JP7013838B2 - Curved surface forming method and curved surface forming device for laminated substrate - Google Patents

Description

The present invention relates to a curved surface forming method and a curved surface forming apparatus for a laminated substrate.

In the application of electronic devices such as touch panels and displays, there is a demand for lightweight, hard-to-break, three-dimensional (3D) curved electronic devices suitable for usage scenes. In particular, for in-vehicle applications and wearable applications, a 3D curved electronic device having excellent design and fit is required. Such electronic devices include a transparent resin substrate and a conductive layer. Examples of the material of the conductive layer include transparent inorganic oxides such as indium oxide, carbon (CNT, graphene), metal nanowayers, metal grids, conductive polymers and the like. However, when the transparency, conductivity and durability are comprehensively judged, the transparent inorganic oxide is most suitable for the electronic device having a 3D curved surface.

The method for manufacturing a 3D curved electronic device is a method of preparing a 3D curved substrate in advance and forming a conductive layer or an organic electronic material layer on the surface thereof, or a method of forming a conductive layer or an organic electronic material layer on a flat plate-shaped substrate. It can be roughly divided into a method of forming a film and then processing it into a 3D curved surface. And various methods are being studied for each of them.

However, in the former method, it is difficult to form a uniform film on a 3D curved substrate, or it is difficult to bond the 3D curved substrates to each other. Further, since a general film-forming device or the like suitable for a flat plate-shaped substrate cannot be used as it is, a film-forming device or the like for a 3D curved substrate is prepared, which leads to a significant cost increase.

In the latter method, the Young's modulus of the inorganic oxide is large, and the inorganic oxide is brittle and easily broken, so that it is difficult to process it into a 3D curved surface. In addition, the strain of the inorganic oxide in the direction along the curved surface tends to be large. Further, when a substrate including a functional layer such as an organic electronic material layer is processed into a convex shape on a conductive layer of an inorganic oxide, the strain generated in the conductive layer propagates to the functional layer, and a large strain is generated in the functional layer. Is likely to occur. Further, when the mechanical properties are non-uniform in the conductive layer, such as when a plurality of thin film transistors (TFTs) are arranged in a matrix on the conductive layer, the distortion of the functional layer varies. It is large and the variation in performance tends to be large. Therefore, it is difficult to obtain excellent reliability while suppressing cost increase with the conventional technique.

Patent Document 1 describes a technique for forming a decorative film having a 3D curved surface, but this decorative film is not applicable to an electronic device.

An object of the present invention is to provide a curved surface forming method and a curved surface forming apparatus for a laminated substrate, which can improve the reliability of a 3D curved surface electronic device while suppressing an increase in cost.

One aspect of the method for forming a curved surface of a laminated substrate is to form a curved surface of a laminated substrate for processing a laminated substrate including a support substrate including a resin substrate of a thermoplastic resin and a conductive layer on the support substrate into a three-dimensional curved surface. The method is characterized by having a step of deforming the elastic sheet while adhering the laminated substrate to the elastic sheet, and adhering the laminated substrate to a temperature-controlled mold to soften the resin substrate. do.

According to the present invention, it is possible to improve the reliability of a 3D curved electronic device while suppressing an increase in cost.

It is a figure which shows the curved surface forming apparatus suitable for the curved surface forming method of the laminated substrate which concerns on 1st Embodiment. It is a figure which shows the curved surface formation method of the laminated substrate which concerns on 1st Embodiment in the order of a process. It is a figure which shows the modification of 1st Embodiment. It is a figure which shows the curved surface forming apparatus suitable for the curved surface forming method of the laminated substrate which concerns on 2nd Embodiment. It is a figure which shows the curved surface formation method of the laminated substrate which concerns on 2nd Embodiment in the order of a process. It is a figure which shows the modification of the 2nd Embodiment. It is sectional drawing which shows the 1st example of a laminated substrate. It is sectional drawing which shows the 2nd example of a laminated substrate. It is sectional drawing which shows the 3rd example of a laminated substrate. It is sectional drawing which shows the 4th example of a laminated substrate. It is sectional drawing which shows the 5th example of a laminated substrate. It is a figure which shows the positional relationship of the layer in the 5th example of a laminated substrate. It is sectional drawing which shows the 6th example of a laminated substrate. It is sectional drawing which shows the 7th example of a laminated substrate. It is sectional drawing which shows the 8th example of a laminated substrate. It is a figure which shows the planar shape of a laminated substrate. It is a figure which shows the crack which occurred in the conductive layer. It is a figure which shows the laminated substrate after processing of Example 14. It is a figure which shows the curved surface formation method of the comparative example in the order of a process.

Hereinafter, embodiments of the present invention will be described with reference to the drawings.

(First Embodiment)
First, a method for forming a curved surface of a laminated substrate according to the first embodiment will be described. FIG. 1 is a diagram showing a curved surface forming apparatus suitable for the curved surface forming method of the laminated substrate according to the first embodiment. FIG. 2 is a diagram showing the method of forming a curved surface of the laminated substrate according to the first embodiment in the order of processes.

The curved surface forming device 100 includes a concave mold 111 and a temperature control unit 116 for adjusting the temperature of the concave mold 111. The concave mold 111 is formed with a hole 115 connecting the bottom surface and the back surface of a three-dimensional (3D) curved surface, for example, a spherical concave surface 112, and the pump 117 is connected to the hole 115. The curved surface forming apparatus 100 includes an elastic rubber sheet 131 arranged so as to close the concave surface 112 on the flat surface 113 around the concave surface 112 of the concave mold 111. The elastic rubber sheet 131 is formed with holes 132 penetrating the front and back surfaces thereof.

When the laminated substrate is processed into a 3D curved surface using the curved surface forming apparatus 100, first, as shown in FIG. 2A, a support substrate including a resin substrate of a thermoplastic resin and a conductive layer on the support substrate are provided. Prepare the laminated substrate 151. Further, the temperature control portion 116 heats and controls the concave mold 111 near the softening temperature (Tg) of the resin substrate. Then, the laminated substrate 151 is placed on the elastic rubber sheet 131 so as to close the holes 132. For example, the temperature of the temperature control is lower than the softening temperature (Tg). The laminated substrate 151 may have a functional layer such as an organic electronic material layer on the conductive layer.

Next, the pump 117 is operated to exhaust the space between the concave surface 112 and the elastic rubber sheet 131. As a result, the elastic rubber sheet 131 is in close contact with the concave surface 112 while being stretched. Further, since the laminated substrate 151 is in close contact with the elastic rubber sheet 131 and approaches the concave mold 111 as the elastic rubber sheet 131 is deformed, heat is transferred from the concave mold 111 to the laminated substrate 151 and is included in the laminated substrate 151. The resin substrate softens. Then, as shown in FIG. 2B, the laminated substrate 151 is in close contact with the concave mold 111, and the laminated substrate 151 is plastically deformed so as to imitate the concave surface 112.

After that, by stopping the operation of the pump 117 and opening the hole 115 to the atmosphere, the elastic rubber sheet 131 returns to its original shape, and the laminated substrate 151 can be released from the concave mold 111. Since the resin substrate is plastically deformed, the laminated substrate 151 maintains its shape following the concave surface 112 even when it is released from the concave mold 111.

In this way, the laminated substrate 151 can be processed into a 3D curved surface.

In the first embodiment, since the elastic rubber sheet 131 expands and contracts isotropically during processing, the laminated substrate 151 is uniformly pressed against the concave mold 111 and adheres to the concave mold 111. Further, the resin substrate contained in the laminated substrate 151 is not softened by heating in advance, but is in close contact with the temperature-controlled concave mold 111 and gradually receives heat to soften. Therefore, according to the first embodiment, the conductive layer contained in the laminated substrate 151 can be deformed while suppressing distortion and cracks in the direction along the curved surface, and the functional layer on the conductive layer is included. It is also possible to suppress distortion and cracks in the functional layer. Even when the mechanical properties are non-uniform in the conductive layer, such as when a plurality of TFTs are arranged in a matrix on the conductive layer, variation in distortion of the functional layer is suppressed and uniform performance is obtained. Can be done.

As shown in FIG. 3, the curved surface forming device 100 may include a convex mold 121 fitted in the concave mold 111 and a temperature control unit 126 for adjusting the temperature of the convex mold 121. When this curved surface forming device 100 is used, the curved surface accuracy is further improved by pressing the laminated substrate 151 with the convex mold 121 heated and temperature-controlled by the temperature control portion 126 after the laminated substrate 151 is in close contact with the concave mold 111. It is possible to do.

(Second embodiment)
Next, a method for forming a curved surface of the laminated substrate according to the second embodiment will be described. FIG. 4 is a diagram showing a curved surface forming apparatus suitable for the curved surface forming method of the laminated substrate according to the second embodiment. FIG. 5 is a diagram showing the method of forming a curved surface of the laminated substrate according to the second embodiment in the order of processes.

The curved surface forming device 200 includes a closed container (chamber) 241, a concave mold 211 in the closed container 241 and a temperature control unit 216 for adjusting the temperature of the concave mold 211. The curved surface forming device 200 includes an elastic rubber sheet 231 that vertically divides the space above the concave mold 211 in the closed container 241. The curved surface forming apparatus 200 includes a substrate holding rubber sheet 233 arranged so as to cover the concave surface 212 with a gap on the flat surface 213 around the 3D curved surface, for example, the spherical concave surface 212 of the concave mold 211. The substrate holding rubber sheet 233 is formed with holes 234 that are narrower than the laminated substrate to be processed and are covered by the laminated substrate. The substrate holding rubber sheet 233 is provided so as to expose a part of the concave surface 212, and even when the laminated substrate is placed, the pressures in the spaces above and below the substrate holding rubber sheet 233 are equal. For example, the substrate holding rubber sheet 233 may have a hole separated from the hole 234 and not covered by the laminated substrate, and the end portion of the substrate holding rubber sheet 233 is a concave surface 212 from the boundary between the concave surface 212 and the flat surface 213. It may be located on the side. The curved surface forming device 200 is provided with a pipe connecting the space on the elastic rubber sheet 231 and the space under the elastic rubber sheet 231, and the bypass valve 218 is provided in this pipe. The gas supply unit 219 is connected to the space above the elastic rubber sheet 231 and the pump 217 is connected to the space below the elastic rubber sheet 231.

When the laminated substrate is processed into a 3D curved surface using the curved surface forming apparatus 200, first, as shown in FIG. 5A, a support substrate including a resin substrate of a thermoplastic resin and a conductive layer on the support substrate are provided. Prepare the laminated substrate 251. Further, the temperature control portion 216 heats and controls the concave mold 211 near the softening temperature (Tg) of the resin substrate. Then, the closed container 241 is opened, the laminated substrate 251 is placed on the substrate holding rubber sheet 233 so as to close the hole 234, and the closed container 241 is closed. The laminated substrate 251 may have a functional layer such as an organic electronic material layer on the conductive layer.

The bypass valve 218 is then opened to operate the pump 217. As a result, the entire inside of the closed container 241 is in a reduced pressure state. After that, the bypass valve 218 is closed, and gas is supplied from the gas supply unit 219 to the space on the elastic rubber sheet 231. As the gas, for example, air or nitrogen gas is supplied. As a result, the elastic rubber sheet 231 extends and adheres to the laminated substrate 251, and the laminated substrate 251 and the substrate holding rubber sheet 233 are pressed against the concave surface 212 and adhere to the laminated substrate 251. At this time, heat is transferred from the concave mold 211 to the laminated substrate 251 so that the resin substrate contained in the laminated substrate 251 is softened. Then, as shown in FIG. 5B, the laminated substrate 251 is plastically deformed so as to imitate the concave surface 212.

After that, by stopping the operation of the pump 217 and the supply of gas from the gas supply unit 219 and opening the closed container 241 to the atmosphere, the elastic rubber sheet 231 returns to its original shape and the laminated substrate 251 is formed into a concave mold 211. You will be able to release the mold from. Since the resin substrate is plastically deformed, the laminated substrate 251 maintains a shape that follows the concave surface 212 even when the resin substrate is released from the concave mold 211.

In this way, the laminated substrate 251 can be processed into a 3D curved surface.

In the second embodiment, since the elastic rubber sheet 231 expands and contracts isotropically during processing, the laminated substrate 251 is uniformly pressed against the concave mold 211 and adheres to the concave mold 211. Further, the resin substrate contained in the laminated substrate 251 is pressed against the temperature-controlled concave mold 211 and adheres to the laminated substrate 251 without being preheated and softened, and gradually receives heat to soften. Therefore, according to the second embodiment, the conductive layer contained in the laminated substrate 251 can be deformed while suppressing distortion and cracks in the direction along the curved surface, and the functional layer on the conductive layer is included. It is also possible to suppress distortion and cracks in the functional layer. Even when the mechanical properties are non-uniform in the conductive layer, such as when a plurality of TFTs are arranged in a matrix on the conductive layer, variation in distortion of the functional layer is suppressed and uniform performance is obtained. Can be done. Laminated substrates including functional layers are suitable for making plastic electronic devices.

As shown in FIG. 6, the curved surface forming device 200 may include a convex mold 221 fitted in the concave mold 211 and a temperature control unit 226 for adjusting the temperature of the convex mold 221. When this curved surface forming device 200 is used, the curved surface accuracy is further improved by pressing the laminated substrate 251 with the convex die 221 heated and temperature-controlled by the temperature control portion 226 after the laminated substrate 251 is in close contact with the concave die 211. It is possible to do.

In the step of opening the bypass valve 218 and operating the pump 217, the pressure in the closed container 241 is preferably 80,000 Pa or less, and in the step of supplying gas from the gas supply unit 219, the pressure on the elastic rubber sheet 231 is reached. The pressure in the space is preferably 0.05 MPa to 1 MPa. Outside the range of these conditions, it may be difficult to obtain good curved surface accuracy.

In the first and second embodiments, it is preferable that the range of the concave surface of the concave mold is wider than that of the laminated substrate to be processed in a plan view. In this case, the entire laminated substrate can be brought into close contact with the concave surface without restraint, and the 3D curved surface can be processed while further suppressing distortion. On the other hand, if the end of the laminated board is fixed in a state where it cannot be moved, or if the end of the laminated board is processed in a state where it is in contact with a surface other than the machined surface of the mold, the fixed part of the laminated board or Distortion is likely to occur from the part that comes into contact with other than the machined surface. When a convex mold is used, the laminated substrate and the convex mold may come into contact with each other at points, so that stress may be concentrated there and distortion may easily occur. The preferred magnitude (stretching amount) of strain in the direction along the curved surface is 1% or less.

In the temperature control, for example, the temperature of the concave mold and the convex mold is set lower than the softening temperature (Tg) of the resin substrate, and the temperature of the flat plate-shaped laminated substrate before being brought into close contact with the concave mold is room temperature or the softening temperature. The temperature is set to be 20 ° C. or more lower than that.

After processing the laminated substrate into a 3D curved surface in the first or second embodiment, additional processing may be performed in order to improve the accuracy of the 3D curved surface. Specifically, a method of holding in a mold, reheating and pressurizing can be adopted, and for example, a molding method such as injection molding and a forming method such as autoclave can be adopted.

When the conductive layer is a transparent conductive layer of an inorganic oxide, the hardness of the surface of the supporting substrate of the conductive layer is preferably 180 MPa or more in order to suppress the cracks. The support substrate is, for example, a resin substrate or includes a resin substrate and a base layer formed on the resin substrate. The hardness of the surface of the support substrate is measured with a nano indenter. According to the present inventors, a thickness using indium oxide as an inorganic oxide on a flat elliptical substrate having a surface hardness of 180 MPa or more, a major axis dimension of 85 mm, and a minor axis dimension of 54.5 mm. When a transparent conductive layer having a diameter of 110 nm was formed and the laminated substrate was processed into a spherical shape having a radius of curvature of 86 mm, it was confirmed that cracks did not occur. By using a support substrate having a hard surface, it is possible to reduce the distortion of the transparent conductive layer during processing.

Here, the components included in the curved surface forming apparatus 100 or 200 will be described.

[Elastic rubber sheet 131, 231]
The elastic rubber sheets 131 and 231 expand and contract by being depressurized or pressurized, and have a function of bringing the laminated substrate into close contact with the mold. The elastic rubber sheet 131 also has a function of transferring the heat of the mold to the laminated substrate. As the material of the elastic rubber sheet, a known elastic rubber material can be used as it is. For example, natural rubber, styrene-butadiene rubber (SBR), isoprene rubber (IR), butadiene rubber (BR), chloroprene rubber (CR), acrylonitrile-butadiene rubber (NBR), butyl rubber (isobutyene isoprene rubber (IIR)), Use ethylene / propylene rubber (EPM), ethylene / propylene / diene rubber (EPDM), urethane rubber (U), silicone rubber (silicone rubber (Si, Q)), fluororubber (FKM), etc. as materials for elastic rubber sheets. Can be done. Thermoplastic elastomers such as styrene-based, olefin-based, ester-based, urethane-based, amide-based, polyvinyl chloride (PVC) -based, and fluorine-based thermoplastic elastomers can also be used as the material of the elastic rubber sheet. The material of the elastic rubber sheet is preferably selected according to conditions such as temperature and pressure when forming a curved surface on the laminated substrate. For example, it is preferable to select a material in consideration of heat resistance, elasticity, etc., depending on the conditions. The thickness of the elastic rubber sheet is, for example, in the range where a curved surface of 0.01 mm to 2.0 mm can be easily formed.

From the viewpoint of the uniformity of deformation of the laminated substrate, it is preferable that the elastic rubber sheet does not easily adhere to the laminated substrate and the mold, and the surface of the elastic rubber sheet in contact with the laminated substrate or the mold becomes slippery. Further, after the curved surface is formed, the elastic rubber sheet is peeled off from the mold and the laminated substrate is removed from the elastic rubber sheet. Therefore, it is preferable that the surface of the elastic rubber sheet is surface-treated to reduce friction. Silicone rubber and fluororubber are particularly preferable as the material of the elastic rubber sheet.

The holes 132 of the elastic rubber sheet 131 are provided to attract and hold the laminated substrate 151 to the elastic rubber sheet 131, and the number of holes 132 may be 1 or 2 or more. The position of the hole 132 can be arbitrarily set according to the shape of the laminated substrate 151.

[Molds 111, 121, 211, 221]
As the concave mold and the convex mold, a general mold can be used as it is as long as it has a 3D curved surface shape formed on the laminated substrate, for example, a curved surface matching the spherical shape and a heat capacity suitable for processing. Specifically, as the mold material, for example, metal materials such as aluminum (Al) and nickel (Ni), glass, ceramics and the like can be used. The temperature control unit has a temperature control heater attached to the inside of the mold or the outer surface of the mold. The surface of the mold may be subjected to general heat resistance treatment, mold release treatment, or both.

The position of the hole 115 of the concave mold 111 can be arbitrarily set according to the shape of the laminated substrate 151.

[Substrate holding rubber sheet]
The substrate holding rubber sheet has a function of holding a laminated substrate and maintaining a space between the laminated substrate and the concave mold. As the material of the substrate holding rubber sheet, the same material as that of the elastic rubber sheet can be used. The thickness and shape of the substrate holding rubber sheet can be set according to the above-mentioned functions of holding the laminated substrate and maintaining the space. Even when the laminated substrate 251 is directly placed on the concave mold 211, if the spaces above and below the laminated substrate 251 communicate with each other and the pressures are equal between them, the substrate holding rubber sheet 233 is not used. It is also good.

Next, an example of a laminated substrate to be formed to form a curved surface will be described.

(First example of laminated substrate)
FIG. 7 is a cross-sectional view showing a first example of the laminated substrate. FIG. 7 (a) shows a state before forming a curved surface, FIG. 7 (b) shows a state after convex processing is performed, and FIG. 7 (c) shows a state after concave processing is performed. show. The first laminated substrate 10 is a conductive layer-forming substrate having a resin substrate 11 made of a thermoplastic resin and a conductive layer 12 on the resin substrate 11. The resin substrate 11 is an example of a support substrate.

As the material of the resin substrate 11, a known thermoplastic resin can be used as it is. For example, polycarbonate, polyethylene terephthalate, polyethylene naphthalate acrylic (polymethylmethacrylate), polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polystyrene, styrene acrylonitrile copolymer, styrene butadiene acrylonitril copolymer, polyethylene, ethylene acetate. Vinyl copolymers, polypropylene, polyacetal, cellulose acetate, polyamide (nylon), polyurethane, fluorine-based (Teflon (registered trademark)) and the like can be used as the material of the resin substrate 11. In particular, polycarbonate and polyethylene terephthalate are preferable in terms of moldability, transparency and cost. The thickness of the resin substrate 11 is, for example, in the range where a curved surface of 0.03 mm to 2.0 mm can be easily formed.

As the material of the conductive layer 12, a known conductive material can be used, and it may be transparent or opaque. Examples of the opaque material include metal materials such as gold (Au), silver (Ag), copper (Cu), aluminum (Al), nickel (Ni), tungsten (W) and molybdenum (Mo). Examples of the transparent material include the above-mentioned inorganic oxide, carbon (carbon nanotube (CNT), graphene), metal nanowayer, metal grid, conductive polymer and the like. Although it depends on the use of the conductive layer 12, the inorganic oxide is dense and has conductivity, and is excellent in conductivity, transparency (transmittance and haze) and reliability, which is particularly preferable. Examples of the inorganic oxide include oxides such as indium (In), tin (Sn), zinc (Zn), and aluminum (Al), and examples of these inorganic oxides include tungsten (W) and titanium (Ti). ), Zinc (Zr), zinc (Zn), antimony (Sb), gallium (Ga), germanium (Ge), fluorine (F) and the like may be added. For example, the thickness of the conductive layer 12 is adjusted according to the amount of current required for the electronic device, and when the conductive layer 12 is composed of an inorganic oxide, the thickness is 50 nm to 500 nm, preferably 200 nm or less. This is because the thicker the conductive layer 12, the more easily damage such as cracks occurs during the curved surface forming process. For example, the sheet resistance of the conductive layer 12 is 300Ω / □ or less. For example, the conductive layer 12 can be formed by a vacuum deposition method, and the vacuum deposition method includes a vacuum deposition method, a sputtering method, an ion plating method, a chemical vapor deposition (CVD) method, and the like. Can be mentioned. Of these, the sputtering method capable of forming a high-speed film is preferable.

By performing the processing of the first or second embodiment with the conductive layer 12 of the laminated substrate 10 on the concave mold side, the convex 3D curved surface shown in FIG. 7B can be formed on the laminated substrate 10. can. Further, by performing the processing of the first or second embodiment with the resin substrate 11 of the laminated substrate 10 on the concave mold side, the concave 3D curved surface shown in FIG. 7C is formed on the laminated substrate 10. Can be done.

The conductive layer 12 is formed on the entire surface or a part of the resin substrate 11. Further, in FIGS. 7 (b) and 7 (c), the entire laminated substrate 10 is processed into a 3D curved surface shape, but only a part of the laminated substrate 10 may be processed into a 3D curved surface shape.

In the laminated substrate 10, since the conductive layer 12 is directly formed on the resin substrate 11, the hardness of the surface of the resin substrate 11 is preferably 180 MPa or more. Examples of such a material include polyethylene terephthalate and polyethylene naphthalate-based materials.

(Second example of laminated substrate)
FIG. 8 is a cross-sectional view showing a second example of the laminated substrate. FIG. 8A shows a state before forming a curved surface, FIG. 8B shows a state after convex processing is performed, and FIG. 8C shows a state after concave processing is performed. show. The second laminated substrate 20 is a conductive layer forming substrate having a base layer 13 on the resin substrate 11, and the conductive layer 12 is formed on the base layer 13. The resin substrate 11 and the base layer 13 are included in the support substrate. Other configurations are the same as those of the first laminated substrate 10.

The base layer 13 is used, for example, to supplement the mechanical properties of the resin substrate 11. For example, even when the resin substrate 11 does not have sufficient hardness as the base of the conductive layer 12, the base layer 13 having a hardness higher than that of the resin substrate 11 can be formed to obtain a base having sufficient hardness. .. The base layer 13 may be used for adjusting the thermal expansion rate. By including the base layer 13 in this way, the material selection range of the resin substrate 11 can be expanded, and a thermoplastic resin having excellent processability can be used for the resin substrate 11. Examples of the material of the base layer 13 include an ultraviolet (UltraViolet: UV) curable resin material and a thermosetting resin material. More specifically, acrylic resin, urethane resin, epoxy resin and the like can be mentioned. The hardness of the base layer 13 is preferably 180 MPa or more. By using the base layer 13 having a hardness of 180 MPa or more, it is possible to further reduce the strain at the time of forming a curved surface when the conductive layer 12 is an inorganic oxide layer. The hardness and thermal expansion rate of the base layer 13 formed of the UV curable resin and the thermosetting resin can be adjusted by adjusting the monomer material, the cross-linking density, the amount of the reaction initiator, and the like. The base layer 13 can be formed by applying a material obtained by mixing at least an organic monomer material having a reactive group and an initiator on the resin substrate 11 and performing a curing treatment such as UV irradiation or heat treatment. The thickness of the base layer 13 is, for example, 0.1 μm to 10 μm. Examples of the coating method include spin coat method, casting method, microgravure coat method, gravure coat method, bar coat method, roll coat method, wire bar coat method, dip coat method, slit coat method, capillary coat method, and spray. Various printing methods such as a coating method, a nozzle coating method, a gravure printing method, a screen printing method, a flexographic printing method, an offset printing method, a reverse printing method, and an inkjet printing method can be used.

By performing the processing of the first or second embodiment with the conductive layer 12 of the laminated substrate 20 on the concave mold side, the convex 3D curved surface shown in FIG. 8B can be formed on the laminated substrate 20. can. Further, by performing the processing of the first or second embodiment with the resin substrate 11 of the laminated substrate 20 on the concave mold side, the concave 3D curved surface shown in FIG. 8C is formed on the laminated substrate 20. Can be done.

(Third example of laminated substrate)
FIG. 9 is a cross-sectional view showing a third example of the laminated substrate. FIG. 9A shows a state before forming a curved surface, FIG. 9B shows a state after convex processing is performed, and FIG. 9C shows a state after concave processing is performed. show. The third laminated substrate 30 is an organic electronic device substrate having an organic electronic material layer 14 on the conductive layer 12. Other configurations are the same as those of the second laminated substrate 20.

The organic electronic material layer 14 is composed of a single layer or a laminated layer, and exhibits functions such as color development, light emission, polarization, and deformation by applying electricity, for example. Conventional organic electronic material layers such as electrochromic, electroluminescence, chemical luminescence, electrophoretic, electrowetting, liquid crystal, and piezoelectric can be used as they are for the organic electronic material layer 14. Inorganic materials such as inorganic nanoparticles may be mixed in the organic electronic material layer 14. The total thickness of the organic electronic material layer 14 is generally 50 μm or less. Examples of the coating method include spin coat method, casting method, microgravure coat method, gravure coat method, bar coat method, roll coat method, wire bar coat method, dip coat method, slit coat method, capillary coat method, and spray. Various printing methods such as a coating method, a nozzle coating method, a gravure printing method, a screen printing method, a flexographic printing method, an offset printing method, a reverse printing method, and an inkjet printing method can be used.

By performing the processing of the first or second embodiment with the organic electronic material layer 14 of the laminated substrate 30 on the concave mold side, the convex 3D curved surface shown in FIG. 9B is formed on the laminated substrate 30. be able to. Further, by performing the processing of the first or second embodiment with the resin substrate 11 of the laminated substrate 30 on the concave mold side, the concave 3D curved surface shown in FIG. 9C is formed on the laminated substrate 30. Can be done. The laminated substrate 30 on which the 3D curved surface is formed can be used, for example, as an organic electronic device substrate. Therefore, an organic electronic device substrate having a 3D curved surface can be obtained with excellent productivity.

(Fourth example of laminated substrate)
FIG. 10 is a cross-sectional view showing a fourth example of the laminated substrate. FIG. 10A shows a state before the curved surface is formed, and FIG. 10B shows a state after the curved surface is processed. The fourth laminated substrate 40 is a conductive layer forming substrate having a laminated substrate 20a and a laminated substrate 20b having the same configuration as the laminated substrate 20. The laminated substrate 20a has a resin substrate 11a, a base layer 13a, and a conductive layer 12a, and the laminated substrate 20b has a resin substrate 11b, a base layer 13b, and a conductive layer 12b. The laminated substrate 40 has a double-sided adhesive layer 41 that adheres the conductive layer 12a and the conductive layer 12b to each other. That is, the laminated substrate 40 has a structure in which the laminated substrate 20a and the laminated substrate 20b are bonded to each other by the double-sided adhesive layer 41. The resin substrates 11a and 11b, the conductive layers 12a and 12b, and the base layers 13a and 13b have the same configurations as the resin substrate 11, the conductive layer 12, and the base layer 13, respectively. The resin substrate 11a and the base layer 13a are included in one support substrate, and the resin substrate 11b and the base layer 13b are included in the other support substrate. The double-sided adhesive layer 41 is, for example, an OCA (Optical Clear Adhesive) tape.

The laminated substrate 40 shown in FIG. 10A can be obtained by, for example, bonding the laminated substrate 20a and the laminated substrate 20b using the double-sided adhesive layer 41. A conventional bonding device can be used for this bonding. Then, by performing the processing of the first or second embodiment with the laminated substrate 20a of the laminated substrate 40 on the concave mold side, the 3D curved surface shown in FIG. 10B can be formed on the laminated substrate 40. .. The laminated substrate 40 on which the curved surface is formed can be used, for example, as a conductive layer forming substrate having a bonded structure.

Generally, in order to bond two curved substrates, a curved substrate whose curvature is controlled with high accuracy is prepared, and a dedicated bonding device with high accuracy is required on the curved substrate. On the other hand, according to the first or second embodiment, it is possible to obtain a laminated substrate 40 having a bonded structure having a 3D curved surface by using a conventional bonding device used for a flat plate-shaped substrate. That is, it is possible to obtain a laminated substrate 40 that can be used as a conductive layer forming substrate at low cost and excellent productivity.

It is preferable to use OCA tape for the double-sided adhesive layer 41 from the viewpoint of optical characteristics and film thickness uniformity. A general adhesive (photo-curing type, thermosetting type) can also be used. The thickness of the double-sided adhesive layer 41 is, for example, 20 μm to 200 μm.

(Fifth example of laminated substrate)
FIG. 11 is a cross-sectional view showing a fifth example of the laminated substrate. FIG. 11A shows a state before the curved surface is formed, and FIG. 11B shows a state after the curved surface is processed. The fifth laminated substrate 50 is an organic electronic device substrate having a laminated substrate 30a and a laminated substrate 30b having the same configuration as the laminated substrate 30. The laminated substrate 30a has a resin substrate 11a, a base layer 13a, a conductive layer 12a and an organic electronic material layer 14a, and the laminated substrate 30b has a resin substrate 11b, a base layer 13b, a conductive layer 12b and an organic electronic material layer 14b. .. The laminated substrate 50 has an organic electronic material layer 14c sandwiched between the organic electronic material layer 14a and the organic electronic material layer 14b. That is, the laminated substrate 50 has a structure in which the laminated substrate 30a and the laminated substrate 30b sandwich the organic electronic material layer 14c. The resin substrates 11a and 11b, the conductive layers 12a and 12b, and the base layers 13a and 13b have the same configurations as the resin substrate 11, the conductive layer 12, and the base layer 13, respectively. Further, for example, the organic electronic material layer 14a is an oxide electrochromic (EC) layer, the organic electronic material layer 14b is a reduced EC layer, and the organic electronic material layer 14c is a solid electrolyte layer. The laminated substrate 50 has a protective layer 51 that covers and protects the conductive layer 12a, the organic electronic material layer 14a, the organic electronic material layer 14c, the organic electronic material layer 14b, and the conductive layer 12b from the side. A part of the conductive layer 12a and a part of the conductive layer 12b are exposed from the protective layer 51 as a drawing portion. FIG. 12 shows the positional relationship between the protective layer and each layer covered by the protective layer in a plan view. 12 (a) shows the positional relationship between the protective layer 51 and the conductive layer 12b, FIG. 12 (b) shows the positional relationship between the protective layer 51 and the conductive layer 12a, and FIG. 12 (c) shows the positional relationship between the protective layer 51 and the conductive layer 12a. The positional relationship between the layer 51 and the organic electronic material layers 14b, 14c and 14a is shown.

The protective layer 51 is formed so as to physically and chemically protect the side surface portion of the laminated substrate 50 (organic electronic device substrate). The protective layer 51 can be formed by, for example, applying a UV curable or thermosetting insulating resin so as to cover the side surface and / or the upper surface and curing the protective layer 51. The thickness of the protective layer 51 is not particularly limited and may be appropriately selected depending on the intended purpose, and is preferably 0.5 μm to 10 μm.

The laminated substrate 50 shown in FIG. 11A is obtained, for example, by laminating a laminated substrate 30a and a laminated substrate 30b with an organic electronic material layer 14c sandwiched between them, and then forming a protective layer 51. .. A conventional bonding device can be used for this bonding. Then, by performing the processing of the first or second embodiment with the laminated substrate 30 of the laminated substrate 50 on the concave mold side, the 3D curved surface shown in FIG. 11B can be formed on the laminated substrate 50. .. The laminated substrate 50 on which the curved surface is formed can be used, for example, as an organic electronic device substrate having a bonded structure.

According to the first or second embodiment, it is possible to obtain a laminated substrate 50 having a bonded structure having a 3D curved surface by using a conventional bonding device used for a flat plate-shaped substrate. That is, it is possible to obtain a laminated substrate 50 that can be used as an organic electronic device substrate at low cost and excellent productivity.

In applications where the color development of the organic electronic material layers 14a and 14c is visually recognized from only one of the resin substrates 11a or 11b, the resin substrate on the visually recognized side is transparent, but the other resin substrate is not transparent. good.

(Sixth example of laminated substrate)
FIG. 13 is a cross-sectional view showing a sixth example of the laminated substrate. FIG. 13A shows a state before the curved surface is formed, and FIG. 13B shows a state after the curved surface is processed. The sixth laminated substrate 60 is an organic electronic device substrate having a laminated substrate 63a and a laminated substrate 63b. The laminated substrate 63a has a resin substrate 11a, a conductive layer 12a, and an organic electronic material layer 14a, and the laminated substrate 63b has a resin substrate 11b, a conductive layer 12b, and an organic electronic material layer 14b. The laminated substrate 63a further has a processing resin substrate 61a and a double-sided adhesive layer 62a, and the processing resin substrate 61a and the resin substrate 11a are bonded to each other by the double-sided adhesive layer 62a. The laminated substrate 63b further has a processing resin substrate 61b and a double-sided adhesive layer 62b, and the processing resin substrate 61b and the resin substrate 11b are bonded to each other by the double-sided adhesive layer 62b. The laminated substrate 60 has an organic electronic material layer 14c sandwiched between the organic electronic material layer 14a and the organic electronic material layer 14b. That is, the laminated substrate 60 has a structure in which the laminated substrate 63a and the laminated substrate 63b sandwich the organic electronic material layer 14c. Like the laminated substrate 50, the laminated substrate 60 has a protective layer 51, and a part of the conductive layer 12a and a part of the conductive layer 12b are exposed from the protective layer 51 as a drawing portion.

The double-sided adhesive layers 62a and 62b have the same configuration as the double-sided adhesive layer 41. The processing resin substrates 61a and 61b are attached to the outside of the resin substrates 11a and 11b by the double-sided adhesive layers 62a and 62b, respectively, to improve the curved surface processing accuracy. Materials that can be used for the resin substrates 11a and 11b can be used for the processing resin substrates 61a and 61b. For example, the thickness of the processing resin substrates 61a and 61b is about the same as the thickness of the resin substrates 11a and 11b. Is. However, it is preferable that the elastic modulus of the processing resin substrates 61a and 61b is smaller than the elastic modulus of the resin substrates 11a and 11b. When the elastic modulus of the resin substrates 61a and 61b for processing is larger than the elastic modulus of the resin substrates 11a and 11b, the neutral axis during bending is formed with the conductive layers 12a and 12b and functional layers such as the organic electronic material layers 14a to 14c. It may be far from the center of the film thickness. In such a case, the strain of the conductive layers 12a and 12b such as the inorganic oxide tends to be large. A material particularly suitable for the resin substrates 61a and 61b for processing is polycarbonate having excellent transparency and processability.

In order to obtain the laminated substrate 60 shown in FIG. 13 (a), for example, the laminated substrate 63a and the laminated substrate 63b are bonded together with the organic electronic material layer 14c sandwiched between them, and then the protective layer 51 is formed. Obtained at. A conventional bonding device can be used for this bonding. Then, by performing the processing of the first or second embodiment with the laminated substrate 63a of the laminated substrate 60 on the concave mold side, the 3D curved surface shown in FIG. 13B can be formed on the laminated substrate 60. .. The laminated substrate 60 on which the curved surface is formed can be used, for example, as an organic electronic device substrate having a bonded structure.

According to the first or second embodiment, it is possible to obtain a laminated substrate 60 having a bonded structure having a 3D curved surface by using a conventional bonding device used for a flat plate-shaped substrate. That is, it is possible to obtain a laminated substrate 60 that can be used as an organic electronic device substrate at low cost and excellent productivity. In particular, since the laminated substrate 60 includes the processing resin substrates 61a and 61b, the processability of the entire laminated substrate 60 can be further improved by selecting the processing resin substrates 61a and 61b having excellent processability. It is possible to obtain a laminated substrate 60 having excellent curved surface accuracy.

After processing the laminated substrate 60 into a 3D curved surface shape, the double-sided adhesive layer 62a may be peeled off from the resin substrate 11a, and the double-sided adhesive layer 62b may be peeled off from the resin substrate 11b. In this case, the processing resin substrates 61a and 61b are removed to obtain a fifth laminated substrate 50.

(7th example of laminated substrate)
FIG. 14 is a cross-sectional view showing a seventh example of the laminated substrate. FIG. 14A shows a state before the curved surface is formed, and FIG. 14B shows a state after the curved surface is processed. The seventh laminated substrate 70 is an organic electronic device substrate having a laminated substrate 73a and a thin film transistor (TFT) substrate 73b. The TFT substrate 73b includes a substrate and electrodes arranged in a matrix on the substrate, and these electrodes are included in the conductive layer. The conductive layer contained in the TFT substrate 73b is divided into a matrix. The laminated substrate 70 has an organic electronic material layer 74 sandwiched between the conductive layer 12a and the TFT substrate 73b. That is, the laminated substrate 70 has a structure in which the laminated substrate 73a and the TFT substrate 73b sandwich the organic electronic material layer 74. The organic electronic material layer 74 is, for example, a microcapsule electrophoresis layer. The laminated substrate 70 has a protective layer 71 that covers and protects the conductive layer 12a and the organic electronic material layer 74 from the side, and a part of the conductive layer 12a is exposed from the protective layer 71 as a drawer portion.

(8th example of laminated substrate)
FIG. 15 is a cross-sectional view showing an eighth example of a laminated substrate. FIG. 15A shows a state before the curved surface is formed, and FIG. 15B shows a state after the curved surface is processed. The eighth laminated substrate 80 is an organic electronic device substrate having a fifth laminated substrate 50 and a double-sided adhesive layer 62a. The resin substrate 11a is adhered to one surface of the double-sided adhesive layer 62a, and the other surface of the double-sided adhesive layer 62a is covered with a protective sheet 81 that can be peeled off from this surface. The protective sheet 81 is used to protect the double-sided adhesive layer 62a and improve the handleability of the laminated substrate 80. As the protective sheet 81, for example, an ethylene film such as a polyethylene film or a polypropylene film is used. The material of the protective sheet 81 can be selected in consideration of the temperature at the time of forming the curved surface and the like. The thickness of the protective sheet 81 is, for example, 10 μm to 500 μm. A release film or a release paper may be used as the double-sided adhesive layer 62a and the protective sheet 81.

The laminated substrate 80 shown in FIG. 15A can be obtained, for example, by attaching a double-sided adhesive layer 62a having a protective sheet 81 on one side to the resin substrate 11a of the laminated substrate 50. Then, by performing the processing of the first or second embodiment with the protective sheet 81 of the laminated substrate 80 on the concave mold side, the 3D curved surface shown in FIG. 15B can be formed on the laminated substrate 80. .. The laminated substrate 80 on which the curved surface is formed can be used, for example, as an organic electronic device substrate having a bonded structure. Further, in the present embodiment, the protective sheet 81 can be peeled off and the double-sided adhesive layer 62a can be attached to a desired curved surface portion. Therefore, the laminated substrate 80 can be attached and arranged even on a portion where a curved surface cannot be formed at the same time as the laminated substrate 80.

In the laminated substrate 60, the protective sheet 81 may be used instead of the processing resin substrates 61a and 61b.

By obtaining an element structure in which a flat plate-shaped organic electronic device substrate is bonded and then processing it into a 3D curved surface, the conventional bonding device can be used as it is, so that the bonding configuration is excellent in productivity. An organic electronic device substrate such as an electrochromic substrate can be obtained. Similarly, it is possible to obtain a transparent conductive substrate having a bonded structure with excellent productivity.

Examples of the present invention will be described below, but the present invention is not limited to these examples.

(Example 1)
In Example 1, the conductive layer-forming substrate in the form of the first laminated substrate 10 was used. As a resin substrate, a planar stretched polycarbonate sheet (PC) substrate having a thickness of 0.3 mm and a diameter of 100 mm was prepared, and a conductive layer was formed on the planar stretched polycarbonate sheet (PC) substrate by a sputtering method. For the formation of the conductive layer, an AgPdCu alloy (APC) target manufactured by Furuya Metals Co., Ltd. was used. The sputtering power at the time of film formation was set to 3 kW, and the film formation time was adjusted so that the thickness of the conductive layer was 100 nm. A Solaris manufactured by Oerlikon was used as the sputtering apparatus. The thickness of the conductive layer was measured by α step D-500 manufactured by KLA-Tenchore. When the sheet resistance of the conductive layer was measured using Loresta-GP manufactured by Mitsubishi Chemical Analytec Co., Ltd. as a 4-terminal resistance measuring machine, the sheet resistance of the conductive layer was 10 mΩ / □ or less.

Then, the conductive layer forming substrate was processed into a 3D curved surface shape by using the curved surface forming apparatus 100. In this processing, a spherical concave mold having a radius of curvature of 131 mm and a diameter of 200 mm was prepared, and a silicone rubber sheet having a thickness of 0.3 mm was used as the elastic rubber sheet. The spherical concave mold used is made of JIS A7075 aluminum alloy. After adjusting the temperature of the concave mold at 146 ° C, the conductive layer forming substrate is placed on the elastic rubber sheet, and the elastic rubber sheet and the conductive layer forming substrate are brought into close contact with the concave mold for 90 seconds by pump suction to be plastically deformed. rice field. Then, by returning the exhaust of the pump suction hole to atmospheric pressure, the elastic rubber sheet and the conductive layer forming substrate were separated from the mold to obtain a conductive layer forming substrate having a spherical 3D curved surface. As the bending process, both convex and concave processing were performed.

Then, the presence or absence of breakage (cracks) was confirmed in the processed conductive layer by observing with scattered diffracted light and observing with a scanning electron microscope (SEM). As a result, no cracks were generated in either the convex processing or the concave processing.

(Examples 2 to 5)
In Examples 2 to 5, the conductive layer forming substrate in the form of the second laminated substrate 20 was used. As a resin substrate, a planar stretched polycarbonate sheet substrate having a thickness of 0.3 mm and a square of 156 mm was prepared, and a base layer was formed on the planar stretched polycarbonate sheet substrate. As the material of the base layer, four types of UV-curable acrylic resins manufactured by Meihan Vacuum Co., Ltd. with adjusted cross-linking densities were used. In Example 2, UC1-088 (acrylic 1) is used, in Example 3, UC1-094 (acrylic 2) is used, in Example 4, UC1-077 (acrylic 3) is used, and in Example 5, UC1-090 (acrylic 4) was used. The thickness of the base layer of Examples 2 and 5 was 9 μm, and the thickness of the base layer of Examples 3 and 4 was 5 μm. Then, the hardness (HIT) of the base layer was measured with a nano indenter (ENT-3100 manufactured by _Elionix Inc.). Next, a conductive layer of an inorganic oxide was formed on the base layer by a sputtering method using an ITO target of In _{2O 3} : 90% by mass and SnO ₂ : 10% by mass. The sputtering power at the time of film formation was set to 6.5 kW, the oxygen / argon (Ar) flow rate ratio was set to 3.6%, and the thickness of the conductive layer was adjusted by the film formation time. A Solaris manufactured by Oerlikon was used as the sputtering apparatus. The thickness of the conductive layer was measured by α step D-500 manufactured by KLA-Tenchore. The sheet resistance of the conductive layer was measured using Loresta-GP manufactured by Mitsubishi Chemical Analytec Co., Ltd. as a 4-terminal resistance measuring machine. Further, a transmittance of 550 nm was measured using a UH4150 manufactured by Hitachi High-Tech Science Co., Ltd. as a spectrophotometer. These results are shown in Table 1.

Next, the conductive layer-forming substrate was processed into a planar shape shown in FIG. 16 using laser light. The contour of the conductive layer forming substrate includes two linear portions parallel to each other and two arcuate curved portions connecting both ends of the straight portions. The distance between the straight portions is 54.5 mm, and the distance between the curved portions (corresponding to the diameter of the arc) is 75.5 mm. Then, the conductive layer forming substrate was processed into a 3D curved surface shape by using the curved surface forming apparatus 100 provided with the convex mold shown in FIG. In this processing, a spherical concave mold having a radius of curvature of 131 mm and a diameter of 200 mm and a convex mold paired with the spherical concave mold are prepared, and a silicone rubber sheet having a thickness of 0.3 mm is prepared as a substrate holding rubber sheet and an elastic rubber sheet. Using. The spherical concave mold and the convex mold used are made of JIS A7075 aluminum alloy. After the temperature of the concave mold is adjusted to 146 ° C, the conductive layer forming substrate is placed on the elastic rubber sheet, and the elastic rubber sheet and the conductive layer forming substrate are brought into close contact with the concave mold for 60 seconds by pump suction to be plastically deformed. rice field. Subsequently, the convex die whose temperature was adjusted to 146 ° C. was lowered, and a press was performed for 90 seconds. Then, by returning the exhaust of the pump suction hole to atmospheric pressure, the elastic rubber sheet and the conductive layer forming substrate were separated from the mold to obtain a conductive layer forming substrate having a spherical 3D curved surface. As the bending process, both convex and concave processing were performed.

Then, the presence or absence of fracture (crack) was confirmed by observing the processed conductive layer with scattered diffracted light and observing with SEM. As a result, as shown in Table 1, in Examples 2 and 3, no cracks were generated in either the convex processing or the concave processing, and in Examples 4 and 5, no cracks were generated in the concave processing and the convex processing was performed. Only cracks occurred. FIG. 17 shows the cracks observed in the convex processing of Example 4. FIG. 17 (a) shows the diffraction result by the scattered diffracted light, and FIG. 17 (b) shows the observation result by SEM. As shown in FIG. 17 (a), the cracks were formed in a circular or elliptical shape. Similar cracks were observed in the convex processing of Example 5.

(Examples 6 to 8)
In Example 6, a conductive layer of an inorganic oxide was formed by a sputtering method using a target of In _{2O 3} : 99% by mass and ZrO ₂ : 1% by mass as the conductive layer. The sputtering power at the time of film formation was set to 6.5 kW, and the oxygen / argon flow rate ratio was set to 2.5%. Other conditions are the same as in Example 3. In Example 7, a concave mold having a radius of curvature of 86 mm was used. Other conditions are the same as in Example 6. In Example 8, the thickness of the conductive layer was set to 220 nm. Other conditions are the same as in Example 6.

Then, the same evaluation as in Example 2 was performed. As a result, as shown in Table 1, no cracks were generated in any of Examples 6 to 8.

(Example 9)
In Example 9, the conductive layer forming substrate was processed into a 3D curved surface using the curved surface forming apparatus 200 shown in FIG. In this processing, a spherical concave mold having a radius of curvature of 131 mm and a diameter of 200 mm was prepared, and a silicone rubber sheet having a thickness of 0.3 mm was used as a substrate holding rubber sheet and an elastic rubber sheet. The spherical concave mold used is made of JIS A7075 aluminum alloy. The conductive layer forming substrate was placed on the elastic rubber sheet, the temperature of the concave mold was adjusted to 141 ° C., the bypass valve was opened, and the pressure in the chamber was reduced to 300 Pa by pump suction. Then, the bypass valve was closed and gas (air) was injected into the space above the elastic rubber sheet through the gas injection port. The air pressure was 0.1 MPa, and the elastic rubber sheet and the conductive layer-forming substrate were brought into close contact with the concave mold for 90 seconds to be plastically deformed. Then, by returning the pressure in the chamber to atmospheric pressure, the elastic rubber sheet and the conductive layer forming substrate were separated from the mold to obtain a conductive layer forming substrate having a spherical 3D curved surface. As the bending process, both convex and concave processing were performed. Other conditions are the same as in Example 2.

Then, the same evaluation as in Example 2 was performed. As a result, as shown in Table 1, no cracks were generated in Example 9.

(Example 10)
In Example 10, the organic electronic device substrate in the form of the third laminated substrate 30 was used. As the organic electronic material layer, (a) a radically polymerizable compound having a triarylamine represented by the following structural formula A, (b) polyethylene glycol diacrylate, (c) a photopolymerization initiator, and (d) tetrahydrofuran are used. A mixture of solutions having a ratio of: b: c: d = 10: 5: 0.15: 85 (mass ratio) is applied and UV-cured in a nitrogen atmosphere to have an oxidation reactivity of 1.5 μm film thickness. Formed an electrochromic layer. As the polyethylene glycol diacrylate, KAYARAD PEG400DA manufactured by Nippon Kayaku Co., Ltd. was used. As the photopolymerization initiator, IRGACURE 184 manufactured by BASF was used. In the third laminated substrate 30, the conductive layer 12 and the organic electronic material layer 14 are formed narrower than the resin substrate 11 and the base layer 13, but in the tenth embodiment, the base layer is entirely on the upper surface of the resin substrate. , Conductive layer and organic electronic material layer were formed. Other conditions are the same as in Example 2.
[Structural formula A]

Then, the same evaluation as in Example 2 was performed. As a result, as shown in Table 1, no cracks were generated in Example 10.

(Example 11)
In Example 11, the conductive layer-forming substrate in the form of the fourth laminated substrate 40 was used. Two conductive layer-forming substrates in the form of the second laminated substrate 20 before bending were prepared, and these were bonded together with a double-sided adhesive layer having a thickness of 50 μm. LA50 (OCA tape) manufactured by Nitto Denko was used as the double-sided adhesive layer. Other conditions are the same as in Example 2.

Then, the same evaluation as in Example 2 was performed. As a result, as shown in Table 1, no cracks were generated in Example 11.

(Example 12)
In Example 12, the organic electronic device substrate in the form of the fifth laminated substrate 50 was used. As the resin substrate, two plane-stretched polycarbonate sheet substrates having a thickness of 0.3 mm and a square of 156 mm were prepared, and a base layer was formed on them. As the material of the base layer, UC1-088 (acrylic 1) manufactured by Meihan Vacuum Co., Ltd. was used. The thickness of the base layer was 9 μm. Then, the hardness (HIT) of the base layer was measured with a nano indenter (ENT-3100 manufactured by _Elionix Inc.). Next, a conductive layer of an inorganic oxide was formed on the base layer by a sputtering method using an ITO target of In _{2O 3} : 90% by mass and SnO ₂ : 10% by mass. The sputtering power at the time of film formation was set to 6.5 kW, the oxygen / argon flow rate ratio was set to 3.6%, and the thickness of the conductive layer was adjusted to 110 nm during the film formation time. A Solaris manufactured by Oerlikon was used as the sputtering apparatus. The conductive layer was formed by using a mask in the region shown in FIG. 12 (a) for one resin substrate and in the region shown in FIG. 12 (b) for the other resin substrate. The thickness of the conductive layer was measured by α step D-500 manufactured by KLA-Tenchore. The sheet resistance of the conductive layer was measured using Loresta-GP manufactured by Mitsubishi Chemical Analytec Co., Ltd. as a 4-terminal resistance measuring machine. Further, a transmittance of 550 nm was measured using a UH4150 manufactured by Hitachi High-Tech Science Co., Ltd. as a spectrophotometer.

Next, in the resin substrate in which the conductive layer was formed in the region shown in FIG. 12 (b), an oxidation-reactive electrochromic layer was formed in the region shown in FIG. 12 (c) by a coating method. The electrochromic layer was formed under the same conditions as in Example 10.

Further, in the resin substrate in which the conductive layer was formed in the region shown in FIG. 12 (a), a reduction-reactive electrochromic layer was formed in the region shown in FIG. 12 (c). In the formation of a reduction-reactive electrochromic layer, a solution containing 1% by mass of polyvinyl butyral added to a methanol dispersion of tin oxide is applied and annealed at 120 ° C. for 5 minutes to form a nanoparticle tin oxide layer having a thickness of 3 μm. Formed. Next, a solution prepared by dissolving 2% by mass of the compound represented by the following structural formula B in 2,2,3,3-tetrafluoropropanol was applied to the surface of the nanoparticle tin oxide layer and adsorbed, and then at 120 ° C. 5 Annealed for minutes. As the methanol dispersion of tin oxide, Cernax manufactured by Nissan Chemical Industries, Ltd. was used.
[Structural formula B]

Then, (a) (FSO ₂ ) _2N -salt of 1-ethyl-3-methylimidazolium, (b) polyethylene glycol diacrylate, and (c) photopolymerization initiator were added to a: b: c = 2: An electrolyte solution was prepared by mixing so as to have a ratio of 1: 0.01 (mass ratio). Then, after filling this electrolyte solution between the oxidation-reactive electrochromic layer and the reduction-reactive electrochromic layer, an annealing treatment at 60 ° C. is performed for 1 minute, and the solution is cured by ultraviolet irradiation and bonded to each other. The body was made. At this time, the filling amount of the electrolyte solution was adjusted so that the average thickness of the solid electrolyte layer was 30 μm. As the polyethylene glycol diacrylate, KAYARAD PEG400DA manufactured by Nippon Kayaku Co., Ltd. was used. As the photopolymerization initiator, IRGACURE 184 manufactured by BASF was used. Further, a UV-curable acrylic material was filled around the organic electronic material layer and UV-cured to form a protective layer. As the UV curable acrylic material, TB3050 manufactured by ThreeBond Co., Ltd. was used.

Then, the same evaluation as in Example 2 was performed. As a result, as shown in Table 1, no cracks were generated in Example 12.

In addition, the color development and decolorization of the organic electronic device substrate was evaluated. In this evaluation, a voltage of 2.0 V was applied so that one drawer of the organic electronic material layer exposed from the protective layer had a positive pole and the other drawer had a negative pole, and a charge of 7 mC / cm ² was injected. did. As a result, it was confirmed that the oxidation-reactive electrochromic layer developed a blue-green color and the reduction-reactive electrochromic layer developed a blue color. It was also confirmed that the color was transparently decolorized by applying −0.6 V, and the decoloring operation was performed normally. The light transmittance was measured with an ultraviolet-visible near-infrared spectrophotometer UH4150 (manufactured by Hitachi High-Tech Science Co., Ltd.).

(Example 13)
In Example 13, the organic electronic device substrate in the form of the sixth laminated substrate 60 was used. As the resin substrate, an optically stretched polyethylene terephthalate (PET) having a thickness of 0.1 mm and a 156 mm square is used, and a planar organic electronic device substrate (electro) is used in the same manner as in Example 12 except that a base layer is not formed. A chromic substrate) was produced. Next, a planar processing resin substrate shown in FIG. 16 was bonded to the outer surfaces of both resin substrates using a double-sided adhesive layer having a thickness of 50 μm. A polycarbonate sheet substrate having a thickness of 0.3 mm was used as the resin substrate for processing, and LA50 (OCA tape) manufactured by Nitto Denko was used as the double-sided adhesive layer.

Then, the same evaluation as in Example 2 was performed. As a result, as shown in Table 1, no cracks were generated in Example 12. In addition, the same color development and decolorization evaluation as in Example 12 was also performed. As a result, it was confirmed that the color development and decolorization operation was normal.

(Example 14)
In Example 14, the organic electronic device substrate in the form of the seventh laminated substrate 70 was used. Commercially available electrophoretic display electronic paper is used for the parts corresponding to the resin substrate, the conductive layer, the organic electronic material layer and the protective layer, and a double-sided adhesive layer having a thickness of 50 μm is used on the resin substrate on the display surface side. Then, the plane-shaped processing resin substrate shown in FIG. 16 was bonded. As the electrophoretic display method electronic paper, GDEP014TT1 manufactured by Eink is used, as the processing resin substrate, a plane-stretched polycarbonate sheet substrate having a thickness of 0.3 mm is used, and as the double-sided adhesive layer, LA50 manufactured by Nitto Denko Co., Ltd. is used. (OCA tape) was used. This electrophoresis display type electronic paper is driven by an active matrix, and the conductive layer is divided and formed in a matrix shape. The outline of GDEP014TT1 is as follows.

Screen Size: 1.43 Inch
Display Resolution: 128 (H) x 296 (V) Pixel
Active Area: 14.464 (H) x 33.448 (V) mm
Pixel Pitch: 0.113 (H) x 0.113 (V) mm
Pixel Configuration: Rectangle
Outline Dimension: 18.3 (H) * 42.7 (V) * 0.607 (D) mm
Module Weight: 0.87 ± 0.1 g

In the curved surface processing, the curved surface forming device 100 shown in FIG. 1 was used. In this processing, a spherical concave mold having a radius of curvature of 86 mm and a diameter of 200 mm was prepared, and a silicone rubber sheet having a thickness of 0.3 mm was used as the elastic rubber sheet. The spherical concave mold used is made of JIS A7075 aluminum alloy. After the temperature of the concave mold is adjusted to 146 ° C, the organic electronic device substrate is placed on the elastic rubber sheet so that the resin substrate for processing is on the bottom, and the elastic rubber sheet and the organic electronic device are placed on the concave mold by pump suction. The substrate was brought into close contact for 150 seconds and plastically deformed. Then, by returning the exhaust of the pump suction hole to atmospheric pressure, the elastic rubber sheet and the organic electronic device substrate were separated from the mold to obtain an organic electronic device substrate having a spherical 3D curved surface.

Then, the same evaluation as in Example 2 was performed. As a result, as shown in Table 1, no cracks were generated in Example 14. Further, as shown in FIG. 18, it was also confirmed that the display operation was normal. FIG. 18A is a photograph showing the state after processing of Example 14, and FIG. 18B is a schematic diagram thereof. As shown in FIG. 18, it was possible to display evenly over the entire display area.

(Example 15)
In Example 15, the organic electronic device substrate in the form of the fifth laminated substrate 50 was used. On one of the resin substrates of the organic electronic device substrate produced in Example 12, a double-sided adhesive layer having a thickness of 50 μm provided with a protective sheet on one side was attached. LA50 (OCA tape) manufactured by Nitto Denko was used as the double-sided adhesive layer, and a polypropylene film having a thickness of 25 μm was used as the protective sheet.

Then, the same evaluation as in Example 2 was performed. As a result, as shown in Table 1, no cracks were generated in Example 15. In addition, the same color development and decolorization evaluation as in Example 12 was also performed. As a result, it was confirmed that the color development and decolorization operation was normal. Further, the protective sheet could be peeled off and attached to a spherical substrate having a radius of curvature of 130 mm using a vacuum bonding device.

(Comparative Example 1)
In Comparative Example 1, the conductive layer-forming substrate prepared in the same manner as in Example 2 was processed into a 3D curved surface using a vacuum forming apparatus. FIG. 19 is a diagram showing the curved surface forming method of the comparative example in the order of processes.

First, as shown in FIG. 19A, the conductive layer forming substrate 351 was heated and softened by using the lower heater 301 and the upper heater 302. The lower heater 301 and the upper heater 302 were halogen heaters, and the heating temperature was 146 ° C. Then, as shown in FIG. 19B, the end portion of the softened conductive layer forming substrate 351 was fixed in the chamber 303 of the vacuum forming apparatus. Then, as shown in FIG. 19 (c), the inside of the chamber 303 was depressurized, and the conductive layer forming substrate 351 was pressed against the convex mold 304 whose temperature was adjusted to 146 ° C. to be plastically deformed. As the convex mold 304, a spherical mold made of JIS A7075 aluminum alloy having a radius of curvature of 131 mm and a diameter of 85 mm was used. After the conductive layer forming substrate 351 is plastically deformed, the inside of the chamber 303 is returned to atmospheric pressure, and the conductive layer forming substrate 351 is separated from the convex mold 304 to form a spherical 3D curved surface. Obtained 351. As the bending process, both convex and concave processing were performed.

Then, the same evaluation as in Example 2 was performed. As a result, as shown in Table 1, in Comparative Example 1, cracks were generated in both the convex processing and the concave processing. This crack was similar to that observed in the convex processing of Example 4 shown in FIG.

Although the preferred embodiments and examples have been described in detail above, the embodiments are not limited to the above-described embodiments and examples, and the above-described embodiments are not deviated from the scope of claims. And various modifications and substitutions can be made to the examples. For example, each of the above embodiments can be combined as appropriate.

10, 20, 30, 40, 50, 60, 70, 80, 151, 251 Laminated substrate 11 Resin substrate 12 Conductive layer 13 Underlayer layer 14,74 Organic electronic material layer 41, 62a, 62b Double-sided adhesive layer 51, 71 Protective layer 61a, 61b Resin substrate for processing 81 Protective sheet 100, 200 Curved surface forming device 111, 211 Concave mold 112, 212 Concave surface 113, 213 Flat surface 115 hole 116, 126, 216 Temperature control part 117, 217 Pump 121, 221 Convex mold 131, 231 Elastic rubber sheet 132 holes 218 Bypass valve 219 Gas supply unit 233 Substrate holding rubber sheet 234 holes 241 Sealed container

Japanese Unexamined Patent Publication No. 2006-82463

Claims (14)

It is a curved surface forming method of a laminated substrate for processing a laminated substrate including a support substrate including a resin substrate of a thermoplastic resin and a conductive layer on the support substrate into a three-dimensional curved surface.
The support substrate has a base layer having a hardness of 440 MPa or more and 680 MPa or less on the resin substrate.
The curved surface of the laminated substrate is characterized by having a step of softening the resin substrate by deforming the elastic sheet while bringing the laminated substrate into close contact with the elastic sheet and bringing the laminated substrate into close contact with a temperature-controlled mold. Forming method. The method for forming a curved surface of a laminated substrate according to claim 1, wherein the elastic sheet is deformed by a pressure difference between spaces sandwiching the elastic sheet. The method for forming a curved surface of a laminated substrate according to claim 1 or 2, wherein the conductive layer is a transparent conductive layer containing an inorganic oxide. The method for forming a curved surface of a laminated substrate according to any one of claims 1 to 3, wherein the conductive layer is divided into a matrix. The curved surface formation of the laminated substrate according to any one of claims 1 to 4, wherein a three-dimensional curved surface larger than the laminated substrate is formed on the surface of the mold in which the laminated substrate is in close contact. Method. The method for forming a curved surface of a laminated substrate according to claim 5, wherein the mold is a concave mold. The method for forming a curved surface of a laminated substrate according to any one of claims 1 to 6 , wherein the thermoplastic resin is polycarbonate or polyethylene terephthalate. The method for forming a curved surface of a laminated substrate according to any one of claims 1 to 7 , wherein the laminated substrate has an organic electronic material layer on the conductive layer. The curved surface forming method for a laminated substrate according to any one of claims 1 to 8 , wherein the laminated substrate has a processing resin substrate on a surface of the support substrate on the side in close contact with the mold. .. The curved surface forming method for a laminated substrate according to claim 9 , wherein the processing resin substrate is adhered to the support substrate by a peelable bonded layer. The curved surface forming method for a laminated substrate according to claim 10, further comprising a step of peeling the processing resin substrate from the support substrate after processing the laminated substrate into a three-dimensional curved surface. The curved surface forming method for a laminated substrate according to any one of claims 1 to 11, wherein the laminated substrate is processed into a three-dimensional curved surface and then the laminated substrate is attached to a support. .. The laminated substrate has a protective sheet adhered to the support substrate via an adhesive layer.
The curved surface forming method according to claim 12 , wherein the protective sheet can be peeled off while leaving the adhesive layer on the support substrate. The curved surface forming method according to claim 1 to 13, wherein the base layer is 0.1 μm to 10 μm.

Images