TW202130501A - Laminated substrate, method for manufacturing laminated body, laminated body, laminated body with components for electronic device, and method for manufacturing electronic device do not easily peel off the formed polyimide film when a polyimide varnish is coated on the surface of the laminated substrate to form a polyimide film - Google Patents

Abstract

The invention relates to a laminated substrate, which has a support substrate made of glass and an adsorption layer arranged on the support substrate. The surface of the adsorption layer side of the support substrate has a peripheral area without the adsorption layer. The adsorption layer has a first main surface on the support substrate side, a second main surface on the opposite side of the first main surface, and an end surface connecting the first main surface and the second main surface. The end surface is an inclined surface that further protrudes toward the first main surface from the second main surface, and the angle formed between the inclined surface and the first main surface is less than 10°. Regarding the laminated substrate of the invention, when a polyimide varnish is coated on the surface of the laminated substrate to form a polyimide film, the formed polyimide film is not easily peeled off.

Description

Laminated substrates, methods for manufacturing laminates, laminates, laminates with components for electronic devices, and methods for manufacturing electronic devices

The present invention relates to a layered substrate, a method of manufacturing a layered body, a layered body, a layered body with components for electronic devices, and a method of manufacturing an electronic device.

Electronic devices such as solar cells (PV), liquid crystal panels (LCD), organic EL (Electroluminescence) panels (OLED), and receiving sensor panels that sense electromagnetic waves, X-rays, ultraviolet rays, visible rays, infrared rays, etc. are working Become thinner and lighter. Along with this, substrates such as polyimide resin substrates used in electronic devices have also become thinner. If the strength of the substrate is insufficient due to the thinning, the operability of the substrate is reduced, which may cause problems in the step of forming electronic device components on the substrate (component forming step).

Therefore, recently, in order to improve the operability of the substrate, a technique using a laminate has been proposed. The above-mentioned laminate system is provided with a polyimide resin substrate on a supporting base material (Patent Document 1). More specifically, it is disclosed in Patent Document 1 that a polyimide varnish can be coated on the cured body layer of a thermosetting resin composition to form a resin varnish cured film (equivalent to a polyimide film), and then apply it to the resin Precision components are arranged on the varnish hardened film. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2018-193544

[The problem to be solved by the invention]

On the other hand, the inventors performed the process of coating polyimide varnish to produce polyimide film described in Patent Document 1. As a result, they found that when polyimide varnish is applied to form a polyimide film, Polyimide film is prone to peeling. It has also been found that peeling occurs particularly easily at the end of the polyimide film.

The subject of the present invention is to provide a multilayer substrate, when a polyimide varnish is coated on the surface to form a polyimide film, the formed polyimide film is not easy to peel off. The subject of the present invention is also to provide a method of manufacturing a laminate, a laminate, a laminate with a member for electronic devices, and a method of manufacturing an electronic device. [Technical means to solve the problem]

The inventors of the present invention conducted intensive research, and as a result, found that the above-mentioned problem can be solved by the following configuration.

(1) A laminated substrate having a supporting substrate made of glass and an adsorption layer arranged on the supporting substrate, On the surface of the support substrate on the side of the adsorption layer, there is a peripheral area where the adsorption layer is not arranged, The adsorption layer has a first main surface on the side of the support substrate, a second main surface on the opposite side to the first main surface, and an end surface connecting the first main surface and the second main surface, The end surface is an inclined surface that protrudes from the second main surface to the first main surface, and The angle between the inclined surface and the first main surface is less than 10°. (2) The multilayer substrate as described in (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 thickness between the first main surface and the second main surface of the adsorption layer is 12 μm or less. (4) The multilayer substrate as described in (1), wherein the thickness between the first main surface and the second main surface of the adsorption layer is 6 μm or more. (5) The multilayer substrate as described in (1), wherein the angle formed by the inclined surface and the first main surface is 5° or less. (6) The multilayer substrate as described in any one of (1) to (5), wherein the width of the peripheral region is 1-30 mm. (7) The multilayer substrate according to any one of (1) to (6), wherein the adsorption layer is a silicone resin layer. (8) The multilayer substrate as described in any one of (1) to (7), which further includes a protective film arranged on the adsorption layer. (9) A method for manufacturing a multilayer substrate as described in any one of (1) to (8), which has: a step of bonding a support base material and a transfer film, and this step is laminating on the support base material A transfer film with a precursor film that becomes an adsorption layer, at this time the support substrate and the transfer film are arranged so that there is a peripheral area on the support substrate where the precursor film is not arranged; and the precursor film heating step, which is used for The adsorption layer is obtained from the precursor film. (10) A method for manufacturing a laminate, which coats the adsorption layer side of the laminate substrate as described in any one of (1) to (7) with a polyimide containing polyimide or its precursor and a solvent In the amine varnish, a polyimide film is formed on the peripheral area and on the adsorption layer, thereby forming a laminate with a supporting substrate, an adsorption layer, and a polyimide film in sequence. (11) A laminated body having: the laminated substrate as described in any one of (1) to (7); and The polyimide film is arranged on the peripheral area of the laminated substrate and on the adsorption layer. (12) A laminated body with components for electronic devices, which has: the laminated body as described in (11); and The electronic device component is arranged on the polyimide film in the laminate. (13) A method of manufacturing an electronic device, comprising: a member forming step of forming a member for an electronic device on the polyimide film of the laminate as described in (11) to obtain a laminate with the member for an electronic device ;and In the separation step, an electronic device having a polyimide film and a member for an electronic device is obtained from a laminate with a member for an electronic device. [Effects of Invention]

According to the present invention, it is possible to provide a laminated substrate. When a polyimide varnish is coated on the surface to form a polyimide film, the formed polyimide film is not easy to peel off. According to the present invention, it is possible to provide a method of manufacturing a laminate, a laminate, a laminate with a member for electronic devices, and a method of manufacturing an electronic device.

Hereinafter, embodiments of the present invention will be described with reference to the drawings. However, the following embodiments are merely examples for explaining the present invention, and the present invention is not limited to the embodiments shown below. Furthermore, various changes and substitutions can be made in 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 described before and after "～" as the lower limit and upper limit.

As the characteristic points of the laminated substrate of the present invention, for example: the end surface of the adsorption layer is set as an inclined surface; the inclination angle of the inclined surface is adjusted to a specific range; Peripheral area. The inventors found that by adopting the above-mentioned configuration, the desired effect can be obtained. The details of obtaining the desired effect are not clear, but it is thought that firstly, a peripheral area is provided on the surface of the supporting substrate, and the polyimide film is arranged on the build-up substrate in such a way that the peripheral area is in contact with the polyimide film As a result, based on the interaction between the polyimide film and the glass supporting substrate, the peeling of the polyimide film from the end is suppressed. It is also believed that by providing the inclined surface with a specific inclination angle at the end, the generation of voids between the polyimide film and the adsorption layer and the supporting substrate can be suppressed. As a result, the peeling of the polyimide film Be suppressed.

＜Multilayer substrates＞ Fig. 1 is a cross-sectional view schematically showing an embodiment of the multilayer substrate of the present invention. FIG. 2 is a top view of the multilayer substrate shown in FIG. 1. FIG. The laminated substrate 10 includes a supporting base 12 made of glass and an adsorption layer 14 arranged on the supporting base 12. As shown in Figures 1 and 2, the adsorption layer 14 has a first main surface 14a on the side of the support base 12, a second main surface 14b on the opposite side to the first main surface 14a, and a connection between the first main surface 14a and the first main surface 14a. 2 End surface 14c of main surface 14b. The end surface 14c of the adsorption layer 14 is an inclined surface protruding from the second main surface 14b to the first main surface 14a. In addition, the shape of the adsorption layer 14 (the shape of the main surface) is rectangular, and all the four end surfaces 14c are inclined surfaces. Moreover, as shown in FIGS. 1 and 2, the surface of the support base 12 on the side of the adsorption layer 14 has a peripheral region 12 a where the adsorption layer 14 is not arranged. In other words, the adsorption layer 14 is disposed on the support base 12 in such a way that a marginal area (peripheral region 12a) that does not contact the adsorption layer 14 remains on the support base 12. In the above-mentioned aspect, the area of the disposition area of the adsorption layer 14 is narrower than the area of the surface (main surface) of the support substrate 12. The above-mentioned peripheral area 12a is equivalent to being located more inside than the outer periphery of the support substrate 12.的区。 The area. Furthermore, in FIGS. 1 and 2, the shape of the support substrate 12 (the shape of the main surface) and the shape of the adsorption layer 14 (the shape of the main surface) are both rectangular to form the outer periphery of the support substrate 12 The adsorption layer 14 is arranged on the support base 12 so as to be parallel to one side of the outer periphery of the adsorption layer 14.

A polyimide varnish is coated on the peripheral area of the support base 12 of the laminated substrate 10 and the second main surface 14b of the adsorption layer 14, and then a polyimide film is formed, which will be described in detail below. A member for an electronic device is formed on the polyimide film, and thereafter, the polyimide film (that is, an electronic device) on which the member for an electronic device is formed is separated. In this way, an electronic device is manufactured. Hereinafter, each layer (support base 12, adsorption layer 14) constituting the multilayer substrate 10 will be described in detail, and thereafter, a method of manufacturing the multilayer substrate 10 will be described in detail.

(Support base material) The supporting substrate 12 is a member that supports and reinforces the polyimide film, such as 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 in which the content of silicon oxide in terms of oxide is 40 to 90% by mass is preferred. As the glass plate, more specifically, a glass plate containing alkali-free borosilicate glass (trade names "AN100" and "AN Wizus" manufactured by AGC Co., Ltd.) and the like can be mentioned. Regarding the manufacturing method of the glass plate, it is usually obtained by melting the glass raw material and forming the molten glass into a plate shape. Such a forming method may be a common method, for example, a float method, a melting method, and a flow hole down-drawing method may be mentioned.

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

As described above, the adsorption layer 14 is not disposed on the peripheral area 12a of the surface of the support substrate 12. That is, the surface of the peripheral region 12a of the support base 12 is exposed. The width W of the peripheral region 12a is not particularly limited, and is preferably 1-30 mm, more preferably 3-10 mm. As shown in FIG. 2, the width W of the so-called peripheral region 12 a corresponds to the distance from the outer periphery of the support base 12 to the outer periphery of the adsorption layer 14. As long as the width of the peripheral region 12a is 30 mm or less, the effective area when forming the electronic device described below becomes larger, thereby improving the manufacturing efficiency of the electronic device. In addition, by making the width of the peripheral region 12a 1 mm or more, the polyimide film becomes more difficult to peel off.

The supporting substrate 12 is preferably low in flexibility. 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.

(Adsorption layer) The adsorption layer 14 is a film used to prevent peeling of the polyimide film disposed thereon. The adsorption layer 14 is disposed on the support substrate 12 in such a manner that the peripheral region 12 a that does not contact the adsorption layer 14 remains on the support substrate 12.

As described above, the end surface 14c of the adsorption layer 14 is an inclined surface protruding from the second main surface 14b to the first main surface 14a. Preferably, all of the plurality of end surfaces 14c are inclined surfaces.

In the adsorption layer 14, the angle θ formed by the inclined surface and the first main surface 14a is less than 10°. Among them, in order to further suppress the peeling of the polyimide film when the polyimide varnish is applied to form the polyimide film, the angle θ is preferably 8° or less, more preferably 5° or less. The lower limit is not particularly limited, but it is preferably 1° or more. The angle θ between the inclined surface of the adsorption layer 14 and the first main surface 14a is determined by the cross-sectional shape of the adsorption layer 14 using a non-contact surface property measuring device "PF-60" manufactured by Mitaka Optical Instruments Co., Ltd. . In more detail, as shown in FIG. 1, the length of the line segment AB and the length of the line segment AC are measured based on the cross-sectional view of the adsorption layer 14, and the angle θ is calculated according to the following formula. θ=arctan(AC/AB)

The adsorption layer 14 may be an organic layer or an inorganic layer. As the material of the organic layer, for example, acrylic resin, polyolefin resin, polyurethane resin, polyimide resin, silicone resin, polyimide silicone resin, and fluororesin may be mentioned. In addition, several types of resins may be mixed to form the adsorption layer 14. Examples of the material of the inorganic layer include oxides, nitrides, oxynitrides, carbides, carbonitrides, silicides, and fluorides. As oxides (preferably metal oxides), nitrides (preferably metal nitrides), oxynitrides (preferably metal oxynitrides), for example, one may cite: selected from Si, Hf, Zr, Ta More than one element of, Ti, Y, Nb, Na, Co, Al, Zn, Pb, Mg, Bi, La, Ce, Pr, Sm, Eu, Gd, Dy, Er, Sr, Sn, In and Ba The oxide, nitride, oxynitride. As carbides (preferably metal carbides) and carbonitrides (preferably metal carbonitrides), for example: carbides of one or more elements selected from Ti, W, Si, Zr and Nb , Carbonitride, Carbon oxide. As the silicide (preferably metal silicide), for example, a silicide of one or more elements selected from Mo, W, and Cr can be mentioned. As the fluoride (preferably a metal fluoride), for example, a fluoride of one or more elements selected from Mg, Y, La, and Ba can be mentioned.

The adsorption layer 14 may also be a plasma polymerized membrane. When the adsorption layer 14 is a plasma polymerized membrane, the material for forming the plasma polymerized membrane can be exemplified: CF ₄ , CHF ₃ , C ₂ H ₆ , C ₃ H ₆ , C ₂ H ₂ , CH ₃ F , C ₄ H ₈ and other fluorocarbon monomers; methane, ethane, propane, ethylene, propylene, acetylene, benzene, toluene and other hydrocarbon monomers; hydrogen, SF ₆ and so on.

Among them, in terms of heat resistance or peelability, the material of the adsorption layer 14 is preferably silicone resin, polyimide silicone resin, more preferably silicone resin, and particularly preferably condensation reaction type silicone A silicone resin formed by ketones. Hereinafter, the form in which the adsorption layer is a silicone resin layer will be described in detail.

The so-called silicone resin is a resin containing a specific organosiloxane unit, and is usually obtained by curing a curable silicone. Curable silicones are classified into addition reaction type silicones, condensation reaction type silicones, ultraviolet curing type silicones, and electron beam curing type silicones according to their curing mechanism. All of them can be used. Among them, condensation reaction type silicones are preferred. As the condensation reaction type silicone, a hydrolyzable organosilane compound or a mixture (monomer mixture) as a monomer, or a partial hydrolysis condensation product obtained by partial hydrolysis and condensation reaction of the monomer or monomer mixture can be preferably used (Organic Polysiloxane). By using this condensation reaction type silicone, a hydrolysis-condensation reaction (sol-gel reaction) is performed to form a silicone resin.

The adsorption layer 14 is preferably formed using a curable composition containing curable silicone. In addition to the curable silicone, the curable composition may also include a solvent, a platinum catalyst (in the case of using an addition reaction type silicone as the curable silicone), a leveling agent, a metal compound, and the like. Examples of the metal element contained in the metal compound include 3d transition metals, 4d transition metals, lanthanide series metals, bismuth (Bi), aluminum (Al), and tin (Sn). The content of the metal compound is not particularly limited and can be adjusted appropriately.

The adsorption layer 14 preferably has a hydroxyl group. A part of the Si-O-Si bond of the silicone resin constituting the adsorption layer 14 is cut, and hydroxyl groups may appear. In addition, when a condensation reaction type silicone is used, its hydroxyl group can become 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 adsorption layer 14 is preferably more than 1 μm, and it is more preferably 6 μm or more in order to make the embedding property of foreign matter more excellent. The above-mentioned thickness is a value obtained by measuring the thickness of the adsorption layer 14 at any position above 5 points by a contact-type film thickness measuring device, and arithmetically averaging them. Furthermore, the so-called excellent foreign matter embedding property means that even if there is a foreign matter between the support base 12 and the adsorption layer 14, the foreign matter will be embedded in the adsorption layer 14. If the embedding of foreign matter is excellent, the adsorption layer will not easily produce convex parts caused by the foreign matter. When the electronic device component is formed on the polyimide film, the breakage of the electronic device component caused by the convex part can be suppressed. Line and other risks. Furthermore, since the voids formed when the above-mentioned protrusions are generated are observed in the form of bubbles, the embedding of foreign objects can be evaluated by the presence or absence of bubbles.

If a polyimide film is formed on a supporting substrate 12 made of glass and subjected to high temperature heat treatment, the polyimide film will turn yellow, so it is difficult to apply to transparent electronic devices. However, although the mechanism is not clear, by forming the adsorption layer 14 on the glass and forming the polyimide film on the adsorption layer 14, the yellowing of the polyimide film caused by the high-temperature heat treatment can be suppressed.

(Protective film) The build-up substrate 10 may also have a protective film arranged to cover the adsorption layer 14. The protective film is a film that protects the surface of the adsorption layer 14 before applying the following polyimide varnish on the adsorption layer 14.

As the material constituting the protective film, for example, polyimide resin, polyester resin (for example, polyethylene terephthalate (PET), polyethylene naphthalate), polyolefin resin (for example, , Polyethylene, polypropylene), polyurethane resin. Among them, polyester resin is preferred, and polyethylene terephthalate is more preferred.

In order to reduce the influence of the force received from the outside, 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. The upper limit of the thickness of the protective film is preferably 500 μm or less, more preferably 300 μm or less, and still more preferably 100 μm or less.

The protective film may further have an adhesive layer on the surface on the side of the adsorption layer 14. As the adhesive layer, a well-known adhesive layer can be used. Examples of the adhesive constituting the adhesive layer include (meth)acrylic adhesives, silicone adhesives, and polyurethane adhesives. In addition, the adhesion layer may be made of resin. Examples of the resin include vinyl acetate resin, ethylene-vinyl acetate copolymer resin, vinyl chloride-vinyl acetate copolymer resin, (meth)acrylic resin, and butyral resin. , Polyurethane resin, polystyrene elastomer. In order to reduce the peeling force when the protective film is peeled off, the surface roughness (Ra) of the protective film is preferably 50 nm or less, more preferably 30 nm or less, and still more preferably 15 nm or less. In addition, in order to maintain a state in which the protective film and the adsorption layer are in close contact, Ra is preferably 0.1 nm or more, and more preferably 0.5 nm or more. The surface roughness (Ra) was measured using a non-contact surface-layer profile measurement system "Vertscan R3300-lite" manufactured by Ryoka Systems.

＜Manufacturing method of multilayer substrate＞ The manufacturing method of the laminated board is not specifically limited, A well-known method can be mentioned. Among them, in order to be more excellent in productivity, the following method can be exemplified. That is, prepare a transfer film that has a temporary support and is arranged on the temporary support and becomes a precursor film for the adsorption layer after heat treatment. The precursor film is attached to a specific position on the glass supporting substrate, and the obtained laminate having the glass supporting substrate, the precursor film and the temporary support is subjected to heat treatment. By applying heat treatment, the end of the precursor film can be fluidized to form the above-mentioned adsorption layer with a specific inclined surface. Furthermore, when the precursor film is attached to the supporting substrate, the precursor film is attached to the supporting substrate in such a way that the aforementioned peripheral region is formed. Moreover, in addition to the above, the precursor film that becomes the adsorption layer after the heat treatment can be arranged at a specific position of the glass support substrate by coating, and the heat treatment is performed to form the adsorption with the specific inclined surface. Floor. As the precursor film, for example, a film formed by applying a heat treatment to a coating film formed by applying a curable composition containing curable silicone can be exemplified. The heating temperature of 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 applying heat treatment to the precursor film, the shape of the end surface of the adsorption layer can be inclined. Furthermore, it is preferable to perform the heat treatment while applying pressure. Specifically, it is preferable to perform heat treatment and pressure treatment using an autoclave. The heating temperature during the heat treatment is preferably 50 to 350°C, more preferably 55 to 300°C, and still more preferably 60 to 250°C. The heating time is preferably 10 to 60 minutes, more preferably 20 to 40 minutes. As the pressure during the pressurization treatment, it is preferably 0.5 to 1.5 MPa, more preferably 0.8 to 1.0 MPa.

In addition, the heat treatment may be performed multiple times. In the case of multiple heating treatments, the heating conditions can be changed each time. For example, when the heating treatment is performed multiple times, the heating temperature can be changed. For example, when the heat treatment is performed twice, the first heat treatment may be performed under the temperature condition of less than 100°C, and the second heat treatment may be performed under the temperature condition of 100°C or higher. In addition, when heat treatment is performed several times, the presence or absence of pressure treatment can be changed. For example, when the heat treatment is performed twice, it can be performed as follows. That is, the pressure treatment is performed in the first heat treatment together, and the pressure treatment is not performed in the second heat treatment. Furthermore, when manufacturing a laminated substrate using a transfer film, the above-mentioned heating treatment may be performed after the temporary support is peeled off, or the heating treatment may be directly performed in a state where the temporary support is arranged on the adsorption layer. In addition, when heat treatment is performed multiple times, the temporary support can be peeled off between each heat treatment. For example, after the first heat treatment is performed, the temporary support may be peeled off, and the second heat treatment may be performed.

Surface treatment can be performed on the surface of the adsorption layer of the build-up substrate. Examples of the surface treatment include corona treatment, plasma treatment, and ultraviolet-ozone treatment, and corona treatment is preferred. In the case of forming a polyimide film on the adsorption layer as described below, in order to reduce the surface roughness of the polyimide film, the surface roughness (Ra) of the adsorption layer is preferably 50 nm or less, more preferably 30 nm or less, more preferably 15 nm or less. Furthermore, in order to maintain the state in which the polyimide film and the adsorption layer are in close contact, Ra is preferably 0.1 nm or more, and more preferably 0.5 nm or more.

The above-mentioned laminated substrate 10 can be used to manufacture a structure having a supporting base 12, an adsorption layer 14, and a supported material in this order. As the supported material, materials other than the polyimide film 18 may be laminated. As the supported material, for example, a polyimide resin film, an epoxy resin film, a photosensitive resist, a polyester resin film (for example, polyethylene terephthalate, polyethylene naphthalate Ester), polyolefin resin film (for example, polyethylene, polypropylene), polyurethane resin film, metal foil (for example, copper foil, aluminum foil), sputtering film (for example, copper, titanium, aluminum, tungsten, Silicon nitride, silicon oxide, amorphous silicon), TGV (Through Glass Via) substrate, thin glass substrate, thin glass substrate with sacrificial layer, ABF (Ajinomoto Build-up Film, Ajinomoto Build-up Film) , Sapphire substrate, silicon substrate, TSV (Through Silicon Via) substrate, LED (Light Emitting Diode, light-emitting diode) chip, display panel (for example, LCD, OLED, μ-LED), artificial diamond, spacer Paper etc.

＜Laminated body and its manufacturing method＞ Using the above-mentioned laminated substrate 10, the laminated body 16 having the supporting base 12, the adsorption layer 14, and the polyimide film 18 shown in FIG. 3 can be manufactured. Specifically, as a method of manufacturing the laminate 16, the following method may be exemplified. That is, a polyimide varnish containing polyimide and a solvent is applied to the side of the adsorption layer 14 of the laminate substrate 10, and the peripheral region 12a is applied. A polyimide film 18 is formed on the upper and the adsorption layer 14 to form a laminated body having a supporting base 12, an adsorption layer 14 and a polyimide film 18 in this order. Hereinafter, the above-mentioned manufacturing method will be described in detail, and thereafter, the structure of the polyimide film 18 will be described in detail.

(Polyimide varnish) The polyimide varnish contains polyimide or its precursor and a solvent. Polyimine is usually obtained by polycondensing tetracarboxylic dianhydride and diamine, and then performing imidization. As polyimide, it is preferable to have solvent solubility. Examples of the tetracarboxylic dianhydride used include aromatic tetracarboxylic dianhydride and aliphatic tetracarboxylic dianhydride. As the diamine used, aromatic diamine and aliphatic diamine can be mentioned. As the aromatic tetracarboxylic dianhydride, for example, pyromellitic dianhydride (1,2,4,5-benzenetetracarboxylic dianhydride), 3,3',4,4'-diphenylmethyl Ketone tetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride. As the aliphatic tetracarboxylic dianhydride, there are cyclic or acyclic aliphatic tetracarboxylic dianhydrides. As the cyclic aliphatic tetracarboxylic dianhydride, for example: 1,2,3,4-cyclobutane Alkyltetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 1,2,4,5-cyclopentanetetracarboxylic dianhydride, etc., as acyclic aliphatic tetracarboxylic acid The acid dianhydride may, for example, be 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-pentanetetracarboxylic dianhydride, and the like. As the 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, 1,3-diaminobenzene. The aliphatic diamine may, for example, be ethylene diamine, hexamethylene diamine, polyethylene glycol bis(3-aminopropyl) ether, polypropylene glycol bis(3-aminopropyl) ether, etc. Cycloaliphatic diamines, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, isophoronediamine, noralkanediamine, etc. Cycloaliphatic diamine.

The so-called polyimide precursor means the polyimide in the state before the imidization (that is, the so-called polyamic acid and/or polyamic acid ester).

The solvent may be a solvent that dissolves the polyimide or its precursor, for example, phenolic solvents (for example, m-cresol), amide solvents (for example, N-methyl-2-pyrrolidone , N,N-dimethylformamide, N,N-dimethylacetamide), lactone-based solvents (for example, γ-butyrolactone, δ-valerolactone, ε-caprolactone, γ -Crotonic acid lactone, γ-caprolactone, α-methyl-γ-butyrolactone, γ-valerolactone, α-acetyl-γ-butyrolactone, δ-caprolactone), sulfenite Solvents (for example, N,N-dimethyl sulfide), ketone solvents (for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone), ester solvents (for example, methyl acetate Ester, ethyl acetate, butyl acetate, dimethyl carbonate).

(order) The method of coating the polyimide varnish on the side of the adsorption layer 14 of the build-up substrate 10 is not particularly limited, and a known method can be exemplified. For example, a spray coating method, a die nozzle coating method, a spin coating method, a dip coating method, a roll coating method, a bar coating method, a screen printing method, and a gravure coating method can be mentioned.

After coating, heat treatment may be performed as needed. As the conditions of the heat treatment, the temperature condition is preferably 50 to 500°C, more preferably 50 to 450°C. The heating time is preferably 10 to 300 minutes, more preferably 20 to 200 minutes. In addition, the heat treatment can be performed multiple times. In the case of multiple heating treatments, the heating conditions can be changed each time.

(Layered body) As shown in FIG. 3, the laminate 16 has a supporting base 12, an adsorption layer 14 and a polyimide film 18. The structure of the support base 12 and the adsorption layer 14 is as described above.

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

The thickness of the polyimide film 18 is preferably 1 μm or more, more preferably 5 μm or more. In terms of flexibility, it is preferably 1 mm or less, and more preferably 0.2 mm or less. In order to form high-definition wiring 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, and still more preferably 10 nm or less. Regarding the thermal expansion coefficient of the polyimide film 18, it is preferable to suppress the warpage of the laminated body 16 after heating or cooling when the difference between the thermal expansion coefficient of the supporting substrate 12 and the thermal expansion coefficient of the polyimide film 18 is small. Specifically, the difference between the thermal expansion coefficient of the polyimide film 18 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 film 18 is not particularly limited, but in terms of the productivity of the electronic device, it is preferably 300 cm ² or more. The polyimide film 18 may be colored or colorless and transparent.

The laminated body 16 can be used for various purposes. For example, the following display device panels, PV, thin-film secondary batteries, semiconductor wafers with circuits formed on the surface, and electronic components such as receiving sensor panels can be exemplified. In these applications, there are also cases where the layered body is exposed (for example, 20 minutes or more) under high temperature conditions (for example, 450° C. or higher) in the 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 (microelectromechanical system, microelectromechanical system) shutter panels, and the like. The receiving sensor panel includes an electromagnetic wave receiving sensor panel, an X-ray receiving sensor panel, an ultraviolet receiving sensor panel, a visible light receiving sensor panel, an infrared receiving sensor panel, etc. The substrate used for the receiving sensor panel can be reinforced with a reinforcing sheet such as resin.

＜Manufacturing method of electronic device＞ The laminate can be used to manufacture an electronic device including a polyimide film and the following electronic device components. The manufacturing method of an electronic device, as shown in Figures 4 and 5, is a method having the following steps, namely, a component forming step, which is placed on the polyimide film 18 of the laminate 16 (the polyimide film 18 and the adsorption layer 14 side is on the surface on the opposite side) forming an electronic device member 20 to obtain a laminate 22 with an electronic device member; and a separation step, which obtains a polyimide film 18 from the laminate 22 with an electronic device member And the electronic device 24 of the electronic device component 20.

Hereinafter, the step of forming the member 20 for an electronic device is referred to as a "member forming step", and the step of separating the electronic device 24 and the support substrate 26 with an adsorption layer is referred to as a "separating step". Hereinafter, the materials and procedures used in each step will be described in detail.

(Component formation step) The component forming step is a step of forming components for electronic devices on the polyimide film 18 of the laminate 16. More specifically, as shown in FIG. 4, an electronic device member 20 is formed on the polyimide film 18 (on the surface of the polyimide film 18 on the opposite side to the adsorption layer 14 side) to obtain an electronic device Use the laminated body 22 of the component. Furthermore, in order to improve the reliability of the electronic device, a barrier layer can be formed on the polyimide film 18. 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 be one layer, two or more layers, or a combination of multiple materials. The film forming method is not particularly limited, and known methods may be mentioned. For example, methods such as plasma CVD (Chemical Vapor Deposition) and sputtering can be cited. First, the electronic device member 20 used in this step will be described in detail, and thereafter, the order of the steps will be described in detail.

(Components for electronic devices) The electronic device member 20 is a member that constitutes at least a part of the electronic device formed on the polyimide film 18 of the laminate 16. More specifically, as the member 20 for electronic devices, for example, panels for display devices, solar cells, thin-film secondary batteries, or electronic parts such as semiconductor wafers with circuits formed on the surface, used for receiving sensor panels, etc. The components (for example, LTPS (Low Temperature Poly Silicon, low temperature polysilicon) and other display device components, components for solar cells, components for thin-film secondary batteries, components for electronic parts, components for receiving sensors), for example, include: U.S. Patent Application Publication No. 2018/0178492 Specification Paragraph [0192] The solar cell component, the same specification Paragraph [0193] The thin film secondary battery component, the same specification Paragraph [0194] Circuits for electronic parts.

(Sequence of steps) The manufacturing method of the above-mentioned laminate 22 with the 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 used to form the electronic device on the polyimide film 18 of the laminate 16 Component 20. The electronic device member 20 may be a part of all the members that are finally formed on the polyimide film 18 (hereinafter, referred to as "partial members"), rather than all of the members that are finally formed on the polyimide film 18 ( Hereinafter, referred to as "all components"). The substrate with partial components peeled from the adsorption layer 14 may be used as a substrate with all components (equivalent to the electronic device described below) in the subsequent steps. Other electronic device members may be formed on the peeling surface of the substrate with all members peeled from the adsorption layer 14. Furthermore, the two electronic device members 20 of the laminated body 22 with the electronic device members may be opposed to each other, and the two pieces of the laminated body with all the members may be assembled together, and then the laminated body with all the members may be self-attached. Peel off two supporting substrates with adsorption layers to manufacture electronic devices.

For example, taking the case of manufacturing OLED as an example, in order to form an organic EL structure on the surface of the polyimide film 18 of the laminate 16 on the opposite side to the adsorption layer 14 side, various layer formation or treatments are performed, For example, forming a transparent electrode; then vaporizing a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, etc. on the surface where the transparent electrode is formed; forming a back electrode; sealing with a sealing plate, etc. As the layer formation or treatment, specifically, for example, film formation treatment, vapor deposition treatment, bonding treatment of sealing plate, etc. may be mentioned.

(Separation step) The separation step is the following step, that is, as shown in FIG. 5, the interface between the adsorption layer 14 and the polyimide film 18 is used as the peeling surface, and the layered body 22 of the member with electronic device obtained in the above member forming step is used, The polyimide film 18 on which the electronic device member 20 is laminated and the support substrate 26 with an adsorption layer are separated into an electronic device 24 including the electronic device member 20 and the polyimide film 18.

In the case where the electronic device member 20 on the peeled polyimide film 18 is a part of all the required constituent members, it is also possible to form the remaining constituent members on the polyimide film 18 after separation .

The method of peeling off the polyimide film 18 and the adsorption layer 14 is not particularly limited. For example, a sharp blade-like object can be inserted into the interface between the polyimide film 18 and the supporting substrate 12 to form a starting point for peeling, and then a mixed fluid of water and compressed air may be blown to peel off. Preferably, the laminated body 22 with the electronic device member is placed on the platen with the support base 12 on the upper side and the electronic device member 20 side on the lower side, and the electronic device member 20 side is vacuum sucked to the pressure On the disk, in this state, the blade-shaped object is first intruded into the interface between the polyimide film 18 and the supporting base 12. Thereafter, a plurality of vacuum chucks are used to suck the support substrate 12 side, and the vacuum chucks are sequentially raised from the vicinity of the position where the blade-shaped object is inserted. In this way, the support base 26 with the adsorption layer can be easily peeled off.

When the electronic device 24 is separated from the laminated body 22 with the electronic device component, by controlling the blowing by the ionizer or controlling the humidity, the fragments of the adsorption layer 14 can be further prevented from being electrostatically attracted to the electronic device 24. The manufacturing method of the above-mentioned electronic device is suitable for manufacturing the display device described in paragraph [0210] of the specification of U.S. Patent Application Publication No. 2018/0178492. As the electronic device 24, for example, the one described in paragraph [0211] of the same specification can be cited .

Moreover, before performing the above-mentioned separation step, it is also possible to cut and remove the area of the laminate where the electronic device member is not arranged. [Example]

Hereinafter, the present invention will be specifically explained through examples, but the present invention is not limited by these examples.

Hereinafter, as a supporting base material, a glass plate containing alkali-free borosilicate glass (coefficient of linear expansion 38×10 ^-7 /°C, trade name "AN100" manufactured by AGC Co., Ltd.) is used. Hereinafter, Examples 1 to 5 are examples, and Examples 6 to 7 are comparative examples.

＜Appearance evaluation＞ The polyimide film in the laminate having the glass plate, the silicone resin layer, and the polyimide film obtained in the following order was visually observed, and evaluated according to the following criteria. A: The polyimide film did not peel off. B: Although a part of the polyimide film was peeled off, it was in a range where there was no practical problem. C: Most or the entire surface of the polyimide film is peeled off, so it is a practically problematic area.

＜Evaluation of the width of the peripheral area＞ Evaluate the width of the peripheral area of the support substrate according to the following criteria. A: The width is 1 mm or more and 10 mm or less B: The width is more than 10 mm and less than 30 mm C: The width exceeds 30 mm and does not reach 1 mm

<Foreign body embedding property> Visually observe the laminated body in which the glass plate, the silicone resin layer, and the PET film are arranged in the following order, and evaluate it according to the following criteria. A: The interface bubbles caused by foreign matter at the glass plate/silicone resin layer interface are 5 or less. B: There are more than 5 interfacial bubbles caused by foreign matter at the glass plate/silicone resin layer interface, and 10 or less. C: There are more than 10 interface bubbles caused by 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 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, water (300 g) was used to wash the crude reaction liquid 3 times. Trimethylsilyl chloride (70 g) was added to the washed crude reaction 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 crude reaction liquid was cooled to 25°C, water (300 g) was used to wash the crude reaction liquid 3 times. The toluene was distilled off under reduced pressure from the washed crude reaction liquid, and after the slurry was made into a slurry state, it was dried overnight with a vacuum dryer, thereby obtaining a white organopolysiloxane compound, that is, curable silicone 1. The number of T units of the sclerosing silicone 1: the number of M units=87:13 (mole ratio). In addition, the M unit means a monofunctional organosilalkoxy unit represented by _{(R) 3} SiO _1/2. The T unit means a _{trifunctional organosilalkoxy unit represented by RSiO 3/2} (R represents a hydrogen atom or an organic group).

(Preparation of curable composition) The curable silicone 1 and heptane are mixed, 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 becomes 50% by mass. In addition, the addition amount of the metal compound was adjusted so that the metal element was 0.1 parts by mass relative to 100 parts by mass of the resin. The obtained mixed solution was filtered using a filter with a pore size of 0.45 μm, thereby obtaining a curable composition. The curable silicone 1 and heptane are mixed, and the organic zirconium compound (zirconium octoate compound) and the organic cerium compound (cerium 2-ethylhexanoate) are further added. The amount of solvent is adjusted so that the solid content concentration becomes 50% by mass. In addition, the addition amount of the metal compound was adjusted so that the metal element was 0.1 parts by mass relative to 100 parts by mass of the resin. The obtained mixed solution was filtered using a filter with a pore size of 0.45 μm, thereby obtaining a curable composition.

(Production of multilayer substrate) Coat the prepared curable composition on the surface of a polyethylene terephthalate film (PET film) (manufactured by Toyobo Co., Ltd., COSMOSHINE A4100), and heat it at 140°C for 10 minutes using a hot plate to form silicon Ketone resin layer. The thickness of the silicone resin layer is 8 μm. Then, after washing with a water-based glass cleaner ("PK-LCG213" manufactured by Parker Corporation), the 200×200 mm glass plate "AN100" (supported by Substrate), and the PET film on which the silicone resin layer is formed are bonded to produce a laminated body in which the glass plate, the silicone resin layer, and the PET film are sequentially arranged. Furthermore, at the time of the above-mentioned bonding, bonding is performed in such a way that a region where the silicone resin layer is not arranged remains on the peripheral region of the surface of the glass plate (refer to FIG. 2). The width W of the peripheral area is 5 mm. Next, the obtained laminate was placed in an autoclave and heated at 60°C and 1 MPa for 30 minutes. After that, the PET film was peeled off, and the laminated substrate including the glass plate and the silicone resin layer was subjected to an annealing treatment at 250° C. for 30 minutes, and then corona treatment was applied to the silicone resin layer. The obtained silicone resin layer has a first main surface on the side of the glass plate, a second main surface opposite to the first main surface, and an end surface connecting the first main surface and the second main surface, and the end surface is from the first main surface. 2 The inclined surface that protrudes from the main surface to the first main surface. The angle formed by the inclined surface and the first principal surface is 3°. The thickness between the first main surface and the second main surface of the silicone resin layer is 8 μm.

(Production of multilayer body) Polyimide varnish (manufactured by Ube Industries Co., Ltd., UPIA-ST-1003) was coated on the surface of the silicone resin layer side of the multilayer substrate obtained above, heated at 60°C for 30 minutes, and then at 120°C It was heated for 30 minutes and then heated at 450°C for 10 minutes to obtain a laminate having a glass plate, a silicone resin layer, and a polyimide film (thickness: 7 μm) in this order. The polyimide film is arranged on the peripheral area of the glass plate and on the silicone resin layer (refer to Figure 3).

<Example 2～Example 14> Adjust the thickness between the first main surface and the second main surface of the silicone resin layer, and the width and angle of the peripheral area as shown in the following Table 1 and Table 2. Other than that, follow the same procedure as in Example 1 to obtain Layered body. Table 1 is the case of using the curable composition containing bismuth, and Table 2 is the case of using the curable composition containing cerium. Furthermore, regarding Examples 6 and 7, and 13 and 14, the curable composition was applied to the entire surface of the glass plate, and the coating film was heated at 250°C for 30 minutes to harden, and silicon was produced on the entire surface of the glass plate. After the ketone resin layer, cut the periphery of the obtained glass plate with silicone resin layer to obtain a laminated body having a glass plate and a silicone resin layer and having smooth sides (hereinafter, also referred to as "laminated body C" ), and then use the laminated body C to implement the above-mentioned contents (the production of the laminated body). That is, regarding the laminate C used in Examples 6 and 7, and 13 and 14, the area of the main surface on the glass plate side with the silicone resin layer is the same as the area of the main surface on the opposite side to the glass plate side, and θ Equivalent to 90° of silicone resin layer.

In Tables 1 and 2, the column of "adsorption layer thickness (μm)" indicates the thickness between the first and second main surfaces of the silicone resin layer. In Table 1 and Table 2, the column of "peripheral area width (mm)" indicates the width of the peripheral area (W in Fig. 2). In Table 1 and Table 2, the "angle (°)" column indicates the angle formed by the first principal surface of the silicone resin layer and the inclined surface. The angle measurement method is as described above.

[Table 1] example Adsorption layer thickness (μm) Width of peripheral area (mm) Angle (°) Evaluation Appearance evaluation Width evaluation Embedding of foreign bodies 1 8 5 3 A A A 2 8 30 3 A B A 3 15 5 3 B A A 4 4 1 3 A A B 5 8 50 3 A C A 6 8 0 90 C C A 7 15 0 90 C C A

[Table 2] example Adsorption layer thickness (μm) Width of peripheral area (mm) Angle (°) Evaluation Appearance evaluation Width evaluation Embedding of foreign bodies 8 8 5 3 A A A 9 8 30 3 A B A 10 15 5 3 B A A 11 4 1 3 A A B 12 8 50 3 A C A 13 8 0 90 C C A 14 15 0 90 C C A

As shown in Table 1 and Table 2, the laminated substrate of the present invention exhibits the desired effect. Especially in the case of using a curable composition containing bismuth, comparing Examples 1 to 3 and 5 with Example 4, it was confirmed that when the thickness of the adsorption layer is 6 μm or more, the foreign body embedding property is more excellent. In addition, according to the comparison between Examples 1 and 3, it was confirmed that when the thickness of the adsorption layer is 12 μm or less, the appearance characteristics are more excellent. The same applies to the case of using the curable composition containing cerium. According to the comparison of Examples 8 to 10 and 12 with Example 11, it was confirmed that when the thickness of the adsorption layer is 6 μm or more, the foreign matter embedding property is more excellent. In addition, from a comparison between Examples 8 and 10, it was confirmed that when the thickness of the adsorption layer was 12 μm or less, the appearance characteristics were more excellent.

<Manufacturing of an organic EL display device (equivalent to an electronic device)> Using the laminates obtained in Examples 1 to 5 and 8 to 12, an organic EL display device was manufactured in the following procedure. First, on the surface of the polyimide film of the multilayer substrate opposite to the glass plate side, a film is formed in the order of silicon nitride, silicon oxide, and amorphous silicon by a plasma CVD method. Secondly, a low concentration of boron is implanted into the amorphous silicon layer by the ion doping device, and heat treatment is performed and dehydrogenation treatment is performed. Secondly, the crystallization treatment of the amorphous silicon layer is performed by the laser annealing device. Secondly, by using photolithography etching and ion doping devices, 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 of the polyimide film opposite to the glass plate side, a silicon oxide film is formed by a plasma CVD method to form a gate insulating film, and then a molybdenum film is formed by a sputtering method. Photolithography etching to form gate electrodes. Secondly, by means of photolithography and ion doping devices, high concentrations of boron and phosphorus are implanted into the respective required regions of the N-type and P-type to form the source region and the drain region. Next, on the side of the polyimide film opposite to the glass plate side, a plasma CVD method is used to form a silicon oxide film to form an interlayer insulating film, and aluminum is formed by a sputtering method, and by using photomicrography The etching performed by the shadow method forms the TFT electrode. Next, heat treatment and hydrogenation treatment are performed in a hydrogen atmosphere, and then a passivation layer is formed by forming a silicon nitride film by a plasma CVD method. Next, an ultraviolet curable resin is coated on the side of the polyimide film opposite to the glass plate side, and a planarization layer and contact holes are formed by photolithography. Next, a film of indium tin oxide is formed by a sputtering method, and a pixel electrode is formed by etching using a photolithography method. Then, using the vapor deposition method, the polyimide film was formed on the side opposite to the glass plate side in sequence with: 4,4',4''-tris(3-methylphenylbenzene) as the hole injection layer Amino) triphenylamine, bis[(N-naphthyl)-N-phenyl]benzidine as a hole transport layer, 2,6-bis[4-[N-(4-methyl) as a light-emitting layer (Oxyphenyl)-N-phenyl)aminostyryl)naphthalene-1,5-dicarbonitrile (BSN-BCN) mixed with 8-hydroxyquinoline aluminum complex (Alq ₃ ) at 40% by volume The medium gain is Alq ₃ as the electron transport layer. Next, aluminum is formed into a film 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 film, another glass plate is bonded via an ultraviolet-curing adhesive layer to seal. According to the above procedure, an organic EL structure is formed on the polyimide film. The structure having an organic EL structure on the polyimide film (hereinafter referred to as panel A) is a laminate with a member for electronic devices. Then, after vacuuming the sealing body side of panel A to the pressure plate, insert a stainless steel cutting tool with a thickness of 0.1 mm into the interface between the polyimide film and the glass plate at the corner of panel A, on the polyimide film The interface with the glass plate forms the starting point for peeling. Then, after the surface of the supporting substrate of the panel A is sucked by the vacuum suction cup, the suction cup is raised. Here, while blowing the electrostatic fluid from the ionizer (manufactured by Keyence Corporation) to the interface, the cutting tool is inserted. Secondly, the electrostatic fluid is blown from the ionizer to the formed gap, and the vacuum chuck is pulled up while the water is injected into the peeling front line. As a result, only the polyimide film on which the organic EL structure was formed remained on the platen, and the support substrate with the silicone resin layer was successfully peeled off. Then, use a laser cutter or scribing-breaking method to cut the separated polyimide film and divide it into a plurality of units, then assemble the polyimide film with the organic EL structure and the counter substrate , Implement the module forming step to make an organic EL display device.

Furthermore, the present invention will be described in detail with reference to specific embodiments, but it is clear to the industry that various changes or modifications can be made without departing from the spirit and scope of the present invention. This application is based on the Japanese patent application 2020-015418 filed on January 31, 2020, the Japanese patent application 2020-074048 filed on April 17, 2020, and the Japanese patent application 2020- filed on June 8, 2020. 099427, the content of which is incorporated into this specification as a reference.

10: Multilayer substrate 12: Support substrate 12a: Peripheral area 14: Silicone resin layer 14a: The first main surface 14b: The second main surface 14c: end face 16: layered body 18: Polyimide film 20: Components for electronic devices 22: Laminated body with components for electronic devices 24: electronic device 26: Supporting substrate with adsorption layer AB: line segment AC: line segment W: width θ: Angle

Fig. 1 is a cross-sectional view schematically showing an embodiment of the multilayer substrate of the present invention. FIG. 2 is a top view of the multilayer substrate shown in FIG. 1. FIG. Fig. 3 is a cross-sectional view schematically showing an embodiment of the laminate of the present invention. Fig. 4 is a diagram for explaining a step of forming a member. Fig. 5 is a diagram for explaining the separation step.

10: Multilayer substrate

12: Support substrate

12a: Peripheral area

14: Silicone resin layer

14a: The first main surface

14b: The second main surface

14c: end face

AB: line segment

AC: line segment

θ: Angle

Claims (13)

A laminated substrate having a supporting substrate made of glass and an adsorption layer arranged on the supporting substrate, On the surface of the support substrate on the side of the adsorption layer, there is a peripheral region where the adsorption layer is not arranged, The adsorption layer has a first main surface on the side of the support substrate, a second main surface on the opposite side to the first main surface, and an end surface connecting the first main surface and the second main surface, The end surface is an inclined surface that protrudes from the second main surface toward the first main surface, and The angle formed by the inclined surface and the first principal surface is less than 10°. The laminated substrate of claim 1, wherein the thickness between the first main surface and the second main surface of the adsorption layer is 50 μm or less. The laminated substrate of claim 1, wherein the thickness between the first main surface and the second main surface of the adsorption layer is 12 μm or less. The laminated substrate of claim 1, wherein the thickness between the first main surface and the second main surface of the adsorption layer is 6 μm or more. The laminated substrate of claim 1, wherein the angle formed by the inclined surface and the first main surface is 5° or less. The laminated substrate according to any one of claims 1 to 5, wherein the width of the peripheral region is 1-30 mm. The multilayer substrate according to any one of claims 1 to 6, wherein the adsorption layer is a silicone resin layer. The laminated substrate according to any one of claims 1 to 7, which further includes a protective film disposed on the adsorption layer. A method for manufacturing a laminated substrate, which is the method for manufacturing a laminated substrate according to any one of claims 1 to 8, comprising: a step of attaching the above-mentioned supporting base material and the transfer film, and this step is performed on the above-mentioned supporting base material The above-mentioned transfer film having a precursor film that becomes the adsorption layer is laminated, and the supporting substrate and the transfer film are arranged so that the supporting substrate has a peripheral area where the precursor film is not arranged; and the precursor The film heating step is used to obtain an adsorption layer from the aforementioned precursor film. A method for manufacturing a laminated body, which coats a polyimide varnish containing polyimide or its precursor and a solvent on the side of the adsorption layer of the laminated substrate as claimed in any one of claims 1 to 7, on the periphery A polyimide film is formed on the region and on the adsorption layer, thereby forming a laminate having the support substrate, the adsorption layer, and the polyimide film in this order. A laminated body having: the laminated substrate according to any one of claims 1 to 7; and The polyimide film is arranged on the peripheral region and the adsorption layer of the laminated substrate. A laminated body with components for electronic devices, which has: the laminated body as claimed in claim 11; and A member for an electronic device is arranged on the polyimide film in the laminate. A manufacturing method of an electronic device, which includes: A component forming step of forming a component for an electronic device on the polyimide film of the laminated body of claim 11 to obtain a laminated body with a component for an electronic device; and In the separation step, an electronic device having the polyimide film and the electronic device member is obtained from the laminate with the electronic device member.

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