TWI820384B - Laminated substrate, manufacturing method of laminated body, laminated body, laminated body with components for electronic device, manufacturing method of electronic device - Google Patents

Abstract

The present invention relates to a laminated substrate, which has a glass support base material and an adsorption layer arranged on the support base material. The surface of the support base material on the adsorption layer side has a peripheral area where no adsorption layer is arranged, and the adsorption layer has The first main surface on the supporting base material side, the second main surface on the opposite side to the first main surface, and the end surface connecting the first main surface and the second main surface. The end surfaces are from the second main surface to the 1. An inclined surface with a protruding main surface, and the angle between the inclined surface and the first main surface does not reach 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 less likely to peel off.

Description

Laminated substrate, manufacturing method of laminated body, laminated body, laminated body with components for electronic device, manufacturing method of electronic device

The present invention relates to a laminated substrate, a method of manufacturing a laminated body, a laminated body, a laminated 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, OLED) panels, and receiving sensor panels that sense electromagnetic waves, X-rays, ultraviolet rays, visible rays, infrared rays, etc. Becoming 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 thinning, the handleability of the substrate may be reduced, which may cause problems in the step of forming components for electronic devices on the substrate (the component forming step).

Therefore, recently, in order to improve the handleability of the substrate, a technology using a laminate system in which a polyimide resin substrate is arranged on a supporting base material has been proposed (Patent Document 1). More specifically, Patent Document 1 discloses that a polyimide varnish can be coated on a thermosetting resin composition cured body layer to form a resin varnish cured film (equivalent to a polyimide film), and the resin can be Precision components are placed on the varnish hardened film.

[Prior technical literature] [Patent Document]

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

On the other hand, the present inventor implemented the process of coating polyimide varnish to form a polyimide film described in Patent Document 1, and found that when the polyimide varnish is coated to form a polyimide film, Polyimide films are prone to peeling. Furthermore, it was found that peeling occurs particularly easily at the ends of the polyimide film.

An object of the present invention is to provide a laminated substrate. When a polyimide varnish is coated on the surface to form a polyimide film, the formed polyimide film is less likely to peel off.

Another object of the present invention is to provide a method for manufacturing a laminated body, a laminated body, a laminated body with components for electronic devices, and a method for manufacturing an electronic device.

The present inventors conducted intensive research and found that the above problems can be solved by the following configuration.

(1) A laminated substrate having a glass support base material and an adsorption layer arranged on the support base material, and having a peripheral area where no adsorption layer is placed on the surface of the adsorption layer side of the support base material, The adsorption layer has a first main surface supporting the substrate, 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 from the second main surface. An inclined surface that protrudes more toward the first main surface, and the angle between the inclined surface and the first main surface does not reach 10°.

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

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

(4) The laminated substrate according to (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 laminated substrate according to (1), wherein the angle formed by the inclined surface and the first main surface is 5° or less.

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

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

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

(9) A method for manufacturing a laminated substrate as described in any one of (1) to (8), which includes: a step of laminating a support base material and a transfer film, which step is to laminate the support base material A transfer film having a precursor film that becomes an adsorption layer. In this case, the support base material and the transfer film are configured so that the support base material has a peripheral area where the precursor film is not disposed; and a precursor film heating step for The adsorbed layer is obtained from the precursor film.

(10) A method for manufacturing a laminated body, which includes coating a polyimide containing polyimide or a precursor thereof and a solvent on the adsorption layer side of the laminated substrate as described in any one of (1) to (7). The amine varnish forms a polyimide film on the peripheral area and the adsorption layer, thereby forming a laminate having a support substrate, an adsorption layer, and a polyimide film in sequence.

(11) A laminated body having: the laminated substrate according to any one of (1) to (7); and a polyimide film disposed on the peripheral region of the laminated substrate and on the adsorption layer.

(12) A laminated body with a member for an electronic device, comprising: the laminated body according to (11); and a member for an electronic device arranged on a polyimide film in the laminated body.

(13) A method for manufacturing an electronic device, which includes a member forming step of forming a member for an electronic device on the polyimide film of the laminated body according to (11) to obtain a laminated body with the member for an electronic device. ; and a separation step of obtaining an electronic device having a polyimide film and a member for an electronic device from the laminate with the component for the electronic device attached thereto.

According to the present invention, it is possible to provide a laminated substrate in which when a polyimide varnish is coated on the surface to form a polyimide film, the formed polyimide film is less likely to peel off.

According to the present invention, a method for manufacturing a laminated body, a laminated body, a laminated body with a member for an electronic device, and a method for manufacturing an electronic device can be provided.

10:Laminated substrate

12: Support base material

12a: Peripheral area

14: Silicone resin layer

14a: 1st main side

14b: 2nd main side

14c: End face

16: Laminated body

18:Polyimide membrane

20: Components for electronic devices

22:Laminated body with components for electronic devices

24:Electronic devices

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 one embodiment of the multilayer substrate of the present invention.

FIG. 2 is a top view of the laminated substrate shown in FIG. 1 .

FIG. 3 is a cross-sectional view schematically showing one embodiment of the laminated body of the present invention.

Fig. 4 is a cross-sectional view for explaining the steps of forming the member.

Figure 5 is a cross-sectional view for explaining the separation step.

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. In addition, various changes and substitutions can be made in the following embodiments without departing from the scope of the present invention.

The numerical range expressed by "~" means the range including the values recorded before and after "~" as the lower limit and upper limit.

Characteristic points of the laminated substrate of the present invention include: making the end surface of the adsorption layer an inclined surface; adjusting the inclination angle of the inclined surface to a specific range; and providing a surface without an adsorption layer on the surface of the supporting base material. Peripheral area.

The present inventor found that by adopting the above-mentioned structure, the desired effect can be obtained. The details of obtaining the desired effect are not clear, but it is thought that first, a peripheral area is provided on the surface of the supporting base material, and the polyimide film is arranged on the laminated substrate so that the peripheral area is in contact with the polyimide film. , thereby, based on the interaction between the polyimide film and the glass support base material, peeling off of the polyimide film and the end is suppressed. It is also believed that by providing an inclined surface with a specific inclination angle at the end, it is possible to suppress the occurrence of gaps between the polyimide film, the adsorption layer and the supporting base material. As a result, peeling of the polyimide film is inhibited.

<Laminated 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 laminated substrate shown in FIG. 1 .

The laminated substrate 10 includes a glass supporting base material 12 and an adsorption layer 14 arranged on the supporting base material 12 .

As shown in FIGS. 1 and 2 , the adsorption layer 14 has a first main surface 14a on the supporting base material 12 side, a second main surface 14b on the opposite side to the first main surface 14a, and connects the first main surface 14a and the second 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 toward the first main surface 14a. Furthermore, the shape of the adsorption layer 14 (the shape of the main surface) is a rectangular shape, and all four end surfaces 14c are inclined surfaces.

Furthermore, as shown in FIGS. 1 and 2 , the surface of the support base 12 on the adsorption layer 14 side has a peripheral region 12 a in which the adsorption layer 14 is not arranged. In other words, the adsorption layer 14 is arranged on the support base material 12 such that an edge-shaped region (peripheral region 12 a ) that is not in contact with the adsorption layer 14 remains on the support base material 12 .

In the aspect described above, the area of the arrangement area of the adsorption layer 14 is narrower than the area of the surface (main surface) of the supporting base material 12 , and the peripheral area 12 a is located further inside than the outer peripheral edge of the supporting base material 12 . area.

Furthermore, in Figures 1 and 2, the shape of the supporting base material 12 (the shape of the main surface) and the shape of the adsorption layer 14 (the shape of the main surface) are both rectangular, so as to form the outer periphery of the supporting base material 12. The adsorption layer 14 is arranged on the support base 12 so that one side thereof is parallel to one side constituting the outer periphery of the adsorption layer 14 .

Polyimide varnish is coated on the peripheral area of the supporting base material 12 of the laminated 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 member for an electronic device is formed on the polyimide film, and then the polyimide film (that is, the 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 material 12, adsorption layer 14) constituting the laminated substrate 10 will be described in detail, and then, a method for manufacturing the laminated 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.

As the type of glass, preferred are alkali-free borosilicate glass, borosilicate glass, soda-lime glass, high silica glass, and other oxide-based glasses containing silica as the main component. As the oxide-based glass, glass having a silicon oxide content of 40 to 90% by mass in terms of oxide is preferred.

More specifically, examples of the glass plate include glass plates containing alkali-free borosilicate glass (trade names "AN100" and "AN Wizus" manufactured by AGC Co., Ltd.).

Regarding the manufacturing method of a glass plate, it is usually obtained by melting a glass raw material and shaping the molten glass into a plate shape. This forming method may be a common method, such as float method, melting method, orifice down-drawing method.

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

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

The width W of the peripheral area 12a is not particularly limited, but is preferably 1 to 30 mm, and more preferably 3 to 10 mm. As shown in FIG. 2 , the width W of the peripheral region 12 a corresponds to the distance from the outer peripheral edge of the supporting base material 12 to the outer peripheral edge 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. Furthermore, by setting the width of the peripheral region 12a to 1 mm or more, the polyimide film becomes more difficult to peel off.

The support base material 12 is preferably low in flexibility. Therefore, the thickness of the supporting base material 12 is preferably 0.3 mm or more, and more preferably 0.5 mm or more.

On the other hand, the thickness of the supporting base material 12 is preferably 1.0 mm or less.

(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 arranged on the support base material 12 such that a peripheral region 12 a that is not in contact with the adsorption layer 14 remains on the support base material 12 .

As mentioned 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 preferable that all the 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 does not reach 10°. Among them, in order to further suppress 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 is preferably 1° or more.

The angle θ formed by the inclined surface of the adsorption layer 14 and the first main surface 14a is determined based on 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. . More specifically, as shown in FIG. 1 , 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 based on the following equation.

θ=arctan(AC/AB)

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

Examples of the material of the organic layer include acrylic resin, polyolefin resin, polyurethane resin, polyimide resin, silicone resin, polyimide silicone resin, and fluororesin. Alternatively, 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, silicones, and fluorides. Examples of oxides (preferably metal oxides), nitrides (preferably metal nitrides), and oxynitrides (preferably metal oxynitrides) include those selected from the group consisting of Si, Hf, Zr, and Ta , Ti, Y, Nb, Na, Co, Al, Zn, Pb, Mg, Bi, La, Ce, Pr, Sm, Eu, Gd, Dy, Er, Sr, Sn, In and Ba, one or more elements of oxides, nitrides, and nitrogen oxides.

Examples of carbides (preferably metal carbides) and carbonitrides (preferably metal carbonitrides) include carbides of one or more elements selected from the group consisting of Ti, W, Si, Zr, and Nb. , carbonitrides, carbon oxides.

Examples of the silicide (preferably metal silicide) include a silicide of one or more elements selected from the group consisting of Mo, W, and Cr.

Examples of the fluoride (preferably metal fluoride) include fluorides of one or more elements selected from the group consisting of Mg, Y, La and Ba.

The adsorption layer 14 may also be a plasma polymerization film.

When the adsorption layer 14 is a plasma polymerization film, examples of materials for forming the plasma polymerization film include: 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 , etc.

Among them, in terms of heat resistance or peelability, as the material of the adsorption layer 14, silicone resin, polyimide silicone resin is preferred, silicone resin is more preferred, and condensation reaction type silicon is particularly preferred. Silicone resin formed from 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 hardening curable silicone. Hardening silicone is classified according to its hardening mechanism into addition reaction type silicone, condensation reaction type silicone, ultraviolet curing type silicone, and electron beam curing type silicone, and any of these can be used. Among them, condensation reaction type silicone is preferred.

As the condensation reaction type silicone, a hydrolyzable organosilane compound as a monomer or a mixture thereof (monomer mixture), or a partially hydrolyzed condensate obtained by subjecting a monomer or a monomer mixture to a partial hydrolysis condensation reaction can be preferably used. (organopolysiloxane).

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 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 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. Part of the Si-O-Si bonds of the silicone resin constituting the adsorption layer 14 is cut, and hydroxyl groups may appear. In addition, when 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, further preferably 12 μm or less. On the other hand, the thickness of the adsorption layer 14 is preferably more than 1 μm, and in order to achieve better foreign matter embedding properties, the thickness is more preferably 6 μm or more. The above-mentioned thickness is a value obtained by measuring the thickness of the adsorption layer 14 at five or more arbitrary positions with a contact-type film thickness measuring device and averaging the results arithmetic.

Furthermore, excellent foreign matter embedding properties means that even if foreign matter is present between the support base material 12 and the adsorption layer 14 , the foreign matter will be embedded in the adsorption layer 14 . If the embedding property of foreign matter is excellent, the adsorption layer will be less likely to generate protrusions caused by foreign matter. When forming an electronic device member on the polyimide film, breakage of the electronic device member caused by the protrusions can be suppressed. line risks. Furthermore, since the voids formed when the above-mentioned convex portions are generated are observed in the form of bubbles, the foreign matter embedding property can be evaluated based on the presence or absence of bubbles.

If a polyimide film is formed on the glass supporting substrate 12 and subjected to high-temperature heat treatment, The polyimide film will turn yellow, making it 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 high-temperature heat treatment can be suppressed.

(protective film)

The laminated substrate 10 may 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 polyimide varnish described below on the adsorption layer 14 .

Examples of materials constituting the protective film include 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 external force, 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 still more preferably 100 μm or less.

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

As the adhesive layer, a known adhesive layer can be used. Examples of the adhesive constituting the adhesive layer include: (meth)acrylic adhesive, silicone adhesive, and polyurethane adhesive.

Furthermore, the adhesive 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 butyraldehyde resin. , polyurethane resin, polystyrene elastomer.

In order to reduce the peeling force when peeling off the protective film, the surface roughness (Ra) of the protective film 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 protective film and the adsorption layer, Ra is preferably 0.1 nm or more, more preferably 0.5 nm or more. Surface roughness (Ra) was measured using the non-contact surface-layer cross-sectional shape measurement system "Vertscan R3300-lite" manufactured by Ryoka Systems.

<Manufacturing method of laminated substrate>

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

Among them, in order to achieve better productivity, for example, a transfer film having a temporary support and a precursor film arranged on the temporary support and heat-treated to become an adsorption layer precursor film is prepared, and the transfer film is The precursor film is bonded to a specific position on the glass support substrate, and the obtained laminate including the glass support substrate, the precursor film, and the temporary support is subjected to a heat treatment. By performing heat treatment, the end portion of the precursor film can be fluidized to form the above-mentioned adsorption layer having a specific inclined surface. Furthermore, when the precursor film is bonded to the supporting base material, the precursor film is bonded to the supporting base material in such a manner that the above-mentioned peripheral region is formed.

In addition, in addition to the above, the precursor film that is heat-treated to become an adsorption layer can also be disposed at a specific position on a glass support substrate by coating, and then heat-treated to form the above-mentioned adsorption layer with a specific inclined surface. layer.

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

As described above, by subjecting the precursor film to heat treatment, the shape of the end surface of the adsorption layer can be made into an inclined surface. Furthermore, during the heat treatment, it is preferably carried out 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 further preferably 60 to 250°C. The heating time is preferably 10 to 60 minutes, more preferably 20 to 40 minutes.

The pressure during the pressure treatment is preferably 0.5 to 1.5 MPa, more preferably 0.8 to 1.0 MPa.

In addition, the heat treatment may be performed a plurality of times. When performing heat treatment multiple times, the heating conditions for each time can be changed.

For example, when performing a plurality of heat treatments, the heating temperature may be changed. For example, when heat treatment is performed twice, the first heat treatment may be carried out at a temperature of less than 100°C, and the second heat treatment may be carried out at a temperature of 100°C or above.

In addition, when heat treatment is performed a plurality of times, the presence or absence of pressure treatment can be changed. For example, when the heat treatment is performed twice, the pressure treatment may be performed together with the first heat treatment, and the pressure treatment may not be performed during 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 peeling off the temporary support, or the heat treatment can be performed directly with the temporary support disposed on the adsorption layer. In addition, when heat treatment is performed a plurality of times, the temporary support may be peeled off between each heat treatment. For example, after the first heat treatment, the temporary support can be peeled off and the Apply the second heat treatment.

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

Examples of surface treatment include corona treatment, plasma treatment, and ultraviolet-ozone treatment, and corona treatment is preferred.

When 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 more 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, more preferably 0.5 nm or more.

The above-mentioned laminated substrate 10 can be used to manufacture a structure including the supporting base material 12, the adsorption layer 14, and the supported material in this order. As the supported material, materials other than the polyimide film 18 may be laminated. Examples of the supported material include polyimide resin films, epoxy resin films, photosensitive resists, and polyester resin films (for example, polyethylene terephthalate, polyethylene naphthalate). ester), polyolefin resin film (e.g., polyethylene, polypropylene), polyurethane resin film, metal foil (e.g., copper foil, aluminum foil), sputtered film (e.g., 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, silicon through hole) 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, a laminated body 16 having a supporting base material 12, an adsorption layer 14, and a polyimide film 18 as shown in FIG. 3 can be produced.

Specifically, as a method of manufacturing the laminated body 16, there is a method of applying a polyimide varnish containing polyimide and a solvent on the adsorption layer 14 side of the laminated substrate 10, and applying the polyimide varnish to the peripheral region 12a. The polyimide film 18 is formed on the adsorption layer 14 and the support base 12, the adsorption layer 14 and the polyimide film 18 are formed in this order.

The above-mentioned manufacturing method will be described in detail below, and then 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.

Polyimide is usually obtained by polycondensing tetracarboxylic dianhydride and diamine and performing imidization. The polyimide is preferably solvent-soluble.

Examples of the tetracarboxylic dianhydride used include aromatic tetracarboxylic dianhydride and aliphatic tetracarboxylic dianhydride. Examples of the diamine used include aromatic diamines and aliphatic diamines.

Examples of aromatic tetracarboxylic dianhydride include: pyromellitic dianhydride (1,2,4,5-benzenetetracarboxylic dianhydride), 3,3',4,4'-diphenylmethyl Ketone tetracarboxylic dianhydride, 3,3',4,4'-biphenyl tetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride.

As aliphatic tetracarboxylic dianhydride, there are cyclic or acyclic aliphatic tetracarboxylic dianhydride. Examples of cyclic aliphatic tetracarboxylic dianhydride include: 1,2,3,4-cyclobutane Alkane tetracarboxylic dianhydride, 1,2,4,5-cyclohexane tetracarboxylic dianhydride, 1,2,4,5-cyclopentane tetracarboxylic dianhydride, etc., as non-cyclic aliphatic tetracarboxylic acids Examples of acid dianhydride include 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-pentanetetracarboxylic dianhydride, and the like.

Examples of the aromatic diamine include: 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.

烷二胺等環式脂肪族二胺。 Examples of aliphatic diamines include ethylene diamine, hexamethylenediamine, polyethylene glycol bis(3-aminopropyl) ether, polypropylene glycol bis(3-aminopropyl) ether, and other non-alphatic diamines. Cyclic aliphatic diamine, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, isophorone diamine, nor

Alkanediamine and other cyclic aliphatic diamines.

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

The solvent may be a solvent that dissolves the polyimide or its precursor. Examples thereof include: phenolic solvents (for example, m-cresol), amide solvents (for example, N-methyl-2-pyrrolidone). , N,N-dimethylformamide, N,N-dimethylacetamide), lactone solvents (for example, γ-butyrolactone, δ-valerolactone, ε-caprolactone, γ - Crotonolactone, γ-caprolactone, α-methyl-γ-butyrolactone, γ-valerolactone, α-acetyl-γ-butyrolactone, δ-caprolactone), triacetin solvents (e.g., N,N-dimethylsterine), ketone solvents (e.g., acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone), ester solvents (e.g., methyl acetate ester, ethyl acetate, butyl acetate, dimethyl carbonate).

(sequence)

The method of coating the polyimide varnish on the adsorption layer 14 side of the laminated substrate 10 is not particularly limited, and a known method may be used. Examples thereof include spray coating, die coating, spin coating, dip coating, roll coating, rod coating, screen printing, and gravure coating.

After coating, heat treatment may be performed if necessary.

As the conditions for heat treatment, the temperature condition is preferably 50 to 500°C, and 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 a plurality of times. When performing heat treatment multiple times, the heating conditions for each time can be changed.

(Laminated body)

As shown in FIG. 3 , the laminated body 16 has a support base material 12 , an adsorption layer 14 and a polyimide film 18 .

The structures of the support base material 12 and the adsorption layer 14 are as described above.

The polyimide film 18 is arranged 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, and more preferably 5 μm or more. In terms of softness, 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 further preferably 10 nm or less.

Regarding the thermal expansion coefficient of the polyimide film 18, it is preferable that the difference between the thermal expansion coefficient of the polyimide film 18 and the thermal expansion coefficient of the supporting base material 12 is small because it can suppress the warpage of the laminated body 16 after heating or cooling. Specifically, the difference in thermal expansion coefficient between the polyimide film 18 and the supporting substrate 12 is preferably 0~90×10 ^-6 /°C, more preferably 0~30×10 ^-6 /°C.

The area of the polyimide film 18 is not particularly limited, but in terms of productivity of electronic devices, 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, it can be used for manufacturing electronic components such as panels for display devices described below, PVs, thin film secondary batteries, semiconductor wafers with circuits formed on their surfaces, and receiving sensor panels. In these applications, there are cases where the laminated body is exposed to high temperature conditions (for example, 450° C. or higher) (for example, for 20 minutes or more) in an atmospheric atmosphere.

Panels for display devices include LCD, OLED, electronic paper, plasma display panels, field emission panels, quantum dot LED panels, micro-LED display panels, MEMS (microelectromechanical system, microelectromechanical system) shutter panels, etc.

The receiving sensor panel includes an electromagnetic wave receiving sensor panel, an X-ray light receiving sensor panel, an ultraviolet light receiving sensor panel, a visible light receiving sensor panel, an infrared light receiving sensor panel, etc. The substrate used for the receiving sensor panel can be reinforced with reinforcing sheets such as resin.

<Manufacturing method of electronic device>

The laminated body can be used to manufacture an electronic device including a polyimide film and a member for an electronic device described below.

The manufacturing method of an electronic device, for example, as shown in FIGS. 4 and 5 , is a method including the following steps, namely, a component forming step on the polyimide film 18 of the laminate 16 (between the polyimide film 18 and the adsorption layer (14 side is the opposite side) forming the electronic device member 20 to obtain a laminated body 22 with the electronic device member; and a separation step to obtain the electronic device member 22 from the laminated body 22 An electronic device 24 having a polyimide film 18 and an electronic device member 20 is obtained.

Hereinafter, the step of forming the member 20 for the electronic device will be called a "member forming step", and the step of separating the electronic device 24 and the support base material 26 with the adsorption layer will be called a "separation step".

The materials and order used in each step are described in detail below.

(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 , the electronic device member 20 is formed on the polyimide film 18 (on the surface of the polyimide film 18 opposite to the adsorption layer 14 side) to obtain an electronic device-attached member. A laminate 22 of components is used.

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 publicly known materials can be used. Examples of materials 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 plurality of materials may be combined. The film forming method is not particularly limited, and known methods can be exemplified. Examples include plasma CVD (Chemical Vapor Deposition), sputtering and other methods.

First, the electronic device member 20 used in this step will be described in detail, and then, the order of the steps will be described in detail.

(Components for electronic devices)

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

(sequence of steps)

The manufacturing method of the above-mentioned laminated body 22 with components for electronic devices is not particularly limited. Depending on the type of the constituent components of the components for electronic devices, a conventionally known method is used to form the laminated body 16 with components for electronic devices on the polyimide film 18 of the laminated body 16 . Component 20.

The electronic device member 20 may be a part (hereinafter, referred to as a "partial member") of all the members finally formed on the polyimide film 18, rather than all of the members finally formed on the polyimide film 18. Hereinafter, referred to as "all components"). The substrate with partial components peeled off from the adsorption layer 14 may also be used as a substrate with all components (corresponding to the electronic device described below) in a subsequent step.

Other electronic device components 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 members 20 of the electronic device member-attached laminated body 22 may be made to face each other, and the two may be laminated together to assemble the all-component-attached laminated body, and then the laminated body with all the components may be assembled therefrom. Peel off two pieces of the supporting base material with the adsorption layer to manufacture an electronic device.

For example, taking 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 side, various layers are performed. Forming or processing, for example, forming a transparent electrode; then evaporating a hole injection layer, a hole transport layer, a luminescent 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. Specific examples of such layer formation or processing include film formation processing, vapor deposition processing, sealing plate bonding processing, and the like.

(separation step)

The separation step is a step in which, as shown in FIG. 5 , 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 electronic device member obtained in the above-mentioned member forming step is used. The polyimide film 18 on which the electronic device member 20 is laminated and the supporting base material 26 with the adsorption layer are separated to obtain an electronic device 24 including the electronic device member 20 and the polyimide film 18 .

When the electronic device member 20 on the peeled polyimide film 18 forms part of all the required constituent members, the remaining constituent members may also be formed 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 base material 12 to form a starting point for peeling, and then a mixed fluid of water and compressed air can be blown to cause peeling.

Preferably, the laminated body 22 with the electronic device member is placed on the pressure plate with the support base 12 as the upper side and the electronic device member 20 side as the lower side, and the electronic device member 20 side is vacuum-suctioned to the pressure plate. On the disk, in this state, a blade-shaped object is first allowed to invade the interface between the polyimide film 18 and the support base material 12 . Thereafter, a plurality of vacuum suction cups are used to adsorb the supporting substrate 12 side, and then automatically Insert the vacuum suction cup near the position where the blade-like object is inserted. In this way, the support base material 26 with the adsorption layer attached can be easily peeled off.

When the electronic device 24 is separated from the laminate 22 with the electronic device member attached thereto, by controlling the blowing by the ionizer or controlling the humidity, the electrostatic adsorption of fragments of the adsorption layer 14 to the electronic device 24 can be further suppressed.

The above-mentioned manufacturing method of an electronic device is suitable for manufacturing a display device described in paragraph [0210] of the specification of US Patent Application Publication No. 2018/0178492. Examples of the electronic device 24 include those described in paragraph [0211] of the same specification. .

Moreover, before performing the said separation process, the area|region of a laminated body where the electronic device member is not arrange|positioned may also be cut and removed.

[Example]

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

Hereinafter, a glass plate containing alkali-free borosilicate glass (linear expansion coefficient: 38×10 ^-7 /°C, trade name "AN100" manufactured by AGC Co., Ltd.) is used as the supporting base material.

In the following, Examples 1 to 5 are examples, and Examples 6 to 7 are comparative examples.

<Appearance evaluation>

Visually observe that the glass plate, silicone resin layer and polyethylene obtained in the following order are: The polyimide film in the imine film laminate was evaluated based on 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 problems.

C: Most or the entire surface of the polyimide film is peeled off, so this is a problematic area for practical use.

<Evaluation of width of peripheral area>

The width of the peripheral area of the support base material was evaluated based on the following criteria.

A: Width is 1mm or more and 10mm or less

B: Width exceeds 10mm and is less than 30mm

C: Width exceeds 30mm and less than 1mm

<Embedding properties of foreign matter>

The laminated body in which the glass plate, the silicone resin layer and the PET film were arranged in this order, obtained in the following order, were visually observed and evaluated based on the following standards.

A: The number of interfacial bubbles caused by foreign matter at the glass plate/silicone resin layer interface is less than 5.

B: The number of interfacial bubbles caused by foreign matter at the glass plate/silicone resin layer interface is more than 5 and less than 10.

C: There are more than 10 interface bubbles caused by foreign matter at the glass plate/silicone resin layer interface.

<Example 1>

(Preparation of hardening silicone)

Add triethoxymethylsilane (179g), toluene (300g), and acetic acid (5g) to a 1L flask, stir the mixture at 25°C for 20 minutes, then heat to 60°C and react 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 three times. Trimethylsilane chloride (70g) 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 three times. Toluene was removed by distillation under reduced pressure from the washed reaction crude liquid, and after being made into a slurry state, it was dried overnight in a vacuum dryer to obtain a white organopolysiloxane compound, that is, curable silicone 1. The number of T units in curable silicone 1: the number of M units = 87:13 (mol ratio). In addition, the M unit means a monofunctional organosiloxy unit represented by (R) ₃ SiO _1/2 . T unit means a trifunctional organosiloxy unit represented by RSiO _3/2 (R represents a hydrogen atom or an organic group).

(Preparation of hardening composition)

The curable silicone 1 and heptane were mixed, and an organic zirconium-based compound (zirconium octoate compound) and an organic bismuth-based compound (bismuth 2-ethylhexanoate) were added. The amount of solvent was adjusted so that the solid content concentration became 50% by mass. In addition, the amount of the metal compound added 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 liquid was filtered using a filter with a pore size of 0.45 μm, thereby obtaining a curable composition.

Curable silicone 1 and heptane were mixed, and an organic zirconium-based compound (zirconium octoate compound) and an organic cerium-based compound (cerium 2-ethylhexanoate) were added. The amount of solvent was adjusted so that the solid content concentration became 50% by mass. In addition, the amount of the metal compound added 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 liquid was filtered using a filter with a pore size of 0.45 μm, thereby obtaining a curable composition.

(Manufacturing of laminated substrates)

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 hot plate to form silicon. Ketone resin layer. The thickness of the silicone resin layer is 8 μm.

Then, after cleaning with a water-based glass cleaner ("PK-LCG213" manufactured by Parker Corporation), a 200×200mm, 0.5mm-thick glass plate "AN100" (support base) washed with pure water was Material) is laminated to the PET film on which the silicone resin layer is formed, and a laminate is produced in which the glass plate, the silicone resin layer, and the PET film are arranged in this order. Furthermore, during the above-mentioned bonding, the glass plates are bonded together in such a manner that a region in which the silicone resin layer is not arranged remains in the peripheral region of the surface of the glass plate (see FIG. 2 ). The width W of the peripheral area is 5 mm.

Next, the obtained laminated body was placed in an autoclave and heated at 60° C. and 1 MPa for 30 minutes. Thereafter, the PET film was peeled off, and the laminated substrate including the glass plate and the silicone resin layer was annealed at 250° C. for 30 minutes, and then the silicone resin layer was subjected to corona treatment. The obtained silicone resin layer has a first main surface on the glass plate 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, and the above end surface is from the first main surface. Starting from the 2nd main surface, it is an inclined surface that becomes more prominent toward the 1st main surface. The angle between the above-mentioned 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 Kosan Co., Ltd.) was applied to the surface of the silicone resin layer side of the laminated substrate obtained above, heated at 60°C for 30 minutes, and then heated at 120°C. Heating for 30 minutes, and then heating at 450° C. for 10 minutes, yielded a laminate having a glass plate, a silicone resin layer, and a polyimide film (thickness: 7 μm) in this order. Polyimide membrane is configured on On the peripheral area of the glass plate and on the silicone resin layer (see Figure 3).

<Example 2~Example 14>

Except for adjusting the thickness between the first main surface and the second main surface of the silicone resin layer, the width and angle of the peripheral area as shown in Table 1 and Table 2 below, the same procedure as in Example 1 was obtained. Laminated body. Table 1 shows the case where a curable composition containing bismuth is used, and Table 2 shows a case where a curable composition containing cerium is used.

Furthermore, regarding Examples 6 and 7, and 13 and 14, a curable composition was applied to the entire surface of the glass plate, the coating film was heated at 250° C. for 30 minutes to cure, and silicon was produced on the entire surface of the glass plate. After the ketone resin layer is formed, the peripheral edge of the obtained glass plate with the silicone resin layer is cut to obtain a laminated body having a glass plate and a silicone resin layer and a smooth side surface (hereinafter also referred to as "laminated body C"). ), and then use the laminated body C to implement the above (preparation of the laminated body). That is, regarding the laminated body C used in Examples 6 and 7, and 13 and 14, the area of the main surface on the glass plate side having 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° silicone resin layer.

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

In Tables 1 and 2, the column "Width of peripheral area (mm)" indicates the width of the peripheral area (W in Figure 2).

In Table 1 and Table 2, the "angle (°)" column indicates the angle between the first main surface of the silicone resin layer and the inclined surface. The method of measuring the angle is as described above.

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

Particularly when using a curable composition containing bismuth, it was confirmed from the comparison of Examples 1 to 3 and 5 and Example 4 that when the thickness of the adsorption layer is 6 μm or more, the foreign matter embedding property is more excellent.

Furthermore, from 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 a curable composition containing cerium. Comparison of Examples 8 to 10 and 12 and Example 11 shows 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 the thickness of the adsorption layer was 12 μm or less. When shaped, the appearance characteristics are more excellent.

<Manufacturing of organic EL display devices (equivalent to electronic devices)>

Using the laminated bodies obtained in Examples 1 to 5 and 8 to 12, an organic EL display device was produced according to the following procedure.

First, on the surface of the polyimide film of the laminated substrate that is opposite to the glass plate side, a film is formed in the order of silicon nitride, silicon oxide, and amorphous silicon by plasma CVD method. Secondly, low-concentration boron is implanted into the amorphous silicon layer through an ion doping device, and heat treatment and dehydrogenation treatment are performed. Secondly, a laser annealing device is used to crystallize the amorphous silicon layer. Secondly, by using photolithographic etching and ion doping equipment, a low concentration of phosphorus is implanted into the amorphous silicon layer to form N-type and P-type TFT (Thin-Film Transistor, 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. The gate electrode is formed by photolithographic etching. Secondly, through photolithography and ion doping equipment, high concentrations of boron and phosphorus are implanted into the required regions of the N-type and P-type to form the source region and the drain region.

Secondly, on the side of the polyimide film opposite to the glass plate side, a silicon oxide film is formed using the plasma CVD method to form an interlayer insulating film, and an aluminum film is formed using a sputtering method and a photomicrograph is used to form a film. The TFT electrode is formed by etching by shadowing method. Next, after heat treatment and hydrogenation in a hydrogen atmosphere, a passivation layer is formed by silicon nitride film formation using a plasma CVD method.

Next, 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 using photolithography. Next, a film of indium tin oxide is formed by sputtering, and the pixel electrode is formed by etching using photolithography. Then, using the evaporation method, a film is sequentially formed on the side of the polyimide film opposite to the glass plate side: 4,4',4"-tris(3-methylphenylphenyl) as the hole injection layer Amino) triphenylamine, bis[(N-naphthyl)-N-phenyl]benzidine as the hole transport layer, 2,6-bis[4-[N-(4-methoxy) as the light-emitting layer phenyl)-N-phenyl]aminostyryl]naphthalene-1,5-dicarbonitrile (BSN-BCN) was mixed in 8-hydroxyquinoline aluminum complex (Alq ₃ ) at 40% by volume The result is Alq ₃ as an electron transport layer. Next, an aluminum film is formed by a sputtering method, and a counter electrode is formed by etching using a photolithography method.

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

Then, after the sealing body side of panel A is vacuum-adsorbed to the pressure plate, a stainless steel cutting tool 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. The interface with the glass plate forms the starting point for peeling. Then, after adsorbing the surface of the supporting base material of panel A with a vacuum suction cup, the suction cup is raised. Here, the cutting tool is inserted while blowing the electrostatic fluid from the ionizer (made by Keyence Corporation) to the interface. Next, continue to blow the electrostatic fluid from the ionizer into the gap formed, and lift the vacuum suction cup while injecting water toward 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 supporting base material with the silicone resin layer was successfully peeled off.

Then, the separated polyimide film is cut using a laser cutter or a scribing-breaking method, and is divided into a plurality of units. Then, the polyimide film and the counter substrate formed with the organic EL structure are assembled. , implement the module forming steps to produce an organic EL display device.

Furthermore, although the present invention will be described in detail with reference to specific embodiments, it is clear to those skilled in the art 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 2020-015418 filed on January 31, 2020, Japanese Patent Application 2020-074048 filed on April 17, 2020, and Japanese Patent Application 2020- filed on June 8, 2020. 099427, the contents are incorporated into this specification as a reference.

10:Laminated substrate

12: Support base material

12a: Peripheral area

14: Silicone resin layer

14a: 1st main side

14b: 2nd main side

14c: End face

AB: line segment

AC: line segment

θ: angle

Claims (8)

A laminated substrate having a glass support base material and an adsorption layer disposed on the support base material, and the surface of the support base material on the adsorption layer side has a peripheral area where the adsorption layer is not disposed, and the above-mentioned The adsorption layer has a first main surface on the supporting base material 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, and the end surface is from the above-mentioned The inclined surface protrudes from the second main surface toward the first main surface, and the angle between the inclined surface and the first main surface is 5° or less, and the adsorption layer is a silicone resin layer. The laminated substrate according to 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 width of the peripheral area is 1~30 mm. The laminated substrate according to any one of claims 1 to 3, further comprising a protective film disposed on the adsorption layer. A method for manufacturing a laminated body, which includes coating a polyimide varnish containing polyimide or its precursor and a solvent on the adsorption layer side of the laminated substrate according to any one of claims 1 to 3, and applying it thereon A polyimide film is formed on the peripheral region and the adsorption layer, thereby forming a laminate including the support base material, the adsorption layer, and the polyimide film. A laminated body comprising: the laminated substrate according to any one of claims 1 to 3; and a polyimide film disposed on the peripheral region and the adsorption layer in the laminated substrate. A laminated body with a member for an electronic device, comprising: the laminated body according to claim 6; and a member for an electronic device arranged on the polyimide film in the laminated body. 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 laminated body according to claim 6 to obtain a laminated body with a member for an electronic device; and separation. A step of obtaining an electronic device having the polyimide film and the electronic device member from the laminate with the electronic device member.