TW202106509A - Laminated substrate, method for manufacturing electronic device, and method for manufacturing laminated substrate comprising a supporting substrate made of glass and a polyimide resin layer arranged on the supporting substrate - Google Patents

Abstract

The present invention relates to a laminated substrate comprising a supporting substrate made of glass and a polyimide resin layer arranged on the supporting substrate. On a surface of the polyimide resin layer opposite to the supporting substrate, the number of protrusions with a long-side length of 3 [mu]m or more and less than 50 [mu]m, a short-side length of less than 50 [mu]m, and a height of less than 5 [mu]m is 0.60/cm2, and the number of protrusions with a long-side length of 3 [mu]m to 1000 [mu]m, a short-side length of less than 20 [mu]m, and a height of less than 1 [mu]m is 0.15/cm2.

Description

Multilayer substrate, manufacturing method of electronic device, and manufacturing method of multilayer substrate

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

Manufacturing such as solar cells; Liquid Crystal Display (LCD); Organic Light-Emitting Diode (OLED); Receiving sensor panels for sensing electromagnetic waves, X-rays, ultraviolet rays, visible rays, infrared rays, etc.; etc. In the case of electronic devices, as described in Patent Document 1, there is disclosed a form in which a polyimide resin layer is used as a substrate. The polyimide resin layer is used in the state of a build-up substrate provided on a glass substrate, and the build-up substrate is provided for manufacturing electronic devices. After the electronic device is formed, the polyimide resin layer is separated from the glass substrate. [Prior Technical Literature] [Patent Literature]

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

[The problem to be solved by the invention]

In recent years, efforts have been made 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 provided with a glass supporting substrate and a polyimide resin layer as described in Patent Document 1, and formed an electronic device component on the polyimide resin layer. During the study of its performance, it was found that there is still room for further improvement in terms of durability. The object of the present invention is to provide a laminated substrate provided with a polyimide resin layer that can manufacture electronic devices with excellent durability (for example, organic EL display devices). Moreover, the object of the present invention is also to provide a method of manufacturing an electronic device and a method of manufacturing a multilayer substrate. [Technical means to solve the problem]

The inventors of the present invention actively studied, and as a result, found that the above-mentioned object can be achieved by the following configuration.

(1) A laminated substrate comprising a supporting substrate made of glass, and a polyimide resin layer arranged on the supporting substrate, and on the surface of the polyimide resin layer opposite to the supporting substrate, The length of the long side is 3 μm or more and less than 50 μm, the length of the short side is less than 50 μm, and the number of protrusions with a height of 5 μm or less is 0.60/cm ² or less. The length of the long side is 3 to 1000 μm, the length of the short side 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 multilayer substrate as described in (1), in which the long side length is 10 μm or more and less than 50 μm in the convex portion, the short side length is less than 50 μm, and the height is less than 1 μm, and contains Na and Cl The number of first protrusions of at least one element is 0.15/cm ² or less. (3) The multilayer substrate as described in (1) or (2), in which the long side length is 3 μm or more and less than 20 μm in the convex portion, the short side length is less than 20 μm, and the height is 5 μm or less, and includes The number of second protrusions of at least one element of Si and Al is 0.25/cm ² or less. (4) The multilayer substrate as described in (3), wherein among the convex portions, the convex portions other than the first convex portion and the second convex portion, that is, the length of the long side is 3 μm or more and less than 50 μm, and the length of the short side is less than 50 μm, the number of third protrusions with a height of 1 μm or less is 0.30/cm ² or less. (5) The multilayer substrate according to any one of (1) to (4), wherein the number of convex portions is 0.20 pcs/cm ² or less. (6) The multilayer substrate according to any one of (1) to (5), wherein the number of recesses is 0.07/cm ² or less. (7) A method of manufacturing an electronic device, comprising the steps of: forming on the surface of the polyimide resin layer of the multilayer substrate described in any one of (1) to (6) on the opposite side of the support substrate The component forming step of obtaining a multilayer substrate with a component for an electronic device; and a step of separating the multilayer substrate with a component for an electronic device to obtain an electronic device having a polyimide resin layer and the component for an electronic device . (8) A method for manufacturing a multilayer substrate, which is the method for manufacturing a multilayer substrate as described in any one of (1) to (6), in which a film-like polyimide resin layer is bonded to a supporting base material, and Manufacture multilayer substrates. (9) The method for manufacturing a multilayer substrate as described in (8), wherein a multilayer film and a supporting base are provided with a polyimide resin layer in the form of a film, and a protective film arranged on one surface of the polyimide resin layer. The materials are bonded together to obtain a laminate in which the support substrate, the polyimide resin layer, and the protective film are arranged in this order, and the protective film is peeled from the laminate to produce a laminate substrate. [Effects of Invention]

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

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 following embodiments. In addition, various changes and substitutions can be added to the following embodiments without departing from the scope of the present invention. The numerical range indicated by "~" means the range that includes the numerical value before and after "~" as the lower limit and the upper limit.

As a characteristic point of the laminated substrate of the present invention, the point of adjusting the number of convex parts and concave parts of a specific shape on the surface of the polyimide resin layer can be exemplified. The inventors of the present invention found that when electronic devices are manufactured using the previous multilayer substrate described in Patent Document 1, the reason for the poor durability of the resulting electronic devices is related to the specific shape of the convex portions on the surface of the polyimide resin layer. Related to the recess. When manufacturing electronic devices such as organic EL display devices, a thin layer is formed by sputtering or the like. However, if there are protrusions and recesses of a specific shape on the polyimide resin layer, a uniform layer cannot be formed, which is easy It becomes a defect, and as a result, the performance of the obtained electronic device is poor. Therefore, by adjusting the number of the above-mentioned protrusions and recesses, the desired effect can be obtained.

＜Multilayer substrates＞ [First example of multilayer substrate] FIG. 1 is a cross-sectional view schematically showing the first example of the multilayer substrate of the embodiment of the present invention. The laminated substrate 10 of the first example includes a supporting base 12 made of glass and a polyimide resin layer 14 arranged on the supporting base 12. In FIG. 1, the area of the polyimide resin layer 14 is smaller than the surface 12a of the support substrate 12, and is not provided on the entire surface 12a of the support substrate 12. However, it is not limited to this form and can also be on the surface of the support substrate 12. 12a, the polyimide resin layer 14 is disposed all over the area.

The support base 12 is a member that supports the polyimide resin layer 14 and functions as a reinforcing plate for reinforcing the polyimide resin layer 14. In addition, the supporting base 12 also functions as a transport substrate when transporting the build-up substrate 10. In the laminated substrate 10, when a force is applied to the direction in which the support base 12 and the polyimide resin layer 14 are peeled off, the support base 12 and the polyimide resin layer 14 are separated into the support base 12 and the polyimide resin layer 14. Although described in detail below, the polyimide resin layer 14 is a substrate used for manufacturing electronic devices. That is, on the surface 14 a of the polyimide resin layer 14, electronic components such as transistors, coils, resistors, etc., and signal lines that constitute electronic devices are formed.

2 is an enlarged cross-sectional view of the surface 14a of the polyimide resin layer 14 in the laminated substrate 10 of the embodiment of the present invention. On the surface 14a of the polyimide resin layer 14, as shown in FIG. 2, the length of the long side is 3 μm or more and less than 50 μm, the length of the short side is less than 50 μm, and the height of the convex part 16 is less than 5 μm. The quantity is less than ^{0.60/cm 2.} In addition, as the lower limit of the shorter side length and height of the convex portion 16, over 0 μm can be mentioned. In addition, as the lower limit of the shorter side length and height of the first to third convex portions described later, over 0 μm may be exemplified. Among them, based on the point that an electronic device with better durability can be manufactured (hereinafter, also referred to as "the point of better effect of the present invention"), the number of the convex portions 16 is preferably 0.20/cm ² or less. As the lower limit, 0.001 pieces/cm ² may be mentioned. In addition, the number/cm ² represents the number of convex portions ^{per 1 cm 2} of the surface 14 a of the polyimide resin layer 14. As a method of calculating the number of the above-mentioned protrusions 16, firstly, an offline defect inspection system (FPI-6000 series) (model: FPI6090D) manufactured by Orbotech is used to obtain a map of all defects on the surface 14a of the polyimide resin layer 14 Like data and coordinate data. Then, calculate the length of the long side and the length of the short side of the defect based on the acquired data. After that, all the defects were observed with a microscope (OLE4100) manufactured by Olympus, and the height of the defects was calculated from the difference with the flat part. After that, calculate the number of protrusions in a specific range based on the obtained long-side length, short-side length and height data of each defect.

In addition, based on FIG. 3, the length of the long side and the length of the short side of the convex portion 16 will be described. 3 is a view of the convex portion 16 viewed from the normal direction of the surface 14a of the polyimide resin layer 14. As shown in FIG. In FIG. 3, the convex portion 16 has an elliptical shape. Next, as shown in Fig. 3, among the two parallel tangents circumscribed to the outer circumference of the convex portion 16, the distance between the two parallel tangents selected in such a way that the tangent distance is the largest is set as the long side length L. The two parallel tangents of a fixed length L are orthogonal and circumscribed to the outer circumference of the convex portion 16. Among the two parallel tangents, the distance between the tangents of the parallel two tangents is selected to be the shortest distance between the tangents. Side length S. In addition, in FIG. 3, the shape of the convex portion 16 when viewed from the normal direction of the surface 14a 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 round or polygonal. Shape, no fixed shape.

In addition, the elements contained in the convex portion 16 can be measured using SEM-EDX (Scanning Electron Microscope/Energy Dispersive X-ray Spectroscopy). 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 the elements contained in the protrusions 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 does the convex portion 16 contain C and O elements and the content of C and O in the polyimide resin layer 14 at positions other than the convex portion 16 Compare and test.

Based on the point of making the effect of the present invention better, in the above-mentioned protrusions, the long side length is 10 μm or more and less than 50 μm, the short side length is less than 50 μm, the height is less than 1 μm, and contains at least 1 of Na and Cl. The number of the first protrusions (hereinafter, also referred to as "first protrusions") of the element is preferably 0.15/cm ² or less, more preferably 0.10/cm ² or less, and even more preferably 0.07/cm ² Below, it is still more preferable to be 0.05 pieces/cm ² or less. As the lower limit, 0.001 pieces/cm ² may be mentioned. Although the details of the cause of the first protrusion are unknown, based on the types of elements it contains, it is presumed to be derived from human sweat. Elements other than Na and Cl may be contained in the first protrusion, and examples include C and O.

Based on the better effect of the present invention, in the above-mentioned protrusions, the long side length is 3 μm or more and less than 20 μm, the short side length is less than 20 μm, and the height is less than 5 μm, and contains at least one of Si and Al The number of second protrusions of the element (hereinafter also referred to as "second protrusions") is preferably 0.25/cm ² or less, more preferably 0.20/cm ² or less, and still more preferably 0.15/cm ² Below, 0.10 pieces/cm ² or less are particularly preferable, and 0.07 pieces/cm ² or less are still more preferable. As the lower limit, 0.001 pieces/cm ² may be mentioned. Although the details of the cause of the second protrusion are unknown, it is estimated that it is derived from a glass supporting substrate based on the types of elements contained. Elements other than Si and Al may be contained in the second convex portion, and examples include C and O.

Based on the better effect of the present invention, among the above-mentioned protrusions, the protrusions other than the first protrusion and the second protrusion, that is, the length of the long side is 3 μm or more and less than 50 μm, and the length of the short side is less than 50 μm. a height of 1 μm or less of the third projecting portion (hereinafter, also referred to as the "third protrusion") of the amount is preferably 0.30 / cm ² or less, more preferably 0.25 pieces / cm ² or less, and further more preferably 0.20 Pieces/cm ² or less, particularly preferably 0.15 pieces/cm ² or less. As described above, the third convex portion is a convex portion that does not conform to the specific size of any one of the first convex portion and the second convex portion. As the lower limit of the number of the third protrusions, 0.001/cm ² may be mentioned. Specific examples of the types of elements contained in the third protrusion include Ca, Fe, Ti, Cr, Ni, and Cu. The third protrusion preferably contains at least one of the elements listed above. . Although the details of the cause of the third protrusion are unknown, it is presumed that the environment contains fine particles of the elements exemplified above, and metal powders such as SUS.

On the surface 14a of the polyimide resin layer 14, the length of the long side shown in FIG. 2 is 3 to 1000 μm, the length of the short side is 20 μm or less, and the number of recesses 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 recess 18, over 0 μm can be mentioned. Among them, based on the better effect of the present invention, the number of recesses 18 is preferably 0.07/cm ² or less. As the lower limit, 0.001 pieces/cm ² may be mentioned. As a method for calculating the number of recesses 18, an offline defect inspection system (FPI-6000 series (model: FPI609D)) manufactured by Orbotech was used to obtain image data of all defects in the entire surface 14a of the polyimide resin layer 14 and Coordinate data. Then, calculate the length of the long side and the length of the short side of the defect based on the acquired data. After that, all the defects were observed with a laser microscope (OLE4100) manufactured by Olympus, and the depth of the defect was calculated from the difference with the flat part. Then, according to the obtained long-side length, short-side length and depth data of each defect, the number of recesses in a specific range is calculated.

The length of the long side and the length of the short side of the concave 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, among the two parallel tangents circumscribed to the outer circumference of the recess 18, the distance between the two parallel tangents selected in such a way that the distance between the tangents is the largest is the long side length L, and the distance between the two parallel tangents and the given length L The two parallel tangents are orthogonal to each other and circumscribed to the outer circumference of the recess 18. The distance between the tangents of the two parallel tangents is selected to maximize the distance between the tangents as the short side length S. In addition, the shape of the recess 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 polygonal shape, or an unfixed shape.

Preferably, there is no convex portion larger than the convex portion 16 on the surface 14 a of the polyimide resin layer 14. A convex part larger than the convex part 16 means a convex part having a long side length of 50 μm or more, or a short side length of 50 μm or more, or a height exceeding 5 μm. In addition, it is preferable that the surface 14a of the polyimide resin layer 14 does not have a concave portion larger than the concave portion 18. A concave portion larger than the concave portion 18 means a concave portion whose long side length exceeds 1000 μm, or the short side length exceeds 20 μm, or the depth exceeds 1 μm.

[Manufacturing method of the first example of multilayer substrate] As the method of manufacturing the laminated substrate of the first example, there is no particular limitation as long as the polyimide resin layer is formed in the number of the above-mentioned specific protrusions and recesses, but it is preferable to laminate the polyimide resin on the support base. The method on the surface of the material. In addition, it is preferable to coat the well-known silane coupling agent on the surface of the supporting substrate before laminating the polyimide resin on the surface of the supporting substrate, and then to coat the supporting substrate with the silane coupling agent. The polyimide resin layer is laminated on the surface of the material.

In addition, as a method of manufacturing a multilayer substrate, it is more preferable to bond a film-like polyimide resin layer and a supporting base material to produce a multilayer substrate, and even more preferably the following method: The laminated film of the amide resin layer and the protective film arranged on the surface of one of the polyimide resin layers is bonded to the supporting substrate to obtain a supporting substrate, a polyimide resin layer and a protective film arranged in sequence The laminated body is peeled off from the laminated body, and a laminated substrate is manufactured (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 supporting base material is protected by the protective film, it prevents foreign matter from adhering to the polyimide resin layer during the manufacture of the laminated substrate. The surface on the opposite side of the base material may be damaged. As a result, it is easy to obtain the desired multilayer substrate. When the film-like polyimide resin layer is bonded to the supporting substrate, it is preferable to implement it in a roll to roll method based on the excellent productivity.

As a method of adjusting the number of protrusions and recesses within a specific range, a method of adjusting the formation conditions of the polyimide resin layer, or a method of performing a cleaning treatment on a build-up substrate described later can be exemplified. In addition, it is preferable to perform a heat treatment on the multilayer substrate, and then to perform a cleaning treatment on the surface of the polyimide resin on the side opposite to the supporting base material. Among them, it is preferable that after obtaining the multilayer substrate by the above-mentioned method X, heat treatment is performed on the multilayer substrate, and thereafter, the surface of the polyimide resin layer on the opposite side of the support substrate is subjected to cleaning treatment. By performing heat treatment, volatile components in and on the surface of the polyimide resin layer are removed, and the generation of volatile components during the manufacture of electronic devices can be suppressed. Particularly, when the laminated substrate is manufactured by the roll-to-roll method in the method X, since the temperature cannot be increased during bonding and volatile components tend to remain in the polyimide resin layer, it is preferable to perform the above-mentioned heat treatment. In addition, by washing the surface of the polyimide resin layer on the side opposite to the support base material, it is possible to remove the foreign matter that may become the convex portion or the foreign matter that may cause the concave portion.

In addition, as the protective film used in the method X, a peelable resin film is preferable. In the method X, in order to prevent the generation of static electricity when the protective film is peeled off, it is preferable to use a static electricity removing device such as an ionizer to remove electricity. If static electricity is generated, foreign matter may adhere to the polyimide resin layer. By using a static electricity removal device, the attachment of the foreign matter can be suppressed. In addition, in the above, the method of using the static electricity removal device has been described, but it is also possible to implement a method of increasing the humidity (humidity: 70% or more) to suppress the generation of static electricity. By performing the above-mentioned treatment, the number of the above-mentioned first or third convex parts can be reduced in particular.

When performing the above-mentioned heat treatment, a heating device is usually used. When arranging the multilayer substrate in the heating device, it is preferable to arrange the multilayer 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 build-up substrate can be prevented from adhering to the polyimide resin layer. By performing the above-mentioned processing, it is possible to reduce the number of the above-mentioned first to third convex parts in particular.

In addition, as specific examples of the heating device used, a hot air heating device and an infrared heating device can be cited. Among them, when using a hot-air heating device, sometimes foreign matter may also move on the surface of the polyimide resin on the opposite side of the support substrate due to the hot air, resulting in recesses. Therefore, in order to reduce the number of recesses, it is better to use infrared rays. heating equipment.

As the conditions of the heating 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 side opposite to the supporting substrate, it is preferable to use a brush for cleaning. By performing the above-mentioned processing, the number of the above-mentioned second and third convex parts can be reduced in particular. As the cleaning treatment, either dry cleaning or wet cleaning can be used, and wet cleaning is preferred. As a specific example of the detergent when performing wet cleaning, an aqueous alkali solution can be mentioned. For wet cleaning, it is better to use a brush. As a specific example of the brush used, a roller brush and a disk brush can be mentioned. Among them, when a roller brush is used, sometimes the end of the bristle tip of the roller brush wipes the surface of the polyimide resin layer on the opposite side of the support substrate to produce recesses. Therefore, it is preferable to reduce the number of recesses. Use a disk brush. The rotation speed when using the brush is not particularly limited, but when using a disc brush, it can be about 300 rpm.

It is possible to carry out cleaning treatment while conveying the multilayer substrate. As the conveying speed, 1 to 10 m/min can be mentioned. During the cleaning process, the multilayer substrate can be fixed by a fixing mechanism such as a nip roller. At this time, in order to reduce the number of recesses, it is preferable to fix the multilayer substrate so 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 fixes the build-up substrate only in contact with the supporting base material. In addition, in order to perform the above-mentioned cleaning treatment, the surface of the polyimide resin layer on the opposite side of the support substrate may be subjected to a hydrophilization treatment such as corona treatment. By applying hydrophilization treatment, the cleaning effect is improved.

[The second example of multilayer substrate] 4 is a cross-sectional view schematically showing the second example of the multilayer substrate of 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. The laminated substrate 10 of the second example is compared with the laminated substrate 10 shown in FIG. 1, except for the silicone resin layer 13 between the supporting base material 12 and the polyimide resin layer 14, and the laminated substrate 10 shown in FIG. The substrate 10 is the same.

In the laminated substrate 10 of the second example, a supporting base 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 12 a of the support base 12, and a polyimide resin layer 14 is provided on the surface 13 a 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 12a of the support substrate 12. In the laminated substrate 10 of the second example, the supporting base 12 and the silicone resin layer 13 function as a reinforcing plate for reinforcing the polyimide resin layer 14.

When heat treatment is performed on the laminated substrate 10, it is preferable that the adhesion force between the support base 12 and the silicone resin layer 13 be 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 substrate 12 with the hydroxyl groups of the silicone resin layer 13 by heat treatment. As a result, if a force is applied in the direction in which the support base 12 and the polyimide resin layer 14 are peeled off, 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 multilayer 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 of the polyimide resin layer. Specifically, the following method is preferred: a curable composition containing curable silicone is applied to the back surface (the side opposite to the surface 14a) of the polyimide resin layer in the form of a film, and the resulting coating film is cured After the silicone resin layer is obtained by the treatment, a supporting base material is laminated on the back surface of the silicone resin layer (the side opposite to the surface 13a), thereby manufacturing a laminated substrate. In more detail, the method of manufacturing the laminated substrate of the second example has at least the following steps: a curable silicone layer is formed on the back side of the polyimide resin layer (the side opposite to the surface 14a), and then placed 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 substrate on the back side of the silicone resin layer (the side opposite to the surface 13a) (layering step). Hereinafter, the above-mentioned steps will be described in detail.

The resin layer forming step is a step of forming a curable silicone layer on the back of the polyimide resin layer, and forming a silicone resin layer on the back 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 the so-called roll-to-roll method in which the silicone resin layer is formed on the back of the polyimide resin layer wound into a roll shape, and the production efficiency is excellent. In this step, in order to form a curable silicone layer on the back surface of the polyimide resin layer, the aforementioned curable composition is applied to the back surface of the polyimide resin layer. Next, it is preferable to perform a hardening treatment on the hardenable silicone layer, thereby forming a hardened layer. Specific examples of the method of coating the curable composition on the back surface of the polyimide resin layer include spray coating, die coating, spin coating, dip coating, roll coating, bar coating, and mesh coating. Plate printing method and gravure printing coating method. Next, the curable silicone coated on the back surface of the polyimide resin layer is cured to form a silicone resin layer.

The curing method for forming the silicone resin layer is not particularly limited, and the best treatment is appropriately performed according to the type of curable silicone used. For example, in the case of using a condensation reaction type silicone and an additional reaction type silicone, as the hardening treatment, a thermal hardening treatment is preferable. The conditions of the thermal curing treatment are implemented within the range of the heat resistance of the polyimide resin layer. For example, the temperature conditions of the thermal curing are preferably 50-400°C, more preferably 100-300°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 layering step is a step of supporting the substrate on the surface area of the silicone resin layer. As a specific example of the method of laminating the supporting base material on the back surface of the silicone resin layer, a method of laminating the supporting base material on the back surface of the silicone resin layer in a normal pressure environment can be exemplified. It is also possible to overlap the supporting substrate on the back of the silicone resin layer as needed, and then use a roller or a pressing member to crimp the supporting substrate to the silicone resin layer. Compression bonding by rolling or pressing is relatively easy to remove air bubbles mixed between the silicone resin layer and the supporting substrate, which is preferable. If pressure bonding is performed by a vacuum lamination method or a vacuum pressing method, mixing of bubbles can be suppressed and good adhesion can be achieved, which is preferable. By crimping under vacuum, it also has the advantage that the bubbles are not easy to grow due to heat treatment even when tiny bubbles remain. When laminating the support substrate, it is preferable to thoroughly clean the surface of the support substrate in contact with the silicone resin layer, and to perform the lamination in a relatively clean environment.

In addition, as a method for manufacturing the laminated substrate of the second example, the following method is particularly preferable: a laminated film provided with a polyimide resin layer in the form of a film and a protective film arranged 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 to obtain a silicone resin layer, and then support the substrate on the back surface of the silicone resin layer, and 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 from the laminated body to manufacture a laminated substrate. In the method of using the protective film as described above, since the protective film protects the surface of the polyimide resin layer on the side opposite to the supporting base material, it prevents foreign matter from adhering to the polyimide resin layer when manufacturing the multilayer substrate. The surface on the opposite side of the substrate is supported, or surface damage occurs. As a result, it is easy to obtain the desired multilayer substrate. The manufacturing method of the silicone resin layer and the method of supporting the substrate on the back surface area of the silicone resin layer are as described above. In addition, the protective film used above can exemplify the form described in the first example. As described in the first example, in order to prevent the generation of static electricity when the protective film is peeled off, it is preferable to use a static electricity removing device such as an ionizer to remove electricity. In addition, as in the first example, it is preferable to perform a heat treatment on the build-up substrate, and thereafter, perform a cleaning treatment on the surface of the polyimide resin layer on the side opposite to the support base material.

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

＜Support base material＞ The supporting substrate 12 made of glass is a member that supports and reinforces the polyimide resin layer 14 and functions as a transport substrate. The supporting substrate 12 is constituted by, for example, a glass plate. The type of glass is preferably alkali-free borosilicate glass, borosilicate glass, soda lime glass, high silica glass, and oxide-based glass mainly composed of other silica. As the oxide-based glass, a glass having a silicon oxide content of 40 to 90% by mass in terms of oxide is preferred. As the glass, a glass plate containing alkali-free borosilicate glass (manufactured by AGC Co., Ltd., trade name "AN100") can be mentioned more specifically. As a manufacturing method of a glass plate, the method of generally melting glass raw materials and shaping the molten glass into a plate shape can be mentioned. Such a forming method may be general, and examples thereof include a float method, a melting method, and a flow hole down-drawing 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 to make the thickness of the support base 12 thicker than the polyimide resin layer 14. Since the supporting base 12 is required to function as a reinforcing plate and a substrate for conveying, it is preferably inflexible. Therefore, the thickness of the supporting substrate 12 is preferably 0.3 mm or more, more preferably 0.5 mm or more. On the other hand, the thickness of the support base 12 is preferably 1.0 mm or less.

<Polyimide resin layer> The polyimide resin layer 14 contains a polyimide resin, and a polyimide film is used, for example. 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 be 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 even more preferably 10 nm or less. As the lower limit of the surface roughness Ra, 0.01 nm or more can be mentioned. Based on the operability of the manufacturing process, 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 1 mm or less, more preferably 0.2 mm or less. Since the difference between the coefficient of thermal expansion of the polyimide resin layer 14 and the coefficient of thermal expansion of the support base 12 is smaller, the deflection after heating or cooling can be suppressed, which is preferable. Specifically, the difference in thermal expansion coefficient between the polyimide resin layer 14 and the support base 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 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 rectangular or circular. In addition, the polyimide resin layer 14 can be formed with 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).

＜Silicone resin layer＞ The silicone resin layer 13 mainly contains silicone resin. The structure of the silicone resin is not particularly limited. The silicone resin is usually obtained by curing (crosslinking and curing) a curable silicone that is cured into a silicone resin. As specific examples of curable silicone, according to its curing mechanism, condensation reaction type silicone, additive reaction type silicone, ultraviolet curing type silicone, and electron beam curing type silicone can be exemplified. 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 method of manufacturing the silicone resin layer 13, as described above, the following method is preferred: the back surface of the polyimide resin layer 14 (the surface opposite to the surface 14a) is coated with curability that becomes the aforementioned silicone resin. For the curable composition of silicone, if necessary, the solvent is removed to form a coating film, and the curable silicone in the coating film is cured, and the silicone resin layer 13 is formed. In addition to the curable silicone, the curable composition may also contain a solvent, a platinum catalyst (in the case of using an additional reactive silicone as the curable silicone), a leveling agent, a metal compound, and the like. Specific examples of metal elements contained in the metal compound include 3d transition metals, 4d transition metals, lanthanide metals, bismuth, aluminum, and tin. Adjust the content of metal compounds appropriately.

The thickness of the silicone resin layer 13 is preferably 100 μm or less, more preferably 50 μm or less, and still 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 4 μm or more. The above-mentioned thickness is obtained by measuring the thickness of the silicone resin layer 13 at any position above 5 points with a contact-type film thickness measuring device, and performing arithmetic average of these.

＜Use of multilayer substrates＞ As the application of the multilayer substrate 10, a display device, a receiving sensor panel, a solar cell, a thin-film secondary cell, an integrated circuit, etc., which will be described later, can be exemplified. There is also a case where the laminated substrate 10 is exposed to a high temperature condition of 450° C. or more for more than 20 minutes in an atmospheric atmosphere. 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 light receiving sensor panel, and an infrared receiving sensor panel. When used in the case of receiving a sensor panel, the polyimide resin layer can also be reinforced with a reinforcing sheet such as resin.

As described above, using the multilayer substrate of the present invention, an electronic device including a polyimide resin layer and an electronic device member is manufactured. As a manufacturing method of an electronic device, the following method can be exemplified: for example, a member for an electronic device is formed on a polyimide resin layer in a build-up substrate, and the supporting base material is peeled from the obtained build-up substrate with a member for an electronic device, and An electronic device having a polyimide resin layer and a member for an electronic device was obtained. In addition, the above-mentioned electronic device member is a member that constitutes at least a part of the electronic device.

In the following, a case where the multilayer substrate 10 of the second example is used is taken as an example to describe the present invention in more detail, but the same applies to the case of using the multilayer substrate 10 of the first example.

The manufacturing method of the electronic device is preferably the following method: forming the electronic device member 20 on the polyimide resin layer 14 of the build-up substrate 10, and after obtaining the build-up substrate 22 with the electronic device member, the silicone resin layer 13 and The interface of the polyimide resin layer 14 is used as a peeling surface, and the obtained laminated substrate 22 with a component for electronic devices is separated into an electronic device (substrate 24 with a component) and a support base 26 with a silicone resin layer. The step of forming the member 20 for an electronic device is called a "member forming step", and the step of separating the substrate 24 with a member and the support base 26 with a silicone resin layer is called a "separating step". In the following, the materials and procedures 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 multilayer substrate 10. More specifically, as shown in FIG. 5, a member 20 for an electronic device is formed on the surface 14a of the polyimide resin layer 14 to obtain a laminated substrate 22 with a member for an electronic device. First, the electronic device component 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 a member that is formed on the polyimide resin layer 14 in the multilayer substrate 10 and constitutes at least a part of the electronic device. More specifically, as the electronic device member 20, a member used for a display device, a receiving sensor panel, a solar cell, a thin-film secondary battery, an integrated circuit, etc. (for example, a display device such as LTPS, etc. Receiving sensor panel member, solar cell member, thin film secondary battery member, and integrated circuit circuit), for example, the solar energy described in paragraph [0192] of the specification of U.S. Patent Application Publication No. 2018/0178492 The battery member, the thin-film secondary battery member described in the same paragraph [0193], and the electronic component circuit described in the same paragraph [0194].

The manufacturing method of the above-mentioned multilayer substrate 22 with a member for electronic device is not particularly limited. According to the type of the constituent member of the member for electronic device, a previously known method is applied to the surface 14a of the polyimide resin layer 14 of the multilayer substrate 10 A member 20 for an electronic device is formed thereon. The electronic device member 20 may be a part of all the members (hereinafter, referred to as "partial member"), instead of all the members that are finally formed on the surface 14a of the polyimide resin layer 14 (hereinafter, referred to as "all members") . It is also possible to set the substrate with partial components peeled from the silicone resin layer 13 as a substrate with all components (equivalent to an electronic device) in a subsequent step. Other electronic device components can be formed on the substrate with all components peeled from the silicone resin layer 13 on the peeled surface. Furthermore, it is also possible to align the two electronic device components of the laminated substrate with the electronic device components to each other, attach the two to assemble the laminated body with all the components, and then attach the two pieces of silicone The supporting substrate of the resin layer is peeled off from the laminate with all the components to manufacture the electronic device.

For example, taking the case of manufacturing OLED as an example, it is performed to form an organic EL structure on the surface (surface 14a) of the polyimide resin layer 14 of the build-up substrate 10 on the side opposite to the silicone resin layer 13 side. A transparent electrode is formed, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, etc. are vapor-deposited 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. As specific examples of the formation or treatment of these layers, film formation treatment, vapor deposition treatment, bonding treatment of a sealing plate, etc. may be mentioned.

The separation step is shown in FIG. 6 as the following steps: the interface between the silicone resin layer 13 and the polyimide resin layer 14 is used as the peeling surface, and the laminated substrate 22 with the electronic device obtained from the above-mentioned member forming step is separated into a laminated layer There are the polyimide resin layer 14 of the electronic device member 20 (the substrate 24 with the member), and the support base 26 with the silicone resin layer, to obtain the electronic device member 20 and the polyimide resin layer 14 of the substrate 24 (electronic device).

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

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, and after a peeling opportunity is given, a mixed fluid of water and compressed air can be blown to peel off. It is preferable to arrange the laminated substrate 22 with the electronic device member on the flat plate so that the supporting base 12 becomes the upper side and the electronic device member 20 side becomes the lower side, and the electronic device member 20 side is vacuum sucked on the flat plate In this state, the blade is first intruded into the interface between the polyimide resin layer 14 and the silicone resin layer 13. After that, a plurality of vacuum suction pads are used to suck the support substrate 12 side, and the vacuum suction pads are sequentially raised from the vicinity of the position where the blade is inserted. In this way, the support base 26 with the silicone resin layer can be easily peeled off.

When the substrate 24 with a component is separated from the laminated substrate 22 with a component for an electronic device, by controlling the blowing or humidity of the ionizer, it is possible to further prevent the fragments of the silicone resin layer 13 from being electrostatically attracted to the substrate 24 with the component. The above-mentioned manufacturing method of the electronic device (substrate 24 with component) is more suitable for the manufacture of the display device described in paragraph [0210] of the specification of US Patent Application Publication No. 2018/0178492, for example, as the substrate 24 with component Examples are as described in the paragraph [0211]. [Example]

In the following, the present invention will be specifically described with examples, but the present invention is not limited by these examples. Examples 1 to 7 and 9 to 15 described later are examples, and Example 8 is a comparative example.

＜Evaluation of the durability of the device＞ The organic EL display device obtained from the laminated substrate of each example was stored in an environment of 60°C and 90% RH, and the storage time of black spots was compared. Those with enlarged black spots for less than 500 hours were evaluated as ×, those with enlarged black spots for 500 hours or more and less than 1000 hours were evaluated as ○, and those with enlarged black spots for more than 1000 hours were evaluated as ⊚.

<Example 1> (Preparation of curable 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, it was further heated to 60°C and reacted for 12 hours. After the obtained crude reaction liquid was cooled to 25°C, the crude reaction liquid was washed 3 times with water (300 g). Trimethylsilyl chloride (70 g) was added to the washed crude reaction solution, and the mixture was stirred at 25°C for 20 minutes, and then heated to 50°C to react for 12 hours. After the obtained crude reaction liquid was cooled to 25°C, the crude reaction liquid was washed 3 times with water (300 g). The toluene was removed under reduced pressure from the reaction crude liquid after washing, and the slurry was put into a slurry state, and then dried in a vacuum dryer overnight to obtain a white organopolysiloxane compound, namely, curable silicone 1. The number of T units of the sclerosing silicone 1: the number of M units=87:13 (molar ratio). In addition, the M unit means a monofunctional organosilicon alkoxy unit represented _{by (R) 3} SiO _1/2. The T unit means a _{trifunctional organosilicon alkoxy unit represented by RSiO 3/2} (R represents a hydrogen atom or an organic group).

(Preparation of curable composition) The curable silicon 1 is mixed with hexane, and an organic zirconium compound (zirconium octoate compound) and an organic bismuth compound (bismuth 2-ethylhexanoate) are further added. The amount of solvent is adjusted so that the solid content concentration is 50% by mass. In addition, the addition amount of the metal compound was adjusted so that the metal element was 0.01 parts by mass relative to 100 parts by mass of the resin. The curable composition was obtained by filtering the resulting mixed liquid with a filter with a pore size of 0.45 μm.

(Production of multilayer body) Peel off one of the polyimide films (manufactured by Toyobo Co., Ltd., trade name "XENOMAX") with a thickness of 0.015 mm 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 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, the glass plate "AN100" (supporting base material), a 200×200 mm thick 0.5 mm glass plate, is washed with a water-based glass cleaner (manufactured by Parkercorp Co., Ltd., "PK-LCG213"), and then washed with pure water. The polyimide film formed with the silicone resin layer is laminated in a roll-to-roll manner to produce a laminated body in which a glass plate, a silicone resin layer, a polyimide film, and a protective film are sequentially arranged.

(Heat treatment and cleaning treatment) The laminate was transported to a heating device, and before being placed in the heating device, the protective film was peeled off, standing in the heating device, and heating at 450° C. for 0.5 hours. After the heat treatment, the laminated substrate was taken out from the heating device, corona treatment was applied to the surface of the polyimide resin layer, and then cleaning treatment with a roller brush was applied to obtain the laminated substrate 1. During the cleaning process, in order to prevent the build-up substrate from moving in the cleaning machine, the build-up substrate is fixed by a fixing mechanism (nip roller). At this time, the fixing mechanism is in contact with the surface of the polyimide resin layer. In addition, when peeling off the protective film, in order to prevent the generation of static electricity, an ionizer is used to reduce the surface charge of the polyimide resin layer. Hereinafter, the countermeasure using an ionizer is referred to as "countermeasure A". In addition, during the heat treatment, the laminated substrate is arranged such that the polyimide resin layer faces downward in the heating device. Hereinafter, the countermeasure for arranging the multilayer substrate with the polyimide resin layer facing downward is referred to as "countermeasure B". In addition, the countermeasure for implementing the corona treatment and cleaning treatment described above is referred to as "countermeasure C". As the heating device, an infrared heating device is used. Hereinafter, the countermeasure using an infrared heating device is referred to as "countermeasure D".

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

In Tables 1 and 2, the case where each countermeasure is implemented is set to "Yes", and the case where each countermeasure is not implemented is set to "None". For example, in Example 2 where the countermeasure C is "None", after the heat treatment, the corona treatment and the cleaning treatment are not performed. In addition, in Example 3 where the countermeasure B is "None", when arranging the multilayer substrate in the heating device, the multilayer substrate is arranged so that the polyimide resin layer faces upward. In addition, in Example 4 where the countermeasure A is "None", the protective film is peeled without using an ionizer. In addition, in Example 10 where the countermeasure D is "None", a hot air heating device is used as the heating device. In addition, in Example 11 where the countermeasure E is "None", a fixing mechanism in contact with the surface of the polyimide resin layer is used. In addition, in Example 12 where the countermeasure F is "None", the cleaning process using a roller brush is implemented.

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 second protrusions on the surface of the polyimide resin layer mentioned above. The number of 2 convex parts and the third convex part (pcs/cm ² ). "Number of convex parts" means the number (total number) of convex parts on the surface of the polyimide resin layer (pieces/cm ² ). "Number of recesses" means the number (total number) of recesses 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 device (equivalent to electronic device)＞ Using the multilayer substrates obtained in Examples 1-15, organic EL display devices were manufactured according to the following procedures. First, on the surface of the polyimide resin layer of the build-up substrate on the opposite side of the glass plate, silicon nitride, silicon oxide, Amorphous silicon. Then, a low-concentration boron is implanted into the amorphous silicon layer by an ion doping device, heat treatment is performed, and dehydrogenation treatment is performed. Then, the crystallization treatment of the amorphous silicon layer is performed by the laser annealing device. Then, by using an etching and ion doping device using photolithography, low-concentration phosphorus is implanted into the amorphous silicon layer to form N-type and P-type TFT (Thin Film Transistor) regions. Next, on the side opposite to the glass plate side of the polyimide resin layer, a silicon oxide film was formed by plasma CVD to form a gate insulating film, and then a molybdenum film was formed by sputtering. The etching of the lithography method forms the gate electrode. Then, by means of photolithography and ion doping devices, high concentrations of phosphorus and boron are implanted into each desired region of N-type and P-type to form a source region and a drain region. Next, on the side opposite to the glass plate side of the polyimide resin layer, a plasma CVD method is used to form a silicon oxide film to form an interlayer insulating film, an aluminum film is formed by a sputtering method, and a photolithography method is used for etching TFT electrodes are formed. Next, heat treatment is performed in a hydrogen atmosphere, and after the hydrogenation treatment is performed, a silicon nitride film is formed by a plasma CVD method to form a passivation layer. Next, on the side opposite to the glass plate side of the polyimide resin layer, an ultraviolet curable resin is applied, and a planarization layer and contact holes are formed by photolithography. Next, an indium tin oxide film is formed by a sputtering method, and a pixel electrode is formed by etching using a photolithography method. Then, by the vapor deposition method, 4,4',4''-tris(3-methylphenyl) as the hole injection layer is sequentially formed on the side of the polyimide resin layer opposite to the glass plate side. Phenylamino) triphenylamine, bis[(N-naphthyl)-N-phenyl]-benzidine as a hole transport layer, in 8-hydroxyquinoline aluminum complex (Alq3) as a light-emitting layer , Mix 40% by volume of 2,6-bis[4-[N-(4-methoxyphenyl)-N-phenyl]aminostyrene]naphthalene-1,5-dicarbonitrile (BSN-BCN) Those, Alq3 as the electron transport layer. Next, an aluminum film is formed by a sputtering method, and a counter electrode is formed by etching using a photolithography method. Next, on the side opposite to the glass plate side of the polyimide resin layer, another glass plate is bonded and sealed via an ultraviolet-curing adhesive layer. Through the above procedure, an organic EL structure is formed on the polyimide resin layer. A structure having an organic EL structure on the polyimide resin layer (hereinafter referred to as panel A.) is a laminated substrate with a member for an electronic device of the present invention. Next, after vacuuming the sealing body side of panel A on the flat plate, insert a stainless steel cutting tool with a thickness of 0.1 mm into the interface between the polyimide resin layer and the silicone resin layer at the corner of panel A, The interface between the resin layer and the silicone resin layer provides an opportunity for peeling. In addition, after the surface of the supporting substrate of the panel A is adsorbed by the vacuum adsorption pad, the adsorption is lifted. Here, while blowing the static elimination fluid from an ionizer (manufactured by Keyence Corporation) to the interface, insert the tool. Next, continue to blow the static elimination fluid from the ionizer to the formed gap, and at the same time, while injecting water into the peeling front line, the vacuum adsorption pad is lifted on the other side. As a result, only the polyimide resin layer on which the organic EL structure is formed remains on the flat plate, and the supporting substrate with the silicone resin layer can be peeled off. Then, using a laser cutter or a scribing-slicing method, the separated polyimide resin layer is cut and divided into a plurality of units, and then the polyimide resin layer forming the organic EL structure is assembled With the counter substrate, the module forming step is implemented to fabricate 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 Countermeasure A Have Have Have no no Have no no Countermeasure B Have Have no Have no no Have no Countermeasure C Have no Have Have Have no no no Number of first 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 Number of protrusions 0.14 0.44 0.29 0.28 0.43 0.59 0.58 0.73 Recess Countermeasure D Have Have Have Have Have Have Have no Countermeasure E no no no no no no no no Countermeasure F no no no no no no no no Number of recesses (total) 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.19 Device durability ◎ ○ ○ ○ ○ ○ ○ X

[Table 2] Table 2 Example 9 Example 10 Example 11 Example 12 Example 13 Example 14 Example 15 Convex Countermeasure A Have Have Have Have Have Have Have Countermeasure B no no no no no no no Countermeasure C no no no no no no no Number of first 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 Number of protrusions 0.59 0.59 0.59 0.59 0.59 0.59 0.59 Recess Countermeasure D Have no Have Have no Have no Countermeasure E Have Have no Have no no Have Countermeasure F Have Have Have no Have no no Number of recesses (total) 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 a specific build-up substrate, it is confirmed that the desired effect is obtained.

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

10: Multilayer substrate 12: Support substrate 12a: surface 13: Silicone resin layer 13a: surface 14: Polyimide resin layer 14a: surface 16: Convex 18: recess 20: Components for electronic devices 22: Multilayer substrate with components for electronic devices 24: Substrate with components 26: Supporting base material with silicone resin layer L: length S: length

FIG. 1 is a cross-sectional view schematically showing the first example of the multilayer substrate of 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 of the embodiment of the present invention. Fig. 3 is a diagram for explaining the length of the long side and the length of the short side of the convex portion. 4 is a cross-sectional view schematically showing the second example of the multilayer substrate of the embodiment of the present invention. Fig. 5 is a cross-sectional view schematically showing the steps of forming a member. Fig. 6 is a cross-sectional view schematically showing the separation step.

Claims (9)

A laminated substrate comprising a supporting substrate made of glass, and a polyimide resin layer arranged on the supporting substrate, and on the surface of the polyimide resin layer opposite to the supporting substrate, The length of the long side is 3 μm or more and less than 50 μm, the length of the short side is less than 50 μm, and the number of protrusions with a height of 5 μm or less is 0.60/cm ² or less, and the length of the long side is 3～1000 μm, short The 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. Such as the multilayer substrate of claim 1, wherein in the above-mentioned protrusions, the length of the long side is 10 μm or more and less than 50 μm, the length of the short side is less than 50 μm, and the height is less than 1 μm, and contains at least one of Na and Cl The number of the first protrusions of the element is 0.15/cm ² or less. For example, the multilayer substrate of claim 1 or 2, wherein in the above-mentioned protrusions, the long side length is 3 μm or more and less than 20 μm, the short side length is less than 20 μm, and the height is less than 5 μm, and contains at least Si and Al The number of second protrusions of one element is 0.25/cm ² or less. Such as the laminated substrate of claim 3, wherein among the above-mentioned convex parts, the convex parts other than the above-mentioned first convex part and the above-mentioned second convex part, that is, the length of the long side is 3 μm or more and less than 50 μm, and the length of the short side is less than 50 μm, the number of third protrusions with a height of 1 μm or less is 0.30/cm ² or less. The laminated substrate according to any one of claims 1 to 4, wherein the number of the above-mentioned protrusions is 0.20 pcs/cm ² or less. The laminated substrate according to any one of claims 1 to 5, wherein the number of the above-mentioned recesses is 0.07/cm ² or less. A method of manufacturing an electronic device, comprising the steps of: forming a member for an electronic device on the surface of the polyimide resin layer of the laminated substrate of any one of claims 1 to 6 on the side opposite to the supporting base material , And obtain a component forming step of a multilayer substrate with components for electronic devices; and A separation step of obtaining an electronic device having the above-mentioned polyimide resin layer and the above-mentioned electronic device member from the above-mentioned laminated substrate with the member for electronic device. A method for manufacturing a multilayer substrate, which is the method for manufacturing a multilayer substrate according to any one of claims 1 to 6, and The film-like polyimide resin layer is bonded to the supporting base material to produce the laminated substrate. The method for manufacturing a laminated substrate according to claim 8, wherein a laminated film having the polyimide resin layer in a film shape, and a protective film arranged on one surface of the polyimide resin layer, and the supporting base material By bonding, a laminate in which the supporting base material, the polyimide resin layer, and the protective film are arranged in this order is obtained, and the protective film is peeled from the laminate to produce the laminate substrate.

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