TWI839306B - Laminated substrate, method for manufacturing laminated body, laminated body, laminated body with component for electronic device, method for manufacturing electronic device - Google Patents

Abstract

The present invention relates to a laminated substrate, which has a glass support substrate and an adsorption layer disposed on the support substrate, wherein the surface of the support substrate on the adsorption layer side has a peripheral area where the adsorption layer is not disposed, the adsorption layer has a first main surface on the support substrate side, a second main surface opposite 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 between the inclined surface and the first main surface is less than 10°. Regarding the laminated substrate of the present invention, when a polyimide varnish is coated on the surface to form a polyimide film, the formed polyimide film is not easy to peel off.

Description

Laminated substrate, method for manufacturing laminated body, laminated body, laminated body with component for electronic device, method for manufacturing electronic device

The present invention relates to a laminate substrate, a method for manufacturing a laminate, a laminate, a laminate with a component for an electronic device, and a method for 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 becoming thinner and lighter. Along with this, substrates such as polyimide resin substrates used in electronic devices are also becoming thinner. If the strength of the substrate is insufficient due to thinning, there is a situation in which the operability of the substrate is reduced, and problems will occur in the step of forming components for electronic devices on the substrate (component formation step).

Therefore, recently, in order to improve the operability of the substrate, a technology using a laminate has been proposed, wherein the laminate has a polyimide resin substrate disposed on a supporting substrate (Patent Document 1). More specifically, Patent Document 1 discloses that a polyimide varnish can be coated on a cured layer of a thermosetting resin composition to form a resin varnish cured film (equivalent to a polyimide film), and precision components can be disposed on the resin varnish cured film. [Prior Technical Document] [Patent Document]

[Patent Document 1] Japanese Patent Publication No. 2018-193544

[The problem the invention is trying to solve]

On the other hand, the inventors of the present invention implemented the process of coating polyimide varnish to prepare polyimide film described in Patent Document 1, and found that when the polyimide varnish is coated to form a polyimide film, the polyimide film is easily peeled off. It is also found that the polyimide film is particularly prone to peeling off at the end of the polyimide film.

The subject of the present invention is to provide a laminate substrate, on the surface of which a polyimide varnish is coated 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 for manufacturing a laminate, a laminate, a laminate with a component for an electronic device, and a method for manufacturing an electronic device. [Technical means for solving the problem]

The inventors of the present invention have conducted intensive research and found that the above-mentioned problem can be solved by the following structure.

(1) A laminate substrate having a glass support substrate and an adsorption layer disposed on the support substrate, The surface of the support substrate on the adsorption layer side has a peripheral area where the adsorption layer is not disposed, The adsorption layer has a first main surface on the support substrate side, 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 between the inclined surface and the first main surface is less than 10°. (2) A laminate 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) A laminated substrate as described in (1), wherein the thickness between the first main surface and the second main surface of the adsorption layer is less than 12 μm. (4) A laminated substrate as described in (1), wherein the thickness between the first main surface and the second main surface of the adsorption layer is more than 6 μm. (5) A laminated substrate as described in (1), wherein the angle between the inclined surface and the first main surface is less than 5°. (6) A laminated substrate as described in any one of (1) to (5), wherein the width of the peripheral region is 1 to 30 mm. (7) A laminated substrate as described in any one of (1) to (6), wherein the adsorption layer is a silicone resin layer. (8) A laminate substrate as described in any one of (1) to (7), further comprising a protective film disposed on the adsorption layer. (9) A method for manufacturing a laminate substrate as described in any one of (1) to (8), comprising: a step of laminating a support substrate and a transfer film, the step of laminating a transfer film having a pre-driver film to be the adsorption layer on the support substrate, wherein the support substrate and the transfer film are disposed so that the support substrate has a peripheral area on which the pre-driver film is not disposed; and a pre-driver film heating step, which is used to obtain the adsorption layer from the pre-driver film. (10) A method for manufacturing a laminate, comprising coating a polyimide varnish comprising polyimide or its precursor and a solvent on the side of the adsorption layer of a laminate substrate as described in any one of (1) to (7), forming a polyimide film on the peripheral region and on the adsorption layer, thereby forming a laminate having a supporting substrate, an adsorption layer, and a polyimide film in sequence. (11) A laminate, comprising: a laminate substrate as described in any one of (1) to (7); and a polyimide film disposed on the peripheral region and on the adsorption layer in the laminate substrate. (12) A laminate with an electronic device component, comprising: a laminate as described in (11); and an electronic device component, which is arranged on a polyimide film in the laminate. (13) A method for manufacturing an electronic device, comprising: a component forming step, in which the electronic device component is formed on the polyimide film of the laminate as described in (11) to obtain the laminate with the electronic device component; and a separation step, in which an electronic device having a polyimide film and an electronic device component is obtained from the laminate with the electronic device component. [Effect of the Invention]

According to the present invention, a laminate substrate can be provided, and when a polyimide varnish is coated on the surface of the laminate substrate to form a polyimide film, the formed polyimide film is not easily peeled off. According to the present invention, a method for manufacturing a laminate, a laminate, a laminate with a component for an electronic device, and a method for manufacturing an electronic device can be provided.

Hereinafter, the embodiments of the present invention will be described with reference to the drawings. However, the embodiments below are only exemplified for the purpose of describing 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 embodiments below without departing from the scope of the present invention. The numerical range indicated by "～" means a range including the numerical values recorded before and after "～" as the lower limit and upper limit.

As the characteristic points of the laminated substrate of the present invention, there are the following examples: the end face of the adsorption layer is set as an inclined surface; the inclination angle of the inclined surface is adjusted to a specific range; and a peripheral area without an adsorption layer is provided on the surface of the supporting substrate. The inventors of the present invention have found that the desired effect can be obtained by adopting the above-mentioned structure. The details of how the desired effect is obtained are not clear, but it is considered that, first, a peripheral area is provided on the surface of the supporting substrate, and the polyimide film is arranged on the laminated substrate in such a manner that the peripheral area is in contact with the polyimide film, thereby suppressing the peeling of the polyimide film from the end due to the interaction between the polyimide film and the glass supporting substrate. It is also believed that by setting a tilted surface with a specific tilt angle at the end, the generation of gaps between the polyimide film and the adsorption layer and the supporting substrate can be suppressed, and as a result, the peeling of the polyimide film is suppressed.

<Multilayer substrate> FIG. 1 is a cross-sectional view schematically showing one embodiment of the multilayer substrate of the present invention. FIG. 2 is a top view of the multilayer substrate shown in FIG. 1. The multilayer substrate 10 has a glass support substrate 12 and an adsorption layer 14 disposed on the support substrate 12. As shown in FIG. 1 and FIG. 2, the adsorption layer 14 has a first main surface 14a on the side of the support substrate 12, a second main surface 14b on the opposite side to the first main surface 14a, and an end surface 14c connecting the first main surface 14a and the second 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. Furthermore, the shape of the adsorption layer 14 (the shape of the main surface) is rectangular, and all four end surfaces 14c are inclined surfaces. In addition, as shown in Figures 1 and 2, the surface of the adsorption layer 14 side of the support substrate 12 has a peripheral area 12a where the adsorption layer 14 is not arranged. In other words, the adsorption layer 14 is arranged on the support substrate 12 in a manner that leaves an edge-shaped area (peripheral area 12a) that is not in contact with the adsorption layer 14 on the support substrate 12. In the above-mentioned state, the area of the arrangement area of the adsorption layer 14 is narrower than the area of the surface (main surface) of the support substrate 12, and the above-mentioned peripheral area 12a is equivalent to an area located more inward than the outer periphery of the support substrate 12. Furthermore, in FIG. 1 and FIG. 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, and the adsorption layer 14 is arranged on the support substrate 12 in such a manner that one side constituting the outer periphery of the support substrate 12 is parallel to one side constituting the outer periphery of the adsorption layer 14.

A polyimide varnish is applied on the peripheral area of the supporting substrate 12 of the laminate substrate 10 and on 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 component for an electronic device is formed on the polyimide film, and then the polyimide film (i.e., the electronic device) on which the component for an electronic device is formed is separated. In this way, an electronic device is manufactured. Below, each layer (supporting substrate 12, adsorption layer 14) constituting the laminate substrate 10 is described in detail, and then the manufacturing method of the laminate substrate 10 is described in detail.

(Support substrate) The support substrate 12 is a member that supports and reinforces the polyimide film, such as a glass plate. As the type of glass, preferably, it is alkali-free borosilicate glass, borosilicate glass, sodium calcium glass, high silica glass, and oxide-based glass with other silicon oxide as the main component. As oxide-based glass, preferably, it is glass with a silicon oxide content of 40 to 90% by mass converted from oxides. As a glass plate, more specifically, it can be exemplified by: a glass plate containing alkali-free borosilicate glass (trade names "AN100" and "AN Wizus" manufactured by AGC Co., Ltd.). Regarding the manufacturing method of the glass plate, it can usually be obtained by melting glass raw materials and forming the molten glass into a plate shape. Such a forming method can be a common method, for example, it can be exemplified by: a floating method, a melting method, and a flow hole down-drawing method.

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

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

The support substrate 12 preferably has low flexibility. Therefore, the thickness of the support substrate 12 is preferably greater than 0.3 mm, and more preferably greater than 0.5 mm. On the other hand, the thickness of the support substrate 12 is preferably less than 1.0 mm.

(Adsorption layer) The adsorption layer 14 is a film used to prevent the polyimide film disposed thereon from peeling off. The adsorption layer 14 is disposed on the support substrate 12 in such a manner that a peripheral region 12a that is not in contact with the adsorption layer 14 is left 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 toward the first main surface 14a. It is preferred that 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°. 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, and more preferably 5° or less. There is no special restriction on the lower limit, and it is preferably 1° or more. The angle θ formed by the inclined surface in the adsorption layer 14 and the first main surface 14a is obtained based on the cross-sectional shape of the adsorption layer 14 using the non-contact surface property measuring device "PF-60" manufactured by Mitaka Optical Co., Ltd. In more detail, as shown in FIG1, based on the cross-sectional view of the adsorption layer 14, the length of the line segment AB and the length of the line segment AC are measured, 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 materials for the organic layer, for example, acrylic resin, polyolefin resin, polyurethane resin, polyimide resin, silicone resin, polyimide silicone resin, and fluororesin can be cited. In addition, several types of resins can be mixed to form the adsorption layer 14. As materials for the inorganic layer, for example, oxides, nitrides, oxynitrides, carbides, carbonitrides, silicides, and fluorides can be cited. Examples of oxides (preferably metal oxides), nitrides (preferably metal nitrides), and oxynitrides (preferably metal oxynitrides) include oxides, nitrides, and oxynitrides of one or more elements selected from Si, Hf, Zr, Ta, Ti, Y, Nb, Na, Co, Al, Zn, Pb, Mg, Bi, La, Ce, Pr, Sm, Eu, Gd, Dy, Er, Sr, Sn, In, and Ba. Examples of carbides (preferably metal carbides) and carbonitrides (preferably metal carbonitrides) include carbides, carbonitrides, and carbon oxides of one or more elements selected from Ti, W, Si, Zr, and Nb. As silicide (preferably metal silicide), for example, silicide of one or more elements selected from Mo, W and Cr can be cited. As fluoride (preferably metal fluoride), for example, fluoride of one or more elements selected from Mg, Y, La and Ba can be cited.

The adsorption layer 14 may also be a plasma polymerization film. When the adsorption layer 14 is _a plasma polymerization film, the material for forming the plasma polymerization film may include: fluorocarbon monomers such as _CF4 , _CHF3 , _C2H6 , _C3H6 , _C2H2 , _CH3F , _C4H8 ; carbon hydrogen monomers such as methane, ethane, _propane , ethylene, propylene, _acetylene , _benzene , toluene; hydrogen, _SF6 , etc.

Among them, in terms of heat resistance or peeling properties, the material of the adsorption layer 14 is preferably silicone resin or polyimide silicone resin, more preferably silicone resin, and particularly preferably silicone resin formed by condensation reaction type silicone. The following describes in detail the form of the adsorption layer being a silicone resin layer.

The so-called silicone resin is a resin containing a specific organic siloxane unit, which 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, and all of them can be used. Among them, condensation reaction type silicones are preferred. As condensation reaction type silicones, hydrolyzable organic silane compounds or mixtures thereof (monomer mixtures) as monomers, or partially hydrolyzed condensates (organopolysiloxanes) obtained by partially hydrolyzing and condensing monomers or monomer mixtures can be preferably used. By using this condensation reaction type silicone and carrying out a hydrolysis-condensation reaction (sol-gel reaction), a silicone resin can be formed.

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

The adsorption layer 14 preferably has a hydroxyl group. A portion of the Si-O-Si bonds of the silicone resin constituting the adsorption layer 14 is cut to generate a hydroxyl group. In addition, when a condensation reaction type silicone is used, the hydroxyl group can become a 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 further preferably 12 μm or less. On the other hand, the thickness of the adsorption layer 14 is preferably more than 1 μm, and more preferably 6 μm or more to achieve better foreign matter embedding performance. The above thickness is the value obtained by measuring the thickness of the adsorption layer 14 at any position of more than 5 points by a contact-type film thickness measuring device and arithmetically averaging the same. Furthermore, the so-called excellent foreign matter embedding performance means that even if there is foreign matter between the supporting substrate 12 and the adsorption layer 14, the foreign matter will be embedded by the adsorption layer 14. If the embedding property of foreign matter is excellent, it is not easy for the adsorption layer to produce convex parts caused by foreign matter. When forming components for electronic devices on the polyimide film, the risk of disconnection in the components for electronic devices caused by convex parts can be suppressed. Furthermore, since the gaps formed when the above-mentioned convex parts are generated are observed in the form of bubbles, the embedding property of foreign matter can be evaluated by whether bubbles are generated.

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

(Protective film) The laminated 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 the polyimide varnish described below is applied on the adsorption layer 14.

Examples of materials for forming the protective film include polyimide resins, polyester resins (e.g., polyethylene terephthalate (PET), polyethylene naphthalate), polyolefin resins (e.g., polyethylene, polypropylene), and polyurethane resins. Among them, polyester resins are 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 further 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 further preferably 100 μm or less.

The protective film may also have a close contact layer on the surface of the adsorption layer 14 side. As the close contact layer, a known adhesive layer can be used. As the adhesive constituting the adhesive layer, for example, (meth) acrylic adhesive, silicone adhesive, polyurethane adhesive. In addition, the close contact layer may also be composed of resin, and as the resin, for example, vinyl acetate resin, ethylene-vinyl acetate copolymer resin, vinyl chloride-vinyl acetate copolymer resin, (meth) acrylic resin, butyral resin, polyurethane resin, polystyrene elastomer can be cited. In order to reduce the peeling force when peeling the protective film, the surface roughness (Ra) of the protective film is preferably less than 50 nm, more preferably less than 30 nm, and further preferably less than 15 nm. In addition, in order to maintain the close contact between the protective film and the adsorption layer, Ra is preferably greater than 0.1 nm, and more preferably greater than 0.5 nm. The surface roughness (Ra) is measured using the non-contact surface-layer cross-section shape measurement system "Vertscan R3300-lite" manufactured by Ryoka Systems.

<Method for manufacturing a laminate substrate> The method for manufacturing a laminate substrate is not particularly limited, and a known method can be cited as an example. Among them, in order to achieve better productivity, the following method can be cited as an example, that is, preparing a transfer film having a temporary support and a pre-drive film arranged on the temporary support and becoming an adsorption layer after heat treatment, bonding the pre-drive film in the transfer film to a specific position on a glass support substrate, and applying heat treatment to the obtained laminate having a glass support substrate, the pre-drive film and the temporary support. By applying heat treatment, the end of the pre-drive film can be fluidized to form the above-mentioned adsorption layer with a specific inclined surface. Furthermore, when the precursor film is bonded to the support substrate, the precursor film is bonded to the support substrate in a manner to form the above-mentioned peripheral area. In addition, in addition to the above, the precursor film that becomes the adsorption layer after heat treatment can be arranged at a specific position of the glass support substrate by coating, and heat treatment can be performed to form the above-mentioned adsorption layer with a specific slope. As the above-mentioned precursor film, for example, a film formed by heat treatment of a coating formed by coating a curable composition containing curable silicone. The heating temperature of the heat treatment of the coating 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 end face shape of the adsorption layer can be made into an inclined surface. Furthermore, during the heat treatment, it is preferred to apply pressure while performing the heat treatment. Specifically, it is preferred to use a high pressure autoclave to perform the heat treatment and the pressure treatment. As the heating temperature during the heat treatment, it is preferably 50 to 350°C, more preferably 55 to 300°C, and further preferably 60 to 250°C. As the heating time, it is preferably 10 to 60 minutes, and more preferably 20 to 40 minutes. As the pressure during the pressure treatment, it is preferably 0.5 to 1.5 MPa, and more preferably 0.8 to 1.0 MPa.

Furthermore, the heat treatment may be performed multiple times. When the heat treatment is performed multiple times, the heating conditions may be changed each time. For example, when the heat treatment is performed multiple times, the heating temperature may be changed. For example, when the heat treatment is performed twice, the first heat treatment may be performed at a temperature lower than 100°C, and the second heat treatment may be performed at a temperature higher than 100°C. Furthermore, when the heat treatment is performed multiple times, the presence or absence of pressurization may be changed. For example, when the heat treatment is performed twice, the pressurization may be performed in the first heat treatment, and the pressurization may not be performed in the second heat treatment. Furthermore, when a transfer film is used to manufacture a laminated substrate, the above-mentioned heat treatment can be performed after the temporary support is peeled off, or the heat treatment can be performed directly when the temporary support is arranged on the adsorption layer. In addition, when multiple heat treatments are performed, the temporary support can be peeled off between each heat treatment. For example, after the first heat treatment, the temporary support can be peeled off and the second heat treatment can be performed.

The surface of the adsorption layer of the laminated substrate may be subjected to surface treatment. Examples of surface treatment include: corona treatment, plasma treatment, and ultraviolet-ozone treatment, preferably corona treatment. In the case where a polyimide film is formed 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, and further preferably 15 nm or less. In addition, in order to maintain the close contact between the polyimide film and the adsorption layer, Ra is preferably 0.1 nm or more, and more preferably 0.5 nm or more.

The laminated substrate 10 can be used to manufacture a structure having the supporting base material 12, the adsorption layer 14 and the supported material in this order. As the supported material, a material other than the polyimide film 18 can also be laminated. Examples of the support material include polyimide resin films, epoxy resin films, photosensitive resists, polyester resin films (e.g., polyethylene terephthalate, polyethylene naphthalate), polyolefin resin films (e.g., polyethylene, polypropylene), polyurethane resin films, metal foils (e.g., copper foil, aluminum foil), sputtered films (e.g., copper, titanium, aluminum, tungsten, silicon nitride, silicon oxide, amorphous silicon), TGV (Through Glass Via) substrates, thin plate glass substrates, thin plate glass substrates with sacrificial layers, ABF (Ajinomoto Build-up Film), sapphire substrates, silicon substrates, TSV (Through Silicon Via) substrates, LED (Light Emitting Diode) substrates, and the like. Emitting Diode) chips, display panels (e.g., LCD, OLED, μ-LED), artificial diamonds, spacer paper, etc.

<Laminated body and its manufacturing method> Using the above-mentioned laminated substrate 10, a laminated body 16 having a supporting substrate 12, an adsorption layer 14 and a polyimide film 18 as shown in FIG. 3 can be manufactured. Specifically, as a manufacturing method of the laminated body 16, the following method can be cited, that is, a polyimide varnish containing polyimide and a solvent is applied to the adsorption layer 14 side of the laminated substrate 10, and a polyimide film 18 is formed on the peripheral area 12a and on the adsorption layer 14, thereby forming a laminated body having a supporting substrate 12, an adsorption layer 14 and a polyimide film 18 in sequence. The above-mentioned manufacturing method is described in detail below, and then the structure of the polyimide film 18 is described in detail.

(Polyimide varnish) Polyimide varnish contains polyimide or its precursor and solvent. Polyimide is usually obtained by condensing tetracarboxylic dianhydride and diamine and performing imidization. Polyimide is preferably solvent-soluble. As tetracarboxylic dianhydride used, aromatic tetracarboxylic dianhydride and aliphatic tetracarboxylic dianhydride can be cited. As diamine used, aromatic diamine and aliphatic diamine can be cited. Examples of aromatic tetracarboxylic dianhydrides include pyromellitic acid dianhydride (1,2,4,5-benzene tetracarboxylic dianhydride), 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-biphenyl tetracarboxylic dianhydride, and 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride. Aliphatic tetracarboxylic dianhydrides include cyclic or non-cyclic aliphatic tetracarboxylic dianhydrides. Examples of cyclic aliphatic tetracarboxylic dianhydrides include 1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2,4,5-cyclohexane tetracarboxylic dianhydride, and 1,2,4,5-cyclopentane tetracarboxylic dianhydride. Examples of non-cyclic aliphatic tetracarboxylic dianhydrides include 1,2,3,4-butane tetracarboxylic dianhydride and 1,2,3,4-pentane tetracarboxylic dianhydride. Examples of aromatic diamines include 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 aliphatic diamines include non-cyclic aliphatic diamines such as ethylenediamine, hexamethylenediamine, polyethylene glycol bis(3-aminopropyl) ether, and polypropylene glycol bis(3-aminopropyl) ether, and cyclic aliphatic diamines such as 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, isophoronediamine, and norbatanediamine.

The so-called precursor of polyimide refers to polyamide before imidization (i.e., polyamic acid and/or polyamide ester).

The solvent may be any solvent capable of dissolving the polyimide or its precursor, and examples thereof include phenolic solvents (e.g., m-cresol), amide solvents (e.g., N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide), lactone solvents (e.g., γ-butyrolactone, δ-valerolactone, ε-caprolactone, γ-crotonolactone, γ-caprolactone, α-methyl-γ-butyrolactone, γ-valerolactone, α-acetyl-γ-butyrolactone, δ-caprolactone), sulfoxide solvents (e.g., N,N-dimethylsulfoxide), ketone solvents (e.g., acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone), and ester solvents (e.g., methyl acetate, ethyl acetate, butyl acetate, dimethyl carbonate).

(Sequence) The method of coating the polyimide varnish on the adsorption layer 14 side of the laminate substrate 10 is not particularly limited, and a known method can be cited. For example, spray coating, die nozzle coating, rotary coating, dip coating, roller coating, rod coating, screen printing, and gravure coating can be cited.

After coating, heat treatment can be performed as needed. As a condition for 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. When performing multiple heat treatments, the heating conditions can be changed each time.

(Laminate) As shown in FIG. 3, the laminate 16 has a support substrate 12, an adsorption layer 14, and a polyimide film 18. The structures of the support 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 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, more preferably 0.2 mm or less. In order to form high-precision 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 further preferably 10 nm or less. Regarding the thermal expansion coefficient of the polyimide film 18, it is better to have a smaller difference with the thermal expansion coefficient of the supporting substrate 12 because it can suppress the warping of the laminate 16 after heating or cooling. 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, 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 in terms of productivity of electronic devices. The polyimide film 18 may be colored or colorless and transparent.

The laminate 16 can be used for various purposes, such as the manufacture of electronic components such as panels for display devices, PV, thin-film secondary batteries, semiconductor wafers with circuits formed on the surface, and receiving sensor panels. In these uses, there is also a situation where the laminate is exposed to high temperature conditions (for example, above 450°C) in an atmospheric atmosphere (for example, for more than 20 minutes). 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) shutter panels, etc. Receiving sensor panels include electromagnetic wave receiving sensor panels, X-ray photosensitive sensor panels, ultraviolet photosensitive sensor panels, visible light photosensitive sensor panels, infrared photosensitive sensor panels, etc. The substrate used in the receiving sensor panel can be reinforced by reinforcing sheets such as resin.

<Method for manufacturing electronic device> An electronic device including a polyimide film and the following electronic device component can be manufactured using a laminate. The method for manufacturing an electronic device is a method having the following steps, as shown in, for example, FIGS. 4 and 5 , namely, a component forming step, in which an electronic device component 20 is formed on the polyimide film 18 of the laminate 16 (on the surface of the polyimide film 18 opposite to the adsorption layer 14 side) to obtain a laminate 22 with an electronic device component attached; and a separation step, in which an electronic device 24 having a polyimide film 18 and an electronic device component 20 is obtained from the laminate 22 with an electronic device component attached.

Hereinafter, the step of forming the component 20 for the electronic device is referred to as the "component forming step", and the step of separating into the electronic device 24 and the supporting substrate 26 with the adsorption layer is referred to as the "separation step". The materials and sequence used in each step are described in detail below.

(Component formation step) The component formation step is a step of forming a component for an electronic device on the polyimide film 18 of the laminate 16. More specifically, as shown in FIG. 4, a component 20 for an electronic device is formed on the polyimide film 18 (on the surface of the polyimide film 18 opposite to the adsorption layer 14), and a laminate 22 with a component for an electronic device is obtained. 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. As materials constituting the barrier layer, for example, silicon nitride and silicon oxide can be cited. In addition, the barrier layer may be one layer, two layers or more, or a combination of multiple materials. The film forming method is not particularly limited, and known methods may be cited. For example, methods such as plasma CVD (Chemical Vapor Deposition) and sputtering may be cited. First, the electronic device component 20 used in this step is described in detail, and then the order of the steps is described in detail.

(Component for electronic device) The component for electronic device 20 is a component constituting at least a part of the electronic device formed on the polyimide film 18 of the laminate 16. More specifically, the electronic device component 20 may include: display device panels, solar cells, thin film secondary batteries, or electronic components such as semiconductor wafers with circuits formed on the surface, components used in receiving sensor panels, etc. (for example, LTPS (Low Temperature Poly Silicon) and other display device components, solar cell components, thin film secondary battery components, electronic component circuits, and receiving sensor components). For example, the solar cell component described in paragraph [0192] of the specification of U.S. Patent Application Publication No. 2018/0178492, the thin film secondary battery component described in paragraph [0193] of the same specification, and the electronic component circuit described in paragraph [0194] of the same specification.

(Sequence of steps) The manufacturing method of the laminate 22 with electronic device components is not particularly limited. According to the type of components constituting the electronic device components, the electronic device component 20 is formed on the polyimide film 18 of the laminate 16 by a previously known method. The electronic device component 20 may be a part of all components ultimately formed on the polyimide film 18 (hereinafter referred to as "partial component"), rather than all components ultimately formed on the polyimide film 18 (hereinafter referred to as "all components"). It is also possible to set the substrate with the attached partial component peeled off from the adsorption layer 14 as the substrate with the attached full component in the subsequent step (equivalent to the electronic device described below). Other components for electronic devices may also be formed on the peeling surface of the substrate with all components peeled off from the adsorption layer 14. Furthermore, two electronic device components 20 with laminated bodies 22 with components for electronic devices may be placed facing each other, and the two laminated bodies with all components may be bonded together to assemble the laminated body with all components, and then the two supporting substrates with adsorption layers may be peeled off from the laminated body with all components to manufacture the electronic device.

For example, in the case of manufacturing 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, various layer formation or processing is performed, such as forming a transparent electrode; further evaporating a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, etc. on the surface formed with the transparent electrode; forming a back electrode; sealing with a sealing plate, etc. As such layer formation or processing, specifically, for example, film formation processing, evaporation processing, and sealing plate bonding processing can be cited.

(Separation step) The separation step is the following step, that is, as shown in FIG5, the interface between the adsorption layer 14 and the polyimide film 18 is used as a peeling surface, and the laminated body 22 with the component for electronic device obtained in the above-mentioned component forming step is separated from the polyimide film 18 with the component for electronic device 20 and the supporting substrate 26 with the adsorption layer, thereby obtaining an electronic device 24 including the component for electronic device 20 and the polyimide film 18.

In the case where the electronic device component 20 on the peeled polyimide film 18 is a part of all the required components, the remaining components may be formed on the polyimide film 18 after separation.

There is no particular limitation on the method of peeling the polyimide film 18 and the adsorption layer 14. For example, a sharp blade-like object may 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. Preferably, the laminate 22 with the electronic device component is placed on a press plate with the supporting substrate 12 as the upper side and the electronic device component 20 as the lower side, and the electronic device component 20 is vacuum-adsorbed onto the press plate, and in this state, the blade-like object is firstly intruded into the interface between the polyimide film 18 and the supporting substrate 12. Afterwards, the support substrate 12 is sucked by a plurality of vacuum suction cups, and the vacuum suction cups are raised sequentially from the vicinity of the position where the blade-like object is inserted. In this way, the support substrate 26 with the adsorption layer attached can be easily peeled off.

When the electronic device 24 is separated from the laminate 22 of the component for the attached electronic device, the electrostatic adsorption of the fragments of the adsorption layer 14 to the electronic device 24 can be further suppressed by controlling the blowing performed by the ionizer or controlling the humidity. The above-mentioned method for manufacturing the electronic device is suitable for manufacturing a display device described in paragraph [0210] of the specification of U.S. Patent Application Publication No. 2018/0178492, and as the electronic device 24, for example, the one described in paragraph [0211] of the same specification can be cited.

Furthermore, before performing the above separation step, the region of the laminate where the components for electronic devices are not arranged may be cut off and removed. [Example]

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to these examples.

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

<Appearance Evaluation> The polyimide film in the laminate having the glass plate, the silicone resin layer and the polyimide film in the order obtained 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 peeled off, it was within the range of no practical problem. C: Most or the entire surface of the polyimide film peeled off, so it was within the range of practical problems.

<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: Width is 1 mm or more and 10 mm or less B: Width is more than 10 mm and less than 30 mm C: Width is more than 30 mm and less than 1 mm

<Foreign matter embedding property> Visually observe the laminated body in which the glass plate, silicone resin layer and PET film are arranged in the following order, and evaluate it according to the following criteria. A: The number of interface bubbles caused by foreign matter at the glass plate/silicone resin layer interface is 5 or less. B: The number of interface bubbles caused by foreign matter at the glass plate/silicone resin layer interface is more than 5 and less than 10. C: The number of interface bubbles caused by foreign matter at the glass plate/silicone resin layer interface is more than 10.

<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, and then heated to 60°C and reacted for 12 hours. The obtained crude reaction solution was cooled to 25°C, and then washed with water (300 g) 3 times. Trimethylsilyl chloride (70 g) was added to the washed crude reaction solution, and the mixture was stirred at 25°C for 20 minutes, and then heated to 50°C and reacted for 12 hours. The obtained crude reaction solution was cooled to 25°C, and then washed with water (300 g) 3 times. Toluene was removed from the washed reaction crude liquid by reduced pressure distillation to obtain a slurry state, which was then dried overnight in a vacuum dryer to obtain a white organic polysiloxane compound, namely, curable silicone 1. The number of T units in curable silicone 1: the number of M units = 87:13 (molar ratio). In addition, the M unit refers to a monofunctional organic silaneoxy unit represented by (R) ₃ SiO _1/2 . The T unit refers to a trifunctional organic silaneoxy unit represented by RSiO _3/2 (R represents a hydrogen atom or an organic group).

(Preparation of curable composition) Curing silicone 1 was mixed with heptane, and an organic zirconium compound (zirconium octanoate compound) and an organic bismuth compound (bismuth 2-ethylhexanoate) were added. The amount of solvent was adjusted so that the solid content concentration was 50 mass %. In addition, the amount of metal compound added was adjusted so that the metal element was 0.1 mass part relative to 100 mass parts of the resin. The obtained mixed solution was filtered using a filter with a pore size of 0.45 μm to obtain a curable composition. Curing silicone 1 was mixed with heptane, and an organic zirconium compound (zirconium octanoate compound) and an organic bismuth compound (bismuth 2-ethylhexanoate) were added. The amount of solvent was adjusted so that the solid content concentration was 50 mass %. In addition, the amount of metal compound added was adjusted so that the metal element was 0.1 mass part relative to 100 mass parts of resin. The obtained mixed solution was filtered using a filter with a pore size of 0.45 μm to obtain a curable composition.

(Preparation of laminated substrate) The prepared curable composition was applied to the surface of a polyethylene terephthalate film (PET film) (manufactured by Toyobo Co., Ltd., COSMOSHINE A4100), and heated at 140°C for 10 minutes using a heating plate to form a silicone resin layer. The thickness of the silicone resin layer was 8 μm. Next, after cleaning with a water-based glass cleaner ("PK-LCG213" manufactured by Parker Corporation), a 200×200 mm, 0.5 mm thick glass plate "AN100" (support substrate) washed with pure water was bonded to a PET film formed with a silicone resin layer to produce a laminate having a glass plate, a silicone resin layer, and a PET film arranged in sequence. Furthermore, during the above bonding, bonding was performed in a manner that an area without a silicone resin layer was left on the peripheral area of the surface of the glass plate (see Figure 2). The width W of the peripheral area was 5 mm. Next, the obtained laminate was placed in an autoclave and heated for 30 minutes at 60°C and 1 MPa. After that, 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 a corona treatment. The silicone resin layer obtained has a first main surface on the glass plate 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, and the end surface is an inclined surface that protrudes from the second main surface to the first main surface. The angle between the inclined surface and the first main 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 laminated body) Polyimide varnish (UPIA-ST-1003 manufactured by Ube Industries) was applied to the surface of the silicone resin layer side of the laminated substrate obtained above, and then heated at 60°C for 30 minutes, then at 120°C for 30 minutes, and then at 450°C for 10 minutes to obtain a laminated body having a glass plate, a silicone resin layer, and a polyimide film (thickness: 7 μm) in sequence. The polyimide film was arranged on the peripheral area of the glass plate and on the silicone resin layer (see Figure 3).

<Example 2 to Example 14> The thickness between the first main surface and the second main surface of the silicone resin layer, the width of the peripheral area, and the angle were adjusted as shown in Tables 1 and 2 below, and the laminate was obtained in the same order as in Example 1. Table 1 is the case of using a curable composition containing bismuth, and Table 2 is the case of using a curable composition containing niobium. Furthermore, regarding Examples 6 and 7, and 13 and 14, a curable composition was coated on the entire surface of a glass plate, the coating was heated at 250°C for 30 minutes to cure, a silicone resin layer was formed on the entire surface of the glass plate, and then the peripheral portion of the glass plate with the silicone resin layer was cut off to obtain a laminate having a glass plate and a silicone resin layer and having a smooth side surface (hereinafter also referred to as "laminate C"), and then the above-mentioned content (laminate formation) was implemented using laminate C. That is, regarding the laminate C used in Examples 6 and 7, and 13 and 14, the silicone resin layer has the same area of the main surface on the glass plate side and the main surface on the side opposite to the glass plate side, and the angle θ is equal to 90°.

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 "Peripheral area width (mm)" column indicates the width of the peripheral area (W in Figure 2). In Tables 1 and 2, the "Angle (°)" column indicates the angle between the first main 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 (°) Reviews Appearance evaluation Width evaluation Foreign body embedment 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 (°) Reviews Appearance evaluation Width evaluation Foreign body embedment 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 Tables 1 and 2, the laminated substrate of the present invention exhibits the desired effect. In particular, when a curable composition containing bismuth is used, it is confirmed that when the thickness of the adsorption layer is 6 μm or more, the foreign matter embedding property is more excellent according to the comparison between Examples 1 to 3 and 5 and Example 4. In addition, it is confirmed that when the thickness of the adsorption layer is 12 μm or less, the appearance characteristics are more excellent according to the comparison between Examples 1 and 3. The same is true when a curable composition containing bismuth is used. According to the comparison between Examples 8 to 10 and 12 and Example 11, it is confirmed that when the thickness of the adsorption layer is 6 μm or more, the foreign matter embedding property is more excellent. Furthermore, based on the comparison between Examples 8 and 10, it was confirmed that when the thickness of the adsorption layer is less than 12 μm, the appearance characteristics are more excellent.

<Manufacturing of an organic EL display device (equivalent to an electronic device)> Using the multilayer bodies obtained in Examples 1 to 5 and 8 to 12, an organic EL display device is manufactured in the following order. First, on the surface of the polyimide film of the multilayer substrate opposite to the glass plate side, silicon nitride, silicon oxide, and amorphous silicon are formed in this order by plasma CVD. Next, a low concentration of boron is injected into the amorphous silicon layer by an ion doping device, and a heat treatment and a dehydrogenation treatment are performed. Next, a crystallization treatment of the amorphous silicon layer is performed by a laser annealing device. Next, by using photolithography etching and ion doping equipment, low-concentration phosphorus is injected 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, a silicon oxide film is formed by plasma CVD to form a gate insulating film, and then molybdenum is formed by sputtering, and a gate electrode is formed by etching using photolithography. Next, by using photolithography and ion doping equipment, high-concentration boron and phosphorus are injected into the required areas of the N-type and P-type to form the source region and the drain region. Next, a silicon oxide film is formed on the side of the polyimide film opposite to the glass plate by plasma CVD to form an interlayer insulating film, and an aluminum film is formed by sputtering and etching by photolithography to form TFT electrodes. Next, a silicon nitride film is formed by plasma CVD after heat treatment and hydrogenation in a hydrogen atmosphere to form a passivation layer. Next, an ultraviolet curable resin is applied on the side of the polyimide film opposite to the glass plate, and a planarization layer and contact holes are formed by photolithography. Next, indium tin oxide was formed by sputtering, and pixel electrodes were formed by etching using photolithography. Then, on the side of the polyimide film opposite to the glass plate, films were formed in order by evaporation: 4,4',4''-tris(3-methylphenylphenylamino)triphenylamine as a hole injection layer, bis[(N-naphthyl)-N-phenyl]benzidine as a hole transport layer, 2,6-bis[4-[N-(4-methoxyphenyl)-N-phenyl]aminostyryl]naphthalene-1,5-dicarbonitrile (BSN-BCN) mixed with 8-hydroxyquinoline aluminum complex (Alq ₃ ) at 40 volume % as a light emitting layer, and Alq ₃ as an electron transport layer. Next, aluminum is formed into a film by sputtering, and a counter electrode is formed by etching using photolithography. Next, another glass plate is bonded to the side of the polyimide film opposite to the glass plate via a UV-curing adhesive layer for sealing. According to the above sequence, 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 laminated body with components for electronic devices. Next, after the sealed body side of panel A is vacuum-adsorbed onto a press plate, a stainless steel blade with a thickness of 0.1 mm is inserted into the interface between the polyimide film and the glass plate at the corner of panel A to form a starting point for peeling at the interface between the polyimide film and the glass plate. Then, after the surface of the support substrate of panel A is sucked by the vacuum suction cup, the suction cup is raised. Here, a destaticizing fluid is blown to the interface from the ionizer (manufactured by Keyence Corporation) while a cutting tool is inserted. Next, a destaticizing fluid is blown to the gap formed from the ionizer, and water is injected to the peeling front while the vacuum suction cup is lifted. As a result, only the polyimide film with the organic EL structure formed remains on the pressure plate, and the support substrate with the silicone resin layer is successfully peeled off. Next, the separated polyimide film is cut by a laser cutter or a scribing-breaking method to be divided into a plurality of units, and then the polyimide film having an organic EL structure is assembled with a counter substrate to perform a module forming step and manufacture an organic EL display device.

In addition, the present invention is described in detail with reference to specific embodiments, but it is clear that various changes or modifications can be made without departing from the spirit and scope of the present invention. This application is based on 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. 2020-099427 filed on June 8, 2020, and the contents thereof are incorporated into this specification as a reference.

10: Laminated substrate 12: Support substrate 12a: Peripheral area 14: Silicone resin layer 14a: First main surface 14b: Second main surface 14c: End surface 16: Laminated body 18: Polyimide film 20: Component for electronic device 22: Laminated body with component for electronic device 24: Electronic device 26: Support substrate with adsorption layer AB: Line segment AC: Line segment W: Width θ: Angle

FIG. 1 is a cross-sectional view schematically showing an implementation of the laminate substrate of the present invention. FIG. 2 is a top view of the laminate substrate shown in FIG. 1. FIG. 3 is a cross-sectional view schematically showing an implementation of the laminate body of the present invention. FIG. 4 is a cross-sectional view for illustrating the component forming step. FIG. 5 is a cross-sectional view for illustrating the separation step.

10: Laminated substrate 12: Support substrate 12a: Peripheral area 14: Silicone resin layer 14a: First main surface 14b: Second main surface 14c: End surface AB: Line segment AC: Line segment θ: Angle

Claims (13)

A laminate substrate having a glass support substrate and an adsorption layer disposed on the support substrate, The surface of the support substrate on the adsorption layer side has a peripheral area where the adsorption layer is not disposed, The adsorption layer has a first main surface on the support substrate side, 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 between the inclined surface and the first main surface is less than 5°, The adsorption layer is a silicone resin layer formed by condensation reaction type silicone. The laminated substrate of claim 1, wherein the adsorption layer has a hydroxyl group. The laminate substrate of claim 1, wherein the adsorption layer comprises a metal compound. The multilayer substrate of claim 3, wherein the metal compound comprises at least one metal element selected from 3d transition metals, 4d transition metals and chrysogenum metals. A laminate substrate as claimed in claim 1 or 3, wherein the thickness of the adsorption layer between the first main surface and the second main surface is greater than 1 μm and less than 12 μm. A laminate substrate as claimed in claim 5, wherein the thickness between the first main surface and the second main surface of the adsorption layer is greater than 1 μm and less than 8 μm. A laminate substrate as claimed in claim 6, wherein the thickness between the first main surface and the second main surface of the adsorption layer is greater than 1 μm and less than 4 μm. The laminate substrate of claim 1 or 3, wherein the width of the peripheral area is 1 to 30 mm. The laminated substrate of claim 1 or 3 further comprises a protective film disposed on the adsorption layer. A method for manufacturing a laminated body, wherein a polyimide varnish comprising polyimide or its precursor and a solvent is coated on the above-mentioned adsorption layer side of the laminated substrate as claimed in claim 1 or 3, and a polyimide film is formed on the above-mentioned peripheral area and on the above-mentioned adsorption layer, thereby forming a laminated body having the above-mentioned supporting substrate, the above-mentioned adsorption layer, and the above-mentioned polyimide film. A laminated body comprising: a laminated substrate as claimed in claim 1 or 3; and a polyimide film disposed on the peripheral region of the laminated substrate and on the adsorption layer. A laminated body with a component for an electronic device, comprising: a laminated substrate as claimed in claim 1 or 3; and a component for an electronic device, which is arranged on the above-mentioned adsorption layer in the above-mentioned laminated substrate. A method for manufacturing an electronic device, comprising: a component forming step, in which a component for an electronic device is formed on the polyimide film of the laminate as claimed in claim 11, thereby obtaining a laminate with a component for an electronic device attached; and a separation step, in which an electronic device having the polyimide film and the component for an electronic device is obtained from the laminate with the component for an electronic device attached.