Laminate, device using same, and method for manufacturing laminate

Abstract

The present invention provides a laminate that can be easily arranged along a three-dimensional curved surface without wrinkles. A laminate according to one embodiment of the present invention comprises: a base material layer formed of a thermoplastic elastomer-containing material; and resin layers discretely provided on the base material layer. The elastic modulus of the resin layers is 50 times or more the elastic modulus of the base material layer.

Description

Laminate, device using the same, and method for manufacturing the laminate.

[0001] The present invention relates to a laminate, a device using the same, and a method for manufacturing a laminate.

[0002] In recent years, there has been a growing demand for sheets with multiple devices mounted at intervals, possessing both flexibility and stretchability. Such sheets are envisioned for use on curved surfaces, such as the human body. They are also intended for use on complex curved surfaces, such as spheres, that cannot be formed from a flat surface without stretching, ensuring wrinkle-free application. Furthermore, they are intended for use in electronic devices with foldable sections or those that can be rolled up.

[0003] Patent Document 1 discloses a circuit board device in which multiple electronic components are provided on a stretchable circuit board. As a method for manufacturing a stretchable circuit board, Patent Document 1 describes etching copper foil on a copper-plated polyimide substrate to form a meander pattern, and then using laser processing to cut out the polyimide portion so that the polyimide width is 250 μm around the wiring, thereby obtaining a stretchable circuit board (Paragraph

[0136] of Patent Document 1, Figure 19).

[0004] Patent Document 2 discloses that a curable resin sheet is obtained by using a styrene-based elastomer, a polymerizable monomer, and a polymerization initiator, and that this is used as a flexible substrate for electrical circuits. It also discloses that by forming an electrical circuit on this flexible substrate, a circuit board device can be obtained in which multiple electronic components are provided on a stretchable circuit board.

[0005] Patent Document 3 discloses a circuit board device in which a sheet with a periodic perforation structure is used as the substrate, and a plurality of electronic components are provided on a stretchable circuit board.

[0006] Patent Document 4 discloses a circuit board device in which a sheet with a convex structure on its surface is used as a substrate, and a plurality of electronic components are provided on a stretchable circuit board.

[0007] Japanese Patent Publication No. 2018-116959, Japanese Patent Publication No. 2017-188546, U.S. Patent Application Publication No. 2010 / 0330338, U.S. Patent Application Publication No. 2014 / 0218872

[0008] In the circuit board manufacturing method described in Patent Document 1, it is necessary to laser-process the polyimide substrate to conform to the meander pattern of the wiring, which results in low productivity. In particular, when the wiring pattern has a narrow pitch, a high degree of precision is required for laser processing, making it unsuitable for mass production. Furthermore, although polyimide substrates are flexible, they are not stretchable, so if the polyimide substrate is not laser-processed, it becomes impossible to give the circuit board stretchability. In addition, when using a circuit board that is attached without wrinkles to a complex curved surface that cannot be formed from a flat surface without stretching, such as a sphere, it is necessary for it to deform and be fixed in roughly that shape once attached to the curved surface.

[0009] Furthermore, when actually manufacturing a laminated film for a device, the resin film and the temporarily fixed substrate have a weak adhesive force once they are temporarily fixed. However, when a base layer mainly composed of thermoplastic elastomer is bonded to this, the resin layer and the base layer adhere, but the base layer and the temporarily fixed substrate adhere only very weakly.

[0010] In the curable sheet described in Patent Document 2, due to its polymeric properties, once the sheet has hardened, when it is deformed to follow a curved surface, a force is constantly applied to return it to its original shape.

[0011] The expandable circuit board described in Patent Document 3 involves localized deformation, which applies localized stress to the circuit. Furthermore, the complex and large processing requirements make it unsuitable for mass production.

[0012] In the application of the expandable substrate described in Patent Document 4 to a curved surface, the shape of the convex structure changes depending on the curvature, causing wrinkles to form. Therefore, it is expected that there will be differences in appearance in areas with different curvatures.

[0013] This invention has been made in view of the above-mentioned problems, and aims to provide a laminate that can be easily arranged wrinkle-free along a three-dimensional curved surface, a device using the same, and a method for manufacturing the laminate.

[0014] In other words, the present invention may include the following embodiments: [1] A laminate comprising a base layer made of a material containing a thermoplastic elastomer and a resin layer discretely provided on the base layer, wherein the elastic modulus of the resin layer is 50 times or more the elastic modulus of the base layer. [2] The laminate according to [1], wherein the area of ​​the base layer is 0.5 times or more the area of ​​the resin layer. [3] The laminate according to [1] or [2], wherein the resin layer comprises any of polyimide, polyamideimide, polyethylene terephthalate, or polyethylene naphthalate, and the total amount of polyimide, polyamideimide, polyethylene terephthalate, and polyethylene naphthalate is 50% by mass or more. [4] The laminate according to any one of [1] to [3], wherein the base layer comprises any of polyester elastomer, polyurethane elastomer, or polyamide elastomer, and the total amount of polyester elastomer, polyurethane elastomer, and polyamide elastomer is 50% by mass or more. [5] A device comprising the laminate according to any one of [1] to [4], wherein the resin layer is provided with at least one of a light-emitting element, a photoelectric conversion layer, and a sensor element. [6] A method for manufacturing the laminate according to any one of [1] to [5], comprising fixing a resin layer on a temporary fixing substrate, machining the resin layer to produce the discretely provided resin layers, and attaching the substrate layer to the discretely provided resin layers. [7] The method for manufacturing the laminate according to [6], wherein the temporary fixing substrate is glass, a silicon wafer, a protective film, or a release film.

[0015] Furthermore, the present invention may include the following embodiments: [8] A method for manufacturing a laminate according to [6] or [7], wherein fixing the resin layer on the temporary fixing substrate comprises forming a silane coupling agent layer on the temporary fixing substrate and attaching the resin layer to the silane coupling agent layer. [9] Attaching the base layer to the discretely provided resin layers comprises, before attaching the base layer, the portion of the silane coupling agent layer exposed by machining of the resin layer is SiO ２ or Si-(CH３ ) ３ A method for producing a laminate according to [8], which includes converting it.

[0016]

[10] The laminate according to any one of [1] to [4], further comprising a device provided on each of the discretely provided resin layers and an expandable wiring pattern that electrically connects the devices.

[11] The laminate according to

[10] , wherein the wiring pattern is a bellows-type metal wiring or an expandable metal paste wiring.

[0017] The laminate according to the present invention has a configuration in which resin layers having an elastic modulus 50 times or more than the elastic modulus of the base layer are discretely provided on a base layer. This makes it easy to stretch and contract the portion of the base layer where the resin layers are not provided, and to arrange the laminate along a three-dimensional curved surface without wrinkles. By using a thermoplastic elastomer for the base layer, it is possible to roughly deform it into the required curved shape by stretching and contracting it even at room temperature, thus providing a wide range of processing options, and it is also easy to roughly deform it into this shape by heating. Furthermore, according to the present invention, it is possible to provide a method for manufacturing a device assembly that can be mass-produced. For example, by providing a device on each of the discretely provided resin layers and connecting the devices with an expandable wiring pattern, it is possible to provide a device assembly that does not hinder the expandability of the portion of the base layer where the resin layers are not provided, and does not stretch or contract the portion where the devices are mounted. Furthermore, if the base layer and / or resin layers are made transparent, the laminate may also be advantageous in terms of photoelectric conversion efficiency when used as a photoelectric conversion element.

[0018] If the above device is a photoelectric conversion element, a curved photoelectric conversion element can be provided by imbuing various curved surfaces with shapes. For example, by excluding the solar cell in the portion with a small radius of curvature, it can conform to various curved surfaces while still functioning as a solar cell. If it is a sensor element, for example, it can be attached to a surface with a changing shape (e.g., skin) to measure biological information. Furthermore, if the above device is a light-emitting element, it can be made into a stretchable display, or a curved display can be provided.

[0019] Furthermore, when a resin layer containing a thermosetting resin is used, a laminate can be formed without an adhesive layer in between, resulting in a highly reliable structure. Moreover, by using the above manufacturing method, even fine patterns can be created without misalignment, and discrete resin layer films can be mechanically aligned using a robotic hand or similar method, or fabricated using a semiconductor-like patterning process without using a photosensitive process with a resist. Therefore, the manufacturing of device clusters is easy, and it is possible to achieve both miniaturization and mass production.

[0020] This is a one-dimensional model of a bond between a resin film and a base film. This is the sample shape when peeled at 90 degrees. This is a schematic cross-sectional view of a resin film attached to a base film. This is a schematic cross-sectional view of a support substrate attached to the side of the base film where the resin film is not bonded. This is a schematic cross-sectional view of a protective film attached around the resin film. This is a schematic cross-sectional view of a photoelectric conversion element placed on a resin film. This is a schematic cross-sectional view of a photoelectric conversion element covered with a sealing adhesive layer and a barrier layer film placed on top. This is a schematic cross-sectional view of a protective film placed on a barrier layer film. This is a schematic cross-sectional view of two electrodes on a PEN film electrically separated by attaching masking tape to the protective film. This is a schematic cross-sectional view of a third electrode layer coated by spin coating. This is a schematic cross-sectional view of a photoelectric conversion element with the protective film and masking tape removed. This is a schematic cross-sectional view of an elastomer film with a protective film attached to the side where the polyimide film is not bonded. This is a schematic cross-sectional view of a protective film laminated to the bonded side of the polyimide film. This is a schematic cross-sectional view after depositing a Cu layer on the polyimide film surface. This is a schematic cross-sectional view after peeling off the protective film on the polyimide film side. This is a schematic cross-sectional view with an LED element placed on the first electrode layer. This is a schematic cross-sectional view with mounting resin applied to the polyimide film so as to cover the first electrode layer and the resin film. This is a schematic cross-sectional view with masking tape applied to electrically separate the two electrodes on the polyimide film. This is a schematic cross-sectional view with nanosilver wire applied by spin coating. This is a schematic cross-sectional view with the protective film and masking tape removed from the LED element. This is a schematic diagram of the bond between the resin film and the substrate film of the embodiment. This is a schematic diagram of the bond between the resin film and the substrate film of Comparative Example 4. This is a schematic diagram of the bond between the resin film and the substrate film of Comparative Example 5. This is an example of a photoelectric conversion element according to the embodiment. This is a diagram showing an exemplary configuration of a display according to the embodiment.

[0021] The present invention will be described in more detail below based on the embodiments described below. However, the present invention is not limited by the embodiments described below, and it is certainly possible to implement it with appropriate modifications within the scope that is consistent with the spirit of the preceding and following descriptions, and all such modifications are included within the technical scope of the present invention. In some cases, hatching and component reference numerals may be omitted in the drawings for convenience, in which case the specification or other drawings should be referred to. Also, the dimensions of various components in the drawings may differ from the actual dimensions, as priority has been given to helping to understand the features of the present invention.

[0022] For ease of reference, examples are shown in the drawings and the notations "above" and "below" are used in this specification, but this embodiment is not necessarily limited thereto. For example, objects and methods that can be realized by the ideas disclosed herein even when the orientation is changed, such as by reversing upside down, are within the scope of disclosure of this embodiment. In this specification, the expressions "containing" and "including" include the concepts of "containing," "including," "substantially consisting of," and "consisting only of." In this specification, "A and / or B" means "either A or B" or "both A and B," and specifically means "A," "B," or "A and B."

[0023] In this specification, the relationship between two components A and B may be described as follows: component B is provided on component A, component B is provided on the upper surface of component A, or component B is in contact with component A. Such descriptions are intended to allow not only cases where component A and component B are in direct contact, but also cases where other components are interposed between them to an extent that does not impede the effect.

[0024] With respect to numerical ranges described stepwise in this specification, the upper or lower limit of a numerical range in one step may be arbitrarily combined with the upper or lower limit of a numerical range in another step. With respect to numerical ranges described in this specification, the upper or lower limit of a numerical range may be replaced with values ​​shown in the examples or values ​​that can be uniquely derived from the examples. In this specification, a numerical range enclosed by "~" means a numerical range that includes the numbers before and after "~" as the lower and upper limits.

[0025] The laminate according to this embodiment (hereinafter also referred to as a laminated film) includes a base layer made of a material containing a thermoplastic elastomer and resin layers discretely provided on the base layer. For example, as shown in Figure 1, a film is provided in which discrete resin layers (hereinafter also referred to as resin films) are bonded to a part of a base layer (hereinafter also referred to as a base film or elastomer film) made of a material containing a thermoplastic elastomer without an adhesive layer. However, they may also be bonded via an adhesive layer.

[0026] <Base Layer> The base layer 32 has elasticity when completed as a device assembly. The base layer 32 is often made of a thermoplastic material, but is not particularly limited. The base layer 32 does not need to have elasticity before being completed as a device assembly.

[0027] The base layer 32 is preferably composed of a material containing a thermoplastic elastomer. The entire base layer 32 may be composed solely of a thermoplastic elastomer, or a thermoplastic elastomer may be used as one of the materials constituting the base layer 32. The base layer 32 may be composed of a mixture of a thermoplastic elastomer and other materials. Examples of other materials include UV absorbers and antioxidants.

[0028] The base layer 32 preferably contains 50% by mass or more of thermoplastic elastomer, more preferably 70% by mass or more, and even more preferably 90% by mass or more. The base layer 32 may contain 100% by mass or less of thermoplastic elastomer, or 95% by mass or less.

[0029] Examples of materials for the base layer 32 include thermoplastic urethane elastomer, thermoplastic olefin elastomer, thermoplastic polyester elastomer, thermoplastic polyamide elastomer, thermoplastic styrene elastomer, and thermoplastic vinyl chloride elastomer.

[0030] The base layer 32 preferably contains at least one selected from the group consisting of polyester elastomer, polyurethane elastomer, and polyamide elastomer, and more preferably contains at least one selected from the group consisting of thermoplastic polyester elastomer, thermoplastic polyurethane elastomer, and thermoplastic polyamide elastomer. The base layer 32 contains any of polyester elastomer, polyurethane elastomer, or polyamide elastomer, and it is more preferable that the total amount of polyester elastomer, polyurethane elastomer, and polyamide elastomer in the base layer 32 (100% by mass) is 50% or more, even more preferable that it is 70% or more, and particularly preferable that it is 90% or more. The base layer 32 may contain 100% or less by mass of any of polyester elastomer, polyurethane elastomer, or polyamide elastomer, or 95% or less by mass.

[0031] The elastic modulus of the base layer 32 is preferably 3.0 MPa or more and 100 MPa or less, more preferably 5.0 MPa or more and 80 MPa or less, and even more preferably 30 MPa or more and 70 MPa or less. Herein, the elastic modulus referred to herein is that which is calculated by the measurement method described in the examples.

[0032] The thickness of the base layer 32 is preferably 50 μm to 200 μm, more preferably 80 μm to 150 μm, and even more preferably 100 μm to 120 μm. This configuration makes it easier to suppress the decrease in transparency and whitening that occurs when crystallization progresses inside the base layer 32 due to cooling or other factors during manufacturing, as the thickness of the base layer 32 is the cause.

[0033] The melting point of the thermoplastic elastomer is preferably 120°C or higher, more preferably 130°C or higher, and even more preferably 140°C or higher. This makes it easier to provide heat resistance to general annealing temperatures when annealing films such as the first electrode layer 12 and the photoelectric conversion layer, which will be described later. The melting point of the thermoplastic elastomer is preferably 210°C or lower, more preferably 200°C or lower, and even more preferably 190°C or lower. This makes it easier to suppress the decrease in stretchability and the decrease in transparency of the film that occurs when crystallinity increases in response to a high melting point.

[0034] The average transmittance of light with wavelengths of 400 nm to 700 nm through the substrate layer 32 is preferably 70% to 99%, more preferably 80% to 95%, and even more preferably 85% to 90%. This configuration makes it possible to create a substrate layer 32 that easily transmits light. For example, by using such a substrate layer in a photoelectric conversion element, it becomes less likely to obstruct the transmission of light to the photoelectric conversion layer. Furthermore, transparency is also easily improved, making it possible to apply it to locations where visibility is required.

[0035] <Temporary Fixing Substrate> The temporary fixing substrate serves as a support when bonding the base film onto the discrete resin layer 14. The temporary fixing substrate is peeled off from the resin layer 14 at some stage before the device assembly is completed.

[0036] As a temporary fixing substrate, any plate-shaped material that can be used as a substrate made of a protective film or inorganic material that does not deform easily will suffice.

[0037] As the material of the substrate of the protective film with little deformation, there are polyolefin resins such as polyethylene and polypropylene; polyamide resins such as nylon 6 and nylon 66; polyester resins such as polyethylene terephthalate, polyethylene naphthalate, polytrimethylene terephthalate, polybutylene terephthalate (PBT), polyethylene-2,6-naphthalate (PEN), and polytrimethylene terephthalate; and copolyester resins obtained by copolymerizing diol components such as diethylene glycol, neopentyl glycol, and polyalkylene glycol, and dicarboxylic acid components such as adipic acid, sebacic acid, phthalic acid, isophthalic acid, and 2,6-naphthalenedicarboxylic acid in the above polyester resins. Among them, polyester resins are preferred in terms of mechanical strength, chemical resistance, and heat resistance.

[0038] Among the above polyester resins, polyethylene terephthalate is most preferred in terms of the balance between physical properties and cost. Depending on the use temperature range, polyethylene naphthalate may also be used.

[0039] Examples of the substrate made of inorganic substances include glass plates, ceramic plates, semiconductor wafers, those mainly composed of metals, etc., and composites of these glass plates, ceramic plates, semiconductor wafers, and metals, such as those laminated, those in which these are dispersed, and those containing fibers of these. The temporary fixing substrate is preferably glass, a silicon wafer, a protective film, or a release film.

[0040] Examples of the glass plate include quartz glass, high-silica glass (96% silica), soda-lime glass, lead glass, aluminoborosilicate glass, borosilicate glass (Pyrex (registered trademark)), borosilicate glass (alkali-free), borosilicate glass (micro sheet), aluminosilicate glass, etc.

[0041] The semiconductor wafers mentioned above are not particularly limited, but examples include silicon wafers, germanium, silicon-germanium, gallium-arsenide, aluminum-gallium-indium, nitrogen-phosphorus-arsenide-antimony, SiC, InP (indium phosphide), InGaAs, GaInNAs, LT, LN, ZnO (zinc oxide), CdTe (cadmium telluride), and ZnSe (zinc selenide). Among these, silicon wafers are preferred, and mirror-polished silicon wafers of 8 inches or larger are particularly preferred.

[0042] The aforementioned metals include single-element metals such as W, Mo, Pt, Fe, Ni, and Au, as well as alloys such as Inconel, Monel, Mnemonic, carbon steel, Fe-Ni Invar alloy, and SuperInvar alloy. Multilayer metal sheets formed by adding other metal layers or ceramic layers to these metals are also included.

[0043] <Discrete Resin Layer> The discrete resin layer 14 is not particularly limited as long as it is a layer formed of resin, but it is preferably a heat-resistant polymer film. If the resin layer 14 is a heat-resistant polymer film, it can withstand the heat when forming the device on the heat-resistant polymer film. However, depending on the device to be placed on top, the resin layer may only need to withstand a process at around 120°C. In this case, polyethylene terephthalate is preferred. Also, depending on the operating temperature range, polyethylene naphthalate is preferred.

[0044] In this specification, a heat-resistant polymer is a polymer having a melting point of, for example, 100°C or higher, preferably 200°C or higher, and more preferably 400°C or higher, and a glass transition temperature of, for example, 100°C or higher, preferably 150°C or higher, and more preferably 250°C or higher. Hereinafter, to avoid complexity, it will also be simply referred to as a polymer. In this specification, the melting point and glass transition temperature are determined by differential thermal analysis (DSC). If the melting point exceeds 500°C, it may be determined whether or not the melting point has been reached by visually observing the thermal deformation behavior when heated at the relevant temperature.

[0045] Examples of the heat-resistant polymer film (hereinafter also simply referred to as polymer film) include polyimide resins such as polyimide, polyamideimide, polyetherimide, and fluorinated polyimide (e.g., aromatic polyimide resins, alicyclic polyimide resins); polyolefin resins such as polyethylene and polypropylene; polyester resins such as copolymerized polyesters such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene-2,6-naphthalate (e.g., fully aromatic polyesters, semi-aromatic polyesters); copolymerized (meth)acrylates represented by polymethyl methacrylate; polycarbonate; polyamide; polysulfone; polyethersulfone; polyetherketone; cellulose acetate; cellulose nitrate; aromatic polyamide; polyvinyl chloride; polyphenol; polyarylate; polyphenylene sulfide; polyphenylene oxide; and polystyrene films. However, the polymer film is often used in processes involving heat treatment at 450°C or higher. Among the polymer films mentioned above, films using so-called super engineering plastics are preferred, and more specifically, examples include aromatic polyimide films, aromatic amide films, aromatic amide-imide films, aromatic benzoxazole films, aromatic benzothiazole films, aromatic benzimidazole films, and the like.

[0046] The resin layer 14 preferably contains at least one selected from the group consisting of polyimide, polyamideimide, and polyester, and more preferably contains at least one selected from the group consisting of polyimide, polyamideimide, polyethylene terephthalate, and polyethylene naphthalate. The resin layer 14 contains any of polyimide, polyamideimide, polyethylene terephthalate, or polyethylene naphthalate, and it is more preferable that the total amount of polyimide, polyamideimide, polyethylene terephthalate, and polyethylene naphthalate in the resin layer 14 (100% by mass) is 50% or more, even more preferable that it is 70% or more, and particularly preferable that it is 90% or more. The resin layer 14 may contain 100% or less by mass of any of polyimide, polyamideimide, polyethylene terephthalate, or polyethylene naphthalate, or 95% or less by mass.

[0047] The elastic modulus of the resin layer 14 is preferably 3.0 GPa or more and 15 GPa or less, more preferably 5.0 GPa or more and 12 GPa or less, and even more preferably 7.0 GPa or more and 9.0 GPa or less.

[0048] As for the resin layer 14, one is selected in which the elastic modulus of the resin layer 14 is 50 times or more the elastic modulus of the base layer 32. Preferably, the elastic modulus of the resin layer 14 is 50 times or more and 1000 times or less the elastic modulus of the base layer 32, more preferably 80 times or more and 400 times or less, and even more preferably 110 times or more and 200 times or less. With such a configuration, it becomes easy to expand and contract the portion of the base layer 32 that does not have the resin layer 14, and to arrange the laminate along a three-dimensional curved surface without wrinkles.

[0049] The area of ​​the base layer 32 is, for example, 0.5 times or more the area of ​​the discrete resin layer 14. Preferably, the area of ​​the base layer 32 is 1.0 to 50 times the area of ​​the discrete resin layer 14, more preferably 1.5 to 25 times, and even more preferably 2.0 to 4.0 times. With this configuration, it becomes easy to expand or contract the portion of the base layer 32 that is not covered by the resin layer 14, thereby arranging the laminate along a three-dimensional curved surface without wrinkles. Note that "area of ​​the resin layer 14" means the sum of the areas of the resin layer 14 when the base layer 32 is viewed from above on the resin layer 14 side, and "area of ​​the base layer 32" means the sum of the areas of the base layer 32 that are not covered by the resin layer 14 when the base layer 32 is viewed from above on the resin layer 14 side. Furthermore, as will be described later, discrete reinforcing layers and the like are provided between the base layer 32 and the resin layer 14, and layers other than the resin layer 14 are also provided on the base layer 32. However, for the above area, the portion where only layers other than the resin layer 14 are provided is treated as the "area of ​​the base layer 32" and calculated accordingly.

[0050] The thickness of the discrete resin layer 14 is preferably 20 μm to 140 μm, more preferably 30 μm to 60 μm, and even more preferably 35 μm to 40 μm. This configuration makes it easier to suppress the decrease in transparency and whitening that occurs when crystallization progresses inside the resin layer 14 due to cooling during manufacturing, etc., because the thickness of the resin layer 14 is the cause.

[0051] The thickness of the discrete resin layer 14 is preferably 0.2 times or more and 1.5 times or less the thickness of the base layer 32, more preferably 0.30 times or more and 1.0 times or less, and even more preferably 0.35 times or more and 0.40 times or less. With this configuration, it becomes easy to expand or contract the portion of the base layer 32 that does not have the resin layer 14, and to arrange the laminate along a three-dimensional curved surface without wrinkles.

[0052] The average transmittance of light with wavelengths of 400 nm to 700 nm through the discrete resin layer 14 is preferably 40% to 99%, more preferably 60% to 95%, and even more preferably 80% to 90%. This configuration makes it possible to create a resin layer 14 that easily transmits light. For example, by using such a resin layer in a photoelectric conversion element, it becomes less likely to obstruct the transmission of light to the photoelectric conversion layer. Furthermore, transparency is also easily improved, making it possible to apply it to locations where visibility is required.

[0053] "Discrete resin layers 14" means that the resin layers 14 are separated in island-like, linear, or other forms, and that the resin layers 14 exist discontinuously on the base layer 32. Preferably, the discrete resin layers 14 are a subset consisting of multiple resin layers 14 sequentially provided with spacing between them in a first direction, as shown in Figure 5, and then sequentially provided with spacing between them in a second direction intersecting the first direction. The first and second directions are, for example, orthogonal. This arrangement of discrete resin layers 14 makes it easy to roughly deform the laminate by expanding or contracting it to the desired curved shape even at room temperature. In the portion of the base layer 32 where no resin layers 14 are provided, for example, only layers having an elastic modulus similar to or smaller than that of the base layer 32 may be provided.

[0054] <Discrete Reinforcement Layer> The above laminate consists of discrete resin layers 14 and a base layer 32, but it is not prohibited to add a discrete reinforcement layer that is slightly larger than the discrete resin layer 14. This discrete reinforcement layer may be provided between the base layer 32 and the resin layer 14 on the side of the base layer 32 where the resin layer 14 is provided, or it may be provided on the side of the base layer 32 opposite to the side where the resin layer 14 is provided. Furthermore, it is desirable that this reinforcement layer has an elastic modulus intermediate between the discrete resin layer and the base layer.

[0055] <Discrete Machining> In the present invention, the process of cutting a resin layer, which is temporarily fixed to a substrate, into even smaller units by machining after laminating resin layers of approximately the same or slightly smaller product units on a substrate layer is called discrete machining. In production, even when producing resin layers larger than the product unit at once, it suffices if the resin layer used for each product unit is the same size as or smaller than the substrate layer of the product size. Examples of such machining include resist and polyimide etching used in the semiconductor field. Existing machining methods can be used, preferably cutting by laser or machining with a Thomson blade.

[0056] <Discrete Resin Layer> In the present invention, the resin layer that has been subjected to such discrete machining is called a discrete resin layer.

[0057] That is, the laminate can be manufactured by fixing a resin layer on a temporary fixing substrate, machining the resin layer to create the above-described discretely provided resin layer (discrete resin layer), and attaching the substrate layer to the discretely provided resin layer. Fixing the resin layer to the temporary fixing substrate is performed, for example, by forming a silane coupling agent layer on the temporary fixing substrate and attaching the resin layer to the silane coupling agent layer. This enables easy fixing of the resin layer.

[0058] Attaching the substrate layer to the discretely provided resin layer may include subjecting the portion of the silane coupling agent layer exposed by machining the resin layer to SiO ２ - conversion or Si-(CH ３ ) ３ - conversion before attaching the substrate layer. By weakening the adhesion of the exposed portion (silane coupling agent) of the temporary fixing substrate through SiO ２ - conversion or Si-(CH ３ ) ３ - conversion, the adhesion between the temporary fixing substrate and the substrate layer is inhibited during the attachment of the substrate layer, and it may be easier to remove the temporary fixing substrate later.

[0059] When the temporary fixing substrate is removed, it is preferable that the base material layer has a substantially uniform thickness without any steps. Specifically, it is preferable that it extends continuously to the surface of the space between multiple discrete resin layers, and that the surface of the base material layer in the space is formed without any steps relative to the surface of the resin layer. In such a configuration, the device formation surface becomes flat, so for example, the device formation surface can be attached to the surface to be attached without any gaps.

[0060] <Shapes that cannot be unfolded into a plane> In the case of cylindrical sides, it is possible to attach the film within the plane without stretching or shrinking it. However, it is difficult to attach the film within the plane without stretching or shrinking it to many quadratic curved surfaces other than cylinders, such as spheres and ellipsoids. In this invention, such shapes are referred to as shapes that cannot be unfolded into a plane.

[0061] <Shape Fixation> Even shapes that cannot be unfolded on the above-mentioned plane can be made to conform to the shape using a stretchable film. In most cases, thermoplastic films can be stretched when heated, allowing them to be unfolded into various shapes, but stretching and then shrinking allows for even greater freedom in conforming to the shape. In this invention, making this deformation permanent is called shape fixing. Shape fixing can involve heating, followed by cooling and deformation at room temperature, but in most cases, adhesion is required afterward.

[0062] <Support Substrate> The support substrate 40 is for supporting the base material layer 32. Although the base material layer 32 is self-adhesive and can adhere to the support substrate 40, it is preferable that the support substrate 40 be provided with an adhesive layer or release layer so that the base material layer 32 and the support substrate 40 can be separated afterward.

[0063] Examples of materials for the support substrate 40 include polyolefin resins such as polyethylene and polypropylene; polyamide resins such as nylon 6 and nylon 66; and polyester resins such as polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyethylene-2,6-naphthalate, and polytrimethylene terephthalate. Furthermore, copolymerized polyester resins may be used, obtained by copolymerizing diol components such as diethylene glycol, neopentyl glycol, and polyalkylene glycol, or dicarboxylic acid components such as adipic acid, sebatic acid, phthalic acid, isophthalic acid, and 2,6-naphthalenedicarboxylic acid. Among these, polyester resins are preferred in terms of mechanical strength, chemical resistance, and heat resistance.

[0064] Among the polyester resins mentioned above, polyethylene terephthalate is the most preferred due to its balance of physical properties and cost.

[0065] <Devices> In this specification, a device is, for example, provided with at least one of a light-emitting element, a photoelectric conversion layer, and a sensor element on a discretely arranged resin layer 14. In this specification, the term "element" may refer to the device itself or to a part of the components of the device. In this specification, devices may include single-sided, double-sided, or multilayer wiring boards for electrical wiring, electronic circuits including active elements such as transistors and diodes, and passive devices such as resistors, capacitors, and inductors, as well as sensor elements for sensing pressure, temperature, light, humidity, etc., biosensor elements, light-emitting elements, image display elements such as liquid crystal displays, electrophoretic displays, and self-luminous displays, wireless and wired communication elements, computing elements, memory elements, MEMS elements, photoelectric conversion elements such as solar cells, power generation elements, energy storage elements, thin-film transistors, and the like. In this specification, a device assembly may have multiple devices of one type, or it may have multiple types of devices. The combination of multiple types of devices is not particularly limited, and for example, multiple devices can be appropriately combined from among the above devices. In device fabrication, a configuration in which the substrate layer 32 is arranged on both sides of the device is possible.

[0066] <Photoelectric Conversion Element> Next, a photoelectric conversion element 17 that can be manufactured using the resin layer 14 according to an embodiment of the present invention will be described. An example of a photoelectric conversion element according to an embodiment of the present invention is shown in Figure 7. The photoelectric conversion element 17 has a configuration in which a laminated structure having a photoelectric conversion function is provided on the resin layer 14. Each of the members constituting the laminated structure (hereinafter also referred to as layers) does not necessarily need to have a configuration that is easily expandable and contractible. A member having a configuration that is easily expandable and contractible means that when the photoelectric conversion section 43 including the photoelectric conversion layer is installed so that the resin layer 14 follows a three-dimensional curved surface, the member can expand and contract to the extent that the photoelectric conversion function is not lost in accordance with the bending of the resin layer 14. In order to realize such an easily expandable and contractible configuration of a member, for example, a material that can impart expandability to the member may be used as the material constituting the member, and / or the physical structure of the member may be a structure that can impart expandability to the member, such as a bellows structure.

[0067] Examples of photoelectric conversion elements 17 include solar cells and photodiodes.

[0068] As shown in Figure 7, the photoelectric conversion element 17 preferably includes a base layer 32, a resin layer 14 discretely laminated thereon, a photoelectric conversion section 43 including a photoelectric conversion layer as a component of the laminated structure, and a first electrode layer 12 disposed between the resin layer 14 and the photoelectric conversion section 43. Since the base layer 32 is easy to install on a three-dimensional curved surface, using it as the base material for the photoelectric conversion element 17 makes it easy to install on a three-dimensional curved surface. This makes it easier to incorporate the photoelectric conversion element 17 into various everyday objects without design constraints. Furthermore, if the base layer 32 and the first electrode layer 12 are transparent, light can be easily transmitted through them, so using the base layer 32 as the base material for the photoelectric conversion element 17 makes it less likely to obstruct the transmission of light to the photoelectric conversion layer. Although not shown in the figure, it is desirable that a gas barrier layer be provided on at least one surface of the resin layer 14. It is also desirable that the protective layer 15 protects the element from mechanical impact and also provides barrier properties. In other words, the protective layer 15 is preferably made of a gas barrier material and has the function of protecting the photoelectric conversion element 17 from moisture and oxygen. The degree of gas barrier properties required will vary depending on the photoelectric conversion element 17.

[0069] The first electrode layer 12 is preferably laminated on the resin layer 14.

[0070] The first electrode layer 12 can be made of a conductive material. It is more preferable that the first electrode layer 12 be a transparent electrode. This makes it easier for light to reach the photoelectric conversion layer. The first electrode layer 12 may be made of only one type of material or of two or more types of materials.

[0071] The first electrode layer 12 can be formed, for example, by depositing or coating the above-mentioned material onto the resin layer 14.

[0072] The third electrode layer 19 can be made of a conductive material. As described above, it is preferable that the third electrode layer 19 has a structure that is easily stretchable. For example, as the third electrode layer 19, a stretchable wiring such as a stretchable metal paste wiring may be used, and / or the third electrode layer 19 may be a stretchable bellows-type metal wiring. It is more preferable that the third electrode layer 19 is a transparent electrode. For example, as the third electrode layer 19, it is preferable to use a transparent stretchable electrode made of a conductive polymer, nanocarbon, nanosilver fiber, or nanosilver particles, which are examples of the stretchable wiring described above. This makes it easier for light to reach the photoelectric conversion layer. The third electrode layer 19 may be made of only one of the above, or it may be made of two or more of the above.

[0073] The third electrode layer 19 and the first electrode layer 12 can be formed, for example, by vapor deposition or coating the above-mentioned material onto the resin layer 14.

[0074] The photoelectric conversion layer may be laminated on the first electrode layer 12. Buffer layers, such as a hole transport layer or an electron transport layer, may be placed between the first electrode layer 12 and the photoelectric conversion layer. The photoelectric conversion layer and the hole transport layer or electron transport layer together may be referred to as the photoelectric conversion section 43.

[0075] The photoelectric conversion layer is preferably composed of a material containing a photoelectric conversion material. The photoelectric conversion layer may be composed of only the photoelectric conversion material, or of the photoelectric conversion material and other materials. As mentioned above, it is not necessarily required that the photoelectric conversion layer have a structure that allows for easy expansion and contraction.

[0076] As photoelectric conversion materials, for example, p-type semiconductors and n-type semiconductors, which are organic semiconductor materials, can be used. The p-type semiconductor and n-type semiconductor each have an independent layer structure, or the structure may consist of stacked layers of p-type and n-type semiconductors. Alternatively, the p-type and n-type semiconductors may be mixed to form a single layer. When the above-mentioned p-type and n-type semiconductors are used as photoelectric conversion materials, the photoelectric conversion element 17 becomes an organic thin-film solar cell. Other photoelectric conversion materials that can be used include materials having a perovskite structure. When a material having a perovskite structure is used as the photoelectric conversion material, the photoelectric conversion element 17 becomes a perovskite solar cell. Since the resin layer 14 is transparent, for example, when the above-mentioned p-type and n-type semiconductors are used as photoelectric conversion materials to make the photoelectric conversion element 17 an organic thin-film solar cell, the photoelectric conversion element 17 as a whole can be made highly transparent. Therefore, even if the photoelectric conversion element 17 is installed on the windows of a building or a car, it will not spoil the appearance of the building or car. Even when the photoelectric conversion element 17 is a perovskite solar cell, the transparency of the resin layer 14 prevents the resin layer 14 from causing any damage to the appearance during installation.

[0077] The photoelectric conversion layer can be formed, for example, by depositing or coating the above-mentioned material onto a resin layer 14 on which the first electrode layer 12 is provided.

[0078] By using a resin layer 14 having an average transmittance of 40% or more for light with wavelengths between 400 nm and 700 nm, it is possible to reduce the obstruction of light transmission to the photoelectric conversion layer.

[0079] The photoelectric conversion element 17 may further have a second electrode layer 18 as a component of the stacked structure. The second electrode layer 18 may be stacked on the photoelectric conversion layer. Preferably, the second electrode layer 18 is provided such that the photoelectric conversion layer is positioned between the second electrode layer 18 and the first electrode layer 12. A buffer layer, such as a hole transport layer or an electron transport layer, may be positioned between the second electrode layer 18 and the photoelectric conversion layer. Furthermore, a buffer layer, such as a hole transport layer or an electron transport layer, may be positioned between the first electrode layer 12 and the photoelectric conversion layer. As shown in Figure 7, the second electrode layer 18 may be configured such that a part of it is stacked on the photoelectric conversion layer and the remaining part of it is stacked on the first electrode layer 12. When looking at Figure 7, if the part facing upwards is the top surface, the part facing downwards is the bottom surface, and the parts facing left and right are the sides, it is preferable that a part of the second electrode layer 18 is positioned so as to be in contact with the top surface and the sides of the photoelectric conversion element 17. Multiple unit structures are provided in the resin layer 14, each in which a first electrode layer 12, a photoelectric conversion layer, and a second electrode layer 18 are arranged in this order. Between adjacent unit structures, the second electrode layer 18 of one unit structure may be electrically connected to the first electrode layer 12 of the other unit structure.

[0080] The second electrode layer 18 can be made of a conductive material. As described above, it is preferable that the second electrode layer 18 has a structure that is easily stretchable. For example, the second electrode layer 18 may be made of stretchable wiring such as stretchable metal paste wiring, and / or the second electrode layer 18 may be made of stretchable bellows-type metal wiring. The second electrode layer 18 may be a transparent electrode. For example, the second electrode layer 18 may be made of a transparent stretchable electrode made of a conductive polymer or nanocarbon, which is an example of the stretchable wiring described above.

[0081] The second electrode layer 18 can be formed, for example, by vapor deposition or coating the above-mentioned material onto the resin layer 14 on which the first electrode layer 12 and the photoelectric conversion layer are provided. The second electrode layer 18 does not necessarily need to cover the entire portion of the photoelectric conversion layer that contributes to power generation; it may also be in the form of a slit.

[0082] The annealing treatment may be performed when the first electrode layer 12, the photoelectric conversion layer, and the second electrode layer 18 are laminated on the resin layer 14, or the annealing treatment may be performed at any stage in which a part of the above layer structure is laminated.

[0083] The photoelectric conversion element 17 may further have a protective layer 15 as a component of the laminated structure. Preferably, the protective layer 15 is laminated on the second electrode layer 18. As shown in Figure 7, a portion of the protective layer 15 may be laminated on the second electrode layer 18, another portion of the protective layer 15 may be laminated on the photoelectric conversion section 43 including the photoelectric conversion layer, and the remaining portion of the protective layer 15 may be laminated on the first electrode layer 12. As shown in Figure 7, the second electrode layer 18 and the photoelectric conversion section 43 including the photoelectric conversion layer may be arranged between the first electrode layer 12 and the protective layer 15. Although not shown, a portion of the protective layer 15 may be laminated on a resin layer 14.

[0084] The protective layer 15 preferably has gas barrier properties. The protective layer 15 may have a structure of two or more layers, including a barrier layer having gas barrier properties. As described above, it is not essential that the protective layer 15 has a structure that is easily expandable and contractible. For example, a stretchable elastomer may be used as part of the material of the protective layer 15.

[0085] As shown in Figure 7, it is conceivable that the light 16 is directed from the side of the photoelectric conversion element 17 where the resin layer 14 is located, but this is not necessarily required. It is also preferable to make the second electrode layer 18 slit-shaped or transparent so that the light is incident from the opposite side of Figure 7, or from both sides.

[0086] The photoelectric conversion element 17 described above can be used, for example, by being attached to the rear window or windshield of an automobile. It can also be easily attached to living organisms, interiors, and home appliances, which have unspecified shapes. Because the photoelectric conversion element 17 uses a resilient substrate layer 32 as its base material, it can be easily attached to the rear window or windshield of an automobile, which have three-dimensional curved surfaces.

[0087] <Display> Next, a display 25 that can be manufactured using the resin layer 14 according to an embodiment of the present invention will be described. An example of a display according to an embodiment of the present invention is shown in Figure 8.

[0088] The display 25 according to an embodiment of the present invention preferably comprises the above-mentioned base material layer 32, the above-mentioned resin layer 14 discretely laminated thereon, and a light-emitting element 21 fixed to the resin layer 14. The display 25 may be a so-called transparent display. Since the base material layer 32 is easy to install on a three-dimensional curved surface, using it as the base material for the display 25 makes it easy to install on a three-dimensional curved surface. This makes it easier to incorporate the display 25 into various everyday objects without design constraints.

[0089] The light-emitting element 21 may be in contact with the resin layer 14. The light-emitting element 21 may not be in contact with the resin layer 14. For example, if a discrete LED element is used as the light-emitting element 21, the electrical connection may be made with solder or silver paste, and the mechanical connection may be made with a flexible mounting adhesive. For example, the light-emitting element 21 may be fixed with other components placed between it and the resin layer 14.

[0090] An LED can be used as the light-emitting element 21. When an organic light-emitting diode is used as the light-emitting element 21, the display 25 becomes an organic EL display. When a micro light-emitting diode is used as the light-emitting element 21, the display 25 becomes, for example, a micro LED display. Each of the components constituting the light-emitting element 21 does not necessarily need to have a structure that is easily expandable and contractible, as described above with respect to the photoelectric conversion element 17, for example.

[0091] The display 25 may further have conductive wiring 22. Preferably, the wiring 22 is fixed to the resin layer 14 and the light-emitting element 21. As described above, the wiring 22 may be configured to be easily expandable, but it is not necessarily required to be easily expandable.

[0092] The display 25 may further have a protective layer 15. The protective layer 15 may be configured such that a portion of it is laminated on the resin layer 14, another portion of it is laminated on the light-emitting element 21, and the remaining portion of it is laminated on the wiring 22. As described above, the protective layer 15 may be configured to be easily expandable, but it is not necessarily required to be easily expandable.

[0093] The third electrode layer 19 can be made of a conductive material. As described above, it is preferable that the third electrode layer 19 has a structure that is easily stretchable. For example, as the third electrode layer 19, a stretchable wiring such as a stretchable metal paste wiring may be used, and / or the third electrode layer 19 may be a stretchable bellows-type metal wiring. It is more preferable that the third electrode layer 19 be a transparent electrode. For example, as the third electrode layer 19, it is preferable to use a transparent stretchable electrode made of a conductive polymer, nanocarbon, nanosilver fiber, or nanosilver particles, which is an example of the stretchable wiring described above. This makes it easier for light to reach the photoelectric conversion layer. The third electrode layer 19 may be made of only one of the above, or it may be made of two or more of the above. Although not shown in the figures, it is desirable that a gas barrier layer be provided on at least one surface of the resin layer 14. It is also desirable that the protective layer 15 protects the element from mechanical shock and also has barrier properties. That is, it is desirable that the protective layer 15 be a gas barrier material and have the function of protecting the photoelectric conversion element 17 from moisture and oxygen. The required level of gas barrier properties varies depending on the light-emitting element 21.

[0094] Since the above-mentioned display 25 can be a display that conforms to a transparent three-dimensional curved surface, it can be used, for example, by being attached to the rear window or windshield of an automobile. It can also be easily attached to living organisms, interiors, and home appliances, which have unspecified shapes. Because the display 25 uses a resilient substrate layer 32 as its base material, it can be easily attached to the rear window or windshield of an automobile, which have a three-dimensional curved surface.

[0095] <Elastic Modulus of the Entire Discrete Laminate> Consider a laminate in which only one row of resin layers are intermittently bonded to a base layer. As an assumption, calculations are performed in one dimension only (Figure 1). The portion where the base layer and the two resin layers are bonded is assumed to deform by the same amount in the stress direction, ignoring warping deformation, etc. Oblique stress, strain, and warping are not considered. Here, the stress in the portion where the base layer and the two resin layers are bonded is the same as in the portion with only the base layer, so an equation is derived from Hooke's Law E = σ / X. E: Young's modulus σ: Uniaxial stress X: Uniaxial strain F / As = Xs・Es F / (As + Af) = Xfs・Es + Xfs・Ef Here, σ: stress As: cross-sectional area of ​​the resin layer Af: cross-sectional area of ​​the base layer F: force applied in the stretching direction (however, when the width of the resin layer and the width of the base layer are the same, it is the force applied to the entire film) Xfs: displacement of the two-layer laminated portion when stress is applied Xs: displacement of the base layer portion when stress is applied Es: Young's modulus of the base layer Ef: Young's modulus of the resin layer By eliminating F from the two equations and rearranging them, the following relationship is obtained. Xfs / Xs = EsAs / (Es+Ef)(As+Af) That is, when Ts=Tf and Ef=100Es, Xs / Xfs ≈ 200, and when Ts=10Tf and Ef=100Es, Xs / Xfs ≈ 110. When the resin layer thickness is the same as the base layer thickness, the part consisting only of the base layer stretches more than 200 times compared to the part with the resin layer. Here, Ts is the thickness of the base layer and Tf is the thickness of the resin layer. Furthermore, when the resin layer thickness is 1 / 10 of the base layer thickness, the part consisting only of the base layer stretches about 110 times compared to the part with the resin layer. In other words, the calculation shows that the stretching is almost entirely in the part consisting only of the base layer, and the part with the resin layer stretches almost nothing (from 1 / 200 to 1 / 110 of the displacement of the base layer).

[0096] According to the example of the device fabrication method, it is possible to create a device assembly that is stretchable. Details of this are disclosed, for example, in WO2020 / 084981, so a detailed explanation is omitted here. However, this is merely one example.

[0097] This application claims the benefit of priority based on Japanese Patent Application No. 2024-176049, filed on 7 October 2024. The entire specification of Japanese Patent Application No. 2024-176049, filed on 7 October 2024, is incorporated herein by reference.

[0098] The present invention will be described in detail below with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist of the invention.

[0099] [Measurement Method and Evaluation Method] <Thickness> A Mitutoyo micrometer was used to measure five points relative to the sheet width. The average value was taken as the sheet thickness.

[0100] <Modulus of Elasticity> A test specimen measuring 10 mm in width and 150 mm in length was cut out so that the winding direction of the sheet was in the longitudinal direction. Using a Shimadzu Autograph AGS-X, the stress was measured when the sheet was stretched to a strain of 5% at a tensile speed of 50 mm / min with an initial chuck distance of 100 mm.

[0101] <Reduced Viscosity> The reduced viscosity (ηsp / C) of polyamic acid was measured at 30°C using an Ubbelohde-type viscosity tube. The solution was prepared by dissolving the polymer in N-methyl-2-pyrrolidone (or N,N-dimethylacetamide) to a polymer concentration of 0.2 g / dl.

[0102] <Average transmittance (%) of light with wavelengths between 400 nm and 700 nm> Measurements were performed using ultraviolet-visible spectroscopy under the following conditions. Transmittance (%) was measured using an integrating sphere with a Shimadzu Corporation UV-Vis-NIR (UV-Vis-NIR) spectrophotometer SolidSpec-3700 (software: UVProve ver. 2.7135). (Measurement conditions) Measurement wavelength: 400 nm to 700 nm Scan speed: Medium speed Slit width: (12 nm) Sampling pitch: 0.5 nm Standard whiteboard: Standard reflector Spectralon Transmission spectra of light with wavelengths between 400 nm and 700 nm were obtained. From this, the average transmittance (%) of light in the wavelength range of 400 nm to 700 nm was calculated.

[0103] <Peel Strength> Sample Preparation for Peel Strength A polyimide film was discretely left on a glass surface, and an elastomer film was placed over it. A small vacuum press (Imoto Seisakusho IMC-1123) was used to press the sample for 5 minutes at 120°C, with a hydraulic gauge reading of 6 MPa (jack output 1 ton, hot plate area 150 mm x 150 mm). At this time, a silicone sheet was placed on one side to try to equalize the pressure. (Peel Strength Measurement) Peel strength (N / cm) was measured by performing a 90° peel using an automatic vertical servo stand (Nihonkai Keisoku Co., Ltd. JSV-1000) with the company's handy force gauge and a 90° peeling jig. See Figure 2 for the sample shape at this time.

[0104] The measurement conditions for the 90° peel strength are as follows: Layer A is peeled off from layer B at a 90° angle. Five measurements are taken, and the average value is used as the measurement value. Measurement temperature: Room temperature (25°C) Peeling speed: 100 mm / min Atmosphere: Air Sample width: 1.0 cm

[0105] <Melting Point> A differential scanning calorimetry analyzer (DSC220) manufactured by Seiko Electronics Industries was used. Specifically, 5 mg of the pellet material to be used as the sample was placed in an aluminum pan, sealed by pressing down on the lid, melted at 250°C in nitrogen for 2 minutes, then cooled to 50°C at a rate of 20°C / min, and then heated from 50°C to 250°C at a rate of 20°C / min to obtain a thermogram curve. The endothermic peak due to melting was determined from the obtained thermogram curve.

[0106] <Ease of Installation on Three-Dimensional Curved Surfaces> The ease of installation of the films of each embodiment and each comparative example on three-dimensional curved surfaces was evaluated using a watch glass manufactured by SCHOT. A watch glass made of borosilicate glass DURAN (registered trademark) with a diameter C of 50 mm and a depth h of 5 mm was used. It is roughly spherical, and the radius of curvature R can be calculated from the following formula: R = h / 2 + C ２The calculated radius of curvature R was 65 mm. Each film was fixed to a 100 mm x 100 mm metal frame. A watch glass was placed on a vacuum apparatus with the convex side facing upwards, and each film, which was larger than the watch glass in its fixed state in the mold, was placed on the edge of the watch glass and vacuum suction was applied. This allowed each film to conform to the convex surface of the watch glass at room temperature, and it was visually checked whether wrinkles had formed in each example film. If many wrinkles formed and the ease of installation on a three-dimensional curved surface was poor, it was evaluated as "B", and if no wrinkles formed and the ease of installation on a three-dimensional curved surface was excellent, it was evaluated as "A". The presence of many wrinkles means that the ease of installation on a three-dimensional curved surface is poor, and the absence of wrinkles means that the ease of installation on a three-dimensional curved surface is excellent. The arc length L of the watch glass was found to be 51.32 from L = Rα (where α (radian) = 2sin －１ (C / 2R). And L / C = 1.026. Therefore, if we ignore the elongation outside the watch glass, each film is stretched by at least 2.6%.

[0107] [Examples of manufacturing base film (base layer)] Various base films were manufactured or prepared as follows, and the average thickness, elastic modulus, and transmittance of light with wavelengths between 400 nm and 700 nm were measured. The results are shown in Table 2.

[0108] (1) Elastomer film 1 As the pellet material, Perprene® P-40H, a thermoplastic polyester elastomer manufactured by Toyobo MC Co., Ltd., was used. The melting point of the pellets was 162°C. The pellet material was melt-extruded into a film shape using a T-die extrusion molding machine (PG30-8 type extruder manufactured by Plastic Technology Co., Ltd.), brought into contact with a mirror-cooled roll at 20°C, and wound up with interleaving paper in between to produce elastomer film 1. The barrel temperature and die temperature during extrusion molding were set to 190°C. Elastomer film 1 is unstretched. The thickness of elastomer film 1 was adjusted by changing the rotation speed of the mirror-cooled roll.

[0109] (2) Elastomer film 2 As the pellet material, Perprene® P-75M, a thermoplastic polyester elastomer manufactured by Toyobo MC Co., Ltd., was used. The melting point of the pellets was 152°C. The pellet material was melt-extruded into a film shape using a T-die extrusion molding machine (PG30-28 type extruder manufactured by Plastic Technology Co., Ltd.), brought into contact with a mirror-cooled roll at 20°C, and wound up with interleaving paper in between to produce elastomer film 2. The barrel temperature and die temperature during extrusion molding were set to 180°C. Elastomer film 2 is unstretched. The thickness of elastomer film 2 was adjusted by changing the rotation speed of the mirror-cooled roll.

[0110] (3) Urethane film and silicone film As the urethane film, UT010 200 μm thick manufactured by Taiyo Co., Ltd. was prepared, and as the silicone film, 6-9085-13 200 μm thick purchased from AS ONE was prepared.

[0111] [Examples of Resin Film (Resin Layer) Manufacturing] Various resin films were manufactured or prepared as follows, and the average thickness, elastic modulus, and light transmittance of wavelengths between 400 nm and 700 nm were measured. The results are shown in Table 2.

[0112] (1) Polyimide Film 1 (Polymamide Acid Polymerization - 1) <Polymamide acid consisting of a diamine having a benzoxazole structure> After purging the reaction vessel equipped with a nitrogen inlet tube, thermometer, and stirring rod with nitrogen, 500 parts by mass of 5-amino-2-(p-aminophenyl)benzoxazole was charged. Next, 8,000 parts by mass of N,N-dimethylacetamide was added and dissolved completely, then 485 parts by mass of pyromellitic dianhydride was added, and Snowtex (DMAC-ST30, manufactured by Nissan Chemical Industries, Ltd.), in which colloidal silica is dispersed in dimethylacetamide, was added so that the silica content was 0.4% by mass. The mixture was stirred at a reaction temperature of 25°C for 48 hours to obtain a pale yellow, viscous polyamic acid solution (A). The ηsp / C of the obtained solution was 4.0 dl / g. Next, the polyamic acid solution was coated onto a stainless steel belt with a squeegee / belt gap of 450 μm. As the first drying step, it was dried in three hot air drying zones at ambient temperature at 90°C for 7 minutes, 90°C for 7 minutes, and 90°C for 7 minutes. After drying, the self-supporting precursor film was peeled off the stainless steel belt to obtain a polyimide precursor film with a thickness of 40 μm. This peeled precursor film was dried on both sides in a hot air drying zone at an ambient temperature of 150°C for 10 minutes. The residual solvent content of the polyimide precursor film was 35.5% by mass. The obtained polyimide precursor film was passed through a continuous drying oven, heat-treated at 200°C for 3 minutes, then heated to 450°C in about 20 seconds, heat-treated at 450°C for 7 minutes, and cooled to room temperature over 5 minutes to obtain a brown polyimide film 1.

[0113] (2) Polyimide film 2 (Preparation of polyamic acid solution A1) After purging the reaction vessel equipped with a nitrogen inlet tube, thermometer and stirring rod with nitrogen, 545 parts by mass of pyromellitic anhydride and 500 parts by mass of 4,4'-diaminodiphenyl ether were dissolved in 8,000 parts by mass of N,N-dimethylacetamide, and Snowtex (DMAC-ST30, manufactured by Nissan Chemical Industries, Ltd.), which is obtained by dispersing colloidal silica in dimethylacetamide, was added so that the amount of silica was as shown in Table 1, and the reaction was carried out in the same manner while maintaining the temperature at 20°C or below to obtain polyamic acid solution A1.

[0114]

[0115] The polyamic acid solution A1 obtained in the manufacturing example was applied to an endless continuous stainless steel belt that had been mirror-finished using a die coater (coating width 1240 mm) and dried at 90-115°C for 10 minutes. After drying, the self-supporting polyamic acid film was peeled from the support and both ends were cut to obtain green films. These obtained green films were passed through a pin tenter having pin sheets arranged so that the pin spacing was constant when the pin sheets were lined up. The film ends were gripped by inserting them into the pins, and the pin sheet spacing was adjusted so that the film would not break and no unnecessary slack would occur, and the films were conveyed so that the final pin sheet spacing was 1140 mm. The imidization reaction was carried out by heating under the following conditions: the first stage at 170°C for 2 minutes, the second stage at 230°C for 2 minutes, and the third stage at 485°C for 6 minutes. The film was then cooled to room temperature for two minutes, the parts with poor flatness at both ends were cut off with a slitter, and the film was rolled up to obtain a brown polyimide film 2.

[0116] (3) Polyimide film 3 After purging the reaction vessel, which is equipped with a nitrogen inlet tube, thermometer, and stirring rod, with nitrogen, 205.8 g (0.480 mol) of 1,4-bis(4-amino-2-trifluoromethylphenoxy)benzene and 1200 g of N,N-dimethylacetamide were charged into the reaction vessel under a nitrogen atmosphere and dissolved. Then, while cooling the reaction vessel, 93.8 g (0.478 mol) of cyclobutanetetracarboxylic dianhydride was added in part as a solid and stirred at room temperature for 12 hours. After that, 1.0 g (5.9 mmol) of 4-methylcyclohexane-1,2-dicarboxylic anhydride was added and stirred for 4 hours, and then diluted with 1000 g of N,N-dimethylacetamide to obtain polyamic acid solution A3 with a reduced viscosity of 5.28 dl / g. To polyamic acid solution A3, which had an amine terminal content of 5 eq / t, a solution of colloidal silica fine particles with an average particle size of 0.08 μm dispersed in N,N-dimethylacetamide was added so that the fine particles constituted 2.0% by mass relative to the polyamic acid, thereby obtaining polyamic acid solution B3 containing fine particles. Polyamic acid solution B3 containing fine particles was coated onto a polyester film with a thickness of 188 μm using a comma coater to achieve a final dry thickness of 7 μm. The polymer solution was supplied after a degassing process and a filtration process through a polymer filter with a filtration accuracy of 3 μm. After heating this thin film at 110°C to 135°C for several minutes, it was peeled off the support to obtain a green film with a volatile component content of 21.1% by mass. The obtained green film was passed through a pin tenter having a pin sheet with pins arranged so that the pin spacing was constant when the pin sheets were lined up. The film ends were gripped by inserting them into the pins, and the pin sheet spacing was adjusted so that the film would not break and no unnecessary slack would occur. The film was then transported so that the final pin sheet spacing was 500 mm, and the imidization reaction was carried out by heating under the following conditions: the first stage at 170°C for 2 minutes, the second stage at 230°C for 2 minutes, and the third stage at 355°C for 6 minutes. After that, it was cooled to room temperature in 2 minutes, the parts of the film at both ends with poor flatness were cut off with a slitter, and it was wound into a roll to obtain a colorless, transparent polyimide film 3.

[0117] (4) PET film and PEN film As the PET film, Toyobo Co., Ltd. A4160, 125 μm thick was used. As the PEN film, Toyobo Co., Ltd. Q65HA, 100 μm thick was used.

[0118]

[0119] [Preparation of temporary fixed substrate] For protective film A, Fujicopian's FIXFILM HG1-50 with a total thickness of 75 μm was used, and for protective film B, Nichiei Kako's PET50-H120 (10) with a total thickness of 65 μm was used.

[0120] [Preparation of Samples for Peel Strength Measurement] For each combination of layers A, B, and C shown in Tables 3 and 4, the films or glass of layers A, B, and C were stacked in the order of layer B, A, and C from top to bottom, as shown in Figure 2. A polyimide film was first placed on a 3 mm thick, 150 mm square SUS plate, and then the structures of layers B, A, and C were stacked on top of it. Another polyimide film was placed on top of that, followed by a silicone rubber sheet, and then a 3 mm thick, 150 mm square SUS plate was placed on top of that. This was then pressed for 5 minutes using a small vacuum press (IMC-1123, manufactured by Imoto Seisakusho) at 120°C, with a hydraulic pressure gauge reading of 6 MPa (jack output 1 ton, hot plate area 150 mm x 150 mm). The peel strength was measured using the method described in the measurement method. The structure was fixed as shown in Figure 2. At this time, it was determined by visual inspection whether the peel mode was at the interface between each layer or material fracture. Measurements were also performed using PET film and PEN film instead of polyimide film. The results are shown in Tables 3 and 4.

[0121] Untreated glass is used as glass 1, glass 2 is glass obtained by peeling off polyimide 1 from a glass substrate in the same manner as in the [resin layer bonding process to temporary fixed substrate] of Example 1, and glass 3 is glass obtained by peeling off polyimide 1 from a glass substrate in the same manner as in the [resin layer bonding process to temporary fixed substrate] of Example 1, followed by ultraviolet / ozone cleaning (UV / O ３Cleaned glass was used. In the table, "+UVO ３ Products marked with '' are UV / Ozone cleaning (UV / O ３ This indicates that the material used was cleaned. For ultraviolet / ozone cleaning, a UV ozone cleaning and modification device (SKR1102N-03, manufactured by Run Technical Service Co., Ltd.) was used, and irradiation was performed for 1 minute at a distance of 30 mm from the lamp. In the examples described herein, the prepared glass substrate was OA11 manufactured by Nippon Electric Glass Co., Ltd., and glass 2 and glass 3 were treated with the above glass substrate.

[0122]

[0123]

[0124] [Preparation of Device Bonding Films] Device bonding films for each example and comparative example were manufactured as described below. The tests and measurements described above were performed on each manufactured film. The composition and various physical properties of the device bonding films are shown in Tables 5 and 6. A schematic diagram of the bonded resin film and elastomer film of the example is shown in Figure 5.

[0125] (Example 1) (1) Resin layer bonding process to temporary fixed substrate A glass substrate with sides of 100 mm and a thickness of 0.7 mm was prepared as a temporary fixed substrate. The glass substrate was subjected to ultrasonic water cleaning and ultraviolet / ozone cleaning (UV / O ３ Cleaning was performed. For ultraviolet / ozone cleaning, a UV ozone cleaning and modification device (SKR1102N-03, manufactured by Ran Technical Service Co., Ltd.) was used, and irradiation was performed for 1 minute at a distance of 30 mm from the lamp.

[0126] A solution was prepared by diluting 3-aminopropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., KBM-903) with isopropanol to a concentration of 1% by mass.

[0127] The glass substrate was placed in a spin coater (Japan Create Co., Ltd., MSC-500S). The solution was dropped onto the glass substrate and rotated at 500 rpm, then rotated at 2000 rpm to coat the glass substrate with the solution. After that, it was left in a clean bench for 1 minute to dry, forming a silane coupling agent layer on the glass substrate.

[0128] A polyimide film 1, a square with sides of 90 mm and a thickness of 38 μm, was attached to the silane coupling agent layer as a resin film. The attachment was carried out so that the center of the glass substrate and the center of the polyimide film 1 were roughly aligned. The attachment was performed using a laminator (MCK Corporation, MRK-1000) in a cleanroom under conditions of 22°C and 55% RH, at a lamination speed of 50 mm / second and a cylinder air source pressure of 0.55 MPa.

[0129] (2) Discrete cutting process: Using a cutter, multiple 3 mm square pieces of polyimide were left on the glass substrate. The distance between the centers of the polyimide pieces was 6 mm in both the vertical and horizontal directions. Unnecessary portions were peeled off and removed.

[0130] (3) Weak adhesion process of the exposed temporary fixed substrate By discrete cutting, a portion of the temporary fixed substrate is exposed as the resin layer is removed. A UV ozone cleaning and modification device (SKR1102N-03, manufactured by Ran Technical Service Co., Ltd.) was used to irradiate the exposed substrate surface for 10 minutes at a distance of 30 mm from the lamp.

[0131] (4) Substrate layer bonding process On the surface where the polyimide film 1 remained discretely on the glass, an elastomer film 1 was placed as the substrate film and pressed for 5 minutes using a small vacuum press (IMC-1123 manufactured by Imoto Seisakusho) at 120°C and a hydraulic pressure gauge reading of 6 MPa (jack output 1 ton, hot plate area 150 mm x 150 mm). At this time, a silicone sheet was placed on one side in order to equalize the pressure.

[0132] (5) After removing the sample from the temporary fixed substrate peeling press and allowing it to cool to about 40°C or below, the sample was manually peeled off the temporary fixed substrate.

[0133] (Examples 2-13) In the following examples, device bonding films were prepared in the same manner as in Example 1, except that the temporary fixing substrate, resin film, and base film used were changed as shown in Table 5. The configuration and various physical properties of the device bonding films in Examples 2-13 are shown in Table 5.

[0134] (Comparative Example 1) An elastomer film 1 (size 100 mm x 100 mm) and a polyimide film 1 (size 100 mm x 100 mm) were layered, and a protective film A was attached to the side of the polyimide film 1 opposite the elastomer film 1. The layers were then sandwiched between silicone sheets and pressed to create a laminated sheet. After pressing, the protective film A was peeled off to obtain a device bonding film. As a result, the elastomer film 1 and polyimide film 1 are bonded together across the entire surface, rather than discretely. To investigate the ease of installation on a three-dimensional curved surface, an attempt was made to attach the device bonding film to the convex surface of a watch glass, but it could not be made to conform to the watch glass without wrinkles.

[0135] (Comparative Example 2) Polyimide film 1 (size 100 mm x 100 mm) was cut from a laminate of protective film A and polyimide film 1 (size 5 mm x 5 mm) with a 5 mm gap between the polyimide films 1. A silicone film was bonded to the side with polyimide film 1, and the two sides were sandwiched with silicone sheets and pressed to create a laminated sheet. However, it peeled off during handling and did not form a laminate.

[0136] (Comparative Example 3) An attempt was made to produce a laminated sheet in the same manner as in Comparative Example 2, except that protective film A was changed to glass and polyimide film 1 was changed to polyimide film 3. However, it peeled off during handling and did not form a laminate.

[0137] (Comparative Example 4) The protective film A of Comparative Example 1 was replaced with glass, and Φ5 mm holes were made vertically and horizontally at a center interval of 8 mm in the polyimide film 1 (size 100 mm x 100 mm) (Figure 6A). After this, it was bonded to the elastomer film 1 (size 100 mm x 100 mm) in the same manner as in Comparative Example 1. As a result, the elastomer film is exposed in the areas with Φ5 mm holes rather than being discrete, and the elastomer film 1 and polyimide film 1 are bonded to the entire surface. To investigate the ease of installation on a three-dimensional curved surface, an attempt was made to attach the device bonding film to the convex surface of a watch glass, but it was not possible to make it conform to the watch glass without wrinkles.

[0138] (Comparative Example 5) A cross-shaped hole measuring 2 mm in width and 8 mm in length was made vertically and horizontally at a center interval of 10 mm in the polyimide film 1 (size 100 mm x 100 mm) of Comparative Example 1 (Figure 6B). The device bonding film was prepared in the same manner as in Comparative Example 1, except that elastomer film 2 (size 100 mm x 100 mm) was laminated instead of elastomer film 1. As a result, the elastomer film 2 is exposed in the cross-shaped hole areas rather than being discrete, and the elastomer film 2 sheet and polyimide film 1 are laminated over the entire surface. To investigate the ease of installation on a three-dimensional curved surface, an attempt was made to attach the device bonding film to the convex surface of a watch glass, but it could not be made to conform to the watch glass without wrinkles.

[0139]

[0140]

[0141] In Tables 5 and 6, the resin film retention rate indicates the percentage of discrete resin films remaining bonded to the flexible layer when peeled from the temporary fixed substrate. In Tables 5 and 6, the elastic modulus ratio is calculated from the elastic moduli shown in Table 2, and is expressed as (elastic modulus of the resin film) / (elastic modulus of the base film). In Tables 5 and 6, the area ratio is expressed as {total area of ​​base film not covered by resin film (design value)} / (total area of ​​resin film).

[0142] [Fabrication of a light-emitting element using a discrete device bonding film] Figure 4 shows a method for fabricating a light-emitting element using a discrete device bonding film. Three polyimide films 1 (resin films 14), each measuring 5 mm x 5 mm, were bonded to an elastomer film 2 (base film 32) measuring 100 mm x 100 mm. Next, a protective film (support base 40) was attached to the side of the resin film 14 that was not bonded (Figure 4A). For the attachment, the side of the elastomer film 2 that was bonded to the polyimide film 1 was vacuum-adhered using a laminator from Crime Products, and the protective film HG2-50EX (manufactured by Fujicopian Co., Ltd.) was laminated to the opposite side. Then, the aforementioned protective film (adhesive protective film 41), which had been laser-cut so that roughly the portion of the polyimide film 1 was exposed, was laminated to the bonded side of the polyimide film 1. At this point, a 1 mm wide masking tape, KOKUYO T-501 (masking tape 44), is applied to create areas on the polyimide film 1 that do not have Cu attached in the next step (Figure 4B).

[0143] Next, a NiCr layer of approximately 15 nm was deposited on the polyimide film surface using a binary magnetron sputtering apparatus, followed by a Cu layer of approximately 250 nm. Subsequently, the thickness of the Cu layer was increased to 5 μm by electroplating (Figure 4C). The NiCr layer and Cu layer correspond to the first electrode layer 12 in Figure 4C. At this time, electricity flowed through the protective film on the polyimide film 1 side, making plating possible. After that, the 1 mm wide tape and the protective film on the polyimide film 1 side were peeled off (Figure 4D).

[0144] Next, silver paste (Dotite room-temperature drying type, Fujikura Chemical Co., Ltd. D-362) was dispensed onto the electrode extraction wiring at the location where the chip would be joined. This solder paste acts as a bump to electrically connect the chip and the electrode extraction wiring. An LED element, Nichia LED element RT-V1 (light-emitting element 21), was placed on top of this and electrically joined (Figure 4E). After this, mounting resin 47 (also called a two-component epoxy adhesive) was applied onto the polyimide film 1 so as to cover the first electrode layer 12 and the resin film 14 (Figure 4F). Subsequently, a protective film 42 with adhesive, FIXFILM HG2-50EX manufactured by Fujicopian Co., Ltd., was attached to the light-emitting element 21, and then a 3 mm wide masking tape 44 (KOKUYO Co., Ltd. T-503) was applied to electrically separate the two electrodes on the polyimide film 1 (Figure 4G). Subsequently, a third electrode layer 19 was formed by spin-coating a few drops of nanosilver wire (T-AG219 from Seikoh PMC) at 1000 rpm for 30 seconds (Figure 4H). Then, the protective film (adhesive protective film 42) and masking tape 44 on the LED element were removed (Figure 4I).

[0145] [Fabrication of Solar Cells Using Discrete Device Bonding Films] A film was fabricated in the same manner as in the example, by bonding a 50 mm x 50 mm PEN film (resin film 14) with a pre-deposited barrier layer to the center of an elastomer film 1 (base film 32) measuring 100 mm x 100 mm (Figure 3A). A protective film (support base material 40) was attached to the side of the elastomer film 1 that did not have the PEN film bonded to it (Figure 3B). For the bonding, the side of the elastomer film 1 with the PEN film (resin film 14) bonded to it was vacuum-adhered using a laminator from Crime Products, and an adhesive protective film 41 HG2-50EX (manufactured by Fujicopian) was laminated to the opposite side. Next, the protective film (adhesive protective film 41) cut out by laser so that approximately half of the PEN film was exposed was also laminated to the side with the PEN film bonded to it (Figure 3C).

[0146] Then, ITO was sputtered onto the surface of the PEN film that was half exposed to create a 100 nm ITO layer. After that, the protective film that had been cut out with a laser so that half of the PEN film was exposed was peeled off. Furthermore, the protective film that had been cut out with a laser so that most of the PEN film was exposed was laminated. The PEN film (size 50 mm x 50 mm) was washed with acetone and dried with clean dry air. A ZnO nanoparticle dispersion manufactured by Avantama was dropped onto it, and coating was performed with a coating gap of 25 μm using a No. 0 bar, and heated at 80°C for 10 mins. This condition results in an electron transport layer of approximately 50 nm. After wiping off the coating with acetone, leaving a 95 mm x 95 mm area, the photoelectric conversion layer solution was dropped onto it, and coating was performed with a coating gap of 50 μm, and heated at 100°C for 5 mins. The conditions for forming the photoelectric conversion layer are approximately 250 nm in thickness. The photoelectric conversion layer solution is made by dissolving equal amounts of poly(3-hexylthiophene-2,5-diyl) and Nanom Spectra (E100H) in chlorobenzene. Next, after wiping off the coating with chlorobenzene, leaving a 95 mm x 95 mm area, HTLsolar (Heraus) was added dropwise, coating was performed with a coating gap of 50 μm, and heated at 80°C for 30 minutes. The conditions for forming the hole transport layer are approximately 400 nm in thickness. After that, the coating was wiped off with pure water, leaving a 40 mm x 40 mm area (Figure 3D). In the explanation of the drawings, the electron transport layer, photoelectric conversion layer, and hole transport layer are collectively referred to as the photoelectric conversion section 43. Subsequently, three 2 mm x 35 mm rectangular electrodes (not shown) were deposited with Ag using a SUS mask designed to allow deposition even in the areas without ITO. A PEN film 45, pre-cut to 40 mm x 45 mm and with a pre-deposited barrier layer, was then attached using Aron Alpha EXTRA 2000 manufactured by Toagosei as the sealing adhesive layer 46 (Figure 3E). The adhesive was applied to the entire surface, and the film was immediately passed through a laminator using a spacer to control the adhesive thickness to 10 μm. Subsequently, a FIXFILM HG2-50EX manufactured by Fujicopian was attached to the PEN film 45 with the barrier layer as an adhesive-backed protective film 42 (Figure 3F).

[0147] Next, a 2 mm wide tape, KOKUYO T-503 (masking tape 44), was applied to the adhesive protective film 42 to electrically separate the two electrodes on the PEN film (Figure 3G). Then, a nano-silver wire (Seikoh PMC T-AG219) was applied by spin coating to form a third electrode layer 19 (Figure 3H). Finally, the protective film 42 and the 3 mm tape were removed from the photoelectric conversion element (Figure 3I). This completed the fabrication of a photoelectric conversion element including a PEN film substrate, PEN film, photoelectric conversion layer, and elastomer film.

[0148] 12 First electrode layer 14 Resin film 15 Protective layer 16 Light 17 Photoelectric conversion element 18 Second electrode layer 19 Third electrode layer 21 Light-emitting element 22 Metal wiring 25 Display 32 Substrate film 32' Joint portion of substrate film and resin film 40 Support substrate 41 Adhesive-coated protective film 42 Adhesive-coated protective film 43 Photoelectric conversion section 44 Masking tape 45 Barrier layer film 46 Sealing adhesive layer 47 Mounting resin 61 Layer A 62 Layer B 63 Layer C 64 Double-sided tape 65 Measurement stand

Claims

1. A laminate comprising a base layer made of a material containing a thermoplastic elastomer, and resin layers discretely provided on the base layer, wherein the elastic modulus of the resin layer is 50 times or more the elastic modulus of the base layer.

2. The laminate according to claim 1, wherein the area of ​​the base material layer is 0.5 times or more the area of ​​the resin layer.

3. The laminate according to claim 1 or 2, wherein the resin layer contains any of polyimide, polyamideimide, polyethylene terephthalate, or polyethylene naphthalate, and contains a total of 50% by mass or more of polyimide, polyamideimide, polyethylene terephthalate, and polyethylene naphthalate.

4. The laminate according to claim 1 or 2, wherein the base layer comprises any of polyester elastomer, polyurethane elastomer, or polyamide elastomer, and contains a total of 50% by mass or more of polyester elastomer, polyurethane elastomer, and polyamide elastomer.

5. A device comprising the laminate according to claim 1 or 2, wherein the resin layer is provided with at least one of a light-emitting element, a photoelectric conversion layer, and a sensor element.

6. A method for manufacturing a laminate according to claim 1, comprising: fixing a resin layer on a temporary fixing substrate; machining the resin layer to produce discretely provided resin layers; and attaching the base material layer to the discretely provided resin layers.

7. The method for manufacturing a laminate according to claim 6, wherein the temporary fixing substrate is glass, a silicon wafer, a protective film, or a release film.

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