WO2020066496A1 - 電子デバイス積層体の製造方法、および、電子デバイス積層体 - Google Patents

電子デバイス積層体の製造方法、および、電子デバイス積層体 Download PDF

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Publication number
WO2020066496A1
WO2020066496A1 PCT/JP2019/034609 JP2019034609W WO2020066496A1 WO 2020066496 A1 WO2020066496 A1 WO 2020066496A1 JP 2019034609 W JP2019034609 W JP 2019034609W WO 2020066496 A1 WO2020066496 A1 WO 2020066496A1
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Prior art keywords
layer
electronic device
organic
gas barrier
substrate
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PCT/JP2019/034609
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English (en)
French (fr)
Japanese (ja)
Inventor
英二郎 岩瀬
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富士フイルム株式会社
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Priority to CN201980062967.3A priority Critical patent/CN112771996A/zh
Priority to JP2020548275A priority patent/JP7112505B2/ja
Priority to KR1020217008830A priority patent/KR102528054B1/ko
Publication of WO2020066496A1 publication Critical patent/WO2020066496A1/ja

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    • 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
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/02—Details
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/02—Details
    • H05B33/04—Sealing arrangements, e.g. against humidity
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/10—Apparatus or processes specially adapted to the manufacture of electroluminescent light sources
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/87—Passivation; Containers; Encapsulations
    • H10K59/873—Encapsulations
    • 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
    • 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 an electronic device laminate and an electronic device laminate.
  • Organic EL (electroluminescence) materials are very sensitive to moisture. Therefore, in an organic EL device using an organic EL material, it is generally known that an organic EL element is sealed with a passivation film having a gas barrier property.
  • a passivation film having a gas barrier property.
  • inorganic materials such as silicon nitride, silicon oxide, and silicon oxynitride exhibiting gas barrier properties are exemplified.
  • the passivation film since the organic EL material is vulnerable to heat, the passivation film must be formed with low energy so as not to damage the organic EL material when forming the passivation film. Therefore, in order to obtain sufficient gas barrier properties with a passivation film, a thick passivation film or a plurality of passivation films must be formed. However, if the passivation film is made thick or a plurality of passivation films are formed, the flexibility becomes poor.
  • a sealing method using an adhesive having high gas barrier performance has been proposed.
  • a method using an adhesive having a high gas barrier performance is more flexible than sealing with a passivation film.
  • the gas barrier property is lower than a configuration in which an inorganic layer is used as a gas barrier layer. Cannot be sufficiently protected, and the organic EL element is deteriorated. In addition, there is a possibility that the organic EL element is deteriorated by the influence of moisture and residual solvent contained in the adhesive.
  • an organic EL device having high flexibility it has been proposed to use a sealing method of bonding a gas barrier film via an adhesive (adhesive).
  • an inorganic layer such as silicon nitride, silicon oxide, and silicon oxynitride exhibiting gas barrier properties is formed on a different substrate from the organic EL element, so that the inorganic layer can be formed with high energy. Therefore, a thin inorganic layer having high gas barrier properties can be formed. Therefore, an organic EL device manufactured by a method of sealing an organic EL element using a gas barrier film is more flexible than an organic EL device manufactured by a method of sealing an organic EL element by a passivation film. It can be an EL device.
  • an organic EL display having flexibility and an organic EL device formed on a three-dimensional curved surface can be obtained by combining with a configuration using a resin film as an element substrate. Further, the method using the gas barrier film has higher productivity than the sealing with the passivation film.
  • Patent Document 1 discloses an organic EL laminate in which a light-emitting element using an organic EL material, an organic EL device having a passivation film covering the light-emitting element, and a transparent sealing substrate are bonded with an adhesive.
  • a top emission type in which the organic EL device emits light toward the sealing substrate, and the sealing substrate includes an inorganic film and an organic film serving as a base of the inorganic film on a support.
  • a gas barrier film in which the surface layer is an inorganic film, the passivation film and the surface inorganic film face each other, and the organic EL device and the gas barrier film are adhered by an adhesive.
  • the entire area between the passivation film and the inorganic film on the surface is filled, and furthermore, at the end of the organic EL device, the gap between the passivation film and the surface is removed.
  • the gap between the film, at the position of the light-emitting element are described narrow organic EL laminate than the gap between the passivation film and the surface of the inorganic film.
  • Patent Document 2 discloses that a substrate, a gas barrier layer provided on one surface of the substrate and having one or more combinations of an inorganic layer and an organic layer serving as a surface on which the inorganic layer is formed, and a gas barrier layer between the substrate and the gas barrier layer. And a peeling organic layer that adheres to the organic layer and peels off from the substrate.
  • Patent Literature 2 describes that a gas barrier layer is transferred from the gas barrier film to an organic EL element via an adhesive layer and sealed.
  • the thickness of the adhesive layer at the end portion is determined by the thickness at the position of the light emitting element (organic EL element) (between the passivation film and the inorganic film). It is described that by making the gap narrower than the gap, the infiltration of moisture from the end face of the adhesive layer is suppressed.
  • the thickness of the adhesive layer can be reduced to only about 1 ⁇ m even if it is thin. Therefore, the gas barrier is used to suppress the deterioration of the organic EL element due to moisture entering from the end face of the adhesive layer. It is necessary to provide a high passivation film. Therefore, although the thickness of the passivation film can be reduced as compared with the configuration having only the passivation film, a certain thickness is required, and it is difficult to obtain higher flexibility.
  • the organic EL element may be deteriorated by the influence of moisture and residual solvent contained in the adhesive.
  • Patent Documents 1 and 2 do not disclose a bonding method capable of reducing the thickness of an adhesive layer when bonding a gas barrier film to such a surface having irregularities.
  • An object of the present invention is to solve such a problem.
  • an electronic device such as an organic EL device is sealed with a gas barrier film
  • the thickness of an adhesive layer can be reduced to prevent deterioration of the element.
  • Another object of the present invention is to provide a method of manufacturing an electronic device laminate capable of producing a highly flexible electronic device laminate, and an electronic device laminate.
  • a gas barrier film having a sealing layer having a heat sealing layer, an inorganic layer, and an organic layer in this order, and a substrate laminated on the organic layer side of the sealing layer so as to be peelable from the sealing layer is prepared.
  • thermocompression bonding step of heating and pressurizing the heat-sealing layer side toward the element forming surface side and press-bonding
  • a peeling step of peeling the substrate from the sealing layer The thickness of the inorganic layer is 100 nm or less
  • a method for producing an electronic device laminate wherein the glass transition temperature of the heat sealing layer is from 20 ° C to 180 ° C.
  • a method for manufacturing a device laminate [3] The method for producing an electronic device laminate according to [1] or [2], wherein the electronic device is an organic electroluminescence device. [4] The method for producing an electronic device laminate according to any one of [1] to [3], wherein in the thermocompression bonding step, heating and pressurizing the gas barrier film are performed with a roller. [5] The method for producing an electronic device laminate according to any one of [1] to [4], wherein heating is performed from the substrate side in the thermocompression bonding step. [6] The method for producing an electronic device laminate according to [5], wherein in the thermocompression bonding step, heating is performed from the electronic device side.
  • the thickness of the adhesive layer can be reduced to prevent deterioration of the element, and the electronic device laminate having high flexibility Can be provided, and a method for manufacturing an electronic device laminate, and an electronic device laminate can be provided.
  • the method for producing an electronic device laminate of the present invention comprises: A step of preparing a sealing layer having a heat sealing layer, an inorganic layer, and an organic layer in this order, and a gas barrier film having a substrate that is laminated on the organic layer side of the sealing layer so as to be peelable from the sealing layer; , A gas-barrier film, on an element forming surface having irregularities of an electronic device, a thermocompression bonding step of heating and pressurizing the heat-sealing layer side toward the element forming surface side and press-bonding, A peeling step of peeling the substrate from the sealing layer,
  • the thickness of the inorganic layer is 100 nm or less, This is a method for producing an electronic device laminate in which the glass transition temperature of the heat sealing layer is from 20 ° C. to 180 ° C.
  • the method for manufacturing an electronic device laminate of the present invention includes a sealing layer having a heat sealing layer, an inorganic layer, and an organic layer in this order, and an organic layer of the sealing layer.
  • a step of preparing a gas barrier film having a substrate releasably laminated from the sealing layer on the side (FIG. 1); It has a thermocompression bonding step (FIGS. 2 to 4) for heating and pressing toward the element forming surface and pressing, and a separation step (FIGS. 4 and 5) for separating the substrate from the sealing layer.
  • FIG. 1 is a cross-sectional view schematically illustrating a gas barrier film used in the method for manufacturing an electronic device laminate according to the present invention.
  • the gas barrier film 40 shown in FIG. 1 has a heat sealing layer 30, an inorganic layer 16, an organic layer 14, and a substrate 32 in this order.
  • the heat sealing layer 30, the inorganic layer 16, and the organic layer 14 are the sealing layers 12 that can be separated from the substrate 32. That is, the gas barrier film 40 is formed to be peelable at the interface between the substrate 32 and the organic layer 14.
  • the gas barrier film 40 is a transfer-type gas barrier film that can transfer the sealing layer 12 to an electronic device.
  • the inorganic layer 16 is a layer that mainly exhibits gas barrier properties
  • the organic layer 14 is a layer that serves as a base layer of the inorganic layer 16.
  • the heat-sealing layer 30 is a layer that flows by heating when the gas barrier film 40 is bonded to an electronic device, and that exhibits adhesiveness.
  • the thickness of the inorganic layer 16 is 100 nm or less.
  • the glass transition temperature Tg of the heat sealing layer 30 is in the range of 20 ° C. to 180 ° C.
  • Each layer of the gas barrier film 40 will be described later in detail.
  • the thermocompression bonding step is a step of bonding the gas barrier film 40 as described above onto the element forming surface of the electronic device 50.
  • an electronic device (organic EL device) 50 having a plurality of organic EL (electroluminescence) elements 54 formed on an element substrate 52 is placed on a table 100.
  • the heat sealing layer 30 of the gas barrier film 40 faces the surface of the electronic device 50 on the organic EL element 54 side (hereinafter, also referred to as the element formation surface).
  • the gas barrier film 40 is pressure-bonded to the electronic device 50 using the roller 102.
  • the roller 102 has a heating unit, and the gas barrier film 40 is pressed while being heated by the roller 102.
  • the table on which the electronic device 50 is mounted also has a heating unit, and the electronic device 50 side is also heated.
  • the thickness of the adhesive layer cannot be significantly changed even when pressure or heating is performed during bonding. Therefore, it is difficult to make the thickness of the adhesive layer thinner.
  • a method of making the thickness of the adhesive layer thinner a method of applying a liquid adhesive to the element forming surface of the electronic device and then bonding a gas barrier film may be considered, but the inorganic layer of the gas barrier film is exposed. When laminating is performed in a state where it has been made, the inorganic layer may be broken and the gas barrier property may be reduced.
  • the heat fusion layer 30 having a glass transition temperature of 20 ° C. to 180 ° C. and melting by heating is used. Accordingly, when the gas barrier film 40 is bonded to the element formation surface of the electronic device 50, the heat fusion layer flows and flows into the concave portion of the element formation surface, and the thickness of the heat fusion layer 30 becomes extremely large. The thickness of the organic EL element 54 of the electronic device 50 and the gas barrier film 40 can be reduced by making the heat sealing layer 30 scattered between the inorganic layer 16 and the electronic device 50.
  • the distance between the inorganic layer 16 and the distance between the electronic device 50 (element substrate 52) and the inorganic layer 16 of the gas barrier film 40 at the end can be reduced.
  • the distance between the inorganic layer 16 and the electronic device 50 (thickness of the heat-sealing layer 30) at the end face after thermocompression bonding can be extremely reduced.
  • the infiltration of moisture from the end face of the heat sealing layer 30 can be prevented, and the deterioration of the organic EL element 54 can be prevented.
  • the heat-sealing layer 30 since the heat-sealing layer 30 is solid until heated, the heat-sealing layer 30 can protect the inorganic layer 16 of the gas barrier film 40 and prevent the inorganic layer 16 from being broken at the time of transportation or bonding. Can be. Further, since the heat-sealing layer 30 is a solid that is heat-sealed, the heat-sealing layer 30 does not contain (small) residual solvent and moisture. Therefore, deterioration of the organic EL element 54 due to residual solvent and moisture can be prevented.
  • the heat-sealing layer flows and flows into the concave portion of the element forming surface. Gas (air) existing in the air can be efficiently removed. Therefore, it is possible to prevent gas (air) from remaining in a concave portion or the like on the element forming surface of the manufactured electronic device laminate 10.
  • the gas barrier film 40 when the thickness of the inorganic layer 16 of the gas barrier film 40 is 100 nm or less and has flexibility, the gas barrier film 40 is pressure-bonded to the uneven surface of the electronic device 50 in the thermocompression bonding step.
  • the inorganic layer 16 since the inorganic layer 16 can be curved in accordance with the unevenness of the element forming surface without cracking, the inorganic layer 16 is curved so that the distance between the inorganic layer 16 and the electronic device 50 becomes small at the end. can do.
  • the transfer type gas barrier film 40 from which the sealing layer 12 and the substrate 32 can be separated is used as the gas barrier film 40. Therefore, when the gas barrier film 40 is pressed against the element forming surface of the electronic device 50 in the thermocompression bonding step, the substrate 32 can be partially peeled from the sealing layer 12, and the sealing layer 12 including the inorganic layer 16 can It becomes easier to follow the irregularities of the formation surface. Thereby, the distance between the inorganic layer 16 and the electronic device 50 after the compression can be further reduced.
  • the heat-fused layer 30 since the heat-fused layer 30 exhibits fluidity only in a heated portion to obtain adhesiveness, it can be bonded to an arbitrary portion. Therefore, for example, when it is difficult to bond the sealing layer 12 over the entire surface of the electronic device 50 in a three-dimensional shape, only the end portion is bonded, and the sealing layer 12 covers the element formation surface of the electronic device 50. In this way, sealing can be performed, and additional sealing can be performed by additionally transferring to a site where the barrier property needs to be particularly increased in view of the shape and physical properties of the element.
  • the heating temperature and the pressure to be applied are adjusted so that the distance between the inorganic layer 16 and the electronic device 50 (element formation surface) at the end after thermocompression bonding is 100 nm or less. Is preferred. By setting the distance between the inorganic layer 16 and the electronic device 50 (element formation surface) at the end after the thermocompression bonding to 100 nm or less, it is possible to appropriately prevent moisture from entering from the end of the heat sealing layer 30. can do.
  • the heating temperature and the pressure to be applied depend on the material and thickness of the heat sealing layer 30, the thickness and hardness of the substrate 32, the state of the unevenness of the electronic device 50, and the necessary thickness of the heat sealing layer. What is necessary is just to set suitably.
  • the heating temperature of the gas barrier film 40 is preferably equal to or higher than the glass transition temperature Tg of the heat sealing layer 30, more preferably Tg + 50 ° C. to Tg + 5 ° C., and Tg + 30 ° C. to Tg + 20 ° C. Is more preferred.
  • the electronic device 50 may be heated in the thermocompression bonding step.
  • the heating temperature on the electronic device 50 side is preferably lower than the heating temperature on the gas barrier film 40 side.
  • the temperature is preferably Tg + 10 ° C. to Tg + 5 ° C., and more preferably Tg + 5 ° C. to Tg ° C.
  • the pressure applied to the gas barrier film 40 and the electronic device 50 is preferably 0.001 MPa to 5 MPa, more preferably 0.01 MPa to 1 MPa, and further preferably 0.1 MPa to 0.5 MPa.
  • the pressure applied to the gas barrier film 40 and the electronic device 50 is 0.01 MPa or more, the heat-sealing layer 30 flowing by heating is moved, and the inorganic layer 16 of the gas barrier film 40 and the element of the electronic device 50 are moved.
  • the thickness of the heat sealing layer 30 can be reduced by shortening the distance from the formation surface.
  • the pressure is if the pressure is too high, the inorganic layer 16 may be broken or the organic EL element 54 may be damaged. Therefore, the pressure is preferably set to 5 MPa or less.
  • thermocompression bonding step a roller is used as a device for pressing the gas barrier film 40 to the electronic device 50.
  • the present invention is not limited to this.
  • a known pressure device such as a pressure device can be used.
  • the roller surface is preferably made of a flexible rubber material.
  • the inorganic layer 16 of the gas barrier film 40 can be prevented from being damaged by unevenness of the element forming surface of the electronic device 50, and the gas barrier film 40 and the electronic device 50 are uniformly bonded. be able to.
  • a member supporting the back surface side of the electronic device 50 may be a member having a smooth and high rigidity, and may be a plate-shaped table having a flat mounting surface as shown in FIG. Alternatively, it may be a roller.
  • a roller When a table is used, there is a possibility that the gas barrier film 40 and the electronic device 50 cannot be uniformly bonded due to air remaining between the electronic device 50 and the table. In this regard, it is preferable to use a roller.
  • the heating means of the roller and / or the table is not particularly limited, and a known heating means may be used.
  • the heating and the pressurization are performed simultaneously by the roller, but the present invention is not limited to this, and the pressure may be applied after the gas barrier film is heated.
  • thermocompression bonding step is preferably performed under reduced pressure to atmospheric pressure or lower.
  • thermocompression bonding process under reduced pressure, it is possible to suppress air from remaining between the gas barrier film 40 and the electronic device 50 when the gas barrier film 40 and the electronic device 50 are bonded to each other.
  • ⁇ Peeling step> In the peeling step, as shown in FIG. 5, the substrate 32 of the gas barrier film 40 is peeled from the sealing layer 12 after the thermocompression bonding step. By peeling off the substrate 32, the overall thickness of the electronic device laminate 10 produced can be reduced to increase flexibility.
  • the electronic device laminate 10 as shown in FIG. 5 can be manufactured by performing the above steps.
  • the electronic device laminate of the present invention which is manufactured by the manufacturing method of the present invention, An electronic device in which an element formation surface has irregularities, Having a heat-fusion layer laminated on the element formation surface, a transfer layer having an inorganic layer and an organic layer in this order, The thickness of the inorganic layer is 100 nm or less, The glass transition temperature of the heat sealing layer is 20 ° C. to 180 ° C., An electronic device laminate in which a distance between an inorganic layer and an electronic device at an end is 100 nm or less.
  • An electronic device laminate 10 shown in FIG. 5 includes an electronic device (organic EL device) 50 having an element substrate 52 and an organic EL element 54, and a sealing layer 12 having a heat fusion layer 30, an inorganic layer 16, and an organic layer 14. And The sealing layer 12 is laminated on the electronic device 50 such that the heat sealing layer 30 is in contact with the surface of the electronic device 50 on which the organic EL element 54 is formed (element forming surface).
  • the thickness of the inorganic layer 16 is 100 nm or less.
  • the flexibility of the inorganic layer 16 can be increased, and the inorganic layer 16 can be curved following the unevenness of the element formation surface of the electronic device 50. Therefore, the distance between the inorganic layer 16 and the electronic device 50 at the end can be reduced, and intrusion of moisture from the end of the heat sealing layer 30 can be prevented.
  • the glass transition temperature of the heat sealing layer 30 is 20 ° C. to 180 ° C. Since the heat-fused layer 30 having a glass transition temperature in the above range is melted by heating, the heat-fused layer 30 is heated and fluidized as in the above-described manufacturing method, so that the gap between the inorganic layer 16 and the electronic device 50 is reduced. Is small.
  • the distance between the inorganic layer 16 and the electronic device 50 at the end is determined by cutting the electronic device laminate 10 in the thickness direction and observing the cross section with a microscope, an SEM (scanning electron microscope), a microscope, or the like. Can be measured.
  • ⁇ Substrate> As the substrate 32 , a known sheet-like material (film, plate-like material) used as a substrate (support) in various gas barrier films and various laminated functional films can be used. Further, as the substrate 32, various sheet materials used as separators (light release separators and heavy release separators) in various optical transparent adhesives (OCA (Optical Clear Adhesive)) can also be used.
  • OCA optical Clear Adhesive
  • the material of the substrate 32 is not limited, and can form the organic layer 14, the inorganic layer 16, and the heat-sealing layer 30, and does not dissolve in a solvent contained in the composition for forming the organic layer 14.
  • Various materials can be used.
  • As the material of the substrate 32 preferably, various resin materials are exemplified. Examples of the material of the substrate 32 include polyethylene (PE), polyethylene naphthalate (PEN), polyamide (PA), polyethylene terephthalate (PET), polyvinyl chloride (PVC), polyvinyl alcohol (PVA), and polyacrylonitrile (PAN).
  • TAC triacetyl cellulose
  • EVOH ethylene-vinyl alcohol copolymer
  • the thickness of the substrate 32 can be set as appropriate according to the application and the material. Although there is no limitation on the thickness of the substrate 32, a transfer type gas barrier film having good flexibility (flexibility) that can sufficiently secure the mechanical strength of the transfer type gas barrier film can be obtained. A transfer type gas barrier film that can be easily peeled off from the sealing layer 12 at the time of transfer can be obtained, and it can easily follow the unevenness of the element forming surface of the electronic device 50 in the thermocompression bonding step. In this case, the thickness is preferably 120 ⁇ m to 5 ⁇ m, and more preferably 100 ⁇ m to 15 ⁇ m.
  • the organic layer 14 is a layer constituting the sealing layer 12, and is a layer serving as a base layer for appropriately forming the inorganic layer 16.
  • the organic layer 14 is an organic layer to which the substrate 32 is removably attached. That is, the organic layer 14 is an organic layer that can be separated from the substrate 32. Therefore, the adhesion between the organic layer 14 and the inorganic layer 16 is stronger than the adhesion between the substrate 32 and the organic layer 14.
  • the inorganic layer 16 formed on the surface of the organic layer 14 is preferably formed by plasma CVD (Chemical Vapor Deposition).
  • the organic layer 14 is etched by the plasma, and a mixture having the components of the organic layer 14 and the components of the inorganic layer 16 is provided between the organic layer 14 and the inorganic layer 16.
  • a layer such as a layer, is formed.
  • the organic layer 14 and the inorganic layer 16 are adhered with very strong adhesion. Therefore, the adhesion between the organic layer 14 and the inorganic layer 16 is much stronger than the adhesion between the substrate 32 and the organic layer 14. 16 does not peel off.
  • the thickness of the organic layer 14 is a thickness of a layer that does not include the above-described mixed layer and that is formed only of components forming the organic layer 14.
  • the organic layer 14 is a base layer for properly forming the inorganic layer 16
  • the organic layer 14 formed on the surface of the substrate 32 is free from irregularities on the surface of the substrate 32 and foreign substances adhering to the surface. Embed.
  • the surface on which the inorganic layer 16 is formed is made appropriate, and the inorganic layer 16 can be formed properly.
  • the organic layer 14 functions as a protective layer for protecting the inorganic layer 16 after the substrate 32 is peeled off.
  • the organic layer 14 preferably has high heat resistance. Specifically, the organic layer 14 preferably has a glass transition point (Tg) of 175 ° C. or higher, more preferably 200 ° C. or higher, even more preferably 250 ° C. or higher.
  • Tg glass transition point
  • the inorganic layer 16 formed on the surface of the organic layer 14 is preferably formed by plasma CVD.
  • the Tg of the organic layer 14 is set to 180 ° C. or higher, the etching and volatilization of the organic layer 14 by plasma during the formation of the inorganic layer 16 are suitably suppressed, and the appropriate organic layer 14 and inorganic layer 16 are preferably formed. It is preferable in that it can be formed into a non-woven fabric.
  • the upper limit of Tg of the organic layer 14 is not limited, but is preferably 500 ° C. or lower.
  • the resin forming the organic layer 14 has a large molecular weight to some extent.
  • the resin forming the organic layer 14 preferably has a molecular weight (weight average molecular weight (Mw)) of 500 or more, more preferably 1,000 or more, and still more preferably 1500 or more.
  • the Tg of the organic layer 14 may be specified by a known method using a differential scanning calorimeter (DSC) or the like. Also, the molecular weight may be measured by a known method using gel permeation chromatography (GPC) or the like. When a commercially available product is used, the Tg and the molecular weight of the organic layer 14 may use catalog values. With respect to the above points, the same applies to the heat sealing layer 30 described later.
  • the organic layer 14 is, for example, a layer made of an organic compound obtained by polymerizing (crosslinking and curing) a monomer, a dimer, an oligomer, and the like.
  • the composition for forming the organic layer 14 may include only one type of organic compound, or may include two or more types of organic compounds.
  • the organic layer 14 contains, for example, a thermoplastic resin and an organic silicon compound.
  • Thermoplastic resins include, for example, polyester, (meth) acrylic resin, methacrylic acid-maleic acid copolymer, polystyrene, transparent fluororesin, polyimide, fluorinated polyimide, polyamide, polyamideimide, polyetherimide, cellulose acylate, polyurethane , Polyether ether ketone, polycarbonate, alicyclic polyolefin, polyarylate, polyether sulfone, polysulfone, fluorene ring-modified polycarbonate, alicyclic modified polycarbonate, fluorene ring-modified polyester, and acrylic compound.
  • the organosilicon compound include polysiloxane.
  • the organic layer 14 preferably contains a radical curable compound and / or a polymer of a cationic curable compound having an ether group from the viewpoints of excellent strength and the glass transition point.
  • the organic layer 14 preferably contains a (meth) acrylic resin whose main component is a polymer such as a monomer or oligomer of (meth) acrylate from the viewpoint of lowering the refractive index of the organic layer 14.
  • the organic layer 14 is more preferably bifunctional or more, such as dipropylene glycol di (meth) acrylate (DPGDA), trimethylolpropane tri (meth) acrylate (TMPTA), dipentaerythritol hexa (meth) acrylate (DPHA).
  • DPGDA dipropylene glycol di (meth) acrylate
  • TMPTA trimethylolpropane tri (meth) acrylate
  • DPHA dipentaerythritol hexa
  • acrylic resin containing as a main component a polymer such as a (meth) acrylate monomer, dimer or oligomer, and more preferably a polymer such as a trifunctional or higher-functional (meth) acrylate monomer, dimer or oligomer.
  • acrylic resin containing as a main component Further, a plurality of these (meth) acrylic resins may be used.
  • the main component is a component having the largest content mass ratio among
  • the organic layer 14 is formed of a resin having an aromatic ring, so that the substrate 32 can be separated.
  • the organic layer 14 preferably contains a resin containing a bisphenol structure as a main component. More preferably, the organic layer 14 contains polyarylate (polyarylate resin (PAR)) as a main component.
  • polyarylate is an aromatic polyester made of a polycondensate of a dihydric phenol such as bisphenol represented by bisphenol A and a dibasic acid such as phthalic acid (terephthalic acid, isophthalic acid). .
  • the adhesion between the substrate 32 and the organic layer 14 is appropriate and easy.
  • the substrate 32 can be peeled off.
  • it since it has appropriate flexibility, it is possible to prevent damage (cracks, cracks, etc.) of the inorganic layer 16 when the substrate 32 is peeled off, and it is possible to stably form an appropriate inorganic layer 16 because of high heat resistance. This is preferable in that the performance degradation of the organic thin film transistor can be prevented and the flexibility of the organic thin film transistor can be increased.
  • a main component means the component with the largest content mass ratio among the components contained.
  • the organic layer 14 When the organic layer 14 is formed of various resins having an aromatic ring, the organic layer 14 may be formed using a commercially available resin as long as the resin has an aromatic ring.
  • Commercially available resins that can be used for forming the organic layer 14 include Unifiner (registered trademark) and U Polymer (registered trademark) manufactured by Unitika Ltd., and Neoprim (registered trademark) manufactured by Mitsubishi Gas Chemical Company, Ltd. Trademark) and the like.
  • the thickness of the organic layer 14 is not limited, but is preferably 0.2 to 6 ⁇ m, more preferably 0.5 to 5 ⁇ m, and still more preferably 1 to 3 ⁇ m.
  • an appropriate inorganic layer 16 can be formed stably, mechanical strength not torn at the time of peeling can be maintained, and good peeling can be achieved. It is preferred in that it does not receive any.
  • the gas barrier film 40 can be reduced in weight and thickness, a highly transparent gas barrier film can be obtained, and good peelability of the substrate 32 can be obtained.
  • the thickness of the organic layer 14 is a thickness of a layer that does not include the above-described mixed layer and that is formed only of components forming the organic layer 14.
  • the organic layer 14 can be formed by a known method according to a material.
  • the organic layer 14 is prepared by preparing a composition (resin composition) obtained by dissolving a resin (organic compound) or the like to be the organic layer 14 in a solvent, applying the composition to the substrate 32, and drying the composition. Can be formed.
  • the resin (organic compound) in the composition may be further polymerized (cross-linked) by irradiating the dried composition with ultraviolet rays, if necessary.
  • the composition for forming the organic layer 14 preferably contains an organic solvent, a surfactant, a silane coupling agent, and the like, in addition to the organic compound.
  • the organic layer 14 is preferably formed by roll-to-roll.
  • roll-to-roll is also referred to as “RtoR”.
  • RtoR refers to a method of feeding a sheet from a roll formed by winding a long sheet, and forming a film while transporting the long sheet in the longitudinal direction. This is a production method in which a material is wound into a roll. By using RtoR, high productivity and production efficiency can be obtained.
  • the organic layer 14 needs to be formed so as to be peelable from the substrate 32. Therefore, a material having releasability may be used as the material of the organic layer 14 as described above, or a release layer may be provided between the organic layer 14 and the substrate 32. As the release layer, a conventionally known release layer can be appropriately used.
  • the peeling force between the substrate 32 and the organic layer 14 is preferably 0.01 to 2 N / 25 mm, more preferably 0.05 to 1 N / 25 mm, and still more preferably 0.1 to 0.8 N / 25 mm.
  • the inorganic layer 16 is a thin film containing an inorganic compound, and is formed at least on the surface of the organic layer 14.
  • the inorganic layer 16 mainly exhibits gas barrier performance.
  • On the surface of the substrate 32 there are regions, such as irregularities and foreign matter, where it is difficult for the inorganic compound to form a film.
  • a region where the inorganic compound is hardly deposited can be covered. Therefore, it is possible to form the inorganic layer 16 on the surface on which the inorganic layer 16 is formed without gaps.
  • the material of the inorganic layer 16 is not limited, and various known inorganic compounds used for the gas barrier layer, which are formed of an inorganic compound exhibiting gas barrier performance, can be used.
  • the material of the inorganic layer 16 include metal oxides such as aluminum oxide, magnesium oxide, tantalum oxide, zirconium oxide, titanium oxide, and indium tin oxide (ITO); metal nitrides such as aluminum nitride; metals such as aluminum carbide Carbides; Silicon oxides such as silicon oxide, silicon oxynitride, silicon oxycarbide, silicon oxynitride carbide; silicon nitrides such as silicon nitride and silicon nitride carbide; silicon carbides such as silicon carbide; hydrides thereof; Inorganic compounds such as the above mixtures; and hydrogen-containing substances thereof.
  • metal oxides such as aluminum oxide, magnesium oxide, tantalum oxide, zirconium oxide, titanium oxide, and indium tin oxide (ITO)
  • silicon nitride, silicon oxide, silicon oxynitride, aluminum oxide, and a mixture of two or more thereof are preferably used because they have high transparency and can exhibit excellent gas barrier performance.
  • a compound containing silicon is preferably used, and among them, silicon nitride is particularly preferably used because it can exhibit excellent gas barrier performance.
  • the thickness of the inorganic layer 16 is 100 nm or less. From the viewpoints of flexibility and gas barrier properties, the thickness of the inorganic layer 16 is preferably equal to or less than 50 nm, more preferably 5 to 50 nm, and still more preferably 10 to 30 nm. It is preferable that the thickness of the inorganic layer 16 be 2 nm or more, since the inorganic layer 16 stably exhibiting sufficient gas barrier performance can be formed. In addition, the inorganic layer 16 is generally brittle, and if it is too thick, there is a possibility that cracks, cracks, peeling, and the like may occur. However, cracks occur when the thickness of the inorganic layer 16 is 50 nm or less. This can be more suitably prevented. Further, flexibility can be increased.
  • the inorganic layer 16 can be formed by a known method according to the material.
  • plasma CVD such as CCP (Capacitively Coupled Plasma) -CVD and ICP (Inductively Coupled Plasma) -CVD, atomic layer deposition (ALD), sputtering such as magnetron sputtering and reactive sputtering, and vacuum
  • atomic layer deposition ALD
  • sputtering such as magnetron sputtering and reactive sputtering
  • vacuum Various vapor-phase film forming methods such as vapor deposition are preferably exemplified.
  • plasma CVD such as CCP-CVD and ICP-CVD is preferably used because the adhesion between the organic layer 14 and the inorganic layer 16 can be improved.
  • the inorganic layer 16 is also preferably formed by RtoR.
  • the heat sealing layer 30 is for bonding the gas barrier film 40 to the element forming surface of the electronic device 50. Further, the heat sealing layer 30 also functions as a protective layer that protects the inorganic layer 16 that exhibits gas barrier performance.
  • the hot-melt adhesive layer 30 uses a hot melt adhesive (HMA).
  • HMA hot melt adhesive
  • the heat-fusion layer 30 made of a hot-melt adhesive is a heat-fusion layer that is solid at room temperature, flows when heated, and exhibits adhesiveness.
  • normal temperature is 23 degreeC.
  • the heat-sealing layer 30 preferably flows at a temperature of 30 to 200 ° C. to exhibit adhesiveness, and the heat-sealing layer 30 flows at a temperature of 40 to 180 ° C. to more preferably exhibit adhesiveness. More preferably, it flows at a temperature of up to 150 ° C. to exhibit adhesiveness.
  • the heat-sealing layer 30 flows at room temperature to exhibit adhesiveness, foil cutting is likely to occur at the time of cutting and transferring the gas barrier film, resulting in a decrease in gas barrier performance and the like.
  • the temperature at which the adhesive material flows and exhibits an adhesive property is too high, the heating temperature required at the time of sticking to the sticking target becomes high, causing thermal damage to the substrate 32, the organic layer 14, and the sticking target. I will.
  • the glass transition temperature Tg of the heat sealing layer 30 is from 20 ° C. to 180 ° C., preferably from 25 ° C. to 150 ° C., more preferably from 40 ° C. to 140 ° C., and from 60 ° C. to 120 ° C. Is more preferred.
  • the material for the heat fusion layer 30 is not limited as long as it is solid at room temperature and can flow by heating to exhibit adhesiveness.
  • the heat sealing layer 30 is preferably composed mainly of an amorphous resin, more preferably composed mainly of an acrylic resin, and is obtained by polymerizing a single acrylate monomer. It is more preferable to use a resin (acryl homopolymer (homoacryl polymer)) as a main component.
  • a resin acryl homopolymer (homoacryl polymer)
  • the use of an amorphous resin, particularly an acrylic resin, as the main component of the heat-sealing layer 30 is preferable in that a highly transparent gas barrier film can be obtained.
  • the main component of the heat-sealing layer 30 be an acrylic homopolymer, in addition to the above-mentioned advantages, in that transferability by heat can be improved, and blocking after winding after curing is difficult.
  • the heat-fusion layer 30 can be a layer that flows at a relatively low temperature and exhibits adhesiveness. Therefore, when high heat resistance is not required for the gas barrier film, the heat sealing layer 30 made of an acrylic homopolymer is preferably used.
  • the heat sealing layer 30 may include a styrene-acrylic copolymer (styrene-modified acrylic resin), a urethane-acrylic copolymer (urethane-modified acrylic resin), and an acrylic resin for adjusting the glass transition temperature, if necessary. It may include one or more selected. By adding these components to the heat fusion layer 30, the Tg of the heat fusion layer 30 can be improved. Therefore, when heat resistance is required for the organic thin film transistor according to the use or the like, the heat sealing layer 30 to which these components are added is preferably exemplified.
  • the hardness of the heat sealing layer 30 can be adjusted, so that the balance of the hardness with the object to be stuck can be adjusted.
  • a urethane acrylic copolymer to the heat-sealing layer 30, the adhesion to the inorganic layer 16 can be improved.
  • the amounts of these components added are not limited, and may be set appropriately according to the components to be added and the desired Tg. However, it is preferable that the added amount of these components is such that the main component of the heat-sealing layer 30 becomes the above-mentioned amorphous resin and acrylic resin.
  • the styrene acrylic copolymer, the urethane acrylic copolymer, and the acrylic resin for adjusting the glass transition point are not limited, and various resins used for adjusting Tg such as resins can be used. These components are also available as commercial products.
  • the styrene acrylic copolymer is exemplified by # 7000 series manufactured by Taisei Fine Chemical Co., Ltd.
  • the urethane acrylic copolymer include Acryt (registered trademark) 8UA series manufactured by Taisei Fine Chemical Co., Ltd. such as Acryt 8UA347H.
  • the acrylic resin for adjusting the glass transition point include PMMA (for example, Dianal (registered trademark) manufactured by Mitsubishi Chemical Corporation) and the like.
  • the thickness of the heat-sealing layer 30 is not limited, and the distance between the inorganic layer 16 and the electronic device 50 at the end portion after the thermocompression bonding is sufficiently increased according to the material of the heat-sealing layer 30. What is necessary is just to set suitably the thickness which can be made thin and sufficient adhesiveness and the protective performance of the inorganic layer 16 are obtained.
  • the thickness of the thermal fusion layer 30 is preferably 1 to 30 ⁇ m, more preferably 2 to 20 ⁇ m, and still more preferably 3 to 10 ⁇ m.
  • the thickness of the heat-sealing layer 30 be 1 ⁇ m or more, since sufficient adhesion can be obtained at the time of transfer, and a decrease in gas barrier performance at the time of peeling the substrate 32 (after transfer) can be prevented.
  • the thickness of the heat fusion layer 30 By setting the thickness of the heat fusion layer 30 to 30 ⁇ m or less, a highly transparent gas barrier film 40 can be obtained in which the distance between the inorganic layer 16 and the electronic device 50 at the end after thermocompression bonding can be sufficiently reduced. This is preferable in that the gas barrier film 40 can be made thinner and lighter.
  • the electronic device 50 is a known organic EL device such as an organic EL display and an organic EL lighting device.
  • the element substrate 52 and the plurality of organic EL elements 54 formed on the element substrate 52 are shown as components of the electronic device 50.
  • the electronic device 50 has other layers. Is also good.
  • the electronic device has a configuration in which an insulating film, a transparent electrode layer (TFT (Thin Film Transistor), thin film transistor), an insulating film, an organic EL element 54, and an insulating film are sequentially stacked on an element substrate 52. You may. Further, a passivation film for protecting the organic EL element 54 may be provided.
  • TFT Thin Film Transistor
  • element substrate 52 various element substrates used as an element substrate in a conventional organic EL device, such as a resin film and a glass substrate, can be used.
  • the organic EL element 54 has the same configuration as the organic EL element of a conventional organic EL device. That is, the organic EL element 54 has a hole injection layer, a hole transport layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, a cathode, and the like.
  • the height of the organic EL element 54 is about 0.1 ⁇ m to 10 ⁇ m.
  • the size of the organic EL element 54 in the plane direction is about 0.1 ⁇ m ⁇ 0.1 ⁇ m to 10 ⁇ m ⁇ 10 ⁇ m.
  • the organic EL device is exemplified as the electronic device.
  • the present invention is not limited to this, and various electronic devices such as a solar cell can be used as the electronic device.
  • an electronic device manufactured by the method for manufacturing an electronic device laminate according to the present invention has less damage to the inorganic layer 16 and exhibits excellent gas barrier performance with high durability over a long period of time. It is suitably used for an organic EL device having an element.
  • Example 1 ⁇ Preparation of gas barrier film> Using a TAC (triacetylcellulose) film (manufactured by FUJIFILM Corporation, thickness 60 ⁇ m, width 1000 mm, length 100 m) as the substrate 32, the sealing layer 12 (organic layer, inorganic layer and heat (Fused layer).
  • TAC triacetylcellulose
  • a polyarylate (Unifina (registered trademark) M-2000H, manufactured by Unitika Ltd.) and cyclohexanone were prepared, weighed at a weight ratio of 5:95, dissolved at room temperature, and coated at a solid concentration of 5%. And The Tg of the polyarylate used is 275 ° C. (catalog value).
  • This coating solution was applied to the substrate by RtoR using a die coater, and passed through a drying zone at 130 ° C. for 3 minutes. Before touching the first film surface touch roll (the roll that touches the surface of the substrate 32 on the side of the sealing layer 12), a protective film of PE (polyethylene) was bonded and wound up later.
  • the thickness of the organic layer 14 formed on the substrate 32 was 2 ⁇ m.
  • a silicon nitride layer was formed as an inorganic layer 16 on the surface of the organic layer 14 using a general RtoR CVD apparatus that forms a film by winding a substrate around a drum.
  • the CVD apparatus includes a film forming apparatus by CCP-CVD, a drum serving as a counter electrode for winding and transporting the substrate, a guide roller for peeling the protective film laminated on the organic layer, a collecting roll for winding the peeled protective film, and a length. It has a loading section of a roll around which a long protective film is wound, a guide roller for laminating the protective film on the surface of the formed inorganic layer, and the like. Note that a CVD apparatus having two or more film forming units (film forming apparatuses) was used.
  • the substrate 32 on which the organic layer 14 is formed is sent out from the roll loaded in the loading section, the protective film is peeled off after passing through the last film surface touch roll before film formation, and the inorganic layer is placed on the exposed organic layer 14.
  • No. 16 was formed.
  • Two electrodes (film-forming units) were used to form the inorganic layer 16, and silane gas, ammonia gas, and hydrogen gas were used as source gases.
  • the supply amounts of the raw material gas were 150 sccm of silane gas, 300 sccm of ammonia gas and 500 sccm of hydrogen gas in the first film formation unit, and 150 sccm of silane gas, 350 sccm of ammonia gas and 500 sccm of hydrogen gas in the second film formation unit.
  • the plasma excitation power was 2.5 kW, and the frequency of the plasma excitation power was 13.56 MHz.
  • a bias power of a frequency of 0.4 MHz and 0.5 kW was supplied to the drum.
  • the temperature of the drum was controlled at 30 ° C. by a cooling means.
  • the deposition pressure was 50 Pa.
  • a protective film of PE was bonded to the film surface of the inorganic layer 16 immediately after film formation, and was wound up later.
  • the thickness of the inorganic layer 16 was 20 nm.
  • the thermal fusion layer 30 was formed on the surface of the inorganic layer 16 by using a general organic film forming apparatus that forms a film by a coating method using RtoR.
  • an acrylic homopolymer (0415BA, manufactured by Taisei Fine Chemical Co., Ltd.) was prepared and diluted with ethyl acetate to obtain a composition having a solid content of 20% by mass.
  • This acrylic homopolymer is amorphous, has a Tg of 20 ° C. and flows at 100 ° C., and exhibits adhesiveness.
  • This composition was applied to the surface of the inorganic layer 16 using a die coater, and then passed through a drying zone at 80 ° C.
  • the passage time in the drying zone was 3 minutes.
  • the composition was dried and cured to form the heat-sealing layer 30 on the surface of the inorganic layer 16.
  • the protective film laminated on the surface of the inorganic layer 16 was peeled off.
  • the thickness of the heat sealing layer formed on the surface of the inorganic layer 16 was 5 ⁇ m.
  • a long transfer-type gas barrier film wound up in a roll was thus prepared. From this long transfer type gas barrier film, the gas barrier film 40 was cut out in a size of 100 mm ⁇ 100 mm.
  • a 100 ⁇ m thick, 100 mm ⁇ 100 mm polyimide layer was formed as a device substrate 52 on a glass substrate, and an organic EL device 54 was formed on the polyimide layer by the following procedure.
  • Tris (8-hydroxyquinolinato) aluminum 60 nm thick -(Second hole transport layer) N, N'-diphenyl-N, N'-dinaphthylbenzidine: film thickness 40 nm -(1st hole transport layer)
  • Copper phthalocyanine 10 nm in film thickness
  • the element substrate on which these layers are formed is loaded into a general sputtering apparatus, and an ITO thin film having a thickness of 0.2 ⁇ m is formed by DC magnetron sputtering using ITO (Indium Tin Oxide) as a target.
  • ITO Indium Tin Oxide
  • the size of the organic EL element 54 was 10 ⁇ m ⁇ 10 ⁇ m, and the height was 5 ⁇ m.
  • the organic EL elements 54 were arranged in a square on the element substrate 52 at a pitch of 50 ⁇ m. Thus, an electronic device (organic EL device) 50 was manufactured.
  • a bonding device for performing the thermocompression bonding step a bonding device having a flat plate-shaped table 100 and a roller 102 disposed above the table 100 was used.
  • the table 100 and the roller 102 each have a heating unit.
  • the roller 102 was made of silicone rubber.
  • the table 100 and the rollers 102 are installed in a decompression chamber, and the inside of the decompression chamber can be decompressed with a rotary pump to perform bonding.
  • the temperature of the table 100 was adjusted to 25 ° C, and the temperature of the roller 102 was set to 90 ° C.
  • the pressure in the decompression chamber was set to 0.1 Pa.
  • the electronic device 50 manufactured as described above was placed on the table 100, and the gas barrier film 40 manufactured as described above was stacked on the element forming surface of the electronic device 50. At that time, the heat sealing layer 30 was directed to the element forming surface side. While pressing the gas barrier film 40 from the substrate 32 side using the roller 102, the roller 102 was moved in parallel from the end portion, and the gas barrier film 40 and the electronic device 50 were thermocompression-bonded.
  • the moving speed of the roller 102 was adjusted to 1 m / min, and the pressure by the roller was adjusted to 0.3 MPa.
  • the distance between the inorganic layer 16 and the electronic device 50 at the end after the pressure bonding was measured and found to be 50 nm. Note that the distance from the end of the gas barrier film 40 to the organic EL element 54 was 0.5 mm.
  • thermocompression bonding step After the thermocompression bonding step, the substrate 32 was peeled off at the interface with the organic layer 14. Thus, an electronic device laminate was produced.
  • Example 2 In the thermocompression bonding step, an electronic device laminate was manufactured in the same manner as in Example 1 except that the temperature of the table 100 was adjusted to 90 ° C. and the temperature of the roller 102 was set to 30 ° C. The distance between the inorganic layer 16 and the electronic device 50 at the end after the pressure bonding was measured and found to be 70 nm.
  • Example 3 An electronic device laminate was produced in the same manner as in Example 1 except that the roller temperature was set to 120 ° C. When the distance between the inorganic layer 16 and the electronic device 50 at the end after the pressure bonding was measured, it was 25 nm.
  • Example 4 An electronic device laminate was produced in the same manner as in Example 1 except that the styrene acrylic polymer was added so that the glass transition temperature Tg of the heat-sealing layer was 80 ° C. The distance between the inorganic layer 16 and the electronic device 50 at the end after the pressure bonding was measured and found to be 80 nm.
  • Example 5 An electronic device laminate was produced in the same manner as in Example 1 except that the pressure by the roller was 1 MPa.
  • Example 6 An electronic device laminate was produced in the same manner as in Example 1 except that the thickness of the inorganic layer was changed to 5 nm. The distance between the inorganic layer 16 and the electronic device 50 at the end after the pressure bonding was measured and found to be 50 nm.
  • Example 7 An electronic device laminate was produced in the same manner as in Example 1, except that the thickness of the inorganic layer was changed to 100 nm. The distance between the inorganic layer 16 and the electronic device 50 at the end after the pressure bonding was measured and found to be 50 nm.
  • Example 8 An electronic device laminate was produced in the same manner as in Example 1 except that the thickness of the heat-sealing layer before the thermocompression bonding step was changed to 10 ⁇ m. The distance between the inorganic layer 16 and the electronic device 50 at the end after the pressure bonding was measured and found to be 70 nm.
  • Example 9 An electronic device laminate was produced in the same manner as in Example 1 except that the thickness of the heat-sealing layer before the thermocompression bonding step was changed to 2 ⁇ m. When the distance between the inorganic layer 16 and the electronic device 50 at the end after the pressure bonding was measured, it was 30 nm.
  • Example 10 An electronic device laminate was produced in the same manner as in Example 1 except that the thickness of the organic layer was changed to 5 ⁇ m. It was 60 nm when the distance between the inorganic layer 16 and the electronic device 50 at the end after the pressure bonding was measured.
  • Example 11 An electronic device laminate was produced in the same manner as in Example 1 except that the thickness of the organic layer was changed to 0.5 ⁇ m. It was 40 nm when the distance between the inorganic layer 16 and the electronic device 50 at the end after the pressure bonding was measured.
  • Example 12 An electronic device laminate was produced in the same manner as in Example 1 except that the thickness of the substrate was changed to 80 ⁇ m.
  • Example 13 An electronic device laminate was produced in the same manner as in Example 1, except that the thickness of the substrate was changed to 40 ⁇ m. When the distance between the inorganic layer 16 and the electronic device 50 at the end after the pressure bonding was measured, it was 30 nm.
  • the adhesive was prepared by adding 48% of epoxy resin (JER1001), 48% of epoxy resin (JER152), and 4% of silane coupling agent (KBM502) to MEK (methyl ethyl ketone) to obtain a 50% weight solution. It was done.
  • This adhesive is applied on the inorganic layer of the gas barrier film so as to have a predetermined thickness, and after the solvent is sufficiently volatilized, the adhesive is attached to an electronic device, and left for 100 hours in an environment of 100 ° C. to be cured.
  • a device laminate was produced. It was 1000 nm when the distance between the inorganic layer and the electronic device at the end after bonding was measured.
  • each electronic device laminate was made to emit light by applying a voltage of 7 V using an SMU2400 type source measure unit manufactured by Keithell Inc. Was measured. Then, it was left for 200 hours in an environment of a temperature of 60 ° C. and a humidity of 90%. After leaving for 200 hours, the electronic device laminate was turned on in the same manner as described above, and the overall luminance was measured again to measure the rate of luminance decrease.
  • AAA brightness reduction is 1% or less.
  • AA The decrease in luminance was 1% or more and less than 3%.
  • B The luminance decrease was 5% or more and less than 8%.
  • C The luminance decrease was 8% or more and less than 10%.
  • D The luminance decrease was 10% or more and less than 30%.
  • E Luminance reduction is 30% or more, and it can be easily visually confirmed that light emission is low. Evaluation is acceptable up to C, and D or less is NG.
  • the electronic device laminate manufactured by the manufacturing method of the present invention has a small decrease in luminance and a small occurrence of dark spots even when left in a high-temperature and high-humidity environment, and has a small occurrence of an organic EL element, as compared with Comparative Examples. It can be seen that the deterioration of can be suppressed. Further, it can be seen that the electronic device laminate manufactured by the manufacturing method of the present invention has higher flexibility than the comparative example.
  • thermocompression bonding step it is easier to heat the heat-fused layer and to flow more easily when the temperature on the substrate side is higher than the temperature on the electronic device side. It can be seen that the pressure can reduce the distance between the inorganic layer and the electronic device. Further, from the comparison between Example 1 and Example 3, in the thermocompression bonding step, the higher the temperature on the substrate side, the more the heat-sealing layer can be heated and flow easily. It can be seen that the distance to the device can be reduced. Also, from the comparison between Example 1 and Example 4, the lower the glass transition temperature Tg of the heat-fused layer is, the more easily the heat-fused layer can flow by heating. It can be seen that the distance between can be reduced.
  • Example 1 From the comparison between Example 1 and Example 5, it is understood that when the pressure in the thermocompression bonding step is high, the distance between the inorganic layer and the electronic device can be reduced. Also, from the comparison of Examples 1 to 5, it can be seen that the smaller the distance between the inorganic layer and the electronic device, the smaller the decrease in luminance after the high humidity heat test, the less occurrence of dark spots, and the higher the durability. In addition, it can be seen that there is little decrease in luminance after the bending test and the flexibility is high.
  • Example 1 shows that when the thickness of the inorganic layer is small, the gas barrier property is low, so that the durability and flexibility are low.
  • the thickness of the inorganic layer is large, the flexibility is low. Therefore, it is understood that 10 nm to 30 nm is preferable.
  • the distance between the inorganic layer after thermocompression bonding and the electronic device can be reduced as the thickness of the heat sealing layer (thickness before the thermocompression bonding step) is smaller. I understand.
  • Example 1 From the comparison between Example 1, Examples 10 and 11, it can be seen that the thinner the organic layer, the shorter the distance between the inorganic layer after thermocompression bonding and the electronic device. This is presumably because, when the organic layer is thick, heat is hardly transmitted to the heat-sealing layer during the thermocompression bonding step, and the fluidity is reduced.

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JP2017043062A (ja) * 2015-08-28 2017-03-02 富士フイルム株式会社 ガスバリアフィルムの製造方法
JP2017117653A (ja) * 2015-12-24 2017-06-29 パイオニア株式会社 発光装置
WO2018163937A1 (ja) * 2017-03-09 2018-09-13 パイオニア株式会社 発光装置

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