JP7151437B2 - 3D CURVED LAMINATED SUBSTRATE AND PRODUCTION METHOD THEREOF - Google Patents

Description

The present invention relates to a three-dimensional curved laminated substrate and a manufacturing method thereof.

In the application of electronic devices such as touch panels and displays, there is a demand for electronic devices that are lightweight, hard to crack, and have a three-dimensional (3D) curved surface that are suitable for various usage scenes. In particular, in-vehicle applications and wearable applications require 3D curved electronic devices with excellent design and fit. Such electronic devices include transparent resin substrates and conductive layers.

A method of manufacturing a 3D curved electronic device includes 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, and a method of forming a conductive layer or an organic electronic material layer on a flat substrate. It can be roughly classified into a method of processing into a 3D curved surface after forming a film.

However, in the former method, it is difficult to form a uniform film on a 3D curved substrate or to bond 3D curved substrates together. In addition, since a general film forming apparatus suitable for flat substrates cannot be used as it is, it is necessary to prepare a film forming apparatus for 3D curved substrates, which leads to a significant increase in cost. Therefore, in recent years, the latter method is considered promising.

Materials for the conductive layer include transparent inorganic oxides such as indium oxide, carbon (CNT, graphene), metal nanowires, metal grids, conductive polymers, and the like. Patent Documents 1 and 2 describe techniques relating to conductive layers of inorganic oxides, and Patent Document 3 describes techniques relating to conductive layers containing metal nanomaterials, carbon nanotubes, and the like.

However, when an attempt is made to obtain a laminated substrate with a 3D curved surface by a method of processing the conductive layer described in Patent Documents 1 and 2 into a 3D curved surface after film formation, the Young's modulus of the inorganic oxide is large, and the inorganic Oxides are brittle and easily broken, making it difficult to process them into 3D curved surfaces. That is, since the conductive layer of inorganic oxide has low flexibility and is easily cracked, the conductive layer cannot withstand biaxial bending and cracks occur. In addition, strain tends to increase in the direction along the curved surface of the inorganic oxide. In addition, when a substrate including a functional layer such as an organic electronic material layer on an inorganic oxide conductive layer is processed into a convex shape, the strain generated in the conductive layer propagates to the functional layer, resulting in a large strain in the functional layer. is likely to occur. Furthermore, 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. The conductive layer described in Patent Document 3 is inferior to the conductive layer of inorganic oxide when comprehensively judging the transparency (transmittance and haze), conductivity and durability. Therefore, with conventional techniques, it is difficult to suppress cracks in the conductive layer while obtaining excellent transparency, conductivity and durability.

SUMMARY OF THE INVENTION An object of the present invention is to provide a three-dimensional curved laminated substrate which is excellent in transparency, conductivity and durability and which can suppress the occurrence of cracks, and a method for manufacturing the same.

One mode of the three-dimensional curved laminated substrate has a support substrate including a thermoplastic resin substrate, and a conductive layer on the support substrate, and the surface hardness of the support substrate is 180 MPa or more. The support substrate has an underlying layer having a surface hardness of 180 MPa or more on the resin substrate, and the underlying layer is harder than the resin substrate .

ADVANTAGE OF THE INVENTION According to this invention, it is excellent in transparency, electroconductivity, and durability, and can suppress generation|occurrence|production of a crack.

1 is a cross-sectional view showing a laminated substrate according to a first embodiment; FIG. FIG. 5 is a cross-sectional view showing a laminated substrate according to a second embodiment; FIG. 10 is a cross-sectional view showing a laminated substrate according to a third embodiment; It is a sectional view showing a layered substrate concerning a 4th embodiment. It is a figure which shows the planar shape of a laminated substrate. FIG. 11 is a cross-sectional view showing a laminated substrate according to a fifth embodiment; FIG. 11 is a diagram showing the positional relationship of layers in a laminated substrate according to a fifth embodiment; 1 is a diagram showing a curved surface forming apparatus suitable for a first example of a method for forming a curved surface of a laminated substrate; FIG. It is a figure which shows the 1st example of the curved-surface formation method of a laminated substrate in process order. It is a figure which shows the modification of a 1st example. FIG. 10 is a diagram showing a curved surface forming apparatus suitable for a second example of the curved surface forming method for a laminated substrate; It is a figure which shows the 2nd example of the curved-surface formation method of a laminated substrate in process order. It is a figure which shows the modification of a 2nd example. FIG. 10 is a diagram showing cracks generated in a conductive layer; FIG. 2 is a diagram (part 1) showing measurement results by the X-ray diffraction method for samples with different sputtering powers; FIG. 2 is a diagram showing measurement results by a nanoindenter for Example 1; FIG. 2 is a diagram (part 2) showing measurement results by the X-ray diffraction method for samples with different sputtering powers; FIG. 10 is a diagram showing measurement results by a nanoindenter for Example 6. FIG. FIG. 10 is a diagram showing measurement results by a nanoindenter for Example 7; FIG. 10 is a diagram showing measurement results by a nanoindenter for Example 8;

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

(First embodiment)
First, a three-dimensional (3D) curved laminated substrate according to the first embodiment will be described. The laminated substrate according to the first embodiment relates to a transparent conductive substrate. FIG. 1 is a cross-sectional view showing a transparent conductive substrate according to the first embodiment. FIG. 1(a) shows the state before forming a curved surface, FIG. 1(b) shows a 3D curved transparent conductive substrate with convex processing, and FIG. 1(c) shows a concave processing. 3D shows a 3D curved transparent conductive substrate.

A 3D curved transparent conductive substrate 10 according to the first embodiment includes a thermoplastic resin substrate 11 and a conductive layer 12 on the resin substrate 11, as shown in FIG. 1(b) or 1(c). have The resin substrate 11 is an example of a support substrate, and the hardness of the surface of the resin substrate 11 is 180 MPa or more. Also, the conductive layer 12 preferably contains indium oxide (In ₂ O ₃ ) having a crystal peak of (222) plane with an H/W value of 0.16 to 5.7. The H/W value is a value obtained by dividing the peak height H (cps) in X-ray diffraction (XRD) by the half width W (°).

The surface hardness of the support substrate is measured with a nanoindenter. According to the present inventors, 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, a thickness using indium oxide as an inorganic oxide is When a transparent conductive layer of 110 nm was formed and this laminated substrate was processed into a spherical shape with a radius of curvature of 86 mm, it was confirmed that no cracks occurred. By using a support substrate with a hard surface, distortion of the transparent conductive layer during processing can be reduced.

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 (polymethyl methacrylate), polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polystyrene, styrene acrylonitrile copolymer, styrene butadiene acrylonitrile copolymer, polyethylene, ethylene acetate A vinyl copolymer, polypropylene, polyacetal, cellulose acetate, polyamide (nylon), polyurethane, fluorine-based (Teflon (registered trademark)), or the like can be used as the material of the resin substrate 11 . Polycarbonate and polyethylene terephthalate are particularly preferred in terms of moldability, transparency and cost. Polyethylene terephthalate and polyethylene naphthalate-based materials are preferred in terms of hardness of 180 MPa or more. The thickness of the resin substrate 11 is, for example, 0.03 mm to 2.0 mm, in a range that facilitates formation of a curved surface.

The conductive layer 12 preferably contains indium oxide with a crystal peak of the (222) plane having an H/W value of 0.16 to 5.7. In XRD, the crystal peak of the (222) plane of indium oxide is detected near 2θ≈32 (deg.). If the crystalline peak of the (222) plane has a H/W value of less than 0.16, or if the crystalline peak of the (222) plane is absent, the crystallinity of the conductive layer 12 is too low, resulting in cracks. Cheap. If the crystal peak has an H/W value of more than 5.7, the crystallinity is too high, and cracks originating from grain boundaries in the conductive layer 12 are likely to occur. Oxidation of tin (Sn), tungsten (W), titanium (Ti), zirconium (Zr), zinc (Zn), aluminum (Al), antimony (Sb), gallium (Ga) and fluorine (F) to indium oxide A single substance or a mixture of substances may be included in the conductive layer 12 . These oxides contribute to improving the carrier density and mobility of indium oxide. The proportion of these oxides in the conductive layer 12 is, for example, 80 mass % or less. As oxides contained in the conductive layer 12 in addition to indium oxide, tin oxide and zirconium oxide are particularly preferable from the viewpoint of conductivity, and the total amount of these oxides in the conductive layer 12 is, for example, 15% by mass or less. is particularly preferred.

The conductive layer 12 can be formed by a vacuum film formation method, and the crystal peak H/W value can be adjusted by the substrate temperature, film formation rate, gas pressure, etc. during vacuum film formation. Heat treatment after film formation is also effective for adjusting the H/W value. Examples of the vacuum film forming method include a vacuum deposition method, a sputtering method, an ion plating method, a chemical vapor deposition (CVD) method, and the like. Among these, the sputtering method capable of high-speed film formation is preferable. In the case of the sputtering method, the H/W value of the crystal peak can be easily controlled by adjusting the sputtering power.

The thickness of the conductive layer 12 is adjusted according to the amount of current required for the electronic device, and is, for example, 50 nm to 500 nm, preferably 200 nm or less. This is because the thicker the conductive layer 12, the more likely it is to suffer damage such as cracks during curved surface formation processing. For example, the sheet resistance of the conductive layer 12 is 300Ω/□ or less. The visible light transmittance of the conductive layer 12 can be adjusted by the thickness and the oxygen ratio of the inorganic oxide such as indium oxide, and is, for example, 70% or more. The conductive layer 12 may contain transparent conductive materials such as highly elastic carbon (carbon nanotubes (CNT), graphene), metal nanowires, metal grids, and conductive polymers. Composite layers of material and inorganic oxide layers may also be used.

The 3D curved transparent conductive substrate 10 shown in FIG. 1(b) or 1(c) is obtained by subjecting the flat transparent conductive substrate 10' shown in FIG. 1(a) to convex processing or concave processing. . The method of convex processing and concave processing will be described later.

The conductive layer 12 is formed on the entire surface or part of the resin substrate 11 . In addition, in FIGS. 1B and 1C, the entire transparent conductive substrate 10 is processed into a 3D curved shape, but even if only a part of the transparent conductive substrate 10 is processed into a 3D curved shape good.

The thermal expansion coefficient of the support substrate, which is the thermal expansion coefficient of the resin substrate 11 in the first embodiment, is preferably 0.7% or less. The coefficient of thermal expansion referred to here is the coefficient of thermal expansion in the temperature range from room temperature to the softening temperature (Tg) of the resin substrate. If the coefficient of thermal expansion exceeds 0.7%, excessive distortion may occur during the formation of curved surfaces, which will be described later. The coefficient of thermal expansion is measured by the tensile load method of ThermoMechanical Analysis (TMA).

According to the first embodiment, the hardness of the surface of the resin substrate 11, which is an example of the support substrate, is appropriate, and the conductive layer 12 contains appropriate indium oxide. Even if it is processed into a curved surface, it is excellent in transparency, conductivity and durability, and can suppress the occurrence of cracks.

(Second embodiment)
Next, a 3D curved laminated substrate according to a second embodiment will be described. A laminated substrate according to the second embodiment relates to a transparent conductive substrate. FIG. 2 is a cross-sectional view showing a transparent conductive substrate according to a second embodiment. FIG. 2(a) shows the state before forming a curved surface, FIG. 2(b) shows a 3D curved transparent conductive substrate with convex processing, and FIG. 2(c) shows a concave processing. 3D shows a 3D curved transparent conductive substrate.

A 3D curved transparent conductive substrate 20 according to the second embodiment has a base layer 13 on a resin substrate 11 , and a conductive layer 12 is formed on the base layer 13 . A support substrate includes a resin substrate 11 and an underlying layer 13 . The hardness of the surface of the underlying layer 13 is 180 MPa or more, and the hardness of the surface of the supporting substrate is also 180 MPa or more. Other configurations are the same as those of the transparent conductive substrate 10 .

The underlying layer 13 is used, for example, to compensate for the mechanical properties of the resin substrate 11 . For example, even if the resin substrate 11 does not have sufficient hardness as an underlayer for the conductive layer 12, by forming the underlayer 13 harder than the resin substrate 11, a support substrate having a surface hardness of 180 MPa or more can be obtained. Obtainable. The underlayer 13 may be used for adjusting the coefficient of thermal expansion. Including the base layer 13 in this manner allows a wide range of materials to be selected for the resin substrate 11 , and a thermoplastic resin having excellent workability can be used for the resin substrate 11 . Materials for the underlayer 13 include, for example, ultraviolet (UltraViolet: UV) curable resin materials and thermosetting resin materials. More specifically, acrylic resins, urethane resins, epoxy resins and the like can be mentioned. The hardness of the surface of the underlayer 13 is preferably 180 MPa or more. By using the underlayer 13 having a surface hardness of 180 MPa or more, the distortion when forming the curved surface of the conductive layer 12 can be further reduced. The hardness and coefficient of thermal expansion of the underlayer 13 made of UV curable resin or thermosetting resin can be adjusted by adjusting the monomer material, crosslink density, amount of reaction initiator, and the like. The underlayer 13 can be formed by applying a material obtained by mixing at least an organic monomer material having a reactive group and an initiator onto the resin substrate 11 and performing curing treatment such as UV irradiation or heat treatment. The thickness of the underlying layer 13 is, for example, 0.1 μm to 10 μm. Examples of coating methods include spin coating, casting, micro gravure coating, gravure coating, bar coating, roll coating, wire bar coating, dip coating, slit coating, capillary coating, and spraying. 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.

The 3D curved transparent conductive substrate 20 shown in FIG. 2(b) or 2(c) is obtained by subjecting the flat transparent conductive substrate 20' shown in FIG. 2(a) to convex processing or concave processing. . The method of convex processing and concave processing will be described later.

The thermal expansion coefficient of the support substrate, here, the laminated structure of the resin substrate 11 and the base layer 13, is preferably 0.7% or less. The coefficient of thermal expansion referred to here is the coefficient of thermal expansion in the temperature range from room temperature to the softening temperature (Tg) of the resin substrate. If the coefficient of thermal expansion exceeds 0.7%, excessive distortion may occur during the formation of curved surfaces, which will be described later. The coefficient of thermal expansion is measured by the TMA tensile load method.

According to the second embodiment, the surface hardness of the resin substrate 11 and the underlying layer 13, which are examples of the support substrate, is appropriate, and the conductive layer 12 contains appropriate indium oxide. Even if it is processed into a 3D curved surface after the formation of , it is excellent in transparency, conductivity and durability, and can suppress the occurrence of cracks.

(Third embodiment)
Next, a 3D curved laminated substrate according to the third embodiment will be described. A laminated substrate according to the third embodiment relates to an organic electronic device substrate. FIG. 3 is a cross-sectional view showing an organic electronic device substrate according to a third embodiment. FIG. 3(a) shows the state before forming a curved surface, FIG. 2(b) shows a 3D curved organic electronic device substrate with convex processing, and FIG. 2(c) shows concave processing. 3D shows a 3D curved organic electronic device substrate.

A 3D curved organic electronic device substrate 30 according to the third embodiment has an organic electronic material layer 14 on a conductive layer 12 . Other configurations are the same as those of the transparent conductive 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 application of electricity, for example. Conventional organic electronic material layers such as electrochromic, electroluminescence, chemical luminescence, electroforetic, electrowetting, liquid crystal, and piezoelectric can be used as the organic electronic material layer 14 as they are. An inorganic material such as inorganic nanoparticles may be mixed in the organic electronic material layer 14 . The total thickness of organic electronic material layer 14 is generally less than 50 μm. Examples of coating methods include spin coating, casting, micro gravure coating, gravure coating, bar coating, roll coating, wire bar coating, dip coating, slit coating, capillary coating, and spraying. 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.

The 3D curved organic electronic device substrate 30 shown in FIG. 3(b) or FIG. 3(c) is obtained by subjecting the planar organic electronic device substrate 30′ shown in FIG. can get. The method of convex processing and concave processing will be described later.

According to the third embodiment, since the surface hardness of the support substrate is suitable and the conductive layer 12 contains suitable indium oxide, the 3D curved surface is formed after the formation of the conductive layer 12 and the organic electronic material layer 14 . Even if processed into a shape, it is excellent in transparency, conductivity and durability, and can suppress the occurrence of cracks.

(Fourth embodiment)
Next, a 3D curved laminated substrate according to a fourth embodiment will be described. A laminated substrate according to the fourth embodiment relates to a transparent conductive substrate. FIG. 4 is a cross-sectional view showing a transparent conductive substrate according to a fourth embodiment. FIG. 4(a) shows a state before forming a curved surface, and FIG. 4(b) shows a 3D curved transparent conductive substrate subjected to curved surface processing.

A 3D curved transparent conductive substrate 40 according to the fourth embodiment has a transparent conductive substrate 20 a and a transparent conductive substrate 20 b having the same configuration as the transparent conductive substrate 20 . The transparent conductive substrate 20a has a resin substrate 11a, a foundation layer 13a and a conductive layer 12a, and the transparent conductive substrate 20b has a resin substrate 11b, a foundation layer 13b and a conductive layer 12b. The transparent conductive substrate 40 has a double-sided adhesive layer 41 that bonds the conductive layers 12a and 12b together. That is, the transparent conductive substrate 40 has a structure in which the transparent conductive substrate 20 a and the transparent conductive substrate 20 b are attached to each other with 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 configurations similar to those of the resin substrate 11, the conductive layers 12, and the base layer 13, respectively. The double-sided adhesive layer 41 is, for example, an OCA (Optical Clear Adhesive) tape.

FIG. 5 is a plan view showing the resin substrate 11a before forming a curved surface. As shown in FIG. 5, before the curved surface is formed, the outline of the resin substrate 11a includes two parallel linear portions and two arcuate curved portions connecting both ends of the linear portions. The base layer 13a, the conductive layer 12a, the double-sided adhesive layer 41, the conductive layer 12b, the base layer 13b, and the resin substrate 11b also have similar contours.

A flat transparent conductive substrate 40' shown in FIG. 4A is obtained by bonding the transparent conductive substrates 20a and 20b together using a double-sided adhesive layer 41, for example. A conventional bonding apparatus can be used for this bonding. Then, by processing the flat transparent conductive substrate 40' into a 3D curved surface, the 3D curved transparent conductive substrate 40 shown in FIG. 4B is obtained. A method for processing into a 3D curved surface will be described later.

In general, in order to bond two curved substrates, it is necessary to prepare curved substrates whose curvature is controlled with high accuracy, and then use a highly accurate dedicated bonding apparatus. On the other hand, according to the fourth embodiment, cracks can be suppressed even if the substrate is processed into a 3D curved surface after film formation and bonding. Thus, a bonded transparent conductive substrate 40 having a three-dimensional curved surface can be obtained. That is, the transparent conductive substrate 40 can be obtained at low cost and with excellent productivity.

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

(Fifth embodiment)
Next, a 3D curved laminated substrate according to a fifth embodiment will be described. A laminated substrate according to the fifth embodiment relates to an organic electronic device substrate. FIG. 6 is a cross-sectional view showing an organic electronic device substrate according to a fifth embodiment. FIG. 6(a) shows a state before forming a curved surface, and FIG. 6(b) shows a 3D curved organic electronic device substrate subjected to curved surface processing.

A 3D curved organic electronic device substrate 50 according to the fifth embodiment has an organic electronic device substrate 30 a and an organic electronic device substrate 30 b having the same configuration as the organic electronic device substrate 30 . The organic electronic device substrate 30a has a resin substrate 11a, a foundation layer 13a, a conductive layer 12a and an organic electronic material layer 14a. The organic electronic device substrate 30b has a resin substrate 11b, a foundation layer 13b, a conductive layer 12b and an organic electronic material It has a layer 14b. The organic electronic device substrate 50 has an organic electronic material layer 14c sandwiched between the organic electronic material layers 14a and 14b. That is, the organic electronic device substrate 50 has a structure in which the organic electronic material layer 14c is sandwiched between the organic electronic device substrates 30a and 30b. The resin substrates 11a and 11b, the conductive layers 12a and 12b, and the base layers 13a and 13b have configurations similar to those of the resin substrate 11, the conductive layers 12, and the base layer 13, respectively. Further, for example, the organic electronic material layer 14a is an oxidized 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 organic electronic device substrate 50 has a protective layer 51 that laterally 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. A portion of the conductive layer 12a and a portion of the conductive layer 12b are exposed from the protective layer 51 as lead portions. FIG. 7 shows the positional relationship in plan view between the protective layer and each layer covered with the protective layer. 7A shows the positional relationship between the protective layer 51 and the conductive layer 12b, FIG. 7B shows the positional relationship between the protective layer 51 and the conductive layer 12a, and FIG. The positional relationship between layer 51 and organic electronic material layers 14b, 14c and 14a is shown.

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

A flat organic electronic device substrate 50' shown in FIG. 6A is obtained, for example, by bonding an organic electronic device substrate 30a and an organic electronic device substrate 30b together with an organic electronic material layer 14c interposed therebetween, and then It is obtained by forming the protective layer 51 . A conventional bonding apparatus can be used for this bonding. Then, by processing the planar organic electronic device substrate 50' into a 3D curved surface, the 3D curved organic electronic device substrate 50 shown in FIG. 6B is obtained. A method for processing into a 3D curved surface will be described later.

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

Here, a curved surface forming apparatus suitable for forming a 3D curved surface will be described.

[First Curved Surface Forming Apparatus]
FIG. 8 is a diagram showing the first curved surface forming apparatus, and FIG. 9 is a diagram showing a 3D curved surface forming method (first processing method) using the first curved surface forming apparatus in order of steps.

This curved surface forming apparatus 100 includes a concave mold 111 and a temperature control section 116 that regulates the temperature of this concave mold 111 . A concave mold 111 is formed with a hole 115 connecting the bottom and back of a three-dimensional (3D) curved, for example spherical, concave surface 112 , and a pump 117 is connected to the hole 115 . The curved surface forming apparatus 100 includes an elastic rubber sheet 131 arranged on the flat surface 113 around the concave surface 112 of the concave mold 111 so as to cover the concave surface 112 . The elastic rubber sheet 131 is formed with holes 132 passing through the front and back.

When processing a laminated substrate into a 3D curved surface using the curved surface forming apparatus 100, first, as shown in FIG. A laminated substrate 151 is prepared. Further, the concave mold 111 is heated and temperature-controlled to the vicinity of the softening temperature (Tg) of the resin substrate by the temperature control unit 116 . Then, the laminated substrate 151 is placed on the elastic rubber sheet 131 so as to close the hole 132 . For example, the temperature for temperature control is set 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 evacuate the space between the concave surface 112 and the elastic rubber sheet 131 . As a result, the elastic rubber sheet 131 stretches and adheres to the concave surface 112 . In addition, since the laminated substrate 151 is brought into close contact with the elastic rubber sheet 131 and approaches the concave mold 111 as the elastic rubber sheet 131 deforms, heat is transferred from the concave mold 111 to the laminated substrate 151 , thereby The resin substrate is softened. Then, as shown in FIG. 9B, the laminated substrate 151 is brought into close contact with the concave mold 111 and is plastically deformed so as to follow the concave surface 112 .

After that, the operation of the pump 117 is stopped and the hole 115 is opened to the atmosphere, so that 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 permanently maintains the shape following the concave surface 112 even after being released from the concave mold 111 .

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

In the first processing method, since the elastic rubber sheet 131 expands and contracts isotropically during processing, the laminated substrate 151 is evenly pressed against the concave mold 111 and adheres thereto. Moreover, the resin substrate included in the laminated substrate 151 is not softened by heating in advance, but is brought into close contact with the temperature-controlled concave mold 111 and is gradually heated and softened. Therefore, according to the first processing method, the conductive layer included in the laminated substrate 151 can be deformed while suppressing distortion and cracks in the direction along the curved surface. can also suppress distortion and cracking of the functional layer. To obtain uniform performance by suppressing variations in distortion of a functional layer even when mechanical characteristics are uneven within the conductive layer, such as when a plurality of TFTs are arranged in a matrix on the conductive layer. can be done.

As shown in FIG. 10 , the curved surface forming apparatus 100 may include a convex mold 121 that fits into the concave mold 111 and a temperature control section 126 that adjusts the temperature of the convex mold 121 . When this curved surface forming apparatus 100 is used, after the laminated substrate 151 is in close contact with the concave mold 111, the laminated substrate 151 is pressed with the convex mold 121 heated and temperature-controlled by the temperature control unit 126, thereby further improving the curved surface accuracy. It is possible to

[Second Curved Surface Forming Apparatus]
FIG. 11 is a diagram showing a second curved surface forming apparatus, and FIG. 12 is a diagram showing a 3D curved surface forming method (second processing method) using the second curved surface forming apparatus in order of steps.

This curved surface forming apparatus 200 includes a closed container (chamber) 241 , a concave mold 211 in this closed container 241 , and a temperature control section 216 that adjusts the temperature of this concave mold 211 . The curved surface forming apparatus 200 includes an elastic rubber sheet 231 that bisects the space above the concave mold 211 within the closed container 241 . The curved surface forming apparatus 200 includes a substrate holding rubber sheet 233 which is arranged on a flat surface 213 surrounding a 3D curved, for example spherical, concave surface 212 of a concave mold 211 so as to cover the concave surface 212 with a gap therebetween. The board holding rubber sheet 233 has a hole 234 which is narrower than the laminated board to be processed and which is covered with the laminated board. The substrate holding rubber sheet 233 is provided so as to expose a part of the concave surface 212, and the pressure in the space above and below the substrate holding rubber sheet 233 is equal even when the laminated substrate is placed. For example, the board-holding rubber sheet 233 may have a hole spaced apart from the hole 234 and not covered with the laminated board, and the edge of the board-holding rubber sheet 233 may extend from the boundary between the concave surface 212 and the flat surface 213 to the concave surface 212 . may be located on the side. The curved surface forming apparatus 200 is provided with a pipe connecting the space above the elastic rubber sheet 231 and the space below the elastic rubber sheet 231, and a bypass valve 218 is provided in this pipe. A gas supply unit 219 is connected to the space above the elastic rubber sheet 231 , and a pump 217 is connected to the space below the elastic rubber sheet 231 .

When processing a laminated substrate into a 3D curved surface using the curved surface forming apparatus 200, first, as shown in FIG. A laminated substrate 251 is prepared. Further, the concave mold 211 is heated and temperature-controlled by the temperature control unit 216 to the vicinity of the softening temperature (Tg) of the resin substrate. Then, the sealed 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 sealed container 241 is closed. The laminated substrate 251 may have a functional layer such as an organic electronic material layer on the conductive layer.

Bypass valve 218 is then opened and pump 217 is activated. As a result, the entire inside of the sealed container 241 is brought into a decompressed state. After that, the bypass valve 218 is closed, and the gas is supplied from the gas supply part 219 to the space above the elastic rubber sheet 231 . As the gas, for example, air or nitrogen gas is supplied. As a result, the elastic rubber sheet 231 expands 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 each other. At this time, since heat is transferred from the concave mold 211 to the laminated substrate 251, the resin substrate included in the laminated substrate 251 is softened. Then, as shown in FIG. 12B, the laminated substrate 251 is plastically deformed so as to conform to the concave surface 212 .

After that, the operation of the pump 217 and the supply of gas from the gas supply unit 219 are stopped, and the airtight container 241 is opened to the atmosphere. It becomes possible to release from the mold. Since the resin substrate is plastically deformed, the laminated substrate 251 permanently maintains the shape following the concave surface 212 even after being released from the concave mold 211 .

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

In the second processing method, 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 thereto. Moreover, the resin substrate included in the laminated substrate 251 is not softened by heating in advance, but is pressed against the temperature-controlled concave mold 211 and adheres thereto, and is gradually softened by receiving heat. Therefore, according to the second processing method, the conductive layer included in the laminated substrate 251 can be deformed while suppressing distortion and cracks in the direction along the curved surface. can also suppress distortion and cracking of the functional layer. To obtain uniform performance by suppressing variations in distortion of a functional layer even when mechanical characteristics are uneven within the conductive layer, such as when a plurality of TFTs are arranged in a matrix on the conductive layer. can be done. A laminated substrate containing a functional layer is suitable for making a plastic electronic device.

As shown in FIG. 13 , the curved surface forming apparatus 200 may include a convex mold 221 that fits into the concave mold 211 and a temperature control section 226 that adjusts the temperature of the convex mold 221 . When using this curved surface forming apparatus 200, after the laminated substrate 251 is in close contact with the concave mold 211, the laminated substrate 251 is pressed with the convex mold 221 heated and temperature-controlled by the temperature control unit 226, thereby further improving the curved surface accuracy. It is possible to

In the process of opening the bypass valve 218 and operating the pump 217, the pressure in the sealed container 241 is preferably 80000 Pa or less. 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 processing methods, the range of the concave surface of the concave mold is preferably wider than the laminated substrate to be processed in plan view. In this case, the entire laminated substrate can be brought into close contact with the concave surface without restraint, and can be processed into a 3D curved surface while further suppressing distortion. On the other hand, if the end of the laminated substrate is fixed in a state where it cannot be moved, or if the end of the laminated substrate is processed in a state where it is in contact with a surface other than the processing surface of the mold, the fixed part of the laminated substrate and the Distortion is likely to occur from parts that are in 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 stress is concentrated there and distortion is likely to occur. A preferable magnitude of strain (amount of expansion/contraction) 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 laminated substrate before being adhered to the concave mold is room temperature or the softening temperature. is set at a temperature 20° C. or more lower than the

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

After obtaining an element structure in which flat organic electronic device substrates are bonded together, it is processed into a 3D curved surface, so that a conventional bonding apparatus can be used as it is, so that the bonding structure is excellent in productivity. Organic electronic device substrates, such as electrochromic substrates, can be obtained. Similarly, it is also possible to obtain a laminated transparent conductive substrate with excellent productivity.

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

[Elastic rubber sheets 131, 231]
The elastic rubber sheets 131 and 231 expand and contract when depressurized or pressurized, and have the 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 (isobutylene-isoprene rubber (IIR)), Use of ethylene-propylene rubber (EPM), ethylene-propylene-diene rubber (EPDM), urethane rubber (U), silicone rubber (silicone rubber (Si, Q)), fluororubber (FKM), etc. as the material for the elastic rubber sheet. can be done. Thermoplastic elastomers such as styrene, olefin, ester, urethane, amide, polyvinyl chloride (PVC), and fluorine can also be used as the material for the elastic rubber sheet. The material of the elastic rubber sheet is preferably selected according to conditions such as temperature and pressure when forming the curved surface on the laminated substrate. For example, it is preferable to select the material in consideration of heat resistance, elasticity, etc., depending on the conditions. The thickness of the elastic rubber sheet is, for example, within a range of 0.01 mm to 2.0 mm which facilitates formation of a curved surface.

From the viewpoint of uniform deformation of the laminated substrate, it is preferable that the elastic rubber sheet is less likely to adhere to the laminated substrate and the mold, and that the surface of the elastic rubber sheet that contacts the laminated substrate or the mold is slippery. 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. Silicone rubber and fluororubber are particularly preferable as the material for 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 the holes 132 may be one or two or more. The positions of the holes 132 can be arbitrarily set according to the shape of the laminated substrate 151 .

[Molds 111, 121, 211, 221]
General molds can be used as the concave mold and the convex mold as long as they have a curved surface suitable for the 3D curved shape to be formed on the laminated substrate, for example, a spherical shape, and a heat capacity suitable for processing. Specifically, metal materials such as aluminum (Al) and nickel (Ni), glass, ceramics, and the like can be used as materials for the mold. The temperature control part 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 or 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 the 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 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 upper and lower spaces of the laminated substrate 251 are communicated with each other and the pressure therebetween becomes equal, the substrate holding rubber sheet 233 is not required. good too.

EXAMPLES The present invention will be described below with reference to Examples, but the present invention is not limited to these Examples.

(Examples 1 to 4)
In Examples 1 to 4, a transparent conductive substrate having the same shape as the second laminated substrate 20 (transparent conductive substrate 20) was used. A planar stretched polycarbonate sheet substrate having a thickness of 0.3 mm and a size of 156 mm square was prepared as a resin substrate, and an underlying layer was formed thereon. As the material of the underlayer, four types of UV curable acrylic resins with adjusted crosslink density manufactured by Meihan Shinku Co., Ltd. were used. In Example 1, UC1-088 (Acrylic 1) was used, in Example 2, UC1-095 (Acrylic 2) was used, in Example 3, UC1-077 (Acrylic 3) was used, and in Example 4, UC1-090 (Acrylic 4) was used. The thickness of the underlayers of Examples 1 and 4 was 9 μm, and the thickness of the underlayers of Examples 2 and 3 was 5 μm. Then, the hardness (H _IT ) and the elastic deformation work rate (η _IT ) of the underlayer were measured with a nanoindenter (PICODENTOR HM500 manufactured by FISCHERSCOPE). Also, the coefficient of thermal expansion of the underlayer was measured in a temperature range from 25° C. (room temperature) to 146° C. using a TMA apparatus (Thermo plus EVO II, manufactured by Rigaku Corporation). Next, an inorganic oxide conductive layer was formed on the underlayer by sputtering using an ITO target of 90% by mass In ₂ O ₃ and 10% by mass SnO ₂ . The sputtering power during film formation was set to 6.5 kW, the oxygen/argon (Ar) flow rate ratio (O ₂ flow rate ratio) was set to 3.6%, and the thickness of the conductive layer was adjusted by the film formation time. Oerlikon's Solaris was used as a sputtering device. The thickness of the conductive layer was measured with an α-step D-500 manufactured by KLA-Tenchore. These results are shown in Tables 1 and 2.

Next, the transparent conductive substrate was processed into a planar shape shown in FIG. 5 using a laser beam. The outline of the transparent conductive substrate includes two straight lines parallel to each other and two arcuate curved lines connecting both ends of the straight lines. The distance between straight sections is 54.5 mm and the distance between curved sections (corresponding to the diameter of the arc) is 75.5 mm. Then, the transmittance of the flat transparent conductive substrate was measured. In this measurement, a UH4150 manufactured by Hitachi High-Tech Science Co., Ltd. was used as a spectrophotometer to measure transmittance at 550 nm. The hardness (H _IT ) and elastic deformation work rate (η _IT ) of the conductive layer were measured with a nanoindenter (ENT-3100 manufactured by Elionix). The crystallinity of the conductive layer was measured with an XRD device (D8 DISCOVER manufactured by BURKER), and the H/W value of the crystal peak of the (222) plane of indium oxide was calculated. The crystallinity measurement conditions were radiation source: Cu tube, 50 kV, 1000 μm, incident angle: 3°, slit width: 1 mm, collimator diameter: 1 mm. The sheet resistance of the conductive layer was measured using Loresta GP manufactured by Mitsubishi Chemical Analytech Co., Ltd. as a four-terminal resistance measuring device. These results are shown in Table 2.

After that, the transparent conductive substrate was processed into a 3D curved surface using a curved surface forming apparatus 100 equipped with a convex mold shown in FIG. In this process, a spherical concave mold with a radius of curvature of 131 mm and a diameter of 200 mm and a convex mold paired therewith were prepared, and a silicone rubber sheet with a thickness of 0.3 mm was used as the elastic rubber sheet. The used spherical concave mold and convex mold are made of an aluminum alloy conforming to JIS A7075. After adjusting the temperature of the concave mold to 146° C., the conductive layer forming substrate was placed on the elastic rubber sheet, and the elastic rubber sheet and the conductive layer forming substrate were brought into close contact with the concave mold for 60 seconds by pump suction to cause plastic deformation. rice field. Subsequently, the convex mold whose temperature was controlled at 146° C. was lowered and pressed for 90 seconds. After that, the elastic rubber sheet and the transparent conductive substrate were released from the mold by returning the exhaust air from the pump suction holes to the atmospheric pressure, thereby obtaining a transparent conductive substrate having a spherical 3D curved surface. As the bending process, both convex process and concave process were performed.

Then, the presence or absence of destruction (cracks) in the conductive layer after processing was confirmed by observation using scattered diffraction light and observation using an SEM. As a result, as shown in Table 2, in Examples 1 and 2, cracks did not occur in both convex machining and concave machining, and in Examples 3 and 4, cracks did not occur in concave machining, and no cracks occurred in convex machining. Only cracks occurred. FIG. 14 shows cracks observed in the convex processing of Example 3. As shown in FIG. FIG. 14(a) shows the result of diffraction by scattered diffraction light, and FIG. 14(b) shows the result of observation by SEM. As shown in FIG. 14(a), the cracks were circular or elliptical. Similar cracks were observed in the convex processing of Example 4 as well.

(Example 5)
In Example 5, the conditions for forming the conductive layer in Example 2 were changed from those in Example 1, and a conductive layer having properties different from those in Example 1 was formed. Other conditions are the same as in Example 1. Tables 1 and 2 show the conditions for forming the conductive layer and the properties of the conductive layer.

Then, the same evaluation as in Example 1 was performed. As a result, as shown in Table 2, in Example 5, no cracks occurred in both the convex machining and the concave machining.

FIG. 15 shows the measurement results by the XRD method for samples with different sputtering powers such as Example 2 and Example 5. In FIG. FIG. 16 shows the measurement results of Example 1 using a nanoindenter. As shown in FIG. 15, the H/W value tends to increase as the sputtering power increases. In the nanointender, the change in load when the probe is pushed in by 10 nm into the film thickness of the conductive layer of 110 nm is evaluated.

(Examples 6-8)
In Examples 6 to 8, a conductive layer of an inorganic oxide was formed by a sputtering method using a target of In ₂ O ₃ : 99% by mass and ZrO ₂ : 1% by mass. In addition, the conditions for forming the conductive layer were varied between Examples 6-8. Other conditions are the same as in Example 1. Tables 1 and 2 show the conditions for forming the conductive layer and the properties of the conductive layer.

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

FIG. 17 shows the measurement results by the XRD method for samples with different sputtering powers such as Examples 6-8. FIG. 18 shows the measurement results with a nanoindenter for Example 6, FIG. 19 shows the measurement results with a nanoindenter for Example 7, and FIG. 20 shows the measurement results with a nanoindenter for Example 8. Show the results. As shown in FIG. 17, the H/W value tends to increase as the sputtering power increases. Also, as shown in FIGS. 18 to 20, there is a tendency that the higher the sputtering power, the higher the elasticity. In particular, in Example 6 (FIG. 18), an elastic deformation power of almost 100% was obtained.

(Example 9)
In Example 9, Example 7 was used as a base, and under the same conditions as in Example 2, an acrylic base layer 2 with a thickness of 5 μm was formed, and a concave mold with a radius of curvature of 86 mm was used. Other conditions are the same as in Example 7.

Then, the same evaluation as in Example 1 was performed. As a result, as shown in Table 2, cracks did not occur in Example 9 either.

(Example 10)
In Example 10, Example 6 was used as a base, and under the same conditions as in Example 2, an acrylic 2 base layer having a thickness of 5 μm was formed. formed. Other conditions are the same as in Example 6.

Then, the same evaluation as in Example 1 was performed. As a result, as shown in Table 2, cracks did not occur in Example 10 either.

(Example 11)
In Example 11, a curved surface forming apparatus 200 shown in FIG. 11 was used to process a transparent conductive substrate into a 3D curved surface. In this process, a spherical concave mold with a radius of curvature of 131 mm and a diameter of 200 mm was prepared, and silicone rubber sheets with a thickness of 0.3 mm were used as the substrate holding rubber sheet and the elastic rubber sheet. The spherical concave mold used was made of an aluminum alloy conforming to JIS A7075. After placing the transparent conductive substrate on the elastic rubber sheet and adjusting the temperature of the concave mold to 141° C., the bypass valve was opened and the pressure in the chamber was reduced to 300 Pa by pump suction. Next, the bypass valve was closed, and gas (air) was injected into the space above the elastic rubber sheet through the gas injection outlet. The air pressure was set to 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 cause plastic deformation. After that, the pressure in the chamber was returned to the atmospheric pressure, whereby the elastic rubber sheet and the transparent conductive substrate were released from the mold, and a transparent conductive substrate having a spherical 3D curved surface was obtained. As the bending process, both convex process and concave process were performed. Other conditions are the same as in Example 1.

Then, the same evaluation as in Example 1 was performed. As a result, as shown in Table 2, cracks did not occur in Example 11 either.

(Example 12)
In Example 11, an organic electronic device substrate having the same form as the third laminated substrate 30 (organic electronic device 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 were used. : b: c: d = 10: 5: 0.15: 85 (mass ratio) was applied and UV cured in a nitrogen atmosphere to obtain a 1.5 μm film thickness of oxidation reactivity to form an electrochromic layer. KAYARAD PEG400DA manufactured by Nippon Kayaku Co., Ltd. was used as polyethylene glycol diacrylate. IRGACURE 184 manufactured by BASF was used as a photopolymerization initiator. 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 underlying layer 13. , a conductive layer and an 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 1 was performed. As a result, as shown in Table 2, cracks did not occur in Example 12 either.

(Example 13)
In Example 13, a transparent conductive substrate having the same shape as the fourth laminated substrate 40 (transparent conductive substrate 40) was used. Two transparent conductive substrates before bending having the same shape as the second laminated substrate 20 were prepared, and these substrates were bonded together with a double-sided adhesive layer having a thickness of 50 μm. As the double-sided adhesive layer, LA50 (OCA tape) manufactured by Nitto Denko was used. Other conditions are the same as in Example 1.

Then, the same evaluation as in Example 1 was performed. As a result, as shown in Table 2, cracks did not occur in Example 13 either.

(Example 14)
In Example 14, an organic electronic device substrate having the same form as the fifth laminated substrate 50 (organic electronic device substrate 50) was used. Two flat stretched polycarbonate sheet substrates having a thickness of 0.3 mm and 156 mm square were prepared as resin substrates, and a base layer was formed thereon. UC1-088 (acrylic 1) manufactured by Meihan Vacuum Co., Ltd. was used as the material for the underlayer. The thickness of the underlayer was 9 μm. Next, the transparent conductive substrate was processed into a planar shape shown in FIG. 5 using a laser beam.

Next, an inorganic oxide conductive layer was formed on the underlayer by sputtering using an ITO target of 90% by mass In ₂ O ₃ and 10% by mass SnO ₂ . The sputtering power during film formation was set to 6.5 kW, the oxygen/argon flow rate ratio (O ₂ 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. Oerlikon's Solaris was used as a sputtering device. The conductive layer was formed in the area shown in FIG. 7A for one resin substrate and in the area shown in FIG. 7B for the other resin substrate using a mask. The thickness of the conductive layer was measured with an α-step D-500 manufactured by KLA-Tenchore.

Next, on the resin substrate on which the conductive layer was formed in the region shown in FIG. 7(b), an oxidation-reactive electrochromic layer was formed in the region shown in FIG. 7(c) by a coating method. The electrochromic layer was formed under the same conditions as in Example 12.

In addition, a reduction-reactive electrochromic layer was formed in the region shown in FIG. 7(c) on the resin substrate on which the conductive layer was formed in the region shown in FIG. 7(a). In the formation of the reductive electrochromic layer, a nanoparticle tin oxide layer with a thickness of 3 μm was formed by applying a solution of tin oxide in methanol to which 1% by mass of polyvinyl butyral was added and annealing the solution at 120° C. for 5 minutes. formed. Then, a solution obtained by dissolving 2% by mass of a 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 for adsorption treatment. Annealed for 1 minute. As the methanol dispersion of tin oxide, Celnax manufactured by Nissan Chemical Industries, Ltd. was used.
[Structural Formula B]

(a) the (FSO ₂ ) ₂ N-salt of 1-ethyl-3-methylimidazolium, (b) polyethylene glycol diacrylate, and (c) a photoinitiator were then added to a:b:c=2: An electrolyte solution was prepared by mixing them at a ratio of 1:0.01 (mass ratio). After filling this electrolyte solution between the oxidation-reactive electrochromic layer and the reduction-reactive electrochromic layer, annealing treatment is performed at 60° C. for 1 minute, and the layers are cured by ultraviolet irradiation and bonded together. made the body. 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. KAYARAD PEG400DA manufactured by Nippon Kayaku Co., Ltd. was used as polyethylene glycol diacrylate. IRGACURE 184 manufactured by BASF was used as a photopolymerization initiator. Furthermore, a protective layer was formed by filling a UV-curable acrylic material around the organic electronic material layer and UV-curing it. TB3050 manufactured by ThreeBond Co., Ltd. was used as the UV curable acrylic material.

Then, the same evaluation as in Example 1 was performed. As a result, as shown in Table 2, cracks did not occur in Example 14 either.

In addition, evaluation of color appearance/discoloration of the organic electronic device substrate was performed. In this evaluation, a voltage of 2.0 V was applied so that one lead portion of the organic electronic material layer exposed from the protective layer became a positive electrode and the other lead portion became a negative electrode, 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. In addition, it was confirmed that when −0.6 V was applied, the film became transparent and decolored, and that the coloring and decoloring operations were performed normally. The light transmittance was measured with an ultraviolet-visible-near-infrared spectrophotometer UH4150 (manufactured by Hitachi High-Tech Science Co., Ltd.).

(Comparative example 1)
Comparative Example 1 is the same as Example 1 except that a polycarbonate sheet substrate having no underlying layer was used based on Example 1.

The hardness (H _IT ) of the underlayer of the polycarbonate sheet substrate was measured with a nanoindenter (PICODENTOR HM500, manufactured by FISCHERSCOPE). Also, the coefficient of thermal expansion of the underlying layer was measured in a temperature range from 25°C (room temperature) to 146°C using a TMA apparatus (Thermo plus EVO II, manufactured by Rigaku Corporation). These results are shown in Tables 1 and 2.

Moreover, the same evaluation as in Example 1 was performed. As a result, in Comparative Example 1, cracks occurred in both the convex machining and the concave machining.

(Comparative example 2)
In Comparative Example 2, a conductive layer similar to that of Example 5 was formed by using Comparative Example 1 as a base and changing the conditions for forming the conductive layer from those of Example 1. Other conditions are the same as in Comparative Example 1. Tables 1 and 2 show the conditions for forming the conductive layer and the properties of the conductive layer.

Moreover, the same evaluation as in Example 1 was performed. As a result, in Comparative Example 2, cracks occurred in both the convex machining and the concave machining.

(Comparative Example 3)
In Comparative Example 3, based on Example 1, the temperatures of the concave mold and the convex mold were adjusted to 25° C. when processing the transparent conductive substrate. Other conditions are the same as in Example 1.

Then, the same evaluation as in Example 1 was performed. As a result, since the resin substrate was not softened, the transparent conductive substrate was not plastically deformed but was elastically deformed, and could not be processed into a 3D curved surface. That is, as shown in Table 2, no cracks occurred in the conductive layer, but a three-dimensionally curved transparent conductive substrate was not obtained.

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

REFERENCE SIGNS LIST 10, 20, 40 transparent conductive substrate 11 resin substrate 12 conductive layer 13 base layer 14 organic electronic material layer 30, 50 organic electronic device substrate 41 double-sided adhesive layer 51 protective layer 100, 200 curved surface forming apparatus 111, 211 concave mold 112, 212 concave surface 113, 213 flat surface 115 hole 116, 126, 216 temperature control unit 117, 217 pump 121, 221 convex mold 131, 231 elastic rubber sheet 132 hole 151, 251 laminated substrate 218 bypass valve 219 gas supply unit 233 substrate holding rubber Sheet 234 Hole 241 Closed container

JP-A-63-906 JP-A-2-276630 Japanese Patent No. 5409094

Claims (6)

a support substrate including a thermoplastic resin substrate;
a conductive layer on the support substrate;
has
The surface hardness of the support substrate is 180 MPa or more ,
A three-dimensional curved laminated substrate , wherein the support substrate has an underlayer having a surface hardness of 180 MPa or more on the resin substrate, and the underlayer is harder than the resin substrate. 2. The three-dimensional curved laminated substrate according to claim 1, wherein the thermoplastic resin is polycarbonate or polyethylene terephthalate. 3. The three-dimensional curved laminated substrate according to claim 1 , further comprising an organic electronic material layer on the conductive layer. 4. The three-dimensional curved laminated substrate according to claim 3 , wherein the organic electronic material layer is an electrochromic layer. 5. The conductive layer according to claim 1 , wherein the conductive layer contains indium oxide having a crystal peak of (222) plane and an H/W value of 0.16 to 5.7. A three-dimensional curved laminated substrate. A method for manufacturing a three-dimensional curved laminated substrate according to any one of claims 1 to 5 ,
a step of forming a conductive layer on a support substrate including a thermoplastic resin substrate to obtain a laminated substrate;
a step of 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 to soften the resin substrate;
A method for manufacturing a three-dimensional curved laminated substrate, comprising:

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