CN114762024A - Method of manufacturing flexible transparent electronic device and article - Google Patents

Abstract

An aspect of the present invention is a method for manufacturing a flexible transparent electronic device, wherein an article having a flexible transparent electronic device (100) formed on a glass support substrate (1) is prepared, the flexible transparent electronic device (100) includes a flexible transparent base material (10), an electronic component (20) formed on the flexible transparent base material (10), and a protective layer (50) made of a transparent resin and covering the electronic component (20), and the flexible transparent electronic device (100) is peeled from the glass support substrate (1) by irradiating ultraviolet laser Light (LB) through the glass support substrate (1) of the article. When preparing an article, a release layer (2) is formed between a glass support substrate (1) and a flexible transparent base material (10), and the release layer (2) contains a resin as a main component and has a lower transmittance of an ultraviolet Laser (LB) than the flexible transparent base material.

Description

Method of manufacturing flexible transparent electronic device and article

Technical Field

The invention relates to a method of manufacturing a flexible transparent electronic device and an article.

Background

Patent document 1 discloses a transparent display device in which a Light Emitting Diode (LED) element formed on a transparent base material is used for a pixel. Such a transparent display device is used for, for example, a front glass of an automobile because its back surface side can be visually recognized through the transparent display device. As a related art, a transparent sensing device in which a micro sensor is provided on a transparent base material is known.

In the present specification, an electronic device in which an electronic component is formed on a transparent base material and the back surface side thereof can be visually recognized, such as a transparent display device or a transparent sensing device, is referred to as a "transparent electronic device". In the transparent electronic device, if the transparent base member is flexible, a "flexible transparent electronic device" can be obtained.

As a method for manufacturing a flexible electronic device, a method is known in which a flexible base material and an electronic element are formed in this order on a glass support substrate, and then the flexible electronic device including the flexible base material and the electronic element is peeled off from the glass support substrate. For example, patent documents 2 and 3 disclose a method of peeling a flexible electronic component from a glass support substrate by irradiating an interface between a flexible base material and the glass support substrate with laser light. This method is called a Laser lift-off (LLO) method.

Patent document 1: japanese patent laid-open publication No. 2006-301650

Patent document 2: international publication No. 2018//029766

Patent document 3: international publication No. 2012/042822

When the LLO method is applied to the method for manufacturing the flexible transparent electronic device, the flexible transparent electronic device is peeled from the glass support substrate by irradiating the interface between the flexible transparent base material and the glass support substrate with laser light. With respect to this method, the inventors have found the following problems.

When the laser beam is irradiated, the flexible transparent base material located at the interface with the glass support substrate is decomposed and peeled from the glass support substrate. In this case, the flexible transparent base material may be damaged by irradiation with laser light, or the electronic component may be damaged by the laser light.

Disclosure of Invention

The present invention has been made in view of such circumstances, and provides a method for manufacturing a flexible transparent electronic device capable of suppressing damage to a flexible transparent base material caused by irradiation with laser light.

The present invention provides a method for manufacturing a flexible transparent electronic device having the structure of [1 ].

[1] A method for manufacturing a flexible transparent electronic device, comprising preparing an article having a flexible transparent electronic device formed on a glass support substrate, wherein the flexible transparent electronic device comprises a flexible transparent base material, an electronic component formed on the flexible transparent base material, and a protective layer made of a transparent resin and covering the electronic component,

and peeling the flexible transparent electronic component from the glass support substrate by irradiating ultraviolet laser light through the glass support substrate of the article,

when preparing the article, a release layer is formed between the glass support substrate and the flexible transparent base material, the release layer mainly containing a resin and having a lower transmittance of the ultraviolet laser than the flexible transparent base material.

[2] The method for manufacturing a flexible transparent electronic device according to [1], wherein in one embodiment of the present invention, the resin is an aromatic ring-containing resin.

[3] The method according to [1] or [2], wherein the glass transition temperature Tg of the resin is 60 ℃ or higher.

[4] The method for manufacturing a flexible transparent electronic device according to [1] or [2], wherein the ultraviolet laser transmittance of the release layer is 50% or less.

[5] The method for manufacturing a flexible transparent electronic device according to [4], wherein the release layer contains an ultraviolet absorber.

[6] The method for manufacturing a flexible transparent electronic device according to [4], wherein the release layer does not contain an ultraviolet absorber, and the ultraviolet laser transmittance of the release layer is 5% or less.

[7]According to [1]～[6]The method for manufacturing a flexible transparent electronic device according to any one of the above, wherein the release layer has a thickness of 10⁴～10¹³Surface resistivity of omega/□.

[8] The method for manufacturing a flexible transparent electronic device according to any one of [1] to [7], wherein the release layer has a surface roughness Ra of 0.5 μm or less.

[9]According to [1]～[8]The method for manufacturing a flexible transparent electronic device according to any one of the above items, wherein the electronic element includes a light emitting diode element, and the light emitting diode element is disposed on the flexible transparent base material at least one for each pixel and has a thickness of 10,000 μm ²The flexible transparent electronic device has a function as a display device.

The present invention provides an article having the following structure [10 ].

[10] An article having a flexible transparent electronic device formed on a glass support substrate, wherein the flexible transparent electronic device comprises a flexible transparent base member, an electronic component formed on the flexible transparent base member, and a protective layer made of a transparent resin covering the electronic component,

a release layer is formed between the glass support substrate and the flexible transparent base material, the release layer mainly containing a resin and having a lower ultraviolet laser transmittance than the flexible transparent base material.

[11] The article according to [10], wherein, in an aspect of the present invention, the resin is an aromatic ring-containing resin.

[12] The article according to [10] or [11], wherein the resin has a glass transition temperature Tg of 60 ℃ or higher.

[13] The article according to any one of [10] to [11], wherein a transmittance of the ultraviolet laser of the release layer is 50% or less.

[14] The article according to [13], wherein the release layer contains an ultraviolet absorber.

[15] The article according to [13], wherein the release layer does not contain an ultraviolet absorber, and the release layer has a transmittance of the ultraviolet laser of 5% or less.

[16]According to [10]]～[15]The article according to any one of the above, wherein the release layer has a thickness of 10⁴～10¹³Surface resistivity of omega/□.

[17] The article according to any one of [10] to [16], wherein the surface roughness Ra of the release layer is 0.5 μm or less.

[18]According to [10]]～[17]The article according to any one of the above, wherein the electronic element includes a light emitting diode element, and the light emitting diode element is disposed on the flexible transparent base material at least one for each pixel and has a thickness of 10,000 μm²The flexible transparent electronic device has a function as a display device in the following area.

According to the present invention, it is possible to provide a method for manufacturing a flexible transparent electronic device capable of suppressing damage to a flexible transparent base material due to irradiation with laser light.

Drawings

Fig. 1 is a schematic partial plan view showing an example of a flexible transparent display device.

Fig. 2 is a sectional view based on the II-II cut line in fig. 1.

Fig. 3 is a cross-sectional view showing an example of a method for manufacturing the flexible transparent display device according to the first embodiment.

Fig. 4 is a cross-sectional view showing an example of a method for manufacturing the flexible transparent display device according to the first embodiment.

Fig. 5 is a cross-sectional view showing an example of the method for manufacturing the flexible transparent display device according to the first embodiment.

Fig. 6 is a cross-sectional view showing an example of the method for manufacturing the flexible transparent display device according to the first embodiment.

Fig. 7 is a cross-sectional view showing an example of the method for manufacturing the flexible transparent display device according to the first embodiment.

Fig. 8 is a cross-sectional view showing an example of the method for manufacturing the flexible transparent display device according to the first embodiment.

Fig. 9 is a cross-sectional view showing an example of the method for manufacturing the flexible transparent display device according to the first embodiment.

Fig. 10 is a cross-sectional view showing an example of a method for manufacturing the flexible transparent display device according to the first embodiment.

Fig. 11 is a cross-sectional view showing an example of a method for manufacturing the flexible transparent display device according to the first embodiment.

Fig. 12 is a cross-sectional view showing an example of the method for manufacturing the flexible transparent display device according to the first embodiment.

Fig. 13 is a cross-sectional view showing an example of the method for manufacturing the flexible transparent display device according to the first embodiment.

Fig. 14 is a schematic plan view of a comb-shaped electrode for measuring surface resistivity.

Fig. 15 is a diagram showing a specific example of each dimension of the comb-shaped electrode shown in fig. 20.

Fig. 16 is a schematic plan view showing an example of the laminated glass of the second embodiment.

Fig. 17 is a schematic cross-sectional view showing an example of the laminated glass according to the second embodiment.

Fig. 18 is a schematic cross-sectional view showing another example of the laminated glass of the second embodiment.

Fig. 19 is a schematic partial plan view showing an example of the flexible transparent display device of the third embodiment.

Fig. 20 is a schematic partial plan view showing an example of a flexible transparent sensing device of the fourth embodiment.

Fig. 21 is a schematic cross-sectional view of the sensor 70.

Detailed Description

Hereinafter, specific embodiments to which the present invention is applied will be described in detail with reference to the drawings. However, the present invention should not be limited to the following embodiments. In addition, the following description and the drawings are appropriately simplified for clarity of explanation.

In the present specification, the term "transparent electronic device" refers to an electronic device in which an electronic component is formed on a transparent base material, and visual information such as a person or a background located on the back side of the electronic device can be visually recognized in a desired use environment.

In the present specification, the term "transparent display device" refers to a display device capable of visually recognizing visual information such as a person or a background on the back side of the display device in a desired use environment. Further, it is determined whether or not the display device is visually recognizable at least in a non-display state, that is, a state where no current is applied. A "transparent display device" is one mode of a "transparent electronic device".

Similarly, in the present specification, the "transparent sensing device" refers to a sensing device capable of visually recognizing visual information such as a person or a background located on the back side of the sensing device in a desired use environment. The "sensing device" refers to a device capable of acquiring various information by a sensor. A "transparent sensing detection device" is one form of a "transparent electronic device".

In the present specification, "transparent" means that the visible light transmittance is 40% or more, preferably 60% or more, and more preferably 70% or more. The transmittance may be 5% or more and the haze value may be 10 or less. If the transmittance is 5% or more, the outdoor can be observed with the same or more brightness as that of the indoor when the outdoor is observed in daytime from the indoor, and sufficient visibility can be ensured.

In addition, if the transmittance is 40% or more, the rear surface side of the transparent display device can be visually recognized without any substantial problem even if the front surface side and the rear surface side of the transparent display device have the same brightness. In addition, if the haze value is 10 or less, the contrast of the background can be sufficiently ensured.

The term "transparent" is used regardless of whether it is colored or not, i.e., whether it is colorless or colored.

The transmittance is a value (%) measured by a method in accordance with ISO 9050. The haze value is a value measured by a method conforming to ISO 14782.

(first embodiment)

< Structure of Flexible transparent display device >

First, the structure of a flexible transparent display device manufactured by the method for manufacturing a flexible transparent display device according to the first embodiment will be described with reference to fig. 1 and 2. Fig. 1 is a schematic partial plan view showing an example of a flexible transparent display device. Fig. 2 is a sectional view based on the II-II cut line in fig. 1.

It is to be understood that the right-hand xyz rectangular coordinate system shown in fig. 1 and 2 is provided for convenience of description of the positional relationship of the components. In general, the positive z-axis direction is vertically upward, and the xy-plane is a horizontal plane.

The flexible transparent display device 100 shown in fig. 1 and 2 is a flexible transparent electronic device including a flexible transparent base material 10, a light emitting section 20, an IC chip 30, a wiring 40, and a protective layer 50. The display region 101 in the flexible transparent display device 100 shown in fig. 1 is a region for displaying an image, which is constituted by a plurality of pixels. In addition, the image contains text. As shown in fig. 1, the display region 101 is formed of a plurality of pixels arranged in a row direction (x-axis direction) and a column direction (y-axis direction). Fig. 1 shows a part of a display region 101, which has 2 pixels in each of the row direction and the column direction, and shows 4 pixels in total. Here, the 1 pixel PIX is shown surrounded by a one-dot chain line. In fig. 1, the flexible transparent base material 10 and the protective layer 50 shown in fig. 2 are omitted. Fig. 1 is a plan view, but for easy understanding, the light emitting unit 20 and the IC chip 30 are indicated by dots.

< planar arrangement of light emitting part 20, IC chip 30, and wiring 40 >

First, a planar arrangement of the light emitting section 20, the IC (Integrated Circuit) chip 30, and the wiring 40 will be described with reference to fig. 1.

As shown in fig. 1, the pixels PIX surrounded by the one-dot chain line are arranged in a matrix form at a pixel pitch Px in the row direction (x-axis direction) and at a pixel pitch Py in the column direction (y-axis direction). Here, as shown in fig. 1, each pixel PIX includes a light emitting portion 20 and an IC chip 30. That is, the light emitting unit 20 and the IC chip 30 are arranged in a matrix at a pixel pitch Px in the row direction (x-axis direction) and at a pixel pitch Py in the column direction (y-axis direction).

The arrangement of the pixels PIX, that is, the light emitting units 20 is not limited to a matrix shape as long as they are arranged in a predetermined direction at a predetermined pixel pitch.

As shown in fig. 1, the light emitting portion 20 in each pixel PIX includes at least one light emitting diode element (hereinafter, LED element). That is, the flexible transparent display device is a display device using an LED element for each pixel PIX, and is called an LED display or the like.

In the example of fig. 1, each of the light emitting portions 20 includes a red-based LED element 21, a green-based LED element 22, and a blue-based LED element 23 as electronic elements. The LED elements 21 to 23 correspond to sub-pixels (sub pixels) constituting 1 pixel. In this way, since each of the light emitting sections 20 has the LED elements 21 to 23 that emit light of red, green, and blue, which are three primary colors of light, the flexible transparent display device can display a full-color image.

Each light emitting unit 20 may include 2 or more LED elements of the same color system. This can enlarge the dynamic range of the image.

The LED elements 21 to 23 have a minute size and are so-called micro LED elements. Specifically, the width (length in the x-axis direction) and the length (length in the y-axis direction) of the LED element 21 of the flexible transparent base material 10 are, for example, 100 μm or less, preferably 50 μm or less, and more preferably 20 μm or less, respectively. The LED elements 22 and 23 are also the same. The lower limit of the width and length of the LED element is, for example, 3 μm or more depending on various conditions in manufacturing.

The LED elements 21-23 in FIG. 1 have the same dimensions, i.e., width and length, but may be different from each other.

The area occupied by each of the LED elements 21-23 on the flexible transparent base material 10 is, for example, 10,000 μm²Hereinafter, it is preferably 1,000. mu.m²Hereinafter, more preferably 100 μm²The following. The lower limit of the area occupied by each LED element is, for example, 10 μm depending on the conditions of manufacture and the like²The above. Here, in the present specification, the occupied area of the components such as the LED element and the wiring is an area in an xy plan view in fig. 1.

The LED elements 21 to 23 shown in fig. 1 are rectangular in shape, but are not particularly limited. For example, square, hexagonal, tapered, cylindrical, etc. configurations are also possible.

Here, the LED elements 21 to 23 have, for example, a mirror structure for efficiently extracting light to the visual recognition side. Therefore, the transmittance of the LED elements 21 to 23 is as low as 10% or less, for example. However, in this flexible transparent display device, as described above, for example, an area of 10,000 μm is used²The following LED elements 21-23 with small size. Therefore, even when the flexible transparent display device is observed from a short distance of about several tens cm to 2m, for example, the LED elements 21 to 23 are hardly visually recognized. In the display region 101, the region having low transmittance is narrow, and the rear surface side is excellent in visibility. Further, the degree of freedom in the arrangement of the wiring 40 and the like is also large.

The "region having a low transmittance in the display region 101" means, for example, a region having a transmittance of 20% or less. The same applies hereinafter.

Further, since the LED elements 21 to 23 of a minute size are used, the LED elements are less likely to be damaged even if the flexible transparent display device is bent. Therefore, the flexible transparent display device can be used by being mounted on a curved transparent plate such as a window glass of an automobile or by being enclosed between 2 curved transparent plates. Here, since the flexible transparent base member 10 is flexible (has flexibility), the flexible transparent display device can be bent.

The LED elements 21 to 23 shown in the figure are chip-type, but are not particularly limited. The LED elements 21 to 23 may be packaged entirely or partially without being encapsulated with resin. The sealing resin may have a lens function, thereby improving the light utilization efficiency and the light extraction efficiency to the outside. In this case, the LED elements 21 to 23 may be individually packaged, or 3in1 chips in which 3 LED elements 21 to 23 are packaged together may be used. Alternatively, each LED element may emit light at the same wavelength, but light of different wavelengths may be extracted by a fluorescent material or the like contained in the encapsulating resin.

When the LED elements 21 to 23 are packaged, the size and area of the LED elements are the size and area in the packaged state, respectively. When 3 LED elements 21-23 are packaged together, the area of each LED element is one third of the whole area.

The LED elements 21 to 23 are not particularly limited, and are made of, for example, an inorganic material. The red LED element 21 is, for example, AlGaAs, GaAsP, GaP, or the like. The green LED element 22 is, for example, InGaN, GaN, AlGaN, GaP, AlGaInP, ZnSe, or the like. The blue LED element 23 is, for example, InGaN, GaN, AlGaN, ZnSe, or the like.

The LED elements 21 to 23 have a light emission efficiency, i.e., an energy conversion efficiency, of, for example, 1% or more, preferably 5% or more, and more preferably 15% or more. When the light emission efficiency of the LED elements 21 to 23 is 1% or more, sufficient luminance can be obtained even with the use of the LED elements 21 to 23 having a minute size as described above, and thus the LED elements can be used as a display device in daytime. In addition, when the light emission efficiency of the LED element is 15% or more, heat generation is suppressed, and therefore, sealing into the laminated glass using the resin adhesive layer is facilitated.

The LED elements 21 to 23 are obtained by cutting crystals grown by, for example, a liquid Phase growth method, an HVPE (Hydride Vapor Phase Epitaxy) method, an MOCVD (Metal Organic Chemical Vapor Deposition) method, or the like. The obtained LED elements 21 to 23 are assembled on the flexible transparent base member 10.

Alternatively, the LED elements 21 to 23 may be formed by peeling off the semiconductor wafer by Micro-Transfer Printing or the like and transferring the peeled semiconductor wafer onto the flexible transparent base material 10.

The pixel pitches Px, Py are, for example, 100 to 3000 μm, preferably 180 to 1000 μm, and more preferably 250 to 400 μm, respectively. By setting the pixel pitches Px and Py in the above ranges, it is possible to achieve high transparency while ensuring sufficient display performance. In addition, a diffraction phenomenon that may occur due to light from the back surface side of the flexible transparent display device can be suppressed.

In addition, the pixel density in the display region 101 of the flexible transparent display device is, for example, 10ppi or more, preferably 30ppi or more, and more preferably 60ppi or more.

The area of 1 pixel PIX can be represented by Px × Py. The area of 1 pixel is, for example, 1 × 10⁴μm²～9×10⁶μm²Preferably 3X 10⁴～1×10⁶μm²More preferably 6X 10⁴～2×10⁶μm². By making the area of 1 pixel 1 × 10⁴μm²～9×10⁶μm²The transparency of the display device can be improved while ensuring appropriate display performance. The area of 1 pixel can be appropriately selected according to the size, application, visible distance, and the like of the display region 101.

The ratio of the occupied area of the LED elements 21 to 23 to the area of 1 pixel is, for example, 30% or less, preferably 10% or less, more preferably 5% or less, and still more preferably 1% or less. By setting the ratio of the occupied area of the LED elements 21-23 to the area of 1 pixel to 30% or less, the transparency and the visibility of the back surface side can be improved.

In fig. 1, 3 LED elements 21 to 23 are arranged in 1 row in the positive direction of the x-axis in sequence in each pixel, but the present invention is not limited thereto. For example, the arrangement order of the 3 LED elements 21 to 23 may be changed. In addition, 3 LED elements 21-23 may be arranged in the y-axis direction. Alternatively, the 3 LED elements 21 to 23 may be arranged at the apexes of a triangle.

In addition, as shown in fig. 1, when each light emitting part 20 includes a plurality of LED elements 21 to 23, the interval between the LED elements 21 to 23 of the light emitting part 20 is, for example, 100 μm or less, preferably 10 μm or less. The LED elements 21-23 may be disposed in contact with each other. This makes it easy to make the first power supply branch line 41a common, and can improve the aperture ratio.

In the example of fig. 1, the arrangement order, arrangement direction, and the like of the plurality of LED elements in each light emitting unit 20 are the same, but may be different. In addition, when each light emitting section 20 includes 3 LED elements that emit light of different wavelengths, LED elements may be arranged in the x-axis direction or the y-axis direction in some of the light emitting sections 20, and LED elements of each color may be arranged at the vertices of a triangle in other light emitting sections 20.

In the example of fig. 1, the IC chip 30 is disposed for each pixel PIX, and is an electronic element that drives the light emitting section 20. Specifically, the IC chip 30 is connected to the LED elements 21 to 23 via the driving lines 45, so that the LED elements 21 to 23 can be driven individually.

Further, the IC chip 30 may be disposed for a plurality of pixels, and the plurality of pixels to which the respective IC chips 30 are connected may be driven. For example, if 1 IC chip 30 is arranged for 4 pixels, the number of IC chips 30 can be reduced to 1/4, which is the number of the example of fig. 1, and the occupied area of the IC chip 30 can be reduced.

The area of the IC chip 30 is, for example, 100,000 μm²Preferably 10,000 μm or less²Hereinafter, it is more preferably 5,000. mu.m²The following. Although the transmittance of the IC chip 30 is as low as 20% or less, by using the IC chip 30 having the above-described size, the region having low transmittance is narrowed in the display region 101, and the visibility on the back surface side is improved.

The IC chip 30 is, for example, a hybrid IC including an analog region and a logic region. The analog area includes, for example, a current control circuit, a voltage transformation circuit, and the like.

Further, an IC chip-equipped LED element in which the LED elements 21 to 23 and the IC chip 30 are packaged together with a resin may be used. Instead of the IC chip 30, a circuit including a Thin Film Transistor (TFT) may be used. Also, the IC chip 30 is not essential.

On the other hand, a micro sensor may be mounted on the IC chip 30. That is, the flexible transparent display device may also be a flexible transparent sensing device at the same time. The micro sensor is described in detail in the fourth embodiment.

The wiring 40 of the present embodiment is a display wiring, and as shown in fig. 1, a plurality of wirings are provided for each of a power supply line 41, a ground line 42, a row data line 43, a column data line 44, and a drive line 45.

In the example of fig. 1, the power supply line 41, the ground line 42, and the column data line 44 extend in the y-axis direction. On the other hand, the line data lines 43 extend in the x-axis direction.

In each pixel PIX, the power supply line 41 and the column data line 44 are provided on the x-axis negative direction side of the light emitting section 20 and the IC chip 30, and the ground line 42 is provided on the x-axis positive direction side of the light emitting section 20 and the IC chip 30. Here, power supply line 41 is provided on the x-axis negative direction side with respect to column data line 44. In each pixel PIX, the row data line 43 is provided on the y-axis negative side of the light emitting section 20 and the IC chip 30.

As will be described in detail later, the power supply line 41 includes a first power supply branch line 41a and a second power supply branch line 41b, as shown in fig. 1. The ground line 42 includes a ground branch line 42 a. The row data line 43 includes a row data branch line 43 a. The column data line 44 includes a column data branch line 44 a. Each branch line is included in the wiring 40.

As shown in fig. 1, each power supply line 41 extending in the y-axis direction is connected to the light emitting portion 20 and the IC chip 30 of each pixel PIX arranged in parallel in the y-axis direction. More specifically, in each pixel PIX, the LED elements 21 to 23 are arranged in order in the x-axis positive direction on the x-axis positive direction side of the power supply line 41. Therefore, the first power branch line 41a branching from the power supply line 41 in the x-axis positive direction is connected to the y-axis positive direction side end portion of the LED elements 21 to 23.

In each pixel PIX, the IC chip 30 is disposed on the negative y-axis side of the LED elements 21 to 23. Therefore, between the LED element 21 and the column data line 44, the second power supply branch line 41b branched from the first power supply branch line 41a in the y-axis negative direction is linearly extended and arranged, and is connected to the x-axis negative direction side of the y-axis positive direction side end portion of the IC chip 30.

As shown in fig. 1, the respective ground lines 42 extending in the y-axis direction are connected to the IC chips 30 of the respective pixels PIX arranged in parallel in the y-axis direction. Specifically, the ground branch line 42a branched from the ground line 42 in the x-axis negative direction is arranged to extend linearly and connected to the x-axis positive direction side end of the IC chip 30.

Here, the ground line 42 is connected to the LED elements 21 to 23 via the ground branch line 42a, the IC chip 30, and the driving line 45.

As shown in fig. 1, each row data line 43 extending in the x-axis direction is connected to the IC chip 30 of each pixel PIX arranged in parallel in the x-axis direction (row direction). Specifically, a line data branch line 43a branched from the line data line 43 in the y-axis positive direction is linearly extended and connected to the y-axis negative direction side end of the IC chip 30.

Here, the row data line 43 is connected to the LED elements 21 to 23 via a row data branch line 43a, the IC chip 30, and the driving line 45.

As shown in fig. 1, each column data line 44 extending in the y-axis direction is connected to the IC chip 30 of each pixel PIX arranged in parallel in the y-axis direction (column direction). Specifically, a column data branch line 44a branched from the column data line 44 in the positive x-axis direction is arranged to extend linearly and connected to the negative x-axis side end of the IC chip 30.

Here, the column data line 44 is connected to the LED elements 21 to 23 via the column data branch line 44a, the IC chip 30, and the driving line 45.

The driving line 45 connects the LED elements 21 to 23 and the IC chip 30 to each pixel PIX. Specifically, in each pixel PIX, 3 drive lines 45 are arranged to extend in the y-axis direction, and the y-axis negative direction side ends of the LED elements 21 to 23 and the y-axis positive direction side end of the IC chip 30 are connected to each other.

The arrangement of the power supply line 41, the ground line 42, the row data line 43, the column data line 44, and their branch lines, and the drive line 45 shown in fig. 1 is only an example, and can be changed as appropriate. For example, at least one of the power supply line 41 and the ground line 42 may be arranged to extend not in the y-axis direction but in the x-axis direction. In addition, the power supply line 41 and the column data line 44 may be interchanged.

The entire configuration shown in fig. 1 may be an inverted configuration in the vertical direction, an inverted configuration in the horizontal direction, or the like. The entire configuration shown in fig. 1 may be an inverted configuration in the vertical direction, an inverted configuration in the horizontal direction, or the like.

The row data line 43, the column data line 44, and their branch lines, and the driving line 45 are not essential.

The wiring 40 is made of metal such as copper (Cu), aluminum (Al), silver (Ag), or gold (Au). Among them, from the viewpoint of low resistivity and cost, a metal containing copper or aluminum as a main component is preferable. In order to reduce the reflectance, the wiring 40 may be coated with a material such as titanium (Ti), molybdenum (Mo), copper oxide, or carbon. In addition, the surface of the coated material may have irregularities.

The width of the wiring 40 in the display region 101 shown in FIG. 1 is, for example, 1 to 100 μm, preferably 3 to 20 μm. Since the width of the wiring 40 is 100 μm or less, the wiring 40 is hardly visually recognized even when the flexible transparent display device is observed from a short distance of about several tens of cm to 2m, for example, and thus the visibility of the back surface side is excellent. On the other hand, in the thickness range described later, if the width of the wiring 40 is set to 1 μm or more, an excessive increase in the resistance of the wiring 40 can be suppressed, and a voltage drop and a decrease in the signal intensity can be suppressed. In addition, a decrease in heat conduction due to the wiring 40 can also be suppressed.

Here, as shown in fig. 1, when the wiring 40 mainly extends in the x-axis direction and the y-axis direction, a cross diffraction image extending in the x-axis direction and the y-axis direction may be generated by light irradiated from the outside of the flexible transparent display device, and visibility of the rear surface side of the flexible transparent display device may be reduced. By reducing the width of each wiring, this diffraction can be suppressed, and the visibility on the back surface side can be further improved. From the viewpoint of suppressing diffraction, the width of the wiring 40 may be 50 μm or less, preferably 10 μm or less, and more preferably 5 μm or less.

The resistivity of the wiring 40 is, for example, 1.0 × 10^－6The content of the acid is less than or equal to omega m,preferably 2.0X 10^－8Omega m or less. The thermal conductivity of the wiring 40 is, for example, 150 to 5,500W/(mK), preferably 350 to 450W/(mK).

The interval between adjacent wirings 40 in the display region 101 shown in FIG. 1 is, for example, 3 to 100 μm, preferably 5 to 30 μm. If there is a region where the wiring 40 is dense, visual recognition of the back surface side may be hindered. Such an interference of visual recognition can be suppressed by setting the interval between the adjacent wirings 40 to 3 μm or more. On the other hand, when the interval between the adjacent wirings 40 is set to 100 μm or less, sufficient display performance can be secured.

In the case where the interval between the wirings 40 is not constant due to the bending of the wirings 40 or the like, the above-mentioned interval between the adjacent wirings 40 is the minimum value thereof.

The ratio of the occupied area of the wiring 40 to the area of 1 pixel is, for example, 30% or less, preferably 10% or less, more preferably 5% or less, and further preferably 3% or less. The transmittance of the wiring 40 is, for example, 20% or less, or as low as 10% or less. However, by setting the ratio of the occupied area of the wiring 40 in 1 pixel to 30% or less, the region with low transmittance in the display region 101 is narrowed, and the visibility on the back surface side is improved.

The total area occupied by the light emitting section 20, the IC chip 30, and the wiring 40 with respect to the area of 1 pixel is, for example, 30% or less, preferably 20% or less, and more preferably 10% or less.

Cross-sectional Structure of Flexible transparent display device

Next, a cross-sectional structure of the flexible transparent display device is explained with reference to fig. 2.

The flexible transparent base member 10 is made of a transparent material having an insulating property. In the example of fig. 2, the flexible transparent base member 10 has a two-layer configuration of a main substrate 11 and an adhesive layer 12.

As described in detail later, the main substrate 11 is made of, for example, a transparent resin.

Examples of the adhesive constituting the adhesive layer 12 include transparent resin adhesives such as epoxy, acrylic, olefin, polyimide, and phenol adhesives.

The primary substrate 11 may be a thin glass plate having a thickness of, for example, 200 μm or less, preferably 100 μm or less. In addition, the adhesive layer 12 is not essential.

Examples of the transparent resin constituting the main substrate 11 include polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), olefin resins such as cycloolefin polymer (COP) and cycloolefin copolymer (COC), cellulose resins such as cellulose, acetyl cellulose and triacetyl cellulose (TAC), imide resins such as Polyimide (PI), amide resins such as Polyamide (PA), amide resins such as Polyamideimide (PAI), carbonate resins such as Polycarbonate (PC), sulfone resins such as Polyethersulfone (PES), p-xylylene silicone resins such as parylene, Polyethylene (PE), polyvinyl chloride (PVC), Polystyrene (PS), polyvinyl acetate (PVAc), polyvinyl alcohol (PVA), vinyl resins such as polyvinyl butyral (PVB), acrylic resins such as polymethyl methacrylate (PMMA), and the like, And urethane resins such as ethylene-vinyl acetate copolymer resins (EVA) and Thermoplastic Polyurethanes (TPU), and epoxy resins.

Among the materials used for the main substrate 11, polyethylene naphthalate (PEN) and Polyimide (PI) are preferable from the viewpoint of improving heat resistance. Further, a cycloolefin polymer (COP), a cycloolefin copolymer (COC), polyvinyl butyral (PVB), or the like is preferable in that the birefringence is low and the distortion and penetration of an image seen through the transparent base material can be reduced.

The above-mentioned materials may be used alone or in combination of two or more. Further, the main substrate 11 may be configured by laminating flat plates of different materials.

The thickness of the entire flexible transparent base member 10 is, for example, 3 to 1000 μm, preferably 5 to 200 μm. The internal transmittance of visible light of the flexible transparent base material 10 is, for example, 50% or more, preferably 70% or more, and more preferably 90% or more.

Further, since the flexible transparent base material 10 is flexible, for example, a flexible transparent display device can be used by being mounted on a curved transparent plate or being sandwiched between 2 curved transparent plates.

As shown in fig. 2, the LED elements 21 to 23 and the IC chip 30 are provided on the adhesive layer 12 which is the flexible transparent base material 10, and are connected to the wiring 40 disposed on the flexible transparent base material 10. In the example of fig. 2, the wiring 40 is constituted by the first metal layer M1 formed on the primary base plate 11 and the second metal layer M2 formed on the adhesive layer 12.

The thickness of the wiring 40, i.e., the total thickness of the first metal layer M1 and the second metal layer M2, is, for example, 0.1 to 10 μ M, preferably 0.5 to 5 μ M. The thickness of the first metal layer M1 is, for example, about 0.5 μ M, and the thickness of the second metal layer M2 is, for example, about 3 μ M.

Specifically, as shown in fig. 2, the ground line 42 extending in the y-axis direction has a two-layer structure including the first metal layer M1 and the second metal layer M2 because of a large amount of current. That is, the adhesive layer 12 is removed at the portion where the ground line 42 is provided, and the second metal layer M2 is formed on the first metal layer M1. Not shown in fig. 2, the power supply line 41, the row data line 43, and the column data line 44 shown in fig. 1 similarly have a two-layer structure including a first metal layer M1 and a second metal layer M2.

Here, as shown in fig. 1, the power supply line 41, the ground line 42, and the column data line 44, which are arranged to extend in the y-axis direction, intersect with the row data line 43, which is arranged to extend in the x-axis direction. Not shown in fig. 2, in the intersection, row data line 43 is formed of only first metal layer M1, and power supply line 41, ground line 42, and column data line 44 are formed of only second metal layer M2. In the intersection, the adhesive layer 12 is provided between the first metal layer M1 and the second metal layer M2, thereby insulating the first metal layer M1 from the second metal layer M2.

Similarly, at the intersection of the column data line 44 and the first power supply branch line 41a shown in fig. 1, the first power supply branch line 41a is formed only by the first metal layer M1, and the column data line 44 is formed only by the second metal layer M2.

In the example of fig. 2, the ground branch line 42a, the drive line 45, and the first power branch line 41a are formed only of the second metal layer M2, and are formed so as to cover the LED elements 21 to 23 and the end portions of the IC chip 30. Not shown in fig. 2, second power supply branch line 41b, row data branch line 43a, and column data branch line 44a are also similarly formed only of second metal layer M2.

As described above, the first power supply branch line 41a is formed only by the first metal layer M1 at the intersection with the column data line 44, and the other portion is formed only by the second metal layer M2. Further, a metal pad made of copper, silver, gold, or the like may be disposed on the wiring 40 formed on the flexible transparent base member 10, and at least one of the LED elements 21 to 23 and the IC chip 30 may be disposed thereon.

The protective layer 50 is a transparent resin formed on substantially the entire surface of the flexible transparent base material 10 so as to cover and protect the light emitting section 20, the IC chip 30, and the wiring 40.

The thickness of the protective layer 50 is, for example, 3 to 1000 μm, preferably 5 to 200 μm.

The protective layer 50 has an elastic modulus of, for example, 10GPa or less. When the elastic modulus is low, the impact at the time of peeling can be absorbed, and the damage of the protective layer 50 can be suppressed.

The internal transmittance of the protective layer 50 for visible light is, for example, 50% or more, preferably 70% or more, and more preferably 90% or more.

Examples of the transparent resin constituting the protective layer 50 include vinyl resins such as Polyethylene (PE), polyvinyl chloride (PVC), Polystyrene (PS), polyvinyl acetate (PVAc), polyvinyl alcohol (PVA), and polyvinyl butyral (PVB), olefin resins such as cycloolefin polymer (COP) and cycloolefin copolymer (COC), polyurethane resins such as Thermoplastic Polyurethane (TPU), polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), acrylic resins such as polymethyl methacrylate (PMMA), and thermoplastic resins such as ethylene-vinyl acetate copolymer resin (EVA).

< method for manufacturing flexible transparent display device >

Next, an example of a method for manufacturing a flexible transparent display device according to the first embodiment will be described with reference to fig. 3 to 13. Fig. 3 to 13 are cross-sectional views showing an example of a method for manufacturing a flexible transparent display device according to the first embodiment. Fig. 3 to 13 are cross-sectional views corresponding to fig. 2.

First, as shown in fig. 3, the peeling layer 2 and the main substrate 11 are sequentially formed on substantially the entire surface of the glass support substrate 1. Here, the glass support substrate 1 and the peeling layer 2 will be explained.

The glass support substrate 1 is a glass substrate for supporting and conveying the flexible transparent display device 100 formed on the glass support substrate 1.

The peeling layer 2 is provided to peel the flexible transparent display device 100 from the glass support substrate 1 as described later. The release layer 2 is mainly composed of a resin and has a lower transmittance of the ultraviolet laser LB than the flexible transparent base material 10. The ultraviolet laser LB transmittance of the release layer 2 is, for example, 50% or less, preferably 30% or less, and more preferably 10% or less.

When the ultraviolet laser beam LB described later is irradiated, a part or the whole of the release layer 2, not the flexible transparent base material 10, is decomposed, whereby the flexible transparent display device 100 is released from the glass support substrate 1. Further, since the release layer 2 absorbs the ultraviolet laser beam LB, the ultraviolet laser beam LB hardly reaches the flexible transparent base material 10. Therefore, damage to the flexible transparent base material 10 due to laser irradiation and damage to electronic components and the like due to the impact can be suppressed.

The thickness of the peeling layer 2 is, for example, 1 to 20 μm, preferably 2 to 10 μm.

The surface roughness Ra of the release layer 2 is, for example, 0.5 μm or less, preferably 0.01 μm or less. The surface roughness Ra of the peeling layer 2 affects the surface roughness of the primary base plate 11 formed on the peeling layer 2. Further, as the surface roughness Ra of the peeling layer 2 is smaller, the first metal layer M1 formed on the primary base plate 11 can be patterned with higher accuracy (see fig. 4).

The surface roughness Ra of the release layer 2 was measured in accordance with JIS B0601, using SURFCOM1400D manufactured by tokyo precision corporation, for example.

The resin constituting the release layer 2 is, for example, a resin (for example, an aromatic ring-containing resin) having a lower transmittance of the ultraviolet laser LB than that of the resin constituting the flexible transparent base material 10 (in particular, the main substrate 11). More specifically, examples of the resin include polyester resins and phenol resins (e.g., novolak resins) having a fluorene derivative skeleton.

The resin constituting the release layer 2 may be made by adding an ultraviolet absorber to the same transparent resin as the main substrate 11, for example. The amount of the ultraviolet absorber added is, for example, 1 to 70 parts by mass based on 100 parts by mass of the whole. Preferably 2 to 50 parts by mass. Further, since the resin constituting the release layer 2 is removed, it is not necessary to be transparent.

The glass transition temperature Tg of the resin constituting the release layer 2 is, for example, 60 ℃ or higher. Preferably 100 ℃ or higher. By setting the glass transition temperature Tg to 60 ℃ or higher, the adhesion of the resin to the surface of the glass support substrate 1 can be reduced, and reattachment of the peeled peel layer 2 to the glass support substrate 1 can be suppressed. In addition, in a state where the flexible transparent base material 10 is formed on the release layer 2 at a temperature lower than the glass transition temperature Tg of the release layer 2, wrinkles and cracks are less likely to occur due to expansion and contraction of the release layer 2. Therefore, the glass transition temperature Tg of the release layer 2 is preferably high.

When a solvent cleaning operation is performed as a step of removing resin residue after peeling by the LLO method as a resin constituting the peeling layer 2, the polyimide has high crystallinity after firing and is difficult to completely remove. Therefore, in the release layer 2, the dissolution rate with respect to acid or alkali is preferably 1.0 × 10^－3μ m/s or more, more preferably 1.0X 10^－2Mu m/s or more.

Examples of the ultraviolet absorber contained in the release layer 2 include organic ultraviolet absorbers such as benzophenone-based, benzotriazole-based, triazine-based, hindered amine-based, and benzoate-based ultraviolet absorbers, and inorganic ultraviolet absorbers such as titanium oxide and zinc oxide.

Further, the release layer 2 may have 10⁴～10¹³Surface resistivity (sheet resistance) of Ω/□. Preferably has a surface resistivity of 10⁷～10¹²Omega/□. More preferably 10⁸～10¹¹Ω/□。

The method for measuring the surface resistivity will be described later.

For example, the release layer 2 may be a resin containing 1 to 90 parts by mass of a conductive filler per 100 parts by mass of the whole. The content of the conductive filler is preferably 30 to 80 parts by mass. Alternatively, the resin may contain 0.01 to 50 parts by mass of the ionic compound based on 100 parts by mass of the whole resin. The content of the ionic compound is preferably 0.1 to 10 parts by mass. Alternatively, the resin itself may be at least one of a conductive polymer and a hydrophilic polymer. Thus, the release layer 2 may have conductivity.

When the release layer 2 has conductivity, it is possible to suppress electrification of the flexible transparent base member 10 when the ultraviolet laser LB described later is irradiated and the flexible transparent display device 100 formed on the glass support substrate 1 is released from the glass support substrate 1. As a result, it is possible to suppress damage to electronic components and the like included in the flexible transparent electronic device 100 due to electrostatic discharge.

Examples of the conductive filler contained in the release layer 2 include powders of copper, aluminum, silver, gold, nickel (Ni), etc., metal fillers such as fibers and foils, carbon fillers such as carbon black, graphite powder, carbon nanotubes and carbon fibers, and tin oxide (SnO) ₂) Indium oxide (In)₂O₃) And a metal oxide filler such as a zinc oxide (ZnO) powder. The conductive filler may be a semiconductor, a powder of a polymer complex, or the like.

The ionic compound contained in the release layer 2 is, for example, an ion conductive agent, an ionic liquid, a surfactant, or the like. Specifically, examples of the ionic compound include cationic conductive agents having a cationic functional group such as a quaternary ammonium salt, a pyridinium salt, and first to third amino groups, anionic conductive agents having an anionic functional group such as a sulfonate group, a sulfate group, a phosphate group, and a phosphonate group, amphoteric conductive agents such as an amino acid group and an amino sulfate group, and organic antistatic compounds having a nonionic functional group such as a polyol group, a polyglycerol group, and a polyethylene glycol group.

Examples of the conductive polymer constituting the release layer 2 include pi-conjugated conductive polymers such as polyacetylene, polyparaphenylene, polythiophene, polypyrrole, and polyaniline.

Examples of the hydrophilic polymer constituting the release layer 2 include a modified vinyl copolymer containing a specific polyether ester amide and a carboxyl group, a comb copolymer of a high molecular monomer having a carboxyl group at the end of a carboxyl-terminated polymethyl methacrylate converted into a methacryloyl group by glycidyl methacrylate, an aminoalkyl acrylate or acrylamide, a quaternized cation modified product thereof, an acrylamide copolymer composed of an ethylene structural unit, an acrylate structural unit, and an acrylamide structural unit, and a polyolefin resin composition to which the copolymer is added.

Next, as shown in fig. 4, the first metal layer M1 is formed on substantially the entire surface of the main substrate 11, and then the first metal layer M1 is patterned by photolithography to form the lower layer wiring. Specifically, lower layer wirings are formed of first metal layer M1 at positions where power supply line 41, ground line 42, row data line 43, column data line 44, and the like shown in fig. 1 are formed.

No lower layer wiring is formed at the intersection of power supply line 41, ground line 42, and column data line 44 with row data line 43.

Next, as shown in fig. 5, the adhesive layer 12 is formed on substantially the entire surface of the main substrate 11, and then the LED elements 21 to 23 and the IC chip 30 are mounted on the adhesive layer 12 having viscosity.

Next, as shown in fig. 6, after forming a film of a photoresist FR1 on substantially the entire surface of the flexible transparent base material 10 including the main substrate 11 and the adhesive layer 12, the photoresist FR1 on the first metal layer M1 is removed by an imprint pattern. Here, the photoresist FR1 at the intersection where the power supply line 41, the ground line 42, and the column data line 44 intersect in the row data line 43 shown in fig. 1 is not removed.

Next, as shown in fig. 7, the adhesive layer 12 at the portion where the photoresist FR1 was removed by dry etching, thereby exposing the first metal layer M1, i.e., the lower layer wiring.

Next, as shown in fig. 8, the photoresist FR1 on the flexible transparent base member 10 is completely removed. Thereafter, a seed layer for plating, not shown, is formed on substantially the entire surface of the flexible transparent base material 10.

Next, as shown in fig. 9, after a photoresist FR2 was formed on substantially the entire surface of the flexible transparent base material 10, the photoresist FR2 at the portion where the upper layer wiring is formed was removed by patterning, thereby exposing the seed layer.

Next, as shown in fig. 10, a second metal layer M2 was formed by plating on the seed layer, which was the portion where the photoresist FR2 was removed. Thereby, the upper layer wiring is formed by the second metal layer M2.

Next, as shown in fig. 11, the photoresist FR2 is removed. Then, the seed layer exposed by removing the photoresist FR2 was removed by etching.

Next, as shown in fig. 12, a protective layer 50 is formed on substantially the entire surface of the flexible transparent base material 10. Therefore, on the glass support substrate 1, the flexible transparent display device 100 is formed via the peeling layer 2. Fig. 12 shows an article according to the present embodiment. As shown in fig. 12, in the article of the present embodiment, a peeling layer 2 is formed between a glass support substrate 1 and a flexible transparent display device 100.

Finally, as shown in fig. 13, ultraviolet laser light LB such as excimer laser light is irradiated from the lower side of the glass support substrate 1 in the drawing, and the flexible transparent display device 100 formed on the glass support substrate 1 is peeled off from the glass support substrate 1. The peeling layer 2 is decomposed by the ultraviolet laser beam LB transmitted through the glass support substrate 1, whereby the flexible transparent display device 100 can be peeled off from the glass support substrate 1.

For example, the entire glass support substrate 1 can be irradiated with the ultraviolet laser beam LB by scanning the linear beam of the ultraviolet laser beam LB. The wavelength of the ultraviolet light is, for example, 400nm or less. The wavelength of the excimer laser used for laser lift-off is, for example, 308nm (xecl) or 248nm (krf).

The peeling layer 2 remaining in the flexible transparent display device 100 after peeling can be removed by cleaning or the like.

The flexible transparent display device 100 can be manufactured through the above processes.

In the method of manufacturing the flexible transparent display device of the present embodiment, the separation layer 2 having a smaller transmittance of the ultraviolet laser LB than the flexible transparent base material 10 is formed between the glass support substrate 1 before separation and the flexible transparent base material 10. That is, the glass support substrate 1 and the flexible transparent base material 10 are not in direct contact, and the peeling layer 2 is formed therebetween. Further, when the ultraviolet laser LB is irradiated, not the flexible transparent base material 10 but the peeling layer 2 is decomposed, thereby peeling the flexible transparent display device 100 from the glass support substrate 1. Further, since the release layer 2 absorbs the ultraviolet laser beam LB, the ultraviolet laser beam LB hardly reaches the flexible transparent base material 10. Therefore, damage to the flexible transparent base material 10 due to laser irradiation and damage to electronic components and the like due to the impact can be suppressed.

< details of the method for measuring surface resistivity >

Here, the method for measuring the surface resistivity will be described in detail with reference to fig. 14.

Fig. 14 is a schematic plan view of a comb-shaped electrode for measuring surface resistivity. As shown in fig. 14, the comb-shaped electrode has a shape in which 5 comb teeth of the first comb-shaped electrode and 4 comb teeth of the second comb-shaped electrode are arranged to face each other differently. In the first comb-shaped electrode and the second comb-shaped electrode, the width of the comb teeth, the length of the comb teeth, and the interval between the comb teeth are equal to each other. Therefore, 4 comb teeth of the second comb-shaped electrode are inserted in the center between the 5 comb teeth of the first comb-shaped electrode.

The surface resistivity ρ is calculated by ρ ═ R × R using the resistance value R and the electrode coefficient R. Here, the resistance value R is calculated by using a current value I and a voltage V measured by the comb electrode, and taking R as V/I. The electrode coefficient r is calculated from the ratio of the length of the adjacent comb teeth to the interval therebetween. For example, in the comb-shaped electrode of fig. 14, at 8 sites, comb teeth of length W3 are adjacent at an interval W2, and at 7 sites, comb teeth of length W4 are adjacent at an interval W1. Therefore, the electrode coefficient r is calculated by (W3/W2) × 8+ (W1/W4) × 7. The electrode coefficient r of the comb electrode is, for example, about 100 to 130.

As the metal constituting the comb-shaped electrode, for example, a material having a small resistance such as platinum, aluminum, or gold is used. For example, platinum is preferred. For example, a metal film constituting the comb-shaped electrode is formed on a substrate having electrical insulation by means of sputtering, vacuum deposition, plating, or the like.

For example, a Pt film was formed as a 20nm film on the surface of the release layer 2(60 mm. times.60 mm) by using a magnetron sputtering coater (Q300 TT manufactured by Quorum technologies) under Ar atmosphere, thereby forming a comb-shaped electrode pattern as shown in FIG. 14. Fig. 15 is a diagram showing specific examples of the dimensions of the comb-shaped electrode shown in fig. 14. The numerical values in fig. 15 are all in mm. In the comb-shaped electrode having the size shown in fig. 15, the electrode coefficient r was 112.75.

In the measurement, for example, a digital ULTRA-high resistance/micro-current meter (ADVANTEST R830A ULTRA HIGH RESISTANCE METER) is used. For example, after the obtained comb-shaped electrode was connected to a copper wire, a voltage of 10V was applied, and the current measurement was started after waiting 3 minutes until the voltage was stabilized. Then, the current value after 3 minutes was read, and the surface resistivity ρ was calculated from the above relational expression.

(second embodiment)

Structure of laminated glass with Flexible transparent display device

Next, the structure of the laminated glass according to the second embodiment will be described with reference to fig. 16 and 17. Fig. 16 is a schematic plan view showing an example of the laminated glass of the second embodiment. Fig. 17 is a schematic cross-sectional view showing an example of the laminated glass according to the second embodiment. The laminated glass 200 shown in fig. 16 and 17 is used for a front glass of a window glass of an automobile, but is not particularly limited.

First, a planar structure of the laminated glass 200 is explained with reference to fig. 16.

As shown in fig. 16, a black shielding portion 201, for example, is provided on the entire periphery of the laminated glass 200. The shielding portion 201 shields sunlight and protects an adhesive for mounting the laminated glass 200 to an automobile from ultraviolet rays. Further, the adhesive cannot be visually recognized from the outside by the shielding portion 201.

As shown in fig. 16, the flexible transparent display device 100 is provided with a non-display region 102 provided around the display region in addition to the display region 101 shown in fig. 1. Here, as described in the first embodiment, the display region 101 is a region in which an image is displayed, and is formed of a plurality of pixels, and thus detailed description thereof is omitted.

Fig. 16 is a plan view, and the non-display region 102 and the shielding portion 201 are indicated by dots for easy understanding.

The non-display region 102 does not include pixels and is a region where no image is displayed. In the non-display region 102, wide wirings connected to the power supply line 41, the ground line 42, the row data line 43, and the column data line 44 shown in fig. 1 are densely provided. The width of the wiring in the non-display region 102 is, for example, 100 to 10,000 μm, preferably 100 to 5,000 μm. The interval between the wirings is, for example, 3 to 5,000 μm, preferably 50 to 1,500 μm.

Therefore, the non-display area 102 is opaque to the display area 101 and cannot be visually recognized from the vehicle interior. Here, if the non-display region 102 is visually recognizable, the design of the laminated glass 200 is degraded. Therefore, in the laminated glass 200 of the second embodiment, at least a part of the non-display region 102 of the flexible transparent display device 100 is provided to the shielding portion 201. The non-display region 102 provided in the shielding portion 201 is hidden by the shielding portion 201 and cannot be visually recognized. Therefore, the design of the laminated glass 200 is improved compared to the case where the entire non-display region 102 can be visually recognized.

Next, a cross-sectional structure of the laminated glass 200 will be described with reference to fig. 17. Fig. 17 is a sectional view in a display area 101 of the flexible transparent display device 100.

As shown in fig. 17, the laminated glass 200 according to the second embodiment has a pair of glass plates 220a and 220b bonded thereto via an interlayer film. The laminated glass 200 includes the flexible transparent display device 100 according to the first embodiment between the pair of glass plates 220a and 220b via the interlayer films 210a and 210 b. The intermediate films 210a and 210b are made of, for example, polyvinyl butyral (PVB).

Here, fig. 18 is a schematic cross-sectional view showing another example of the laminated glass of the second embodiment. In the laminated glass 200 shown in fig. 18, the protective layer 50 of the flexible transparent display device 100 is composed of, for example, polyvinyl butyral (PVB), which also functions as an interlayer. Therefore, in the laminated glass 200 shown in fig. 18, the interlayer film 210a formed on the protective layer 50 in fig. 17 can be omitted.

(third embodiment)

< Structure of Flexible transparent display device >

Next, the structure of the flexible transparent display device of the third embodiment is explained with reference to fig. 19. Fig. 19 is a schematic partial plan view showing an example of the flexible transparent display device of the third embodiment. As shown in fig. 19, the flexible transparent display device of the present embodiment includes a sensor 70 in a display region 101 in addition to the structure of the flexible transparent display device of the first embodiment shown in fig. 1.

In the example shown in fig. 19, the sensor 70 is provided between predetermined pixels PIX, and is connected to the power supply line 41 and the ground line 42. In addition, detection data detected by the sensor 70 is output via a data output line 46 extending in the y-axis direction from the sensor 70. On the other hand, the sensor 70 is controlled by inputting a control signal to the sensor 70 via a control signal line 47 extending to the sensor 70 in the y-axis direction. The sensor 70 may be a single sensor or a plurality of sensors. The plurality of sensors 70 may be arranged at predetermined intervals, for example, in the x-axis direction or the y-axis direction.

In the following description, a case where the flexible transparent display device of the present embodiment is mounted on a front glass of a window glass of an automobile will be described. That is, the flexible transparent display device of the present embodiment can also be applied to the laminated glass of the second embodiment.

The sensor 70 is, for example, an illuminance sensor (e.g., a light receiving element) for detecting illuminance inside and outside the vehicle. For example, the luminance of the display area 101 based on the LED elements 21 to 23 is controlled in accordance with the illuminance detected by the sensor 70. For example, the luminance of the display region 101 based on the LED elements 21 to 23 is increased as the illuminance outside the vehicle is increased relative to the illuminance inside the vehicle. With this structure, the visibility of the flexible transparent display device is further improved.

The sensor 70 may be an infrared sensor (e.g., a light receiving element) or an image sensor (e.g., a CMOS (Complementary Metal-Oxide-Semiconductor) image sensor) for sensing a line of sight of an observer (e.g., a driver). For example, the flexible transparent display device is driven only in the case where the sensor 70 senses a line of sight. For example, in the case where a flexible transparent display device is used for the laminated glass shown in fig. 16, the flexible transparent display device does not block the view of the observer unless the observer directs the line of sight to the flexible transparent display device, and is therefore preferable. Alternatively, the sensor 70 as an image sensor may detect a motion of the observer, and based on the motion, for example, the flexible transparent display device may be turned on or off, or the display screen may be switched.

The other structure is the same as that of the flexible transparent display device of the first embodiment.

(fourth embodiment)

< Structure of Flexible transparent sensing detecting device >

Next, the structure of the flexible transparent sensing device of the fourth embodiment is explained with reference to fig. 20. Fig. 20 is a schematic partial plan view showing an example of a flexible transparent sensing device according to the fourth embodiment. The flexible transparent sensing device shown in fig. 20 is a flexible transparent electronic device having a structure in which the sensor 70 is provided in each pixel PIX in place of the light emitting section 20 and the IC chip 30 in the structure of the flexible transparent display device shown in fig. 1. That is, the flexible transparent sensing device shown in fig. 20 does not have a display function because it does not include the light emitting section 20.

The sensor 70 is not particularly limited, and in the flexible transparent sensing device shown in fig. 20, it is a CMOS image sensor. That is, the flexible transparent sensor detection device shown in fig. 20 includes an imaging region 301 including a plurality of pixels PIX arranged in a row direction (x-axis direction) and a column direction (y-axis direction), and has an imaging function. Fig. 20 shows a part of the imaging area 301, and the number of pixels is 2 in each of the row direction and the column direction, and the total number of pixels is 4. Here, the 1 pixel PIX is shown surrounded by a one-dot chain line. In fig. 20, the flexible transparent base material 10 and the protective layer 50 are omitted as in fig. 1. Fig. 20 is a plan view, and the sensor 70 is indicated by dots for easy understanding.

In the example shown in fig. 20, 1 sensor 70 is provided for each pixel PIX, and is disposed between and connected to the power supply line 41 and the ground line 42 extending in the y-axis direction. In addition, detection data detected by the sensor 70 is output via a data output line 46 extending in the y-axis direction from the sensor 70. On the other hand, the sensor 70 is controlled by inputting a control signal to the sensor 70 via a control signal line 47 extending to the sensor 70 in the y-axis direction. The control signal is, for example, a synchronization signal, a reset signal, or the like.

The power supply line 41 may be connected to a battery, not shown.

Here, fig. 21 is a schematic sectional view of the sensor 70. The sensor 70 shown in fig. 21 is a back-illuminated CMOS image sensor. The sensor 70 as an image sensor is not particularly limited, and may be a surface-illumination type CMOS image sensor or a CCD (Charge-coupled device) image sensor.

As shown in fig. 21, each sensor 70 includes a wiring layer, a semiconductor substrate, color filters CF1 to CF3, and microlenses ML1 to ML 3. Here, an internal wiring IW is formed inside the wiring layer. Further, photodiodes PD1 to PD3 are formed inside the semiconductor substrate.

A semiconductor substrate (e.g., a silicon substrate) is formed on the wiring layer. The internal wiring IW formed inside the wiring layer connects the wiring 40 (the power supply line 41, the ground line 42, the data output line 46, and the control signal line 47) and the photodiodes PD1 to PD 3. When light is irradiated to the photodiodes PD1 to PD3, currents are output from the photodiodes PD1 to PD 3. The currents output from the photodiodes PD1 to PD3 are amplified by an amplifier circuit, not shown, and output via the internal wiring IW and the data output line 46.

The color filters CF1 to CF3 are formed on the photodiodes PD1 to PD3 formed inside the semiconductor substrate, respectively. The color filters CF1 to CF3 are, for example, a red filter, a green filter, and a blue filter, respectively.

The microlenses ML1 to ML3 are placed on the color filters CF1 to CF3, respectively. The light condensed by the microlenses ML1 to ML3 as convex lenses is incident on the photodiodes PD1 to PD3 through the color filters CF1 to CF3, respectively.

The sensor 70 of the present embodiment has an area of 250,000 μm occupied on the flexible transparent base material 10²The following micro-sized micro-sensor. In other words, in the present specification, the micro-sensor means a micro-sensor having an area of 250,000 μm in a plan view²The following micro-sized sensors. The occupation area of the sensor 70 is preferably 25,000 μm, for example²Hereinafter, more preferably 2,500. mu.m²The following. The lower limit of the area occupied by the sensor 70 is, for example, 10 μm depending on various conditions in manufacturing²The above.

The shape of the sensor 70 shown in fig. 20 is a rectangle, but is not particularly limited.

The flexible transparent sensing device of the present embodiment can also be applied to the laminated glass of the second embodiment. When the flexible transparent sensor detection device of the present embodiment is mounted on a front glass of a window glass of a vehicle (e.g., an automobile), for example, an image of at least one of the inside and the outside of the vehicle can be acquired by the sensor 70. That is, the flexible transparent sensing device of the present embodiment has a function as a drive recorder.

Further, the sensor 70 in the flexible transparent sensing device of the fourth embodiment may also be single. The sensor 70 in the flexible transparent sensing device according to the fourth embodiment is not limited to the image sensor, and may be an illuminance sensor, an infrared sensor, or the like as exemplified in the third embodiment. The sensor 70 may be a radar sensor, a Lidar sensor, or the like. The vehicle window glass on which the flexible transparent sensing device using the sensor 70 is mounted can monitor, for example, the inside and outside of a vehicle.

That is, the sensor 70 of the fourth embodiment is provided withThe occupation area on the flexible transparent base member 10 is 250,000 μm²The following micro-sensor may be used, but is not particularly limited. For example, the sensor 70 may be a temperature sensor, an ultraviolet sensor, an electric wave sensor, a pressure sensor, an acoustic sensor, a velocity/acceleration sensor, or the like.

The other structure is the same as that of the flexible transparent display device of the first embodiment.

[ examples ] A method for producing a compound

The following examples are given to illustrate the present invention, but the present invention is not limited to the following examples. Examples 1 to 5, 7 and 8 are examples of the present invention. Example 6 is a comparative example.

< example 1 >

[ formation of the Release layer 2 and Flexible transparent base Material 10 ]

First, a polyimide solution was applied by spin coating onto a glass support substrate 1 made of alkali-free glass having a thickness of 0.9mm and a square of 99.5 mm. This coating film was heated at 190 ℃ for 10 minutes in the air, whereby a polyimide release layer 2 was formed on the glass support substrate 1. The surface roughness Ra was 0.004. mu.m.

Next, a novolac-type epoxy solution was coated on the peeling layer 2 by spin coating. The coating film was heated at 140 ℃ for 4 minutes in the air, irradiated with ultraviolet rays of 500mJ, and further heated at 175 ℃ for 1 hour in an oven, whereby a flexible transparent base material 10 made of a novolak type epoxy resin was formed on the release layer 2.

[ formation of protective layer 50 ]

2 pieces of soda-lime glass (100 mm square) having a thickness of 2mm and 1 piece of PVB film (15mil) having a thickness of 0.38mm were prepared. A PVB film for the protective layer 50 and an ETFE film for peeling were laminated in this order on a flexible transparent base material 10 formed on a glass support substrate 1 via a peeling layer 2, and the laminate was vacuum-packed with 2 soda-lime glass sheets sandwiched therebetween. After the vacuum-packed laminate was heated at 100 ℃ for 1 hour, the ETFE film for peeling and 2 soda-lime glasses were removed, thereby forming a protective layer 50 made of PVB.

< example 2 >

A polyimide solution (ECRIOS, manufactured by Mitsui chemical) was used as a material for the release layer 2, and heated at 220 ℃ for 2 hours. Thus, the release layer 2 made of polyimide was obtained. Then, an acrylic resin (a mixture of 70 parts by mass of A-DCP manufactured by Xinzhongmura chemical industry, 30 parts by mass of U-6 LPA manufactured by Xinzhongmura chemical industry, and 3 parts by mass of Omnirad184, a polymerization initiator manufactured by IGMResins B.V. Co.) was applied to the release layer 2 by spin coating. By irradiating the coating film with ultraviolet rays of 2000mJ, a flexible transparent base material 10 made of acrylic resin is formed on the release layer 2. Otherwise, the same procedure was followed as in example 1.

< example 3 >

The release layer 2 was formed in the same manner as in example 2 except that a fluorene-based polyester solution (OKP-2 manufactured by Osaka gas chemicals) was used and the resultant was heated at 90 ℃ for 5 minutes and at 110 ℃ for 2 minutes in this order. Thus, a fluorene-based polyester resin release layer 2 was obtained.

< example 4 >

The release layer 2 was formed in the same manner as in example 1 except that a novolak/photosensitizer solution (OFPR-800 LB available from Tokyo chemical industries, Ltd.) was used and the resultant was heated at 140 ℃ for 5 minutes. Thus, a release layer 2 made of novolak resin containing 1 to 55 parts by mass of a photosensitizer based on 100 parts by mass of the whole was obtained.

< example 5 >

As the material of the release layer 2, novolak/TiO was used₂Solution (KAYAHARD GPH-65 manufactured by Nippon chemical Co., Ltd.: glass transition temperature Tg of 63-69 ℃ and OPTOLAKE2120Z manufactured by Nippon chemical Co., Ltd.: TiO)₂A mixed solution having a particle diameter of 13 nm) was heated at 110 ℃ for 5 minutes, and the reaction mixture was heated in the same manner as in example 2 except that the temperature was changed. Thus, 50 parts by mass of TiO was contained per 100 parts by mass of the whole₂ A peeling layer 2 made of novolac resin as an ultraviolet absorber.

< example 6 >

The release layer 2 was formed in the same manner as in example 2 except that a novolak solution (TR 4020G manufactured by Asahi organic materials industries, Ltd.: glass transition temperature Tg of 150 to 170 ℃) was used and heated at 150 ℃ for 5 minutes. Thus, the peeling layer 2 made of novolac resin was obtained.

< example 7 >

The release layer 2 was formed in the same manner as in example 2 except that a novolak/ultraviolet absorber solution (a mixed solution of TR4020G manufactured by asahi organic materials and Tinuvin477 manufactured by BASF) was used and heated at 150 ℃. Thus, a release layer 2 made of a novolak resin containing 4 parts by mass of a Hydroxyphenyltriazine (HPT) -based ultraviolet absorber was obtained, assuming that the whole was 100 parts by mass. The surface roughness Ra was 0.003. mu.m.

< example 8 >

The release layer 2 was formed in the same manner as in example 2 except that a novolak/ultraviolet absorber solution (a mixed solution of TR4020G manufactured by asahi organic materials industries, ltd. and Tinuvin477 manufactured by BASF) was used and heated at 150 ℃ for 5 minutes. Thus, the peeling layer 2 made of a novolac resin containing about 14 parts by mass of a Hydroxyphenyltriazine (HPT) -based ultraviolet absorber was obtained, taking 100 parts by mass as a whole. The surface roughness Ra was 0.004. mu.m.

[ peeling of resin film by LLO method ]

With respect to the peeling layers 2 obtained in examples 1 to 8, whether or not peeling from the glass support substrate 1 was possible was evaluated by the LLO method. As the laser light source, XeCl having an oscillation wavelength of 308nm was used, using an excimer laser device manufactured by LIGHT TEC. The irradiation energy density of the laser was 590mJ/cm²、750mJ/cm²、900mJ/cm²、1080mJ/cm²And sequentially until the peeling layer 2 is peeled off. The beam size in the sample plane was 30.3mm x 0.704 mm.

In table 1, the symbol "o" indicates that the peeling layer 2 was peeled off, and the energy density at the time of peeling is described. Symbol x represents that even if the energy density is 1080mJ/cm²And peeling was not possible.

[ film thickness, surface roughness Ra and transmittance of peeling layer 2 ]

The release layers 2 obtained in examples 1 to 8 were measured for film thickness and surface roughness (arithmetic mean roughness) Ra using SURFCOM1400D manufactured by tokyo precision corporation. The results of measuring the film thickness are shown in table 1. The significand is 2 bits.

The release layers 2 obtained in examples 1 to 8 were evaluated for transmittance T of light having a wavelength of 308nm_308nm[％]. Transmittance T_308nmThe measurement was carried out at room temperature using SolidSpec-3700 DUV manufactured by Shimadzu corporation as a standard. The transmittance T is shown in Table 1_308nmThe measurement result of (3). The significand is 2 bits.

[ Table 1]

The flexible transparent base materials 10 in examples 1 and 4 are made of the same material, and the transmittance T of the flexible transparent base material 10_308nmIs 7.5%. The flexible transparent base member 10 in examples 2, 3, 5 to 8 is made of the same material, and the transmittance T of the flexible transparent base member 10_308nmIs 84%.

As shown in Table 1, the transmittance T in the release layer 2 was_308nmTransmittance T of the flexible transparent base material (10)_308nmIn examples 1 to 5, 7 and 8, the peeling was performed by the LLO method regardless of the type of resin. Further, it is found that the transmittance T of the release layer 2 is preferable_308nmThe absolute value of (A) is 50% or less. On the other hand, the transmittance T in the release layer 2_308nmTransmittance T of the flexible transparent base material (10)_308nmHigh transmittance T of the peeling layer 2_308nmIn example 6 in which the absolute value of (a) is larger than 50%, peeling by the LLO method was not performed.

The present invention is not limited to the above-described embodiments, and can be modified as appropriate without departing from the scope of the invention.

This application claims priority based on japanese application patent application 2019-235574, filed on 26.12.2019, the entire disclosure of which is incorporated herein by reference.

Description of the reference numerals:

1 … glass support substrate; 2 … a release layer; 10 … a flexible transparent substrate; 11 … a main substrate; 12 … an adhesive layer; 20 … a light-emitting portion; 21 to 23 … LED elements; 30 … IC chip; 40 … wiring; 41 … power lines; 41a … first power supply branch line; 41b … second power supply branch line; 42 … ground line; 42a … ground branch line; 43 … row data lines; 43a … row data branch lines; 44 … column data lines; 44a … column data branch line; 45 … drive line; 46 … data-out line; 47 … control signal lines; 50 … a protective layer; a 70 … sensor; 100 … flexible transparent display device; 101 … display area; 102 … non-display area; 200 … laminated glass (glazing); 201 … shield; 210a, 210b … intermediate film; 220a, 220b … glass sheets; 301 … shooting area; CF 1-CF 3 … color filters; FR1, FR2 … photoresists; IW … internal wiring; m1 … first metal layer; m2 … second metal layer; ML 1-ML 3 … micro lens; PD 1-PD 3 … photodiodes; PIX … pixels.

Claims (18)

1. A method for manufacturing a flexible transparent electronic device, comprising preparing an article having a flexible transparent electronic device formed on a glass support substrate, wherein the flexible transparent electronic device comprises a flexible transparent base material, an electronic component formed on the flexible transparent base material, and a protective layer made of a transparent resin and covering the electronic component,

and peeling the flexible transparent electronic device from the glass support substrate by irradiating ultraviolet laser light through the glass support substrate of the article,

the method of manufacturing a flexible transparent electronic device is characterized in that,

in preparing the article, a release layer is formed between the glass support substrate and the flexible transparent base material, the release layer mainly containing a resin and having a lower transmittance of the ultraviolet laser than the flexible transparent base material.

2. The method of manufacturing a flexible transparent electronic device according to claim 1,

the resin is an aromatic ring-containing resin.

3. The method of manufacturing a flexible transparent electronic device according to claim 1 or 2,

the glass transition temperature Tg of the resin is 60 ℃ or higher.

4. A method of manufacturing a flexible transparent electronic device according to any one of claims 1 to 3,

The ultraviolet laser transmittance of the release layer is 50% or less.

5. The method of manufacturing a flexible transparent electronic device according to claim 4,

the release layer contains an ultraviolet absorber.

6. The method of manufacturing a flexible transparent electronic device according to claim 4,

the release layer does not contain an ultraviolet absorber,

the ultraviolet laser transmittance of the release layer is 5% or less.

7. The method of manufacturing a flexible transparent electronic device according to any one of claims 1 to 6,

the release layer has a thickness of 10⁴～10¹³Surface resistivity of omega/□.

8. The method of manufacturing a flexible transparent electronic device according to any one of claims 1 to 7,

the surface roughness Ra of the release layer is less than or equal to 0.5 mu m.

9. The method of manufacturing a flexible transparent electronic device according to any one of claims 1 to 8,

the electronic component comprises a light-emitting diode component,

the light emitting diode elements are arranged at least one per pixel on the flexible transparent substrate and have a size of 10,000 μm respectively²The followingThe area of (a) is,

The flexible transparent electronic device has a function as a display device.

10. An article having a flexible transparent electronic device formed on a glass support substrate, wherein the flexible transparent electronic device comprises a flexible transparent base material, an electronic component formed on the flexible transparent base material, and a protective layer made of a transparent resin covering the electronic component,

the article is characterized in that it is characterized in that,

a release layer is formed between the glass support substrate and the flexible transparent base material, the release layer mainly containing a resin and having a lower ultraviolet laser transmittance than the flexible transparent base material.

11. The article of claim 10,

the resin is an aromatic ring-containing resin.

12. The article according to claim 10 or 11,

the glass transition temperature Tg of the resin is 60 ℃ or higher.

13. The article according to any one of claims 10 to 12,

the ultraviolet laser transmittance of the release layer is 50% or less.

14. The article according to claim 13,

the release layer contains an ultraviolet absorber.

15. The article according to claim 13,

The release layer does not contain an ultraviolet absorber,

the ultraviolet laser transmittance of the release layer is 5% or less.

16. The article according to any one of claims 10 to 15,

the release layer has a thickness of 10⁴～10¹³Surface resistivity of omega/□.

17. The article according to any one of claims 10 to 16,

the surface roughness Ra of the release layer is less than or equal to 0.5 mu m.

18. The article according to any one of claims 10 to 17,

the electronic component comprises a light-emitting diode component,

the light emitting diode elements are arranged at least one per pixel on the flexible transparent substrate and have a size of 10,000 μm respectively²The area of the following (A) is,

the flexible transparent electronic device has a function as a display device.

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