WO2015059934A1 - Resin composition, substrate, method of manufacturing electronic device and electronic devices - Google Patents

Resin composition, substrate, method of manufacturing electronic device and electronic devices Download PDF

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Publication number
WO2015059934A1
WO2015059934A1 PCT/JP2014/005385 JP2014005385W WO2015059934A1 WO 2015059934 A1 WO2015059934 A1 WO 2015059934A1 JP 2014005385 W JP2014005385 W JP 2014005385W WO 2015059934 A1 WO2015059934 A1 WO 2015059934A1
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WO
WIPO (PCT)
Prior art keywords
group
electronic element
resin composition
atom
resin film
Prior art date
Application number
PCT/JP2014/005385
Other languages
French (fr)
Inventor
Hideo Umeda
Ritsuya Kawasaki
Toshihiko Katayama
Yusuke Inoue
Jun Okada
Mizuho INOUE
Manabu Naito
Original Assignee
Sumitomo Bakelite Company Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication date
Application filed by Sumitomo Bakelite Company Limited filed Critical Sumitomo Bakelite Company Limited
Priority to JP2016524605A priority Critical patent/JP2016535804A/en
Priority to CN201480057961.4A priority patent/CN105658729A/en
Priority to KR1020167010357A priority patent/KR20160078351A/en
Publication of WO2015059934A1 publication Critical patent/WO2015059934A1/en

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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/10Polyamides derived from aromatically bound amino and carboxyl groups of amino-carboxylic acids or of polyamines and polycarboxylic acids
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05BELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00Electroluminescent light sources
    • H05B33/10Apparatus or processes specially adapted to the manufacture of electroluminescent light sources
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C08G69/32Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from aromatic diamines and aromatic dicarboxylic acids with both amino and carboxylic groups aromatically bound
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D177/00Coating compositions based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D177/10Polyamides derived from aromatically bound amino and carboxyl groups of amino carboxylic acids or of polyamines and polycarboxylic acids
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/10OLED displays
    • H10K59/12Active-matrix OLED [AMOLED] displays
    • H10K59/1201Manufacture or treatment
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/80Manufacture or treatment specially adapted for the organic devices covered by this subclass using temporary substrates
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K77/00Constructional details of devices covered by this subclass and not covered by groups H10K10/80, H10K30/80, H10K50/80 or H10K59/80
    • H10K77/10Substrates, e.g. flexible substrates
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/50Physical properties
    • C08G2261/57Physical properties photorefractive, e.g. change of refractive index
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2650/00Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G2650/02Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterized by the type of post-polymerisation functionalisation
    • C08G2650/04End-capping
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00Organic light-emitting devices
    • H10K50/80Constructional details
    • H10K50/85Arrangements for extracting light from the devices
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00Energy generation through renewable energy sources
    • Y02E10/50Photovoltaic [PV] energy
    • Y02E10/549Organic PV cells

Definitions

  • the present invention relates to a resin composition, a substrate, a method of manufacturing an electronic device and an electronic device.
  • an illuminating device such as an organic EL (electroluminescence) illuminating device and a light emitting diode illuminating device
  • a substrate used therein should have transparency. Therefore, as such a substrate used for the illuminating device, it is known to use a substrate formed of a transparent resin material such as polyethylene terephthalate and polycarbonate (for example, the patent document 1).
  • the emitted light when light is emitted from a light emitting element provided in the illuminating device, the emitted light passes through the transparent substrate and then is extracted outside the illuminating device. Namely, the light emitted from the light emitting element transmits out to the device through the transparent substrate and then reaches to a targeted object. In this way, the targeted object is illuminated with the light. Therefore, it is required that the emitted light should pass through the transparent substrate with high efficiency. Namely, it is required that the illuminating device should have high extraction efficiency of the light.
  • the emitted light having a large incidence angle with respect to the substrate is totally reflected.
  • This total reflection of the light in the illuminating device causes a problem in that the light extraction efficiency of the illuminating device tends to become low.
  • the present invention includes the following features (1) to (19).
  • a resin composition comprising: a polymer; and a solvent dissolving the polymer, wherein the resin composition is used to form a layer, and when refractive indexes of the layer along two perpendicular in-plane directions thereof are respectively defined as "Nx" and "Ny” and a refractive index of the layer along a thickness direction thereof is defined as "Nz", Nx, Ny and Nz satisfy a relationship of "(Nx+Ny)/2-Nz" > 0.01.
  • the resin composition according to the above (5), wherein the rigid structure contains at least one of a structure derived from 4,4'-diamino-2,2'-bistrifluoromethyl benzidine (PFMB) and a structure derived from terephthaloyl dichloride (TPC).
  • PFMB 4,4'-diamino-2,2'-bistrifluoromethyl benzidine
  • TPC terephthaloyl dichloride
  • a substrate used for forming an electronic element thereon comprising: a plate-like base member having a first surface and a second surface opposite to the first surface; and an electronic element formation layer provided at a side of the first surface of the base member, containing a polymer and configured to be capable of forming the electronic element on the electronic element formation layer, wherein when refractive indexes of the electronic element formation layer along two perpendicular in-plane directions thereof are respectively defined as "Nx" and "Ny” and a refractive index of the electronic element formation layer along a thickness direction thereof is defined as "Nz", Nx, Ny and Nz satisfy a relationship of "(Nx+Ny)/2-Nz" > 0.01.
  • a method of manufacturing an electronic device comprising: preparing a substrate, the substrate including, a plate-like base member having a first surface and a second surface opposite to the first surface, and an electronic element formation layer provided at a side of the first surface of the base member and containing a polymer, wherein when refractive indexes of the electronic element formation layer along two perpendicular in-plane directions thereof are respectively defined as "Nx" and "Ny” and a refractive index of the electronic element formation layer along a thickness direction thereof is defined as "Nz", Nx, Ny and Nz satisfy a relationship of "(Nx+Ny)/2-Nz" > 0.01; forming the electronic element on a surface of the electronic element formation layer opposite to the base member; forming a cover layer so as to cover the electronic element; irradiating the electronic element formation layer with light to thereby peel off the electronic element formation layer from the base member in an interface between the base member and the electronic element formation layer; and separating the electronic device including the electronic element, the
  • the present invention it is possible to form a layer by using the resin composition containing the polymer and the solvent dissolving the polymer, wherein when refractive indexes of the layer along two perpendicular in-plane directions thereof are respectively defined as "Nx" and "Ny” and a refractive index of the layer along a thickness direction thereof is defined as "Nz", Nx, Ny and Nz satisfy a relationship of "(Nx+Ny)/2-Nz" > 0.01.
  • This layer formed by using the resin composition is used as the electronic element formation layer (substrate) provided in the electronic device.
  • the light emitted from the light emitting element passes through the electronic element formation layer and then is extracted outside the electronic device.
  • the layer as the electronic element formation layer provided in the electronic device, it is possible to improve the light extraction efficiency of the light emitted from the light emitting element and extracted outside the device.
  • FIG. 1 is a plan view which shows an embodiment of an organic electroluminescence illuminating device manufactured by applying a method of manufacturing an electronic device of the present invention.
  • FIG. 2 is a sectional view of the organic electroluminescence illuminating device shown in FIG. 1 which is taken along an A-A line of FIG. 1.
  • FIG. 3 is a sectional view which shows an embodiment of a sensor element manufactured by applying the method of manufacturing the electronic device of the present invention.
  • FIG. 4 is a vertical sectional view to illustrate the method of manufacturing the organic electroluminescence illuminating device shown in FIGs. 1 and 2 or the sensor element shown in FIG. 3 (method of manufacturing the electronic device of the present invention).
  • organic electroluminescence illuminating device organic EL illuminating device
  • sensor element a sensor element
  • FIG. 1 is a plan view which shows an embodiment of the organic electroluminescence illuminating device manufactured by applying the method of manufacturing the electronic device of the present invention.
  • FIG. 2 is a sectional view of the organic electroluminescence illuminating device shown in FIG. 1 which is taken along an A-A line of FIG. 1.
  • the front side of paper in FIG. 1 will be referred to as "upper”
  • the back side of paper in FIG. 1 will be referred to as "lower”
  • the upper side in FIG. 2 will be referred to as "upper”
  • the lower side in FIG. 2 will be referred to as "lower”.
  • An organic EL illuminating device 1 shown in FIGs. 1 and 2 includes a resin film (electronic element formation layer) A formed of the resin composition of the present invention, a plurality of light emitting elements C and a sealing portion B.
  • a case, in which a closed space is formed is constituted from the resin film A and the sealing portion B, and the light emitting elements C are provided inside the closed space of the case.
  • each of the light emitting elements C has a square shape in a planar view thereof.
  • the nine light emitting elements C in the closed space are provided on the resin film A so as to be arranged at regular intervals in a reticular pattern (in a matrix pattern of 3 x 3).
  • the organic EL illuminating device 1 having such a configuration can be considered as an illuminating device having a structure for extracting light emitted from the light emitting elements C from a side of the resin film A (through the resin film A).
  • the plurality of light emitting elements C are provided on the resin film (electronic element formation layer) A so as to form the reticular pattern.
  • each of the light emitting elements C includes an anode 302, a cathode 306, a hole transport layer 303, an emission layer 304 and an electron transport layer 305.
  • the anode 302 and the cathode 306 are provided so as to face each other. Further, the hole transport layer 303, the emission layer 304 and the electron transport layer 305 are laminated in this order from the anode 302 between the anode 302 and the cathode 306.
  • the light emitted from the light emitting elements C passes through the resin film A and then is extracted outside the organic EL illuminating device 1. Namely, the light emitted from the light emitting elements C transmits out to the organic EL illuminating device 1 through the resin film A and then reaches to a targeted object. In this way, the targeted object is illuminated with the light.
  • the organic EL illuminating device 1 capable of emitting predetermined color.
  • FIG. 3 is a sectional view which shows an embodiment of the sensor element manufactured by applying the method of manufacturing the electronic device of the present invention.
  • the upper side in FIG. 3 will be referred to as "upper”
  • the lower side in FIG. 3 will be referred to as "lower”.
  • the sensor element of the present invention is, for example, a sensor element that can be used in an input device.
  • the sensor element of the present invention is a sensor element including the resin film (electronic element formation layer) A formed of the resin composition of the present.
  • the sensor element of the present invention is a sensor element formed on the resin film A on the base member 500.
  • the sensor element of the present invention is a sensor element that can be peeled off from the base member 500.
  • Examples of the sensor element of the present invention includes an optical sensor element for capturing an image, an electromagnetic sensor element for sensing an electromagnetic wave, a radiation sensor element for sensing radiation such as X-rays, a magnetic sensor element for sensing a magnetic field, a capacitive sensor element for sensing a change of capacitance charge, a pressure sensor element for sensing a change of pressure, a touch sensor element and a piezoelectric sensor element.
  • Examples of the input device using the sensor element of the present invention includes a radiation (X-rays) imaging device using the radiation (X-rays) sensor element, a visible-light imaging device using the optical sensor element, a magnetic sensing device using the magnetic sensor element, a touch panel using the touch sensor element or the pressure sensor element, a finger authenticating device using the optical sensor element and a light emitting device using the piezoelectric sensor.
  • the input device using the sensor element of the present invention may further have a function of an output device such as a displaying function and the like.
  • an optical sensor element including a photodiode will be described as one example of the sensor element of the present invention.
  • a sensor element 10 shown in FIG. 3 includes the resin film (electronic element formation layer) A formed of the resin composition of the present invention and a plurality of pixel circuits 11 provided on the resin film A.
  • each of the pixel circuits 11 includes a photodiode (photoelectric conversion element) 11A and a thin-film transistor (TFT) 11B serving as a driver element for the photodiode 11A.
  • TFT thin-film transistor
  • a gate insulating film 21 is provided on the resin film A.
  • the gate insulating film 21 is constituted of a single layer film including any one of a silicon oxide (SiO 2 ) film, a silicon oxynitride (SiON) film and a silicon nitride (SiN) film; or a laminated film including two of more of these films.
  • a first interlayer insulating film 12A is provided on the gate insulating film 21, a first interlayer insulating film 12A is provided on the gate insulating film 21, a first interlayer insulating film 12A is provided.
  • the first interlayer insulating film 12 A is constituted of a silicon oxide film, a silicon nitride film or the like. This first interlayer insulating film 12A can also serve as a protective film (passivation film) to cover the top of the thin-film transistor 11B described below.
  • the photodiode 11A is formed on a selective region of the resin film A through the gate insulating film 21 and the first interlayer insulating film 12A.
  • the photodiode 11A includes a lower electrode 24 formed on the first interlayer insulating film 12A, a n-type semiconductor layer 25N, an i-type semiconductor layer 25I, a p-type semiconductor layer 25P, an upper electrode 26 and a wiring layer 27.
  • the lower electrode 24, the n-type semiconductor layer 25N, the i-type semiconductor layer 25I, the p-type semiconductor layer 25P, the upper electrode 26 and the wiring layer 27 are laminated from the side of the first interlayer insulating film 12A in this order.
  • the upper electrode 26 serves as an electrode for supplying, for example, a reference potential (bias potential) to a photoelectric conversion layer during a photoelectric conversion.
  • the photoelectric conversion layer is constituted of the n-type semiconductor layer 25N, the i-type semiconductor layer 25I and the p-type semiconductor layer 25P.
  • the upper electrode 26 is connected to the wiring layer 27 serving as a power supply wiring for supplying the reference potential.
  • This upper electrode 26 is constituted of a transparent conductive film of ITO (indium tin oxide) or the like.
  • the thin-film transistor 11B is constituted of, for example, a field effect transistor (FET).
  • the thin-film transistor 11B includes a gate electrode 20, a gate insulating film 21, a semiconductor film 22, a source electrode 23S and a drain electrode 23D.
  • the gate electrode 20 is formed of titanium (Ti), Al, Mo, tungsten (W), chromium (Cr) or the like and formed on the resin film A.
  • the gate insulating film 21 is formed on the gate electrode 20.
  • the semiconductor layer 22 has a channel region and is formed on the gate insulating film 21.
  • the source electrode 23S and the drain electrode 23D are formed on the semiconductor film 22. In this embodiment, the drain electrode 23D is connected to the lower electrode 24 of the photodiode and the source electrode 23S is connected to a relay electrode 28 of the sensor element 10.
  • a second interlayer insulating film 12B, a first flattened film 13A, a protective film 14 and a second flattened film 13B are laminated on the photodiode 11A and the thin-film transistor 11B in this order. Further, an opening 3 is formed on the first flattened film 13A so as to correspond to the vicinity of the selective region on which the photodiode 11A is formed.
  • the light transmitting from outside into the sensor element 10 passes through the resin film A and reaches to the photodiodes 11A. As a result, it is possible to sensor the light transmitting from outside into the sensor element 10.
  • the organic EL illuminating device 1 having the configuration as described above or the sensor element 10 having the configuration as described above is manufactured by, for example, using the resin composition of the present invention as follows. That is, the organic EL illuminating device 1 or the sensor element 10 can be manufactured by using the method of manufacturing the electronic device of the present invention.
  • FIG. 4 is a vertical sectional view to illustrate the method of manufacturing the organic electroluminescence illuminating device shown in FIGs. 1 and 2 or the sensor element shown in FIG. 3 (method of manufacturing the electronic device of the present invention).
  • the upper side in FIG. 4 will be referred to as "upper”
  • the lower side in FIG. 4 will be referred to as "lower”.
  • the substrate (substrate of the present invention) includes a plate-like base member 500 having a first surface and a second surface opposite to the first surface; and the resin film (electronic element formation layer) A.
  • the resin film A is provided at a side of the first surface of the base member 500.
  • the base member 500 having the first surface and the second surface, and having light transparency is prepared.
  • glass, a metal, silicone, a resin or the like is used as a constituent material for the base member 500. These materials may be used alone or in combination of two or more as appropriate.
  • the resin film A is formed on the first surface (one surface) of the base member 500.
  • the substrate including the base member 500 and the resin film A laminated composite material in FIG. 4 is obtained.
  • the resin composition of the present invention is used to form the resin film A.
  • the resin composition of the present invention contains a polymer and a solvent dissolving the polymer.
  • the resin film (electronic element formation layer) A containing the polymer is formed, wherein when refractive indexes (wavelength: 589.3 nm) of the resin film A along two perpendicular in-plane directions thereof are respectively defined as "Nx" and "Ny” and a refractive index (wavelength: 589.3 nm) of the resin film A along a thickness direction thereof is defined as "Nz", Nx, Ny and Nz satisfy a relationship of "(Nx+Ny)/2-Nz" > 0.01.
  • Examples of the method of forming the resin film A include a method in which the resin composition (varnish) is supplied on the first surface of the base member 500 by using a die coat method as shown in FIG. 4(A), and thereafter the resin composition is dried and heated (referred to FIG. 4(B)).
  • a method of supplying the resin composition on the first surface of the base member 500 is not limited to the die coat method.
  • Various kinds of liquid-phase film formation methods such as an ink jet method, a spin coat method, a bar coat method, a roll coat method, a wire bar coat method and a dip coat method can be used as such a method.
  • the resin composition of the present invention contains the polymer and the solvent dissolving the polymer.
  • a heating treatment is carried out to the resin film A under the temperature in the range from approximately +40 degrees Celsius of a boiling point of the solvent to approximately +100 degrees Celsius of the boiling point of the solvent, more preferably in the range from approximately +60 degrees Celsius of the boiling point of the solvent to approximately +80 degrees Celsius of the boiling point of the solvent, even more preferably at approximately +70 degrees Celsius of the boiling point of the solvent.
  • the temperature of the heating treatment in this step [1-B] is in the range of approximately 200 to 250 degrees Celsius.
  • a heating time (duration) in this step [1-B] is in the range of more than approximately 1 minute but less than approximately 30 minutes.
  • this step [1-B], in which the resin film A is formed on the base member 500, may include a step of curing the resin film A after drying and heating the resin composition.
  • a temperature of curing the resin film A depends on performance of a heating apparatus, but is preferably in the range of 220 to 420 degrees Celsius, more preferably in the range of 280 to 400 degrees Celsius, further more preferably in the range of 330 to 370 degrees Celsius, and even more preferably in the range of 340 to 370 degrees Celsius.
  • a time (duration) of curing the resin film A is in the range of 5 to 300 minutes or 30 to 240 minutes.
  • the nine (plurality of) light emitting elements (electronic elements) C are formed on the resin film A provided in the obtained substrate so as to form the reticular pattern.
  • the anodes (individual electrodes) 302 are formed on the resin film A in the reticular pattern.
  • each of the hole transport layers 303 is formed on the corresponding anode 302 so as to cover it.
  • each of the emission layers 304 is formed on the corresponding hole transport layer 303 so as to cover it.
  • each of the electron transport layers 305 is formed on the corresponding emission layer 304 so as to cover it.
  • each of the cathodes 306 is formed on the corresponding electron transport layer 305 so as to cover it.
  • each layer formed in the steps [2-A] to [2-E] can be formed by using a gas-phase film formation method such as a sputter method, a vacuum deposition method and a CVD method or a liquid-phase film formation method such as an ink jet method, a spin coat method and a casting method.
  • a gas-phase film formation method such as a sputter method, a vacuum deposition method and a CVD method
  • a liquid-phase film formation method such as an ink jet method, a spin coat method and a casting method.
  • the sealing portion B is prepared. Then, the sealing portion B is provided on the resin film A so as to cover each of the light emitting elements C. In this way, the closed space of the case is formed by the resin film A and the sealing portion B. In the closed space, the light emitting elements C are sealed with the resin film A and the sealing portion B.
  • the sealing with the resin film A and the sealing portion B as described above can be performed by interposing an adhesive between the resin film A and the sealing portion B and then drying the adhesive.
  • the organic EL illuminating device 1 including the resin film A, the light emitting elements C and the sealing portion B is formed on the base member 500 (referred to FIG. 4(C)).
  • the resin film (electronic element formation layer) A is irradiated with light from a side of the base member 500.
  • the resin film A is peeled off from the first surface of the base member 500 in an interface between the base member 500 and the resin film A.
  • the organic EL illuminating device (electronic device) 1 is separated from the base member 500 (referred to FIG. 4(D)).
  • the light to be irradiated to the resin film A is not particularly limited to a specific kind as long as the resin film A can be peeled off from the first surface of the base member 500 in the interface between the base member 500 and the resin film A by irradiating the resin film A with the light.
  • the light is preferably laser light. By using the laser light, it is possible to reliably peel off the resin film A from the base member 500 in the interface between the base member 500 and the resin film A.
  • examples of the laser light include an excimer laser of a pulse oscillator type or a continuous emission type, a carbon dioxide laser, a YAG laser and a YVO 4 laser.
  • the substrate (substrate of the present invention) including the base member 500 and the resin film (electronic element formation layer) A formed on the base member 500 is prepared. Since a step for forming the resin film A on the base member 500 is identical to that of the method of manufacturing the organic electroluminescence illuminating device 1 described above, description to the step for forming the resin film A on the base member 500 is omitted here (referred to FIGs. 4(A) and 4(B)).
  • the sensor element 10 described above is formed on the resin film A provided in the obtained substrate.
  • a method for forming the sensor element 10 on the resin film A is not particularly limited to a specific method. The formation of the sensor element 10 on the resin film A can be carried out with a known suitable method appropriately selected or modified for manufacturing a desired sensor element.
  • the sensor element 10 including the resin film A, the pixel circuits 11 is formed on the base member 500 (referred to FIG. 4(C)).
  • the resin film (electronic element formation layer) A is irradiated with the light from the side of the base member 500 to peel off the sensor element (electronic device) 10 from the base member 500 (referred to FIG. 4(D)). Since a step for peeling off the sensor element 10 from the base member 500 is identical to the above-mentioned step for peeling off the organic EL illuminating device 1 from the base member 500, description to the step for peeling off the sensor element 10 from the base member 500 is omitted here.
  • the organic EL illuminating device 1 having the configuration as described above, it is required that the light emitted from the light emitting elements C should pass through the resin film A with high efficiency. However, the emitted light having a large incidence angle with respect to the resin film A is totally reflected. This total reflection of the light in the organic EL illuminating device 1 causes a problem in that light extraction efficiency of the organic EL illuminating device 1 tends to become low.
  • the sensor element 10 having the configuration as described above, it is required that the light transmitting from outside into the sensor element 10 should pass through the resin film A with high efficiency. However, the emitted light having a large incidence angle with respect to the resin film A is totally reflected. This total reflection of the light in the sensor element 10 causes a problem in that light introduction efficiency of the sensor element 10 tends to become low.
  • the present inventors focused on a value of Rth (thickness direction phase difference) and carefully reviewed a relationship between the value of Rth (thickness direction phase difference) and the total reflection of the light incident onto the resin film A.
  • the present inventors have found that it is possible to solve the above problem by setting a value of "(Nx+Ny)/2-Nz" included in the above expression (1) (i.e., an out-of-plane birefringence (dn out )) to be more than 0.01, that is, by satisfying the relationship of "(Nx+Ny)/2-Nz" > 0.01.
  • the present inventors have found that even if the light emitted from the light emitting elements C has the large incidence angle with respect to the resin film A, it is possible to appropriately suppress or prevent the light from being totally reflected by setting the value of "(Nx+Ny)/2-Nz" to satisfy the above relationship, and thereby improving the light extraction efficiency of the above-mentioned organic EL illuminating device 1 and the light introduction efficiency of the sensor element 10. Based on such a finding, the present inventors have completed the present invention.
  • the resin film A having the configuration as described above can be formed by using the resin composition of the present invention which contains the polymer and the solvent dissolving the polymer.
  • the resin composition of the present invention which contains the polymer and the solvent dissolving the polymer.
  • the polymer is used as a main material for the resin film (electronic element formation layer) A constituted of the resin composition.
  • the polymer is contained in the resin composition in order to form the resin film A so as to satisfy the relationship of "(Nx+Ny)/2-Nz" > 0.01.
  • the polymer is not particularly limited to a specific kind as long as the resin film A can satisfy the relationship of "(Nx+Ny)/2-Nz" > 0.01.
  • the polymer include an aromatic polyamide, an aromatic polyimide (and/or an aromatic polyamic acid), an alicyclic polyamide and an alicyclic polyimide. These polymers may be used alone or in combination of two or more. Among them, the aromatic polyamide or the aromatic polyimide (and/or an aromatic polyamic acid) is preferably used as the polymer.
  • the aromatic polyamide or the aromatic polyimide is preferably used as the polymer.
  • the aromatic polyamide is a wholly aromatic polyamide.
  • the wholly aromatic polyamide refers to that all of amide bonds included in a main chain of the aromatic polyamide are bonded to each other through the aromatic group (aromatic ring) without bonding to each other through a chain or cyclic aliphatic group.
  • the aromatic polyamide contains a rigid structure (rigid component) preferably in an amount of 60 mol% or more, and more preferably in an amount of 95 mol% or more.
  • the rigid structure refers to that a monomer component (repeating unit) constituting the aromatic polyamide has linearity in a main structure (skeleton) thereof.
  • the rigid structure is the repeating unit represented by the general formula (I), the general formula (VI) or the general formula (VII).
  • Ar 1 examples include a structure derived from terephthaloyl dichloride (TPC) and concrete examples of Ar 2 include a structure derived from 4,4'-diamino-2,2'-bistrifluoromethyl benzidine (PFMB).
  • TPC terephthaloyl dichloride
  • PFMB 4,4'-diamino-2,2'-bistrifluoromethyl benzidine
  • a number average molecular weight (Mn) of the aromatic polyamide is preferably 6.0 x 10 4 or more, more preferably 6.5 x 10 4 or more, more preferably 7.0 x 10 4 or more, further more preferably 7.5 x 10 4 or more and even more preferably 8.0 x 10 4 or more. Further, the number average molecular weight of the aromatic polyamide is preferably 1.0 x 10 6 or less, more preferably 8.0 x 10 5 or less, further more preferably 6.0 x 10 5 or less, and even more preferably 4.0 x 10 5 or less.
  • the resin film A By using the aromatic polyamide satisfying the above condition, it is possible for the resin film A to reliably provide a function as a foundation layer in the organic EL illuminating device 1 or the sensor element 10. Further, it is possible to reliably set the value of "(Nx+Ny)/2-Nz" of the resin film A to fall within the range described above.
  • the number average molecular weight (Mn) and a weight average molecular weight (Mw) of the aromatic polyamide are measured with a Gel Permeation Chromatography. Specifically, they are measured by using the method in the following Examples.
  • molecular weight distribution of the aromatic polyamide is preferably 5.0 or less, more preferably 4.0 or less, more preferably 3.0 or less, further more preferably 2.8 or less, further more preferably 2.6 or less, and even more preferably 2.4 or less. Further, the molecular weight distribution of the aromatic polyamide is preferably 2.0 or more.
  • the aromatic polyimide and the aromatic polyamic acid are respectively a wholly aromatic polyimide and a wholly aromatic polyamic acid.
  • the wholly aromatic polyimide and/or the wholly aromatic polyamic acid as the polymer for the resin film A, it is possible to reliably set the value of "(Nx+Ny)/2-Nz" of the formed resin film A to fall within the above range.
  • the wholly aromatic polyimide and the wholly aromatic polyamic acid refer to that all of imide bonds included in a main chain of the aromatic polyimide or the aromatic polyamic acid are bonded to each other through the aromatic group (aromatic ring) without bonding to each other through a chain or cyclic aliphatic group.
  • a number average molecular weight (Mn) of each of the aromatic polyimide and the aromatic polyamic acid is preferably 6.0 x 10 4 or more, more preferably 6.5 x 10 4 or more, more preferably 7.0 x 10 4 or more, further more preferably 7.5 x 10 4 or more, and even more preferably 8.0 x 10 4 or more.
  • the number average molecular weight of each of the aromatic polyimide and the aromatic polyamic acid is preferably 1.0 x 10 6 or less, more preferably 8.0 x 10 5 or less, further more preferably 6.0 x 10 5 or less, and even more preferably 4.0 x 10 5 or less.
  • the resin film A By using the aromatic polyimide and/or the aromatic polyamic acid satisfying the above condition, it is possible for the resin film A to reliably provide a function as a foundation layer in the organic EL display device 1 or the sensor element 10. Further, it is possible to reliably set the value of "(Nx+Ny)/2-Nz" of the resin film A to fall within the range described above.
  • the number average molecular weight (Mn) and a weight average molecular weight (Mw) of each of the aromatic polyimide and the aromatic polyamic acid are measured with a Gel Permeation Chromatography. Specifically, they are measured by using the method in the following Examples.
  • molecular weight distribution of each of the aromatic polyimide and the aromatic polyamic acid is preferably 5.0 or less, more preferably 4.0 or less, more preferably 3.0 or less, further more preferably 2.8 or less, further more preferably 2.6 or less, and even more preferably 2.4 or less. Further, the molecular weight distribution of each of the aromatic polyimide and the aromatic polyamic acid is preferably 2.0 or more.
  • each of the aromatic polyamide and the aromatic polyimide (and/or the aromatic polyamic acid) is obtained through a step of re-precipitating it after each of the aromatic polyamide and the aromatic polyimide (and/or the aromatic polyamic acid) is synthesized.
  • the aromatic polyamide or the aromatic polyimide (and/or the aromatic polyamic acid) obtained through the step of re-precipitation it is possible for the resin film A to reliably provide the function as the foundation layer in the organic EL illuminating device 1 or the sensor element 10. Further, it is possible to reliably set the value of "(Nx+Ny)/2-Nz" of the resin film A to fall within the range described above.
  • one or both of a terminal -COOH group and a terminal -NH 2 group of the polymer are end-capped.
  • the end-capping of the terminals is preferable from the point of view of enhancement of heat resistance property of the film (namely, resin film A).
  • the terminals of the polymer can be end-capped by either being reacted with benzoyl chloride in the case where each terminal thereof is -NH 2, or by being reacted with aniline in the case where each terminal thereof is -COOH.
  • the method of end-capping is not limited to this method.
  • the resin composition may contain an inorganic filler in addition to the polymer in an amount such that the resin film A is not broken when the resin film A is peeled off from the base member 500 in the above mentioned method of manufacturing the organic EL illuminating device 1 or the sensor element 10.
  • an inorganic filler in addition to the polymer in an amount such that the resin film A is not broken when the resin film A is peeled off from the base member 500 in the above mentioned method of manufacturing the organic EL illuminating device 1 or the sensor element 10.
  • This inorganic filler is not particularly limited to a specific kind, but is preferably formed into a particle shape or is preferably constituted of a fiber.
  • a constituent material for the inorganic filler is not particularly limited to a specific material as long as it is an inorganic material.
  • examples of such a constituent material for the inorganic filler include a metal oxide such as silica, alumina and a titanium oxide; a mineral such as mica; glass; and a mixture of them. These materials may be used singly or in combination of two or more of them.
  • examples of a kind of glass include E glass, C glass, A glass, S glass, D glass, NE glass, T glass, low permittivity glass and high permittivity glass.
  • an average fiber diameter of the fiber is preferably in the range of 1 to 1000 nm.
  • the fiber may be formed of single fibers.
  • the single fibers included therein are arranged without paralleling with each other and to be sufficiently spaced apart from each other so that a liquid precursor of a matrix resin enters among the single fibers.
  • the average fiber diameter corresponds to an average diameter of the single fibers.
  • the fiber may constitute one line of thread in which a plurality of single fibers is bundled.
  • the average fiber diameter is defined as an average value of a diameter of the one line of thread.
  • the average fiber diameter is measured by the method in the Examples. Further, from a point of view of improving the transparency of the film, the average fiber diameter of the fiber is preferably small.
  • a refractive index of the polymer included in the resin composition (polymer solution) and a refractive index of the inorganic filler are preferably close to each other.
  • a difference of refractive indexes of a material to be used as the fiber and the polymer in the wavelength of 589 nm is 0.01 or less, it becomes possible to form a film having high transparency regardless of the fiber diameter.
  • examples of a method of measuring the average fiber diameter include a method of observing the fiber with an electronic microscope.
  • an average particle size of the particles is preferably in the range of 1 to 1000 nm.
  • the average particle size of the particles refers to a diameter corresponding to an average projection circle. Specifically, the average particle size of the particles is measured by the method in the Examples.
  • a shape of each of the particles is not particularly limited to a specific shape.
  • examples of such a shape include a spherical shape, a perfect spherical shape, a rod shape, a plate shape and a combined shape of them.
  • the average particle size of the particles is preferably small.
  • the refractive index of the polymer included in the resin composition (polymer solution) and the refractive index of the inorganic filler are preferably close to each other. This makes it possible to further improve the transparency of the resin film A. For example, in the case where a difference of refractive indexes of the material to be used as the particles and the polymer in the wavelength of 589 nm is 0.01 or less, it becomes possible to form the resin film A having high transparency regardless of the particle size.
  • examples of a method of measuring the average particle size include a method of measuring the average particle size with a particle size analyzer.
  • a ratio of the inorganic filler in a solid matter contained in the resin composition (polymer solution) is not particularly limited to a specific value, but is preferably in the range of 1 to 50 volume%, more preferably in the range of 2 to 40 volume%, and even more preferably in the range of 3 to 30 volume%.
  • a ratio of the polymer in the solid matter contained in the resin composition (polymer solution) is not particularly limited to a specific value, but is preferably in the range of 50 to 99 volume%, more preferably in the range of 60 to 98 volume%, and even more preferably in the range of 70 to 97 volume%.
  • solid matter refers to a component other than the solvent contained in the resin composition in this specification.
  • a volume conversion of the solid matter, a volume conversion of the inorganic filler and/or a volume conversion of the polymer can be calculated from each component usage at the time of preparing the polymer solution. Alternatively, they can be also calculated by removing the solvent from the polymer solution.
  • the resin composition may contain an antioxidant, an ultraviolet absorbing agent, a dye, a pigment, a filler such as another inorganic filler and the like, if needed, in the degrees to which the function of the foundation layer in the organic EL illuminating device 1 or the sensor element 10 is not impaired and the resin film A can satisfy the relationship of "(Nx+Ny)/2-Nz" > 0.01.
  • a ratio of the solid matter contained in the resin composition is preferably 1 volume% or more, more preferably 2 volume% or more and even more preferably 3 volume% or more. Further, the ratio of the solid matter contained in the resin composition is preferably 40 volume% or less, more preferably 30 volume% or less and even more preferably 20 volume% or less.
  • the solvent in terms of enhancement of solubility of the polymer to the solvent, is preferably a polar solvent or a mixed solvent containing one or more polar solvents.
  • the solvent in terms of enhancement of solubility of the polymer to the solvent and enhancement of the adhesion between the resin film A and the base member 500, is preferably cresol; N,N-dimethyl acetamide (DMAc); N-methyl-2-pyrrolidinone (NMP); dimethyl sulfoxide (DMSO); 1,3-dimethyl-imidazolidinone (DMI); N,N-dimethyl formamide (DMF); butyl cellosolve (BCS); gamma-butyrolactone (GBL) or a mixed solvent containing at least one of cresol, N,N-dimethyl acetamide (DMAc), N-methyl-2-pyrrolidinone (NMP), dimethyl sulfoxide (DM
  • the resin composition as described above can be manufactured by, for example, using a manufacturing method including the following steps (a) to (d).
  • the resin composition of the present invention is not limited to a resin composition manufactured by using the following manufacturing method.
  • the step (a) is carried out for obtaining a mixture by dissolving at least one aromatic diamine in a solvent.
  • the step (b) is carried out for obtaining free hydrochloric acid and a polyamide solution by reacting the at least one aromatic diamine with at least one aromatic dicarboxylic acid dichloride in the mixture.
  • the step (c) is carried out for removing the free hydrochloric acid in the mixture by reaction with a trapping reagent.
  • the step (d) is carried out for adding the inorganic filler to the mixture.
  • examples of the aromatic dicarboxylic acid dichloride as described above include the following compounds.
  • TPC Terephthaloyl dichloride
  • IPC Isophthaloyl dichloride
  • examples of the aromatic diamine as described above include the following compounds.
  • the diaminodiphenyl sulfone may be 4,4'-diaminodiphenyl sulfone as expressed by the above formula, 3,3'-diaminodiphenyl sulfone or 2,2'-diaminodiphenyl sulfone.
  • the aromatic polyamide is prepared via a condensation polymerization in a solvent, where hydrochloric acid generated in the reaction is trapped by a trapping reagent such as propylene oxide (PrO).
  • a trapping reagent such as propylene oxide (PrO).
  • reaction of hydrochloric acid with the trapping reagent yields a volatile product.
  • the trapping reagent in terms of use of the polyamide solution in the method, is propylene oxide.
  • the trapping reagent is added to the mixture before or during the step (c). By adding the trapping reagent before or during the step (c), it is possible to reduce a degree of viscosity and generation of condensation in the mixture after the step (c), and thereby, improving productivity of the polyamide solution. These effects become especially remarkable when the trapping reagent is an organic reagent such as propylene oxide.
  • the method further includes a step of end-capping one or both of the terminal -COOH group and the terminal -NH 2 group of the aromatic polyamide.
  • the terminals of the aromatic polyamide can be end-capped by either being reacted with benzoyl chloride in the case where each terminal thereof is -NH 2, or by being reacted with aniline in the case where each terminal thereof is -COOH.
  • the method of end-capping is not limited to this method.
  • the aromatic polyamide in terms of use of the polyamide solution in the method, is first isolated from the polyamide solution by precipitation and re-dissolution in a solvent prior to the addition of the inorganic filler.
  • a re-precipitation can be carried out by a known method.
  • the re-precipitation can be carried out by precipitating the aromatic polyamide by adding it to, for example, methanol, ethanol, isopropyl alcohol or the like; washing the aromatic polyamide; and re-dissolving the aromatic polyamide to the solvent.
  • the solvent described above can be used as a solvent for producing the polymer solution.
  • the polyamide solution in terms of use of the polyamide solution in the method, is produced so that the solution contains no inorganic salts.
  • the resin composition can be manufactured.
  • the resin film A formed by using the resin composition obtained through the steps described above contains the polymer.
  • the resin film A preferably satisfies the relationship of "(Nx+Ny)/2-Nz" > 0.02, more preferably satisfies the relationship of "(Nx+Ny)/2-Nz” > 0.03, and even more preferably satisfies the relationship of "(Nx+Ny)/2-Nz” > 0.05.
  • a total light transmittance of the resin film A, which is formed by using the resin composition, in a sodium line (D line) is set to preferably 60% or more, more preferably 65% or more, further more preferably 70% or more, and even more preferably 80% or more.
  • the resin film A can have excellent light extraction efficiency.
  • the resin film A contains the polymer, it is possible to easily obtain the resin film A having the total light transmittance falling within such an above range.
  • a coefficient of thermal expansion (CTE) of the resin film A is preferably 100.0 ppm/K or less, more preferably 80 ppm/K or less, further more preferably 60 ppm/K or less, and even more preferably 40 ppm/K or less.
  • the CTE of the resin film A can be obtained with a thermal mechanical analyzer (TMA).
  • TMA thermal mechanical analyzer
  • an amount of the inorganic filler contained in the resin film A is preferably in the range of 1 to 50 volume%, more preferably in the range of 2 to 40 volume%, and even more preferably in the range of 3 to 30 volume%, with respect to the volume of the resin film A.
  • an amount of the inorganic filler contained in the resin film A is preferably in the range of 1 to 50 volume%, more preferably in the range of 2 to 40 volume%, and even more preferably in the range of 3 to 30 volume%, with respect to the volume of the resin film A.
  • an average thickness of the resin film A is not particularly limited a specific value, but is preferably 50 micrometers or less, more preferably 30 micrometers or less, and even more preferably 20 micrometers or less.
  • the average thickness is preferably 1 micrometer or more, more preferably 2 micrometers or more, and even more preferably 3 micrometers or more.
  • the shape of the light emitting element C (light emitting area) in the planar view thereof is the square shape in this embodiment, but is not limited thereto. It may be an arbitrary shape such as a polygonal shape (e.g., a triangular shape, a hexagonal shape) and a round shape (e.g., an exact circular shape, an elliptical shape).
  • a polygonal shape e.g., a triangular shape, a hexagonal shape
  • a round shape e.g., an exact circular shape, an elliptical shape
  • the present invention is not limited thereto.
  • each component may be replaced with an arbitrary one capable of providing the same function.
  • an arbitrary component may be added to them.
  • one or more steps may be further added for the arbitrary purpose.
  • the method of manufacturing the electronic device of the present invention is used to manufacture the organic EL illuminating device including the organic EL element as the light emitting element and the sensor element including the photodiode.
  • the method of manufacturing the electronic device of the present invention is not limited thereto.
  • the method of manufacturing the electronic device of the present invention may be used to not only manufacture other illuminating devices such as a light emitting diode illuminating device including a light emitting diode as the light emitting element, but also manufacture various kinds of electronic devices such as an input device including a sensor element as the electronic element, a display device including a display element as the electronic element, an optical device including an optical element as the electronic element and a solar cell including a photoelectric conversion element as the electronic element.
  • other illuminating devices such as a light emitting diode illuminating device including a light emitting diode as the light emitting element
  • various kinds of electronic devices such as an input device including a sensor element as the electronic element, a display device including a display element as the electronic element, an optical device including an optical element as the electronic element and a solar cell including a photoelectric conversion element as the electronic element.
  • the resin composition was applied onto a flat glass substrate (10 cm x 10 cm, "EAGLE XG” produced by Corning Inc., U.S.A.) with a spin coat method.
  • the resin composition was dried at a temperature of 60 degrees Celsius for 30 minutes or more to obtain a film. Thereafter, the temperature was raised from 60 degrees Celsius to 350 degrees Celsius. The film was subjected to a curing treatment by keeping the temperature of 350 degrees Celsius for 30 minutes under vacuum atmosphere or inert atmosphere. By doing so, a resin film was formed on the glass substrate.
  • a thickness of the resin film was 23 micrometers.
  • Example 2> A resin composition of the Example 2 was prepared in the same manner as the Example 1, except that the combination of TPC and IPC was changed to a combination of TPC (0.955 g, 0.00450 mol) and IPC (1.166 g, 0.00550 mol) as the dichloride component used in the step ⁇ 3>. Thereafter, a resin film of the Example 2 was formed on the glass substrate by using the resin composition in the same manner as the Example 1.
  • a thickness of the obtained resin film was 25 micrometers.
  • ⁇ Comparative Example> A resin composition of the Comparative Example was prepared in the same manner as the Example 1, except that the combination of TPC and IPC was changed to a combination of TPC (0.212 g, 0.00100 mol) and IPC (1.908 g, 0.00900 mol) as the dichloride component used in the step ⁇ 3>. Thereafter, a resin film of the Comparative Example was formed on the glass substrate by using the resin composition in the same manner as the Example 1.
  • a thickness of the obtained resin film was 22 micrometers.
  • Total Light Transmittance A total light transmittance of the resin film in a D line (sodium line) was measured by using a haze meter ("NDH-2000" produced by NIPPON DENSHOKU INDUSTRIES CO., LTD.).
  • a value of "(Nx+Ny)/2-Nz" of the resin film was obtained as follows. First, a phase difference of the resin film between 0 degrees and 40 degrees was measured by using a phase difference measuring equipment ("KOBRA-21 ADH” produced by Oji Scientific Instruments) in a wavelength dispersion measuring mode (in which light having a wavelength of 479.2 nm, light having a wavelength of 545.4 nm, light having a wavelength of 630.3 nm and light having a wavelength of 748.9 nm were used). Next, a phase difference of the resin film between 0 degrees and 40 degrees in the wavelength of 550 nm was calculated by using a Sellmeier's expression. The value of "(Nx+Ny)/2-Nz" in the wavelength of 550 nm was obtained based on the phase difference value and a refractive index of the resin film.
  • each of the resin films obtained in the Examples has high total light transmittance.

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Abstract

Provided are a resin composition and a substrate that are capable of being used for manufacturing an electronic device having excellent light extraction efficiency. The resin composition contains a polymer and a solvent dissolving the polymer. The resin composition is used to form a layer, and when refractive indexes of the layer along two perpendicular in-plane directions thereof are respectively defined as "Nx" and "Ny" and a refractive index of the layer along a thickness direction thereof is defined as "Nz", Nx, Ny and Nz satisfy a relationship of "(Nx+Ny)/2-Nz" > 0.01. Further, a method of manufacturing the electronic device by using such a substrate, and the electronic device are also provided.

Description

RESIN COMPOSITION, SUBSTRATE, METHOD OF MANUFACTURING ELECTRONIC DEVICE AND ELECTRONIC DEVICES
The present invention relates to a resin composition, a substrate, a method of manufacturing an electronic device and an electronic device.
In an illuminating device (electronic device) such as an organic EL (electroluminescence) illuminating device and a light emitting diode illuminating device, it is required that a substrate used therein should have transparency. Therefore, as such a substrate used for the illuminating device, it is known to use a substrate formed of a transparent resin material such as polyethylene terephthalate and polycarbonate (for example, the patent document 1).
In such an illuminating device, when light is emitted from a light emitting element provided in the illuminating device, the emitted light passes through the transparent substrate and then is extracted outside the illuminating device. Namely, the light emitted from the light emitting element transmits out to the device through the transparent substrate and then reaches to a targeted object. In this way, the targeted object is illuminated with the light. Therefore, it is required that the emitted light should pass through the transparent substrate with high efficiency. Namely, it is required that the illuminating device should have high extraction efficiency of the light.
However, in the above illuminating device, the emitted light having a large incidence angle with respect to the substrate is totally reflected. This total reflection of the light in the illuminating device causes a problem in that the light extraction efficiency of the illuminating device tends to become low.
JP-A 2009-289460
It is an object of the present invention to provide a resin composition and a substrate that are capable of being used for manufacturing an electronic device having excellent light extraction efficiency. It is another object of the present invention to provide a method of manufacturing the electronic device using such a substrate and the electronic device.
In order to achieve the objects described above, the present invention includes the following features (1) to (19).
(1) A resin composition comprising:
a polymer; and
a solvent dissolving the polymer,
wherein the resin composition is used to form a layer, and when refractive indexes of the layer along two perpendicular in-plane directions thereof are respectively defined as "Nx" and "Ny" and a refractive index of the layer along a thickness direction thereof is defined as "Nz", Nx, Ny and Nz satisfy a relationship of "(Nx+Ny)/2-Nz" > 0.01.
(2) The resin composition according to the above (1), wherein the polymer is an aromatic polyamide.
(3) The resin composition according to the above (2), wherein the aromatic polyamide contains a rigid structure in an amount of 60 mol% or more.
(4) The resin composition according to the above (3), wherein the rigid structure is a repeating unit represented by the following general formula:
Figure JPOXMLDOC01-appb-I000001
where n represents an integer number of 1 to 4, Ar1 is represented by the following general formula (A) or (B):
Figure JPOXMLDOC01-appb-I000002
Figure JPOXMLDOC01-appb-I000003
(where p=4; each of R1, R4 and R5 is selected from the group consisting of a hydrogen atom, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom and an iodine atom), an alkyl group, a substituted alkyl group such as a halogenated alkyl group, a nitro group, a cyano group, a thioalkyl group, an alkoxy group, a substituted alkoxy group such as a halogenated alkoxy group, an aryl group, a substituted aryl group such as a halogenated aryl group, an alkyl ester group, a substituted alkyl ester group, and a combination of them; and G1 is selected from the group consisting of a covalent bond, a CH2 group, a C(CH3)2 group, a C(CF3)2 group, a C(CX3)2 group (X represents a halogen atom.), a CO group, an oxygen atom, a sulfur atom, an SO2 group, an Si(CH3)2 group, a 9,9-fluorene group, a substituted 9,9-fluorene group and an OZO group (Z represents an aryl group or substituted aryl group such as a phenyl group, a biphenyl group, a perfluorobiphenyl group, a 9,9-bisphenyl fluorene group and a substituted 9,9-bisphenyl fluorene group.).), and Ar2 is represented by the following general formula (C) or (D):
Figure JPOXMLDOC01-appb-I000004
Figure JPOXMLDOC01-appb-I000005
(where p=4; each of R6, R7 and R8 is selected from the group consisting of a hydrogen atom, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom and an iodine atom), an alkyl group, a substituted alkyl group such as a halogenated alkyl group, a nitro group, a cyano group, a thioalkyl group, an alkoxy group, a substituted alkoxy group such as a halogenated alkoxy group, an aryl group, a substituted aryl group such as a halogenated aryl group, an alkyl ester group, a substituted alkyl ester group, and a combination of them; and G2 is selected from the group consisting of a covalent bond, a CH2 group, a C(CH3)2 group, a C(CF3)2 group, a C(CX3)2 group (X represents a halogen atom.), a CO group, an oxygen atom, a sulfur atom, an SO2 group, an Si(CH3)2 group, a 9,9-fluorene group, a substituted 9,9-fluorene group and an OZO group (Z represents an aryl group or substituted aryl group such as a phenyl group, a biphenyl group, a perfluorobiphenyl group, a 9,9-bisphenyl fluorene group and a substituted 9,9-bisphenyl fluorene group.).).)
(5) The resin composition according to the above (5), wherein the rigid structure contains at least one of a structure derived from 4,4'-diamino-2,2'-bistrifluoromethyl benzidine (PFMB) and a structure derived from terephthaloyl dichloride (TPC).
(6) The resin composition according to the above (2), wherein the aromatic polyamide is a wholly aromatic polyamide.
(7) The resin composition according to the above (2), wherein at least one terminal of the aromatic polyamide is end-capped.
(8) The resin composition according to the above (1), wherein a total light transmittance of the layer in a sodium line (D line) is 60% or more.
(9) The resin composition according to the above (1), wherein the resin composition further contains an inorganic filler.
(10) A substrate used for forming an electronic element thereon, comprising:
a plate-like base member having a first surface and a second surface opposite to the first surface; and
an electronic element formation layer provided at a side of the first surface of the base member, containing a polymer and configured to be capable of forming the electronic element on the electronic element formation layer,
wherein when refractive indexes of the electronic element formation layer along two perpendicular in-plane directions thereof are respectively defined as "Nx" and "Ny" and a refractive index of the electronic element formation layer along a thickness direction thereof is defined as "Nz", Nx, Ny and Nz satisfy a relationship of "(Nx+Ny)/2-Nz" > 0.01.
(11) The substrate according to the above (10), wherein a coefficient of thermal expansion (CTE) of the electronic element formation layer is 100 ppm/K or less.
(12) The substrate according to the above (10), wherein an average thickness of the electronic element formation layer is in the range of 1 to 50 micrometers.
(13) The substrate according to the above (10), wherein the electronic element is an organic EL element.
(14) A method of manufacturing an electronic device, comprising:
preparing a substrate, the substrate including,
a plate-like base member having a first surface and a second surface opposite to the first surface, and
an electronic element formation layer provided at a side of the first surface of the base member and containing a polymer,
wherein when refractive indexes of the electronic element formation layer along two perpendicular in-plane directions thereof are respectively defined as "Nx" and "Ny" and a refractive index of the electronic element formation layer along a thickness direction thereof is defined as "Nz", Nx, Ny and Nz satisfy a relationship of "(Nx+Ny)/2-Nz" > 0.01;
forming the electronic element on a surface of the electronic element formation layer opposite to the base member;
forming a cover layer so as to cover the electronic element;
irradiating the electronic element formation layer with light to thereby peel off the electronic element formation layer from the base member in an interface between the base member and the electronic element formation layer; and
separating the electronic device including the electronic element, the cover layer and the electronic element formation layer from the base member.
(15) The method according to the above (14), wherein a coefficient of thermal expansion (CTE) of the electronic element formation layer is 100 ppm/K or less.
(16) The method according to the above (14), wherein an average thickness of the electronic element formation layer is in the range of 1 to 50 micrometers.
(17) The method according to the above (14), wherein the polymer is an aromatic polyamide.
(18) The method according to the above (17), wherein the aromatic polyamide contains a rigid structure in an amount of 60 mol% or more.
(19) An electronic device manufactured by using the method defined by the above (14).
According to the present invention, it is possible to form a layer by using the resin composition containing the polymer and the solvent dissolving the polymer, wherein when refractive indexes of the layer along two perpendicular in-plane directions thereof are respectively defined as "Nx" and "Ny" and a refractive index of the layer along a thickness direction thereof is defined as "Nz", Nx, Ny and Nz satisfy a relationship of "(Nx+Ny)/2-Nz" > 0.01. This layer formed by using the resin composition is used as the electronic element formation layer (substrate) provided in the electronic device. In the electronic device, the light emitted from the light emitting element passes through the electronic element formation layer and then is extracted outside the electronic device. By using the layer as the electronic element formation layer provided in the electronic device, it is possible to improve the light extraction efficiency of the light emitted from the light emitting element and extracted outside the device.
FIG. 1 is a plan view which shows an embodiment of an organic electroluminescence illuminating device manufactured by applying a method of manufacturing an electronic device of the present invention. FIG. 2 is a sectional view of the organic electroluminescence illuminating device shown in FIG. 1 which is taken along an A-A line of FIG. 1. FIG. 3 is a sectional view which shows an embodiment of a sensor element manufactured by applying the method of manufacturing the electronic device of the present invention. FIG. 4 is a vertical sectional view to illustrate the method of manufacturing the organic electroluminescence illuminating device shown in FIGs. 1 and 2 or the sensor element shown in FIG. 3 (method of manufacturing the electronic device of the present invention).
Hereinafter, a resin composition, a substrate, a method of manufacturing an electronic device and an electronic device according to the present invention will be described in detail based on the preferred embodiments shown in the accompanying drawings.
First, prior to describing the resin composition, the substrate and the method of manufacturing the electronic device according to the present invention, description will be made on an organic electroluminescence illuminating device (organic EL illuminating device) and a sensor element, which are manufactured by using the method of manufacturing the electronic device of the present invention. Namely, the organic electroluminescence illuminating device and the sensor element will be first described as examples of the electronic device of the present invention.
<Organic EL Illuminating Device>
First, the organic electroluminescence illuminating device manufactured by applying the method of manufacturing the electronic device of the present invention will be described. FIG. 1 is a plan view which shows an embodiment of the organic electroluminescence illuminating device manufactured by applying the method of manufacturing the electronic device of the present invention. FIG. 2 is a sectional view of the organic electroluminescence illuminating device shown in FIG. 1 which is taken along an A-A line of FIG. 1. In the following description, the front side of paper in FIG. 1 will be referred to as "upper", and the back side of paper in FIG. 1 will be referred to as "lower", and the upper side in FIG. 2 will be referred to as "upper", and the lower side in FIG. 2 will be referred to as "lower".
An organic EL illuminating device 1 shown in FIGs. 1 and 2 includes a resin film (electronic element formation layer) A formed of the resin composition of the present invention, a plurality of light emitting elements C and a sealing portion B.
In this organic EL illuminating device 1, a case, in which a closed space is formed, is constituted from the resin film A and the sealing portion B, and the light emitting elements C are provided inside the closed space of the case. By providing the light emitting elements C in the closed space of the case, it is possible to ensure airtightness with respect to the light emitting elements C, and thereby enabling to prevent oxygen or moisture from penetrating to the light emitting elements C.
In this embodiment, there are nine light emitting elements (organic EL elements) C in the closed space of the case. Each of the light emitting elements C has a square shape in a planar view thereof. The nine light emitting elements C in the closed space are provided on the resin film A so as to be arranged at regular intervals in a reticular pattern (in a matrix pattern of 3 x 3).
As shown in FIG. 2, the organic EL illuminating device 1 having such a configuration can be considered as an illuminating device having a structure for extracting light emitted from the light emitting elements C from a side of the resin film A (through the resin film A).
As described above, the plurality of light emitting elements C are provided on the resin film (electronic element formation layer) A so as to form the reticular pattern.
In this embodiment, each of the light emitting elements C includes an anode 302, a cathode 306, a hole transport layer 303, an emission layer 304 and an electron transport layer 305. The anode 302 and the cathode 306 are provided so as to face each other. Further, the hole transport layer 303, the emission layer 304 and the electron transport layer 305 are laminated in this order from the anode 302 between the anode 302 and the cathode 306.
In the organic EL illuminating device 1 having such a configuration, the light emitted from the light emitting elements C passes through the resin film A and then is extracted outside the organic EL illuminating device 1. Namely, the light emitted from the light emitting elements C transmits out to the organic EL illuminating device 1 through the resin film A and then reaches to a targeted object. In this way, the targeted object is illuminated with the light. By appropriately combining the kind of light emitting materials and the like included in the emission layers 304 of the respective light emitting elements C, it is possible to obtain the organic EL illuminating device 1 capable of emitting predetermined color.
<Sensor element>
Next, the sensor element manufactured by applying the method of manufacturing the electronic device of the present invention will be described. FIG. 3 is a sectional view which shows an embodiment of the sensor element manufactured by applying the method of manufacturing the electronic device of the present invention. In the following description, the upper side in FIG. 3 will be referred to as "upper", and the lower side in FIG. 3 will be referred to as "lower".
The sensor element of the present invention is, for example, a sensor element that can be used in an input device. In one or plurality of embodiments of this discloser, the sensor element of the present invention is a sensor element including the resin film (electronic element formation layer) A formed of the resin composition of the present. In one or plurality of embodiments of this discloser, the sensor element of the present invention is a sensor element formed on the resin film A on the base member 500. In one or plurality of embodiments of this discloser, the sensor element of the present invention is a sensor element that can be peeled off from the base member 500.
Examples of the sensor element of the present invention includes an optical sensor element for capturing an image, an electromagnetic sensor element for sensing an electromagnetic wave, a radiation sensor element for sensing radiation such as X-rays, a magnetic sensor element for sensing a magnetic field, a capacitive sensor element for sensing a change of capacitance charge, a pressure sensor element for sensing a change of pressure, a touch sensor element and a piezoelectric sensor element.
Examples of the input device using the sensor element of the present invention includes a radiation (X-rays) imaging device using the radiation (X-rays) sensor element, a visible-light imaging device using the optical sensor element, a magnetic sensing device using the magnetic sensor element, a touch panel using the touch sensor element or the pressure sensor element, a finger authenticating device using the optical sensor element and a light emitting device using the piezoelectric sensor. The input device using the sensor element of the present invention may further have a function of an output device such as a displaying function and the like.
Hereinafter, an optical sensor element including a photodiode will be described as one example of the sensor element of the present invention.
A sensor element 10 shown in FIG. 3 includes the resin film (electronic element formation layer) A formed of the resin composition of the present invention and a plurality of pixel circuits 11 provided on the resin film A.
In this sensor element 10, each of the pixel circuits 11 includes a photodiode (photoelectric conversion element) 11A and a thin-film transistor (TFT) 11B serving as a driver element for the photodiode 11A. By sensing light passing through the resin film A with each of the photodiodes 11A, the sensor element 10 can serve as an optical sensor element.
On the resin film A, a gate insulating film 21 is provided. The gate insulating film 21 is constituted of a single layer film including any one of a silicon oxide (SiO2) film, a silicon oxynitride (SiON) film and a silicon nitride (SiN) film; or a laminated film including two of more of these films. On the gate insulating film 21, a first interlayer insulating film 12A is provided. The first interlayer insulating film 12 A is constituted of a silicon oxide film, a silicon nitride film or the like. This first interlayer insulating film 12A can also serve as a protective film (passivation film) to cover the top of the thin-film transistor 11B described below.
The photodiode 11A is formed on a selective region of the resin film A through the gate insulating film 21 and the first interlayer insulating film 12A. The photodiode 11A includes a lower electrode 24 formed on the first interlayer insulating film 12A, a n-type semiconductor layer 25N, an i-type semiconductor layer 25I, a p-type semiconductor layer 25P, an upper electrode 26 and a wiring layer 27. The lower electrode 24, the n-type semiconductor layer 25N, the i-type semiconductor layer 25I, the p-type semiconductor layer 25P, the upper electrode 26 and the wiring layer 27 are laminated from the side of the first interlayer insulating film 12A in this order.
The upper electrode 26 serves as an electrode for supplying, for example, a reference potential (bias potential) to a photoelectric conversion layer during a photoelectric conversion. The photoelectric conversion layer is constituted of the n-type semiconductor layer 25N, the i-type semiconductor layer 25I and the p-type semiconductor layer 25P. The upper electrode 26 is connected to the wiring layer 27 serving as a power supply wiring for supplying the reference potential. This upper electrode 26 is constituted of a transparent conductive film of ITO (indium tin oxide) or the like.
The thin-film transistor 11B is constituted of, for example, a field effect transistor (FET). The thin-film transistor 11B includes a gate electrode 20, a gate insulating film 21, a semiconductor film 22, a source electrode 23S and a drain electrode 23D.
The gate electrode 20 is formed of titanium (Ti), Al, Mo, tungsten (W), chromium (Cr) or the like and formed on the resin film A. The gate insulating film 21 is formed on the gate electrode 20. The semiconductor layer 22 has a channel region and is formed on the gate insulating film 21. The source electrode 23S and the drain electrode 23D are formed on the semiconductor film 22. In this embodiment, the drain electrode 23D is connected to the lower electrode 24 of the photodiode and the source electrode 23S is connected to a relay electrode 28 of the sensor element 10.
Further, in the sensor element 10 of this embodiment, a second interlayer insulating film 12B, a first flattened film 13A, a protective film 14 and a second flattened film 13B are laminated on the photodiode 11A and the thin-film transistor 11B in this order. Further, an opening 3 is formed on the first flattened film 13A so as to correspond to the vicinity of the selective region on which the photodiode 11A is formed.
In the sensor element 10 having such a configuration, the light transmitting from outside into the sensor element 10 passes through the resin film A and reaches to the photodiodes 11A. As a result, it is possible to sensor the light transmitting from outside into the sensor element 10.
(Method of Manufacturing Organic EL Illuminating Device 1 or Sensor Element 10)
The organic EL illuminating device 1 having the configuration as described above or the sensor element 10 having the configuration as described above is manufactured by, for example, using the resin composition of the present invention as follows. That is, the organic EL illuminating device 1 or the sensor element 10 can be manufactured by using the method of manufacturing the electronic device of the present invention.
FIG. 4 is a vertical sectional view to illustrate the method of manufacturing the organic electroluminescence illuminating device shown in FIGs. 1 and 2 or the sensor element shown in FIG. 3 (method of manufacturing the electronic device of the present invention). In the following description, the upper side in FIG. 4 will be referred to as "upper", and the lower side in FIG. 4 will be referred to as "lower".
First, description will be made on the method of manufacturing the organic electroluminescence illuminating device 1 shown in FIGs. 1 and 2.
[1] First, the substrate (substrate of the present invention) is prepared. The substrate (substrate of the present invention) includes a plate-like base member 500 having a first surface and a second surface opposite to the first surface; and the resin film (electronic element formation layer) A. The resin film A is provided at a side of the first surface of the base member 500.
[1-A] First, the base member 500 having the first surface and the second surface, and having light transparency is prepared.
For example, glass, a metal, silicone, a resin or the like is used as a constituent material for the base member 500. These materials may be used alone or in combination of two or more as appropriate.
[1-B] Next, the resin film A is formed on the first surface (one surface) of the base member 500. As a result, the substrate including the base member 500 and the resin film A (laminated composite material in FIG. 4) is obtained.
The resin composition of the present invention is used to form the resin film A. The resin composition of the present invention contains a polymer and a solvent dissolving the polymer. By using such a resin composition, the resin film (electronic element formation layer) A containing the polymer is formed, wherein when refractive indexes (wavelength: 589.3 nm) of the resin film A along two perpendicular in-plane directions thereof are respectively defined as "Nx" and "Ny" and a refractive index (wavelength: 589.3 nm) of the resin film A along a thickness direction thereof is defined as "Nz", Nx, Ny and Nz satisfy a relationship of "(Nx+Ny)/2-Nz" > 0.01.
Examples of the method of forming the resin film A include a method in which the resin composition (varnish) is supplied on the first surface of the base member 500 by using a die coat method as shown in FIG. 4(A), and thereafter the resin composition is dried and heated (referred to FIG. 4(B)).
In this regard, it is to be noted that a method of supplying the resin composition on the first surface of the base member 500 is not limited to the die coat method. Various kinds of liquid-phase film formation methods such as an ink jet method, a spin coat method, a bar coat method, a roll coat method, a wire bar coat method and a dip coat method can be used as such a method.
Further, as described above, the resin composition of the present invention contains the polymer and the solvent dissolving the polymer. By using such a resin composition, it is possible to obtain the resin film A containing the polymer and satisfying the relationship of "(Nx+Ny)/2-Nz" > 0.01. This resin composition of the present invention will be described later.
In one or plurality of embodiments of this disclosure, in terms of suppression of curvature deformation and/or enhancement of dimension stability, a heating treatment is carried out to the resin film A under the temperature in the range from approximately +40 degrees Celsius of a boiling point of the solvent to approximately +100 degrees Celsius of the boiling point of the solvent, more preferably in the range from approximately +60 degrees Celsius of the boiling point of the solvent to approximately +80 degrees Celsius of the boiling point of the solvent, even more preferably at approximately +70 degrees Celsius of the boiling point of the solvent. In one or plurality of embodiments of this disclosure, in terms of suppression of curvature deformation and/or enhancement of dimension stability, the temperature of the heating treatment in this step [1-B] is in the range of approximately 200 to 250 degrees Celsius. In one or plurality of embodiments of this disclosure, in terms of suppression of curvature deformation and/or enhancement of dimension stability, a heating time (duration) in this step [1-B] is in the range of more than approximately 1 minute but less than approximately 30 minutes.
Further, this step [1-B], in which the resin film A is formed on the base member 500, may include a step of curing the resin film A after drying and heating the resin composition. A temperature of curing the resin film A depends on performance of a heating apparatus, but is preferably in the range of 220 to 420 degrees Celsius, more preferably in the range of 280 to 400 degrees Celsius, further more preferably in the range of 330 to 370 degrees Celsius, and even more preferably in the range of 340 to 370 degrees Celsius. A time (duration) of curing the resin film A is in the range of 5 to 300 minutes or 30 to 240 minutes.
[2] Next, the nine (plurality of) light emitting elements (electronic elements) C are formed on the resin film A provided in the obtained substrate so as to form the reticular pattern.
[2-A] First, the anodes (individual electrodes) 302 are formed on the resin film A in the reticular pattern.
[2-B] Next, each of the hole transport layers 303 is formed on the corresponding anode 302 so as to cover it.
[2-C] Next, each of the emission layers 304 is formed on the corresponding hole transport layer 303 so as to cover it.
[2-D] Next, each of the electron transport layers 305 is formed on the corresponding emission layer 304 so as to cover it.
[2-E] Next, each of the cathodes 306 is formed on the corresponding electron transport layer 305 so as to cover it.
In this regard, each layer formed in the steps [2-A] to [2-E] can be formed by using a gas-phase film formation method such as a sputter method, a vacuum deposition method and a CVD method or a liquid-phase film formation method such as an ink jet method, a spin coat method and a casting method.
[3] Next, the sealing portion B is prepared. Then, the sealing portion B is provided on the resin film A so as to cover each of the light emitting elements C. In this way, the closed space of the case is formed by the resin film A and the sealing portion B. In the closed space, the light emitting elements C are sealed with the resin film A and the sealing portion B.
In this regard, the sealing with the resin film A and the sealing portion B as described above can be performed by interposing an adhesive between the resin film A and the sealing portion B and then drying the adhesive.
By carrying out the steps [1] to [3] as described above, the organic EL illuminating device 1 including the resin film A, the light emitting elements C and the sealing portion B is formed on the base member 500 (referred to FIG. 4(C)).
[4] Next, the resin film (electronic element formation layer) A is irradiated with light from a side of the base member 500.
By doing so, the resin film A is peeled off from the first surface of the base member 500 in an interface between the base member 500 and the resin film A.
As a result, the organic EL illuminating device (electronic device) 1 is separated from the base member 500 (referred to FIG. 4(D)).
The light to be irradiated to the resin film A is not particularly limited to a specific kind as long as the resin film A can be peeled off from the first surface of the base member 500 in the interface between the base member 500 and the resin film A by irradiating the resin film A with the light. The light is preferably laser light. By using the laser light, it is possible to reliably peel off the resin film A from the base member 500 in the interface between the base member 500 and the resin film A.
Further, examples of the laser light include an excimer laser of a pulse oscillator type or a continuous emission type, a carbon dioxide laser, a YAG laser and a YVO4 laser.
By carrying out the steps [1] to [4] as described above, it is possible to obtain the organic EL illuminating device 1 peeled off from the base member 500.
Next, description will be made on the method of manufacturing the sensor element shown in FIG. 3.
[1] First, in the same manner as the method of manufacturing the organic electroluminescence illuminating device 1 shown in FIGs. 1 and 2, the substrate (substrate of the present invention) including the base member 500 and the resin film (electronic element formation layer) A formed on the base member 500 is prepared. Since a step for forming the resin film A on the base member 500 is identical to that of the method of manufacturing the organic electroluminescence illuminating device 1 described above, description to the step for forming the resin film A on the base member 500 is omitted here (referred to FIGs. 4(A) and 4(B)).
[2] Next, the sensor element 10 described above is formed on the resin film A provided in the obtained substrate. A method for forming the sensor element 10 on the resin film A is not particularly limited to a specific method. The formation of the sensor element 10 on the resin film A can be carried out with a known suitable method appropriately selected or modified for manufacturing a desired sensor element.
By carrying out the steps [1] to [2] as described above, the sensor element 10 including the resin film A, the pixel circuits 11 is formed on the base member 500 (referred to FIG. 4(C)).
[3] Next, the resin film (electronic element formation layer) A is irradiated with the light from the side of the base member 500 to peel off the sensor element (electronic device) 10 from the base member 500 (referred to FIG. 4(D)). Since a step for peeling off the sensor element 10 from the base member 500 is identical to the above-mentioned step for peeling off the organic EL illuminating device 1 from the base member 500, description to the step for peeling off the sensor element 10 from the base member 500 is omitted here.
By carrying out the steps [1] to [3] as described above, it is possible to obtain the sensor element 10 peeled off from the base member 500.
In the organic EL illuminating device 1 having the configuration as described above, it is required that the light emitted from the light emitting elements C should pass through the resin film A with high efficiency. However, the emitted light having a large incidence angle with respect to the resin film A is totally reflected. This total reflection of the light in the organic EL illuminating device 1 causes a problem in that light extraction efficiency of the organic EL illuminating device 1 tends to become low.
In the sensor element 10 having the configuration as described above, it is required that the light transmitting from outside into the sensor element 10 should pass through the resin film A with high efficiency. However, the emitted light having a large incidence angle with respect to the resin film A is totally reflected. This total reflection of the light in the sensor element 10 causes a problem in that light introduction efficiency of the sensor element 10 tends to become low.
Here, when the refractive indexes of the resin film A along the two perpendicular in-plane directions thereof are respectively defined as "Nx" and "Ny", the refractive index of the resin film A along the thickness direction thereof is defined as "Nz", and a thickness of the resin film A is defined as "d", a phase difference of the resin film A along the thickness direction thereof "Rth" (thickness direction phase difference) is represented by the following expression (1).
Rth = {(Nx+Ny)/2-Nz} x d (1)
The present inventors focused on a value of Rth (thickness direction phase difference) and carefully reviewed a relationship between the value of Rth (thickness direction phase difference) and the total reflection of the light incident onto the resin film A. As a result, the present inventors have found that it is possible to solve the above problem by setting a value of "(Nx+Ny)/2-Nz" included in the above expression (1) (i.e., an out-of-plane birefringence (dnout)) to be more than 0.01, that is, by satisfying the relationship of "(Nx+Ny)/2-Nz" > 0.01. Specifically, the present inventors have found that even if the light emitted from the light emitting elements C has the large incidence angle with respect to the resin film A, it is possible to appropriately suppress or prevent the light from being totally reflected by setting the value of "(Nx+Ny)/2-Nz" to satisfy the above relationship, and thereby improving the light extraction efficiency of the above-mentioned organic EL illuminating device 1 and the light introduction efficiency of the sensor element 10. Based on such a finding, the present inventors have completed the present invention.
As described above, the resin film A having the configuration as described above can be formed by using the resin composition of the present invention which contains the polymer and the solvent dissolving the polymer. Hereinafter, detailed description will be made on constituent materials contained in the resin composition of the present invention.
<Polymer>
The polymer is used as a main material for the resin film (electronic element formation layer) A constituted of the resin composition. The polymer is contained in the resin composition in order to form the resin film A so as to satisfy the relationship of "(Nx+Ny)/2-Nz" > 0.01.
As described above, the polymer is not particularly limited to a specific kind as long as the resin film A can satisfy the relationship of "(Nx+Ny)/2-Nz" > 0.01. Examples of the polymer include an aromatic polyamide, an aromatic polyimide (and/or an aromatic polyamic acid), an alicyclic polyamide and an alicyclic polyimide. These polymers may be used alone or in combination of two or more. Among them, the aromatic polyamide or the aromatic polyimide (and/or an aromatic polyamic acid) is preferably used as the polymer. By using the aromatic polyamide or the aromatic polyimide as the polymer, it is possible to easily form the resin film A so as to satisfy the relationship of "(Nx+Ny)/2-Nz" > 0.01. Further, it is also possible to efficiently perform the peeling-off of the resin film A in the interface between the base member 500 and the resin film A by irradiating the resin film A with the light.
Further, it is preferred that the aromatic polyamide is a wholly aromatic polyamide. By using the wholly aromatic polyamide as the polymer for the resin film A, it is possible to reliably set the value of "(Nx+Ny)/2-Nz" of the formed resin film A to fall within the above range. In this regard, it is to be noted that the wholly aromatic polyamide refers to that all of amide bonds included in a main chain of the aromatic polyamide are bonded to each other through the aromatic group (aromatic ring) without bonding to each other through a chain or cyclic aliphatic group.
In view of the foregoing, it is preferred that the aromatic polyamide has a repeating unit represented by the following general formula (I):
Figure JPOXMLDOC01-appb-I000006
where x represents an integer of 1 or more, Ar1 is represented by the following general formula (II) or (III):
Figure JPOXMLDOC01-appb-I000007
(where p=4; each of R1, R4 and R5 is selected from the group consisting of a hydrogen atom, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom and an iodine atom), an alkyl group, a substituted alkyl group such as a halogenated alkyl group, a nitro group, a cyano group, a thioalkyl group, an alkoxy group, a substituted alkoxy group such as a halogenated alkoxy group, an aryl group, a substituted aryl group such as a halogenated aryl group, an alkyl ester group, a substituted alkyl ester group, and a combination of them; and G1 is selected from the group consisting of a covalent bond, a CH2 group, a C(CH3)2 group, a C(CF3)2 group, a C(CX3)2 group (X represents a halogen atom.), a CO group, an oxygen atom, a sulfur atom, an SO2 group, an Si(CH3)2 group, a 9,9-fluorene group, a substituted 9,9-fluorene group and an OZO group (Z represents an aryl group or substituted aryl group such as a phenyl group, a biphenyl group, a perfluorobiphenyl group, a 9,9-bisphenyl fluorene group and a substituted 9,9-bisphenyl fluorene group.).), and Ar2 is represented by the following general formula (IV) or (V):
Figure JPOXMLDOC01-appb-I000008
Figure JPOXMLDOC01-appb-I000009
(where p=4; each of R6, R7 and R8 is selected from the group consisting of a hydrogen atom, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom and an iodine atom), an alkyl group, a substituted alkyl group such as a halogenated alkyl group, a nitro group, a cyano group, a thioalkyl group, an alkoxy group, a substituted alkoxy group such as a halogenated alkoxy group, an aryl group, a substituted aryl group such as a halogenated aryl group, an alkyl ester group, a substituted alkyl ester group, and a combination of them; and G2 is selected from the group consisting of a covalent bond, a CH2 group, a C(CH3)2 group, a C(CF3)2 group, a C(CX3)2 group (X represents a halogen atom.), a CO group, an oxygen atom, a sulfur atom, an SO2 group, an Si(CH3)2 group, a 9,9-fluorene group, a substituted 9,9-fluorene group and an OZO group (Z represents an aryl group or substituted aryl group such as a phenyl group, a biphenyl group, a perfluorobiphenyl group, a 9,9-bisphenyl fluorene group and a substituted 9,9-bisphenyl fluorene group.).).
Further, the aromatic polyamide contains a rigid structure (rigid component) preferably in an amount of 60 mol% or more, and more preferably in an amount of 95 mol% or more. By setting the amount of the rigid structure in the aromatic polyamide to fall within the above range, it is possible to further improve crystallizability of the aromatic polyamide. This makes it possible to more reliably form the resin film A so as to satisfy the relationship of "(Nx+Ny)/2-Nz" > 0.01.
In the present specification, the rigid structure refers to that a monomer component (repeating unit) constituting the aromatic polyamide has linearity in a main structure (skeleton) thereof. Specifically, the rigid structure is the repeating unit represented by the general formula (I), the general formula (VI) or the general formula (VII). Further, Ar1 in the repeating unit represented by the general formula (I) is represented by the following general formula (A) or (B):
Figure JPOXMLDOC01-appb-I000010
Figure JPOXMLDOC01-appb-I000011
(where p=4; each of R1, R4 and R5 is selected from the group consisting of a hydrogen atom, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom and an iodine atom), an alkyl group, a substituted alkyl group such as a halogenated alkyl group, a nitro group, a cyano group, a thioalkyl group, an alkoxy group, a substituted alkoxy group such as a halogenated alkoxy group, an aryl group, a substituted aryl group such as a halogenated aryl group, an alkyl ester group, a substituted alkyl ester group, and a combination of them; and G1 is selected from the group consisting of a covalent bond, a CH2 group, a C(CH3)2 group, a C(CF3)2 group, a C(CX3)2 group (X represents a halogen atom.), a CO group, an oxygen atom, a sulfur atom, an SO2 group, an Si(CH3)2 group, a 9,9-fluorene group, a substituted 9,9-fluorene group and an OZO group (Z represents an aryl group or substituted aryl group such as a phenyl group, a biphenyl group, a perfluorobiphenyl group, a 9,9-bisphenyl fluorene group and a substituted 9,9-bisphenyl fluorene group.).), and Ar2 in the repeating unit represented by the general formula (I) is represented by the following general formula (C) or (D):
Figure JPOXMLDOC01-appb-I000012
Figure JPOXMLDOC01-appb-I000013
(where p=4; each of R6, R7 and R8 is selected from the group consisting of a hydrogen atom, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom and an iodine atom), an alkyl group, a substituted alkyl group such as a halogenated alkyl group, a nitro group, a cyano group, a thioalkyl group, an alkoxy group, a substituted alkoxy group such as a halogenated alkoxy group, an aryl group, a substituted aryl group such as a halogenated aryl group, an alkyl ester group, a substituted alkyl ester group, and a combination of them; and G2 is selected from the group consisting of a covalent bond, a CH2 group, a C(CH3)2 group, a C(CF3)2 group, a C(CX3)2 group (X represents a halogen atom.), a CO group, an oxygen atom, a sulfur atom, an SO2 group, an Si(CH3)2 group, a 9,9-fluorene group, a substituted 9,9-fluorene group and an OZO group (Z represents an aryl group or substituted aryl group such as a phenyl group, a biphenyl group, a perfluorobiphenyl group, a 9,9-bisphenyl fluorene group and a substituted 9,9-bisphenyl fluorene group.).).)
Concrete examples of Ar1 include a structure derived from terephthaloyl dichloride (TPC) and concrete examples of Ar2 include a structure derived from 4,4'-diamino-2,2'-bistrifluoromethyl benzidine (PFMB).
Further, a number average molecular weight (Mn) of the aromatic polyamide is preferably 6.0 x 104 or more, more preferably 6.5 x 104 or more, more preferably 7.0 x 104 or more, further more preferably 7.5 x 104 or more and even more preferably 8.0 x 104 or more. Further, the number average molecular weight of the aromatic polyamide is preferably 1.0 x 106 or less, more preferably 8.0 x 105 or less, further more preferably 6.0 x 105 or less, and even more preferably 4.0 x 105 or less. By using the aromatic polyamide satisfying the above condition, it is possible for the resin film A to reliably provide a function as a foundation layer in the organic EL illuminating device 1 or the sensor element 10. Further, it is possible to reliably set the value of "(Nx+Ny)/2-Nz" of the resin film A to fall within the range described above.
In the present specification, the number average molecular weight (Mn) and a weight average molecular weight (Mw) of the aromatic polyamide are measured with a Gel Permeation Chromatography. Specifically, they are measured by using the method in the following Examples.
Further, molecular weight distribution of the aromatic polyamide (=Mw/Mn) is preferably 5.0 or less, more preferably 4.0 or less, more preferably 3.0 or less, further more preferably 2.8 or less, further more preferably 2.6 or less, and even more preferably 2.4 or less. Further, the molecular weight distribution of the aromatic polyamide is preferably 2.0 or more. By using the aromatic polyamide satisfying the above condition, it is possible for the resin film A to reliably provide the function as the foundation layer in the organic EL illuminating device 1 or the sensor element 10. Further, it is possible to reliably set the value of "(Nx+Ny)/2-Nz" of the resin film A to fall within the range described above.
Regarding the aromatic polyimide and the aromatic polyamic acid, it is preferred that the aromatic polyimide and the aromatic polyamic acid are respectively a wholly aromatic polyimide and a wholly aromatic polyamic acid. By using the wholly aromatic polyimide and/or the wholly aromatic polyamic acid as the polymer for the resin film A, it is possible to reliably set the value of "(Nx+Ny)/2-Nz" of the formed resin film A to fall within the above range. In this regard, it is to be noted that the wholly aromatic polyimide and the wholly aromatic polyamic acid refer to that all of imide bonds included in a main chain of the aromatic polyimide or the aromatic polyamic acid are bonded to each other through the aromatic group (aromatic ring) without bonding to each other through a chain or cyclic aliphatic group.
In view of the foregoing, it is preferred that the aromatic polyimide and/or the aromatic polyamic acid have a first repeating unit represented by the following general formula (VI), and a second repeating unit represented by the following general formula (VI'):
Figure JPOXMLDOC01-appb-I000014
Figure JPOXMLDOC01-appb-I000015
where Ali is selected from the group consisting of single or multi ring alicyclic units each having a carbon number of 4 to 20, Ar1 is selected from the group consisting of "cardo" units represented by the following general formula (VII):
Figure JPOXMLDOC01-appb-I000016
(where n= 1 to 4; R1 is selected from the group consisting of a hydrogen atom, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom and an iodine atom), an alkyl group, a substituted alkyl group such as a halogenated alkyl group, a nitro group, a cyano group, a thioalkyl group, an alkoxy group, a substituted alkoxy group such as a halogenated alkoxy group, an aryl group, a substituted aryl group such as a halogenated aryl group, an alkyl ester group, a substituted alkyl ester group, and a combination of them; each R1 may be the same as or different from each other; and the ring is a single or multi alicyclic or aromatic unit with or without substituent groups.).
Further, a number average molecular weight (Mn) of each of the aromatic polyimide and the aromatic polyamic acid is preferably 6.0 x 104 or more, more preferably 6.5 x 104 or more, more preferably 7.0 x 104 or more, further more preferably 7.5 x 104 or more, and even more preferably 8.0 x 104 or more. Further, the number average molecular weight of each of the aromatic polyimide and the aromatic polyamic acid is preferably 1.0 x 106 or less, more preferably 8.0 x 105 or less, further more preferably 6.0 x 105 or less, and even more preferably 4.0 x 105 or less. By using the aromatic polyimide and/or the aromatic polyamic acid satisfying the above condition, it is possible for the resin film A to reliably provide a function as a foundation layer in the organic EL display device 1 or the sensor element 10. Further, it is possible to reliably set the value of "(Nx+Ny)/2-Nz" of the resin film A to fall within the range described above.
In the present specification, the number average molecular weight (Mn) and a weight average molecular weight (Mw) of each of the aromatic polyimide and the aromatic polyamic acid are measured with a Gel Permeation Chromatography. Specifically, they are measured by using the method in the following Examples.
Further, molecular weight distribution of each of the aromatic polyimide and the aromatic polyamic acid (=Mw/Mn) is preferably 5.0 or less, more preferably 4.0 or less, more preferably 3.0 or less, further more preferably 2.8 or less, further more preferably 2.6 or less, and even more preferably 2.4 or less. Further, the molecular weight distribution of each of the aromatic polyimide and the aromatic polyamic acid is preferably 2.0 or more. By using the aromatic polyimide and/or the aromatic polyamic acid satisfying the above condition, it is possible for the resin film A to reliably provide the function as the foundation layer in the organic EL display device 1 or the sensor element 10. Further, it is possible to reliably set the value of "(Nx+Ny)/2-Nz" of the resin film A to fall within the range described above.
Furthermore, it is preferred that each of the aromatic polyamide and the aromatic polyimide (and/or the aromatic polyamic acid) is obtained through a step of re-precipitating it after each of the aromatic polyamide and the aromatic polyimide (and/or the aromatic polyamic acid) is synthesized. By using the aromatic polyamide or the aromatic polyimide (and/or the aromatic polyamic acid) obtained through the step of re-precipitation, it is possible for the resin film A to reliably provide the function as the foundation layer in the organic EL illuminating device 1 or the sensor element 10. Further, it is possible to reliably set the value of "(Nx+Ny)/2-Nz" of the resin film A to fall within the range described above.
In one or plurality of embodiments of this disclosure, one or both of a terminal -COOH group and a terminal -NH2 group of the polymer are end-capped. The end-capping of the terminals is preferable from the point of view of enhancement of heat resistance property of the film (namely, resin film A). The terminals of the polymer can be end-capped by either being reacted with benzoyl chloride in the case where each terminal thereof is -NH2, or by being reacted with aniline in the case where each terminal thereof is -COOH. However, the method of end-capping is not limited to this method.
<Inorganic Filler>
The resin composition may contain an inorganic filler in addition to the polymer in an amount such that the resin film A is not broken when the resin film A is peeled off from the base member 500 in the above mentioned method of manufacturing the organic EL illuminating device 1 or the sensor element 10. By using the resin composition containing the inorganic filler, it is possible to reduce a coefficient of thermal expansion of the resin film A.
This inorganic filler is not particularly limited to a specific kind, but is preferably formed into a particle shape or is preferably constituted of a fiber.
Further, a constituent material for the inorganic filler is not particularly limited to a specific material as long as it is an inorganic material. Examples of such a constituent material for the inorganic filler include a metal oxide such as silica, alumina and a titanium oxide; a mineral such as mica; glass; and a mixture of them. These materials may be used singly or in combination of two or more of them. In this regard, examples of a kind of glass include E glass, C glass, A glass, S glass, D glass, NE glass, T glass, low permittivity glass and high permittivity glass.
In the case where the inorganic filler is constituted of the fiber, an average fiber diameter of the fiber is preferably in the range of 1 to 1000 nm. By using the resin composition containing the inorganic filler having the above average fiber diameter, it is possible for the resin film A to reliably provide the function as the foundation layer in the organic EL illuminating device 1 or the sensor element 10. Further, it is possible to reliably set the value of "(Nx+Ny)/2-Nz" of the resin film A to fall within the range described above.
Here, the fiber may be formed of single fibers. The single fibers included therein are arranged without paralleling with each other and to be sufficiently spaced apart from each other so that a liquid precursor of a matrix resin enters among the single fibers. In this case, the average fiber diameter corresponds to an average diameter of the single fibers. Further, the fiber may constitute one line of thread in which a plurality of single fibers is bundled. In this case, the average fiber diameter is defined as an average value of a diameter of the one line of thread. Specifically, the average fiber diameter is measured by the method in the Examples. Further, from a point of view of improving the transparency of the film, the average fiber diameter of the fiber is preferably small. Further, a refractive index of the polymer included in the resin composition (polymer solution) and a refractive index of the inorganic filler are preferably close to each other. For example, in the case where a difference of refractive indexes of a material to be used as the fiber and the polymer in the wavelength of 589 nm is 0.01 or less, it becomes possible to form a film having high transparency regardless of the fiber diameter. Further, examples of a method of measuring the average fiber diameter include a method of observing the fiber with an electronic microscope.
Further, in the case where the inorganic filler is formed into the particle shape, an average particle size of the particles is preferably in the range of 1 to 1000 nm. By using the resin composition containing the inorganic filler in the form of the particle having the above average particle size, it is possible for the resin film A to reliably provide the function as the foundation layer in the organic EL illuminating device 1 or the sensor element 10. Further, it is possible to reliably set the value of "(Nx+Ny)/2-Nz" of the resin film A to fall within the range described above.
Here, the average particle size of the particles refers to a diameter corresponding to an average projection circle. Specifically, the average particle size of the particles is measured by the method in the Examples.
A shape of each of the particles is not particularly limited to a specific shape. Examples of such a shape include a spherical shape, a perfect spherical shape, a rod shape, a plate shape and a combined shape of them. By using the inorganic filler having such a shape, it is possible to reliably set the value of "(Nx+Ny)/2-Nz" of the resin film A to fall within the range described above.
Further, the average particle size of the particles is preferably small. Further, the refractive index of the polymer included in the resin composition (polymer solution) and the refractive index of the inorganic filler are preferably close to each other. This makes it possible to further improve the transparency of the resin film A. For example, in the case where a difference of refractive indexes of the material to be used as the particles and the polymer in the wavelength of 589 nm is 0.01 or less, it becomes possible to form the resin film A having high transparency regardless of the particle size. Further, examples of a method of measuring the average particle size include a method of measuring the average particle size with a particle size analyzer.
A ratio of the inorganic filler in a solid matter contained in the resin composition (polymer solution) is not particularly limited to a specific value, but is preferably in the range of 1 to 50 volume%, more preferably in the range of 2 to 40 volume%, and even more preferably in the range of 3 to 30 volume%. On the other hand, a ratio of the polymer in the solid matter contained in the resin composition (polymer solution) is not particularly limited to a specific value, but is preferably in the range of 50 to 99 volume%, more preferably in the range of 60 to 98 volume%, and even more preferably in the range of 70 to 97 volume%.
In this regard, it is to be noted that the "solid matter" refers to a component other than the solvent contained in the resin composition in this specification. A volume conversion of the solid matter, a volume conversion of the inorganic filler and/or a volume conversion of the polymer can be calculated from each component usage at the time of preparing the polymer solution. Alternatively, they can be also calculated by removing the solvent from the polymer solution.
<Other Components>
Furthermore, the resin composition may contain an antioxidant, an ultraviolet absorbing agent, a dye, a pigment, a filler such as another inorganic filler and the like, if needed, in the degrees to which the function of the foundation layer in the organic EL illuminating device 1 or the sensor element 10 is not impaired and the resin film A can satisfy the relationship of "(Nx+Ny)/2-Nz" > 0.01.
<Amount of Solid Matter>
A ratio of the solid matter contained in the resin composition is preferably 1 volume% or more, more preferably 2 volume% or more and even more preferably 3 volume% or more. Further, the ratio of the solid matter contained in the resin composition is preferably 40 volume% or less, more preferably 30 volume% or less and even more preferably 20 volume% or less. By setting the ratio of the solid matter contained in the resin composition to fall within the above range, it is possible for the resin film A to reliably provide the function as the foundation layer in the organic EL illuminating device 1 or the sensor element 10. Further, it is possible to reliably form the resin film A so as to satisfy the relationship of "(Nx+Ny)/2-Nz" > 0.01.
<Solvent>
One to be able to solve the polymer is used as the solvent, which is used to prepare a varnish (liquid material) containing the resin composition.
In one or plurality of embodiments of this disclosure, in terms of enhancement of solubility of the polymer to the solvent, the solvent is preferably a polar solvent or a mixed solvent containing one or more polar solvents. In one or plurality of embodiments of this disclosure, in terms of enhancement of solubility of the polymer to the solvent and enhancement of the adhesion between the resin film A and the base member 500, the solvent is preferably cresol; N,N-dimethyl acetamide (DMAc); N-methyl-2-pyrrolidinone (NMP); dimethyl sulfoxide (DMSO); 1,3-dimethyl-imidazolidinone (DMI); N,N-dimethyl formamide (DMF); butyl cellosolve (BCS); gamma-butyrolactone (GBL) or a mixed solvent containing at least one of cresol, N,N-dimethyl acetamide (DMAc), N-methyl-2-pyrrolidinone (NMP), dimethyl sulfoxide (DMSO), 1,3-dimethyl-imidazolidinone (DMI), N,N-Dimethyl formamide (DMF), butyl cellosolve (BCS) and gamma-butyrolactone (GBL); a combination thereof or a mixed solvent containing at least one of the polar solvent thereof.
<Method of Manufacturing Resin Composition>
The resin composition as described above can be manufactured by, for example, using a manufacturing method including the following steps (a) to (d).
Hereinafter, description will be made on a case where the aromatic polyamide is used as the polymer and the resin composition contains the inorganic filler.
However, the resin composition of the present invention is not limited to a resin composition manufactured by using the following manufacturing method.
The step (a) is carried out for obtaining a mixture by dissolving at least one aromatic diamine in a solvent. The step (b) is carried out for obtaining free hydrochloric acid and a polyamide solution by reacting the at least one aromatic diamine with at least one aromatic dicarboxylic acid dichloride in the mixture. The step (c) is carried out for removing the free hydrochloric acid in the mixture by reaction with a trapping reagent. The step (d) is carried out for adding the inorganic filler to the mixture.
In one or more embodiments of the method for manufacturing the polyamide solution of this disclosure, examples of the aromatic dicarboxylic acid dichloride include compounds represented by the following general formulas (VIII) and (IX):
Figure JPOXMLDOC01-appb-I000017
Figure JPOXMLDOC01-appb-I000018
where p=4, each of R1, R4 and R5 is selected from the group consisting of a hydrogen atom, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom and an iodine atom), an alkyl group, a substituted alkyl group such as a halogenated alkyl group, a nitro group, a cyano group, a thioalkyl group, an alkoxy group, a substituted alkoxy group such as a halogenated alkoxy group, an aryl group, a substituted aryl group such as a halogenated aryl group, an alkyl ester group, a substituted alkyl ester group, and a combination of them, and G1 is selected from the group consisting of a covalent bond, a CH2 group, a C(CH3)2 group, a C(CF3)2 group, a C(CX3)2 group (X represents a halogen atom.), a CO group, an oxygen atom, a sulfur atom, an SO2 group, an Si(CH3)2 group, a 9,9-fluorene group, a substituted 9,9-fluorene group and an OZO group (Z represents an aryl group or substituted aryl group such as a phenyl group, a biphenyl group, a perfluorobiphenyl group, a 9,9-bisphenyl fluorene group and a substituted 9,9-bisphenyl fluorene group.).
Specifically, examples of the aromatic dicarboxylic acid dichloride as described above include the following compounds.
Terephthaloyl dichloride (TPC)
Figure JPOXMLDOC01-appb-I000019
Isophthaloyl dichloride (IPC)
Figure JPOXMLDOC01-appb-I000020
4,4'-biphenyldicarbonyl dichloride (BPDC)
Figure JPOXMLDOC01-appb-I000021
In one or more embodiments of the method for manufacturing the polyamide solution of this disclosure, examples of the aromatic diamine include compounds represented by the following general formulas (X) to (XI):
Figure JPOXMLDOC01-appb-I000022
Figure JPOXMLDOC01-appb-I000023
where p=4, m=1 or 2, and where each of R6, R7 and R8 is selected from the group consisting of a hydrogen atom, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom), an alkyl group, a substituted alkyl group such as a halogenated alkyl group, a nitro group, a cyano group, a thioalkyl group, an alkoxy group, a substituted alkoxy group such as a halogenated alkoxy group, an aryl group, a substituted aryl group such as a halogenated aryl group, an alkyl ester group, a substituted alkyl ester group, and combinations thereof, each R6 is the same or different, each R7 is the same or different, each R8 is the same or different, and G2 is selected from the group consisting of a covalent bond, a CH2 group, a C(CH3)2 group, a C(CF3)2 group, a C(CX3)2 group (X represents a halogen atom.), a CO group, an O atom, an S atom, an SO2 group, an Si (CH3)2 group, a 9,9-fluorene group, a substituted 9,9-fluorene group, and an OZO group (Z represents an aryl group or substituted aryl group such as a phenyl group, a biphenyl group, a perfluorobiphenyl group, a 9,9-bisphenyl fluorene group and a substituted 9,9-bisphenyl fluorene group.).
Specifically, examples of the aromatic diamine as described above include the following compounds.
4,4'-diamino-2,2'-bistrifluoromethyl benzidine (PFMB)
Figure JPOXMLDOC01-appb-I000024
9,9-bis(4-aminophenyl) fluorine (FDA)
Figure JPOXMLDOC01-appb-I000025
9,9-bis(3-fluoro-4-aminophenyl) fluorine (FFDA)
Figure JPOXMLDOC01-appb-I000026
4,4'-diamino-2,2'-bistrifluoromethoxyl benzidine (PFMOB)
Figure JPOXMLDOC01-appb-I000027
4,4'-diamino-2,2'-bistrifluoromethyl diphenyl ether (6FODA)
Figure JPOXMLDOC01-appb-I000028
Bis(4-amino-2-trifluoromethyl phenyloxyl) benzene (6FOQDA)
Figure JPOXMLDOC01-appb-I000029
Bis(4-amino-2-trifluoromethyl phenyloxyl) biphenyl (6FOBDA)
Figure JPOXMLDOC01-appb-I000030
4,4'-diaminodiphenyl sulfone (DDS)
Figure JPOXMLDOC01-appb-I000031
Regarding the diaminodiphenyl sulfone (DDS), the diaminodiphenyl sulfone may be 4,4'-diaminodiphenyl sulfone as expressed by the above formula, 3,3'-diaminodiphenyl sulfone or 2,2'-diaminodiphenyl sulfone.
In one or more embodiments of the method for manufacturing the polyamide solution of this disclosure, the aromatic polyamide is prepared via a condensation polymerization in a solvent, where hydrochloric acid generated in the reaction is trapped by a trapping reagent such as propylene oxide (PrO).
In one or plurality of embodiments of this disclosure, the reaction of hydrochloric acid with the trapping reagent yields a volatile product.
In one or plurality of embodiments of this disclosure, in terms of use of the polyamide solution in the method, the trapping reagent is propylene oxide. In one or plurality of embodiments of this disclosure, the trapping reagent is added to the mixture before or during the step (c). By adding the trapping reagent before or during the step (c), it is possible to reduce a degree of viscosity and generation of condensation in the mixture after the step (c), and thereby, improving productivity of the polyamide solution. These effects become especially remarkable when the trapping reagent is an organic reagent such as propylene oxide.
In one or plurality of embodiments of this disclosure, in terms of enhancement of heat resistance property of the resin film A, the method further includes a step of end-capping one or both of the terminal -COOH group and the terminal -NH2 group of the aromatic polyamide. The terminals of the aromatic polyamide can be end-capped by either being reacted with benzoyl chloride in the case where each terminal thereof is -NH2, or by being reacted with aniline in the case where each terminal thereof is -COOH. However, the method of end-capping is not limited to this method.
In one or plurality of embodiments of this disclosure, in terms of use of the polyamide solution in the method, the aromatic polyamide is first isolated from the polyamide solution by precipitation and re-dissolution in a solvent prior to the addition of the inorganic filler.
A re-precipitation can be carried out by a known method. In one or plurality of embodiments of this disclosure, the re-precipitation can be carried out by precipitating the aromatic polyamide by adding it to, for example, methanol, ethanol, isopropyl alcohol or the like; washing the aromatic polyamide; and re-dissolving the aromatic polyamide to the solvent.
The solvent described above can be used as a solvent for producing the polymer solution.
In one or plurality of embodiments of this disclosure, in terms of use of the polyamide solution in the method, the polyamide solution is produced so that the solution contains no inorganic salts.
By taking the steps as described above, the resin composition can be manufactured.
Further, the resin film A formed by using the resin composition obtained through the steps described above contains the polymer. Thus, it is possible to form the resin film A to satisfy the relationship of "(Nx+Ny)/2-Nz" > 0.01. In particular, the resin film A preferably satisfies the relationship of "(Nx+Ny)/2-Nz" > 0.02, more preferably satisfies the relationship of "(Nx+Ny)/2-Nz" > 0.03, and even more preferably satisfies the relationship of "(Nx+Ny)/2-Nz" > 0.05. By forming the resin film A to satisfy the above condition, it is possible to further improve the light extraction efficiency of the light passing through the resin film A.
Furthermore, a total light transmittance of the resin film A, which is formed by using the resin composition, in a sodium line (D line) is set to preferably 60% or more, more preferably 65% or more, further more preferably 70% or more, and even more preferably 80% or more. By setting the total light transmittance of the resin film A to fall within the above range, the resin film A can have excellent light extraction efficiency. According to the present invention, since the resin film A contains the polymer, it is possible to easily obtain the resin film A having the total light transmittance falling within such an above range.
A coefficient of thermal expansion (CTE) of the resin film A is preferably 100.0 ppm/K or less, more preferably 80 ppm/K or less, further more preferably 60 ppm/K or less, and even more preferably 40 ppm/K or less. In this regard, it is to be noted that the CTE of the resin film A can be obtained with a thermal mechanical analyzer (TMA). By setting the CTE to fall within the range described above, it is possible to reliably suppress or prevent warpage in the substrate including the base member 500 and the resin film A. Therefore, it is possible to improve a yield ratio of the organic EL illuminating device 1 or the sensor element 10 obtained by using such a substrate.
In the case where the resin film A contains the inorganic filler, an amount of the inorganic filler contained in the resin film A is preferably in the range of 1 to 50 volume%, more preferably in the range of 2 to 40 volume%, and even more preferably in the range of 3 to 30 volume%, with respect to the volume of the resin film A. By adding the inorganic filler to the resin film A in the above amount, it is possible to easily set the value of "(Nx+Ny)/2-Nz" and the CTE to fall within the ranges described above. In this regard, a volume conversion of the resin film A and/or a volume conversion of the inorganic filler can be respectively calculated from component usages at the time of preparing the resin composition, or they can be also obtained by measuring the volume of the resin film A.
Further, an average thickness of the resin film A is not particularly limited a specific value, but is preferably 50 micrometers or less, more preferably 30 micrometers or less, and even more preferably 20 micrometers or less. In addition, the average thickness is preferably 1 micrometer or more, more preferably 2 micrometers or more, and even more preferably 3 micrometers or more. By using the resin film A having the above average thickness, it is possible for the resin film A to reliably provide the function as the foundation layer in the organic EL illuminating device 1 or the sensor element 10. Further, it is possible to reliably suppress or prevent generation of cracks in the resin film A.
The shape of the light emitting element C (light emitting area) in the planar view thereof is the square shape in this embodiment, but is not limited thereto. It may be an arbitrary shape such as a polygonal shape (e.g., a triangular shape, a hexagonal shape) and a round shape (e.g., an exact circular shape, an elliptical shape).
Although the descriptions have been made on the resin composition, the substrate, the method of manufacturing the electronic device and the electronic device of the present invention based on the embodiments, the present invention is not limited thereto.
For example, in the resin composition and the substrate of the present invention, each component may be replaced with an arbitrary one capable of providing the same function. Alternatively, an arbitrary component may be added to them.
Further, in the method of manufacturing the electronic device of the present invention, one or more steps may be further added for the arbitrary purpose.
Further, in the above embodiments, the method of manufacturing the electronic device of the present invention is used to manufacture the organic EL illuminating device including the organic EL element as the light emitting element and the sensor element including the photodiode. However, the method of manufacturing the electronic device of the present invention is not limited thereto. For example, the method of manufacturing the electronic device of the present invention may be used to not only manufacture other illuminating devices such as a light emitting diode illuminating device including a light emitting diode as the light emitting element, but also manufacture various kinds of electronic devices such as an input device including a sensor element as the electronic element, a display device including a display element as the electronic element, an optical device including an optical element as the electronic element and a solar cell including a photoelectric conversion element as the electronic element.
Hereinafter, the present invention will be described based on specific examples in detail.
1. Preparation of Resin Composition and Formation of Resin Film
<Example 1>
<Preparation of Resin Composition>
<1> PFMB (3.2024 g, 0.01 mol) and DMAc (30 ml) were added to a 250 ml three necked round bottom flask, which is equipped with a mechanical stirrer, a nitrogen inlet and outlet, in order to obtain a solution.
<2> After the PFMB was completely dissolved, PrO (1.4 g, 0.024 mol) was added to the solution. Then, the solution was cooled to 0 degrees Celsius.
<3> Under stirring, TPC (1.485 g, 0.00700 mol) and IPC (0.636 g, 0.0030 mol) were added to the solution, and then the flask wall was washed with DMAc (1.5 ml).
<4> After two hours, benzoyl chloride (0.032 g, 0.23 mmol) was added to the solution and stirred for more two hours.
<Formation of Resin Film (Polyamide Film)>
A resin film was formed on a glass substrate by using the prepared resin composition.
That is, first, the resin composition was applied onto a flat glass substrate (10 cm x 10 cm, "EAGLE XG" produced by Corning Inc., U.S.A.) with a spin coat method.
Next, the resin composition was dried at a temperature of 60 degrees Celsius for 30 minutes or more to obtain a film. Thereafter, the temperature was raised from 60 degrees Celsius to 350 degrees Celsius. The film was subjected to a curing treatment by keeping the temperature of 350 degrees Celsius for 30 minutes under vacuum atmosphere or inert atmosphere. By doing so, a resin film was formed on the glass substrate.
In this regard, a thickness of the resin film was 23 micrometers.
<Example 2>
A resin composition of the Example 2 was prepared in the same manner as the Example 1, except that the combination of TPC and IPC was changed to a combination of TPC (0.955 g, 0.00450 mol) and IPC (1.166 g, 0.00550 mol) as the dichloride component used in the step <3>. Thereafter, a resin film of the Example 2 was formed on the glass substrate by using the resin composition in the same manner as the Example 1.
In this regard, a thickness of the obtained resin film was 25 micrometers.
<Comparative Example>
A resin composition of the Comparative Example was prepared in the same manner as the Example 1, except that the combination of TPC and IPC was changed to a combination of TPC (0.212 g, 0.00100 mol) and IPC (1.908 g, 0.00900 mol) as the dichloride component used in the step <3>. Thereafter, a resin film of the Comparative Example was formed on the glass substrate by using the resin composition in the same manner as the Example 1.
In this regard, a thickness of the obtained resin film was 22 micrometers.
2. Evaluation
The resin film obtained from the resin composition of each of the Examples and the Comparative Example was evaluated in accordance with the following methods.
<Total Light Transmittance>
A total light transmittance of the resin film in a D line (sodium line) was measured by using a haze meter ("NDH-2000" produced by NIPPON DENSHOKU INDUSTRIES CO., LTD.).
<Birefringence>
A value of "(Nx+Ny)/2-Nz" of the resin film was obtained as follows. First, a phase difference of the resin film between 0 degrees and 40 degrees was measured by using a phase difference measuring equipment ("KOBRA-21 ADH" produced by Oji Scientific Instruments) in a wavelength dispersion measuring mode (in which light having a wavelength of 479.2 nm, light having a wavelength of 545.4 nm, light having a wavelength of 630.3 nm and light having a wavelength of 748.9 nm were used). Next, a phase difference of the resin film between 0 degrees and 40 degrees in the wavelength of 550 nm was calculated by using a Sellmeier's expression. The value of "(Nx+Ny)/2-Nz" in the wavelength of 550 nm was obtained based on the phase difference value and a refractive index of the resin film.
The total light transmittance and the value of "(Nx+Ny)/2-Nz" of the resin film formed from the resin composition obtained in each of the Examples and the Comparative Example as described above were shown in Table 1 below as results. Then, the results were evaluated.
Figure JPOXMLDOC01-appb-T000001
As shown in Table 1, in each of the resin films obtained in the Examples, the value of "(Nx+Ny)/2-Nz" of the resin film was more than 0.01. In contrast, each of the resin films obtained in the Comparative Example could not satisfy such a relationship.
Further, each of the resin films obtained in the Examples has high total light transmittance.

Claims (19)

  1. A resin composition comprising:
    a polymer; and
    a solvent dissolving the polymer,
    wherein the resin composition is used to form a layer, and when refractive indexes of the layer along two perpendicular in-plane directions thereof are respectively defined as "Nx" and "Ny" and a refractive index of the layer along a thickness direction thereof is defined as "Nz", Nx, Ny and Nz satisfy a relationship of "(Nx+Ny)/2-Nz" > 0.01.
  2. The resin composition according to claim 1, wherein the polymer is an aromatic polyamide.
  3. The resin composition according to claim 2, wherein the aromatic polyamide contains a rigid structure in an amount of 60 mol% or more.
  4. The resin composition according to claim 3, wherein the rigid structure is a repeating unit represented by the following general formula:
    Figure JPOXMLDOC01-appb-I000032
    where n is an integer number of 1 to 4, Ar1 is represented by the following general formula (A) or (B):
    Figure JPOXMLDOC01-appb-I000033
    Figure JPOXMLDOC01-appb-I000034
    (where p=4; each of R1, R4 and R5 is selected from the group consisting of a hydrogen atom, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom and an iodine atom), an alkyl group, a substituted alkyl group such as a halogenated alkyl group, a nitro group, a cyano group, a thioalkyl group, an alkoxy group, a substituted alkoxy group such as a halogenated alkoxy group, an aryl group, a substituted aryl group such as a halogenated aryl group, an alkyl ester group, a substituted alkyl ester group, and a combination of them; and G1 is selected from the group consisting of a covalent bond, a CH2 group, a C(CH3)2 group, a C(CF3)2 group, a C(CX3)2 group (X represents a halogen atom.), a CO group, an oxygen atom, a sulfur atom, an SO2 group, an Si(CH3)2 group, a 9,9-fluorene group, a substituted 9,9-fluorene group and an OZO group (Z represents an aryl group or substituted aryl group such as a phenyl group, a biphenyl group, a perfluorobiphenyl group, a 9,9-bisphenyl fluorene group and a substituted 9,9-bisphenyl fluorene group.).), and Ar2 is represented by the following general formula (C) or (D):
    Figure JPOXMLDOC01-appb-I000035
    Figure JPOXMLDOC01-appb-I000036
    (where p=4; each of R6, R7 and R8 is selected from the group consisting of a hydrogen atom, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom and an iodine atom), an alkyl group, a substituted alkyl group such as a halogenated alkyl group, a nitro group, a cyano group, a thioalkyl group, an alkoxy group, a substituted alkoxy group such as a halogenated alkoxy group, an aryl group, a substituted aryl group such as a halogenated aryl group, an alkyl ester group, a substituted alkyl ester group, and a combination of them; and G2 is selected from the group consisting of a covalent bond, a CH2 group, a C(CH3)2 group, a C(CF3)2 group, a C(CX3)2 group (X represents a halogen atom.), a CO group, an oxygen atom, a sulfur atom, an SO2 group, an Si(CH3)2 group, a 9,9-fluorene group, a substituted 9,9-fluorene group and an OZO group (Z represents an aryl group or substituted aryl group such as a phenyl group, a biphenyl group, a perfluorobiphenyl group, a 9,9-bisphenyl fluorene group and a substituted 9,9-bisphenyl fluorene group.).).)
  5. The resin composition according to claim 4, wherein the rigid structure contains at least one of a structure derived from 4,4'-diamino-2,2'-bistrifluoromethyl benzidine (PFMB) and a structure derived from terephthaloyl dichloride (TPC).
  6. The resin composition according to claim 2, wherein the aromatic polyamide is a wholly aromatic polyamide.
  7. The resin composition according to claim 2, wherein at least one terminal of the aromatic polyamide is end-capped.
  8. The resin composition according to claim 1, wherein a total light transmittance of the layer in a sodium line (D line) is 60% or more.
  9. The resin composition according to claim 1, wherein the resin composition further contains an inorganic filler.
  10. A substrate used for forming an electronic element thereon, comprising:
    a plate-like base member having a first surface and a second surface opposite to the first surface; and
    an electronic element formation layer provided at a side of the first surface of the base member, containing a polymer and configured to be capable of forming the electronic element on the electronic element formation layer,
    wherein when refractive indexes of the electronic element formation layer along two perpendicular in-plane directions thereof are respectively defined as "Nx" and "Ny" and a refractive index of the electronic element formation layer along a thickness direction thereof is defined as "Nz", Nx, Ny and Nz satisfy a relationship of "(Nx+Ny)/2-Nz" > 0.01.
  11. The substrate according to claim 10, wherein a coefficient of thermal expansion (CTE) of the electronic element formation layer is 100 ppm/K or less.
  12. The substrate according to claim 10, wherein an average thickness of the electronic element formation layer is in the range of 1 to 50 micrometers.
  13. The substrate according to claim 10, wherein the electronic element is an organic EL element.
  14. A method of manufacturing an electronic device, comprising:
    preparing a substrate, the substrate including,
    a plate-like base member having a first surface and a second surface opposite to the first surface, and
    an electronic element formation layer provided at a side of the first surface of the base member and containing a polymer,
    wherein when refractive indexes of the electronic element formation layer along two perpendicular in-plane directions thereof are respectively defined as "Nx" and "Ny" and a refractive index of the electronic element formation layer along a thickness direction thereof is defined as "Nz", Nx, Ny and Nz satisfy a relationship of "(Nx+Ny)/2-Nz" > 0.01;
    forming the electronic element on a surface of the electronic element formation layer opposite to the base member;
    forming a cover layer so as to cover the electronic element;
    irradiating the electronic element formation layer with light to thereby peel off the electronic element formation layer from the base member in an interface between the base member and the electronic element formation layer; and
    separating the electronic device including the electronic element, the cover layer and the electronic element formation layer from the base member.
  15. The method according to claim 14, wherein a coefficient of thermal expansion (CTE) of the electronic element formation layer is 100 ppm/K or less.
  16. The method according to claim 14, wherein an average thickness of the electronic element formation layer is in the range of 1 to 50 micrometers.
  17. The method according to claim 14, wherein the polymer is an aromatic polyamide.
  18. The method according to claim 17, wherein the aromatic polyamide contains a rigid structure in an amount of 60 mol% or more.
  19. An electronic device manufactured by using the method defined by claim 14.
PCT/JP2014/005385 2013-10-25 2014-10-23 Resin composition, substrate, method of manufacturing electronic device and electronic devices WO2015059934A1 (en)

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