KR102510793B1 - Laminated substrate, method for manufacturing laminate, laminate, laminate with components for electronic devices, method for manufacturing electronic devices - Google Patents

Abstract

The present invention has a support substrate made of glass, and an adsorption layer disposed on the support substrate, and on the surface of the support substrate on the adsorption layer side, there is a peripheral region in which the adsorption layer is not disposed, and the adsorption layer is disposed on the support substrate side. It has a first main surface, a second main surface opposite to the first main surface, and an end surface connected to the first main surface and the second main surface, and the end surface protrudes from the second main surface toward the first main surface. And, the angle formed by the inclined surface and the first main surface is less than 10°, and relates to a laminated substrate. In the multilayer substrate of the present invention, when a polyimide film is formed by applying a polyimide varnish on the surface thereof, peeling of the formed polyimide film is less likely to occur.

Description

Laminate substrate, method for manufacturing a laminate, laminate, laminate with a member for electronic devices, method for manufacturing an electronic device

The present invention relates to a laminated substrate, a method for manufacturing a laminate, a laminate, a laminate with an electronic device member, and a method for manufacturing an electronic device.

solar cell (PV); liquid crystal panels (LCDs); Organic EL panels (OLED); A receiving sensor panel that detects electromagnetic waves, X-rays, ultraviolet rays, visible rays, infrared rays, and the like; BACKGROUND ART Thinning and weight reduction of electronic devices such as these are progressing. In connection with it, the thinning of board|substrates, such as a polyimide resin board used for electronic devices, is also advancing. If the strength of the substrate is insufficient due to thinning, the handleability of the substrate may decrease, causing problems in the process of forming a member for an electronic device on the substrate (member formation process) or the like.

Then, in recent years, in order to improve the handleability of the substrate, a technique of using a laminate in which a polyimide resin substrate is disposed on a supporting substrate has been proposed (Patent Document 1). More specifically, in Patent Document 1, a polyimide varnish is applied on a thermosetting resin composition cured body layer, a resin varnish cured film (corresponding to a polyimide film) is formed, and precision elements are disposed on the resin varnish cured film. What can be done is disclosed.

Japanese Unexamined Patent Publication No. 2018-193544

On the other hand, when the present inventors performed a process for producing a polyimide film by applying the polyimide varnish described in Patent Document 1, it was found that peeling of the polyimide film is easy to occur when the polyimide film is formed by applying the polyimide varnish. did In particular, it was found that peeling easily occurs at the end of the polyimide film.

An object of the present invention is to provide a laminated board in which peeling of the formed polyimide film is unlikely to occur when a polyimide film is formed by applying a polyimide varnish on the surface thereof.

This invention also makes it a subject to provide the manufacturing method of a laminated body, a laminated body, a laminated body with a member for electronic devices, and the manufacturing method of an electronic device.

As a result of earnest examination, the inventors of the present invention found that the above-described problems could be solved by the following structures.

(1) a support substrate made of glass, and an adsorption layer disposed on the support substrate;

On the surface of the support substrate on the side of the adsorption layer, there is a peripheral region where no adsorption layer is disposed;

The adsorption layer has a first main surface on the supporting substrate side, a second main surface on the opposite side to the first main surface, and an end face connected to the first main surface and the second main surface,

The end face is an inclined surface protruding from the second main surface toward the first main surface,

A laminated substrate wherein an angle formed between an inclined surface and a first principal surface is less than 10°.

(2) The laminated substrate according to (1), wherein the thickness between the first main surface and the second main surface of the adsorption layer is 50 µm or less.

(3) The laminated substrate according to (1), wherein the adsorption layer has a thickness between the first main surface and the second main surface of 12 µm or less.

(4) The laminated substrate according to (1), wherein the adsorption layer has a thickness between the first main surface and the second main surface of 6 µm or more.

(5) The laminated substrate according to (1), wherein the angle between the inclined surface and the first principal surface is 5° or less.

(6) The laminated substrate according to any one of (1) to (5), wherein the width of the edge region is 1 to 30 mm.

(7) The laminated substrate according to any one of (1) to (6), wherein the adsorption layer is a silicone resin layer.

(8) The laminated substrate according to any one of (1) to (7) further comprising a protective film disposed on the adsorption layer.

(9) a bonding step of the supporting substrate and the transfer film, in which a transfer film having a precursor film serving as an adsorption layer is bonded onto the supporting substrate, and at this time, the supporting substrate is disposed so as to have a peripheral region in which the precursor film is not disposed, and the precursor film The method for manufacturing a laminated substrate according to any one of (1) to (5), comprising a precursor film heating step for obtaining an adsorbed layer from the above.

(10) A polyimide varnish containing polyimide or a precursor thereof and a solvent is applied to the adsorption layer side of the multilayer substrate described in any one of (1) to (7) to form a polyimide film on the peripheral region and on the adsorption layer. A method for producing a laminate, comprising forming a laminate having a supporting substrate, an adsorption layer, and a polyimide film in this order.

(11) The laminated substrate according to any one of (1) to (7);

A laminate having a polyimide film disposed on a peripheral region and an adsorption layer in a laminated substrate.

(12) the laminate according to (11);

A laminate with a member for electronic devices having a member for electronic devices disposed on the polyimide film in the laminate.

(13) A member forming step of forming a member for electronic devices on the polyimide film of the laminate described in (11) to obtain a laminate with members for electronic devices;

The manufacturing method of an electronic device provided with the separation process of obtaining the electronic device which has a polyimide film and the member for electronic devices from the laminated body with the member for electronic devices.

According to the present invention, when a polyimide film is formed by applying a polyimide varnish on its surface, it is possible to provide a laminated board in which peeling of the formed polyimide film is unlikely to occur.

ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of a laminated body, a laminated body, a laminated body with a member for electronic devices, and the manufacturing method of an electronic device can be provided.

1 is a cross-sectional view schematically showing one embodiment of a laminated substrate of the present invention.
Fig. 2 is a top view of the laminated substrate shown in Fig. 1;
Fig. 3 is a cross-sectional view schematically showing one embodiment of the laminate of the present invention.
4 is a view for explaining a member forming process;
5 is a diagram for explaining a separation process;

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described with reference to drawings. However, as for this invention, the following embodiment is illustrative for demonstrating this invention, and is not limited to the embodiment described below. In addition, various modifications and substitutions can be made to the following embodiments without departing from the scope of the present invention.

A numerical range expressed using "to" means a range including the numerical values described before and after "to" as the lower limit and the upper limit.

Characteristic points of the laminated board of the present invention are that the end surface of the adsorption layer is an inclined plane, the inclination angle of the inclined plane is adjusted within a predetermined range, and the peripheral edge where the adsorption layer is not disposed on the surface of the supporting base material. It can be mentioned that the area is being prepared.

The present inventors have found that desired effects can be obtained by employing the above structures. Although the details of obtaining the desired effect are unknown, first, a peripheral region is provided on the surface of the supporting base material, and the polyimide film is placed on a laminated substrate so that the peripheral region and the polyimide film are in contact with each other, thereby forming a polyimide film and a glass supporting base material. Based on the interaction, it is thought that the separation of the polyimide film and the edge is suppressed. In addition, it is thought that by providing an inclined surface having a predetermined inclination angle at the end, generation of voids or the like between the polyimide film, the adsorption layer, and the supporting substrate is suppressed, and as a result, peeling of the polyimide film is suppressed.

<Laminate board>

1 is a cross-sectional view schematically showing one embodiment of a laminated substrate of the present invention. FIG. 2 is a top view of the laminated board shown in FIG. 1;

The laminated substrate 10 includes a support substrate 12 made of glass and an adsorption layer 14 disposed on the support substrate 12 .

1 and 2, the adsorption layer 14 has a first main surface 14a on the supporting substrate 12 side, a second main surface 14b on the opposite side to the first main surface 14a, and , and has an end face 14c connected to the first main surface 14a and the second main surface 14b.

The end surface 14c of the adsorption layer 14 is an inclined surface projecting from the second main surface 14b toward the first main surface 14a. In addition, the shape of the adsorbing layer 14 (shape of the main surface) is rectangular, and all four end surfaces 14c are inclined surfaces.

1 and 2, on the surface of the support substrate 12 on the side of the adsorption layer 14, there is a peripheral region 12a where the adsorption layer 14 is not disposed. In other words, the adsorbing layer 14 is disposed on the supporting substrate 12 so that a frame-shaped region (periphery region 12a) not in contact with the adsorbing layer 12 remains on the supporting substrate 12 .

In the above aspect, the area of the area where the adsorption layer 14 is placed is smaller than the area of the surface (main surface) of the supporting substrate 12, and the peripheral area 12a is inside the outer periphery of the supporting substrate 12 corresponds to the area located in

1 and 2, both the shape of the supporting base material 12 (shape of the main surface) and the shape of the adsorption layer 14 (the shape of the main surface) are rectangular, constituting the outer periphery of the supporting base material 12. The adsorption layer 14 is disposed on the supporting substrate 12 so that one side constituting the outer periphery of the adsorption layer 14 is parallel to one side of the adsorption layer 14 .

Although described in detail later, polyimide varnish is applied on the peripheral region of the support substrate 12 of the laminated substrate 10 and on the second main surface 14b of the adsorption layer 14, and then the polyimide film is applied. is formed A member for electronic devices is formed on this polyimide film, and then the polyimide film (namely, electronic device) on which the member for electronic devices is formed is isolate|separated. In this way, an electronic device is manufactured.

Hereinafter, each layer constituting the laminated substrate 10 (support substrate 12 and adsorption layer 14) will be described in detail, and then the manufacturing method of the laminated substrate 10 will be described in detail. .

(supporting material)

The supporting substrate 12 is a member that supports and reinforces the polyimide film, and is, for example, a glass plate.

As the kind of glass, alkali-free borosilicate glass, borosilicate glass, soda-lime glass, high-silica glass, and other oxide-based glasses containing silicon oxide as a main component are preferable. As oxide type glass, the glass whose content of silicon oxide by oxide conversion is 40-90 mass % is preferable.

More specifically, as a glass plate, the glass plate (brand name "AN100" by AGC Co., Ltd., "AN Wizus") etc. which consist of alkali-free borosilicate glass are mentioned.

The manufacturing method of a glass plate is obtained by melting glass raw materials normally and shape|molding molten glass into plate shape. Such a molding method may be a general one, and examples thereof include a float method, a fusion method, and a slot down-draw method.

The shape (shape of the main surface) of the supporting substrate 12 is not particularly limited, but is preferably rectangular.

As described above, the adsorption layer 14 is not disposed on the peripheral region 12a of the surface of the supporting substrate 12 . That is, the surface of the peripheral region 12a of the support substrate 12 is exposed.

The width W of the edge region 12a is not particularly limited, but is preferably 1 to 30 mm, and more preferably 3 to 10 mm. As shown in FIG. 2 , the width W of the edge region 12a corresponds to the distance from the outer periphery of the supporting substrate 12 to the outer periphery of the adsorption layer 14 .

If the width of the edge region 12a is 30 mm or less, the effective area at the time of forming an electronic device described later becomes wider, and the manufacturing efficiency of the electronic device is improved. Further, when the width of the edge region 12a is 1 mm or more, peeling of the polyimide film is more difficult to occur.

The supporting substrate 12 preferably has low flexibility. Therefore, the thickness of the supporting substrate 12 is preferably 0.3 mm or more, and more preferably 0.5 mm or more.

On the other hand, as for the thickness of the support base material 12, 1.0 mm or less is preferable.

(adsorption layer)

The adsorption layer 14 is a film for preventing peeling of the polyimide film disposed thereon.

The adsorbing layer 14 is disposed on the supporting substrate 12 so that a peripheral region 12a not in contact with the adsorbing layer 12 remains on the supporting substrate 12 .

As described above, the end surface 14c of the adsorption layer 14 is an inclined surface projecting from the second main surface 14b toward the first main surface 14a. It is preferable that all of the plurality of end surfaces 14c are inclined surfaces.

In the adsorption layer 14, the angle θ between the inclined surface and the first main surface 14a is less than 10°. Especially, the angle θ is preferably 8° or less, and more preferably 5° or less, from the viewpoint of more suppressing peeling of the polyimide film when the polyimide film is formed by applying the polyimide varnish. The lower limit is not particularly limited, but is preferably 1° or more.

The angle θ formed by the inclined surface and the first main surface 14a in the adsorption layer 14 was determined by using a non-contact surface property measuring device “PF-60” manufactured by Mitaka Koki Co., Ltd. of the adsorption layer 14. It is obtained from the cross-sectional shape. More specifically, as shown in FIG. 1 , the length of the line segment AB and the length of the line segment AC are measured from the sectional view of the adsorption layer 14, and the angle θ is calculated from the following formula.

θ = arctan(AC/AB)

The adsorption layer 14 may be an organic layer or an inorganic layer.

Examples of the material of the organic layer include acrylic resins, polyolefin resins, polyurethane resins, polyimide resins, silicone resins, polyimide silicone resins, and fluororesins. In addition, the adsorption layer 14 may be constituted by mixing several types of resins.

Examples of the material of the inorganic layer include oxides, nitrides, oxynitrides, carbides, carbonitrides, silicides, and fluorides. Examples of oxides (preferably metal oxides), nitrides (preferably metal nitrides), and oxynitrides (preferably metal oxynitrides) include Si, Hf, Zr, Ta, Ti, Y, Nb, Oxides, nitrides, acids of at least one element selected from Na, Co, Al, Zn, Pb, Mg, Bi, La, Ce, Pr, Sm, Eu, Gd, Dy, Er, Sr, Sn, In, and Ba. Nitrides are mentioned.

Examples of the carbides (preferably metal carbides) and carbonitrides (preferably metal carbonitrides) include carbides and carbonitrides of at least one element selected from Ti, W, Si, Zr, and Nb; Carbonates are mentioned.

As a silicide (preferably, a metal silicide), the silicide of 1 or more types of elements selected from Mo, W, and Cr is mentioned, for example.

As a fluoride (preferably a metal fluoride), the fluoride of one or more types of elements selected from Mg, Y, La, and Ba is mentioned, for example.

The adsorption layer 14 may be a plasma polymerization film.

When the adsorption layer 14 is a plasma polymerization film, the material forming the plasma polymerization film is CF ₄ , CHF ₃ , C ₂ H ₆ , C ₃ H ₆ , C ₂ H ₂ , CH ₃ F, C ₄ H ₈ , etc. of fluorocarbon monomers, hydrocarbon monomers such as methane, ethane, propane, ethylene, propylene, acetylene, benzene, and toluene, hydrogen, and SF ₆ .

Among them, from the viewpoint of heat resistance and peelability, as the material of the adsorption layer 14, a silicone resin and a polyimide silicone resin are preferable, a silicone resin is more preferable, and a silicone resin formed of condensation reaction type silicone is more preferable. .

Hereinafter, an aspect in which the adsorption layer is a silicone resin layer will be described in detail.

The silicone resin is a resin containing a predetermined organosiloxy unit, and is usually obtained by curing curable silicone. Curable silicone is classified into addition reaction type silicone, condensation reaction type silicone, ultraviolet curable silicone and electron beam curing type silicone according to their curing mechanism, but all can be used. Especially, condensation reaction type silicone is preferable.

As the condensation-reactive silicone, a monomeric hydrolysable organosilane compound or a mixture thereof (monomer mixture), or a partially hydrolyzed condensation product obtained by subjecting a monomer or monomer mixture to a partial hydrolytic condensation reaction (organopolysiloxane) can be preferably used. can

A silicone resin can be formed by advancing a hydrolysis/condensation reaction (sol-gel reaction) using this condensation reaction type silicone.

The adsorption layer 14 is preferably formed using a curable composition containing curable silicone.

The curable composition may contain, in addition to the curable silicone, a solvent, a platinum catalyst (when an addition reaction type silicone is used as the curable silicone), a leveling agent, a metal compound, and the like. As a metal element contained in a metal compound, a 3d transition metal, a 4d transition metal, a lanthanoid metal, bismuth (Bi), aluminum (Al), and tin (Sn) are mentioned, for example. The content of the metal compound is not particularly limited and is appropriately adjusted.

The adsorption layer 14 preferably has a hydroxyl group. A part of the Si-O-Si bonds constituting the silicone resin of the adsorption layer 14 may be broken, and a hydroxyl group may appear. In the case of using condensation-reactive silicone, the hydroxyl group can be used as the hydroxyl group of the adsorption layer 14.

The thickness between the first main surface 14a and the second main surface 14b of the adsorption layer 14 is preferably 50 μm or less, more preferably 30 μm or less, and still more preferably 12 μm or less. On the other hand, the thickness of the adsorbent layer 14 is preferably more than 1 µm, and more preferably 6 µm or more in terms of more excellent foreign matter embedment properties. The above thickness is obtained by measuring the thickness of the adsorption layer 14 at five or more arbitrary positions with a contact-type film thickness measuring device and arithmetic average of them.

In addition, excellent foreign material embedding property means that even if a foreign material exists between the supporting base material 12 and the adsorption layer 14, the foreign material is embedded by the adsorption layer 14. If the embedding property of foreign matter is excellent, convexities due to foreign matter are less likely to occur in the adsorption layer, and when the member for electronic device is formed on the polyimide film, the risk of disconnection or the like in the member for electronic device due to the convexity is suppressed. do. In addition, since the void formed when the convex portion is generated is observed as a bubble, the foreign matter embeddability can be evaluated by the presence or absence of the bubble.

When a polyimide film is formed on the support substrate 12 made of glass and subjected to high-temperature heat treatment, the polyimide film turns yellow, making application to a transparent electronic device difficult. By the way, although the mechanism is unclear, by forming the adsorption layer 14 on the glass and forming the polyimide film on the adsorption layer 14, yellowing of the polyimide film due to high-temperature heat treatment can be suppressed.

(protective film)

The laminated substrate 10 may have a protective film disposed so as to cover the adsorption layer 14 .

The protective film is a film that protects the surface of the adsorption layer 14 until a polyimide varnish described later is applied on the adsorption layer 14 .

As a material constituting the protective film, for example, polyimide resin, polyester resin (eg polyethylene terephthalate (PET), polyethylene naphthalate), polyolefin resin (eg polyethylene, polypropylene), polyurethane Resin can be mentioned. Especially, a polyester resin is preferable and a polyethylene terephthalate is more preferable.

The thickness of the protective film is preferably 20 μm or more, more preferably 30 μm or more, and still more preferably 50 μm or more, in order to reduce the influence of external force. As an upper limit of the thickness of a protective film, 500 micrometers or less are preferable, 300 micrometers or less are more preferable, and 100 micrometers or less are still more preferable.

The protective film may further have an adhesive layer on the surface on the adsorption layer 14 side.

As the adhesive layer, a known adhesive layer can be used. Examples of the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer include (meth)acrylic pressure-sensitive adhesives, silicone-based pressure-sensitive adhesives, and urethane-based pressure-sensitive adhesives.

In addition, the adhesive layer may be comprised of resin, and as resin, for example, vinyl acetate resin, ethylene-vinyl acetate copolymer resin, vinyl chloride-vinyl acetate copolymer resin, (meth)acrylic resin, butyral resin, polyurethane A resin and a polystyrene elastomer are mentioned.

The surface roughness (Ra) of the protective film is preferably 50 nm or less, more preferably 30 nm or less, still more preferably 15 nm or less, since the peeling force when the protective film is peeled is reduced. Ra is preferably 0.1 nm or more, and more preferably 0.5 nm or more, since the protective film and the adsorption layer can maintain close contact. Surface roughness (Ra) is measured using a non-contact surface/layer cross-sectional shape measurement system "Vertscan R3300-lite" manufactured by Ryoka Systems Co., Ltd.

<Method of manufacturing laminated board>

The manufacturing method of the laminated substrate is not particularly limited, and publicly known methods can be cited.

Among them, in terms of higher productivity, a transfer film having a temporary support and a precursor film that becomes an adsorption layer after heat treatment disposed on the temporary support is prepared, and the precursor film in the transfer film is bonded to a predetermined position on a glass support substrate. Then, a method of performing a heat treatment on a laminate having a glass supporting base material, a precursor film, and a temporary support body obtained is exemplified. By performing the heat treatment, the edge of the precursor film is fluidized, and the adsorption layer having the above-described predetermined inclined surface is formed. In addition, when bonding the precursor film onto the supporting substrate, the precursor film is bonded onto the supporting substrate so that the above-mentioned peripheral region is formed.

In addition to the above, an adsorption layer having the above-described predetermined inclined surface is formed by disposing a precursor film to become an adsorption layer after heat treatment at a predetermined position on a glass support substrate by application, and performing heat treatment.

Examples of the precursor film include a film formed by applying a curable composition containing curable silicone and subjecting the formed coating film to heat treatment. The heating temperature for the heat treatment of the coating film is preferably 50 to 200°C, and the heating time is preferably 5 to 20 minutes.

As described above, by subjecting the precursor film to heat treatment, the shape of the end surface of the adsorption layer can be made into an inclined surface. In addition, in the case of heat treatment, it is preferable to carry out while applying pressure. Specifically, it is preferable to perform heat treatment and pressure treatment using an autoclave.

The heating temperature in the heat treatment is preferably 50 to 350°C, more preferably 55 to 300°C, and still more preferably 60 to 250°C. As heating time, 10 to 60 minutes are preferable, and 20 to 40 minutes are more preferable.

As the pressure at the time of the pressure treatment, 0.5 to 1.5 MPa is preferable, and 0.8 to 1.0 MPa is more preferable.

In addition, you may perform heat treatment multiple times. In the case of performing the heat treatment a plurality of times, you may change each heating condition.

For example, when performing heat treatment multiple times, you may change heating temperature. For example, when heat treatment is performed twice, the first heat treatment may be performed under temperature conditions of less than 100°C, and the second heat treatment may be performed under temperature conditions of 100°C or higher.

In addition, when performing heat treatment multiple times, you may change the presence or absence of pressure treatment. For example, when heat processing is performed twice, a form in which a pressure treatment is performed together in the heat treatment of the first time, and a pressure treatment is not performed in the heat treatment of the second time may be used.

In addition, when manufacturing a laminated substrate using a transfer film, the heat treatment may be performed after the temporary support is peeled off, or the heat treatment may be performed while the temporary support is disposed on the adsorption layer. In addition, when performing heat treatment multiple times, you may peel a temporary support body between each heat treatment. For example, after performing the heat treatment of the first time, the temporary support may be peeled off and the heat treatment of the second time may be performed.

Surface treatment may be performed on the surface of the adsorption layer of the laminated substrate.

As surface treatment, corona treatment, plasma treatment, and UV ozone treatment are mentioned, for example, and corona treatment is preferable.

As will be described later, when a polyimide film is formed on the adsorption layer, the surface roughness (Ra) of the adsorption layer is preferably 50 nm or less, more preferably 30 nm or less, because the surface roughness of the polyimide film is reduced. 15 nm or less is more preferable. Further, Ra is preferably 0.1 nm or more, and more preferably 0.5 nm or more, since the polyimide film and the adsorption layer can maintain close contact.

Using the laminated substrate 10 described above, a structure having the support substrate 12, the adsorption layer 14, and the support material in this order can be manufactured. As the support material, materials other than the polyimide film 18 can also be laminated. As the support material, for example, polyimide resin film, epoxy resin film, photosensitive resist, polyester resin film (eg polyethylene terephthalate, polyethylene naphthalate), polyolefin resin film (eg polyethylene, polypropylene) , polyurethane resin film, metal foil (eg copper foil, aluminum foil), sputter film (eg copper, titanium, aluminum, tungsten, silicon nitride, silicon oxide, amorphous silicon), TGV substrate, thin glass substrate , thin glass substrates with a sacrificial layer, ABF, sapphire substrates, silicon substrates, TSV substrates, LED chips, display panels (eg LCD, OLED, µ-LED), artificial diamonds, laminates, and the like.

<Laminate and manufacturing method thereof>

Using the laminated substrate 10 described above, the laminate 16 including the supporting substrate 12, the adsorbing layer 14, and the polyimide film 18 shown in FIG. 3 can be manufactured.

Specifically, as a method of manufacturing the laminate 16, a polyimide varnish containing polyimide and a solvent is applied to the adsorbed layer 14 side of the laminated substrate 10, and adsorbed onto the peripheral region 12a. A method of forming a polyimide film 18 on the layer 14 to form a laminate having the support substrate 12, the adsorption layer 14, and the polyimide film 18 in this order is mentioned. there is.

Below, the manufacturing method described above will be described in detail, and then the configuration of the polyimide film 18 will be described in detail.

(polyimide varnish)

A polyimide varnish contains polyimide or its precursor, and a solvent.

A polyimide is usually obtained by polycondensing tetracarboxylic dianhydride and diamine and imidating it. As polyimide, what has solvent solubility is preferable.

Examples of tetracarboxylic dianhydride to be used include aromatic tetracarboxylic dianhydride and aliphatic tetracarboxylic dianhydride. As diamine to be used, aromatic diamine and aliphatic diamine are mentioned.

As aromatic tetracarboxylic dianhydride, for example, pyromellitic anhydride (1,2,4,5-benzenetetracarboxylic dianhydride), 3,3',4,4'-benzophenone tetracarboxylic acid dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, and 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride.

Examples of the aliphatic tetracarboxylic dianhydride include cyclic or acyclic aliphatic tetracarboxylic dianhydride, and examples of the cyclic aliphatic tetracarboxylic dianhydride include 1,2,3,4-cyclobutanetetracarboxylic dianhydride. , 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 1,2,4,5-cyclopentanetetracarboxylic dianhydride, etc. are mentioned. Examples of acyclic aliphatic tetracarboxylic dianhydride include , 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-pentanetetracarboxylic dianhydride, and the like.

As aromatic diamine, for example, 4,4'-oxydiaminobenzene (4,4'-diaminodiphenyl ether), 1,3-bis-(3-aminophenoxy)benzene, 4,4'-bis -(3-aminophenoxy)biphenyl, 1,4-diaminobenzene, and 1,3-diaminobenzene.

Examples of the aliphatic diamine include acyclic aliphatic diamines such as ethylenediamine, hexamethylenediamine, polyethylene glycol bis(3-aminopropyl) ether and polypropylene glycol bis(3-aminopropyl) ether, and 1,3-bis(aminomethyl)cyclo and cyclic aliphatic diamines such as hexane, 1,4-bis(aminomethyl)cyclohexane, isophoronediamine, and norbornanediamine.

The precursor of polyimide means polyamic acid (so-called polyamic acid and/or polyamic acid ester) in a state before imidation.

The solvent may be any solvent that dissolves polyimide or a precursor thereof, and examples thereof include phenolic solvents (eg m-cresol) and amide solvents (eg N-methyl-2-pyrrolidone, N ,N-dimethylformamide, N,N-dimethylacetamide), lactone solvents (eg, γ-butyrolactone, δ-valerolactone, ε-caprolactone, γ-crotonolactone, γ-hexa Nolactone, α-methyl-γ-butyrolactone, γ-valerolactone, α-acetyl-γ-butyrolactone, δ-hexanolactone), sulfoxide-based solvents (e.g., N,N-dimethyl sulfoxide), ketone solvents (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone), ester solvents (eg, methyl acetate, ethyl acetate, butyl acetate, dimethyl carbonate). can

(procedure)

The method of applying the polyimide varnish to the adsorption layer 14 side of the laminated substrate 10 is not particularly limited, and a known method may be used. For example, spray coating method, die coating method, spin coating method, dip coating method, roll coating method, bar coating method, screen printing method, and gravure coating method are mentioned.

After application, heat treatment may be performed if necessary.

As conditions for heat treatment, the temperature conditions are preferably 50 to 500°C, and more preferably 50 to 450°C. The heating time is preferably 10 to 300 minutes, and more preferably 20 to 200 minutes.

In addition, you may perform heat treatment multiple times. In the case of performing the heat treatment a plurality of times, you may change each heating condition.

(Laminate)

As shown in FIG. 3 , the laminate 16 includes a supporting substrate 12 , an adsorption layer 14 , and a polyimide film 18 .

The configurations of the supporting substrate 12 and the adsorption layer 14 are as described above.

The polyimide film 18 is disposed on the peripheral region of the support substrate 12 and on the adsorption layer 14 (on the second main surface 14b and end surface 14c of the adsorption layer 14).

The thickness of the polyimide film 18 is preferably 1 μm or more, and more preferably 5 μm or more. From the point of flexibility, 1 mm or less is preferable, and 0.2 mm or less is more preferable.

In order to form high-precision wiring and the like of electronic devices on the polyimide film 18, the surface of the polyimide film 18 is preferably smooth. Specifically, the surface roughness Ra of the polyimide film 18 is preferably 50 nm or less, more preferably 30 nm or less, still more preferably 10 nm or less.

As for the coefficient of thermal expansion of the polyimide film 18, a smaller difference in coefficient of thermal expansion with the supporting base material 12 is preferable because warpage of the layered product 16 after heating or cooling can be suppressed. Specifically, the difference in thermal expansion coefficient between the polyimide film 18 and the supporting substrate 12 is preferably 0 to 90 × 10 ^-6 /°C, and more preferably 0 to 30 × 10 ^-6 /°C.

The area of the polyimide film 18 is not particularly limited, but is preferably 300 cm 2 or more from the viewpoint of productivity of the electronic device.

The polyimide film 18 may be colored or colorless and transparent.

The laminate 16 can be used for various purposes, and is used for manufacturing electronic components such as display panels, PVs, thin-film secondary batteries, semiconductor wafers with circuits formed on the surface, and receiving sensor panels, which will be described later. can be heard In these uses, there are cases where the laminate is exposed (eg, 20 minutes or longer) under high temperature conditions (eg, 450°C or higher) in an atmospheric atmosphere.

Panels for display devices include LCD, OLED, electronic paper, plasma display panels, field emission panels, quantum dot LED panels, micro LED display panels, MEMS shutter panels, and the like.

The receiving sensor panel includes an electromagnetic wave receiving sensor panel, an X-ray receiving sensor panel, an ultraviolet light receiving sensor panel, a visible light receiving sensor panel, an infrared light receiving sensor panel, and the like. The substrate used for the receiving sensor panel may be reinforced with a reinforcing sheet made of resin or the like.

<Method of manufacturing electronic device>

Using the laminate, an electronic device including a polyimide film and a member for an electronic device described later is manufactured.

As shown in FIGS. 4 and 5 , for example, the manufacturing method of the electronic device is on the polyimide film 18 of the laminate 16 (on the adsorption layer 14 side of the polyimide film 18). On the opposite surface), the member forming step of forming the electronic device member 20 to obtain the electronic device member provided laminate 22, and from the electronic device member equipped laminate 22, the polyimide film ( 18) and a method comprising a separation step of obtaining the electronic device 24 having the member 20 for electronic devices.

Hereinafter, the process of forming the electronic device member 20 is referred to as a "member formation process", and the process of separating the electronic device 24 and the support base material 26 with an adsorption layer is referred to as a "separation process".

Below, the material and procedure used in each process are demonstrated in detail.

(member forming process)

The member formation process is a process of forming a member for electronic devices on the polyimide film 18 of the laminate 16 . More specifically, as shown in FIG. 4, the electronic device member 20 is placed on the polyimide film 18 (on the surface of the polyimide film 18 on the opposite side to the adsorption layer 14 side). It forms and obtains the laminated body 22 with the member for electronic devices.

In addition, a barrier layer may be formed on the polyimide film 18 to improve the reliability of the electronic device. The material of the barrier layer is not particularly limited, and known materials can be used. Examples of the material constituting the barrier layer include silicon nitride and silicon oxide. In addition, the barrier layer may consist of one layer, two or more layers, or a combination of a plurality of materials. The method for forming the film is not particularly limited, and known methods may be used. For example, methods such as plasma CVD and sputtering may be used.

First, the member 20 for electronic devices used at this process is demonstrated in detail, and the procedure of a process is demonstrated in detail after that.

(Material for electronic devices)

The electronic device member 20 is a member constituting at least a part of an electronic device formed on the polyimide film 18 of the laminate 16 . More specifically, as the electronic device member 20, a member used for a panel for a display device, a solar cell, a thin film secondary battery, or an electronic component such as a semiconductor wafer having a circuit formed on its surface, a receiving sensor panel, etc. (eg For example, a member for a display device such as LTPS, a member for a solar cell, a member for a thin film secondary battery, a circuit for an electronic component, a member for a receiving sensor), for example The member for solar cells described in paragraph [0192], the member for thin-film secondary batteries described in paragraph [0193], and the circuit for electronic components described in paragraph [0194] are exemplified.

(Sequence of process)

The manufacturing method of the above-mentioned laminate 22 with a member for electronic device is not particularly limited, and the polyimide film 18 of the laminate 16 is a conventionally known method depending on the type of the constituent member of the member for electronic device. The member 20 for electronic devices is formed on it.

Even if the member 20 for electronic devices is not all of the members finally formed in the polyimide film 18 (hereinafter referred to as "all members"), but a part of all members (hereinafter referred to as "partial members"). do. The substrate with partial members separated from the adsorption layer 14 can also be used as a substrate with full members (corresponding to an electronic device described later) in a subsequent step.

On the substrate with all materials separated from the adsorption layer 14, another electronic device member may be formed on the peeling surface. Further, the electronic device members 20 of the two electronic device member equipped laminates 22 are opposed to each other, both are bonded to assemble a full member equipped laminated body, and then from the full member equipped laminated body. An electronic device can also be manufactured by peeling the support base material with an adsorption layer of 2 sheets.

For example, in the case of manufacturing an OLED, in order to form an organic EL structure on the surface of the polyimide film 18 of the laminate 16 opposite to the adsorption layer 14 side, a transparent electrode is used. various layer formation and processing such as depositing a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, etc. on the surface on which the transparent electrode is formed, forming a back electrode, and sealing with a sealing plate. It is done. As these layer formation and processing, specifically, a film-forming process, a vapor deposition process, the bonding process of a sealing plate, etc. are mentioned, for example.

(separation process)

As shown in FIG. 5, in the separation step, the interface between the adsorption layer 14 and the polyimide film 18 is used as a peeling surface from the laminate 22 with members for electronic devices obtained in the member formation step, An electronic device comprising the electronic device member 20 and the polyimide film 18 separated into the polyimide film 18 on which the electronic device member 20 is laminated and the support substrate 26 provided with an adsorption layer ( 24) is the process of obtaining

In the case where the electronic device member 20 on the peeled polyimide film 18 is a part of formation of a required precursor member, the remaining constituent members can also be formed on the polyimide film 18 after separation.

A method of separating the polyimide film 18 and the adsorption layer 14 is not particularly limited. For example, a sharp blade-like object is inserted into the interface between the polyimide film 18 and the support base material 12 to provide an opportunity for peeling, and then a mixed fluid of water and compressed air can be sprayed to separate it.

Preferably, the laminated body 22 with members for electronic devices is installed on a surface plate so that the supporting base material 12 is on the upper side and the member 20 side for electronic devices is on the lower side, and the member 20 side for electronic devices is placed thereon. is vacuum adsorbed on the platen, and in this state, the blade-like material is first penetrated into the interface between the polyimide film 18 and the supporting substrate 12. After that, the supporting base material 12 side is adsorbed with a plurality of vacuum suction pads, and the vacuum suction pads are raised sequentially from the vicinity of the portion where the blade-like object was inserted. In that case, the support substrate 26 with an adsorption layer can be easily peeled off.

When the electronic device 24 is separated from the electronic device member-attached laminate 22, the pieces of the adsorption layer 14 are electrostatically absorbed by the electronic device 24 by controlling the spraying by the ionizer and the humidity. can be more suppressed.

The manufacturing method of the electronic device described above is suitable for manufacturing the display device described in, for example, paragraph [0210] of the specification of US Patent Application Publication No. 2018/0178492, and as the electronic device 24, for example, the same paragraph [ 0211].

In addition, before performing the said separation process, you may cut and remove the area|region where the member for electronic devices of a laminated body is not arrange|positioned.

[Example]

The present invention will be specifically described below by examples and the like, but the present invention is not limited by these examples.

Below, as a supporting base material, a glass plate (coefficient of linear expansion of 38×10 ^-7 /°C, trade name "AN100" manufactured by AGC Co., Ltd.) made of non-alkali borosilicate glass was used.

Hereinafter, Examples 1 to 5 are Examples, and Examples 6 to 7 are Comparative Examples.

<Appearance evaluation>

The polyimide film in the laminated body having the glass plate, the silicone resin layer, and the polyimide film in this order obtained in the procedure at the later stage was visually observed and evaluated according to the following criteria.

A: Peeling of the polyimide film did not occur.

B: Although peeling occurred in a part of the polyimide film, it was within a range that had no problem in practical use.

C: Peeling occurred on most or the entire surface of the polyimide film, but it was within the range of no problem in practical use.

<Evaluation of the width of the leading area>

The width of the peripheral region of the supporting substrate was evaluated according to the following criteria.

A: The width is 1 mm or more and 10 mm or less

B: Width greater than 10 mm and 30 mm or less

C: width greater than 30 mm and less than 1 mm

<Foreign Substance Embedding>

The glass plate, the silicone resin layer, and the laminated body in which the PET film were arranged in this order were visually observed and evaluated according to the following criteria.

A: The number of bubbles at the interface between the glass plate and the silicone resin layer due to foreign matter was 5 or less.

B: The number of interfacial bubbles due to foreign matter at the glass plate/silicone resin layer interface was more than 5 and was 10 or less.

C: There were more than 10 interfacial bubbles due to foreign matter at the glass plate/silicone resin layer interface.

<Example 1>

(Preparation of curable silicone)

Triethoxymethylsilane (179 g), toluene (300 g), and acetic acid (5 g) were added to a 1 L flask, and the mixture was stirred at 25°C for 20 minutes, then heated to 60°C and reacted for 12 hours. After the obtained reaction crude liquid was cooled to 25°C, the reaction crude liquid was washed 3 times with water (300 g). Chlorotrimethylsilane (70 g) was added to the washed reaction crude liquid, and the mixture was stirred at 25°C for 20 minutes, then heated to 50°C and reacted for 12 hours. After the obtained reaction crude liquid was cooled to 25°C, the reaction crude liquid was washed 3 times with water (300 g). Toluene was distilled off under reduced pressure from the washed reaction crude liquid to form a slurry, and then cured silicone 1 as a white organopolysiloxane compound was obtained by drying overnight in a vacuum dryer. Curable silicone 1 was the number of T units: the number of M units = 87:13 (molar ratio). In addition, M unit means the 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 Curable Composition)

Curable silicone 1 and heptane were mixed, and an organic zirconium compound (octyl acid zirconium compound) and an organic bismuth compound (2-ethylhexanoate bismuth) were added. The amount of solvent was adjusted so that the solid content concentration would be 50% by mass. In addition, the addition amount of the metal compound was adjusted so that the metal element was 0.1 part by mass with respect to 100 parts by mass of the resin. A curable composition was obtained by filtering the obtained liquid mixture using a filter having a pore diameter of 0.45 µm.

Curable silicone 1 and heptane were mixed, and an organic zirconium-based compound (octyl acid zirconium compound) and an organic cerium-based compound (2-ethyl cerium hexanoate) were added. The amount of solvent was adjusted so that the solid content concentration would be 50% by mass. In addition, the addition amount of the metal compound was adjusted so that the metal element was 0.1 part by mass with respect to 100 parts by mass of the resin. A curable composition was obtained by filtering the obtained liquid mixture using a filter having a pore diameter of 0.45 µm.

(Manufacture of laminated board)

A silicone resin layer was formed by applying the prepared curable composition on the surface of a polyethylene terephthalate film (PET film) (Cosmo Shine A4100, manufactured by Toyobo Co., Ltd.) and heating at 140°C for 10 minutes using a hot plate. The thickness of the silicone resin layer was 8 µm.

Subsequently, a 200 × 200 mm, 0.5 mm thick glass plate "AN100" (support substrate) washed with pure water after washing with an aqueous glass cleaner ("PK-LCG213" manufactured by Parker Corporation), and a silicone resin layer The formed PET films were bonded together to prepare a laminate in which a glass plate, a silicone resin layer, and a PET film were arranged in this order. Moreover, in the case of the said bonding, bonding was performed so that the area|region where a silicone resin layer is not arrange|positioned may remain in the edge area of the surface of a glass plate (refer FIG. 2). The width W of the peripheral region was 5 mm.

Next, the obtained laminate was placed in an autoclave and heated for 30 minutes at 60°C and 1 MPa. Thereafter, the PET film was peeled off, and the laminated substrate including the glass plate and the silicone resin layer was annealed at 250° C. for 30 minutes, and then the silicone resin layer was subjected to corona treatment. The obtained silicone resin layer has a first main surface on the side of the glass plate, a second main surface on the side opposite to the first main surface, and an end surface connected to the first main surface and the second main surface, and the end surface has a first main surface from the second main surface. It was an inclined surface protruding toward the main surface. The angle formed by the inclined surface and the first principal surface was 3°. The thickness between the 1st main surface and the 2nd main surface of the silicone resin layer was 8 micrometers.

(Manufacture of laminated body)

Polyimide varnish (Ube Kosan Co., Ltd., Upia-ST-1003) was applied to the surface of the silicone resin layer side of the laminated substrate obtained above, and after heating at 60 ° C. for 30 minutes, further heating at 120 ° C. for 30 minutes, It heated at 450 degreeC for 10 minutes, and obtained the laminated body which has a glass plate, a silicone resin layer, and a polyimide film (thickness: 7 micrometers) in this order. The polyimide film was disposed on the edge region of the glass plate and on the silicone resin layer (see Fig. 3).

<Examples 2 to 14>

According to the same procedure as in Example 1, except that the thickness between the first main surface and the second main surface of the silicone resin layer, the width of the peripheral region, and the angle were adjusted as shown in Tables 1 and 2 described later, A laminate was obtained. Table 1 shows the case of using a curable composition containing bismuth, and Table 2 shows the case of using a curable composition containing cerium.

In Examples 6 and 7 and 13 and 14, the curable composition was applied to the entire surface of the glass plate, and the coating was cured by heating at 250 ° C. for 30 minutes to form a silicone resin layer on the entire surface of the glass plate. After cutting the periphery of the obtained glass plate with a silicone resin layer to obtain a laminate (hereinafter also referred to as “laminate C”) having a glass plate and a silicone resin layer and having a smooth side surface, the laminate C is used The above (preparation of the laminate) was carried out. That is, in the laminate C used in Examples 6 and 7 and 13 and 14, the area of the main surface of the silicone resin layer on the glass plate side is the same as the area of the main surface on the opposite side to the glass plate side, and θ corresponds to 90°. It had a silicone resin layer.

In Tables 1 and 2, the "adsorption layer thickness (μm)" column indicates the thickness between the first main surface and the second main surface of the silicone resin layer.

In Tables 1 and 2, the column "width of edge region (mm)" indicates the width of the edge region (W in Fig. 2).

In Table 1 and Table 2, the "angle (degree)" column shows the angle formed by the 1st main surface of a silicone resin layer and an inclined surface. The angle measurement method is as described above.

As shown in Table 1 and Table 2, the laminated substrate of the present invention exhibited desired effects.

In particular, when a curable composition containing bismuth was used, a comparison between Examples 1 to 3 and 5 and Example 4 confirmed that when the thickness of the adsorption layer was 6 µm or more, the foreign matter embedding property was more excellent.

Further, from the comparison between Examples 1 and 3, it was confirmed that the appearance characteristics were more excellent when the thickness of the adsorption layer was 12 µm or less.

Similar to the case where a curable composition containing cerium was used, a comparison between Examples 8 to 10 and 12 and Example 11 confirmed that when the thickness of the adsorption layer was 6 μm or more, the foreign matter embedding property was better.

Further, from the comparison between Examples 8 and 10, it was confirmed that the appearance characteristics were more excellent when the thickness of the adsorption layer was 12 µm or less.

<Manufacture of organic EL display device (corresponding to electronic device)>

Using the laminates obtained in Examples 1 to 5 and 8 to 12, organic EL display devices were manufactured according to the following procedure.

First, on the surface of the polyimide film of the laminate substrate on the opposite side to the glass plate side, films of silicon nitride, silicon oxide, and amorphous silicon were formed in this order by the plasma CVD method. Next, a low-concentration boron was implanted into the amorphous silicon layer using an ion doping device, and heat treatment was performed to perform dehydrogenation treatment. Next, crystallization of the amorphous silicon layer was performed using a laser annealing device. Next, from an etching and ion doping device using a photolithography method, low-concentration phosphorus was implanted into the amorphous silicon layer to form N-type and P-type TFT areas.

Next, on the side opposite to the glass plate side of the polyimide film, a silicon oxide film is formed by the plasma CVD method to form a gate insulating film, then a molybdenum film is formed by the sputtering method, and a gate electrode is formed by etching using the photolithography method. formed. Next, high-concentration boron and phosphorus were implanted into desired areas of the N type and P type, respectively, by a photolithography method and an ion doping device to form a source area and a drain area.

Next, on the opposite side of the polyimide film from the glass plate side, an interlayer insulating film was formed by forming a silicon oxide film by the plasma CVD method, and a TFT electrode was formed by forming an aluminum film by the sputtering method and etching using the photolithography method. Next, after performing a hydrogenation process by heat treatment in a hydrogen atmosphere, a passivation layer was formed by film formation of nitrogen silicon by a plasma CVD method.

Next, an ultraviolet curable resin was applied to the side opposite to the glass plate side of the polyimide film, and a flattening layer and contact holes were formed by photolithography. Next, indium tin oxide was formed into a film by sputtering, and pixel electrodes were formed by etching using a photolithography method. Subsequently, 4,4',4"-tris(3-methylphenylphenylamino)triphenylamine as a hole injection layer and bis[(N-nap as a hole transport layer) ethyl)-N-phenyl]benzidine, 2,6-bis[4-[N-(4-methoxyphenyl)-N-phenyl]aminostyryl] to 8-quinolinol aluminum complex (Alq ₃ ) as the light emitting layer A mixture of 40% by volume of naphthalene-1,5-dicarbonitrile (BSN-BCN) and Alq ₃ were formed as an electron transport layer in this order. Next, an aluminum film was formed by sputtering, followed by photolithography. A counter electrode was formed by etching.

Next, on the side opposite to the glass plate side of the polyimide film, another glass plate was bonded via an ultraviolet curable adhesive layer, and sealed. According to the above procedure, an organic EL structure was formed on the polyimide film. A structure (hereinafter referred to as panel A) having an organic EL structure on a polyimide film is a laminate with members for electronic devices.

Subsequently, after vacuum adsorbing the sealing body side of Panel A to the surface plate, a stainless steel blade with a thickness of 0.1 mm was inserted into the interface between the polyimide film and the glass plate at the corner of Panel A, and the interface between the polyimide film and the glass plate was peeled off. was given an opportunity. Then, after adsorbing the surface of the support substrate of panel A with the vacuum suction pad, the suction pad was lifted. Here, insertion of the blade was performed while spraying an antistatic fluid to the interface from an ionizer (manufactured by Keyence Corporation). Next, the vacuum adsorption pad was pulled up while continuously spraying antistatic fluid from the ionizer toward the formed air gap and spraying water onto the peeling wire. As a result, the support substrate with the silicone resin layer could be peeled off, leaving only the polyimide film on which the organic EL structure was formed on the surface plate.

Subsequently, the separated polyimide film is cut using a laser cutter or a scribe-break method to divide into a plurality of cells, and then the polyimide film on which the organic EL structure is formed and the counter substrate are assembled, and a module formation step is performed to perform the organic EL structure. An EL display device was fabricated.

Although this invention was detailed also demonstrated with reference to the specific embodiment, it is clear for those skilled in the art that various changes and correction can be added without deviating from the mind and range of this invention.

This application relates to Japanese Patent Application No. 2020-015418 filed on January 31, 2020, Japanese Patent Application No. 2020-074048 filed on April 17, 2020, and Japanese Patent Application No. 2020-074048 filed on June 8, 2020. It is based on Patent Application No. 2020-099427, the content of which is incorporated herein by reference.

10: laminated board
12: supporting substrate
14: silicone resin layer
16: laminate
18: polyimide film
20: member for electronic device
22: laminated body with members for electronic devices
24: electronic device
26: support substrate provided with adsorption layer

Claims (13)

A support substrate made of glass and an adsorption layer disposed on the support substrate,
On the surface of the support substrate on the side of the adsorption layer, there is a peripheral region in which the adsorption layer is not disposed;
The adsorption layer has a first main surface on the side of the supporting substrate, a second main surface on the opposite side to the first main surface, and an end surface connected to the first main surface and the second main surface;
The end face is an inclined surface protruding from the second main surface toward the first main surface,
A laminated substrate in which an angle formed between the inclined surface and the first principal surface is 5° or less, and wherein the adsorption layer is a silicone resin layer. According to claim 1,
A laminated substrate wherein a thickness between the first main surface and the second main surface of the adsorption layer is 50 μm or less. According to claim 1,
A laminated substrate wherein the width of the peripheral region is 1 to 30 mm. According to any one of claims 1 to 3,
A laminated substrate further comprising a protective film disposed on the adsorption layer. A polyimide varnish containing polyimide or a precursor thereof and a solvent is applied to the adsorption layer side of the laminate substrate according to any one of claims 1 to 3, and polyimide is applied on the peripheral region and on the adsorption layer. A method for producing a laminate comprising forming a film to form a laminate comprising the supporting substrate, the adsorption layer, and the polyimide film. The laminated substrate according to any one of claims 1 to 3;
A laminate having a polyimide film disposed on the peripheral region and on the adsorption layer in the laminated substrate. The laminate according to claim 6;
A laminate with a member for electronic device having a member for electronic device disposed on the polyimide film in the laminate. A member forming step of forming a member for electronic devices on the polyimide film of the laminate according to claim 6 to obtain a laminate with members for electronic devices;
The manufacturing method of an electronic device provided with the separation process of obtaining the electronic device which has the said polyimide film and the said electronic device member from the said laminated body with the said electronic device member. delete delete delete delete delete

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