TWI813882B - Laminated substrate, method of manufacturing electronic device, and method of manufacturing laminated substrate - Google Patents

Abstract

The present invention relates to a laminated substrate having a glass supporting base material and a polyimide resin layer disposed on the supporting base material, and the polyimide resin layer is on the opposite side to the supporting base material. On the surface, the number of protrusions with a long side length of 3 μm or more and less than 50 μm, a short side length of less than 50 μm, and a height of less than 5 μm is 0.60/cm ² , and the long side length is 3 to 1000 μm, the short side length is 20 μm or less, and the number of recesses with a depth of 1 μm or less is 0.15/ ^cm2 or less.

Description

Manufacturing method of laminated substrate, electronic device, and manufacturing method of laminated substrate

The present invention relates to a laminated substrate, a manufacturing method of an electronic device, and a manufacturing method of a laminated substrate.

Manufacturing such as solar cells; LCD panels (LCD, Liquid Crystal Display); organic EL display devices (OLED, Organic Light-Emitting Diode); receiving sensor panels that sense electromagnetic waves, X-rays, ultraviolet rays, visible light, infrared rays, etc.; etc. In the case of electronic devices, as described in Patent Document 1, a form using a polyimide resin layer as a substrate is disclosed. The polyimide resin layer is used in the state of a laminated substrate provided on a glass substrate, and the laminated substrate is provided for manufacturing electronic devices. After forming the electronic device, the polyimide resin layer is separated from the glass substrate. [Prior technical literature] [Patent Document]

[Patent Document 1] Japanese Patent Application Laid-Open No. 2015-104843

[Problem to be solved by the invention]

In recent years, there has been an effort to further improve the durability of electronic devices represented by organic electroluminescence (EL) display devices. The inventors of the present invention used a laminated substrate having a glass support base material and a polyimide resin layer as described in Patent Document 1, and formed an electronic device using a member for an electronic device on the polyimide resin layer. When studying its performance, it was found that there is room for further improvement in terms of durability. An object of the present invention is to provide a laminated substrate having a polyimide resin layer that can produce an electronic device with excellent durability (such as an organic EL display device). Furthermore, another object of the present invention is to provide a method of manufacturing an electronic device and a method of manufacturing a laminated substrate. [Technical means to solve problems]

The inventors of the present invention actively studied and found that the above object can be achieved by the following configuration.

(1) A laminated substrate having a glass supporting base material and a polyimide resin layer disposed on the supporting base material, and on the surface of the polyimide resin layer opposite to the supporting base material, The number of protrusions with a long side length of 3 μm or more and less than 50 μm, a short side length of less than 50 μm, and a height of 5 μm or less is 0.60/cm ² or less. The long side length is 3 to 1000 μm, the short side length is 20 μm, and the number of recesses with a depth of 1 μm or less is 0.15/cm ² or less. (2) The laminated substrate according to (1), wherein the long side length of the convex portion is 10 μm or more and less than 50 μm, the short side length is less than 50 μm, and the height is 1 μm or less, and contains Na and Cl The number of first convex parts of at least one element is 0.15/cm ² or less. (3) The laminated substrate as described in (1) or (2), wherein the protruding portion has a long side length of 3 μm or more and less than 20 μm, a short side length of less than 20 μm, and a height of 5 μm or less, and includes The number of second convex parts of at least one element consisting of Si and Al is 0.25 pieces/cm ² or less. (4) The laminated substrate according to (3), wherein among the convex portions, the length of the convex portions other than the first convex portion and the second convex portion is 3 μm or more and less than 50 μm, and the short side length is less than 50 μm. 50 μm, and the number of third convex parts with a height of 1 μm or less is 0.30/ ^cm2 or less. (5) The laminated substrate according to any one of (1) to (4), wherein the number of protrusions is 0.20/cm ² or less. (6) The laminated substrate according to any one of (1) to (5), wherein the number of recessed portions is 0.07/cm ² or less. (7) A method of manufacturing an electronic device, which includes the step of forming a A member forming step for obtaining a laminated substrate with a member for an electronic device and a laminated substrate with a member for an electronic device; and a separation step for obtaining an electronic device having a polyimide resin layer and a member for an electronic device from the laminated substrate with the member for an electronic device. . (8) A method for manufacturing a laminated substrate, which is the method for manufacturing a laminated substrate according to any one of (1) to (6), wherein a film-like polyimide resin layer is bonded to a supporting base material, and Manufacturing of laminated substrates. (9) The method for manufacturing a laminated substrate according to (8), wherein a laminated film including a film-like polyimide resin layer and a protective film disposed on one surface of the polyimide resin layer and a support base are used The materials are bonded together to obtain a laminated body in which the supporting base material, the polyimide resin layer and the protective film are arranged in sequence, and the protective film is peeled off from the laminated body to produce a laminated substrate. [Effects of the invention]

According to the present invention, it is possible to provide a laminated substrate having a polyimide resin layer that can produce an electronic device with excellent durability (for example, an organic EL display device). Furthermore, according to the present invention, a method of manufacturing an electronic device and a method of manufacturing a laminated substrate can be provided.

Hereinafter, embodiments of the present invention will be described with reference to the drawings. However, the following embodiments are examples for explaining the present invention, and the present invention is not limited to the embodiments shown below. In addition, various changes and substitutions can be made to the following embodiments without departing from the scope of the present invention. The numerical range expressed by "~" means the range including the values written before and after "~" as the lower limit and upper limit.

A characteristic feature of the laminated substrate of the present invention is the ability to adjust the number of protrusions and recesses of a specific shape on the surface of the polyimide resin layer. The present inventors discovered that when an electronic device was manufactured using the conventional laminated substrate described in Patent Document 1, the reason why the resulting electronic device had poor durability was related to the specific shape of the convex portion on the surface of the polyimide resin layer. related to the concavity. When manufacturing electronic devices such as organic EL display devices, thin layers are formed by sputtering, etc. However, at this time, if there are convex portions and concave portions of specific shapes on the polyimide resin layer, a uniform layer cannot be formed and it is easy to form a thin layer. become defects, resulting in poor performance of the resulting electronic device. Therefore, by adjusting the number of the above-mentioned convex portions and concave portions, the desired effect can be obtained.

＜Laminated substrate＞ [Example 1 of built-up substrate] FIG. 1 is a cross-sectional view schematically showing a first example of a laminated substrate according to the embodiment of the present invention. The laminated substrate 10 of the first example includes a glass supporting base material 12 and a polyimide resin layer 14 arranged on the supporting base material 12 . In FIG. 1 , the area of the polyimide resin layer 14 is smaller than the surface 12 a of the supporting base material 12 , and is not disposed on the entire surface 12 a of the supporting base material 12 . However, it is not limited to this form, and may also be provided on the surface of the supporting base material 12 . The polyimide resin layer 14 is arranged over the entire area of 12a.

The supporting base material 12 is a member that supports the polyimide resin layer 14 and functions as a reinforcing plate that reinforces the polyimide resin layer 14 . In addition, the support base material 12 also functions as a transportation substrate when the laminated substrate 10 is transported. In the laminated substrate 10 , when a force is applied in a direction in which the support base material 12 and the polyimide resin layer 14 are peeled off, the support base material 12 and the polyimide resin layer 14 are separated. Although described in detail below, the polyimide resin layer 14 is a substrate used for manufacturing electronic devices. That is, on the surface 14a of the polyimide resin layer 14, electronic components such as transistors, coils, resistors, and signal lines constituting the electronic device are formed.

FIG. 2 is an enlarged cross-sectional view of the surface 14a of the polyimide resin layer 14 in the laminated substrate 10 according to the embodiment of the present invention. On the surface 14a of the polyimide resin layer 14, the length of the long side shown in Figure 2 is 3 μm or more and less than 50 μm, the length of the short side is less than 50 μm, and the height is 5 μm or less. The quantity is less than 0.60 pieces/ ^cm2 . In addition, as the lower limit of the short side length and height of the convex portion 16, for example, it exceeds 0 μm. In addition, the lower limit of the short side length and height of the first to third convex portions described below may be, for example, over 0 μm. Among them, the number of convex portions 16 is preferably 0.20 pcs/cm ² or less in order to produce an electronic device with better durability (hereinafter, also referred to as “the aspect with better effects of the present invention”). An example of the lower limit is 0.001 pieces/cm ² . In addition, pieces/cm ² represents the number of convex portions per 1 cm ² on the surface 14a of the polyimide resin layer 14. As a method of calculating the number of the above-mentioned convex portions 16, first, an offline defect inspection system (FPI-6000 series) manufactured by Orbotech (Model: FPI6090D) is used to obtain a map of all defects in the entire surface 14a of the polyimide resin layer 14. Image data and coordinate data. Then, calculate the long side length and short side length of the defect based on the obtained data. Thereafter, all defects were observed with a microscope (OLE4100) manufactured by Olympus Corporation, and the height of the defects was calculated based on the difference from the flat portion. Then, based on the obtained data of the long side length, short side length and height of each defect, the number of convex parts within a specific range is calculated.

In addition, the length of the long side and the length of the short side of the convex portion 16 will be described based on FIG. 3 . FIG. 3 is a view of the convex portion 16 viewed from the normal direction of the surface 14 a of the polyimide resin layer 14 . In Fig. 3, the convex portion 16 has an elliptical shape. Next, as shown in FIG. 3 , among the two parallel tangent lines circumscribing the outer circumference of the convex portion 16 , the distance between the two parallel tangent lines selected so as to maximize the tangent distance is set as the long side length L, and the given Among the two parallel tangent lines of a fixed length L that are orthogonal and circumscribe the outer circumference of the convex portion 16, the distance between the tangent lines of the two parallel tangent lines is selected in such a way that the distance between the tangent lines is the largest and is set to be the shortest. Side length S. In addition, in FIG. 3 , the shape of the convex portion 16 when viewed from the normal direction of the surface 14 a of the polyimide resin layer 14 is an elliptical shape, but the convex portion 16 is not limited to this shape, and may also be a perfect circle or a polygonal shape. Shape, no fixed shape.

In addition, the elements contained in the convex portions 16 can be measured using SEM-EDX (scanning electron microscope/energy dispersive X-ray spectrometry). That is, the specific convex portion 16 on the surface 14a of the polyimide resin layer 14 can be observed by SEM, and the elements contained in the convex portion 16 can be specified by EDX. Specific examples of elements contained in the convex portions 16 include C, O, Si, Al, Na, Cl, Fe, S, Mg, Ca, Ti, Zn, Cr, Ni, and Cu. In addition, the polyimide resin layer 14 itself also contains C and O elements, but whether the protrusions 16 contain C and O elements is related to the C and O content of the polyimide resin layer 14 at locations other than the protrusions 16 Test by comparison.

In order to make the effect of the present invention better, the long side length of the above-mentioned convex part is 10 μm or more and less than 50 μm, the short side length is less than 50 μm, the height is 1 μm or less, and at least 1 of Na and Cl is included. The number of the first convex parts (hereinafter, also referred to as "first convex parts") of the first element is preferably 0.15 pieces/cm ² or less, more preferably 0.10 pieces/cm ² or less, and more preferably 0.07 pieces/cm ² or less, more preferably 0.05 pieces/cm ² or less. An example of the lower limit is 0.001 pieces/cm ² . Although the details of the cause of the first convex part are unknown, based on the types of elements contained, it is speculated that it comes from human sweat. The first convex portion may also contain elements other than Na and Cl, and examples thereof include C and O.

Based on the fact that the effect of the present invention is better, the long side length of the above-mentioned convex portion is 3 μm or more and less than 20 μm, the short side length is less than 20 μm, the height is 5 μm or less, and contains at least one kind of Si and Al. The number of the second convex parts of the element (hereinafter also referred to as "second convex parts") is preferably 0.25 pieces/cm ² or less, more preferably 0.20 pieces/cm ² or less, and still more preferably 0.15 pieces/cm ² or less, preferably 0.10 pieces/cm ² or less, still more preferably 0.07 pieces/cm ² or less. An example of the lower limit is 0.001 pieces/cm ² . Although the details of the cause of the formation of the second convex portion are unknown, based on the types of elements contained, it is presumed that they originate from the glass support base material. The second convex portion may also contain elements other than Si and Al, and examples thereof include C and O.

Based on the better effect of the present invention, among the above-mentioned convex parts, the convex parts other than the first convex part and the second convex part, that is, the long side length is 3 μm or more and less than 50 μm, and the short side length is less than 50 μm. The number of third convex parts with a height of 1 μm or less (hereinafter, also referred to as "third convex parts") is preferably 0.30 pieces/cm ² or less, more preferably 0.25 pieces/cm ² or less, and still more preferably 0.20 pieces/cm 2 or less. ^No./cm2 or less, preferably no more than 0.15/ ^cm2 . As described above, the third convex portion is a convex portion that does not meet the specific size of any of the first convex portion and the second convex portion. An example of the lower limit of the number of third convex portions is 0.001 pieces/cm ² . Specific examples of the types of elements contained in the third convex portion include Ca, Fe, Ti, Cr, Ni, and Cu. The third convex portion preferably contains at least one of the elements listed above. . Although the details of the cause of the formation of the third convex portion are unknown, it is presumed that the environment contains fine particles of the elements listed above and metal powder such as SUS.

In the surface 14a of the polyimide resin layer 14, the long side length shown in Figure 2 is 3 to 1000 μm, the short side length is 20 μm or less, and the number of recessed portions 18 with a depth of 1 μm or less is 0.15/ cm ² . In addition, as the lower limit of the short side length and depth of the recessed portion 18, for example, it exceeds 0 μm. Among them, in view of the better effect of the present invention, the number of recessed portions 18 is preferably 0.07 pieces/cm ² or less. An example of the lower limit is 0.001 pieces/cm ² . As a method for calculating the number of recessed portions 18, an offline defect inspection system (FPI-6000 series (model: FPI609D) manufactured by Orbotech) is used to obtain image data of all defects in the entire surface 14a of the polyimide resin layer 14 and Coordinate data. Then, based on the obtained data, calculate the long side length and short side length of the defect. Thereafter, all defects were observed with a laser microscope (OLE4100) manufactured by Olympus Corporation, and the depth of the defects was calculated based on the difference from the flat portion. Then, based on the obtained data of the long side length, short side length and depth of each defect, the number of recesses within a specific range is calculated.

The length of the long side and the length of the short side of the recessed portion 18 are defined by the same procedure as the length of the long side and the length of the short side of the convex portion 16 described above. Specifically, the distance between the two parallel tangent lines circumscribed around the outer circumference of the recessed portion 18 is selected so as to maximize the distance between the tangent lines as the long side length L. Among the two parallel tangent lines that are orthogonal and circumscribe the outer circumference of the recessed portion 18, the distance between the two parallel tangent lines is selected so that the distance between the tangent lines is the largest and is set as the short side length S. In addition, the shape of the recessed portion 18 when viewed from the normal direction of the surface 14a of the polyimide resin layer 14 is not particularly limited, and may be a perfect circle, an ellipse, a polygon, or any other shape.

It is preferable that there is no convex part larger than the convex part 16 on the surface 14a of the polyimide resin layer 14. A convex part larger than the convex part 16 means a convex part whose long side length is more than 50 μm, or whose short side length is more than 50 μm, or whose height exceeds 5 μm. Moreover, it is preferable that there is no recessed part larger than the recessed part 18 in the surface 14a of the polyimide resin layer 14. A recess larger than the recess 18 means a recess whose long side length exceeds 1000 μm, or whose short side length exceeds 20 μm, or whose depth exceeds 1 μm.

[Manufacturing method of the first example of the laminated substrate] The method of manufacturing the laminated substrate of the first example is not particularly limited as long as the polyimide resin layer is formed to have the above-mentioned specific number of convex portions and concave portions. However, it is preferable that the polyimide resin layer is laminated on a support base. The surface method of the material. In addition, it is preferable to apply a well-known silane coupling agent to the surface of the supporting base material before laminating the polyimide resin layer on the surface of the supporting base material, and then, to coat the supporting base with the silane coupling agent. A polyimide resin layer is laminated on the surface of the material.

Furthermore, as a method of manufacturing a laminated substrate, a method of laminating a film-shaped polyimide resin layer and a supporting base material to manufacture a laminated substrate is more preferred, and further more preferred is a method of laminating a film-shaped polyimide resin layer to a supporting base material. The laminated film of the imine resin layer and the protective film disposed on one surface of the polyimide resin layer is bonded to the supporting base material to obtain a supporting base material, polyimide resin layer and protective film arranged in sequence. The laminated body is peeled off from the laminated body to produce a laminated substrate (hereinafter also referred to as "Method X"). In particular, in the method of using a protective film, since the surface of the polyimide resin layer opposite to the support base material is protected by the protective film, foreign matter is suppressed from adhering to the polyimide resin layer and the support when manufacturing the laminated substrate. The surface on the opposite side of the base material may be damaged, and as a result, it is easy to obtain the desired laminated substrate. When laminating the film-like polyimide resin layer and the supporting base material, it is preferable to implement it in a roll-to-roll method in view of excellent productivity.

As a method of adjusting the number of convex portions and recessed portions within a specific range, there may be a method of adjusting the formation conditions of the polyimide resin layer, or a method of cleaning a laminated substrate described below. In addition, it is preferable to perform a heat treatment on the laminated substrate, and then perform a cleaning treatment on the surface of the polyimide resin opposite to the supporting base material. Among them, it is preferable to perform a heat treatment on the laminated substrate after obtaining the laminated substrate by the above-mentioned method By performing heat treatment, volatile components in the polyimide resin layer and on the surface are removed, thereby suppressing the generation of volatile components during the production of electronic devices. In particular, when the laminated substrate is manufactured in a roll-to-roll manner in Method In addition, by cleaning the surface of the polyimide resin layer on the opposite side to the supporting base material, foreign matter that may become convex portions or may cause concave portions can be removed.

In addition, as the protective film used in method X, a peelable resin film is preferred. In method When static electricity is generated, foreign matter may adhere to the polyimide resin layer. By using a static electricity removing device, the adhesion of the foreign matter can be suppressed. In addition, the method of using a static electricity removing device has been described above, but it is also possible to increase the humidity (humidity: 70% or more) to suppress the generation of static electricity. By performing the above process, the number of the above-mentioned first convex portions or third convex portions can be reduced.

When performing the above-mentioned heat treatment, a heating device is usually used. When disposing the laminated substrate in the heating device, it is preferable to dispose the laminated substrate in the heating device with the polyimide resin facing downward. By arranging the polyimide resin layer downward, foreign matter falling from the heating device toward the laminated substrate can be prevented from adhering to the polyimide resin layer. By performing the above process, the number of the above-mentioned first to third convex portions can be reduced.

Moreover, as a specific example of the heating device used, a hot air heating device and an infrared heating device can be mentioned. Among them, when a hot air heating device is used, foreign matter sometimes moves on the surface of the polyimide resin opposite to the supporting base material due to the hot air, causing concavities. Therefore, in order to reduce the number of concavities, it is better to use infrared rays. Heating device.

As the conditions for the heat treatment, the heating temperature is preferably 450 to 550°C, the heating time is preferably 5 minutes to 1 hour, and the heating rate is preferably 1 to 100°C/min.

In addition, when cleaning the surface of the polyimide resin layer on the opposite side to the supporting base material, it is preferable to use a brush for cleaning. By performing the above process, the number of the above-mentioned second convex portions and third convex portions can be reduced. The cleaning treatment may be either dry cleaning or wet cleaning, and wet cleaning is preferred. Specific examples of detergents used in wet cleaning include aqueous alkaline solutions. When cleaning wet, it is better to use a brush. Specific examples of brushes used include roller brushes and disc brushes. Among them, when a roller brush is used, the ends of the bristle tips of the roller brush may wipe the surface of the polyimide resin layer on the opposite side to the supporting base material, causing recesses. Therefore, in order to reduce the number of recesses, it is preferable. Use a disk brush. The rotation speed when using a brush is not particularly limited, but when using a disc brush, it can be about 300 rpm.

Cleaning can be performed while transporting the laminated substrate. As a conveyance speed, 1-10 m/min is mentioned, for example. During the cleaning process, the laminated substrate can be fixed by a fixing mechanism such as nip rollers. At this time, in order to reduce the number of recesses, it is preferable to fix the laminated substrate in such a manner that the fixing mechanism does not contact the surface of the polyimide resin layer opposite to the supporting base material. Specifically, it is preferable to use a fixing mechanism that only contacts the support base material to fix the laminated substrate. In order to perform the above-mentioned cleaning treatment, a hydrophilic treatment such as corona treatment may be performed on the surface of the polyimide resin layer opposite to the supporting base material. By implementing hydrophilic treatment, the cleaning effect is improved.

[Example 2 of built-up substrate] FIG. 4 is a cross-sectional view schematically showing a second example of the laminated substrate according to the embodiment of the present invention. In addition, in the laminated substrate 10 of the second example shown in FIG. 4 , the same components as those of the laminated substrate 10 of the first example shown in FIG. 1 are denoted by the same reference numerals, and detailed descriptions are omitted. Compared with the laminated substrate 10 shown in FIG. 1 , the laminated substrate 10 of the second example is different from the laminated substrate 10 shown in FIG. 1 except that there is a silicone resin layer 13 between the supporting base material 12 and the polyimide resin layer 14 . The substrate 10 is the same.

In the laminated substrate 10 of the second example, a supporting base material 12, a silicone resin layer 13, and a polyimide resin layer 14 are laminated in this order. A silicone resin layer 13 is provided on the surface 12a of the supporting base material 12, and a polyimide resin layer 14 is provided on the surface 13a of the silicone resin layer 13. Although the silicone resin layer 13 and the polyimide resin layer 14 have the same size, they are smaller than the surface 12 a of the supporting base material 12 . In the laminated substrate 10 of the second example, the supporting base material 12 and the silicone resin layer 13 function as reinforcing plates that reinforce the polyimide resin layer 14 .

When the laminated substrate 10 is subjected to heat treatment, it is preferable that the adhesion force between the supporting base material 12 and the silicone resin layer 13 is greater than the adhesion force between the silicone resin layer 13 and the polyimide resin layer 14 . This can be produced by bonding the hydroxyl groups of the supporting base material 12 with the hydroxyl groups of the silicone resin layer 13 through heat treatment. As a result, when force is applied in the direction of peeling the support base material 12 and the polyimide resin layer 14, peeling occurs between the silicone resin layer 13 and the polyimide resin layer 14. Thereby, the polyimide resin layer 14 can be separated.

[Manufacturing method of the second example of the laminated substrate] The method of manufacturing the laminated substrate of the second example is preferably a method of forming a silicone resin layer on the back side of the polyimide resin layer. Specifically, the following method is preferred: applying a curable composition containing curable silicone to the back surface (the side opposite to the surface 14a) of a film-like polyimide resin layer, and curing the resulting coating film. After the silicone resin layer is obtained through the treatment, a supporting base material is laminated on the back surface of the silicone resin layer (the side opposite to the surface 13a) to produce a laminated substrate. More specifically, the method of manufacturing the laminated substrate of the second example includes at least the following steps: forming a curable silicone layer on the back side of the polyimide resin layer (the side opposite to the surface 14a), and forming a curable silicone layer on the polyimide resin layer. A step of forming a silicone resin layer on the back side of the amine resin layer (resin layer forming step); and a step of laminating a supporting base material on the back side of the silicone resin layer (the side opposite to the surface 13a) (lamination step). Each of the above steps will be described in detail below.

The resin layer forming step is a step of forming a curable silicone layer on the back side of the polyimide resin layer, and forming a silicone resin layer on the back side of the polyimide resin layer. Through this step, a substrate with a silicone resin layer including a polyimide resin layer and a silicone resin layer in sequence is obtained. The substrate with the silicone resin layer can be manufactured by a so-called roll-to-roll method in which a silicone resin layer is formed on the back of a polyimide resin layer rolled into a roll and then rolled into a roll again, so that the production efficiency is excellent. In this step, in order to form a curable silicone layer on the back of the polyimide resin layer, the above-mentioned curable composition is coated on the back of the polyimide resin layer. Next, it is preferable to perform a hardening treatment on the curable silicone layer, thereby forming a hardened layer. Specific examples of the method for coating the curable composition on the back surface of the polyimide resin layer include spray coating, die coating, spin coating, dip coating, roll coating, rod coating, and mesh coating. plate printing method and gravure printing coating method. Then, the curable silicone coated on the back side of the polyimide resin layer is hardened to form a silicone resin layer.

The curing method used to form the silicone resin layer is not particularly limited, and an optimal treatment is appropriately performed depending on the type of curable silicone used. For example, when condensation reaction type silicone and additional reaction type silicone are used, thermal hardening treatment is preferred as the hardening treatment. The conditions for the thermal hardening treatment are carried out within the range of the heat resistance of the polyimide resin layer. For example, the temperature conditions for thermal hardening are preferably 50 to 400°C, and more preferably 100 to 300°C. The heating time is preferably 10 to 300 minutes, more preferably 20 to 120 minutes. The silicone resin layer 13 will be described below.

The laminating step is a step of laminating a supporting base material on the surface of the silicone resin layer. As a specific example of the method of laminating the support base material on the back surface of the silicone resin layer, a method of laminating the support base material on the back surface of the silicone resin layer under a normal pressure environment can be cited. If necessary, the supporting base material may be overlapped on the back side of the silicone resin layer, and then a roller or pressing member may be used to press the supporting base material to the silicone resin layer. Pressure bonding by rolling or pressing is preferred because it is relatively easy to remove air bubbles mixed between the silicone resin layer and the supporting base material. It is preferable to use the vacuum lamination method or the vacuum pressing method for pressure bonding because it can suppress the mixing of air bubbles and achieve good adhesion. By performing pressure bonding under vacuum, there is also the advantage that even if tiny bubbles remain, the bubbles are less likely to grow due to heat treatment. When laminating the supporting base material, it is preferable to fully clean the surface of the supporting base material that is in contact with the silicone resin layer, and to laminate the supporting base material in a relatively clean environment.

In addition, as a method of manufacturing the laminated substrate of the second example, the following method is particularly preferred: a laminated film having a film-like polyimide resin layer and a protective film disposed on one surface of the polyimide resin layer. The surface opposite to the protective film is coated with a curable composition containing curable silicone, and the resulting coating film is cured. After obtaining the silicone resin layer, a supporting base material is laminated on the back of the silicone resin layer. A laminated body in which a supporting base material, a silicone resin layer, a polyimide resin layer and a protective film are arranged in this order is obtained, and the protective film is peeled off from the laminated body to produce a laminated substrate. In the method using the protective film as described above, since the surface of the polyimide resin layer opposite to the supporting base material is protected by the protective film, adhesion of foreign matter to the polyimide resin layer is suppressed when manufacturing a laminated substrate. The surface on the opposite side of the supporting base material may be damaged, and as a result, the desired laminated substrate may be easily obtained. The method of manufacturing the silicone resin layer and the method of laminating the supporting substrate on the back side of the silicone resin layer are as described above. In addition, the protective film used above can be in the form described in the first example. As explained in the first example, in order to prevent the generation of static electricity when peeling off the protective film, it is preferable to use a static electricity removing device such as an ionizer to eliminate static electricity. In addition, as in the first example, it is preferable to perform a heat treatment on the laminated substrate, and then perform a cleaning treatment on the surface of the polyimide resin layer opposite to the supporting base material.

Hereinafter, the supporting base material 12 , the polyimide resin layer 14 and the silicon resin layer 13 constituting the laminated substrate 10 will be described in detail.

＜Support base material＞ The glass supporting base material 12 is a member that supports and reinforces the polyimide resin layer 14 and functions as a transport substrate. The supporting base material 12 is made of, for example, a glass plate. As the type of glass, preferred are alkali-free borosilicate glass, borosilicate glass, soda-lime glass, high silica glass, and other oxide-based glasses containing silica as the main component. As the oxide-based glass, glass having a silicon oxide content of 40 to 90% by mass in terms of oxide is preferred. More specifically, as glass, a glass plate containing alkali-free borosilicate glass (manufactured by AGC Co., Ltd., trade name "AN100") can be cited. An example of a method for producing a glass plate is a method of generally melting a glass raw material and shaping the molten glass into a plate shape. Such forming methods may be general ones, and examples thereof include float method, melting method, and orifice downdraft method.

The thickness of the supporting substrate 12 may be thicker or thinner than the polyimide resin layer 14 . Based on the rationality of the laminated substrate 10 , it is preferable that the thickness of the supporting base material 12 is thicker than that of the polyimide resin layer 14 . Since the supporting base material 12 is required to function as a reinforcing plate and a transport substrate, it is preferably non-flexible. Therefore, the thickness of the supporting base material 12 is preferably 0.3 mm or more, and more preferably 0.5 mm or more. On the other hand, the thickness of the supporting base material 12 is preferably 1.0 mm or less.

<Polyimide Resin Layer> The polyimide resin layer 14 contains polyimide resin, and a polyimide film, for example, is used. Specific examples of commercially available polyimide films include "XENOMAX" manufactured by Toyobo Co., Ltd. and "UPILEX 25S" manufactured by Ube Kosan Co., Ltd. In order to form high-definition wiring and the like constituting an electronic device, it is preferable that the surface 14a of the polyimide resin layer 14 is smooth. Specifically, the surface roughness Ra of the surface 14a of the polyimide resin layer 14 is preferably 50 nm or less, more preferably 30 nm or less, and still more preferably 10 nm or less. An example of the lower limit of surface roughness Ra is 0.01 nm or more. Based on the operability of the manufacturing steps, the thickness of the polyimide resin layer 14 is preferably 1 μm or more, more preferably 5 μm or more, and even more preferably 10 μm or more. Based on flexibility, the thickness of the polyimide resin layer 14 is preferably less than 1 mm, more preferably less than 0.2 mm. The smaller the difference between the thermal expansion coefficient of the polyimide resin layer 14 and the thermal expansion coefficient of the supporting base material 12, the smaller the thermal expansion coefficient of the polyimide resin layer 14 and the supporting base material 12 can suppress the deflection after heating or cooling, so it is preferable. Specifically, the difference in thermal expansion coefficient between the polyimide resin layer 14 and the supporting base material 12 is preferably 0 to 90×10 ^-6 /°C, more preferably 0 to 30×10 ^-6 /°C.

The area of the polyimide resin layer 14 (the area of the surface 14a) is not particularly limited, but is preferably smaller than the area of the supporting base material 12. On the other hand, based on the productivity of the electronic device, the area of the polyimide resin layer 14 is preferably 300 cm ² or more. The shape of the polyimide resin layer 14 is not particularly limited, and may be a rectangular shape or a circular shape. In addition, an orientation plane (a flat part formed on the outer periphery of the substrate) and a notch (at least one V-shaped notch formed on the outer periphery of the substrate) can be formed on the polyimide resin layer 14 .

<Silicone resin layer> The silicone resin layer 13 mainly contains silicone resin. The structure of the silicone resin is not particularly limited. Silicone resin can usually be obtained by curing silicone hardening (cross-linking hardening) into curable silicone resin. Specific examples of curable silicones include condensation reaction type silicone, additional reaction type silicone, ultraviolet curing type silicone, and electron beam curing type silicone, depending on the curing mechanism. The weight average molecular weight of the curable silicone is preferably 5,000 to 60,000, more preferably 5,000 to 30,000.

As the manufacturing method of the silicone resin layer 13, as mentioned above, the following method is preferable: Coating the back surface of the polyimide resin layer 14 (the surface opposite to the surface 14a) containing the curable silicone resin. From the curable composition of silicone, the solvent is removed if necessary to form a coating film, and the curable silicone in the coating film is hardened to form the silicone resin layer 13 . In addition to curable silicone, the curable composition may also include a solvent, a platinum catalyst (when an additional reactive silicone is used as the curable silicone), a leveling agent, a metal compound, etc. Specific examples of the metal element contained in the metal compound include 3d transition metals, 4d transition metals, lanthanide series metals, bismuth, aluminum and tin. Appropriately adjust the content of metal compounds.

The thickness of the silicone resin layer 13 is preferably 100 μm or less, more preferably 50 μm or less, and even more preferably 30 μm or less. On the other hand, the thickness of the silicone resin layer 13 is preferably more than 1 μm, more preferably more than 4 μm. The above-mentioned thickness is obtained by measuring the thickness of the silicone resin layer 13 at five or more arbitrary positions using a contact-type film thickness measuring device and averaging the results.

＜Use of laminated substrate＞ Examples of uses of the laminated substrate 10 include display devices, receiving sensor panels, solar cells, thin film secondary batteries, integrated circuits, etc., which will be described later. There are also cases where the laminated substrate 10 is exposed to high temperature conditions such as 450° C. or higher in the atmosphere for more than 20 minutes. Specific examples of display devices include LCD, OLED, electronic paper, plasma display panels, field emission panels, quantum dot LED panels, micro-LED display panels, and MEMS (Micro Electro Mechanical Systems) shutter panels. . Specific examples of the receiving sensor panel include an electromagnetic wave receiving sensor panel, an X-ray receiving sensor panel, an ultraviolet receiving sensor panel, a visible ray receiving sensor panel, and an infrared receiving sensor panel. When used to receive a sensor panel, the polyimide resin layer can also be reinforced by reinforcing sheets of resin or the like.

As described above, an electronic device including a polyimide resin layer and an electronic device member is manufactured using the laminated substrate of the present invention. An example of a method for manufacturing an electronic device is a method of forming a member for an electronic device on a polyimide resin layer in a laminated substrate, peeling the supporting base material from the obtained laminated substrate with the member for an electronic device, and An electronic device including a polyimide resin layer and an electronic device member was obtained. In addition, the above-mentioned member for an electronic device is a member constituting at least a part of the electronic device.

In the following, the present invention will be described in more detail using the laminated substrate 10 of the second example as an example. However, the same applies to the case of using the laminated substrate 10 of the first example.

A preferred method for manufacturing an electronic device is as follows: forming an electronic device member 20 on the polyimide resin layer 14 of the laminated substrate 10, obtaining the laminated substrate 22 with the electronic device member, and then combining the silicone resin layer 13 and The interface of the polyimide resin layer 14 serves as a peeling surface, and the obtained laminated substrate 22 with components for electronic devices is separated into an electronic device (substrate 24 with components) and a supporting base material 26 with a silicone resin layer. The step of forming the electronic device member 20 is called a "member forming step", and the step of separating the substrate 24 with the member and the supporting base material 26 with the silicone resin layer is called a "separation step". In the following, the materials and order used in each step are described in detail.

The component forming step is a step of forming components for electronic devices on the polyimide resin layer 14 of the laminated substrate 10 . More specifically, as shown in FIG. 5 , the electronic device member 20 is formed on the surface 14 a of the polyimide resin layer 14 to obtain the electronic device member-attached laminated substrate 22 . First, the electronic device member 20 used in this step will be described in detail, and the sequence of subsequent steps will be described in detail.

The electronic device member 20 is formed on the polyimide resin layer 14 in the laminated substrate 10 and constitutes at least a part of the electronic device. More specifically, examples of the electronic device member 20 include members used for display devices, receiving sensor panels, solar cells, thin film secondary batteries, integrated circuits, etc. (for example, display device members such as LTPS, Components for receiving sensor panels, components for solar cells, components for thin-film secondary batteries, and circuits for integrated circuits), for example, the solar energy described in paragraph [0192] of the specification of U.S. Patent Application Publication No. 2018/0178492 Components for batteries, components for thin film secondary batteries described in the same paragraph [0193], and circuits for electronic components described in the same paragraph [0194].

The manufacturing method of the above-mentioned laminated substrate 22 with components for electronic devices is not particularly limited. Depending on the type of components for the electronic device, the surface 14a of the polyimide resin layer 14 of the laminated substrate 10 is formed on the surface 14a of the polyimide resin layer 14 of the laminated substrate 10 by a conventionally well-known method. The electronic device member 20 is formed on it. The electronic device member 20 may be a part of all the members (hereinafter referred to as "partial members"), rather than all the members finally formed on the surface 14a of the polyimide resin layer 14 (hereinafter referred to as "all members") . The substrate with some components peeled off from the silicone resin layer 13 can also be used as a substrate with all components (equivalent to an electronic device) in subsequent steps. The substrate with all components peeled off from the silicone resin layer 13 can be used to form other electronic device components on the peeled surface. Furthermore, the electronic device components of the two laminated substrates with the electronic device components can also be made to face each other, and the two are laminated together to assemble the laminated body with all the components, and then the two silicone-attached laminates can be assembled. The support base material of the resin layer is peeled off from the laminate with all the components attached, and an electronic device is manufactured.

For example, taking the case of manufacturing OLED as an example, in order to form an organic EL structure on the surface (surface 14a) of the polyimide resin layer 14 of the multilayer substrate 10 opposite to the silicone resin layer 13 side, A transparent electrode is formed, and then a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, etc. are evaporated on the surface on which the transparent electrode is formed, a back electrode is formed, and various layers such as sealing with a sealing plate are formed or processed. Specific examples of such layer formation or processing include film formation processing, vapor deposition processing, sealing plate bonding processing, and the like.

As shown in FIG. 6 , the separation step is as follows: using the interface between the silicone resin layer 13 and the polyimide resin layer 14 as a peeling surface, the laminated substrate 22 with electronic device components obtained in the above component forming step is separated into laminated layers. There is a polyimide resin layer 14 of the electronic device component 20 (the component-attached substrate 24 ), and a supporting base material 26 with the silicone resin layer, thereby obtaining the electronic device component 20 and the polyimide resin layer. 14 components of the substrate 24 (electronic device).

When the electronic device member 20 on the peeled polyimide resin layer 14 forms part of all necessary constituent members, the remaining constituent members can also be formed on the polyimide resin layer 14 after separation. superior.

The method of peeling off the polyimide resin layer 14 and the silicone resin layer 13 is not particularly limited. For example, a sharp blade can be inserted into the interface between the polyimide resin layer 14 and the silicone resin layer 13 to give an opportunity for peeling, and then a mixed fluid of water and compressed air can be blown to peel off. Preferably, the laminated substrate 22 with the electronic device member 20 is placed on a flat plate so that the supporting base material 12 is on the upper side and the electronic device member 20 side is on the lower side, and the electronic device member 20 side is vacuum-suctioned on the flat plate. On, and in this state, the blade-shaped object is first invaded into the interface between the polyimide resin layer 14 and the silicon resin layer 13 . Thereafter, a plurality of vacuum adsorption pads are used to adsorb the supporting substrate 12 side, and the vacuum adsorption pads are sequentially raised from the vicinity of the position where the blade is inserted. In this way, the supporting base material 26 with the silicone resin layer can be easily peeled off.

When the component-attached substrate 24 is separated from the laminated substrate 22 with electronic device components, by controlling the blowing of the ionizer or the humidity, the fragments of the silicone resin layer 13 can be further suppressed from electrostatic adsorption to the component-attached substrate 24 . The above-mentioned manufacturing method of the electronic device (the substrate 24 with the component) is more suitable for the manufacturing of the display device described in paragraph [0210] of the specification of US Patent Application Publication No. 2018/0178492. As the substrate 24 with the component, for example An example is as recorded in paragraph [0211]. [Example]

In the following, the present invention will be described in detail using Examples, etc., but the present invention is not limited by these Examples. Examples 1 to 7 and 9 to 15 described below are examples, and Example 8 is a comparative example.

＜Evaluation of device durability＞ The organic EL display devices obtained from the laminated substrates of each example were stored in an environment of 60°C and 90% RH, and the storage times of black spots were compared. Those with enlarged black spots after less than 500 hours are evaluated as ×, those with more than 500 hours but less than 1000 hours with enlarged black spots are evaluated as ○, those with more than 1000 hours with enlarged black spots are evaluated as ◎.

<Example 1> (Preparation of hardening silicone) In a 1L flask, add triethoxymethylsilane (179 g), toluene (300 g), and acetic acid (5 g), and stir the mixture at 25°C. After 20 minutes, the mixture was further heated to 60°C and allowed to react for 12 hours. After the obtained crude reaction liquid was cooled to 25°C, the crude reaction liquid was washed three times with water (300 g). Trimethylsilane chloride (70 g) was added to the crude reaction solution after cleaning, and the mixture was stirred at 25°C for 20 minutes, then heated to 50°C and allowed to react for 12 hours. After the obtained crude reaction liquid was cooled to 25°C, the crude reaction liquid was washed three times with water (300 g). Toluene was distilled off under reduced pressure from the crude reaction liquid after cleaning, and after being brought to a slurry state, it was dried overnight in a vacuum dryer to obtain a white organopolysiloxane compound, curable silicone 1. The number of T units of hardening silicone 1: the number of M units = 87:13 (mol ratio). In addition, the M unit means a monofunctional organosiloxy unit represented by (R) ₃ SiO _1/2 . The T unit means a trifunctional organosiloxy unit represented by RSiO _3/2 (R represents a hydrogen atom or an organic group).

(Preparation of hardening composition) Curable silicon 1 and hexane were mixed, and an organic zirconium-based compound (zirconium octoate compound) and an organic bismuth-based compound (bismuth 2-ethylhexanoate) were added. The solvent amount was adjusted so that the solid content concentration would be 50% by mass. In addition, the amount of the metal compound added was adjusted so that the metal element was 0.01 parts by mass relative to 100 parts by mass of the resin. The obtained mixture was filtered using a filter with a pore size of 0.45 μm to obtain a curable composition.

(Production of laminated body) Peel off one of the protective films of a polyimide film with a thickness of 0.015 mm (manufactured by Toyobo Co., Ltd., trade name "XENOMAX") with protective films on both sides, and place it on the surface of the polyimide film on the side where the protective film is peeled off On the top, apply the prepared curable composition and heat it at 140°C for 10 minutes using a hot plate to form a silicone resin layer. The thickness of the silicone resin layer is 10 μm. Next, clean the 200×200 mm, 0.5 mm thick glass plate "AN100" (support base material) with a water-based glass cleaner (Parkercorp Co., Ltd., "PK-LCG213"), and then clean it with pure water. The polyimide film formed with the silicone resin layer is laminated in a roll-to-roll manner to produce a laminate in which the glass plate, the silicone resin layer, the polyimide film and the protective film are arranged in this order.

(Heating treatment and cleaning treatment) The above-mentioned laminated body was transported to a heating device, and before leaving it still in the heating device, the protective film was peeled off, left in the heating device, and heated at 450° C. for 0.5 hours. After the heat treatment, the laminated substrate is taken out from the heating device, corona treatment is performed on the surface of the polyimide resin layer, and then cleaning treatment using a roller brush is performed to obtain the laminated substrate 1 . During the cleaning process, in order to prevent the laminated substrate from moving in the cleaning machine, a fixing mechanism (pinch roller) is used to fix the laminated substrate. At this time, the fixing mechanism is in contact with the surface of the polyimide resin layer. In addition, in order to prevent static electricity from being generated when peeling off the protective film, an ionizer is used to reduce the surface charge of the polyimide resin layer. Hereinafter, the countermeasure using an ionizer is referred to as "Measure A". Moreover, during the heat treatment, the laminated substrate is arranged so that the polyimide resin layer faces downward in the heating device. Hereinafter, the countermeasure of arranging the laminated substrate with the polyimide resin layer facing downward is referred to as "Measure B". In addition, the countermeasure of performing the above-mentioned corona treatment and cleaning treatment is called "Measure C". As the heating device, an infrared heating device is used. Hereinafter, the countermeasure using an infrared heating device is referred to as "Measure D".

＜Examples 2～15＞ As shown in Tables 1 and 2, a laminated substrate was obtained according to the same procedure as Example 1, except for changing which of the measures A to F was implemented (heat treatment and cleaning treatment). In addition, Countermeasure E means to use a fixing mechanism that does not come into contact with the surface of the polyimide resin layer when fixing the laminated substrate in the cleaning machine. Also, Countermeasure F refers to the countermeasure of using a disk brush during cleaning.

In Tables 1 and 2, the situation where each countermeasure is implemented is regarded as "yes", and the situation where each countermeasure is not implemented is regarded as "no". For example, in Example 2 where Countermeasure C is "None", corona treatment and cleaning treatment are not performed after the heat treatment. Moreover, in Example 3 in which the countermeasure B is "none", when the laminated substrate is placed in the heating device, the laminated substrate is placed with the polyimide resin layer facing upward. Furthermore, in Example 4 in which Countermeasure A is "None", the protective film was peeled off without using an ionizer. Furthermore, in Example 10 in which the countermeasure D is "none", a hot air heating device is used as the heating device. Furthermore, in Example 11 in which the countermeasure E is "none", a fixing mechanism in contact with the surface of the polyimide resin layer is used. Moreover, in Example 12 in which the countermeasure F is "None", a cleaning process using a roller brush was performed.

In Tables 1 and 2, "the number of first protrusions", "the number of second protrusions", and "the number of third protrusions" respectively represent the first and third protrusions on the surface of the polyimide resin layer. The number of 2 convex parts and the 3 rd convex parts (pieces/cm ² ). "The number of convex parts" means the number (total number) of convex parts on the surface of the polyimide resin layer (pieces/cm ² ). "The number of recessed parts" represents the number (total number) of recessed parts on the surface of the polyimide resin layer (pieces/cm ² ). The method of measuring the convex portion and the concave portion is as described above.

<Manufacturing of organic EL display devices (equivalent to electronic devices)> Using the laminated substrates obtained in Examples 1 to 15, an organic EL display device was produced according to the following procedure. First, on the surface of the polyimide resin layer of the laminated substrate on the opposite side to the glass plate, films of silicon nitride, silicon oxide, and Amorphous silicon. Next, a low-concentration boron is implanted into the amorphous silicon layer through an ion doping device, followed by heat treatment and dehydrogenation treatment. Then, the amorphous silicon layer is crystallized using a laser annealing device. Next, by using photolithographic etching and ion doping equipment, low-concentration phosphorus is implanted into the amorphous silicon layer to form N-type and P-type TFT (Thin Film Transistor: thin film transistor) regions. Next, a silicon oxide film is formed on the side of the polyimide resin layer opposite to the glass plate by plasma CVD. After forming a gate insulating film, a molybdenum film is formed by sputtering. By using light The gate electrode is formed by photolithographic etching. Next, high-concentration phosphorus and boron are implanted into each desired region of the N-type and P-type through photolithography and ion doping equipment to form a source region and a drain region. Next, on the side of the polyimide resin layer opposite to the glass plate side, silicon oxide is deposited by the plasma CVD method to form an interlayer insulating film, an aluminum film is deposited by the sputtering method and etched by the photolithography method. Form TFT electrodes. Then, heat treatment is performed in a hydrogen atmosphere, and after hydrogenation treatment, a silicon nitride film is formed by a plasma CVD method to form a passivation layer. Next, ultraviolet curable resin is coated on the side of the polyimide resin layer opposite to the glass plate side, and a planarization layer and contact holes are formed by photolithography. Next, an indium tin oxide film is formed by sputtering, and the pixel electrode is formed by etching using photolithography. Then, by evaporation method, 4,4',4''-tris(3-methylphenyl) as a hole injection layer is sequentially formed on the side of the polyimide resin layer opposite to the glass plate side. Phenylamine)triphenylamine, bis[(N-naphthyl)-N-phenyl]-benzidine as the hole transport layer, and 8-hydroxyquinoline aluminum complex (Alq3) as the light-emitting layer , mix 40 volume % of 2,6-bis[4-[N-(4-methoxyphenyl)-N-phenyl]aminostyrene]naphthalene-1,5-dicarboxonitrile (BSN-BCN) Or, Alq3 as the electron transport layer. Next, an aluminum film is formed by sputtering, and a counter electrode is formed by etching using photolithography. Then, another glass plate is bonded to the side of the polyimide resin layer opposite to the glass plate through an ultraviolet curable adhesive layer and sealed. Through the above procedure, an organic EL structure is formed on the polyimide resin layer. A structure having an organic EL structure on a polyimide resin layer (hereinafter referred to as panel A) is a laminated substrate with components for electronic devices of the present invention. Next, after the sealing body side of panel A is vacuum-adsorbed to the flat plate, a stainless steel cutting tool with a thickness of 0.1 mm is inserted into the interface between the polyimide resin layer and the silicone resin layer at the corner of panel A, and the polyimide is The interface between the resin layer and the silicone resin layer provides an opportunity for peeling. And, after adsorbing the surface of the support base material of panel A with a vacuum adsorption pad, the adsorption pad is allowed to rise. Here, the cutter is inserted while blowing the antistatic fluid from the ionizer (made by Keyence Corporation) to the interface. Next, the antistatic fluid is continued to be blown from the ionizer to the formed gap, and at the same time, the vacuum adsorption pad is lifted up while injecting water to the peeling front line. As a result, only the polyimide resin layer on which the organic EL structure is formed remains on the flat plate, and the supporting base material with the silicone resin layer can be peeled off. Next, the separated polyimide resin layer is cut using a laser cutter or a scribing-fragmentation method, and divided into a plurality of units, and then assembled to form a polyimide resin layer with an organic EL structure. and a counter substrate, and perform the module forming step to produce an organic EL display device.

[Table 1] Table 1 example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 convex part Countermeasure A have have have without without have without without Countermeasure B have have without have without without have without Countermeasure C have without have have have without without without Number of 1st convex parts 0.01 0.01 0.06 0.08 0.13 0.06 0.08 0.13 Number of 2nd convex parts 0.05 0.20 0.10 0.05 0.10 0.25 0.20 0.25 Number of 3rd convex parts 0.08 0.23 0.13 0.15 0.20 0.28 0.30 0.35 The number of convex parts 0.14 0.44 0.29 0.28 0.43 0.59 0.58 0.73 concavity Countermeasure D have have have have have have have without Countermeasure E without without without without without without without without Countermeasure F without without without without without without without without Number of recesses (total number) 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.19 Device durability ◎ ○ ○ ○ ○ ○ ○ ×

[Table 2] Table 2 Example 9 Example 10 Example 11 Example 12 Example 13 Example 14 Example 15 convex part Countermeasure A have have have have have have have Countermeasure B without without without without without without without Countermeasure C without without without without without without without Number of 1st convex parts 0.06 0.06 0.06 0.06 0.06 0.06 0.06 Number of 2nd convex parts 0.25 0.25 0.25 0.25 0.25 0.25 0.25 Number of 3rd convex parts 0.28 0.28 0.28 0.28 0.28 0.28 0.28 The number of convex parts 0.59 0.59 0.59 0.59 0.59 0.59 0.59 concavity Countermeasure D have without have have without have without Countermeasure E have have without have without without have Countermeasure F have have have without have without without Number of recesses (total number) 0.04 0.08 0.10 0.09 0.14 0.15 0.13 Device durability ◎ ○ ○ ○ ○ ○ ○

As shown in Tables 1 and 2, when using specific build-up substrates, it is confirmed that the desired effects are obtained.

This application is based on Japanese Patent Application No. 2019-106248 filed on June 6, 2019, the content of which is incorporated herein by reference.

10:Laminated substrate 12: Support base material 12a: Surface 13: Silicone resin layer 13a: Surface 14:Polyimide resin layer 14a: Surface 16:convex part 18: concave part 20: Components for electronic devices 22:Laminated substrate with components for electronic devices 24: Base plate with attached components 26: Support base material with silicone resin layer L: length S: length

FIG. 1 is a cross-sectional view schematically showing a first example of a laminated substrate according to the embodiment of the present invention. 2 is an enlarged cross-sectional view of the surface of the polyimide resin layer in the first example of the laminated substrate according to the embodiment of the present invention. Figure 3 is a diagram for explaining the length of the long side and the length of the short side of the convex portion. FIG. 4 is a cross-sectional view schematically showing a second example of the laminated substrate according to the embodiment of the present invention. Fig. 5 is a cross-sectional view schematically showing the steps of forming the member. Fig. 6 is a cross-sectional view schematically showing the separation step.

Claims (7)

A laminated substrate comprising a glass supporting base material, a silicone resin layer disposed on the supporting base material, and a polyimide resin layer disposing on the silicone resin layer, wherein the silicone resin layer The thickness is more than 1 μm and less than 100 μm. On the surface of the polyimide resin layer opposite to the support base material, the length of the long side is more than 3 μm and less than 50 μm, the length of the short side is less than 50 μm, and the height is 5 μm. The number of the following convex parts is 0.60/ ^cm2 or less, the long side length is 3~1000μm, the short side length is 20μm, and the number of concave parts with a depth of 1μm or less is 0.15/ ^cm2 or less. The laminated substrate of Claim 1, wherein the protrusion has a long side length of 10 μm or more and less than 50 μm, a short side length of less than 50 μm, a height of 1 μm or less, and contains at least one element of Na and Cl. The number of convex parts is 0.15/ ^cm2 or less. The laminated substrate of claim 1 or 2, wherein the protrusions have a long side length of 3 μm or more and less than 20 μm, a short side length of less than 20 μm, a height of 5 μm or less, and contain at least one element of Si and Al. The number of second convex parts is 0.25/cm ² or less. The laminated substrate according to Claim 3, wherein among the above-mentioned protrusions, the protrusions other than the above-mentioned first protrusion and the above-mentioned second protrusion have a long side length of 3 μm or more and less than 50 μm, a short side length less than 50 μm, and a height The number of third convex portions of 1 μm or less is 0.30/cm ² or less. The laminated substrate according to claim 1 or 2, wherein the number of the above-mentioned convex portions is 0.20 pieces/cm ² or less. The laminated substrate according to claim 1 or 2, wherein the number of the recesses is 0.07/cm ² or less. A method of manufacturing an electronic device, which uses the laminated substrate according to any one of claims 1 to 6 to manufacture the electronic device, and includes the following steps: rolling to roll on the above-mentioned polyimide resin layer The step of forming the above-mentioned silicone resin layer in a manner to obtain a substrate with a silicone resin layer; the step of laminating the above-mentioned supporting base material on the surface of the silicone resin layer of the above-mentioned substrate with a silicone resin layer to produce the above-mentioned laminated substrate; A member forming step of forming an electronic device member on the surface of the polyimide resin layer opposite to the supporting base material to obtain a laminated substrate with an electronic device member; and A separation step of laminating a substrate to obtain an electronic device having the polyimide resin layer and the electronic device member.