WO2014119648A1 - Stratifié, procédé de production de stratifié et procédé de fabrication de dispositif électronique souple - Google Patents

Stratifié, procédé de production de stratifié et procédé de fabrication de dispositif électronique souple Download PDF

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Publication number
WO2014119648A1
WO2014119648A1 PCT/JP2014/052052 JP2014052052W WO2014119648A1 WO 2014119648 A1 WO2014119648 A1 WO 2014119648A1 JP 2014052052 W JP2014052052 W JP 2014052052W WO 2014119648 A1 WO2014119648 A1 WO 2014119648A1
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Prior art keywords
polymer film
laminate
inorganic substrate
film
coupling agent
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PCT/JP2014/052052
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English (en)
Japanese (ja)
Inventor
奥山　哲雄
俊之 土屋
勝貴 中瀬
郷司 前田
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東洋紡株式会社
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Priority to JP2014559733A priority Critical patent/JP6447135B2/ja
Publication of WO2014119648A1 publication Critical patent/WO2014119648A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • C09J5/06—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving heating of the applied adhesive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/12—Mountings, e.g. non-detachable insulating substrates
    • H01L23/14—Mountings, e.g. non-detachable insulating substrates characterised by the material or its electrical properties
    • H01L23/145—Organic substrates, e.g. plastic
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/46—Manufacturing multilayer circuits
    • H05K3/4611—Manufacturing multilayer circuits by laminating two or more circuit boards
    • H05K3/4626—Manufacturing multilayer circuits by laminating two or more circuit boards characterised by the insulating layers or materials
    • H05K3/4635—Manufacturing multilayer circuits by laminating two or more circuit boards characterised by the insulating layers or materials laminating flexible circuit boards using additional insulating adhesive materials between the boards
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/416—Additional features of adhesives in the form of films or foils characterized by the presence of essential components use of irradiation
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2400/00—Presence of inorganic and organic materials
    • C09J2400/10—Presence of inorganic materials
    • C09J2400/12—Ceramic
    • C09J2400/123—Ceramic in the substrate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2400/00—Presence of inorganic and organic materials
    • C09J2400/10—Presence of inorganic materials
    • C09J2400/14—Glass
    • C09J2400/143—Glass in the substrate
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
    • H05K3/389—Improvement of the adhesion between the insulating substrate and the metal by the use of a coupling agent, e.g. silane

Definitions

  • a flexible polymer film is temporarily fixed on a rigid temporary supporting inorganic substrate to form a laminate, and then various electronic devices are formed on the polymer film, and then the polymer film is peeled off together with the electronic device portion.
  • the present invention relates to a manufacturing technique for obtaining a flexible electronic device, and the laminate.
  • Functional elements such as semiconductor elements, MEMS elements, and display elements are used as electronic components in information communication equipment (broadcast equipment, mobile radio, portable communication equipment, etc.), radar, high-speed information processing devices, etc. Conventionally, it is generally formed or mounted on an inorganic substrate such as glass, a silicon wafer, or a ceramic substrate.
  • an inorganic substrate such as glass, a silicon wafer, or a ceramic substrate.
  • a relatively high temperature is often used in the process of forming a functional element.
  • a temperature range of about 200 to 500 ° C. is used in forming a functional element such as polysilicon or an oxide semiconductor.
  • heating at about 450 ° C. may be required for dehydrogenation.
  • a temperature range of about 200 to 300 ° C. is required.
  • the temperature range exemplified here is not so high for inorganic materials, but it can be said that it is considerably high for polymer films and adhesives generally used for laminating polymer films. I don't get it.
  • the polymer film used, the adhesive used for bonding, and the adhesive also require sufficient heat resistance.
  • the polymer film solution or precursor solution is applied onto the inorganic substrate and then dried and cured on the inorganic substrate.
  • a technique for forming a film and using it for the application is known.
  • the polymer film obtained by such means is brittle and easily torn, the functional element is often destroyed when it is peeled from the inorganic substrate. In particular, it is extremely difficult to peel off a device having a large area, and it is not possible to obtain a yield that can be industrially established.
  • the present inventors as a laminate of a polymer film and a support for forming a functional element, use a polyimide film that has excellent heat resistance and is strong and can be made into a thin film as a coupling agent.
  • a laminated body obtained by bonding to a support (inorganic layer) made of an inorganic material via a film was proposed (Patent Documents 1 to 3).
  • the laminate described in Patent Documents 1 to 3 described above it is possible to bond a polymer film and an inorganic substrate without using a so-called adhesive or adhesive element, and the laminate is a thin film. Exfoliation of the polymer film does not occur even when exposed to the high temperatures required to fabricate the device. Therefore, it is possible to produce an electronic device on a polymer film by subjecting the laminate to a process for forming an electronic device directly on an inorganic substrate such as a conventional glass plate or silicon wafer. A flexible electronic device can be realized by peeling the molecular film from the inorganic substrate.
  • the polymer film itself In the vicinity where foreign matter exists, the polymer film itself is in a raised state, which becomes an obstructive factor in pattern formation using photolithographs and high-definition patterns such as microcontact printing, and good electronic device formation There is a case that cannot be performed.
  • Such foreign matter can be reduced by cleaning the surface of the inorganic substrate and the surface of the polymer film and cleaning the work environment.
  • an essential problem of this technique is the generation of foreign matters due to the silane coupling agent itself.
  • Silane coupling agents are easily affected by moisture and other factors present in the handling environment, and aggregates can easily be formed.
  • aggregates of silane coupling agents that are generated unintentionally in solution or the like are also present.
  • the inventors of the present application have found that the aggregate is dispersed as a foreign substance together with the silane coupling agent on the inorganic substrate. The adverse effects of such foreign substances are as described above.
  • the present invention has been made paying attention to the above-mentioned circumstances, and by fundamentally changing the coating method of the silane coupling agent, the aggregate of the silane coupling agent is prevented from adhering to the inorganic substrate.
  • the present invention provides a laminate with excellent quality and a uniform adhesive force between the polymer film / inorganic substrate and solves the problems in industrial production.
  • the roughness of the surface of the inorganic substrate after peeling the polymer film is small, and it becomes possible to re-apply the silane coupling agent after a simple cleaning operation and use it as a substrate. Sexually improves.
  • the present inventors have successfully applied a silane coupling agent to an inorganic substrate in a gas phase so that no foreign matter is present between the polymer film and the inorganic substrate.
  • a silane coupling agent to an inorganic substrate in a gas phase so that no foreign matter is present between the polymer film and the inorganic substrate.
  • the present invention has the following configuration.
  • the foreign matter is a foreign matter containing a silicon atom.
  • the polymer film is a polyimide film having a thickness of 3 ⁇ m or more. Or 2.
  • the inorganic substrate is a glass plate having an area of 1000 cm 2 or more. ⁇ 3.
  • the silane coupling agent has a chemical structure having one silicon atom per molecule.
  • a method for producing a laminate comprising the following steps (1) to (3): (1) forming a silane coupling agent layer on the inorganic substrate by exposing the inorganic substrate to the gasified silane coupling agent; (2) Step of superposing a polymer film subjected to surface activation treatment on the silane coupling agent layer (3) Step of adhering both by heating and pressing
  • a method for producing a laminate comprising the following steps (1) to (3): (1) A step of forming a silane coupling agent layer on an inorganic substrate by exposing the inorganic substrate to a gasified silane coupling agent. (2) A polymer solution or a polymer precursor solution is added to the silane cup.
  • Step of applying on the ring agent layer (3) Step of drying and heating the polymer solution or polymer precursor solution to obtain a laminate as a polymer film 9.
  • the step (1) is performed under substantially atmospheric pressure. Or 8.
  • the step (1) is performed under reduced pressure.
  • the laminate has a good adhesion part and an easy peeling part with different adhesive strengths between the polymer film and the inorganic substrate, and the good adhesion part and the easy peeling part have a predetermined pattern. 6. It is formed, ⁇ 10.
  • the manufacturing method of the laminated body in any one of. 12 10.
  • the good adhesion part and the easy peeling part form a predetermined pattern.
  • the manufacturing method of the laminated body 13. After the formation of the silane coupling agent layer, by irradiating a part of the silane coupling agent layer with active energy rays, the good adhesion portion and the easily peelable portion form a predetermined pattern. 11. The manufacturing method of the laminated body.
  • the silane coupling agent layer is masked on a part of the inorganic substrate in a predetermined pattern when the silane coupling agent is formed, or after the silane coupling agent layer is formed,
  • a device formation process Sometimes it is possible to create a desired pattern of a good adhesion part having sufficient adhesive strength that does not cause peeling of the polymer film and an easy peeling part that can peel the polymer film relatively easily, It is possible to make a cut along the periphery of the easily peelable part and peel off the functional element part formed in the area.
  • the surface of the inorganic substrate after peeling of the polymer film in the present invention has high smoothness, and a silane coupling layer is formed again by a relatively simple cleaning operation to be used as a material for the laminate. It also has the effect of being able to. More preferably, in the present invention, if a polymer film having high heat resistance is used, bonding can be performed without using an adhesive or pressure-sensitive adhesive that is inferior in heat resistance.
  • the element can be formed using a high temperature of preferably 230 ° C. or higher, more preferably 260 ° C. or higher. In general, semiconductors, dielectrics, and the like can be formed at a high temperature to obtain a thin film with better film quality, so that higher performance functional elements can be expected.
  • a flexible electronic device in which devices such as a dielectric element, a semiconductor element, a MEMS element, a display element, a light emitting element, a photoelectric conversion element, a piezoelectric conversion element, and a thermoelectric conversion element are formed on a film substrate.
  • devices such as a dielectric element, a semiconductor element, a MEMS element, a display element, a light emitting element, a photoelectric conversion element, a piezoelectric conversion element, and a thermoelectric conversion element are formed on a film substrate.
  • the laminate of the present invention is a laminate comprising at least an inorganic substrate, a silane coupling agent, and a polymer film.
  • an inorganic substrate is used as a support for the polymer film.
  • the inorganic substrate may be any plate-like material that can be used as a substrate made of an inorganic material, for example, a glass plate, a ceramic plate, a semiconductor wafer, a material mainly made of metal, etc., and these glass plates, ceramic plates, Examples of silicon wafers and metal composites include those obtained by laminating them, those in which they are dispersed, and those containing these fibers.
  • the glass plate examples include quartz glass, high silicate glass (96% silica), soda lime glass, lead glass, aluminoborosilicate glass, borosilicate glass (Pyrex (registered trademark)), borosilicate glass (non-alkali), Borosilicate glass (microsheet), aluminosilicate glass and the like are included.
  • the ceramic plate examples include Al2O3, Mullite, AlN, SiC, Si3N4, BN, crystallized glass, Cordierite, Spodumene, Pb-BSG +.
  • a silicon wafer As the semiconductor wafer, a silicon wafer, a semiconductor wafer, a compound semiconductor wafer, or the like can be used.
  • the silicon wafer is obtained by processing single crystal or polycrystalline silicon on a thin plate, and is n-type or p-type. This includes all doped silicon wafers, intrinsic silicon wafers, etc., and silicon wafers with silicon oxide layers and various thin films deposited on the surface of silicon wafers.
  • germanium, silicon- Germanium, gallium-arsenic, aluminum-gallium-indium, nitrogen-phosphorus-arsenic-antimony, SiC, InP (indium phosphorus), InGaAs, GaInNAs, LT, LN, ZnO (zinc oxide), CdTe (cadmium tellurium), ZnSe ( Semiconductor wafers and compounds such as zinc selenide) A semiconductor wafer or the like can be used.
  • the metal examples include single element metals such as W, Mo, Pt, Fe, Ni, and Au, alloys such as Inconel, Monel, Nimonic, carbon copper, Fe—Ni-based Invar alloy, and Super Invar alloy.
  • a multilayer metal plate formed by adding other metal layers and ceramic layers to these metals is also included. In this case, if the total CTE with the additional layer is low, Cu, Al or the like is also used for the main metal layer.
  • the metal used as the additional metal layer is limited as long as it has strong adhesion to the polyimide film, no diffusion, and good chemical resistance and heat resistance. Although it is not, chromium, nickel, TiN, and Mo containing Cu are mentioned as a suitable example.
  • the planar portion of the inorganic substrate is desirably sufficiently flat.
  • the PV value of the surface roughness is 50 nm or less, more preferably 20 nm or less, and still more preferably 5 nm or less. If it is rougher 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, and still more preferably 1.3 mm or less from the viewpoint of handleability.
  • the thickness is not particularly limited, but 0.07 mm or more, preferably 0.15 mm or more, and more preferably 0.3 mm or more is preferably used.
  • the area of the inorganic substrate is preferably a large area from the viewpoint of production efficiency and cost of the laminate and the flexible electronic device. It is preferably 1000 cm 2 or more, 150 It is more preferably 0 cm 2 and further preferably 2000 cm 2 .
  • the silane coupling agent in the present invention refers to a compound having a function of physically or chemically interposing between the temporary support and the polymer film and enhancing the adhesive force between the two.
  • the silane coupling agent include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- ( Aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrime
  • silane coupling agent examples include n-propyltrimethoxysilane, butyltrichlorosilane, 2-cyanoethyltriethoxysilane, cyclohexyltrichlorosilane, decyltrichlorosilane, diacetoxydimethylsilane, Ethoxydimethylsilane, dimethoxydimethylsilane, dimethoxydiphenylsilane, dimethoxymethylphenylsilane, dodecyltrichlorosilane, dodecyltrimethoxysilane, ethyltrichlorosilane, hexyltrimethoxysilane, octadecyltriethoxysilane, octadecyltrimethoxysilane, n-octyltrichlorosilane , N-octyltriethoxys
  • the silane coupling agent preferably used in the present invention is preferably a silane coupling agent having a chemical structure having one silicon atom per molecule of the coupling agent.
  • particularly preferred silane coupling agents include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2 -(Aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysi
  • the silane coupling agent is applied in a solution state in which the silane coupling agent is diluted with a solvent such as alcohol.
  • the present invention is characterized in that this silane coupling agent coating step is performed via a gas phase. That is, in the present invention, the coating is performed by exposing the inorganic substrate to the vapor of the silane coupling agent, that is, the substantially gaseous silane coupling agent.
  • the vapor of the silane coupling agent can be obtained by heating the silane coupling agent in a liquid state to a temperature from 40 ° C. to the boiling point of the silane coupling agent.
  • the boiling point of the silane coupling agent varies depending on the chemical structure, but is generally in the range of 100 to 250 ° C. However, heating at 200 ° C. or higher is not preferable because the organic group of the silane coupling agent may cause a side reaction.
  • the environment for heating the silane coupling agent may be under pressure, at about normal pressure, or under reduced pressure, but is preferably at about normal pressure or under reduced pressure in order to promote vaporization of the silane coupling agent. Since many silane coupling agents are flammable liquids, it is preferable to perform the vaporizing operation in an airtight container, preferably after replacing the inside of the container with an inert gas.
  • the time for exposing the inorganic substrate to the silane coupling agent is not particularly limited, but is within 20 hours, preferably within 60 minutes, more preferably within 15 minutes, and even more preferably within 1 minute.
  • the inorganic substrate temperature during exposure of the inorganic substrate to the silane coupling agent is controlled to an appropriate temperature between ⁇ 50 ° C. and 200 ° C. depending on the type of the silane coupling agent and the desired thickness of the silane coupling agent layer. It is preferable.
  • the inorganic substrate exposed to the silane coupling agent is preferably heated to 70 ° C. to 200 ° C., more preferably 75 ° C. to 150 ° C. after the exposure.
  • the hydroxyl group on the surface of the inorganic substrate reacts with the alkoxy group or silazane group of the silane coupling agent, and the silane coupling agent treatment is completed.
  • the time required for heating is about 10 seconds to 10 minutes. If the temperature is too high or the time is too long, the coupling agent may be deteriorated. If it is too short, the treatment effect cannot be obtained. If the substrate temperature being exposed to the silane coupling agent is already 80 ° C. or higher, the subsequent heating can be omitted.
  • the inorganic substrate it is preferable to expose the inorganic substrate to the silane coupling agent vapor while holding the silane coupling agent application surface of the inorganic substrate downward.
  • the coated surface of the inorganic substrate inevitably faces up before and after coating, so there is a possibility that floating foreign substances and the like in the working environment are deposited on the surface of the inorganic substrate. I can't deny it.
  • the inorganic substrate can be held downward. It is possible to greatly reduce the adhesion of foreign substances in the environment. It is preferable to clean the surface of the inorganic substrate before the silane coupling agent treatment by means such as short wavelength UV / ozone irradiation, or cleaning with a liquid cleaning agent.
  • the coating amount and thickness of the coupling agent a single molecular layer is theoretically sufficient, and a thickness that can be ignored in terms of mechanical design is sufficient. Generally, it is less than 400 nm (less than 0.4 ⁇ m), preferably 200 nm or less (0.2 ⁇ m or less), more practically 100 nm or less (0.1 ⁇ m or less), more preferably 50 nm or less, still more preferably 10 nm or less. However, when the calculation is in the region of 5 nm or less, it is assumed that the coupling agent is present not in the form of a uniform coating but in a cluster shape, which is not preferable.
  • the film thickness of the coupling agent layer can be determined by ellipsometry or calculation from the concentration of the coupling agent solution at the time of coating and the coating amount.
  • patterning treatment can be performed on the inorganic substrate side.
  • patterning refers to creating a region where the coating amount or activity of the coupling agent is intentionally manipulated.
  • the laminate has a good adhesion part and an easy peeling part with different adhesive strengths between the inorganic substrate and the polymer film, and the good adhesion part and the easy peeling part form a predetermined pattern.
  • An example of the patterning treatment is a method of manipulating the coating amount of the silane coupling agent using a mask prepared in advance with a predetermined pattern when applying the silane coupling agent.
  • the active energy ray irradiation means the operation of irradiating energy rays such as ultraviolet rays, electron rays, X-rays, etc., and ozone gas generated near the irradiated surface simultaneously with the ultraviolet ray irradiation light effect as in the ultraviolet ray irradiation treatment of an extremely short wavelength. Include gas exposure effects.
  • patterning can be performed by corona treatment, vacuum plasma treatment, atmospheric pressure plasma treatment, sandblasting and treatment, or the like.
  • polymer film in the present invention polyethylene, polypropylene, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, wholly aromatic polyester, other copolymerized polyester, polymethyl methacrylate, other copolymerized acrylate, polycarbonate, polyamide, poly Sulfone, polyether sulfone, polyether ketone, polyamideimide, polyetherimide, aromatic polyimide, alicyclic polyimide, fluorinated polyimide, cellulose acetate, cellulose nitrate, aromatic polyamide, polyvinyl chloride, polyphenol, polyarylate, polyphenylene A film made of sulfide, polyphenylene oxide, polystyrene or the like can be used.
  • a polymer having a heat resistance of 100 ° C. or higher that is, a so-called engineering plastic film.
  • the heat resistance refers to a
  • the polymer film of the present invention can be obtained by a melt stretching method for the thermoplastic polymer material among the polymer materials.
  • a solution casting method is mainly used.
  • a technique of applying a polymer material itself or a precursor solution onto an inorganic substrate and drying it to form a film can be used.
  • the thickness of the polymer film of the present invention is preferably 3 ⁇ m or more, more preferably 11 ⁇ m or more, further preferably 24 ⁇ m or more, still more preferably 45 ⁇ m or more.
  • the upper limit of the thickness of the polymer film is not particularly limited, but is preferably 250 ⁇ m or less, more preferably 150 ⁇ m or less, and even more preferably 90 ⁇ m or less, as required for a flexible electronic device.
  • the polymer film particularly preferably used in the present invention is a polyimide film, and aromatic polyimide, alicyclic polyimide, polyamideimide, polyetherimide and the like can be used.
  • aromatic polyimide, alicyclic polyimide, polyamideimide, polyetherimide and the like can be used.
  • a polyimide-based 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 obtained by applying a polyamic acid (polyimide precursor) solution obtained by reacting diamines and tetracarboxylic acids in a solvent to a polyimide film support and drying it to obtain a green film (“precursor film”).
  • a polyamic acid (polyimide precursor) solution obtained by reacting diamines and tetracarboxylic acids in a solvent
  • precursor film obtained by reacting diamines and tetracarboxylic acids in a solvent
  • precursor film a green film
  • precursor film a green film
  • the green film is subjected to a high-temperature heat treatment on a support for forming a polyimide film or in a state of being peeled from the support to cause a dehydration ring-closing reaction.
  • diamine which comprises a polyamic acid there is no restriction
  • combination can be used.
  • aromatic diamines are preferable, and among aromatic diamines, aromatic diamines having a benzoxazole structure are more preferable.
  • aromatic diamines having a benzoxazole structure are used, it is possible to develop a high elastic modulus, a low heat shrinkage, and a low linear expansion coefficient as well as a high heat resistance.
  • Diamines may be used alone or in combination of two or more.
  • the aromatic diamine having a benzoxazole structure is not particularly limited.
  • aromatic diamine other than the aromatic diamine having the benzoxazole structure described above examples include 2,2′-dimethyl-4,4′-diaminobiphenyl, 1,4-bis [2- (4-aminophenyl). ) -2-propyl] benzene (bisaniline), 1,4-bis (4-amino-2-trifluoromethylphenoxy) benzene, 2,2′-ditrifluoromethyl-4,4′-diaminobiphenyl, 4,4 '-Bis (4-aminophenoxy) biphenyl, 4,4'-bis (3-aminophenoxy) biphenyl, bis [4- (3-aminophenoxy) phenyl] ketone, bis [4- (3-aminophenoxy) phenyl ] Sulfide, bis [4- (3-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (3-aminophenoxy) phenyl Nyl] propane, 2,2
  • Examples of the aliphatic diamines include 1,2-diaminoethane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,8-diaminooctane, and the like.
  • Examples of the alicyclic diamines include 1,4-diaminocyclohexane, 4,4′-methylenebis (2,6-dimethylcyclohexylamine), and the like.
  • the total amount of diamines other than aromatic diamines is preferably 20% by mass or less, more preferably 10% by mass or less, and still more preferably 5% by mass or less of the total diamines. It is.
  • the aromatic diamine is preferably 80% by mass or more of the total diamines, more preferably 90% by mass or more, and still more preferably 95% by mass or more.
  • the tetracarboxylic acids constituting the polyamic acid include aromatic tetracarboxylic acids (including acid anhydrides), aliphatic tetracarboxylic acids (including acid anhydrides), and alicyclic tetracarboxylic acids that are commonly used for polyimide synthesis. Acids (including acid anhydrides thereof) can be used. Among them, aromatic tetracarboxylic acid anhydrides and alicyclic tetracarboxylic acid anhydrides are preferable, aromatic tetracarboxylic acid anhydrides are more preferable from the viewpoint of heat resistance, and alicyclic from the viewpoint of light transmission. Group tetracarboxylic acids are more preferred.
  • anhydride structures in the molecule may be one or two, but those having two anhydride structures (dianhydrides) are preferred. Good. Tetracarboxylic acids may be used alone or in combination of two or more.
  • alicyclic tetracarboxylic acids examples include alicyclic tetracarboxylic acids such as cyclobutanetetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, and 3,3 ′, 4,4′-bicyclohexyltetracarboxylic acid. Carboxylic acids and their acid anhydrides are mentioned.
  • dianhydrides having two anhydride structures are preferred.
  • alicyclic tetracarboxylic acids may be used independently and may use 2 or more types together.
  • the alicyclic tetracarboxylic acids are, for example, preferably 80% by mass or more of all tetracarboxylic acids, more preferably 90% by mass or more, and further preferably 95% by mass or more.
  • aromatic tetracarboxylic acids are not particularly limited, but are preferably pyromellitic acid residues (that is, those having a structure derived from pyromellitic acid), and more preferably acid anhydrides thereof.
  • aromatic tetracarboxylic acids include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 4,4′-oxydiphthalic dianhydride, 3 , 3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, 2,2-bis [4- (3,4-di Carboxyphenoxy) phenyl] propanoic anhydride and the like.
  • the aromatic tetracarboxylic acids are, for example, preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably 95% by mass or more of all tetracarboxylic acids.
  • the polyimide film of the present invention preferably has a glass transition temperature of 250 ° C. or higher, preferably 300 ° C. or higher, more preferably 350 ° C. or higher, or no glass transition point observed in the region of 500 ° C. or lower.
  • the glass transition temperature in the present invention is determined by differential thermal analysis (DSC).
  • the linear expansion coefficient (CTE) of the polymer film of the present invention is preferably ⁇ 5 ppm / K to +20 ppm / K, more preferably ⁇ 5 ppm / K to +15 ppm / K, and further preferably 1 ppm / K to +10 ppm / K.
  • CTE linear expansion coefficient
  • the breaking strength of the polymer film in the present invention is 60 MPa or more, preferably 120 MP or more, more preferably 240 MPa or more.
  • the upper limit of the breaking strength is not limited, but is practically less than about 1000 MPa.
  • the breaking strength of the polymer film refers to an average value in the vertical direction and the horizontal direction of the polymer film.
  • the adhesive strength between the polymer film and the inorganic substrate needs to be 1 ⁇ 2 or less of the breaking strength of the polymer film. Suppose that in the laminate of the present invention using a film having a thickness of 10 ⁇ m, the adhesive strength of the film was 0.5 N / cm.
  • the adhesive strength is preferably 1/3 or less, more preferably 1/4 or less of the breaking strength of the polymer film.
  • the good adhesion portion refers to a portion where the adhesive strength between the inorganic substrate and the polyimide film is strong
  • the easy peelable portion refers to a portion where the adhesion strength between the inorganic substrate and the polyimide film is weak.
  • the adhesive strength of the easily peelable portion is preferably 1/2 or less, more preferably 1/3 or less, and further preferably 1/4 or less of the adhesive strength of the good adhesive portion.
  • the lower limit value of the adhesive strength is not particularly limited, it is preferably 0.5 N / cm or more at the good adhesion portion and 0.01 N / cm or more at the easy peel portion.
  • the thickness unevenness of the polymer film in the present invention is preferably 20% or less, more preferably 12% or less, still more preferably 7% or less, and particularly preferably 4% or less. When the thickness unevenness exceeds 20%, it tends to be difficult to apply to narrow portions.
  • the thickness unevenness of a film can be calculated
  • pieces positions from a film to be measured at random with a contact-type film thickness meter, measuring film thickness. Film thickness spots (%) 100 x (maximum film thickness-minimum film thickness) ⁇ average film thickness
  • the polymer film in the present invention is preferably obtained in the form of being wound as a long polyimide film having a width of 300 mm or more and a length of 10 m or more at the time of production, and is a roll wound around a winding core.
  • the thing of the form of a polyimide film is more preferable.
  • lubricants are added to and contained in the film to provide fine irregularities on the polymer film surface to ensure slipperiness.
  • the lubricant (particles) are preferably fine particles made of an inorganic substance, such as metals, metal oxides, metal nitrides, metal carbonides, metal acid salts, phosphates, carbonates, talc, mica, clay, and others. Particles made of clay minerals and the like can be used.
  • metal oxides such as silicon oxide, calcium phosphate, calcium hydrogen phosphate, calcium dihydrogen phosphate, calcium pyrophosphate, hydroxyapatite, calcium carbonate, glass filler, phosphates, and carbonates can be used. Only one type of lubricant may be used, or two or more types may be used.
  • the volume average particle diameter of the lubricant (particles) is usually 0.001 to 10 ⁇ m, preferably 0.03 to 2.5 ⁇ m, more preferably 0.05 to 0.7 ⁇ m, still more preferably 0.05 to 0.3 ⁇ m.
  • the volume average particle diameter is based on a measurement value obtained by a light scattering method. If the particle diameter is smaller than the lower limit, industrial production of the polymer film becomes difficult, and if the particle diameter exceeds the upper limit, the surface irregularities become too large and the sticking strength becomes weak, which may cause practical problems.
  • the amount of the lubricant added is 0.02 to 50% by mass, preferably 0.04 to 3% by mass, more preferably 0.08 to 1.% by mass with respect to the polymer component in the polymer film. 2% by mass. If the amount of lubricant added is too small, it is difficult to expect the effect of lubricant addition, and there is a case where the slipperiness is not sufficiently secured, which may hinder the production of polymer film. Even if the slipperiness is ensured, the smoothness may be lowered, the breaking strength or breaking elongation of the polymer film may be lowered, or the CTE may be raised.
  • a single-layer polymer film in which the lubricant is uniformly dispersed may be used.
  • one surface may be a polymer film containing a lubricant. It is good also as a multilayer polymer film comprised by the polymer film which is comprised and the other surface does not contain a lubricant, or contains the lubricant, even if it contains a lubricant.
  • fine unevenness is given to the surface of one layer (film), so that the slipperiness can be secured by the layer (film), and good handling properties and productivity are secured. it can.
  • a multilayer polymer film is first formed into a film using a raw material for a polymer film that does not contain a lubricant, and is placed on the film at least on one side of the process. It can obtain by apply
  • film formation is performed using a polymer film material containing a lubricant, and a film is obtained by applying a polymer film material not containing a lubricant during the process or after film formation is completed.
  • a lubricant preferably an average particle diameter of 0.05 to About 2.5 ⁇ m
  • 0.02 mass% to 50 mass% preferably 0.04 to 3 mass%, more preferably 0.08 to 1.2 mass%
  • a small amount thereof preferably less than 0.02% by mass, more preferably less than 0.01% by mass with respect to polymer solids in the polyamic acid solution
  • the method of multilayering (lamination) of the multilayer polymer film is not particularly limited as long as no problem occurs in the adhesion between both layers, and any method may be used as long as the adhesion is achieved without using an adhesive layer or the like.
  • a polyimide film for example, i) a method in which one polyimide film is produced and then the other polyamic acid solution is continuously applied onto the polyimide film to imidize, and ii) one polyamic acid solution is cast.
  • the other polyamic acid solution is continuously applied onto the polyamic acid film and then imidized, iii) a method by co-extrusion, iv) a lubricant is not contained or the content thereof is
  • An example is a method of imidizing a polyamic acid solution containing a large amount of a lubricant on a film formed with a small amount of a polyamic acid solution by spray coating, T-die coating, or the like.
  • the ratio of the thickness of each layer in the multi-layer polymer film is not particularly limited, but the polymer layer containing a large amount of the lubricant (a) is a layer, the polymer does not contain the lubricant or the content thereof is small.
  • the layer is the (b) layer
  • the (a) layer / (b) layer is preferably 0.05 to 0.95. If the (a) layer / (b) layer exceeds 0.95, the smoothness of the (b) layer tends to be lost. On the other hand, if it is less than 0.05, the effect of improving the surface properties is insufficient and the slipperiness is lost. May be.
  • the polymer film used in the present invention is preferably subjected to a surface activation treatment.
  • the surface activation treatment By the surface activation treatment, the surface of the polymer film is modified to a state in which a functional group is present (so-called activated state), and adhesion to the inorganic substrate is improved.
  • the surface activation treatment in the present invention is a dry or wet surface treatment.
  • As the dry treatment of the present invention treatment of irradiating active energy rays such as ultraviolet rays, electron beams, and X-rays on the surface, corona treatment, vacuum plasma treatment, atmospheric pressure plasma treatment, flame treatment, and intro treatment can be used. .
  • the wet treatment examples include a treatment in which the film surface is brought into contact with an acid or alkali solution.
  • the surface activation treatment preferably used in the present invention is a plasma treatment, which is a combination of a plasma treatment and a wet acid treatment.
  • the plasma treatment is not particularly limited, but includes RF plasma treatment in vacuum, microwave plasma treatment, microwave ECR plasma treatment, atmospheric pressure plasma treatment, corona treatment, etc., gas treatment containing fluorine, ion Includes ion implantation using a source, treatment using PBII, flame treatment exposed to thermal plasma, and intro treatment.
  • RF plasma treatment, microwave plasma treatment, and atmospheric pressure plasma treatment in vacuum are preferable.
  • Appropriate conditions for the plasma treatment include oxygen plasma, plasma containing fluorine such as CF4 and C2F6, plasma known to have a high etching effect, or physical energy such as Ar plasma on the polymer surface. It is desirable to use plasma with a high effect of applying and physically etching. Further, it is also preferable to add plasma such as CO2, H2, and N2, a mixed gas thereof, and further water vapor. When aiming at processing in a short time, a plasma having a high plasma energy density, a high kinetic energy of ions in the plasma, and a high number density of active species are desirable. From this point of view, microwave plasma treatment, microwave ECR plasma treatment, plasma irradiation with an ion source that easily implants high-energy ions, PBII method, and the like are also desirable.
  • Such surface activation treatment cleans the polymer surface and produces more active functional groups.
  • the generated functional group is bonded to the coupling agent layer by hydrogen bonding or chemical reaction, and the polymer film layer and the coupling agent layer can be firmly bonded.
  • the plasma treatment the effect of etching the surface of the polymer film can also be obtained.
  • protrusions due to the lubricant may inhibit the adhesion between the film and the inorganic substrate.
  • it is possible to remove the lubricant particles in the vicinity of the film surface by thinly etching the surface of the polymer film by plasma treatment to expose a part of the lubricant particles and then treating with hydrofluoric acid. .
  • the surface activation treatment may be performed only on one side of the polymer film or on both sides.
  • the polymer film is placed in contact with the electrode on one side in the plasma treatment with parallel plate electrodes, so that only the side of the polymer film not in contact with the electrode is subjected to plasma treatment. be able to.
  • plasma treatment can be performed on both sides.
  • single-sided processing becomes possible by performing plasma processing in the state which stuck the protective film on the single side
  • a protective film a PET film with an adhesive or an olefin film can be used as a protective film.
  • the patterning treatment can be performed on the polymer film side.
  • patterning refers to creating a region where the activity of the surface activation treatment is intentionally manipulated.
  • the laminate has a good adhesion part and an easy peeling part with different adhesive strengths between the inorganic substrate and the polymer film, and the good adhesion part and the easy peeling part form a predetermined pattern.
  • An example of the patterning process is a method of manipulating the surface activation process amount using a mask prepared in a predetermined pattern in advance when the surface activation process is performed. Further, when performing the surface activation treatment, it is possible to form a pattern by using a technique such as masking or scanning operation together.
  • the surface of the polymer film after the surface activation can be further subjected to another active energy ray treatment in combination with masking or scanning to realize the intensity of activity.
  • the active energy ray irradiation means the operation of irradiating energy rays such as ultraviolet rays, electron rays, X-rays, etc., and ozone gas generated near the irradiated surface simultaneously with the ultraviolet ray irradiation light effect as in the ultraviolet ray irradiation treatment of an extremely short wavelength. Include gas exposure effects.
  • patterning can be performed by corona treatment, vacuum plasma treatment, atmospheric pressure plasma treatment, sandblasting and treatment, or the like.
  • an inorganic substrate on which a silane coupling agent layer thin film is formed in a predetermined pattern is used as a temporary support, and a polymer film is bonded through the silane coupling agent layer, or dry film formation is performed.
  • a laminate is obtained.
  • a polymer film is bonded, a laminated body is obtained by overlaying the activated surface of the polymer film on a temporary supporting inorganic substrate on which a silane coupling agent layer is formed, and heating and pressing.
  • the pressurizing / heating treatment may be performed while heating a press, a laminate, a roll laminate, or the like, for example, in an atmospheric atmosphere or in a vacuum.
  • a method of heating under pressure in a flexible bag can also be applied. From the viewpoint of improving productivity and reducing the processing cost brought about by high productivity, press or roll lamination in an air atmosphere is preferable, and a method using rolls (roll lamination or the like) is particularly preferable.
  • the pressure during the pressure heat treatment is preferably 1 MPa to 20 MPa, more preferably 3 MPa to 10 MPa. If the pressure is too high, the support may be damaged. If the pressure is too low, a non-adhering part may be produced, resulting in insufficient adhesion.
  • the temperature during the pressure heat treatment is within a range not exceeding the heat resistance temperature of the polymer film to be used. In the case of a non-thermoplastic polyimide film, treatment at 150 ° C. to 400 ° C., more preferably 250 ° C. to 350 ° C. is preferred.
  • the pressure heat treatment can be performed in an atmospheric pressure atmosphere as described above, but is preferably performed under vacuum in order to obtain a stable adhesive strength on the entire surface.
  • the degree of vacuum by a normal oil rotary pump is sufficient, and about 10 Torr or less is sufficient.
  • an apparatus that can be used for pressure heat treatment for example, “11FD” manufactured by Imoto Seisakusho can be used to perform pressing in a vacuum, and a roll-type film laminator in vacuum or a vacuum is used.
  • “MVLP” manufactured by Meiki Seisakusho Co., Ltd. can be used to perform vacuum laminating such as a film laminator that applies pressure to the entire glass surface at once with a thin rubber film.
  • the pressure heat treatment can be performed separately in a pressure process and a heating process.
  • the polymer film and the inorganic substrate are pressurized (preferably about 0.2 to 50 MPa) at a relatively low temperature (eg, a temperature of less than 120 ° C., more preferably 95 ° C. or less) to ensure adhesion between the two.
  • a relatively low temperature eg, a temperature of less than 120 ° C., more preferably 95 ° C. or less
  • a relatively high temperature at normal pressure for example, 120 ° C. or more, more preferably 120 to 250 ° C., still more preferably 150 to 230 ° C.
  • a polymer film layer is formed by applying a polymer solution or a polymer precursor solution onto an inorganic substrate on which a silane coupling agent layer is formed, and drying and forming a film.
  • a method for applying the solution known methods such as dip coating, spin coating, curtain coating, and slit die coating can be used.
  • the polyimide resin a polyamic acid solution obtained by polycondensation of a diamine and a tetracarboxylic acid or an acid anhydride thereof as a raw material for the polyimide resin in a solution is predetermined on the temporary support inorganic substrate of the present invention.
  • the polyimide film is formed on an inorganic substrate for temporary support by applying the film so as to have a thickness of 5 mm and drying, heat treatment or chemical imidization treatment.
  • the preferred film thickness is 7 to 100 ⁇ m, preferably 15 to 80 ⁇ m, and more preferably 23 to 45 ⁇ m.
  • the polyimide resin layer obtained by such a method is relatively brittle, often tearing during the peeling, and often difficult to peel off from the inorganic substrate.
  • the silane coupling agent Since there are few foreign substances and aggregates present in the layer, the film based on such defects is hardly torn, and as a result, the yield at the time of peeling is greatly improved.
  • the electronic device in the present invention refers to an electronic circuit including an active element such as a wiring board, a transistor, and a diode that carries electric wiring, and a passive device such as a resistor, a capacitor, and an inductor, and others such as pressure, temperature, light, and humidity.
  • An image display element such as a sensor element, a light emitting element, a liquid crystal display, an electrophoretic display, and a self-luminous display, a wireless, wired communication element, an arithmetic element, a memory element, a MEMS element, a solar cell, a thin film transistor, and the like.
  • a method of peeling a polymer film from a laminate a method in which strong light is radiated from the inorganic substrate side and the adhesive part between the inorganic substrate and the polymer film is thermally decomposed or photodecomposed and peeled off is used. Weaker, peel off the polymer film with a force less than the elastic strength limit value of the polymer film, expose to heated water, heated steam, etc., weaken the bond strength between the inorganic substrate and the polymer film interface, etc. Can be illustrated.
  • the region where the adhesive force between the polymer film and the inorganic substrate is reduced by the patterning process (easy peeling part)
  • the flexible electronic device can be obtained by forming an electronic device on the outer peripheral portion of the region and then cutting off the area where the electronic device of the polymer film is formed from the inorganic substrate.
  • a method of cutting the polymer film along the outer periphery of the easily peelable portion of the laminate a method of cutting the polymer film with a cutting tool such as a blade or a method of relatively scanning the laser and the laminate can be used.
  • a method of cutting a molecular film, a method of cutting a polymer film by relatively scanning a water jet and a laminate, a method of cutting a polymer film while cutting a glass layer slightly with a semiconductor chip dicing device, etc. are used. be able to.
  • a combination of these methods a method of superimposing ultrasonic waves on a cutting tool, or adding a reciprocating operation or an up / down operation to improve cutting performance can be appropriately employed.
  • the position where the cut is made only needs to include at least part of the easily peelable portion, and basically may be cut according to a predetermined pattern. From the viewpoint of error absorption, productivity, etc., it may be determined as appropriate.
  • the method of peeling the polymer film from the support is not particularly limited, but is a method of rolling from the end with tweezers, etc., and sticking the adhesive tape to one side of the cut portion of the polymer film with the device, and then the tape part
  • a method of winding from a part of a polymer film with a device after vacuum suction of one side of the cut part can be employed.
  • stress may be applied to the device at that portion and the device may be destroyed. It is desirable to peel off with.
  • the inorganic substrate can be reused by completely removing the remaining polymer film from the supporting substrate after peeling off the target electronic device and performing a simple cleaning treatment or the like.
  • a conventional silane coupling agent layer is formed by liquid coating, the polymer film is peeled off on the surface of the inorganic substrate due to the adhesion of silane coupling agent aggregates or other foreign substances, and irregularities or silane cups are formed.
  • the thickness of the ring agent layer is present, and in order to reuse it, it is necessary to polish the surface layer of the inorganic substrate to ensure a flat surface. According to the coating method of the present invention, the quality of the inorganic substrate surface after peeling of the polymer film is good, and re-polishing is unnecessary.
  • ⁇ Thickness of polymer film> The thickness of the polymer film was measured using a micrometer ("Millitron 1245D” manufactured by FineLuf).
  • CTE Linear expansion coefficient
  • the glass transition temperature of the polymer film was determined from the presence or absence of heat absorption / dissipation due to the structural change in the range from room temperature to 500 ° C.
  • the thickness (nm) of the coupling agent layer (SC layer) is separately prepared on a cleaned Si wafer by preparing a sample obtained by applying and drying the coupling agent in the same manner as in each example and comparative example, The film thickness of the coupling agent layer formed on this Si wafer was measured by an ellipsometry method using a spectroscopic ellipsometer (“FE-5000” manufactured by Photo) under the following conditions.
  • Reflection angle range 45 ° to 80 ° Wavelength range: 250 nm to 800 nm Wavelength resolution: 1.25 nm Spot diameter: 1mm tan ⁇ ; Measurement accuracy ⁇ 0.01 cos ⁇ ; Measurement accuracy ⁇ 0.01 Measurement: Method Rotating analyzer method Deflector angle: 45 ° Incident angle: Fixed at 70 ° Analyzer: 0-360 ° in 11.25 ° increments Wavelength: 250 nm to 800 nm The film thickness was calculated by fitting by a non-linear least square method.
  • the wavelength dependence C1 to C6 was obtained by the following formula.
  • a silane coupling agent is applied to the temporary support inorganic substrate by a predetermined method, and then a polymer film is laminated through a predetermined process.
  • the adhesive strength between the temporary support inorganic plate and the polymer film is defined in JIS C6471. According to the described 180 degree peeling method, it measured on condition of the following. In addition, the sample used for this measurement masks a half of 60 mm ⁇ 120 mm with respect to a square substrate of 120 mm ⁇ 120 mm, performs thin film processing on the remaining half of the region, and provides a temporary supporting inorganic substrate for evaluation. did.
  • the size of the film is 110 mm ⁇ 200 mm
  • an unadhered portion of the polyimide film is provided on one side, this portion is used for “grabbing”, and the film portion of the measurement sample is cut with a knife,
  • the width was measured to be 10 mm.
  • Atmosphere Atmosphere Measurement sample width: 10 mm ⁇ Appearance> About quality, it is the result in the visual inspection of the whole laminated body.
  • ⁇ Dust density> Sampling a 30mm x 30mm area, observing the sampling area with a microscope with a length measurement function of 100x magnification, and measuring the major axis length of foreign matter confirmed by 100x magnification with a magnification of 400x Then, the number of those having a size of 10 ⁇ m or more was factored and divided by the observation area to obtain the foreign substance density.
  • the final thickness of the polyamic acid solution V1 obtained above is applied to the smooth surface (non-sliding material surface) of a long polyester film (“A-4100” manufactured by Toyobo Co., Ltd.) having a width of 1050 mm using a slit die.
  • the film was applied so that (film thickness after imidization) was 25 ⁇ m, dried at 105 ° C. for 20 minutes, and then peeled from the polyester film to obtain a self-supporting polyamic acid film having a width of 920 mm.
  • the obtained self-supporting polyamic acid film was heated stepwise in a temperature range of 150 ° C. to 420 ° C.
  • the polyamic acid solution V3 obtained above was used to form a final film thickness (non-sliding material surface) on a smooth surface (non-sliding material surface) of a long polyester film (“A-4100” manufactured by Toyobo Co., Ltd.) having a width of 1050 mm using a comma coater. (Film thickness after imidization) is applied so that it corresponds to 5 ⁇ m, and then the polyamic acid solution V2 is applied using a slit die so that the final film thickness is 38 ⁇ m including V3, and dried at 105 ° C. for 25 minutes.
  • the obtained self-supporting polyamic acid film was subjected to heat treatment with a pin tenter and subjected to imidization by performing heat treatment at the first stage 180 ° C. ⁇ 5 minutes, the second stage 220 ° C. ⁇ 5 minutes, the third stage 495 ° C. ⁇ 10 minutes, The pin grip portions at both ends were dropped with a slit to obtain a long polyimide film F3 (1000 m roll) having a width of 850 mm.
  • the properties of the obtained film F3 are shown in Table 1.
  • a plasma-treated polyimide film P2 was obtained in the same manner except that the polyimide film F2 obtained in Production Example 2 was used instead of the polyimide film F1. Furthermore, plasma treatment was similarly performed on one side of the film F3 on the layer side not containing the lubricant to obtain a film P3. Instead of the polyimide film F1, a 100 ⁇ m thick polyethylene terephthalate film A4100 (manufactured by Toyobo Co., Ltd.) was used to obtain a plasma-treated film P4. Similarly, instead of the polyimide film F1, a 100 ⁇ m thick polyethylene naphthalate film “Teonex” (manufactured by Teijin Limited) was used to obtain a plasma-treated film P5.
  • a predetermined mask made of a stainless steel plate having a thickness of 1 mm is overlaid on the plasma-treated polyimide film P2 obtained by using the polyimide film F2, and UV / ozone for 120 seconds using a UV / ozone irradiation apparatus manufactured by LAN Technical Service. Irradiation was performed to obtain a patterned plasma treated film PP2.
  • Table 2 shows the characteristics of the obtained plasma treated film and the patterned plasma treated film.
  • ⁇ Coupling agent layer formation on inorganic substrate> ⁇ Application example 1> Using a vacuum chamber having a hot plate, a silane coupling agent was applied to the inorganic substrate under the following conditions. 100 parts by mass of a silane coupling agent (“KBM-903” manufactured by Shin-Etsu Chemical Co., Ltd .: 3-aminopropyltrimethoxysilane) was filled in a petri dish and allowed to stand on a hot plate. At this time, the hot plate temperature is 25 ° C.
  • KBM-903 manufactured by Shin-Etsu Chemical Co., Ltd .: 3-aminopropyltrimethoxysilane
  • a 300 mm ⁇ 350 mm ⁇ 0.7 mmt Pyrex glass plate is held horizontally at a location 300 mm away from the liquid surface of the silane coupling agent, the vacuum chamber is closed, and the oxygen concentration is 0.1 at atmospheric pressure. Nitrogen gas was introduced until it became less than%, then nitrogen gas was stopped, the inside of the chamber was depressurized to 3 ⁇ 10 ⁇ 4 Pa, the hot plate temperature was raised to 120 ° C. and held for 10 minutes, and the silane coupling agent vapor was maintained. After that, the hot plate temperature is lowered, and at the same time, clean nitrogen gas is gently introduced into the vacuum chamber to return to atmospheric pressure, the glass plate is taken out, and the hot plate is heated to 100 ° C. in a clean environment.
  • KBM-903 manufactured by Shin-Etsu Chemical Co., Ltd .: 3-aminopropyltrimethoxysilane
  • a 100 mm ⁇ 100 mm ⁇ 1.0 mmt soda-lime glass plate is held horizontally at a location 100 mm away from the liquid surface of the silane coupling agent, and the petri dish lid is opened and held for 15 minutes for silane coupling.
  • Silane coupling agent (“KBM-903” manufactured by Shin-Etsu Chemical Co., Ltd .: 3-aminopropyltrimethoxysilane) 0.5 part by mass and 99.5 parts by mass of isopropyl alcohol were stirred and mixed in a clean glass container. A coupling agent solution was obtained.
  • a 300 mm ⁇ 350 mm ⁇ 0.7 mmt Pyrex glass plate was set on a spin coater manufactured by Japan Create Co., Ltd. First, 50 ml of isopropyl alcohol was dropped onto the center of the glass and washed by shaking off at 500 rpm, and then prepared in advance.
  • silane coupling agent solution About 30 ml of the silane coupling agent solution was dropped on the center of the glass plate, and the solution was shaken off by shaking the silane coupling agent solution at 500 ml for 10 seconds and then rotating the rotation speed to 1500 rpm for 20 seconds. Next, the glass plate is taken out from the stopped spin coater, placed on a hot plate at 100 ° C. in a clean environment with the silane coupling agent applied surface facing up, and heat-treated for about 3 minutes to form a silane coupling agent layer. The obtained inorganic substrate S3 was obtained.
  • ⁇ Application example 4> In the same manner as in Application Example 3, a silane coupling agent layer was formed on a 100 mm ⁇ 100 mm ⁇ 1.0 mmt soda-lime glass plate by a spin coater to obtain an inorganic plate S4.
  • Example 1 The plasma processing surface of the plasma processing film P1 trimmed to a rectangle of 280 mm ⁇ 330 mm is overlapped with the silane coupling agent layer side of the obtained inorganic substrate S1 so that the inorganic substrate surface is exposed 10 mm, and a laminator manufactured by Climb Products Co., Ltd. was used for temporary lamination at an inorganic substrate side temperature of 100 ° C., a roll pressure during lamination of 5 kg / cm 2, and a roll speed of 5 mm / second.
  • the polymer film after temporary lamination did not peel off due to its own weight, but had such adhesiveness that it was easily peeled off when the film edge was scratched.
  • the obtained temporary laminate substrate was put in a clean oven, heated at 200 ° C. for 30 minutes, and then allowed to cool to room temperature to obtain a laminate L1 of the present invention.
  • Table 4 shows the properties of the obtained laminate.
  • a laminate was produced using the inorganic substrate S1 and the plasma treatment film shown in the table.
  • the heating temperature in the clean oven was 140 ° C.
  • the plasma-treated film P5 it was 175 ° C.
  • Table 4 shows the properties of the obtained laminate.
  • Example 6> Using the obtained inorganic substrate S1 and the patterned plasma treatment film PP2, the same operation was performed to obtain a laminate L6.
  • the part of the patterned plasma-treated film that was not irradiated with UV / ozone was evaluated as a normal part, and the irradiated part was evaluated as an easily peelable part.
  • the plasma treatment surface of the plasma treatment film P1 trimmed into a 280 mm ⁇ 330 mm rectangle is overlapped on the silane coupling agent layer of the obtained inorganic substrate S1C so that the inorganic substrate surface is exposed 10 mm, and a laminator manufactured by Climb Products Co. is applied.
  • the laminate was temporarily laminated at an inorganic substrate temperature of 100 ° C., a roll pressure of 5 kg / cm 2 during lamination, and a roll speed of 5 mm / second.
  • the polymer film after temporary lamination did not peel off due to its own weight, but had such adhesiveness that it was easily peeled off when the film edge was scratched. Thereafter, the obtained temporary laminate substrate was put in a clean oven, heated at 200 ° C. for 30 minutes, and then allowed to cool to room temperature, to obtain a laminate C1 of the present invention.
  • Table 4 shows the properties of the obtained laminate.
  • Examples 7 to 11 The plasma processing surface of the plasma processing film P1 trimmed into a 90 mm ⁇ 90 mm rectangle is stacked on the side of the silane coupling agent layer of the inorganic substrate S2 so that the edge of the inorganic substrate surface is exposed by 5 mm, and the vacuum pressing machine manufactured by Imoto Seisakusho is used.
  • the laminate was sandwiched between upper and lower cushioning materials, pressed at a hot plate temperature of 300 ° C. for 20 minutes under vacuum, and cooled to room temperature to obtain a laminate L7.
  • laminates were similarly obtained using the plasma-treated films P2 to P5.
  • Example 12 Using the patterned inorganic substrate SP1 and the plasma-treated film P2, the same procedure as in Example 1 was followed to obtain a laminate L12.
  • Example 13 Using the patterned inorganic substrate SP1 and the patterned plasma-treated film PP2, the same procedure as in Example 1 was followed to obtain a laminate L13.
  • the shape of the mask used for the patterning process on the inorganic plate side and the shape of the mask used for the patterning process on the plasma processing film side are the same, and both the processed parts are arranged so as to overlap each other. .
  • the part where UV / ozone irradiation was not performed was evaluated as a normal part, and the irradiated part was evaluated as an easily peelable part.
  • the results are shown in Table 4.
  • the polyamic acid solution obtained in Production Example 2 was applied to the patterned inorganic substrate SP1 with a die coater so that the final film thickness was 25 ⁇ m, placed in an explosion-proof oven and dried at 80 ° C. for 100 minutes, and then 200 The temperature was raised to 5 ° C./minute up to 5 ° C., held at 200 ° C. for 60 minutes, then heated up to 480 ° C. at 10 ° C./minute, held at 480 ° C. for 5 minutes, and then 30 ° C./minute at 100 ° C.
  • the laminate L14 was obtained by opening the oven door and cooling to near room temperature to form a polymer film layer directly on the inorganic substrate surface. The results are shown in Table 4.
  • a 5 nm chromium layer and a 40 nm gold layer were formed by sputtering, and a source electrode and a drain electrode were formed by photolithography.
  • an epoxy resin serving as an insulating layer and dam layer is applied, and a dam layer having a thickness of 250 nm for a semiconductor layer including a source electrode and a drain electrode is formed by ablation with a UV-YAG laser to a diameter of 100 ⁇ m.
  • the via was also formed at the same time as a connection point with the upper electrode.
  • polythiophene which is an organic semiconductor
  • a silver paste was buried in the via portion, and an aluminum wiring was formed as an upper electrode to form a thin film transistor array having 640 ⁇ 480 pixels.
  • the obtained thin film transistor array was used as a back plane, and an electrophoretic display medium was overlaid on the front plane to form a display element.
  • the yield and display performance of the transistor were determined by ON / OFF of each pixel. As a result, the thin film transistor arrays obtained in the examples all had good display performance.
  • the laminate C1 as a comparative example the display of 12 lines in the vertical direction and 5 lines in the horizontal direction was defective.
  • the polymer film part is burned out with a UV-YAG laser along the outer periphery of the patterning part, and thinned from the edge of the cut
  • peeling was performed using a blade on a razor to scoop up, both could be easily peeled off and a flexible electrophoretic display device could be obtained.
  • a peeling operation was performed so as to scoop up and a flexible electrophoretic display device was obtained in the same manner. It was confirmed that the obtained flexible electrophoretic display device has practically sufficient flexibility without deterioration in display performance even when it is wound around a cylinder having a diameter of 3 mm, except for the one obtained from L14.
  • the flexible electrophoretic display device obtained from L14 there was no problem with winding around a cylinder with a diameter of 5 mm, but when wound around a cylinder with a diameter of 3 mm, the end of the polymer film was torn. This is because the polymer film itself is slightly brittle.
  • ⁇ Application example 2> In the laminate L1 obtained in Example 1, after peeling the flexible electrophoretic display device in Application Example 1, the Pyrex glass plate that was the original substrate was placed in a 10% aqueous sodium hydroxide solution at room temperature. It was immersed for 20 hours, then washed with water, and then cleaned with a glass substrate glass cleaning device. Using the glass plate after washing, a silane coupling agent layer was formed on the same surface as that used in Example 1 again in the same manner as in Example 1, and the same procedure was followed to obtain a laminate. The quality of the obtained laminate was good, and the foreign matter density was 0.5 / cm 2 , indicating that it could be fully recycled.
  • the temperature of the laminate was set to 2 ° C.
  • plasma treatment was applied to the polymer film surface of the laminate.
  • the plasma treatment conditions were argon gas, frequency 13.56 MHz, output 200 W, gas pressure 1 ⁇ 10 ⁇ 3 Torr, treatment temperature 2 ° C., treatment time 2 minutes.
  • a nickel magnetron (chromium 10 mass%) alloy target is used to perform a 1 nm / nm process by a DC magnetron sputtering method in an argon atmosphere.
  • a nickel-chromium alloy coating (underlayer) having a thickness of 11 nm was formed at a rate of seconds. Subsequently, the temperature of the laminated body was set to 2 ° C., and sputtering was performed. Then, copper was vapor-deposited at a rate of 10 nm / second to form a copper thin film having a thickness of 0.22 ⁇ m. Thus, the laminated board with a base metal thin film formation film was obtained from each laminated body. The thicknesses of the copper and NiCr layers were confirmed by the fluorescent X-ray method.
  • a laminated board with a base metal thin film forming film from each film is fixed to a Cu frame, and an electroplating solution (copper sulfate 80 g / l, sulfuric acid 210 g / l, HCl, gloss, using a copper sulfate plating bath).
  • a thick copper plating layer (thickening layer) having a thickness of 4 ⁇ m was formed by immersing in a small amount of the agent and flowing 1.5 A / dm 2 of electricity. Then, it heat-processed for 10 minutes at 120 degreeC, it dried, and the copper foil layer was formed in the polymer film surface of a laminated body.
  • the wiring patterns obtained from the laminates of Examples 7 to 11 had no disconnection or short circuit, and the pattern shape was good.
  • disconnection was observed in part. It was concluded that the wiring shape of the disconnection part was such that the wiring was thin and faint, and that the exposure in the photoresist process was hindered. Further, it was found that the polymer film portion was in a convex state at the disconnection site, and foreign matter was present between the polymer film and the glass substrate.
  • the laminate of the present invention is useful for the production of flexible electronic devices and is also excellent in substrate recyclability.
  • the laminate of the present invention is not only capable of easily peeling a polymer film with an electronic device from an inorganic substrate after the electronic device is prepared, but also an aggregate of silane coupling agents used for adhesion of the laminate. Is a layered product in which the adhesion between the polymer film and the inorganic substrate is homogenized, and the contribution to the industry is great. Furthermore, according to the present invention, the roughness of the inorganic substrate surface after peeling the polymer film is small, and it becomes possible to re-apply the silane coupling agent after a simple cleaning operation and use it as a substrate. Sexually improves.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Power Engineering (AREA)
  • Laminated Bodies (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

Le problème décrit par la présente invention est de procurer un stratifié de bonne qualité afin de fabriquer un dispositif électronique souple, qui est obtenu par stratification d'un film polymère, tel qu'un film de polyimide ou un film de polyester, sur un substrat inorganique et qui est décollé après qu'un dispositif y a été formé ; un procédé de production du stratifié ; et un procédé de fabrication du dispositif électronique souple. La solution selon l'invention consiste à former une couche d'agent d'accrochage à base de silane sur un substrat inorganique, tel qu'une plaque de verre, en phase vapeur, puis y stratifier un film polymère activé et y appliquer une pression et une chaleur, ce qui permet d'obtenir un stratifié qui présente moins de substances étrangères entre le film polymère et le substrat inorganique. Un dispositif électronique peut être formé avec un rendement élevé sur le stratifié ainsi obtenu et un dispositif électronique souple peut être fabriqué efficacement par séparation d'avec le substrat inorganique.
PCT/JP2014/052052 2013-02-04 2014-01-30 Stratifié, procédé de production de stratifié et procédé de fabrication de dispositif électronique souple WO2014119648A1 (fr)

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WO2016043180A1 (fr) * 2014-09-19 2016-03-24 ユニチカ株式会社 Stratifié et procédé de fabrication d'un dispositif souple
JP2017149041A (ja) * 2016-02-25 2017-08-31 東洋紡株式会社 積層体およびその製造方法
JP2017149040A (ja) * 2016-02-25 2017-08-31 東洋紡株式会社 積層体およびその製造方法
JP2017196740A (ja) * 2016-04-25 2017-11-02 東洋紡株式会社 積層体の製造方法
JP2017202570A (ja) * 2016-05-09 2017-11-16 東洋紡株式会社 積層体および積層体の製造方法
CN108448139A (zh) * 2018-05-16 2018-08-24 深圳市善营自动化股份有限公司 一种燃料电池膜电极的制作方法及设备
JP2018144285A (ja) * 2017-03-02 2018-09-20 東洋紡株式会社 ガスバリア層付きポリイミド／無機基板積層体およびその製造方法
KR20190112033A (ko) * 2017-01-25 2019-10-02 도요보 가부시키가이샤 고분자 필름 적층 기판 및 플렉시블 전자 디바이스의 제조 방법
US20210040608A1 (en) * 2019-08-05 2021-02-11 GM Global Technology Operations LLC Method for bonding a polymeric material to a substrate
CN112512792A (zh) * 2018-08-20 2021-03-16 东洋纺株式会社 层叠体以及层叠体的制造方法
WO2023286686A1 (fr) * 2021-07-16 2023-01-19 東洋紡株式会社 Corps multicouche de substrat inorganique et film polymère transparent résistant à la chaleur
WO2023286685A1 (fr) * 2021-07-16 2023-01-19 東洋紡株式会社 Stratifié de substrat inorganique et film polymère résistant à la chaleur
WO2023127679A1 (fr) * 2021-12-28 2023-07-06 四国化成工業株式会社 Liquide de traitement de surface pour métal
WO2023127681A1 (fr) * 2021-12-28 2023-07-06 四国化成工業株式会社 Film de revêtement organique, et procédé de fabrication de celui-ci

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TWI685518B (zh) * 2018-07-31 2020-02-21 國立中興大學 電路板及其製備方法
TWI747288B (zh) * 2019-12-12 2021-11-21 友達光電股份有限公司 晶片
WO2022024820A1 (fr) 2020-07-29 2022-02-03 東洋紡株式会社 Procédé de fabrication de dispositif électronique flexible

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WO2016031746A1 (fr) * 2014-08-25 2016-03-03 東洋紡株式会社 Film polymère revêtu par une couche d'agent de couplage au silane
JPWO2016031746A1 (ja) * 2014-08-25 2017-06-15 東洋紡株式会社 シランカップリング剤層積層高分子フィルム
US10857762B2 (en) 2014-08-25 2020-12-08 Toyobo Co., Ltd. Polymer film coated with a layer of silane coupling agent
EP3187331A4 (fr) * 2014-08-25 2018-04-25 Toyobo Co., Ltd. Film polymère revêtu par une couche d'agent de couplage au silane
WO2016043180A1 (fr) * 2014-09-19 2016-03-24 ユニチカ株式会社 Stratifié et procédé de fabrication d'un dispositif souple
JPWO2016043180A1 (ja) * 2014-09-19 2017-07-06 ユニチカ株式会社 積層体およびフレキシブルデバイスの製造方法
JP2020006691A (ja) * 2014-09-19 2020-01-16 ユニチカ株式会社 積層体およびフレキシブルデバイスの製造方法
JP2017149041A (ja) * 2016-02-25 2017-08-31 東洋紡株式会社 積層体およびその製造方法
JP2017149040A (ja) * 2016-02-25 2017-08-31 東洋紡株式会社 積層体およびその製造方法
JP2017196740A (ja) * 2016-04-25 2017-11-02 東洋紡株式会社 積層体の製造方法
JP2017202570A (ja) * 2016-05-09 2017-11-16 東洋紡株式会社 積層体および積層体の製造方法
KR102476038B1 (ko) 2017-01-25 2022-12-08 도요보 가부시키가이샤 고분자 필름 적층 기판 및 플렉시블 전자 디바이스의 제조 방법
KR20190112033A (ko) * 2017-01-25 2019-10-02 도요보 가부시키가이샤 고분자 필름 적층 기판 및 플렉시블 전자 디바이스의 제조 방법
JP2018144285A (ja) * 2017-03-02 2018-09-20 東洋紡株式会社 ガスバリア層付きポリイミド／無機基板積層体およびその製造方法
CN108448139A (zh) * 2018-05-16 2018-08-24 深圳市善营自动化股份有限公司 一种燃料电池膜电极的制作方法及设备
CN112512792A (zh) * 2018-08-20 2021-03-16 东洋纺株式会社 层叠体以及层叠体的制造方法
US20210040608A1 (en) * 2019-08-05 2021-02-11 GM Global Technology Operations LLC Method for bonding a polymeric material to a substrate
WO2023286686A1 (fr) * 2021-07-16 2023-01-19 東洋紡株式会社 Corps multicouche de substrat inorganique et film polymère transparent résistant à la chaleur
WO2023286685A1 (fr) * 2021-07-16 2023-01-19 東洋紡株式会社 Stratifié de substrat inorganique et film polymère résistant à la chaleur
WO2023127679A1 (fr) * 2021-12-28 2023-07-06 四国化成工業株式会社 Liquide de traitement de surface pour métal
WO2023127681A1 (fr) * 2021-12-28 2023-07-06 四国化成工業株式会社 Film de revêtement organique, et procédé de fabrication de celui-ci

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