIG. 6 is a schematic cross-sectional view showing an example of a replica mold according to an embodiment of the present disclosure. FIG. 7 is a flowchart showing an example of a replica mold manufacturing method according to an embodiment of the present disclosure. FIG. 8 is a flowchart showing an example of an imprinting method according to an embodiment of the present disclosure. FIG. 9A is a schematic diagram showing an example of an imprinting apparatus according to an embodiment of the present disclosure. FIG. 9B is a schematic diagram showing another example of an imprinting apparatus according to an embodiment of the present disclosure. FIG. 10 is a schematic diagram showing another example of an imprinting apparatus according to an embodiment of the present disclosure. FIG. 11A is an enlarged view of region X in FIG. 9A, FIG. 9B, or FIG. 10, and is a schematic cross-sectional view showing an example of a molded body. FIG. 11B is an enlarged view of region X in FIG. 9A, FIG. 9B, or FIG. 10, and is a schematic cross-sectional view showing another example of the molded body.

[0011] Hereinafter, embodiments of the present disclosure 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 disclosure. Furthermore, in this disclosure, unless otherwise specified, the use of "to" to indicate a range of values ​​means that the values ​​before and after the range are included as the lower and upper limits.

[0012] Furthermore, when describing embodiments of the present disclosure with reference to the drawings, identical components may be denoted by the same reference numerals in each drawing, and duplicate descriptions may be omitted. Furthermore, the number, position, size, shape, etc. of components are not limited to the embodiments of the present disclosure, and may be any number, position, size, shape, etc. that is preferable for implementing the present disclosure.

[0013] (Laminate) A laminate according to an embodiment of the present disclosure includes a protective layer, a glass layer, and an adhesive layer that bonds the protective layer and the glass layer, wherein the protective layer has a modulus of elasticity of 1.5 GPa or more and 10 GPa or less at 25° C., and the adhesive layer has a modulus of elasticity of 1 GPa or more and 10 GPa or less at 25° C. The laminate according to an embodiment of the present disclosure may further include other layers as necessary.

[0014] 1 is a schematic cross-sectional view showing an example of a laminate 50 according to a first embodiment. The laminate 50 is formed by laminating a protective layer 10, an adhesive layer 11, and a glass layer 12 in this order.

[0015] The average thickness of the laminate 50 is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 400 μm or less, more preferably 300 μm or less, and even more preferably 50 μm or more and 300 μm or less. In the present disclosure, the "average thickness" of the laminate 50 means the sum (total thickness) of the average thicknesses of all layers contained in the laminate 50, which will be described later.

[0016] <Protective Layer> The protective layer 10 provides handleability to the glass layer 12. An adhesive layer 11 is disposed on one surface of the protective layer 10.

[0017] The elastic modulus of the protective layer 10 at 25° C. is not particularly limited as long as it is 1.5 GPa or more and 10 GPa or less, but is preferably 1.5 GPa or more and 7 GPa or less, and more preferably 1.5 GPa or more and 5 GPa or less. If the elastic modulus of the protective layer 10 at 25° C. is less than 1.5 GPa or exceeds 10 GPa, the handleability of the glass layer 12 becomes poor.

[0018] In the present disclosure, the elastic modulus of the protective layer 10 at 25°C is a value measured by a nanoindentation method using a nanoindenter (e.g., a Triboindenter manufactured by Hysitron Inc.) The elastic modulus is measured using a conical indenter (spherical indenter: radius of curvature 10 μm) at 25°C by a single indentation method with an indentation depth of approximately 2 μm.

[0019] The material constituting the protective layer 10 is not particularly limited as long as it has a modulus of elasticity at 25°C of 1.5 GPa or more and 10 GPa or less, and examples thereof include polyethersulfone resins, polycarbonate resins, epoxy resins, acrylic resins, polyester resins such as polyethylene terephthalate and polyethylene naphthalate, polyolefin resins, cycloolefin resins such as norbornene resins, polyimide resins, polyamide resins, polyimideamide resins, polyarylate resins, polysulfone resins, polyetherimide resins, etc. These may be used alone or in combination of two or more.

[0020] Examples of polyester resins include polyethylene terephthalate resin, polybutylene terephthalate resin, polyethylene naphthalate resin, polybutylene naphthalate resin, and copolymer resins of these resins.

[0021] The protective layer 10 may contain various additives such as a polymerization initiator, a coupling agent, a diluent, an antioxidant, a modifier, a surfactant, a dye, a pigment, a discoloration inhibitor, an ultraviolet absorber, a softener, a stabilizer, a plasticizer, an antifoaming agent, a reinforcing agent, etc. The type, number, and amount of additives contained in the protective layer 10 are not particularly limited and can be selected appropriately depending on the purpose.

[0022] The shape of the protective layer 10 is not particularly limited and can be appropriately selected from any shape, but a film shape is preferred.

[0023] In the laminate 50, the protective layer 10 may be a single layer or a multilayer body, but is preferably a single layer.

[0024] The average thickness of the protective layer 10 is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 10 μm or more and 250 μm or less, more preferably 10 μm or more and 200 μm or less, and even more preferably 20 μm or more and 200 μm or less. When the average thickness of the protective layer 10 is 10 μm or more and 250 μm or less, handling properties can be imparted to the laminate 50. In addition, the laminate 50 can be easily rolled, and when used in an imprinting method, productivity can be improved.

[0025] In the present disclosure, the "average thickness" of the protective layer 10 means the average value of thicknesses at three points arbitrarily selected from the protective layer 10. The thickness of the protective layer 10 can be measured using a known film thickness measuring device (for example, R1-205, PEACOCK (registered trademark), manufactured by Ozaki Manufacturing Co., Ltd.).

[0026] The protective layer 10 may be formed by appropriately curing a resin, or a commercially available product may be used as is. Examples of commercially available products for the protective layer 10 include COSMOSHINE (registered trademark) A4360 (manufactured by Toyobo Co., Ltd.).

[0027] <Adhesive Layer> The adhesive layer 11 mainly prevents breakage of the glass layer 12 of the laminate 50, prevents the glass layer 12 from scattering if broken, and provides flexibility to the laminate 50. The adhesive layer 11 is disposed between the protective layer 10 and the glass layer 12, and bonds the protective layer 10 and the glass layer 12 together.

[0028] In the present disclosure, "flexible" refers to a state in which the laminate 50 has plasticity that allows bending deformation. Therefore, since the laminate 50 has plasticity that allows bending deformation, the laminate 50 can be easily rolled.

[0029] Note that the adhesive layer 11 "adhering" the protective layer 10 to the glass layer 12 means that the protective layer 10 and the glass layer 12 are fixed together and cannot be peeled off in an environment at 25°C. Therefore, this is different from "adhering" which maintains its adhesiveness even after a lapse of time after application and is easily peeled off in an environment at 25°C. In other words, the adhesive layer 11 is not an adhesive layer. In the present disclosure, an "adhesive layer" is defined as one having an elastic modulus of less than 1 GPa at 25°C.

[0030] However, the adhesive layer 11 can be peeled off by applying heat or active energy rays depending on the constituent materials.

[0031] The elastic modulus of the adhesive layer 11 at 25°C is not particularly limited as long as it is 1 GPa or more and 10 GPa or less, but is preferably 1 GPa or more and 8 GPa or less, and more preferably 1 GPa or more and 5 GPa or less. If the elastic modulus of the adhesive layer 11 at 25°C is less than 1 GPa, the glass layer 12 is likely to break and, if the glass layer 12 breaks during transportation, it will shatter. If the elastic modulus of the adhesive layer 11 at 25°C exceeds 10 GPa, the flexibility of the laminate 50 will be insufficient, making it difficult to roll the laminate 50, and when used in an imprinting method, productivity may be insufficient. On the other hand, if the elastic modulus of the adhesive layer 11 at 25°C is 1 GPa or more and 10 GPa or less, the glass layer 12 is unlikely to break and, even if the glass layer 12 breaks during transportation, it will not shatter. Furthermore, the laminate 50 has flexibility, making it easy to roll the laminate 50.

[0032] In the present disclosure, the elastic modulus of the adhesive layer 11 is a value measured by a nanoindentation method using a nanoindenter (e.g., a Triboindenter manufactured by Hysitron Inc.) The elastic modulus is measured using a conical indenter (spherical indenter: radius of curvature 10 μm) at 25° C. using a single indentation method with an indentation depth of approximately 2 μm.

[0033] The material for forming the adhesive layer 11 is not particularly limited as long as it has a modulus of elasticity at 25° C. of 1 GPa or more and 10 GPa or less, and examples thereof include curable resins that are cured by heat or active energy rays.

[0034] Examples of active energy rays include ultraviolet rays, electron beams, α rays, β rays, γ rays, X rays, etc. These may be used alone or in combination of two or more.

[0035] Examples of curable resins include polyethersulfone resins, polycarbonate resins, epoxy resins, acrylic resins, polyester resins such as polyethylene terephthalate and polyethylene naphthalate, polyolefin resins, cycloolefin resins such as norbornene resins, polyimide resins, polyamide resins, polyimideamide resins, polyarylate resins, polysulfone resins, and polyetherimide resins. These may be used alone or in combination of two or more. Among these, epoxy resins are preferred as the material for forming the adhesive layer 11.

[0036] The epoxy resin is not particularly limited as long as it is a resin having an epoxy group in the molecule, and examples thereof include bisphenol types such as bisphenol A type, bisphenol F type, bisphenol S type, or water additives thereof; novolak types such as phenol novolak type and cresol novolak type; nitrogen-containing ring types such as triglycidyl isocyanurate type and hydantoin type; alicyclic types; aliphatic types; aromatic types such as naphthalene type and biphenyl type; glycidyl types such as glycidyl ether type, glycidyl amine type and glycidyl ester type; dicyclo types such as dicyclopentadiene type; ester types; ether ester types; and modified types thereof. These may be used alone or in combination of two or more types.

[0037] In addition to the curable resin, the adhesive layer 11 may contain various additives such as a polymerization initiator, a coupling agent, a diluent, an antioxidant, a denaturant, a surfactant, a dye, a pigment, a discoloration inhibitor, an ultraviolet absorber, a softener, a stabilizer, a plasticizer, an antifoaming agent, and a reinforcing agent. When the adhesive layer 11 contains a coupling agent, the adhesion between the protective layer 10 and the glass layer 12 can be improved. The type, number, and amount of additives contained in the adhesive layer 11 are not particularly limited and can be selected appropriately depending on the purpose.

[0038] The shape of the adhesive layer 11 is not particularly limited and can be appropriately selected from any shape.

[0039] In the laminate 50, the adhesive layer 11 may be a single layer or a multilayer body, but is preferably a single layer.

[0040] The average thickness of the adhesive layer 11 is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 0.5 μm to 10 μm, more preferably 1 μm to 5 μm, and even more preferably 1 μm to 3 μm. When the average thickness of the adhesive layer 11 is 1 μm to 10 μm, the glass layer 12 is less likely to break, and even if the glass layer 12 breaks during transportation, it is less likely to shatter. Furthermore, the adhesive layer 11 has flexibility, making it easy to form the laminate 50 into a roll.

[0041] In the present disclosure, the "average thickness" of the adhesive layer 11 means the average value of thicknesses at three points arbitrarily selected from the adhesive layer 11. The thickness of the adhesive layer 11 can be measured using a known film thickness measuring device (for example, R1-205, PEACOCK (registered trademark), manufactured by Ozaki Manufacturing Co., Ltd.).

[0042] <Glass Layer> The glass layer 12 mainly maintains the dimensions of the laminate 50. The glass layer 12 is disposed on the surface of the adhesive layer 11 opposite to the surface on which the protective layer 10 is disposed.

[0043] In the present disclosure, the term "surface of adhesive layer 11 on which protective layer 10 is disposed" is not limited to the case where adhesive layer 11 and protective layer 10 are adjacent to each other, and other layers may be present between adhesive layer 11 and protective layer 10. Similarly, the term "glass layer 12" is not limited to the case where adhesive layer 11 and glass layer 12 are adjacent to each other, and other layers may be present between adhesive layer 11 and glass layer 12.

[0044] The material for forming the glass layer 12 is not particularly limited, but is preferably inorganic glass.

[0045] 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.

[0046] 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.

[0047] 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.

[0048] The shape of the glass layer 12 is not particularly limited and can be appropriately selected from any shape, but a plate shape is preferred.

[0049] In the laminate 50, the glass layer 12 may be a single layer or a multilayer body, but is preferably a single layer.

[0050] The average thickness of the glass layer 12 is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 10 μm or more and 250 μm or less, more preferably 10 μm or more and 200 μm or less, and even more preferably 30 μm or more and 200 μm or less. When the average thickness of the glass layer 12 is 10 μm or more, it is less likely to break and is easy to handle. Furthermore, when the average thickness of the glass layer 12 is 250 μm or less, flexibility can be imparted to the laminate 50, making it easier to roll the laminate 50 and improving productivity when used in an imprinting method.

[0051] In the present disclosure, the "average thickness" of the glass layer 12 means the average value of thicknesses at three points arbitrarily selected from the glass layer 12. The thickness of the glass layer 12 can be measured using a known film thickness measuring device (for example, R1-205, PEACOCK (registered trademark), manufactured by Ozaki Manufacturing Co., Ltd.).

[0052] The method for forming the glass layer 12 is not particularly limited and can be selected appropriately depending on the purpose. For example, the glass layer 12 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 it to form it. The method for forming the glass layer 12 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 12 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 12 may also be subjected to a surface treatment such as a coupling treatment.

[0053] Furthermore, commercially available glass may be used as is for the glass layer 12, or commercially available inorganic glass may be polished to a desired thickness and used. 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.), G-Leaf (registered trademark) (manufactured by Nippon Electric Glass Co., Ltd.), OA-10G (manufactured by Nippon Electric Glass Co., Ltd.), D263 (registered trademark), and AF45 (registered trademark) (all manufactured by Schott Corporation).

[0054] The laminate 50 according to the first embodiment has the above-described configuration, and therefore is less likely to shatter when the glass layer 12 is broken.

[0055] Furthermore, the laminate 50 according to the first embodiment has flexibility and can be suitably wound into a laminate roll. Fig. 2 is a schematic perspective view showing an example of a laminate roll 100 in which the laminate 50 according to the first embodiment is wound into a roll. The laminate roll 100 is suitably used in a roll-to-roll imprint method.

[0056] The laminate roll 100 may have a core material 150 in addition to the laminate 50. The laminate roll 100 has the laminate 50 wound multiple times around the outer periphery of the core material 150. The diameter of the core material 150 in a cross-sectional view can be selected appropriately depending on the size of the device in which the laminate roll 100 is used (mounted). As a guideline, the diameter of the core material 150 in a cross-sectional view is set so that the bending stress applied to the glass layer 12 in the following formula is 50 MPa or less. However, this is not necessarily limited to this as long as the effects of the present disclosure can be obtained. Bending stress (MPa) = [(elastic modulus of glass layer) × (average thickness of glass layer / 2)] / (diameter of core material / 2)

[0057] The length (length in the winding direction of the laminate roll 100) and width (length in the direction perpendicular to the winding direction of the laminate roll 100) of the laminate 50 in the laminate roll 100 are not particularly limited and can be selected appropriately depending on the purpose, but the length is preferably long, more preferably 10 m or more, even more preferably 50 m or more, and particularly preferably 100 m or more. There is no particular limit to the upper limit of the length of the laminate 50 and it can be selected appropriately depending on the application of the laminate roll 100. The width is preferably 1 cm or more and 300 cm or less, more preferably 5 cm or more and 200 cm or less.

[0058] The protective layer 10 and the glass layer 12 of the laminate 50 may be disposed on either the inner surface 100a or the outer surface 100b of the laminate roll 100. That is, the inner surface 100a may be the protective layer 10, or the inner surface 100a may be the glass layer 12. By forming the inner surface 100a as the glass layer 12, compressive stress is applied to the outermost surface of the glass layer 12, making it less likely to break even in roll form.

[0059] 3 is a schematic cross-sectional view showing a modification of the laminate 50 according to the first embodiment. The laminate 50 is formed by laminating a protective layer 10, an adhesive layer 11, a glass layer 12, and a glass protective layer 13 in this order.

[0060] The laminate 50 according to the modified example of the first embodiment has the same configuration as the laminate 50 according to the first embodiment, except that it has a glass protective layer 13 that protects the glass layer 12 as another layer.

[0061] <<Glass Protective Layer>> The glass protective layer 13 mainly protects the glass layer 12 from physical impacts and the like. The glass protective layer 13 is disposed on the surface of the glass layer 12 opposite to the surface on which the adhesive layer 11 is disposed. The glass protective layer 13 is temporarily attached to the glass layer 12.

[0062] In the present disclosure, the "surface opposite to the surface of the glass layer 12 on which the adhesive layer 11 is arranged" on which the glass protective layer 13 is arranged is not limited to the case where the glass protective layer 13 and the glass layer 12 are adjacent to each other, and other layers may be present between the glass protective layer 13 and the glass layer 12.

[0063] Glass protective layer 13 protects glass layer 12 until laminate 50 is put into use. Temporarily attaching glass protective layer 13 to the surface of glass layer 12 can prevent scratches, holes, and the like from being caused by, for example, a falling object with a sharp tip.

[0064] The material for the glass protective layer 13 is not particularly limited, but a plastic material is preferred. Among these, polyester-based resins such as polyethylene terephthalate; (meth)acrylic resins such as polymethyl methacrylate; and polyethylene-based resins are preferred because of their high protective effect on the glass layer 12. In the present disclosure, "(meth)acrylic" refers to "methacrylic" or "acrylic."

[0065] The glass protective layer 13 preferably has an adhesive layer on the attachment surface of the glass layer 12. As the glass protective layer 13, a self-adhesive film may be used in which the resin layer and the adhesive layer constituting the glass protective layer 13 are laminated by co-extrusion.

[0066] The average thickness of the glass protective layer 13 is not particularly limited, but is preferably from 10 μm to 250 μm, more preferably from 10 μm to 200 μm, even more preferably from 20 μm to 200 μm, and particularly preferably from 50 μm to 150 μm.

[0067] In the present disclosure, the "average thickness" of the glass protective layer 13 refers to the average value of thicknesses at three points arbitrarily selected from the glass protective layer 13. The thickness of the glass protective layer 13 can be measured using a known film thickness measuring device (for example, R1-205, PEACOCK (registered trademark), manufactured by Ozaki Manufacturing Co., Ltd.).

[0068] <<Manufacturing Method>> The manufacturing method of the laminate 50 is not particularly limited and can be appropriately selected depending on the purpose. For example, the laminate 50 can be manufactured by laminating the glass layer 12, the adhesive layer 11, the protective layer 10, and, as necessary, other layers. In the manufacturing method of the laminate 50, the order of lamination is not particularly limited. For example, the adhesive layer 11 and the protective layer 10 may be laminated in this order on the glass layer 12, or a laminate in which the adhesive layer 11 and the protective layer 10 have been laminated in advance may be laminated on the glass layer 12. The adhesive layer 11 and the protective layer 10 may be cured after each layer is laminated.

[0069] Examples of methods for forming the adhesive layer 11 and the protective layer 10 include a method in which a thermosetting resin or an active energy ray-curable resin is applied to the surface of an adjacent layer (for example, the adhesive layer 11 in the case of the protective layer 10, or the glass layer 12 or the protective layer 10 in the case of the adhesive layer 11), and then the layers are attached, and the thermosetting resin or the active energy ray-curable resin is then cured by heat treatment or ultraviolet irradiation. The irradiation conditions for ultraviolet light irradiation are not particularly limited, but it is preferable that the cumulative irradiation light amount is 100 mJ / cm. ２ ~2,000mJ / cm ２ The conditions for the heat treatment are not particularly limited, but it is preferable that the heating temperature is 100°C to 200°C and the heating time is 5 minutes to 30 minutes. After applying a thermosetting resin or an active energy ray curable resin to the surface of adjacent layers, the thermosetting resin or the active energy ray curable resin may be semi-cured before bonding the layers. The conditions for semi-curing are not particularly limited, but it is preferable that the heating temperature is 100°C to 200°C and the heating time is 5 minutes to 30 minutes. ２ ~1,000mJ / cm ２ This can be done by irradiating ultraviolet light.

[0070] The method for manufacturing the laminate roll 100 in which the laminate 50 is rolled is not particularly limited and can be appropriately selected depending on the purpose. For example, the laminate roll 100 can be manufactured by laminating the glass layer 12 formed in a long length, the adhesive layer 11, the protective layer 10, and other layers as necessary using a roll-to-roll method, and winding the laminate roll 100 around an appropriate core material 150.

[0071] (Substrate for imprinting) The substrate for imprinting according to the embodiment of the present disclosure includes the laminate according to the embodiment of the present disclosure. The substrate for imprinting according to the embodiment of the present disclosure may further include other members or layers as necessary.

[0072] 4 is a schematic cross-sectional view showing an example of an imprint substrate 200 according to a first embodiment. The imprint substrate 200 is formed by laminating a protective layer 10, an adhesive layer 11, and a glass layer 12 in this order.

[0073] The imprint substrate 200 has the same configuration as the laminate 50, except that it is a substrate used in an imprint method.

[0074] The imprint substrate 200 may be wound into a roll. The imprint substrate 200 wound into a roll has the same configuration as the laminate roll 100.

[0075] When the imprinting substrate 200 is used in an imprinting method, an imprinting composition, which is a molding material, is disposed on at least one of the surfaces of the glass layer 12 opposite to the surface on which the adhesive layer 11 is disposed and the protective layer 10 opposite to the surface on which the adhesive layer 11 is disposed. Specifically, the imprinting composition is disposed on at least one of the surfaces of the imprinting substrate 200 opposite to the surface on which the adhesive layer 11 is disposed of the glass layer 12 and the surface on which the adhesive layer 11 is disposed of the protective layer 10, and the imprinting composition is cured while being brought into contact with a desired mold, thereby producing an imprint laminate having the imprinting substrate 200 and an imprint layer to which the shape of the mold has been transferred.

[0076] When the imprinting composition is disposed on the surface of the glass layer 12 opposite to the surface on which the adhesive layer 11 is disposed, the adhesive layer 11 and the protective layer 10 can be peeled off by applying heat or active energy rays to the imprint laminate, thereby producing a laminate of the glass layer 12 and the imprint layer.

[0077] 5 is a schematic cross-sectional view showing a modification of the imprint substrate 200 according to the first embodiment. The imprint substrate 200 is formed by laminating a protective layer 10, an adhesive layer 11, a glass layer 12, and a glass protective layer 13 in this order.

[0078] The imprint substrate 200 according to the modified example of the first embodiment has the same configuration as the imprint substrate 200 according to the first embodiment, except that it has a glass protection layer 13 that protects the glass layer 12 as another layer.

[0079] The glass protective layer 13 has the same configuration as the glass protective layer 13 of the laminate 50 .

[0080] <<Manufacturing Method>> The manufacturing method of the imprint substrate 200 is not particularly limited and can be appropriately selected depending on the purpose. For example, the imprint substrate 200 can be manufactured by laminating a glass layer 12, an adhesive layer 11, a protective layer 10, and, as necessary, other layers. In the manufacturing method of the imprint substrate 200, the order of lamination is not particularly limited. For example, the adhesive layer 11 and the protective layer 10 may be laminated in this order on the glass layer 12, or a laminate in which the adhesive layer 11 and the protective layer 10 are previously laminated may be laminated on the glass layer 12. The adhesive layer 11 and the protective layer 10 may be cured after each layer is laminated.

[0081] The adhesive layer 11 and the protective layer 10 can be formed by the same method as the method for forming the adhesive layer 11 and the protective layer 10 in the laminate 50 .

[0082] Furthermore, when the substrate for imprinting 200 is wound into a roll, the substrate for imprinting 200 can be manufactured in the same manner as the laminate roll 100 .

[0083] (Replica Mold) A replica mold according to an embodiment of the present disclosure comprises a laminate according to an embodiment of the present disclosure, and a resin layer having concave and convex portions on at least one of the side of the glass layer of the laminate opposite to the side on which the adhesive layer is disposed and the side of the protective layer of the laminate opposite to the side on which the adhesive layer is disposed. The imprinting substrate according to an embodiment of the present disclosure may further include other members or layers as necessary.

[0084] 6 is a schematic cross-sectional view showing an example of a replica mold 300 according to an embodiment of the present disclosure. The replica mold 300 is formed by laminating a protective layer 10, an adhesive layer 11, a glass layer 12, and a resin layer 14 in this order.

[0085] The replica mold 300 has the same configuration as the laminate 50 except that it has a resin layer 14 .

[0086] <Resin Layer> The resin layer 14 is a layer that constitutes a mold that imparts a concave-convex shape to the molding material in the replica mold 300, and has convex portions 15 and concave portions 16. The concave portions 16 are surrounded by the convex portions 15, and the bottom surfaces of the concave portions are lower than the top surfaces of the convex portions. In Figure 6, the convex portions 15 and concave portions 16 are arranged at a constant pitch, but the arrangement of the convex portions 15 and concave portions 16 is not particularly limited and can be adjusted as appropriate depending on the desired shape.

[0087] The material constituting the resin layer 14 is not particularly limited, but can be appropriately selected from among those that are flexible and have the rigidity and hardness required for a mold, and examples thereof include thermoplastic resins and heat- or active energy ray-curable resins.

[0088] The thermoplastic resin is not particularly limited, and examples thereof include polyolefin-based resins, polystyrene-based resins, polyvinyl chloride resins, polyvinylidene chloride-based resins, polyacrylonitrile-based resins, polyamide-based resins, polyetherimides, polyamideimides, polyester-based resins, polycarbonate-based resins, polyacetal-based resins, vinyl acetate resins, polyvinyl acetal, thermoplastic polyurethane elastomers, acrylic-based resins, polyphenylene-based resins, fluororesins, polyvinyl alcohol, polyvinylpyrrolidone, cellulose derivatives, phenol-based resins, urea-based resins, melamine-based resins, furan-based resins, alkyd-based resins, unsaturated polyester-based resins, diallyl phthalate-based resins, epoxy-based resins, silicone-based resins, polyimide-based resins, polyurethane-based resins, and guanamine-based resins.

[0089] The thermosetting resin is not particularly limited, and examples thereof include phenolic resins, urea resins, melamine resins, furan resins, alkyd resins, unsaturated polyester resins, diallyl phthalate resins, epoxy resins, silicone resins, polyimide resins, polyurethane resins, and guanamine resins.

[0090] The active energy ray-curable resin is not particularly limited, and examples thereof include acrylic resins, silicone resins, and ester resins.

[0091] In addition to the above-mentioned resin material, the resin layer 14 may contain various additives such as a polymerization initiator, a coupling agent, a diluent, an antioxidant, a denaturant, a surfactant, a dye, a pigment, a discoloration inhibitor, an ultraviolet absorber, a softener, a stabilizer, a plasticizer, an antifoaming agent, a reinforcing agent, etc. The type, number, and amount of additives contained in the resin layer 14 are not particularly limited and can be selected appropriately depending on the purpose.

[0092] In the laminate 50, the resin layer 14 is preferably a single layer.

[0093] The thickness of the resin layer 14 is not particularly limited and can be appropriately selected depending on the shape of the desired molded product.

[0094] The shape of the replica mold 300 is not particularly limited, and examples thereof include a plate shape, an endless belt shape, a roll shape, and other endless shapes. Among these, endless shapes such as an endless belt shape and a roll shape are preferred because they have good continuous transportability and high productivity when used in an imprinting method.

[0095] <<Manufacturing Method>> The method for manufacturing the replica mold 300 is not particularly limited and can be appropriately selected depending on the purpose. For example, the replica mold 300 can be manufactured by laminating a long glass layer 12, an adhesive layer 11, a protective layer 10, a resin layer 14, and, as necessary, other layers. In the manufacturing method for the replica mold 300, the glass layer 12, the adhesive layer 11, and the protective layer 10 can be manufactured in the same manner as the manufacturing method for the laminate 50. Furthermore, the glass layer 12, the adhesive layer 11, and the protective layer 10 of the replica mold 300 may be manufactured using the laminate 50 of the present disclosure, or the imprinting substrate 200 of the present disclosure.

[0096] The method for forming the resin layer 14 is not particularly limited and can be appropriately selected depending on the purpose, but it can be suitably manufactured by the replica mold manufacturing method of the present disclosure described below.

[0097] (Method for manufacturing replica mold) A method for manufacturing a replica mold according to an embodiment of the present disclosure includes an application step of applying a resin composition between a master mold having an uneven portion and at least one of a surface of the glass layer of the laminate according to the present disclosure opposite to a surface on which the adhesive layer is disposed and a surface of the protective layer of the laminate according to the present disclosure opposite to a surface on which the adhesive layer is disposed, and a transfer step of transferring the shape of the uneven portion of the master mold to the resin composition. The method for manufacturing a replica mold according to an embodiment of the present disclosure may further include other steps such as a curing step and a demolding step, as necessary.

[0098] 7 is a flowchart illustrating an example of a method for manufacturing a replica mold according to an embodiment of the present disclosure. The method for manufacturing a replica mold according to an embodiment of the present disclosure includes an applying step (S1), a transferring step (S2), a curing step (S3), and a demolding step (S4).

[0099] <Application Step> The application step (S1) is a step of applying a resin composition between at least one of the surface of the glass layer 12 of the laminate 50 of the present disclosure opposite to the surface on which the adhesive layer 11 is disposed and the surface of the protective layer 10 of the laminate 50 of the present disclosure opposite to the surface on which the adhesive layer 11 is disposed, and a master mold having an uneven portion.

[0100] The master mold having the concave and convex portions is not particularly limited and can be appropriately selected from known master molds used in imprinting methods, and examples thereof include a master plate for bit-patterned media (BPM) having fine concave and convex portions.

[0101] The material of the master mold is not particularly limited and can be appropriately selected depending on the purpose. Examples include silicon, silicon oxide film, quartz glass, resin, and metal.

[0102] The uneven portion of the master mold may be formed by, for example, photolithography or electron beam lithography.

[0103] The pattern of the projections and recesses of the master mold is not particularly limited and can be appropriately selected from desired projections and recesses. The width or diameter and depth of the recesses and protrusions of the master mold are not particularly limited and can be appropriately selected depending on the purpose.

[0104] The resin composition used in the applying step (S1) is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include thermoplastic resins, heat- or active energy ray-curable resins, etc. When the imprinting method is a thermal imprinting method, a thermoplastic resin or a thermosetting resin is used, and when the imprinting method is a photoimprinting method, an active energy ray-curable resin is used. Specific examples of thermoplastic resins, thermosetting resins, and active energy ray-curable resins are as described above in the section (replica mold).

[0105] The method for applying the resin composition in the application step (S1) is not particularly limited, and examples thereof include die coating, roll coating, gravure coating, inkjet printing, spray coating, spin coating, flow coating, blade coating, and dip coating.

[0106] <Transfer Step> The transfer step (S2) is a step of transferring the shape of the concave and convex portions of the master mold to the resin composition.

[0107] When the resin composition is a thermoplastic resin, in the transfer step, a master mold having concave and convex portions is pressed against the resin composition in a softened state, thereby transferring a shape based on the concave and convex portions of the master mold, preferably a concave and convex pattern, to the resin composition, thereby forming a resin layer.

[0108] Furthermore, when the resin composition is an active energy ray-curable resin, the resin composition is cured in the next curing step (S3) while being pressed against a master mold having an uneven portion in an uncured state before being exposed to active energy rays, thereby forming a resin layer 14 in which the resin composition is cured.

[0109] <Curing Step> The curing step (S3) is a step of curing the resin composition. The resin composition is cured while being pressed against the master mold having the concave and convex portions, thereby forming a resin layer 14.

[0110] When the resin composition is an active energy ray-curable resin, the active energy ray used for curing is not particularly limited and can be appropriately selected depending on the type of resin composition, and examples thereof include ultraviolet rays, electron beams, α rays, β rays, γ rays, X-rays, etc. These may be used alone or in combination of two or more.

[0111] <Mold Releasing Step> The mold releasing step (S4) is a step of releasing the master mold having concave-convex portions from the resin layer 14 after the curing step (S3). This separates the resin layer 14 from the master mold having concave-convex portions, and it is possible to obtain the resin layer 14 to which the concave-convex pattern based on the concave-convex portions of the master mold having concave-convex portions has been transferred.

[0112] By the above method, the replica mold 300 of the present disclosure shown in FIG. 6 can be suitably manufactured.

[0113] (Imprinting method) An imprinting method according to an embodiment of the present disclosure includes: an applying step of applying a molding material between a mold having a concave-convex portion and at least one of a surface of the glass layer of the laminate of the present disclosure opposite to a surface on which the adhesive layer is disposed and a surface of the protective layer of the laminate of the present disclosure opposite to a surface on which the adhesive layer is disposed, and a transfer step of transferring the shape of the concave-convex portion of the mold to the molding material. The imprinting method according to an embodiment of the present disclosure may further include other steps such as a curing step and a demolding step, as necessary.

[0114] 8 is a flowchart showing an example of an imprinting method according to an embodiment of the present disclosure. The imprinting method according to the first embodiment includes an applying step (S11), a transferring step (S12), a curing step (S13), and a demolding step (S14).

[0115] The imprint method according to the first embodiment is suitably performed by the imprint apparatus according to an embodiment of the present disclosure.

[0116] <Application step> The application step (S11) is a step of applying a molding material between at least one of the surface of the glass layer 12 of the laminate 50 opposite to the surface on which the adhesive layer 11 is arranged and the surface of the protective layer 10 of the laminate 50 opposite to the surface on which the adhesive layer 11 is arranged, and a mold having an uneven portion.

[0117] The mold having the concave-convex portion is not particularly limited and can be appropriately selected from known master molds used in imprinting methods, such as a master disk for bit-patterned media (BPM) having fine concave and convex portions. Furthermore, a replica mold according to an embodiment of the present disclosure may be used as the mold having the concave-convex portion. The use of the replica mold according to an embodiment of the present disclosure is preferable because it is economical and does not easily shatter when the glass layer 12 of the laminate 50 is broken.

[0118] The molding material used in the applying step (S11) is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include thermoplastic resins, heat- or active energy ray-curable resins, etc. When the imprinting method is a thermal imprinting method, a thermoplastic resin or a thermosetting resin is used, and when the imprinting method is a photoimprinting method, an active energy ray-curable resin is used. Examples of the thermoplastic resin, thermosetting resin, and active energy ray-curable resin include the same resin compositions as those used in the applying step (S1) of the replica mold manufacturing method of the present disclosure.

[0119] The method for applying the molding material in the application step (S11) is not particularly limited, and examples thereof include die coating, roll coating, gravure coating, inkjet printing, spray coating, spin coating, flow coating, blade coating, and dip coating.

[0120] <Transfer Step> The transfer step (S12) is a step of transferring the shape of the concave and convex portions of the mold to the molding material.

[0121] When the molding material is a thermoplastic resin, in the transfer process, a mold having an uneven portion is pressed against the softened material, thereby transferring the shape based on the uneven portion of the mold, preferably the uneven pattern, to the molding material, thereby forming a molded body.

[0122] Furthermore, when the molding material is a curable resin, the molding material is cured in the next curing step (S13) by pressing a mold having an uneven portion against the uncured state before applying heat or active energy rays, thereby forming a molded body in which the molding material is cured.

[0123] <Curing Step> The curing step (S13) is a step of curing the molding material. The molding material is pressed against a mold having projections and recesses and cured to form a molded body.

[0124] When the molding material is an active energy ray-curable resin, the active energy ray used for curing is not particularly limited and can be appropriately selected depending on the type of resin composition, and examples thereof include ultraviolet rays, electron beams, α rays, β rays, γ rays, X-rays, etc. These may be used alone or in combination of two or more.

[0125] <Mold Release Step> The mold release step (S14) is a step of releasing the mold having the concave-convex portions from the molded product after the curing step (S13). This separates the molded product from the mold having the concave-convex portions, and a molded product having a concave-convex pattern transferred thereto based on the concave-convex portions of the mold having the concave-convex portions can be obtained.

[0126] (Imprinting Apparatus) An imprinting apparatus according to an embodiment of the present disclosure includes a laminate according to the present disclosure, an application unit that applies a molding material to at least one of a surface of the glass layer of the laminate opposite to a surface on which the adhesive layer is disposed and a surface of the protective layer of the laminate opposite to a surface on which the adhesive layer is disposed, a mold having an uneven portion that molds the molding material, a curing unit that hardens the molding material, and a take-up roll that winds up a molded body having the laminate and a cured product of the molding material. The imprinting apparatus according to an embodiment of the present disclosure may further include other components as necessary.

[0127] First Embodiment Fig. 9A is a schematic diagram showing an example of an imprinting apparatus according to an embodiment of the present disclosure. Fig. 9B is a schematic diagram showing another example of an imprinting apparatus according to an embodiment of the present disclosure. An imprinting apparatus 400 according to the first embodiment includes a laminate roll 100 having a laminate 50, an application unit 402, a mold 300A, a curing unit 403, a take-up roll 404, a laminate transport roller 406, and a mold transport roller 407. The imprinting apparatus 400 is a roll-to-roll imprinting apparatus.

[0128] <Laminate Roll 100 and Laminate 50> The laminate 50 is transported from the laminate roll 100 in the direction of the take-up roll 404. The laminate roll 100, the laminate transport roller 406, and the take-up roll 404 rotate in the same direction (the direction of the arrows), thereby transporting the laminate 50.

[0129] <Applying Unit> The applying unit 402 is a member that applies the molding material 405 onto the laminate 50. The molding material 405 applied onto the laminate 50 is transported together with the laminate 50.

[0130] Examples of the application unit 402 include a die coater, a roll coater, a gravure coater, a spray coater, a spin coater, a flow coater, a blade coater, an inkjet printer, and a screen printer.

[0131] The molding material 405 is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include thermoplastic resins, and heat- or active energy ray-curable resins.

[0132] <Mold> The mold 300A is a member that molds the molding material 405. In the imprint apparatus 400 according to the first embodiment, the mold 300A is in the form of an endless belt, and is operated by the rotation of the mold transport rollers 407. That is, when the mold transport rollers 407 rotate in the direction of the arrow, the endless belt-shaped mold 300A operates in the same direction as the rotation direction of the mold transport rollers 407.

[0133] In Figure 9, the number of mold transport rollers 407 is four, but this is not limited to this and can be selected appropriately depending on the configuration of the imprinting apparatus 400, and may be two, three, five or more.

[0134] The mold 300A can be appropriately selected from known molds used in imprinting methods. It may also be a replica mold according to an embodiment of the present disclosure. The replica mold according to the present disclosure is preferable because it is economical and does not easily shatter when the glass layer 12 of the laminate 50 is broken.

[0135] The stack 50 and the mold 300A are operated simultaneously, so that the molding material 405 on the stack 50 is transported between the stack 50 and the mold 300A.

[0136] <Curing section> The curing section 403 is a member that cures the molding material 405. Examples of the curing section 403 include a heater such as a heater; and a light source that irradiates active energy rays such as ultraviolet light, visible light, and infrared light. The curing section 403 can be appropriately selected depending on the type of molding material 405. When the molding material 405 is a thermoplastic resin or a thermosetting resin, a heater is preferred. When the molding material 405 is an active energy ray-curable resin, a light source is preferred.

[0137] Examples of light sources for irradiating active energy rays include ultraviolet fluorescent lamps, ultraviolet LEDs, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, carbon arc lamps, etc. When the active energy rays are visible light, examples of the light source include visible light fluorescent lamps, visible light incandescent lamps, visible LEDs, etc.

[0138] In the embodiment shown in Fig. 9A, when the curing unit 403 is a heater, the molding material 405 is heated and cured via the laminate 50. In the embodiment shown in Fig. 9B, when the curing unit 403 is a heater, the molding material 405 is heated and cured via the mold 300A.

[0139] In the embodiment shown in Fig. 9A, when the curing section 403 is a light source, the molding material 405 is irradiated with active energy rays through the laminate 50 and cured. In the embodiment shown in Fig. 9B, when the curing section 403 is a light source, the molding material 405 is irradiated with active energy rays through the mold 300A and cured.

[0140] <Winding Roll> The winding roll 404 is a member that winds up the molded body 500 having the laminate 50 and the resin layer 20 formed by curing the molding material 405. The winding roll 404 rotates in the same direction as the laminate roll 100.

[0141] 11A and 11B are enlarged views of region X in FIGS. 9A and 9B. Fig. 11A is a schematic cross-sectional view showing an example of a molded body 500, and is a schematic cross-sectional view showing an example of a molded body 500 in which a resin layer 20 having a concave-convex pattern made of a cured product of a molding material is formed on the surface opposite to the surface on which the adhesive layer 11 of the glass layer 12 of the laminate 50 is disposed. Fig. 11B is a schematic cross-sectional view showing another example of a molded body 500, and is a schematic cross-sectional view showing an example of a molded body 500 in which a resin layer 20 having a concave-convex pattern made of a cured product of a molding material is formed on the surface opposite to the surface on which the adhesive layer 11 of the protective layer 10 of the laminate 50 is disposed.

[0142] By using the above-described imprinting apparatus 400, a molded body 500 is obtained having a resin layer 20 with an uneven pattern made of a cured product of a molding material on one side of a laminate 50 made of a protective layer 10, an adhesive layer 11, and a glass layer 12.

[0143] 10 is a schematic diagram showing a modification of the imprinting apparatus according to the first embodiment. The imprinting apparatus 400A according to the modification of the first embodiment has the same configuration as the imprinting apparatus 400 according to the first embodiment, except that it has a roll-shaped mold 300B instead of the endless belt-shaped mold 300A in the imprinting apparatus 400 according to the first embodiment.

[0144] The roll-shaped mold 300B is a member that molds the molding material 405. The roll-shaped mold 300B moves in the direction of the arrow by rotating itself.

[0145] The mold 300B can be appropriately selected from known molds used in imprinting methods. It may also be a replica mold according to an embodiment of the present disclosure. When the mold 300B is a replica mold according to an embodiment of the present disclosure, it is preferable in that it is economical and does not easily shatter when the glass layer 12 of the laminate 50 is broken.

[0146] The stack 50 and the mold 300B are simultaneously operated, so that the molding material 405 on the stack 50 is transported between the stack 50 and the mold 300B.

[0147] The molded body 500 obtained by the imprint apparatus 400A according to the modified example of the first embodiment is similar to the molded body 500 obtained by the imprint apparatus 400 according to the first embodiment. Therefore, Figures 11A and 11B are also enlarged views of region X in Figure 10.

[0148] 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.

[0149] Example 1 An epoxy adhesive having a post-curing modulus of elasticity of 5.0 GPa was applied to the entire surface of one surface of a glass sheet (G-Leaf (registered trademark), manufactured by Nippon Electric Glass Co., Ltd.) measuring an average thickness of 50 μm, a length of 300 cm, and a width of 200 cm to form the glass layer 12, so that the post-curing average thickness would be 3 μm. Next, a polyester film (modulus of elasticity: 3.0 GPa, Cosmoshine (registered trademark) A4360, manufactured by Toyobo Co., Ltd.) measuring an average thickness of 100 μm, a length of 300 cm, and a width of 200 cm was laminated on the adhesive-coated surface to form the protective layer 10. Next, ultraviolet light (wavelength: 365 nm, intensity: 300 mJ / cm) was applied from a high-pressure mercury lamp. ２ The adhesive was cured by irradiating the adhesive with the above-mentioned radiation from the glass layer 12 side, thereby forming an adhesive layer 11. In this way, a laminate 50 having the cross-sectional structure shown in FIG. 1 and including the glass layer 12, the adhesive layer 11, and the protective layer 10 laminated in this order was produced.

[0150] Example 2 A laminate 50 was produced in the same manner as in Example 1, except that the glass layer 12 (G-Leaf (registered trademark), manufactured by Nippon Electric Glass Co., Ltd.) having an average thickness of 50 μm, a length of 300 cm, and a width of 200 cm was used instead of glass (G-Leaf (registered trademark), manufactured by Nippon Electric Glass Co., Ltd.) having an average thickness of 100 μm, a length of 300 cm, and a width of 200 cm.

[0151] Example 3 A laminate 50 was produced in the same manner as in Example 1, except that the glass layer 12 (G-Leaf (registered trademark), manufactured by Nippon Electric Glass Co., Ltd.) having an average thickness of 50 μm, a length of 300 cm, and a width of 200 cm was used instead of the glass layer 12 (G-Leaf (registered trademark), manufactured by Nippon Electric Glass Co., Ltd.) having an average thickness of 200 μm, a length of 300 cm, and a width of 200 cm.

[0152] Example 4 A laminate 50 was produced in the same manner as in Example 1, except that the glass layer 12 (G-Leaf (registered trademark), manufactured by Nippon Electric Glass Co., Ltd.) having an average thickness of 50 μm, a length of 300 cm, and a width of 200 cm was used instead of glass (G-Leaf (registered trademark), manufactured by Nippon Electric Glass Co., Ltd.) having an average thickness of 300 μm, a length of 300 cm, and a width of 200 cm.

[0153] Comparative Example 1 A glass sheet of Comparative Example 1 was made of only a glass layer 12 of glass (G-Leaf (registered trademark), manufactured by Nippon Electric Glass Co., Ltd.) having an average thickness of 100 μm, a length of 300 cm and a width of 200 cm.

[0154] Comparative Example 2 A laminate was produced in the same manner as in Example 2, except that an acrylic adhesive (CS9861UAS, manufactured by Nitto Denko Corporation) having a modulus of elasticity after curing of 0.4 GPa was applied so as to give an average thickness after curing of 25 μm, instead of an epoxy adhesive having a modulus of elasticity after curing of 5 GPa applied so as to give an average thickness after curing of 3 μm.

[0155] Comparative Example 3 A laminate was produced in the same manner as in Example 1, except that the polyester film (elastic modulus: 3.0 GPa, COSMOSHINE (registered trademark) A4360, manufactured by Toyobo Co., Ltd.) used as the protective layer 10 was changed to a polypropylene film (elastic modulus: 0.6 GPa, TORAYFAN (registered trademark) NO ZK207, manufactured by Toray Industries, Inc.) having an average thickness of 100 μm, a length of 300 cm, and a width of 200 cm.

[0156] <<Presence or absence of shatter and secondary damage>> Each of the laminates produced in Examples 1 to 4 and Comparative Examples 2 and 3 and the glass sheet of Comparative Example 1 was intentionally broken by the following method to evaluate the "presence or absence of shatter and secondary damage."

[0157] Specifically, each of the laminates produced in Examples 1 to 4 and Comparative Examples 2 to 3 and the glass sheet of Comparative Example 1 was wound around a roll having a diameter of 20 mm with the glass layer facing outward, thereby damaging the glass layer of each of the laminates produced in Examples 1 to 4 and Comparative Examples 2 to 3 or the glass layer of Comparative Example 1. The presence or absence of damage to the glass layer, the presence or absence of shattered glass layers, and the presence or absence of further damage to the glass layer due to the shattered glass layers (referred to as "secondary damage") were confirmed, and evaluated based on the following evaluation criteria. The results are shown in Table 1 below. -Evaluation criteria- A: The glass layer was damaged but not shattered, and there was no secondary damage. B: The glass layer was damaged, not shattered, and there was no secondary damage, but the laminate was stretched. C: The glass layer was damaged and shattered, and there was secondary damage.

[0158]

[0159] In the laminates 50 of Examples 1 to 4, in which the modulus of elasticity of the protective layer 10 at 25°C was 1.5 GPa or more and 10 GPa or less and the modulus of elasticity of the adhesive layer 11 at 25°C was 1 GPa or more and 10 GPa or less, none of the laminates 50 shattered when the glass layer 12 was broken, and no secondary damage occurred. In Comparative Example 2, because the modulus of elasticity of the adhesive layer was less than 1 GPa, shattering could not be suppressed when the glass layer 12 was broken, and secondary damage occurred. The shattering of the glass layer 12 and secondary damage can also lead to damage and malfunction of the imprinting device if it is transported through the imprinting device. In Comparative Example 3, because the modulus of elasticity of the protective layer 10 was less than 1.5 GPa, the laminate stretched when the glass layer 12 was broken, which further damaged the glass layer 12.

[0160] Examples of aspects of the present invention include the following. <1> A laminate comprising a protective layer, a glass layer, and an adhesive layer bonding the protective layer and the glass layer, wherein the protective layer has a modulus of elasticity at 25°C of 1.5 GPa to 10 GPa, and the adhesive layer has a modulus of elasticity at 25°C of 1 GPa to 10 GPa. <2> The laminate according to <1>, wherein the glass layer has an average thickness of 10 μm to 200 μm. <3> The laminate according to <1> or <2>, which is wound into a roll. <4> A substrate for imprinting, comprising the laminate according to any one of <1> to <3>. <5> A replica mold, comprising the laminate according to any one of <1> to <3>, and comprising a resin layer having an uneven portion on at least one of a side of the glass layer opposite to a side on which the adhesive layer is disposed and a side of the protective layer opposite to a side on which the adhesive layer is disposed. <6> A method for manufacturing a replica mold, comprising: an applying step of applying a resin composition between at least one of a surface of the glass layer of the laminate described in any one of <1> to <3> opposite to a surface on which the adhesive layer is disposed and a surface of the protective layer of the laminate opposite to a surface on which the adhesive layer is disposed and a master mold having a concave-convex portion, and a transferring step of transferring a shape of the concave-convex portion of the master mold to the resin composition. <7> An imprinting apparatus, comprising: the laminate described in any one of <1> to <3>; an applying unit that applies a molding material to at least one of a surface of the glass layer of the laminate opposite to a surface on which the adhesive layer is disposed and a surface of the protective layer of the laminate opposite to a surface on which the adhesive layer is disposed, a mold having a concave-convex portion that molds the molding material, a curing unit that hardens the molding material, and a take-up roll that winds up a molded body having the laminate and a cured product of the molding material. <8> The imprinting apparatus according to <7>, wherein the mold having the concave-convex portion is the replica mold according to <5>.<9> An imprinting method comprising: an applying step of applying a molding material between a mold having a concave-convex portion and at least one of a surface of the glass layer of the laminate according to any one of <1> to <3> opposite to a surface on which the adhesive layer is disposed and a surface of the protective layer of the laminate opposite to a surface on which the adhesive layer is disposed, and a transfer step of transferring a shape of the concave-convex portion of the mold to the molding material. <10> The imprinting method according to <9>, wherein the mold is the replica mold according to <5>.

[0161] 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.

[0162] The laminate according to an embodiment of the present invention and the imprinting substrate according to an embodiment of the present invention are resistant to shattering when the glass layer is broken, making them suitable for use as substrates for nanoimprinting and applicable to various fields such as biomedicine, micro- and nanofluidics, data storage, electronics, and microelectromechanical devices. Furthermore, the replica mold according to an embodiment of the present invention is resistant to shattering when the glass layer is broken and is economical, making it suitable for use as a mold for nanoimprinting. The imprinting apparatus according to an embodiment of the present invention is capable of continuous transport, has high productivity, and is resistant to shattering when the glass layer of the laminate is broken, making it suitable for use as a mold for nanoimprinting.

[0163] This international application claims priority based on Japanese Patent Application No. 2024-049868, filed on March 26, 2024, the entire contents of which are incorporated herein by reference.

[0164] 10: Protective layer 11: Adhesive layer 12: Glass layer 13: Glass protective layer 14: Resin layer 20: Resin layer 50: Laminate 100: Laminate roll 100a: Inner surface 100b: Outer surface 150: Core material 200: Imprinting substrate 300: Replica mold 300A: Mold 300B: Mold 400: Imprinting device 400A: Imprinting device 402: Application section 403: Curing section 404: Take-up roll 405: Molding material 406: Laminate transport roller 407: Mold transport roller 500: Molded body S1, S11: Application step S2, S12: Transfer process S3, S13: Curing process S4, S14: Mold release process

Claims

1. A laminate comprising a protective layer, a glass layer, and an adhesive layer that bonds the protective layer and the glass layer, wherein the modulus of elasticity of the protective layer at 25°C is 1.5 GPa or more and 10 GPa or less, and the modulus of elasticity of the adhesive layer at 25°C is 1 GPa or more and 10 GPa or less.

2. The laminate according to claim 1, wherein the average thickness of the glass layer is 10 μm or more and 200 μm or less.

3. The laminate according to claim 1 or 2, which is wound into a roll.

4. An imprint substrate comprising the laminate according to any one of claims 1 to 3.

5. A replica mold comprising: a laminate according to any one of claims 1 to 3; and a resin layer having irregularities on at least one of the side of the glass layer of the laminate opposite to the side on which the adhesive layer is disposed, and the side of the protective layer of the laminate opposite to the side on which the adhesive layer is disposed.

6. A method for manufacturing a replica mold, comprising: an application step of applying a resin composition between at least one of the surface of the glass layer of the laminate described in any one of claims 1 to 3 opposite to the surface on which the adhesive layer is disposed and the surface of the protective layer of the laminate opposite to the surface on which the adhesive layer is disposed, and a master mold having a concave-convex portion; and a transfer step of transferring the shape of the concave-convex portion of the master mold to the resin composition.

7. An imprinting device comprising: a laminate according to any one of claims 1 to 3; an application unit that applies a molding material onto at least one of the surface of the laminate opposite to the surface on which the adhesive layer of the glass layer is disposed and the surface of the laminate opposite to the surface on which the adhesive layer of the protective layer is disposed; a mold having an uneven portion that forms the molding material; a hardening unit that hardens the molding material; and a winding roll that winds up a molded body comprising the laminate and the hardened product of the molding material.

8. The imprinting apparatus according to claim 7, wherein the mold having the concave and convex portions is the replica mold according to claim 5.

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