WO2022024820A1 - Procédé de fabrication de dispositif électronique flexible - Google Patents

Procédé de fabrication de dispositif électronique flexible Download PDF

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Publication number
WO2022024820A1
WO2022024820A1 PCT/JP2021/026826 JP2021026826W WO2022024820A1 WO 2022024820 A1 WO2022024820 A1 WO 2022024820A1 JP 2021026826 W JP2021026826 W JP 2021026826W WO 2022024820 A1 WO2022024820 A1 WO 2022024820A1
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Prior art keywords
aqueous solution
electronic device
inorganic substrate
film
polymer film
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PCT/JP2021/026826
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English (en)
Japanese (ja)
Inventor
桂也 ▲徳▼田
直樹 渡辺
哲雄 奧山
郷司 前田
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東洋紡株式会社
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Application filed by 東洋紡株式会社 filed Critical 東洋紡株式会社
Priority to KR1020227016119A priority Critical patent/KR20230044351A/ko
Priority to JP2022540189A priority patent/JPWO2022024820A1/ja
Priority to CN202180036802.6A priority patent/CN115668460A/zh
Publication of WO2022024820A1 publication Critical patent/WO2022024820A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
    • H01L21/77—Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in, or on, a common substrate
    • H01L21/78—Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in, or on, a common substrate with subsequent division of the substrate into plural individual devices
    • H01L21/7806—Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in, or on, a common substrate with subsequent division of the substrate into plural individual devices involving the separation of the active layers from a substrate
    • H01L21/7813—Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in, or on, a common substrate with subsequent division of the substrate into plural individual devices involving the separation of the active layers from a substrate leaving a reusable substrate, e.g. epitaxial lift off
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/02—Inorganic compounds
    • C11D7/04—Water-soluble compounds
    • C11D7/06—Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/02—Inorganic compounds
    • C11D7/04—Water-soluble compounds
    • C11D7/10—Salts
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/32—Organic compounds containing nitrogen
    • C11D7/3218—Alkanolamines or alkanolimines
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02041—Cleaning
    • H01L21/02043—Cleaning before device manufacture, i.e. Begin-Of-Line process
    • H01L21/02052—Wet cleaning only
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02041—Cleaning
    • H01L21/02079—Cleaning for reclaiming
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
    • H01L21/77—Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in, or on, a common substrate
    • H01L21/78—Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in, or on, a common substrate with subsequent division of the substrate into plural individual devices
    • H01L21/82—Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in, or on, a common substrate with subsequent division of the substrate into plural individual devices to produce devices, e.g. integrated circuits, each consisting of a plurality of components
    • H01L21/84—Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in, or on, a common substrate with subsequent division of the substrate into plural individual devices to produce devices, e.g. integrated circuits, each consisting of a plurality of components the substrate being other than a semiconductor body, e.g. being an insulating body
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/80—Manufacture or treatment specially adapted for the organic devices covered by this subclass using temporary substrates
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K77/00—Constructional details of devices covered by this subclass and not covered by groups H10K10/80, H10K30/80, H10K50/80 or H10K59/80
    • H10K77/10—Substrates, e.g. flexible substrates
    • H10K77/111—Flexible substrates

Definitions

  • the present invention relates to a method for manufacturing a flexible electronic device such as a flexible display, a flexible sensor array, and a stretchable electronic device.
  • Functional elements such as semiconductor elements, MEMS elements, and display elements are used as electronic components in information communication devices (broadcasting devices, mobile radios, portable communication devices, etc.), radars, high-speed information processing devices, etc.
  • information communication devices broadcasting devices, mobile radios, portable communication devices, etc.
  • radars high-speed information processing devices, etc.
  • inorganic substrate such as a glass, a silicon wafer, or a ceramic base material.
  • attempts have been made to form various functional elements on a polymer film.
  • Patent Documents 1 to 3 The process of applying a polymer solution or precursor solution, drying it to form a film, forming a desired element (functional element) on it, and then peeling it off from the support, or applying a film to a support made of an inorganic substance.
  • a process of temporarily fixing, forming a desired element in the form of a film, and then peeling from the support has been developed (Patent Documents 1 to 3).
  • a relatively high temperature is often used in the process of forming a functional element.
  • a temperature range of about 120 to 500 ° C. is used.
  • heating at about 450 ° C. may be required for dehydrogenation.
  • a temperature range of about 150 to 250 ° C. is also required for producing a hydrogenated amorphous silicon thin film.
  • the temperature range illustrated here is not so high for inorganic materials, but it must be said that it is considerably high for polymer films and adhesives generally used for bonding polymer films. I don't get it.
  • the above-exemplified process of applying a polymer solution or precursor solution to a support made of an inorganic substance, drying it to form a film, forming a desired element on the support, and then peeling it off from the support is a polymer film.
  • This is a technique devised because it is not possible to obtain a heat-resistant adhesive means for temporarily attaching a film to an inorganic substrate.
  • the polymer film obtained by such means is firmly adhered to the inorganic substrate, even if it is attempted to be peeled from the inorganic substrate, it is brittle and easily torn, so that the functional element is destroyed when peeling from the inorganic substrate. In many cases, it ends up. In particular, it is extremely difficult to peel off a device having a large area, and the productivity is not sufficient.
  • the present inventors have used a polyimide film as a laminate of a polymer film for forming a functional element and a support, which has excellent heat resistance and is tough and can be thinned, as a coupling agent.
  • a laminated body which is bonded to a support (inorganic layer) made of an inorganic substance through a film (Patent Document 4).
  • the polymer film is originally a flexible material, and there is no problem in stretching or bending it.
  • the electronic device formed on the polymer film has a fine structure in which a conductor made of an inorganic substance and a semiconductor are combined in a predetermined pattern, and stress such as minute expansion and contraction and bending and stretching is performed. This destroys the structure and impairs the characteristics of the device. Such stress is likely to occur when the electronic device is peeled off from the inorganic substrate together with the polymer film.
  • the present inventors have further improved and partially inactivated the inorganic substrate treated with the coupling agent to form a high activity portion and a low activity portion of the coupling agent.
  • a molecular film is bonded, a good adhesive part that is relatively difficult to peel off and an easy peeling part that is relatively easy to peel off are created, and an electronic device is formed in the easy peeling part, and the easy peeling part / good of the polymer film.
  • Patent Document 7 A technique for reusing glass by performing sonic cleaning, cleaning with a cleaning agent, hydrofluoric acid cleaning, asher treatment, heat treatment or puffing treatment has been proposed (Patent Document 7). Further, a technique has been proposed in which a polyimide and a glass substrate are bonded together by a specific method, and the used glass substrate is washed with a 10% sodium hydroxide solution so that the glass substrate can be reused (Patent Document 8). ..
  • the laminate can be subjected to a process of directly forming an electronic device on a conventional inorganic substrate such as a glass plate or a silicon wafer.
  • a conventional inorganic substrate such as a glass plate or a silicon wafer.
  • the inorganic substrate used as the temporary support substrate has traces of the treatment used for adhering the polymer film and the residue of the polymer film left without being peeled off. It is difficult to use.
  • Patent Documents 6 to 8 are technical proposals including the reuse of such inorganic substrates, mainly glass substrates.
  • Patent Document 6 describes that the glass substrate can be reused by alkaline cleaning, but specific alkaline cleaning conditions are not shown.
  • Patent Document 7 also describes that the glass substrate can be reused by various cleaning treatments including alkaline cleaning, heat treatment, and buffing treatment. Not listed. Further, heat treatment and asher treatment are exemplified. These treatments are effective in removing organic components, but less effective in treating inorganic components. Furthermore, the organic components that originally adhered are often carbonized to form a strong stick. In the puffing process, there is a high possibility that the glass surface will be scratched, the reusable use will be narrowed, and it will be difficult to divert it to at least the same use.
  • the present invention has the following configuration.
  • [1] (a) Step of cleaning the inorganic substrate with the aqueous solution A, (B) A step of forming a polymer film on a part or all of at least one surface of the inorganic substrate to obtain a laminate. (C) A step of forming an electronic device on the polymer film of the laminated body, (D) A method for manufacturing a flexible electronic device, comprising a step of peeling the electronic device together with a polymer film from an inorganic substrate, wherein the aqueous solution A is any one of the following (1) to (3).
  • the aqueous solution A is an alkaline aqueous solution, and the content of divalent or higher polyvalent metal ions contained in the alkaline aqueous solution is 10 ppm or less.
  • the method for manufacturing a flexible electronic device according to [1], wherein the alkaline aqueous solution in (1) is an aqueous solution of sodium hydroxide or potassium hydroxide.
  • the step (a) cleaning in the above (2) is The flexibility according to [1], [5] or [6], which comprises a step of charging an inorganic substrate, urea, and water into a closed container and heating the mixture in a temperature range of 60 ° C. or higher and 150 ° C. or lower. How to make an electronic device.
  • the aqueous solution A is an alkaline aqueous solution, and the content of divalent or higher polyvalent metal ions contained in the alkaline aqueous solution is 10 ppm or less.
  • the laminate is obtained by adhering a film containing a solvent and a polyamic acid to an inorganic substrate and then drying and chemically reacting to form a polyimide film [1] to [8].
  • the method for manufacturing a flexible electronic device according to any one of the above.
  • the glass substrate by performing a predetermined treatment including cleaning with a predetermined aqueous solution A on an inorganic substrate, preferably a glass substrate, the glass substrate can be used repeatedly, and the variable cost in the manufacturing cost of the flexible electronic device can be reduced. It can be significantly reduced.
  • various techniques have been proposed for removing organic substances remaining on the surface of an inorganic substrate and reusing the inorganic substrate by cleaning the inorganic substrate such as a glass substrate with the aqueous solution A.
  • the washing with the aqueous solution A purifies the surface of the inorganic substrate by hydrolyzing an organic substance, particularly a polymer compound, and making it water-soluble mainly as an alkaline salt of a carboxylic acid.
  • the present inventors found that foreign matter adhered to the inner wall surface of the washing tank in the rinsing process after washing, and as a result of analysis, the adhered foreign matter was a water-insoluble substance composed of an organic substance and a metal having a valence of divalent or higher. I found out that there was. That is, it is considered that the foreign matter is a multivalent metal ion having a valence of divalent or higher existing in the system, forming an insoluble salt with the organic substance solubilized by the alkaline washing treatment and precipitating in the tank.
  • the aqueous solution A is any one of the above (1) to (3).
  • keeping the concentration of divalent or higher cations, preferably metal ions, in the alkaline aqueous solution used for the cleaning treatment within a predetermined range suppresses the formation of insoluble salts of such organic substances and polyvalent metals. It has the effect of preventing recontamination of the washed inorganic substrate.
  • the polyvalent metal ions that are easily mixed in the system here are alkaline earth metal ions, and in particular, calcium ions and magnesium ions are also present as impurities in the alkaline compound, and therefore need to be intentionally removed.
  • Sodium hydroxide and potassium hydroxide are preferable as the inorganic alkaline compound used in the alkaline aqueous solution used in the present invention. These are inexpensively available as industrial raw materials.
  • the present invention in order to maintain the hydrolyzing action of the organic substance by the alkaline aqueous solution, it is preferable to control the hydroxide concentration in the cleaning system so as to be higher than the carbonate concentration.
  • the carbonate concentration becomes higher than the hydroxide concentration, the hydrolyzing action is reduced, the water-soluble organic matter tends to form an insoluble salt with the polyvalent metal ion, and the washed matter is easily recontaminated. Therefore, the present invention preferably realizes a manufacturing method for obtaining a highly clean inorganic substrate by appropriately controlling the carbonate concentration as well as the polyvalent metal ion concentration.
  • divalent or higher metal ions exist as impurities of inorganic alkali, and although it is possible to reduce their content by purification or the like, it is difficult to completely remove them from the viewpoint of cost.
  • a method of cleaning with an alkaline solution containing one or more compounds selected from the group consisting of ammonia, urea and organic alkaline compounds With this method, it is relatively easy to prevent the mixing of divalent metal ions as impurities. That is, when a cleaning liquid is formed by combining an inorganic alkali and an organic alkali compound, it is difficult to completely prevent the mixing of divalent metals, but the action of the organic alkali compound has the effect of preventing the insolubilization of the dissolved organic matter.
  • a step of charging an inorganic substrate, urea, and water in a closed container and heating them in a temperature range of 60 ° C. or higher and 150 ° C. or lower is included.
  • urea When urea is heated in the presence of water, it decomposes into ammonia, and this ammonia exerts a strong cleaning action.
  • odorless and harmless urea can be used at least at the time of preparation, and since ammonia is almost an aqueous solution at the time of recovery, it is recovered as a solid such as ammonium chloride by neutralizing with hydrochloric acid, for example. be able to.
  • ammonia, hydrochloric acid, and ammonium chloride can all be removed by evaporation or sublimation by heating, so that the procedure for reusing the substrate becomes easy. Naturally, it is much safer than hydrazine, which is very similar in elemental composition.
  • an alkaline solution containing one or more compounds selected from the group consisting of ammonia, urea, and an organic alkaline compound specified by the present invention can be used once for cleaning an inorganic substrate, preferably. Since the glass substrate can be used repeatedly, the variable cost in the manufacturing cost of the flexible electronic device can be significantly reduced.
  • the heating temperature is preferably 70 ° C. or higher, more preferably 80 ° C. or higher. Further, it is preferably 140 ° C. or lower, more preferably 130 ° C. or lower.
  • (3) is a method of washing with an aqueous solution of one or more compounds selected from the group consisting of an alkali metal perchlorate and an alkali metal permanganate.
  • the method (3) no precipitation of insoluble salts derived from divalent metal ions is observed. This is probably due to the strong oxidizing action of perchlorate and permanganate, which decomposes organic matter until it has a sufficiently low molecular weight, and can exert sufficient adhesive strength to reattach to the tank wall and inorganic substrate. It is presumed that it did not exist.
  • the inorganic substrate preferably the glass substrate, can be repeatedly used, and the manufacturing cost of the flexible electronic device can be increased. Variable costs can be significantly reduced.
  • the present invention is a manufacturing method for obtaining a flexible electronic device by forming an electronic device on the polymer film surface of a laminate composed of a polymer film and an inorganic substrate, and then peeling the electronic device together with the polymer film from the inorganic substrate. It defines the processing method of the inorganic substrate in the above.
  • the present invention is a method for manufacturing an electronic device.
  • the electronic device in the present invention includes an electronic active element such as a transistor and a diode, a passive element such as a resistor, a capacitor, and an inductor, a transducer that converts an external stimulus into an electric signal, or a transducer that converts an electric signal into another energy, and a power supply element.
  • a storage element, etc. is a general term for electronic circuit modules and systems that realize some function by combining a single or a plurality of different types.
  • each electronic device may be connected to each other via a flexible or stretchable electrical junction. More specifically, it is a flexible display element, a flexible sensor array, a flexible photoelectric conversion element, a flexible thermoelectric conversion element, a flexible transducer, a MEMS element, an arithmetic element, a storage element, and the like.
  • Flexible display devices include organic EL display devices, liquid crystal displays, micro light emitting diode display devices, electrophoresis display devices, quantum dot display devices, etc., and color filter arrays, light guide films, etc. used in these display devices. Etc. are also included.
  • an inorganic substrate is used as a support for the polymer film.
  • the inorganic substrate may be a plate-shaped substrate that can be used as a substrate made of an inorganic substance, for example, a glass substrate, a ceramic substrate, a semiconductor wafer, a metal plate, a metal foil, etc., and a laminated or composite thereof. Examples include those containing these fibers.
  • Glass substrates that can be used as inorganic substrates include quartz glass, high silicate glass (96% silica), soda lime glass, lead glass, aluminoborosilicate glass, borosilicate glass (Pylex®), and borosilicate. Includes glass (non-alkali), borosilicate glass (microsheet), aluminosilicate glass and the like. Among these, those having a linear expansion coefficient of 5 ppm / ° C.
  • a substrate having a metal such as chromium, nickel, nichrome, molybdenum, or tungsten, or a thin film such as metal oxide, metal nitride, silicon nitride, aluminum nitride, or silicon carbide formed on the surface of these glass substrates may be used. ..
  • the flat portion of the inorganic substrate is sufficiently flat.
  • the surface roughness Ra is, for example, 10 nm or less, preferably 3 nm or less, and more preferably 0.9 nm or less.
  • the PV value of the surface roughness is, for example, 50 nm or less, preferably 20 nm or less, and more preferably 5 nm or less. If it is coarser than this, the adhesive strength between the polymer film and the inorganic substrate may be insufficient.
  • the thickness of the inorganic substrate is not particularly limited, but is preferably 10 mm or less, more preferably 3 mm or less, still more preferably 1.3 mm or less, from the viewpoint of handleability.
  • the lower limit of the thickness is not particularly limited, but for example, 0.07 mm or more, preferably 0.15 mm or more, more preferably 0.3 mm or more is used.
  • the inorganic substrate in the present invention preferably has a size of at least 4900 cm 2 or more in area. It is preferable that the inorganic substrate of the present invention is substantially rectangular with at least the short side of 700 mm or more.
  • the area of the inorganic substrate is preferably 5000 cm 2 or more, more preferably 10000 cm 2 or more, and further preferably 18000 cm 2 or more.
  • the length on the short side of the rectangle of the inorganic substrate in the present invention is preferably 730 mm or more, more preferably 840 mm or more, and further preferably 1000 mm or more.
  • substantially rectangular means that R, a notch, a notch, an orifra, etc. at the corner of the rectangle are allowed.
  • polymer film in the present invention examples include polyethylene, polypropylene, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, total aromatic polyester, other copolymerized polyester, polymethylmethacrylate, other copolymerized acrylate, polycarbonate, polyamide, and poly.
  • What is particularly effective and useful in the present invention is a polymer having a heat resistance of preferably 100 ° C. or higher, more preferably 150 ° C. or higher, a so-called engineering plastic film.
  • heat resistance refers to the property that the glass transition temperature or heat distortion temperature is 100 ° C. or higher (preferably 150 ° C. or higher).
  • the condensed polymer film (condensation type polymer film) preferably used in the present invention is polyester, polyamide, polyamideimide, polyimide, polybenzazole, polyimide benzazol, polyethylene naphthalate film, liquid crystal polymer film, and more preferably. Is a polyimide film, a polyethylene naphthalate film or a liquid crystal polymer film.
  • the polymer film preferably used in the present invention is a polyimide film, a polyamide film, a polyamide-imide film, a polybenzoxazole film, a polyimide benzoxazole film, and an aromatic polyimide, an alicyclic polyimide, a polyamide-imide, a polyetherimide, or the like is used. Can be done.
  • a polyimide resin film having colorless transparency but particularly when forming a back element of a reflective or self-luminous display. This is not the case.
  • a polyimide film is a green film (“precursor film”) in which a polyamic acid (polyimide precursor) solution obtained by reacting diamines and tetracarboxylic acids in a solvent is applied to a support for producing a polyimide film and dried. It is also referred to as "polyimide acid film”), and is obtained by subjecting a green film to a high temperature heat treatment on a support for producing a polyimide film or in a state of being peeled off from the support to carry out a dehydration ring closure reaction.
  • a polyimide film obtained from a polyimide resin containing the following chemical composition can be exemplified.
  • -Polyimide resin obtained from pyromellitic acid and diaminodiphenyl ether, -Polyimide resin obtained from biphenyltetracarboxylic and phenylenediamine, -Polyimide resin obtained from pyromellitic acid and phenylenediamine, -Polyimide resin using a diamine compound having a benzoxazole skeleton as a diamine component, -Polyimide resin using cyclohexyltetracarboxylic dian or cyclobutanetetracarboxylic acid, -Polyimide resin using alicyclic tetracarboxylic acid and aromatic diamine having an amide bond -Polyimide resin using a monomer containing fluorine, -Polyimide resin using a monomer containing sulfur
  • these are examples of the main components of tetracarboxylic acid or diamine, and are copolymerized by blending the second and third components.
  • a polymer blend by combining polyimides having a plurality of compositions, a polyimide resin obtained by polymer alloying, a polyimide resin into which an inorganic filler or a polydimethylsiloxane component is introduced, or the like may be used.
  • a polyimide film having a structure in which polyimide resins having different compositions are laminated in the thickness direction can also be used.
  • the laminate of the present invention can be obtained by bonding the polymer film to the inorganic substrate.
  • a known adhesive or adhesive can be used for bonding. Further, both can be joined to form a laminated body by surface treatment of a polymer film and / or an inorganic substrate.
  • a polymer solution or a solution of a polymer precursor is applied to an inorganic substrate and dried, or if necessary, heating or a catalyst is allowed to cause a chemical reaction to cause a polymer.
  • the laminate of the present invention can be obtained by converting the precursor into a target polymer. Examples of the polymer precursor include polyamic acid as a precursor of polyimide.
  • a polymer solution or a polymer precursor solution is used as a self-supporting semi-dry film, that is, a solvent and a polymer, or a film containing a solvent and a polymer precursor is used as an inorganic substrate. It is also possible to use a method of adhering and then drying or causing a chemical reaction with drying to form a laminate of a polymer film and an inorganic substrate.
  • the thickness of the polymer film is preferably 3 ⁇ m or more and 120 ⁇ m or less. It is preferably 4 ⁇ m or more, more preferably 5 ⁇ m or more, and further preferably 8 ⁇ m or more because the mechanical properties are good. Further, it is preferably 100 ⁇ m or less, more preferably 80 ⁇ m or less, and further preferably 60 ⁇ m or less because the transparency becomes good.
  • the laminate of the present invention it is also preferable to bond the polymer film and the inorganic substrate via a silane coupling agent or an adhesive.
  • the silane coupling agent refers to a compound containing 10% by mass or more of a Si (silicon) component. Further, it is preferable that the structure has an alkoxy group. Moreover, it is desirable that it does not contain a methyl group.
  • the silane coupling agent layer the intermediate layer between the polymer film and the inorganic substrate can be made thinner, so there is less degassing component during heating, it is difficult to elute even in the wet process, and even if elution occurs, it remains in a trace amount. It is effective.
  • the silane coupling agent preferably contains a large amount of silicon oxide component in order to improve heat resistance, and particularly preferably has heat resistance at a temperature of about 400 ° C.
  • the thickness of the silane coupling agent layer is preferably less than 0.2 ⁇ m.
  • the range used as a flexible electronic device is preferably 100 nm or less (0.1 ⁇ m or less), more preferably 50 nm or less, and further preferably 10 nm. When normally produced, it is about 0.10 ⁇ m or less. Further, in a process in which it is desired to use as little silane coupling agent as possible, it can be used even at 5 nm or less. If it is 1 nm or less, the peel strength may decrease or some parts may not be attached, so that it is preferably 1 nm or more.
  • the silane coupling agent in the present invention is not particularly limited, but one having an amino group or an epoxy group is preferable.
  • Specific examples of the silane coupling agent include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, and N-2- (amino).
  • the adhesive in the present invention is an adhesive used for the purpose of adhering a polymer film and an inorganic substrate, and an adhesive that can withstand the process of forming an electronic device is preferable.
  • epoxy adhesives acrylic adhesives, phenol resin adhesives, polyester-melamine adhesives, polyurethane resin adhesives, polyamide adhesives, polyimide adhesives, silicone adhesives, fluororesin adhesives Examples of agents can be used.
  • Such an adhesive is required not to be easily thermally deformed at a temperature of at least 150 ° C., to have no outgassing that interferes with the electronic device forming process, to have no elution of impurities during the wet process, and to form an electronic device.
  • the peeling means at this time a known method such as so-called laser peeling that irradiates strong light from the inorganic substrate side can be used.
  • a silicone-based adhesive is particularly preferable.
  • the thickness of the adhesive layer is preferably more than 100 nm (more than 0.1 ⁇ m), more preferably 0.5 ⁇ m or more, still more preferably 1 ⁇ m or more in the range used as a flexible electronic device. Further, it is preferably 50 ⁇ m or less, more preferably 20 ⁇ m or less, and further preferably 10 ⁇ m or less.
  • the means for peeling the polymer film from the support is not particularly limited, and a known method may be used.
  • a method of peeling the polymer film from the laminate a method of irradiating strong light from the inorganic substrate side and thermally decomposing or photodegrading the bonding portion between the inorganic substrate and the polymer film to peel them off, and preliminarily determining the adhesive strength.
  • a method of peeling off the polymer film with a force less than the elastic strength limit value of the polymer film after weakening it, a method of exposing it to heated water, heated steam, etc. to weaken the bond strength between the inorganic substrate and the polymer film and peel it off. Can be exemplified.
  • peeling methods include a method of winding from the end with a tweezers, a method of attaching an adhesive tape to one side of the cut portion of the polymer film with a device and then winding from the tape portion, and a method of winding the polymer film with a device.
  • a gripping white can be obtained by vacuum-adsorbing one side of the cut portion and then winding it from that portion, or by not adhering a part of the polymer film to the inorganic plate in advance or by letting a part of the polymer film protrude from the inorganic substrate. The method etc. can be adopted.
  • the inorganic substrate is washed with the aqueous solution A.
  • cleaning means exposing the inorganic substrate, which is the object to be cleaned, to the aqueous solution A, which is the cleaning liquid, for a certain period of time or longer.
  • the exposure means that the inorganic substrate and the treatment liquid are brought into direct contact with each other, and may be simply immersed in the treatment liquid.
  • the treatment liquid is appropriately stirred while being immersed in the treatment liquid.
  • the treatment liquid is brought into contact with the substrate while flowing.
  • the treatment liquid can be discharged from the discharge hole in the form of a shower or a spray to bring the treatment liquid into contact with the inorganic substrate.
  • the aqueous solution A in the present invention is any of the following (1) to (3).
  • the aqueous solution A is an alkaline aqueous solution (hereinafter, also simply referred to as an alkaline aqueous solution), and the content of divalent or higher polyvalent metal ions contained in the alkaline aqueous solution is 10 ppm or less (hereinafter, the aqueous solution A (hereinafter, also referred to as an alkaline aqueous solution). Also called 1).).
  • the alkaline aqueous solution means an aqueous solution of an alkaline compound.
  • an inorganic alkali is preferable, and more specifically, lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, and cesium hydroxide, which are hydroxides of an alkali metal, are preferable.
  • the lower limit of the preferable concentration of the alkaline aqueous solution is 0.01 mol / L or more, preferably 0.03 mol / L, and more preferably 0.1 mol / L.
  • the upper limit of the concentration is 2.5 mol / L, preferably 1.2 mol / L, and more preferably 0.5 mol / L.
  • (2) is an alkaline aqueous solution containing one or more compounds selected from the group consisting of ammonia, urea, and an organic alkaline compound (hereinafter, also referred to as aqueous solution A (2)).
  • the organic alkali compound is preferably an ammonium hydroxide compound represented by the general formula (4).
  • General formula (4) ⁇ (R 1 ) 3 - N + -R 2 ⁇ ⁇ OH-
  • R 1 is preferably H (hydrogen) or an alkyl group having C1 to 8 (carbon atoms 1 to 8). The more preferable number of C (carbon) of R 1 is 2 to 7, and more preferably 3 to 6.
  • R 2 is preferably H (hydrogen), an alkyl group having C1 to 8 (carbon atoms 1 to 8), or a hydroxyalkyl group having C1 to 8 (carbon atoms 1 to 8).
  • the number of C (carbon) of R2 is more preferably 2 to 7, and even more preferably 3 to 6.
  • a plurality of R 1s may be the same or different. However, not all R 1 and R 2 are hydrogen.
  • the ammonium hydroxide compound include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, and tetraoctylammonium hydroxide.
  • a lower alcohol compound having an amino group such as monoaminoethanol, diaminoethanol, triaminoethanol, diethanolamine, and triethanolamine can also be used.
  • an organic alkaline compound and an inorganic alkaline compound in combination.
  • the inorganic alkali compound lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide and the like, which are hydroxides of an alkali metal, can be used.
  • the organic alkaline compound and the inorganic alkaline compound are used in combination, it is preferable to use an excessive amount of the organic alkaline compound.
  • an alkaline solution containing monoethanolamine and sodium hydroxide can be shown as one preferred embodiment.
  • the lower limit of the preferable concentration of the alkaline solution is 0.01 mol / L or more, more preferably 0.03 mol / L, and further preferably 0.1 mol / L as the content of the total alkaline compound.
  • the upper limit of the concentration is preferably 2.5 mol / L, more preferably 1.2 mol / L, and further preferably 0.5 mol / L.
  • (3) is an aqueous solution containing one or more compounds selected from the group consisting of a perchlorate alkali metal salt and a permanganate alkali metal salt (hereinafter, also referred to as aqueous solution A (3)).
  • the inorganic substrate is washed with the aqueous solution A (3).
  • the lower limit of the preferable concentration of the aqueous solution of one or more compounds selected from the group consisting of the alkali metal perchlorate and the alkali metal permanganate is 0.01 mol / L or more, preferably 0.03 mol / L. Yes, more preferably 0.1 mol / L.
  • the upper limit of the concentration is preferably 2.5 mol / L, preferably 1.2 mol / L, and more preferably 0.5 mol / L.
  • An aqueous solution of an alkali metal perchlorate can be obtained by electrolyzing an aqueous solution of an alkali metal chlorate.
  • An existing method may be used for preparing an aqueous solution of an alkali metal perchloric acid accompanied by electrolysis.
  • Japanese Patent Publication No. 2019-524991, Japanese Patent Publication No. 2013-91829, and Japanese Patent Publication No. 2011-58043 may be used.
  • the technique disclosed in the publication may be used.
  • As the alkali metal salt a sodium salt is preferably used because it has a high water solubility.
  • the concentration of the permanganate alkali metal salt in water should be 90% or less, and the pH should be maintained at about 10-14 with sodium hydroxide or hydroxide. It is preferable to add potassium.
  • a potassium salt is preferably used as the alkaline salt. As an example, a mixed aqueous solution of potassium permanganate 20 to 80 g / liter and sodium hydroxide 10 to 60 g / liter can be exemplified.
  • the content of the divalent or higher multivalent metal ion contained in the aqueous solution A in the present invention is preferably 10 ppm (mg / L) or less, and more preferably 5 ppm (mg / L) or less. Since there is a detection limit for the lower limit, no particular lower limit is set.
  • the polyvalent metal ions are alkaline earth metals and transition metal divalent to hexavalent ions, such as beryllium, magnesium, calcium, strontium, barium, scandium, aluminum, titanium, vanadium, chromium, manganese, iron, and so on.
  • Ions such as cobalt, nickel, copper, zinc, gallium, arsenic, yttrium, zirconium, niobium, molybdenum, cadmium, indium, tin, antimony, tungsten, thallium, lead and bismuth can be exemplified.
  • the polyvalent ions that are particularly noteworthy are calcium and magnesium, which are easily brought in as impurities in water and alkali metals, and iron, nickel, chromium, vanadium, manganese, and molybdenum ions derived from pipe and bathtub materials.
  • the concentration of these polyvalent metal ions is the evaporation obtained by precipitating the metal content that was present in the alkaline aqueous solution in a solid state without being ionized (that is, not dissolving) by the centrifugal sedimentation method and heating the supernatant portion. It can be determined by atomic absorption spectrometry of dry matter.
  • the polyvalent metal ion concentration of the present invention is the sum of all metals having a valence of divalent or higher among the metal elements detected by the above analysis method.
  • tap water is deionized with an ion exchange resin and further filtered with a column filter for ultrapure water to produce ultrapure water. Then, a high-purity alkaline compound purified to a desired concentration may be added and dissolved.
  • the aqueous solution A of the present invention is preferably used at a temperature of 5 to 90 ° C. Since the treatment effect depends on the temperature, it is possible to adjust the time with other processes by adjusting the temperature according to the line speed of the treatment process. However, at high temperatures, the volatilization rate of water becomes high, and it may be difficult to control the concentration of the alkaline aqueous solution.
  • the exposure time to the alkaline aqueous solution of the present invention is preferably about 10 seconds to 1 hour in the case of immersion washing, and 5 seconds to 10 minutes in the case of exposure to a fluid alkaline aqueous solution such as a spray.
  • a neutralization treatment (called an acid neutralization step) is further performed with a dilute acid aqueous solution, and then the washing with water is performed again.
  • a neutralization treatment (called an acid neutralization step) is further performed with a dilute acid aqueous solution, and then the washing with water is performed again.
  • the aqueous solution A (1) and the aqueous solution A (2) are alkaline aqueous solutions, it is preferable to perform acid neutralization.
  • the dilute acid aqueous solution dilute sulfuric acid, dilute hydrochloric acid, acetic acid aqueous solution and citric acid aqueous solution can be preferably used.
  • the dilute acid concentration is preferably 0.0001 mol / L to 0.05 mol / L.
  • rinsing is performed using neutral washing water having a divalent or higher polyvalent metal ion content of 10 ppm or less. Is preferable. Even if the concentration of polyvalent metal ions in the alkaline aqueous solution used in the cleaning step is controlled within a predetermined range, if polyvalent metal ions are present in the subsequent washing step, hydrolysis of organic substances that may remain on the surface of the inorganic substrate.
  • the content of the polyvalent metal ion is preferably 5 ppm or less because the substance may be insoluble and chloride to form a fixed substance on the surface of the substrate.
  • Rinse refers to an operation of washing away (washing) the alkaline aqueous solution used in the washing step and the dilute acid aqueous solution used in the acid neutralization step. Therefore, after the step of (a) washing the inorganic substrate with an alkaline aqueous solution, and (b) forming a polymer film on a part or all of at least one surface of the inorganic substrate to form a laminate. It is preferable to carry out before the obtaining step. Further, as the cleaning liquid (rinsing liquid), for example, tap water can be deionized with an ion exchange resin and further filtered with an ultrapure water column filter to prepare an ultrapure water rinse liquid.
  • the pH of the washing liquid is preferably 6.5 or more and 7.5 or less, more preferably 6.8 or more and 7.2 or less, and further preferably 6.9 or more and 7.1 or less.
  • the carbonate concentration can be determined by the sequential titration method according to the potentiometric titration method.
  • the mass ratio of the hydroxide concentration to the carbonate concentration is preferably 100/0 to more than 50/50, more preferably 99.9 / 0.1 to 90 /. It is 10, more preferably 99.8 / 0.2 to 99/1.
  • the inorganic substrate of the present invention can be reused by peeling off the polymer film containing the flexible electronic device and then going through the steps (a) to (d) again. That is, by cleaning the used inorganic substrate again, a polymer film can be formed on the same surface or the back surface of the inorganic substrate and used again for manufacturing a flexible electronic device. Specifically, after the step (d) of peeling the electronic device together with the polymer film from the inorganic substrate, (A)'The step of cleaning the inorganic substrate with the aqueous solution A, (B)'A step of forming a polymer film on a part or all of at least one surface of the inorganic substrate to obtain a laminate.
  • the flexible electronic device is manufactured again by including the step of peeling the electronic device together with the polymer film from the inorganic substrate and the step of the aqueous solution A being any one of the following (1) to (3). can do. Further, the inorganic substrate peeled off in the step (d)'can be reused in the same manner.
  • the aqueous solution A is an alkaline aqueous solution, and the content of divalent or higher polyvalent metal ions contained in the alkaline aqueous solution is 10 ppm or less.
  • ⁇ Thickness of polymer film> The thickness of the polymer film was measured using a micrometer (“Millitron 1245D” manufactured by Fine Wolf Co., Ltd.), and the average value of 10 points was obtained.
  • CTE Linear expansion coefficient of polymer film>
  • MD direction flow direction
  • TD direction width direction
  • the expansion and contraction rate was measured under the following conditions, and the intervals at 15 ° C. (30 ° C. to 45 ° C., 45 ° C. to 60 ° C.).
  • the expansion / contraction rate / temperature at fixed was measured, this measurement was performed up to 300 ° C., and the average value of all the measured values measured in the MD direction and the TD direction was calculated as the linear expansion coefficient (CTE).
  • ⁇ Multivalent metal ion concentration> Centrifuge the liquid to be measured with a centrifuge at a rotation speed of 2500 rpm (centrifugal acceleration 900 G) for 60 minutes, take out the supernatant, put it in a ceramic evaporating dish, heat it at 150 ° C for 30 minutes, and dry it.
  • the sample was prepared by solidification. Quantitative analysis by atomic absorption spectroscopy was performed using the sample, and alkali metals and silver were removed from the detected metals, and the rest were totaled to obtain the polyvalent metal ion concentration.
  • the calibration curve was prepared using AR grade, a metal standard solution for atomic absorption spectroscopy manufactured by Hayashi Junyaku Kogyo Co., Ltd. Since the peaks of K and Na, which are intentionally added components, are excessive, the lower limit of detection is about 0.1 ppm. Furthermore, elements not detected in the raw water used in the preparation of the alkaline aqueous solution are excluded from the measurement.
  • ⁇ Hydroxide concentration, carbonate concentration> The hydroxide concentration and the carbonate concentration were determined by a sequential titration method using a 0.1 mol / L hydrochloric acid standard solution and an automatic titrator (manufactured by Hiranuma Sangyo Co., Ltd.). When the concentration of the analysis target was high, the analysis was performed by diluting with ultrapure water so that the concentration was 1 g / L or less.
  • ⁇ Visual inspection, blister defect density> The number of blister defects with a size of 30 ⁇ m or more was counted by a defect inspection device, and the number of defects per 100 square cm was ranked as follows. ⁇ : 0 to 1 piece / 100 square cm ⁇ : 2 or more and 5 or less ⁇ : 6 or more and 15 or less ⁇ : 16 or more and 100 or less XX: 101 or more Also, observe the handleability such as peelability of the film and the appearance quality such as the presence or absence of wrinkles. And recorded.
  • the remaining polyamic acid film GFa was peeled off from the polyester film, and heat-treated with a pin tenter for the first stage at 150 ° C. ⁇ 5 minutes, the second stage at 220 ° C. ⁇ 5 minutes, and the third stage at 495 ° C. ⁇ 10 minutes.
  • the pin gripping portions at both ends were dropped by slits to obtain a long polyimide film IF1 (1000 m roll) having a width of 645 mm.
  • the characteristics of the obtained film IFa are shown in Table 1.
  • DABAN 4-amino-N- (4-aminophenyl) benzamide
  • DMAC N-dimethylacetamide
  • the polyamic acid solution Vb was applied onto a smooth surface (non-slip material surface) of a polyester film having a width of 1300 mm (“A-4100” manufactured by Toyobo Co., Ltd.), which is a support for producing a polyimide film, using a die coater.
  • the coating width was 1200 mm), and the mixture was dried at 90 to 115 ° C. for 10 minutes.
  • the polyamic acid film that became self-supporting after drying was peeled off from the support and both ends were cut to obtain a polyamic acid film GFb.
  • a part of the polyamic acid film GFb was wound together with the polyester film to form a polyamic acid film roll.
  • the remaining polyamic acid film GFb was conveyed by a pin tenter so that the final pin sheet spacing was 1140 mm, and the first stage was 170 ° C. for 2 minutes, the second stage was 230 ° C. for 2 minutes, and the third stage was 350 ° C. 6
  • the film was heat-treated for 1 minute, then cooled to room temperature in 2 minutes, and the poorly flat portions of both ends of the film were cut off with a slitter and rolled up into a roll to obtain a polyimide film IFb having a thickness of 25 ⁇ m.
  • the characteristics of the obtained film IFb are shown in Table 1.
  • a (1) -2 (comparative example)> Preparation of alkaline aqueous solution The operation was the same as in A (1) -1 except that tap water not subjected to ion exchange treatment and ultrapure water column treatment was used as raw water to obtain an alkaline aqueous solution KQ2.
  • the obtained sodium chlorate aqueous solution is transferred to an electrolytic cell having a platinum electrode, and while monitoring the amount of perchlorate ion by ion chromatography, electrolysis is performed until the perchlorate ion / chlorate ion (mol ratio) becomes 1 or more.
  • the operation was carried out to obtain a cleaning solution A (3) -1 containing sodium perchlorate.
  • cleaning solution A (3) -2 (aqueous solution containing potassium permanganate)>
  • the ultrapure water obtained by further filtering the water deionized with the ion exchange resin with a column filter for ultrapure water was used as the raw material water.
  • the raw water was placed in a polyethylene (PE) container, and purified potassium permanganate and high-purity potassium hydroxide were carefully and gradually added so that the liquid temperature did not exceed 50 ° C due to heat of hydration.
  • An aqueous solution of potassium permanganate 0.5 mol / L and sodium hydroxide 0.3 mol / L was obtained. This is referred to as cleaning liquid A (3) -2.
  • Example 1 Laminated body by IF lami method (A (1))> (First-generation laminate by IF Lami method)
  • a glass substrate 370 ⁇ 470 mm, 0.7 mm thick Rotus Glass manufactured by Corning Inc.
  • As a cleaning treatment for the inorganic substrate it is immersed in an alkaline aqueous solution KQ1 whose temperature has been adjusted to 40 ° C., shaken for 10 minutes, then immersed in the ultrapure water used in the preparation of the alkaline aqueous solution while being shaken, rinsed, and then 0.
  • One side of the polyimide film IFa was subjected to atmospheric pressure plasma treatment under a nitrogen atmosphere to obtain a plasma-treated film.
  • the plasma-treated surface and the surface-treated inorganic substrate were bonded together with a hot roll laminator, and after bonding, the mixture was heated at 150 ° C. for 10 minutes to obtain the first-generation laminated body MLia-KQ1-. I got 1G.
  • the laminate manufacturing process shown here is referred to as the IF lami method.
  • the glass substrate from which the film was peeled off from the first-generation laminate MLia-KQ1-1G was used in place of the virgin glass substrate in the first-generation laminate fabrication.
  • the operation was carried out in the same manner as in the first generation to obtain the second generation laminated body MLia-KQ1-2G.
  • a simulated operation for manufacturing an electronic device was performed in the same manner.
  • Example 4 The operation was carried out in the same manner as in Example 1 except that the polyimide film IFb was used instead of the polyimide film IFa, and the recyclability of the substrate up to the 4th generation was evaluated. The results are shown in Table 3. The results were as good as in Example 1.
  • a polyamic acid solution (varnish) Va was applied onto the substrate with a bar coater so that the final film thickness was 15 ⁇ m, and the temperature was adjusted to 450 ° C. in an inert oven at 120 ° C. for 7 minutes, 250 ° C. for 5 minutes, and 450 ° C. The mixture was heated for 5 minutes to obtain a first-generation laminate Mva-NQ1s-1G by the varnish method.
  • the first-generation laminates Mvb-NQ1s-1G and Mvb-KQ2s-1G for varnish were obtained by using the polyamic acid solution (varnish) shown in Table 4 and the alkaline aqueous solution used for washing.
  • the test was interrupted because the blister defect density reached the XX (101 or more per 100 square cm) level when the polymer film was laminated during the production of the 5th generation. Calcium carbonate and magnesium carbonate were detected when the composition of foreign particles confirmed in the blister was evaluated.
  • Examples 7 and 8 laminated body by GF method>
  • the same cleaning treatment as in Example 1 was performed on the inorganic substrate.
  • a roll of the polyamic acid film GFa wound together with the polyester film was unwound, an inorganic substrate was placed on the surface of the polyamic acid film, and the two were bonded together with a roll laminator having a roll temperature of 80 ° C.
  • the polyamic acid film was cut to the same size as the polyester film substrate, and then the polyester film was peeled off from the polyamic acid film to obtain a GFa laminate composed of the inorganic substrate and the polyamic acid film.
  • the GFa laminate was heat-treated at 250 ° C.
  • the polyamic acid film GFb is laminated on the inorganic substrate after the cleaning treatment, the polyester film is peeled off, and then heat-treated in nitrogen at 150 ° C. for 10 minutes and at 280 ° C. for 10 minutes, and the laminate by the GF method Mgb-KQ1 Obtained -1G.
  • each laminated body was repeatedly subjected to an electronic device fabrication simulation operation, film peeling, and substrate reuse until the fifth generation, and the blister defect density was observed. The results are shown in Table 4. In each case, the substrate could be reused without any problem until the 5th generation.
  • Laminated body by IF lami method (A (2))> First-generation laminated body by IF Lami method (A (2) 1-1G)
  • the inorganic substrate a Lotus Glass manufactured by Corning Inc. having a thickness of 370 ⁇ 470 mm and a thickness of 0.7 mm was used.
  • the inorganic substrate was sealed, immersed in an alkaline solution A (2) -1 whose temperature was adjusted to 30 ° C., shaken for 30 minutes, spray-rinsed with ultrapure water, and then 0.1% by mass. It was soaked in dilute hydrochloric acid for 3 minutes, rinsed twice with ultrapure water, and then dried with clean dry air at 120 ° C.
  • the washed inorganic substrate is exposed to the vapor of the silane coupling agent: N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane in a closed chamber heated to 40 ° C. for 5 minutes, and then exposed to the vapor.
  • the surface of the inorganic substrate was treated by heating in clean nitrogen at 100 ° C. for 15 minutes.
  • One side of the polyimide film IFa is subjected to atmospheric pressure plasma treatment under a nitrogen atmosphere to form a plasma-treated film, and the plasma-treated surface and the surface-treated inorganic substrate are bonded with a hot roll laminator so as to overlap with each other. After the combination, the mixture was heated at 150 ° C. for 10 minutes to obtain a first-generation laminate A (2) 1-1G.
  • the laminate manufacturing process shown here is referred to as the IF lami method.
  • the film on which the amorphous silicon thin film was deposited was peeled off from the laminated body A (2) 1-1G by inserting a blade at the end of the film to form a hook. No particular abnormality was observed at the time of peeling.
  • Example 10 (A (2) 2-1G to 5G)> The operation was carried out in the same manner except that the alkaline solution A (2) -1 in Example 9 was replaced with the alkaline solution A (2) -2.
  • a glass substrate washed with the alkaline solution A (2) -2 and a laminate A (2) 2-1G were prepared by the IF lami method, and the same electronic device fabrication simulation operation as in Example 9 was performed, and after the film was peeled off.
  • the reuse of the glass substrate was repeated until the 5th generation, and the state of the laminated body was evaluated and observed. As a result, it was confirmed that the blister density was ⁇ level to ⁇ level and that it could be reused repeatedly until at least the 5th generation.
  • Example 11 (A (2) 3-1G to 5G)> The operation was carried out in the same manner except that the alkaline solution A (2) -1 in Example 9 was replaced with the alkaline solution A (2) -3 and the temperature of the alkaline solution A (2) -3 was set to 60 ° C.
  • a glass substrate washed with the alkaline solution A (2) -3 and a laminate A (2) 3-1G were prepared by the IF lami method, and the same electronic device fabrication simulation operation as in Example 9 was performed, and after the film was peeled off. The reuse of the glass substrate was repeated until the 5th generation, and the state of the laminated body was evaluated and observed. As a result, it was confirmed that the blister density was ⁇ level to ⁇ level and that it could be reused repeatedly until at least the 5th generation.
  • Example 12 (A (2) 4-1G to 5G)> The operation was carried out in the same manner as in Example 9 except that the polyimide film IFb was used instead of the polyimide film IFa, and the recyclability of the inorganic substrate up to the fifth generation was evaluated.
  • the blister density was ⁇ level to ⁇ level in all generations, and the results were as good as in Example 9.
  • Example 13 (A (2) 5-1G to 5G)> Similarly, the same operation as in Example 10 was performed except that the polyimide film IFb was used instead of the polyimide film IFa, and the recyclability of the inorganic substrate up to the fifth generation was evaluated. The blister density was ⁇ level to ⁇ level in all generations, and the results were as good as in Example 10.
  • Example 14 (A (2) 6-1G to 5G)> Similarly, the same operation as in Example 11 was performed except that the polyimide film IFb was used instead of the polyimide film IFa, and the recyclability of the inorganic substrate up to the fifth generation was evaluated. The blister density was ⁇ level to ⁇ level in all generations, and the results were as good as in Example 11.
  • Laminated body by varnish method (A (2) 7-1G to 5G)> First-generation laminated body by varnish method (A (2) 7-1G)
  • a Lotus Glass manufactured by Corning Inc. having a thickness of 370 ⁇ 470 mm and a thickness of 0.7 mm was used.
  • an alkaline solution 2 at 30 ° C. is sprayed for 5 minutes in a roller transport type spray cleaning machine, then spray rinsed twice with ultrapure water and then dried with clean dry air at 80 ° C. I let you.
  • a polyamic acid solution (varnish) Va was applied onto the substrate with a bar coater so that the final film thickness was 15 ⁇ m, and the temperature was adjusted to 450 ° C. in an inert oven at 120 ° C. for 7 minutes, 250 ° C. for 5 minutes, and 450 ° C. The mixture was heated for 5 minutes to obtain a first-generation laminate A (2) 7-1G by the varnish method.
  • the electronic device fabrication simulated operation, film peeling, and substrate reuse were repeated until the fifth generation, and the blister defect density was observed. ..
  • the blister density was ⁇ level to ⁇ level in all generations, and it was possible to obtain a good laminate with few blister defects in any generation, and it was also possible to use it for electronic device operation.
  • Example 16 GF method (A (2) 8-1G to 5G)> First, the inorganic substrate was washed with the same alkaline solution A (2) -1 as in Example 9. Next, a roll of the polyamic acid film GFa wound together with the polyester film was unwound, an inorganic substrate was placed on the surface of the polyamic acid film, and the two were bonded together with a roll laminator having a roll temperature of 80 ° C. Then, the polyamic acid film was cut together with the polyester film to the same size as the inorganic substrate, and then the polyester film was peeled off from the polyamic acid film to obtain a GFa laminate composed of the inorganic substrate and the polyamic acid film.
  • the GFa laminate was heat-treated at 250 ° C. for 8 minutes and at 450 ° C. for 8 minutes to obtain a laminate A (2) 8-1G by the GF method.
  • the electronic device fabrication simulated operation, film peeling, and substrate reuse were repeated until the fifth generation, and the blister defect density was observed. ..
  • Example 17 (A (2) 9-1G to 5G)>
  • the same glass substrate as in Example 9 1000 parts by mass of water and 50 parts by mass of urea are charged, sealed, the temperature is raised to 121 ° C., held for 60 minutes, cooled to room temperature, and opened under ventilation. The glass substrate was taken out. There was a strong ammonia odor at the time of opening, suggesting that urea was decomposed into ammonia. The process up to this point is called autoclave processing.
  • Example 9 After that, rinsing, neutralization with dilute hydrochloric acid, rerinsing, and drying are performed in the same manner as in Example 9, and then the laminate production by the varnish method and the electronic device production simulation operation and the film peeling are performed in the same manner as in Example 7, and the autoclave of this example is performed.
  • the substrate was repeatedly reused by the treatment until the 5th generation, and the blister defect density was observed.
  • the blister density was ⁇ level to ⁇ level in all generations, and the substrate could be reused without any problem until the 5th generation.
  • Example 18 Laminated body by IF lami method (A (3))> (First-generation laminated body by IF Lami method (A (3) 1-1G))
  • the inorganic substrate a Lotus Glass manufactured by Corning Inc. having a thickness of 370 ⁇ 470 mm and a thickness of 0.7 mm was used.
  • the inorganic substrate is immersed in the cleaning liquid A (3) -1 whose temperature has been adjusted to 70 ° C., shaken for 10 minutes, then spray-rinsed twice with ultrapure water, and then with clean dry air at 120 ° C. It was dried.
  • the washed inorganic substrate is exposed to the vapor of the silane coupling agent: N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane in a closed chamber heated to 40 ° C. for 5 minutes, and then exposed to the vapor.
  • the surface of the inorganic substrate was treated by heating in clean nitrogen at 100 ° C. for 15 minutes.
  • One side of the polyimide film IFa is subjected to atmospheric pressure plasma treatment under a nitrogen atmosphere to form a plasma-treated film, and the plasma-treated surface is bonded with a hot roll laminator so that the surface-treated inorganic substrate overlaps with each other. After the combination, the mixture was heated at 150 ° C. for 10 minutes to obtain a first-generation laminate A (3) 1-1G.
  • the laminate manufacturing process shown here is referred to as the IF lami method.
  • Example 19 (A (3) 2-1G)> The same operation was performed except that the cleaning liquid A (3) -1 in Example 18 was replaced with the cleaning liquid A (3) -2.
  • a laminated body was prepared by the IF lami method with the glass substrate washed with the cleaning liquid A (3) -2, and the same electronic device fabrication simulation operation as in Example 18 and the reuse of the glass substrate after film peeling were performed. The state of the laminated body was evaluated and observed repeatedly until the generation. As a result, it was confirmed that the blister density was ⁇ level to ⁇ level and that it could be reused repeatedly until at least the 5th generation.
  • Example 20 (A (3) 3-1G)> The operation was carried out in the same manner as in Example 18 except that the polyimide film IFb was used instead of the polyimide film IFa, and the recyclability of the inorganic substrate up to the fifth generation was evaluated.
  • the blister density was ⁇ level to ⁇ level in all generations, and the results were as good as in Example 18.
  • Example 21 (A (3) 4-1G)> Similarly, the same operation as in Example 19 was performed except that the polyimide film IFb was used instead of the polyimide film IFa, and the recyclability of the inorganic substrate up to the fifth generation was evaluated.
  • the blister density was ⁇ level to ⁇ level in all generations, and the results were as good as in Example 19.
  • Laminated body by varnish method (A (3) 5-1G to 5G)> First-generation laminated body by varnish method (A (3) 5-1G)
  • a Lotus Glass manufactured by Corning Inc. having a thickness of 370 ⁇ 470 mm and a thickness of 0.7 mm was used.
  • a roller transport type spray washer was used to spray the cleaning liquid A (3) -1 at 60 ° C for 5 minutes, then spray rinsed twice with ultrapure water, and then cleaned at 80 ° C. It was dried with dry air.
  • a polyamic acid solution (varnish) Va was applied onto the substrate with a bar coater so that the final film thickness was 15 ⁇ m, and the temperature was adjusted to 450 ° C. in an inert oven at 120 ° C. for 7 minutes, 250 ° C. for 5 minutes, and 450 ° C. The mixture was heated for 5 minutes to obtain a first-generation laminate (A (3) 5-1G) by the varnish method.
  • a (3) 5-1G the electronic device fabrication simulated operation, film peeling, and substrate reuse were repeated up to the fifth generation in accordance with Example 18, and the blister defect density was determined. Observed. As a result, the blister density was ⁇ level to ⁇ level in each generation, and it was possible to obtain a good laminate with few blister defects in any generation, and it was also possible to use it for electronic device operation.
  • Example 22 (A (3) 6-1G to 5G)> The same operation was performed except that the cleaning liquid A (3) -2 was used instead of the cleaning liquid A (3) -1 of Example 21, and the recyclability of the inorganic substrates from the first generation to the fifth generation was evaluated.
  • the blister density was ⁇ level to ⁇ level in all generations, and the results were as good as in Example 21.
  • Example 23 GF method (A (3) 7-1G-5G)> First, the substrate was cleaned with the same cleaning solution A (3) -2 as in Example 19. Next, a roll of the polyamic acid film GFa wound together with the polyester film was unwound, an inorganic substrate was placed on the surface of the polyamic acid film, and the two were bonded together with a roll laminator having a roll temperature of 80 ° C. Then, the polyamic acid film was cut together with the polyester film to the same size as the inorganic substrate, and then the polyester film was peeled off from the polyamic acid film to obtain a GFa laminate composed of the inorganic substrate and the polyamic acid film. Next, the GFa laminate was heat-treated at 250 ° C.
  • Example 24 (A (3) 8-1G to 5G)>
  • the polyamic acid film GFb was laminated on the cleaned inorganic substrate, the polyester film was peeled off, and then heat-treated in nitrogen at 150 ° C. for 10 minutes and at 280 ° C. for 10 minutes, and then laminated by the GF method.
  • Body A (3) 8-1G was obtained.
  • the electronic device fabrication simulation operation, film peeling, and reuse of the inorganic substrate were repeated until the fifth generation, and the blister defect density was observed. did.
  • the blister density was ⁇ level to ⁇ level in all generations, and the inorganic substrate could be reused without any problem until the 5th generation.
  • the substrate can be reused by subjecting the substrate to a cleaning treatment satisfying specific conditions, so that variable costs can be significantly reduced in the manufacture of flexible electronic devices. Is possible.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Manufacturing Of Printed Circuit Boards (AREA)

Abstract

Selon l'invention, il est possible de recycler un substrat de support temporaire lors du processus de fabrication d'un dispositif électronique flexible, et ainsi d'abaisser le coût de fabrication de ce dispositif électronique flexible.　Plus précisément, l'invention concerne un procédé de fabrication de dispositif électronique flexible qui est caractéristique en ce qu'il inclut : (a) une étape au cours de laquelle un substrat inorganique est nettoyé à l'aide d'une solution aqueuse (A) ; (b) une étape au cours de laquelle un film polymère est formé sur une partie ou sur l'ensemble d'au moins une des faces dudit substrat inorganique, et un stratifié est obtenu ; (c) une étape au cours de laquelle un dispositif électronique est formé sur le film polymère dudit stratifié ; et (d) une étape au cours de laquelle ledit dispositif électronique est décollé du substrat inorganique avec le film polymère. Ladite solution aqueuse (A) consiste en l'une des solutions (1) à (3) suivantes.　(1) La solution aqueuse (A) consiste en une solution aqueuse alcaline, la teneur en ions métalliques polyvalents divalents ou plus contenus dans ladite solution aqueuse alcaline, étant inférieure ou égale à １０ｐｐｍ. (2) La solution aqueuse (A) consiste en une solution aqueuse alcaline qui contient au moins une sorte de composé choisie dans un groupe constitué d'un ammoniac, d'une urée et d'un composé alcalin organique. (3) La solution aqueuse (A) consiste en une solution aqueuse qui contient au moins une sorte de composé choisie dans un groupe constitué d'un sel de métal alcalin d'acide perchlorique et d'un sel de métal alcalin d'acide permanganique.
PCT/JP2021/026826 2020-07-29 2021-07-16 Procédé de fabrication de dispositif électronique flexible WO2022024820A1 (fr)

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JP2022540189A JPWO2022024820A1 (fr) 2020-07-29 2021-07-16
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JPH05283839A (ja) * 1992-01-23 1993-10-29 Minnesota Mining & Mfg Co <3M> フレキシブル回路の作製方法
JP2001277424A (ja) * 2000-04-03 2001-10-09 Mitsubishi Shindoh Co Ltd 金属化ポリイミドフィルムおよびその製造方法
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