WO2012046736A1 - Élément électroluminescent organique, et son procédé de production - Google Patents

Élément électroluminescent organique, et son procédé de production Download PDF

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Publication number
WO2012046736A1
WO2012046736A1 PCT/JP2011/072882 JP2011072882W WO2012046736A1 WO 2012046736 A1 WO2012046736 A1 WO 2012046736A1 JP 2011072882 W JP2011072882 W JP 2011072882W WO 2012046736 A1 WO2012046736 A1 WO 2012046736A1
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group
film
organic
atoms
substituent
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PCT/JP2011/072882
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English (en)
Japanese (ja)
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小野　善伸
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住友化学株式会社
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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/02—Details
    • H05B33/04—Sealing arrangements, e.g. against humidity
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/10—Apparatus or processes specially adapted to the manufacture of electroluminescent light sources
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/84—Passivation; Containers; Encapsulations
    • H10K50/844—Encapsulations
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass

Definitions

  • the present invention relates to an organic EL device and a manufacturing method thereof.
  • An organic EL (Electro Luminescence) element has a structure in which a plurality of thin films are laminated. Flexibility can be imparted to the element itself by appropriately setting the thickness and material of each thin film.
  • the entire apparatus on which the organic EL element is mounted can be a flexible apparatus.
  • Organic EL elements deteriorate when exposed to the open air.
  • the electron injection layer that constitutes a part of the organic EL element often contains Li or Na that easily reacts with oxygen or moisture. Therefore, the electron injection layer is more easily deteriorated when exposed to the outside air. Therefore, the organic EL element is usually provided on a film having a high gas barrier property that hardly transmits oxygen or moisture.
  • a film having a high gas barrier property a film formed by forming a thin film made of an inorganic oxide such as silicon oxide, silicon nitride, silicon oxynitride, and aluminum oxide on a plastic substrate has been proposed.
  • PVD physical vapor deposition
  • CVD chemical vapor deposition
  • a film having a high gas barrier property using such a film forming method for example, Japanese Patent Laid-Open No. 4-89236 (Patent Document 1) discloses a laminated vapor deposition formed by laminating two or more silicon oxide vapor deposited films. A film having a membrane layer is disclosed.
  • Patent Document 2 a film having ceramic-based inorganic barrier films and polymer films laminated alternately is disclosed in JP-T-2002-532850 (Patent Document 2).
  • Patent Document 1 has a problem that the gas barrier property is not always sufficient and the gas barrier property is lowered by being bent.
  • Patent Document 2 According to the film described in Patent Document 2, it is expected that the gas barrier property is improved and the decrease in the gas barrier property due to bending is suppressed. However, the film production process described in Patent Document 2 has a problem that it is complicated and requires a long production time.
  • An object of the present invention is to provide an organic EL element itself, in particular, an organic EL element in which an electron injection layer constituting a part thereof is not easily deteriorated, and a high gas barrier property, and the gas barrier property is hardly lowered even when the film is bent. And an organic EL device comprising a film that can be formed in a short time by a simple process.
  • the present invention relates to an organic EL device including a first film and an organic EL element provided on the first film.
  • the organic EL element has a pair of electrodes, a light emitting layer disposed between the electrodes, and an electron injection layer disposed between the electrodes.
  • the electron injection layer includes an ionic polymer.
  • the first film has a gas barrier layer containing silicon (silicon atoms), oxygen (oxygen atoms) and carbon (carbon atoms), and the amount (number of silicon atoms) of the total amount of silicon atoms, oxygen atoms and carbon atoms.
  • Ratio atomic ratio of silicon
  • ratio (number of oxygen atoms) of oxygen atoms atomic ratio of oxygen
  • ratio (number of carbon atoms) of carbon atoms number of carbon atoms
  • thickness direction of the gas barrier layer A silicon distribution curve, an oxygen distribution curve, and a carbon distribution curve representing the relationship between the distance from one surface of the gas barrier layer in the film thickness direction) and the following conditions: (I) In a region of 90% or more in the thickness direction (film thickness direction) of the gas barrier layer, the number of silicon atoms among the ratio of the number of silicon atoms, the ratio of the number of oxygen atoms, and the ratio of the number of carbon atoms Is the second largest value, (Ii) the carbon distribution curve has at least one extreme value; and (iii) the difference (absolute value) between the maximum value and the minimum value of the ratio ratio of the number of carbon atoms in the carbon distribution curve is 5 atomic% ( at%) or more, Meet.
  • the present invention also includes a step of forming an organic EL element having a pair of electrodes, a light emitting layer disposed between the electrodes, and an electron injection layer including an ionic polymer disposed between the electrodes, silicon atoms, oxygen
  • the method of manufacturing an organic electroluminescent apparatus including the process of bonding a film and a said 2nd film.
  • the gas barrier layer includes a ratio of the number of silicon atoms, a ratio of the number of oxygen atoms, and a ratio of the number of carbon atoms to the total amount of silicon atoms, oxygen atoms, and carbon atoms, and the gas barrier layer in the thickness direction of the gas barrier layer.
  • a silicon distribution curve, an oxygen distribution curve, and a carbon distribution curve representing the relationship between the distance from one surface and the following conditions are as follows: (I) In the region of 90% or more in the thickness direction of the gas barrier layer, the ratio of the number of silicon atoms is the second among the ratio of the number of silicon atoms, the ratio of the number of oxygen atoms, and the ratio of the number of carbon atoms.
  • the carbon distribution curve has at least one extreme value; and (iii) the difference between the maximum value and the minimum value of the ratio ratio of the number of carbon atoms in the carbon distribution curve is 5 atomic% or more.
  • an organic EL device in which deterioration due to outside air is suppressed, and a high gas barrier property and a gas barrier property are lowered even when the film is bent.
  • An organic EL device including a film that is difficult and can be formed in a short time by a simple process can be realized.
  • the organic EL device includes a first film and an organic EL element provided on the first film.
  • the organic EL element has a pair of electrodes, a light emitting layer disposed between the electrodes, and an electron injection layer disposed between the electrodes.
  • the electron injection layer includes an ionic polymer.
  • the first film has a gas barrier layer containing silicon atoms, oxygen atoms, and carbon atoms.
  • the organic EL device usually has a support substrate and an organic EL element provided on the support substrate.
  • the organic EL device may further include a sealing member that is bonded to the support substrate while an organic EL element is interposed between the organic EL device and the support substrate.
  • the first film of the organic EL device according to the present embodiment may be used as a support substrate on which an organic EL element is provided, or may be used as a sealing member bonded to the support substrate.
  • a second film is further provided as a support substrate and the first film is provided as a sealing member will be described.
  • Organic EL elements mounted on organic EL devices can be broadly classified into the following three types of elements. That is, the organic EL element is (I) a so-called bottom emission type element that emits light toward the support base on which the organic EL element is mounted, and (II) the light toward the side opposite to the support base.
  • the so-called top emission type element that emits light, and (III) is broadly divided into double-sided light emitting type elements that emit light toward the support substrate and emit light toward the opposite side of the support substrate Can do.
  • the organic EL element mounted on the organic EL device according to this embodiment may be any type of element.
  • an organic EL device provided with a top emission type element will be described with reference to FIG. 1, and then an organic EL device provided with a bottom emission type element will be described with reference to FIG. .
  • FIG. 1 is a cross-sectional view schematically showing an organic EL device according to an embodiment.
  • the organic EL element 2 is mounted on the second film 1.
  • the first film 11 is disposed on the second film 1 with the organic EL element 2 interposed therebetween, and seals the organic EL element 2 together with the second film 1.
  • the first film 11 and the second film 1 are bonded to each other through the adhesive layer 4.
  • the organic EL element 2 is covered with a protective layer 3 as necessary. By providing this protective layer 3, the organic EL element 2 can be protected from the adhesive layer 4.
  • the organic EL element 2 shown in FIG. 1 is a top emission type element and emits light toward the first film 11. Therefore, the first film 11 needs to be formed by a member that transmits light.
  • the second film 1 corresponding to the support substrate may be formed of an opaque member that does not transmit light.
  • the second film 1 a plastic film or a metal film can be used, and a metal film is preferable. Since the metal film has a higher gas barrier property than a plastic film or the like, the gas barrier property of the organic EL device can be improved.
  • the metal film for example, a thin plate of Al, Cu or Fe and a thin plate of an alloy such as stainless steel can be used.
  • the first film 11 has a gas barrier layer 5 containing silicon atoms, oxygen atoms and carbon atoms.
  • the 1st film 11 is comprised from the base material 6 and the gas barrier layer 5 provided on the main surface by the side of the organic EL element 2 of the base material 6.
  • FIG. The gas barrier layer 5 has high gas barrier properties by satisfying the conditions (i), (ii), and (iii) described later, and can further suppress a decrease in gas barrier properties when bent.
  • the organic EL element according to this embodiment includes an electron injection layer containing an ionic polymer.
  • the electron injection layer according to this embodiment includes an ionic polymer, the electron injection layer is less likely to be deteriorated by outside air than a conventional electron injection layer containing Li or Na.
  • the organic EL device according to the present embodiment is sealed with the first film 11 and the second film 1 having a high gas barrier property as described above, thereby realizing the organic EL device 13 that is not easily deteriorated by the outside air. be able to.
  • An organic EL device including an electron injection layer containing an ionic polymer is stable in the air, and therefore, the deterioration in the air proceeds very slowly. For this reason, it is not always necessary to form a protective film, which is essential in the conventional organic EL element, and the number of steps in manufacturing the organic EL element can be reduced.
  • the organic EL element according to the present embodiment is not easily deteriorated even if the process (conveying process and sealing process) until the sealing process is completed in the air, it is conventionally in a vacuum or an inert gas atmosphere.
  • the sealing process can be performed in the atmosphere where the sealing process has been performed. This eliminates the need for a large and complicated manufacturing apparatus that has conventionally been required to create a vacuum or inert gas atmosphere.
  • a large and complicated production for placing a large apparatus such as a continuous laminating apparatus in a vacuum atmosphere or an inert gas atmosphere. Equipment was previously required.
  • the organic EL device according to the present embodiment such a manufacturing facility is unnecessary, and the organic EL device can be manufactured with a very simple manufacturing facility.
  • FIG. 2 is a cross-sectional view schematically showing an organic EL device 13 according to another embodiment.
  • the organic EL device 13 shown in FIG. 2 differs from the embodiment shown in FIG. 1 in the organic EL element 2 and the second film 1.
  • the organic EL element 2 of the present embodiment is a bottom emission type element, and emits light toward the second film 1 corresponding to the support base material. Therefore, the 2nd film 1 needs to be a film which shows a light transmittance.
  • the second film 1 of the present embodiment is not particularly limited as long as it is a light-transmitting film, but contains silicon atoms, oxygen atoms, and carbon atoms in the same manner as the first film 11 from the viewpoint of gas barrier properties.
  • the second gas barrier layer 8 is preferably provided.
  • the second film 1 includes a base material 7 and a second gas barrier layer 8 provided on the main surface of the base material 7 on the organic EL element 2 side.
  • the second gas barrier layer 8 has a high gas barrier property and is further bent by satisfying conditions (i), (ii) and (iii) described later. It is possible to suppress a decrease in gas barrier property when
  • an organic EL device can be manufactured with a very simple manufacturing facility as in the above-described embodiment.
  • a double-sided light emitting organic EL element may be provided in place of the bottom emission organic EL element.
  • the organic EL element may be sealed with the first film and the second film using the second film as the sealing member and the first film having the gas barrier layer as the supporting substrate.
  • an additional film may be further bonded to the second film and / or the first film.
  • Additional films include a protective film that protects the surface of the organic EL device, an antireflection film that prevents reflection of external light incident on the organic EL device, a light extraction film that increases the light extraction efficiency, and a phase of light.
  • the additional film is bonded to one side or both sides of the second film and / or the first film.
  • FIG. 13 is a cross-sectional view showing an organic EL device according to another embodiment.
  • the organic EL element 2 is provided on the first film using the first film as a supporting base material.
  • the organic EL device does not include the second film.
  • the adhesive layer 4 is a layer that adheres the first film and the second film in a state where the organic EL element is disposed between them.
  • the adhesive used for the adhesive layer 4 preferably has a high gas barrier property.
  • the light transmittance of the adhesive layer 4 is preferably high. In this case, from the viewpoint of light extraction efficiency, the absolute value of the difference in refractive index between the layer in contact with the adhesive layer 4 and the adhesive layer 4 is preferably small.
  • a curable adhesive such as a thermosetting adhesive and a photocurable adhesive is suitable.
  • thermosetting resin adhesives examples include epoxy adhesives and acrylate adhesives.
  • the epoxy adhesive examples include an adhesive containing an epoxy compound selected from bisphenol A type epoxy resin, bisphenol F type epoxy resin, and phenoxy resin.
  • acrylate adhesive for example, a monomer as a main component selected from acrylic acid, methacrylic acid, ethyl acrylate, butyl acrylate, 2-hexyl acrylate, acrylamide, acrylonitrile, hydroxyl acrylate, and the like, and copolymerizable with the main component And an adhesive containing a simple monomer.
  • photo-curable adhesive examples include radical adhesives and cationic adhesives.
  • radical adhesives include adhesives containing epoxy acrylate, ester acrylate, ester acrylate, and the like.
  • cationic adhesives examples include adhesives containing epoxy resins, vinyl ether resins, and the like.
  • the protective layer is provided so as to cover the organic EL element. By providing this protective layer, the organic EL element can be protected from the adhesive layer.
  • the protective layer preferably has a function of blocking moisture and oxygen in the atmosphere and protecting the organic EL element from these until the organic EL element is sealed by the first film.
  • the material used for the protective layer examples include a metal material that is stable in the air, an inorganic insulating material having excellent barrier properties, and an organic insulating material.
  • the metal material is selected from, for example, Al, Cu, Ag, Au, Pt, Ti, Cr, Co, and Ni.
  • Inorganic insulating material for example, SiO 2, SiN, selected from SiOxNy and SiOxCy. Parylene or the like is used as the organic insulating material.
  • the protective layer formed from a metal material is formed by, for example, a vacuum deposition method, a sputtering method, or a plating method.
  • the protective layer formed from an inorganic insulating material is formed by, for example, a sputtering method, a CVD method, or a laser ablation method.
  • the protective layer formed of an organic insulating material is formed by, for example, a film forming method including vacuum vapor deposition of a monomer gas and polymerization on a vapor deposition film (coating surface) containing the monomer.
  • a second film 1 having an organic EL element formed on the main surface is prepared.
  • the second film 1 is one in which the organic EL element is formed on the main surface, wound into a roll together with the organic EL element, and temporarily stored in the wound state.
  • the wound second film 1 and the organic EL element are stored in, for example, a vacuum, an inert gas atmosphere, or an air atmosphere. Among these, it is preferable to store in an inert gas atmosphere or an air atmosphere, and it is more preferable to store in an air atmosphere.
  • the organic EL element according to the present embodiment is gradually deteriorated by the atmosphere, so that the wound second film 1 and the organic EL element can be stored in the atmosphere.
  • the device for producing the organic EL device is not complicated, and the organic EL device can be manufactured by a simple process.
  • a mode in which a film in which an organic EL element is formed in advance on the main surface of the second film 1 and the first film are bonded together will be described.
  • a film in which an organic EL element is formed in advance on the main surface of the first film may be bonded to the second film.
  • FIG. 3 is a diagram schematically showing an apparatus for manufacturing an organic EL device.
  • the second film 1 and the first film 11 are bonded together, and an additional film 820 is bonded to the first film 11.
  • An organic EL element is formed in advance on the second film 1.
  • the unwinding roll 500 sends out the 2nd film 1 in which the organic EL element was previously formed on it.
  • the unwinding roll 510 sends out the first film 11.
  • the adhesive agent is apply
  • the first film 11 and the second film 1 are passed between two rolls (first bonding rolls 511 and 512) in a state where the organic EL element is disposed therebetween.
  • the 1st film 11 supplied via the conveyance roll 513 and the 2nd film 1 are bonded together via the 1st adhesion layer, and also 1st adhesion is carried out by hardening device 611 for the 1st adhesion layer.
  • the layer is cured (solidified).
  • an adhesive is applied by a coating device 610 for the second adhesive layer provided downstream of the curing device 611, and a second adhesive layer is further formed.
  • the second bonding rolls 521 and 522 cause the first film 11 and the additional film 820 fed from the unwinding roll 520 and supplied via the transporting roll 523 to pass through the second adhesive layer.
  • the second adhesive layer is cured (solidified) by the curing device 621 for the second adhesive layer.
  • the formed organic EL device is wound up by a winding roll 530.
  • the above-described bonding step can be performed, for example, in a vacuum, in an inert gas atmosphere, or in an air atmosphere. Among these, an inert gas atmosphere or an air atmosphere is preferable, and an air atmosphere is more preferable. As described above, since the organic EL element according to the present embodiment is gradually deteriorated by the air, it is possible to perform the bonding step in the air atmosphere. When the bonding step is performed in the atmosphere in the air, the device for manufacturing the organic EL device is not complicated, and the organic EL device can be manufactured by a simple process.
  • the organic EL device formed by bonding the first film 11 and the second film 1 is taken up by a take-up roll 530.
  • the wound organic EL device is stored in, for example, a vacuum, an inert gas atmosphere, or an air atmosphere. Especially, it is preferable to store in an inert gas atmosphere or air atmosphere, and it is still more preferable to store in air atmosphere.
  • the organic EL element according to the present embodiment is gradually deteriorated by the atmosphere, and is wound by being wound by the first film 11 and the second film 1 having a high gas barrier property.
  • the organic EL device can be stored in the atmosphere. When the wound organic EL device is stored in the air, the device for producing the organic EL device is not complicated, and the organic EL device can be manufactured by a simple process.
  • the second film in which the organic EL element is formed on the main surface is temporarily wound and stored.
  • the present invention is not limited to this form, and the organic film is formed on the main surface of the second film.
  • the first film may be bonded without winding up the second film.
  • the additional film for example, the above-described film is used.
  • one additional film is bonded, but two or more additional films may be bonded sequentially.
  • the order of bonding is appropriately changed according to the stacking order of the organic EL devices.
  • the first film 11 Next, the first film 11 will be described.
  • One of the features of the organic EL device of the present embodiment is the first film, particularly the gas barrier layer 5 thereof.
  • the gas barrier layer 5 of the first film will be described first.
  • the first film has a gas barrier layer containing silicon atoms, oxygen atoms, and carbon atoms.
  • the ratio of the number of silicon atoms (the atomic ratio of silicon), the ratio of the number of oxygen atoms (the atomic ratio of oxygen) and the ratio of the number of carbon atoms (the atomic ratio of carbon to the total amount of silicon atoms, oxygen atoms and carbon atoms ) Is measured while changing the distance from one surface of the gas barrier layer in the thickness direction (film thickness direction) of the gas barrier layer, thereby expressing the relationship between the atomic ratio of each atom and the distance from the surface of the gas barrier layer.
  • a silicon distribution curve, an oxygen distribution curve, and a carbon distribution curve can be obtained.
  • These curves obtained from the gas barrier layer according to the present embodiment satisfy the following conditions (i), (ii), and (iii).
  • the silicon atomic ratio is the second largest value among the silicon atomic ratio, oxygen atomic ratio, and carbon atomic ratio.
  • the carbon distribution curve has at least one extreme value.
  • the difference (absolute value) between the maximum value and the minimum value of the atomic ratio of carbon in the carbon distribution curve is 5 at% or more.
  • condition (i) means that the following formula (1) or the following formula (2) is satisfied in a region of 90% or more in the thickness direction of the gas barrier layer.
  • the gas barrier layer described above is usually formed on a substrate. That is, the first film includes a base material and a gas barrier layer formed on the base material. Examples of the base material of the first film include a colorless and transparent resin film or resin sheet.
  • polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN); polyolefin resins such as polyethylene (PE), polypropylene (PP) and cyclic polyolefin; Resin; Polycarbonate resin; Polystyrene resin; Polyvinyl alcohol resin; Saponified ethylene-vinyl acetate copolymer; Polyacrylonitrile resin; Acetal resin; and Polyimide resin.
  • polyester-based resins and polyolefin-based resins are preferable, and PET and PEN are more preferable from the viewpoints of high heat resistance, low coefficient of linear expansion, and low manufacturing cost.
  • These resin may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the thickness of the base material of the first film can be appropriately set in consideration of the stability when the first film is manufactured.
  • the thickness of the substrate of the first film is preferably in the range of 5 to 500 ⁇ m from the viewpoint that the film can be conveyed even in a vacuum.
  • the thickness of the base material of the first film is more preferably 50 to 200 ⁇ m, More preferably, it is 50 to 100 ⁇ m.
  • the first film substrate prefferably to subject the first film substrate to a surface activation treatment for cleaning the surface from the viewpoint of adhesion to a gas barrier layer described later.
  • a surface activation treatment for cleaning the surface from the viewpoint of adhesion to a gas barrier layer described later.
  • Examples of such surface activation treatment include corona treatment, plasma treatment, and flame treatment.
  • the gas barrier layer according to this embodiment is formed on at least one surface of the substrate.
  • the 1st film concerning this embodiment should just be provided with the gas barrier layer which contains a silicon atom, an oxygen atom, and a carbon atom, and satisfy
  • the first film may have another layer that does not satisfy at least one of the above conditions (i), (ii), and (iii).
  • the gas barrier layer or other layer may further contain nitrogen atoms, aluminum atoms, and the like.
  • the gas barrier property of the gas barrier layer is deteriorated. It is preferable that the region satisfying the above formula (1) or (2) occupies 90% or more of the thickness of the gas barrier layer. This ratio is more preferably 95% or more, and still more preferably 100%.
  • the carbon distribution curve needs to have at least one extreme value as the condition (ii).
  • the carbon distribution curve preferably has two extreme values, and more preferably has three or more extreme values.
  • the gas barrier property of the gas barrier layer decreases when the first film is bent.
  • the distance in the thickness direction between adjacent extreme values of the carbon distribution curve is preferably 200 nm or less, and more preferably 100 nm or less.
  • the extreme value means a maximum value or a minimum value in a distribution curve obtained by plotting an atomic ratio of an element with respect to a distance from the surface of the gas barrier layer in the thickness direction of the gas barrier layer.
  • the maximum value is a point in the distribution curve where the value of the atomic ratio of the element changes from increasing to decreasing with the change in the distance from the surface of the gas barrier layer, and the atomic ratio value of the element at that point.
  • the atomic ratio of the element at the point where the value of the atomic ratio of the element at the position where the distance from the surface of the gas barrier layer in the thickness direction of the gas barrier layer from this point is further changed by 20 nm is reduced by 3 at% or more.
  • the minimum value is a point where the value of the atomic ratio of the element changes from decreasing to increasing as the distance from the surface of the gas barrier layer changes, and compared with the value of the atomic ratio of the element at that point,
  • the atomic ratio of the element at the point where the value of the atomic ratio of the element at a position where the distance from the surface in the thickness direction of the gas barrier layer from the point is further changed by 20 nm further increases by 3 at% or more.
  • the gas barrier layer according to the present embodiment requires that the difference between the maximum value and the minimum value of the atomic ratio of carbon in the carbon distribution curve is 5 at% or more as the condition (iii).
  • the difference between the maximum value and the minimum value of the atomic ratio of carbon is more preferably 6 at% or more, and further preferably 7 at% or more. If the difference is less than 5 at%, the gas barrier property of the gas barrier layer is lowered when the first film is bent.
  • the upper limit of this difference is not particularly limited, but is usually about 30 at%.
  • the oxygen distribution curve of the gas barrier layer preferably has at least one extreme value, more preferably has at least two extreme values, and more preferably has at least three extreme values.
  • the oxygen distribution curve has an extreme value
  • the gas barrier property of the gas barrier layer tends to be less likely to be lowered when the first film is bent.
  • the oxygen distribution curve of the gas barrier layer has at least three extreme values
  • the difference in the distance from the surface of each is preferably 200 nm or less, and more preferably 100 nm or less.
  • the difference between the maximum value and the minimum value of the oxygen atomic ratio in the oxygen distribution curve of the gas barrier layer is preferably 5 at% or more, more preferably 6 at% or more, and even more preferably 7 at% or more.
  • the upper limit of this difference is not particularly limited, but is usually about 30 at%.
  • the difference between the maximum value and the minimum value of the atomic ratio of silicon in the silicon distribution curve of the gas barrier layer is preferably less than 5 at%, more preferably less than 4 at%, and even more preferably less than 3 at%. When this difference is less than the above upper limit, the gas barrier properties of the gas barrier layer tend to be particularly high.
  • Oxygen carbon distribution curve difference between maximum and minimum values Expresses the relationship between the distance from the surface of the gas barrier layer in the thickness direction and the ratio of the total amount of oxygen atoms and carbon atoms to the total amount of silicon atoms, oxygen atoms, and carbon atoms (atomic ratio of oxygen and carbon)
  • the difference between the maximum value and the minimum value of the total atomic ratio of oxygen and carbon is preferably less than 5 at%, more preferably less than 4 at%, and more preferably less than 3 at%. Further preferred. When this difference is less than the above upper limit, the gas barrier properties of the gas barrier layer tend to be particularly high.
  • the silicon distribution curve, oxygen distribution curve, carbon distribution curve, and oxygen carbon distribution curve are obtained by combining X-ray photoelectron spectroscopy (XPS) measurement with rare gas ion sputtering such as argon. It can be created by so-called XPS depth profile measurement in which surface composition analysis is sequentially performed while being exposed.
  • XPS depth profile measurement in which surface composition analysis is sequentially performed while being exposed.
  • a distribution curve obtained by such XPS depth profile measurement can be created, for example, with the vertical axis as the atomic ratio (unit: at%) of each element and the horizontal axis as the etching time (sputtering time).
  • the etching time generally correlates with the distance from the surface of the gas barrier layer in the thickness direction of the gas barrier layer.
  • the “distance from one surface of the gas barrier layer in the thickness direction of the gas barrier layer” is the distance from the surface of the gas barrier layer calculated from the relationship between the etching rate and the etching time employed in the XPS depth profile measurement.
  • an argon (Ar +) rare gas ions sputter method using the adopted as an etching ion species the etching rate (etching rate) was 0.05 nm / sec ( It is preferable to set the value in terms of SiO 2 thermal oxide film.
  • the gas barrier layer is substantially uniform in the film surface direction (direction parallel to the main surface (surface) of the gas barrier layer).
  • the gas barrier layer is substantially uniform in the film surface direction
  • “the gas barrier layer is substantially uniform in the film surface direction” means that an oxygen distribution curve and a carbon distribution curve are measured at any two measurement points on the film surface of the gas barrier layer by XPS depth profile measurement.
  • the oxygen carbon distribution curve is created, the number of extreme values of the carbon distribution curve obtained at any two measurement points is the same, and the maximum value of the carbon atomic ratio in each carbon distribution curve The difference from the minimum value is the same as each other or the difference is within 5 at%.
  • the carbon distribution curve is preferably substantially continuous.
  • “the carbon distribution curve is substantially continuous” means that a portion in which the atomic ratio of carbon in the carbon distribution curve changes discontinuously is not included. Specifically, this is because the distance (x, unit: nm) from the surface of the gas barrier layer in the thickness direction calculated from the etching rate and etching time, and the atomic ratio of carbon (c, unit: at). %) In relation to the following formula (F1): ⁇ 1.0 ⁇ (dc / dx) ⁇ 1.0 (F1) It means that the condition represented by is satisfied.
  • the first film according to the present embodiment may include at least one gas barrier layer that satisfies all of the above conditions (i), (ii), and (iii), and the first film has the above condition (i).
  • (Ii) and (iii) may be provided with two or more gas barrier layers.
  • the materials of the plurality of gas barrier layers may be the same or different.
  • these gas barrier layers may be formed on one surface of the base material, and are formed on both surfaces of the base material, respectively. Also good.
  • the first film may include a thin film layer that does not have gas barrier properties.
  • the silicon atoms and oxygen in the gas barrier layer when the atomic ratio of silicon, the atomic ratio of oxygen, and the atomic ratio of carbon satisfy the condition expressed by the formula (1), the silicon atoms and oxygen in the gas barrier layer
  • the atomic ratio of the silicon atom content to the total amount of atoms and carbon atoms is preferably 25 to 45 at%, more preferably 30 to 40 at%.
  • the atomic ratio of the oxygen atom content to the total amount of silicon atoms, oxygen atoms and carbon atoms in the gas barrier layer is preferably 33 to 67 at%, more preferably 45 to 67 at%.
  • the atomic ratio of the carbon atom content to the total amount of silicon atoms, oxygen atoms and carbon atoms in the gas barrier layer is preferably 3 to 33 at%, and more preferably 3 to 25 at%.
  • silicon atoms and oxygen in the gas barrier layer when the atomic ratio of silicon, the atomic ratio of oxygen, and the atomic ratio of carbon satisfy the condition expressed by the formula (2), silicon atoms and oxygen in the gas barrier layer
  • the atomic ratio of the silicon atom content to the total amount of atoms and carbon atoms is preferably 25 to 45 at%, more preferably 30 to 40 at%.
  • the atomic ratio of the oxygen atom content to the total amount of silicon atoms, oxygen atoms and carbon atoms in the gas barrier layer is preferably 1 to 33 at%, and more preferably 10 to 27 at%.
  • the atomic ratio of the carbon atom content to the total amount of silicon atoms, oxygen atoms and carbon atoms in the gas barrier layer is preferably 33 to 66 at%, and more preferably 40 to 57 at%.
  • the thickness of the gas barrier layer is preferably 5 to 3000 nm, more preferably 10 to 2000 nm, and still more preferably 100 to 1000 nm. When the thickness of the gas barrier layer is within these numerical ranges, more excellent gas barrier properties such as oxygen gas barrier properties and water vapor barrier properties can be obtained, and a decrease in gas barrier properties due to bending tends to be more effectively suppressed.
  • the total thickness of the gas barrier layers is usually 10 to 10000 nm, preferably 10 to 5000 nm, more preferably 100 to 3000 nm. Preferably, it is 200 to 2000 nm.
  • the total thickness of the gas barrier layer is within these numerical ranges, more excellent gas barrier properties such as oxygen gas barrier properties and water vapor barrier properties can be obtained, and a decrease in gas barrier properties due to bending tends to be more effectively suppressed. is there.
  • the first film may further include a primer coat layer, a heat-sealable resin layer, an adhesive layer, and the like, if necessary, in addition to the base material of the first film and the gas barrier layer.
  • a primer coat layer can be formed using a primer coat agent capable of improving the adhesion between the substrate and the gas barrier layer.
  • the heat-sealable resin layer can be appropriately formed using a known heat-sealable resin.
  • the adhesive layer can be appropriately formed using a normal adhesive, and the plurality of first films may be bonded to each other by such an adhesive layer.
  • the gas barrier layer of the first film is preferably a layer formed by a plasma chemical vapor deposition method.
  • the gas barrier layer formed by the plasma enhanced chemical vapor deposition method is a plasma chemical vapor phase in which a base of the first film is disposed on a pair of film forming rolls, and plasma is generated by discharging between the pair of film forming rolls.
  • a layer formed by a growth method is more preferable.
  • the film forming gas used for such plasma chemical vapor deposition preferably includes an organosilicon compound and oxygen.
  • the oxygen content in the film forming gas is preferably less than or equal to the theoretical oxygen amount necessary for complete oxidation of the entire amount of the organosilicon compound in the film forming gas.
  • the gas barrier layer of the first film is preferably a layer formed by a continuous film forming process. Details of a method for forming a gas barrier layer using such a plasma chemical vapor deposition method will be described in a method for producing a first film described later.
  • the first film can be produced by forming a gas barrier layer on the surface of the substrate of the first film.
  • plasma chemical vapor deposition plasma CVD
  • the plasma enhanced chemical vapor deposition method may be a Penning discharge plasma type chemical vapor deposition method.
  • a plasma discharge in a space between a plurality of film forming rolls using a pair of film forming rolls, and each of the pair of film forming rolls. More preferably, a substrate is disposed on the substrate, and plasma is generated by discharging between the pair of film forming rolls.
  • a pair of film forming rolls in this manner, a base material existing on the other film forming roll while forming a gas barrier layer on the base material existing on one film forming roll during film formation.
  • a gas barrier layer can be simultaneously formed on the upper layer.
  • a thin film gas barrier layer
  • a gas barrier layer having the same structure can be simultaneously formed at a double film formation rate.
  • An apparatus that can be used for manufacturing the first film by such a plasma chemical vapor deposition method is not particularly limited, but includes at least a pair of film forming rolls and a plasma power source, and the pair of components is formed.
  • An apparatus capable of discharging between the film rolls is preferable. For example, by using the manufacturing apparatus shown in FIG. 4, it is possible to manufacture the first film by the roll-to-roll method while using the plasma chemical vapor deposition method.
  • FIG. 4 is a schematic diagram illustrating an example of a manufacturing apparatus that can be suitably used to manufacture the first film according to the present embodiment.
  • the same or corresponding elements are denoted by the same reference numerals, and overlapping descriptions are omitted as appropriate.
  • the manufacturing apparatus shown in FIG. 4 includes a feed roll 701, transport rolls 21, 22, 23, and 24, a pair of film forming rolls 31 and 32 disposed opposite to each other, a gas supply pipe 41, and a plasma generation power source. 51, magnetic field generators 61 and 62 installed inside the film forming rolls 31 and 32, and a winding roll 702.
  • a vacuum chamber (not shown).
  • This vacuum chamber is connected to a vacuum pump (not shown), and the pressure in the vacuum chamber can be appropriately adjusted by such a vacuum pump.
  • each film-forming roll is for plasma generation so that a pair of film-forming rolls (film-forming roll 31 and film-forming roll 32) can function as a pair of counter electrodes.
  • the power supply 51 is connected. By supplying electric power from the plasma generating power source 51, a discharge is generated in the space between the film forming roll 31 and the film forming roll 32, and thereby plasma is generated in the space between the film forming roll 31 and the film forming roll 32. Can be generated.
  • the film-forming roll 31 and the film-forming roll 32 are also used as electrodes, the material and design may be changed as appropriate so that they can also be used as electrodes.
  • the pair of film forming rolls are preferably arranged so that their central axes are substantially parallel on the same plane. In this way, a pair of film-forming rolls (film-forming rolls 31 and 32) are arranged, and the gas barrier layer is formed on each film-forming roll, thereby comparing with the case where the film is formed on one film-forming roll.
  • the film formation rate can be doubled.
  • the films having the same structure can be stacked, it is possible to at least double the number of extreme values in the carbon distribution curve.
  • the gas barrier layer can be efficiently formed on the surface of the substrate 6.
  • magnetic field generators 61 and 62 are provided inside the film forming roll 31 and the film forming roll 32.
  • the magnetic field generators 61 and 62 are fixed so as not to rotate even if the film forming roll rotates.
  • the diameters of the film forming rolls 31 and 32 are preferably substantially the same from the viewpoint of forming a thin film more efficiently.
  • the diameters of the film forming rolls 31 and 32 are preferably 5 to 100 cm from the viewpoint of discharge conditions, chamber space, and the like.
  • the base material 6 is disposed on a pair of film forming rolls (film forming roll 31 and film forming roll 32) so that the surfaces of the base material 6 face each other.
  • a pair of film forming rolls film forming roll 31 and film forming roll 32
  • each of the base materials 6 existing between the pair of film forming rolls is generated when the plasma is generated by discharging between the film forming roll 31 and the film forming roll 32.
  • the winding roll 702 is not particularly limited as long as it can wind the substrate 6 on which the gas barrier layer is formed, and is appropriately selected from commonly used rolls.
  • the gas supply pipe 41 only needs to be able to supply or discharge the raw material gas at a predetermined speed.
  • a power source of a normal plasma generating apparatus can be used as appropriate.
  • the plasma generating power supply 51 supplies power to the film forming roll 31 and the film forming roll 32 connected to the power supply 51, and makes it possible to use these as counter electrodes for discharge. Since the plasma generating power source 51 can perform plasma CVD more efficiently, it is possible to use a power source (such as an AC power source) that can alternately reverse the polarity of a pair of film forming rolls. preferable.
  • the plasma generation power source 51 can set the applied power to 100 W to 10 kW and the AC frequency to 50 Hz to 500 kHz in order to perform plasma CVD more efficiently.
  • the magnetic field generators 61 and 62 normal magnetic field generators can be used as appropriate.
  • the base material 6 in addition to the base material of the first film, a film having a gas barrier layer formed in advance can be used. Thus, by using a film having a gas barrier layer formed in advance as the substrate 6, it is possible to increase the thickness of the gas barrier layer.
  • a film forming gas such as a raw material gas
  • the film gas is decomposed by plasma, and a gas barrier layer is formed on the surface of the substrate 6 on the film forming roll 31 and on the surface of the substrate 6 on the film forming roll 32 by the plasma CVD method.
  • the base material 6 is conveyed by the delivery roll 701, the film formation roll 31 and the like, respectively. Therefore, a gas barrier is formed on the surface of the base material 6 by a roll-to-roll continuous film formation process. A layer is formed.
  • the source gas in the film forming gas used for forming the gas barrier layer is appropriately selected according to the material of the gas barrier layer to be formed.
  • the source gas for example, an organosilicon compound containing silicon can be used.
  • the source gas may contain monosilane as a silicon source in addition to the organosilicon compound.
  • the source gas is, for example, hexamethyldisiloxane, 1,1,3,3-tetramethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propylsilane, At least one organosilicon compound selected from the group consisting of phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, and octamethylcyclotetrasiloxane including.
  • organosilicon compounds hexamethyldisiloxane and 1,1,3,3-tetramethyldisiloxane are preferable from the viewpoints of handling properties of the compound and gas barrier properties of the resulting gas barrier layer.
  • organosilicon compounds can be used individually by 1 type or in combination of 2 or more types.
  • the film forming gas may contain a reactive gas in addition to the source gas.
  • a gas that reacts with the raw material gas to form an inorganic compound such as oxide or nitride can be appropriately selected and used.
  • a reaction gas for forming an oxide for example, oxygen or ozone can be used.
  • the reaction gas for forming the nitride for example, nitrogen or ammonia can be used. These reaction gases are used alone or in combination of two or more. For example, when oxynitride is formed, a reaction gas for forming an oxide and a reaction gas for forming a nitride can be combined.
  • a carrier gas may be used as necessary in order to supply a source gas into the vacuum chamber.
  • a discharge gas may be used as necessary in order to generate plasma discharge.
  • a carrier gas and a discharge gas known ones can be used as appropriate.
  • a rare gas such as helium, argon, neon, and xenon, or hydrogen can be used as the carrier gas or the discharge gas.
  • the ratio of the source gas and the reactive gas is higher than the ratio of the amount of the reactive gas that is theoretically required to completely react the raw material gas and the reactive gas. It is preferable not to make the ratio of the reaction gas excessive.
  • a thin film (gas barrier layer) satisfying all the above conditions (i), (ii) and (iii) can be formed particularly efficiently.
  • the deposition gas contains an organosilicon compound and oxygen
  • the amount of oxygen in the deposition gas is less than or equal to the theoretical oxygen amount required to fully oxidize the entire amount of the organosilicon compound in the deposition gas. Is preferred.
  • a gas containing hexamethyldisiloxane organosilicon compound: HMDSO: (CH 3 ) 6 Si 2 O :) as a source gas and oxygen (O 2 ) as a reaction gas is used as a film forming gas
  • organosilicon compound: HMDSO: (CH 3 ) 6 Si 2 O :) as a source gas
  • oxygen (O 2 ) as a reaction gas
  • a film-forming gas containing hexamethyldisiloxane (HMDSO, (CH 3 ) 6 Si 2 O) as a source gas and oxygen (O 2 ) as a reaction gas is reacted by plasma CVD to form a silicon-oxygen-based material.
  • HMDSO hexamethyldisiloxane
  • O 2 oxygen
  • the following reaction formula (3) in the film-forming gas (CH 3 ) 6 Si 2 O + 12O 2 ⁇ 6CO 2 + 9H 2 O + 2SiO 2 (3)
  • the reaction represented by this occurs and silicon dioxide is formed.
  • the amount of oxygen necessary to completely oxidize 1 mol of hexamethyldisiloxane is 12 mol.
  • a uniform silicon dioxide film can be formed when 12 moles or more of oxygen is contained in 1 mole of hexamethyldisiloxane and completely reacted in the film forming gas.
  • the oxygen amount is set to a stoichiometric ratio of 12 with respect to 1 mol of hexamethyldisiloxane so that the reaction of the above formula (3) does not proceed completely. It is preferable to make it less than a mole.
  • the raw material hexamethyldisiloxane and the reaction gas oxygen are supplied from the gas supply unit to the film formation region to form a film, so the molar amount (flow rate) of oxygen in the reaction gas
  • the molar amount (flow rate) is 12 times the molar amount (flow rate) of the raw material hexamethyldisiloxane
  • the reaction does not proceed completely, and oxygen is compared to the stoichiometric ratio. It is thought that the reaction is often completed only when a large excess is supplied.
  • the molar amount (flow rate) of oxygen may be about 20 times or more the molar amount (flow rate) of hexamethyldisiloxane as a raw material. Therefore, the molar amount (flow rate) of oxygen with respect to the molar amount (flow rate) of the raw material hexamethyldisiloxane is preferably an amount of 12 times or less (more preferably 10 times or less) which is the stoichiometric ratio. .
  • the molar amount (flow rate) of oxygen with respect to the molar amount (flow rate) of hexamethyldisiloxane in the film forming gas is greater than 0.1 times the molar amount (flow rate) of hexamethyldisiloxane. It is preferable that the amount is more than 0.5 times.
  • the pressure in the vacuum chamber (degree of vacuum) can be adjusted as appropriate according to the type of source gas, but is preferably in the range of 0.1 Pa to 50 Pa.
  • an electrode drum connected to the plasma generating power supply 51 (in this embodiment, the film forming rolls 31 and 32 are installed).
  • the conveyance speed (line speed) of the substrate 6 can be appropriately adjusted according to the type of source gas, the pressure in the vacuum chamber, etc., but is preferably 0.1 to 100 m / min, 0.5 More preferably, it is ⁇ 20 m / min.
  • line speed is less than the lower limit, wrinkles due to heat tend to occur in the film, and when the line speed exceeds the upper limit, the thickness of the formed gas barrier layer tends to be thin.
  • the second film when the light emitted from the organic EL element is emitted to the outside through the second film, the second film needs to be formed of a member that exhibits light transmittance. In that case, it is preferable that the 2nd film has a 2nd gas barrier layer similarly to the 1st film.
  • the second gas barrier layer contains silicon atoms, oxygen atoms, and carbon atoms, and the silicon distribution curve, oxygen distribution curve, and carbon distribution curve in the second gas barrier layer satisfy the above-described conditions (i ) To (iii) are satisfied.
  • This second gas barrier layer can be formed by the same method as the gas barrier layer in the first film described above.
  • the second gas barrier layer may have exactly the same configuration as the gas barrier layer of the first film, but as long as the oxygen distribution curve and the carbon distribution curve satisfy the conditions (i) to (iii),
  • the film may have a different structure from the gas barrier layer.
  • the organic EL element according to the present embodiment is formed on the second film or the first film before the step of bonding the first film and the second film.
  • the organic EL device has a pair of electrodes composed of an anode and a cathode, a light emitting layer provided between the electrodes, and an electron injection layer provided between the electrodes.
  • a predetermined layer may be provided between the pair of electrodes as necessary.
  • the light emitting layer is not limited to one layer, and a plurality of layers may be provided.
  • the organic EL device according to this embodiment includes an electron injection layer between the light emitting layer and the cathode.
  • Examples of the layer provided between the cathode and the light emitting layer include an electron injection layer, an electron transport layer, and a hole blocking layer.
  • the layer in contact with the cathode is referred to as an electron injection layer, and the layer excluding this electron injection layer is referred to as an electron transport layer.
  • the electron injection layer has a function of improving the electron injection efficiency from the cathode.
  • the electron transport layer has a function of improving electron injection from the layer in contact with the surface on the cathode side.
  • the hole blocking layer has a function of blocking hole transport. When the electron injection layer and / or the electron transport layer has a function of blocking hole transport, these layers may also serve as the hole blocking layer.
  • the hole blocking layer has a function of blocking hole transport can be confirmed, for example, by fabricating a device that allows only the hole current to flow and reducing the current value.
  • Examples of the layer provided between the anode and the light emitting layer include a hole injection layer, a hole transport layer, and an electron block layer.
  • the layer in contact with the anode is called a hole injection layer, and the layers other than the hole injection layer are positive. It is called a hole transport layer.
  • the hole injection layer has a function of improving the hole injection efficiency from the anode.
  • the hole transport layer has a function of improving hole injection from a layer in contact with the surface on the anode side.
  • the electron blocking layer has a function of blocking electron transport. When the hole injection layer and / or the hole transport layer have a function of blocking electron transport, these layers may also serve as the electron block layer.
  • the electron blocking layer has a function of blocking electron transport can be confirmed, for example, by producing an element that allows only an electron current to flow and reducing the current value.
  • the electron injection layer and the hole injection layer may be collectively referred to as a charge injection layer, and the electron transport layer and the hole transport layer may be collectively referred to as a charge transport layer.
  • An example of the layer structure that the organic EL element of the present embodiment can have is shown below.
  • the organic EL element of the present embodiment may have two or more light emitting layers.
  • structural unit A when the laminate sandwiched between the anode and the cathode is referred to as “structural unit A”, the configuration of the organic EL element having two light emitting layers is as follows. And the layer structure shown in the following g). The two (structural unit A) layer structures may be the same or different. g) Anode / (constituent unit A) / charge generation layer / (constituent unit A) / cathode
  • (structural unit A) / charge generation layer” is “structural unit B”
  • examples of the configuration of the organic EL device having three or more light-emitting layers include the layer configuration shown in h) below.
  • Anode / (Structural unit B) x / (Structural unit A) / Cathode The symbol “x” represents an integer of 2 or more, and (Structural unit B) x is a stack composed of the structural units B stacked in x stages. Represents the body.
  • a plurality of (structural unit B) layer configurations may be the same or different.
  • the charge generation layer is a layer that generates holes and electrons by applying an electric field.
  • Examples of the charge generation layer include a thin film containing vanadium oxide, indium tin oxide (abbreviated as ITO), molybdenum oxide, and the like.
  • the order of the layers to be laminated, the number of layers, and the thickness of each layer can be appropriately set in consideration of the light emission efficiency and the element lifetime.
  • an electrode exhibiting light transmittance is used as the anode.
  • an electrode exhibiting light transmittance a thin film of metal oxide, metal sulfide, metal, or the like can be used, and an electrode having high electrical conductivity and light transmittance is preferable.
  • a thin film containing indium oxide, zinc oxide, tin oxide, ITO, indium zinc oxide (abbreviated as IZO), gold, platinum, silver, copper, or the like is used.
  • a thin film made of ITO, IZO, or tin oxide is preferable.
  • Examples of the method for producing the anode include a vacuum deposition method, a sputtering method, an ion plating method, and a plating method.
  • an organic transparent conductive film such as polyaniline or a derivative thereof and polythiophene or a derivative thereof may be used.
  • the thickness of the anode is appropriately set in consideration of required characteristics and process simplicity, and is, for example, 10 nm to 10 ⁇ m, preferably 20 nm to 1 ⁇ m, and more preferably 50 nm to 500 nm.
  • the hole injection material constituting the hole injection layer includes oxides such as vanadium oxide, molybdenum oxide, ruthenium oxide, and aluminum oxide, phenylamine compounds, starburst amine compounds, phthalocyanines, amorphous carbon, polyaniline And polythiophene derivatives.
  • Examples of the method for forming the hole injection layer include film formation from a solution containing a hole injection material.
  • a hole injection layer can be formed by applying a solution containing a hole injection material by a predetermined application method to form a film, and solidifying the formed solution.
  • the solvent used for film formation from a solution is not particularly limited as long as it dissolves the hole injection material.
  • Chlorine solvents such as chloroform, methylene chloride and dichloroethane, ether solvents such as tetrahydrofuran, toluene and xylene
  • aromatic hydrocarbon solvents such as acetone, ketone solvents such as acetone and methyl ethyl ketone, ester solvents such as ethyl acetate, butyl acetate and ethyl cellosolve acetate, and water.
  • coating methods spin coating method, casting method, micro gravure coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method, dip coating method, spray coating method, screen printing method, flexographic printing method, offset Examples thereof include a printing method and an ink jet printing method.
  • the thickness of the hole injection layer is appropriately set in consideration of required characteristics and process simplicity, and is, for example, 1 nm to 1 ⁇ m, preferably 2 nm to 500 nm, and more preferably 5 nm to 200 nm.
  • ⁇ Hole transport layer> As the hole transport material constituting the hole transport layer, polyvinylcarbazole or a derivative thereof, polysilane or a derivative thereof, a polysiloxane derivative having an aromatic amine in a side chain or a main chain, a pyrazoline derivative, an arylamine derivative, a stilbene derivative, Triphenyldiamine derivative, polyaniline or derivative thereof, polythiophene or derivative thereof, polyarylamine or derivative thereof, polypyrrole or derivative thereof, poly (p-phenylenevinylene) or derivative thereof, and poly (2,5-thienylenevinylene) or Examples thereof include derivatives thereof.
  • hole transport materials include polyvinyl carbazole or derivatives thereof, polysilane or derivatives thereof, polysiloxane derivatives having aromatic amine compound groups in the side chain or main chain, polyaniline or derivatives thereof, polythiophene or derivatives thereof, poly Polymeric hole transport materials such as arylamines or derivatives thereof, poly (p-phenylene vinylene) or derivatives thereof, and poly (2,5-thienylene vinylene) or derivatives thereof are preferred. More preferable hole transport materials are polyvinyl carbazole or a derivative thereof, polysilane or a derivative thereof, and a polysiloxane derivative having an aromatic amine in a side chain or a main chain.
  • the low molecular hole transport material is preferably used by being dispersed in a polymer binder.
  • the method for forming the hole transport layer is not particularly limited, but in the case of a low molecular hole transport material, film formation from a mixed solution containing a polymer binder and a hole transport material can be exemplified.
  • molecular hole transport materials include film formation from a solution containing a hole transport material.
  • the solvent used for film formation from a solution is not particularly limited as long as it can dissolve a hole transport material.
  • Chlorine solvents such as chloroform, methylene chloride and dichloroethane, ether solvents such as tetrahydrofuran, toluene and xylene
  • aromatic hydrocarbon solvents such as ketone solvents such as acetone and methyl ethyl ketone, and ester solvents such as ethyl acetate, butyl acetate and ethyl cellosolve acetate.
  • the polymer binder combined with the hole transport material does not extremely impede charge transport, and that absorption with respect to visible light is weak.
  • the polymer binder is selected from, for example, polycarbonate, polyacrylate, polymethyl acrylate, polymethyl methacrylate, polystyrene, polyvinyl chloride, and polysiloxane.
  • the thickness of the hole transport layer varies depending on the material used, and is appropriately set so that the drive voltage and the light emission efficiency are appropriate.
  • the hole transport layer must have at least a thickness that does not cause pinholes. If the hole transport layer is too thick, the driving voltage of the device increases. Therefore, the thickness of the hole transport layer is, for example, 1 nm to 1 ⁇ m, preferably 2 nm to 500 nm, more preferably 5 nm to 200 nm.
  • the light emitting layer is usually formed of an organic substance (light emitting material) that mainly emits fluorescence and / or phosphorescence, or the organic substance and a dopant that assists the organic substance.
  • the dopant is added, for example, to improve the luminous efficiency or to change the emission wavelength.
  • the organic substance contained in the light emitting layer may be a low molecular compound or a high molecular compound.
  • the light emitting layer preferably contains a polymer compound.
  • the light emitting layer preferably contains a high molecular compound having a polystyrene-reduced number average molecular weight of 10 3 to 10 8 .
  • Examples of the light emitting material constituting the light emitting layer include the following dye materials, metal complex materials, polymer materials, and dopant materials.
  • dye-based materials include cyclopentamine derivatives, tetraphenylbutadiene derivative compounds, triphenylamine derivatives, oxadiazole derivatives, pyrazoloquinoline derivatives, distyrylbenzene derivatives, distyrylarylene derivatives, pyrrole derivatives, thiophene ring compounds. Pyridine ring compounds, perinone derivatives, perylene derivatives, oligothiophene derivatives, oxadiazole dimers, pyrazoline dimers, quinacridone derivatives, and coumarin derivatives.
  • Metal complex materials examples include rare earth metals such as Tb, Eu and Dy, and central metals selected from Al, Zn, Be, Ir and Pt, oxadiazole, thiadiazole, phenylpyridine, phenylbenzimidazole, and the like.
  • a metal complex having a ligand selected from a quinoline structure and the like can be given.
  • metal complexes having light emission from triplet excited state such as iridium complexes and platinum complexes, aluminum quinolinol complexes, benzoquinolinol beryllium complexes, benzoxazolyl zinc complexes, benzothiazole zinc complexes, azomethyl zinc complexes, porphyrin zinc complexes, And a phenanthroline europium complex.
  • Polymer material As polymer materials, polyparaphenylene vinylene derivatives, polythiophene derivatives, polyparaphenylene derivatives, polysilane derivatives, polyacetylene derivatives, polyfluorene derivatives, polyvinylcarbazole derivatives, the above dye materials or metal complex light emitting materials are polymerized. Materials etc. can be mentioned.
  • examples of materials that emit blue light include distyrylarylene derivatives, oxadiazole derivatives, and polymers thereof, polyvinylcarbazole derivatives, polyparaphenylene derivatives, and polyfluorene derivatives. .
  • polymer materials such as polyvinyl carbazole derivatives, polyparaphenylene derivatives, and polyfluorene derivatives are preferred.
  • Examples of materials that emit green light include quinacridone derivatives, coumarin derivatives, and polymers thereof, polyparaphenylene vinylene derivatives, and polyfluorene derivatives.
  • polymer materials such as polyparaphenylene vinylene derivatives and polyfluorene derivatives are preferable.
  • Examples of materials that emit red light include coumarin derivatives, thiophene ring compounds, and polymers thereof, polyparaphenylene vinylene derivatives, polythiophene derivatives, and polyfluorene derivatives. Of these, polymer materials such as polyparaphenylene vinylene derivatives, polythiophene derivatives, and polyfluorene derivatives are preferred.
  • a material that emits white light a mixture of materials that emit light in the above-described blue, green, and red colors, or a component that becomes a material that emits light in each color as a monomer, and a polymer obtained by polymerizing this as a material are used. Also good.
  • an element that emits white light as a whole may be realized by stacking light emitting layers formed using materials that emit light of each color.
  • Dopant material examples include perylene derivatives, coumarin derivatives, rubrene derivatives, quinacridone derivatives, squalium derivatives, porphyrin derivatives, styryl dyes, tetracene derivatives, pyrazolone derivatives, decacyclene, and phenoxazone.
  • the thickness of the light emitting layer is usually about 2 nm to 200 nm.
  • a method for forming the light emitting layer a method of applying a solution containing a light emitting material, a vacuum deposition method, a transfer method, or the like can be used.
  • the solvent used for film formation from a solution include the same solvents as those described above used for forming a hole injection layer from a solution.
  • coating methods such as coating methods, spray coating methods, and nozzle coating methods
  • printing methods such as gravure printing methods, screen printing methods, flexographic printing methods, offset printing methods, reverse printing methods, and inkjet printing methods.
  • a printing method such as a gravure printing method, a screen printing method, a flexographic printing method, an offset printing method, a reverse printing method, and an inkjet printing method is preferable in that pattern formation and multicolor coating are easy.
  • a vacuum deposition method can be used in the case of a low molecular compound exhibiting sublimability.
  • a method of forming a light emitting layer only at a desired portion by laser transfer or thermal transfer can also be used.
  • an electron transport material constituting the electron transport layer a commonly used material can be used, such as an oxadiazole derivative, anthraquinodimethane or a derivative thereof, benzoquinone or a derivative thereof, naphthoquinone or a derivative thereof, anthraquinone or a derivative thereof, Tetracyanoanthraquinodimethane or derivatives thereof, fluorenone derivatives, diphenyldicyanoethylene or derivatives thereof, diphenoquinone derivatives, or metal complexes of 8-hydroxyquinoline or derivatives thereof, polyquinoline or derivatives thereof, polyquinoxaline or derivatives thereof, and polyfluorene or Examples thereof include derivatives thereof.
  • electron transport materials include oxadiazole derivatives, benzoquinone or derivatives thereof, anthraquinones or derivatives thereof, or metal complexes of 8-hydroxyquinoline or derivatives thereof, polyquinoline or derivatives thereof, polyquinoxaline or derivatives thereof, and poly Fluorene or its derivatives are preferred, 2- (4-biphenylyl) -5- (4-tert-butylphenyl) -1,3,4-oxadiazole, benzoquinone, anthraquinone, tris (8-quinolinol) aluminum, and polyquinoline Is more preferable.
  • the method for forming the electron transport layer is not particularly limited.
  • a vacuum deposition method from powder, or film formation from a solution or a molten state can be exemplified
  • film formation from a solution or a melt state can be exemplified. be able to.
  • a polymer binder may be used in combination. Examples of the method for forming an electron transport layer from a solution include the same film formation method as the method for forming a hole injection layer from a solution described above.
  • the thickness of the electron transport layer varies depending on the material used, and is appropriately set so that the drive voltage and the light emission efficiency are appropriate.
  • the electron transport layer needs to have at least a thickness that does not generate pinholes, and if it is too thick, the drive voltage of the device increases. Accordingly, the thickness of the electron transport layer is, for example, 1 nm to 1 ⁇ m, preferably 2 nm to 500 nm, and more preferably 5 nm to 200 nm.
  • the electron injection layer includes an ionic polymer.
  • an ionic polymer constituting the electron injection layer for example, a structural unit having one or more groups selected from the group consisting of a group represented by the following formula (1) and a group represented by the following formula (2): Examples include polymers.
  • a structural unit having one or more groups selected from the group consisting of the group represented by the formula (1) and the group represented by the formula (2) And a polymer containing 15 to 100 mol%.
  • Q 1 represents a divalent organic group
  • Y 1 represents —CO 2 ⁇ , —SO 3 ⁇ , —SO 2 — or —PO 3 2 ⁇
  • M 1 represents a metal cation.
  • Z 1 is F ⁇ , Cl ⁇ , Br ⁇ , I ⁇ , OH ⁇ , R a SO 3 ⁇ , R a COO ⁇ , ClO ⁇ , ClO 2 ⁇ .
  • n1 represents an integer of 0 or more
  • a1 represents an integer of 1 or more
  • b1 represents an integer of 0 or more
  • a1 and b1 is the charge of the group represented by the formula (1) Selected to be 0.
  • R a is a carbon atom with or without substituents
  • Q 2 represents a divalent organic group
  • Y 2 represents a carbo cation, an ammonium cation, a phosphonyl cation or a sulfonyl cation or an iodonium cation
  • M 2 represents F ⁇ , Cl ⁇ , Br ⁇ , I ⁇ , OH ⁇ , R b SO 3 ⁇ , R b COO ⁇ , ClO ⁇ , ClO 2 ⁇ , ClO 3 ⁇ , ClO 4 ⁇ , SCN ⁇ , CN ⁇ , NO 3 ⁇ , SO 4 2 ⁇ , HSO 4 ⁇ , PO 4 3 ⁇ , HPO 4 2 ⁇ , H 2 PO 4 ⁇ , BF 4 — or PF 6 —
  • Z 2 represents a metal cation or an ammonium
  • R b represents an alkyl group having 1 to 30 carbon atoms with or without a substituent or an aryl group having 6 to 50 carbon atoms with or without a substituent.
  • the ionic polymer may further have a group represented by the following formula (3).
  • the group represented by the formula (3) may be contained in the structural unit of the ionic polymer.
  • the structural unit having a group represented by the formula (3) includes one or more groups selected from the group consisting of the group represented by the formula (1) and the group represented by the formula (2).
  • the structural unit may be the same as the unit, or another structural unit.
  • a structural unit having at least one of a group represented by formula (1), a group represented by formula (2), and a group represented by formula (3) Examples thereof include a polymer containing 15 to 100 mol% of all structural units.
  • Q 3 represents a divalent organic group
  • Y 3 represents —CN or formulas (4), (5), (6), (7), (8), (9), (10), (11) or (12) represents a group
  • n3 represents an integer of 0 or more.
  • R ′′ represents a hydrogen atom, a monovalent hydrocarbon group with or without a substituent, —COOH, —SO 3 H, —OH, —SH, —NR c 2 , —CN or —C ( ⁇ O) NR c 2
  • R ′ ′′ represents a trivalent hydrocarbon group with or without a substituent
  • a3 represents an integer of 1 or more
  • a4 represents an integer of 0 or more
  • R c represents an alkyl group having 1 to 30 carbon atoms with or without a substituent or an aryl group having 6 to 50 carbon atoms with or without a substituent.
  • the ionic polymer is composed of a structural unit represented by formula (13), a structural unit represented by formula (15), a structural unit represented by formula (17), and a structural unit represented by formula (20). It is preferable that 15 to 100 mol% of one or more structural units selected from the group is contained in all the structural units.
  • R 1 represents a monovalent group having a group represented by Formula (14), and Ar 1 has a (2 + n4) -valent fragrance with or without a substituent other than R 1.
  • n4 represents an integer of 1 or more, and when there are a plurality of R 1 s , they may be the same or different.
  • R 2 represents a (1 + m1 + m2) -valent organic group.
  • Q 1 , Q 3 , Y 1 , M 1 , Z 1 , Y 3 , n1, a1, b1, and n3 are the same as described above.
  • m2 each independently represents an integer greater than or equal to 1.
  • Q 1 , Q 3 , Y 1 , M 1 , Z 1 , Y 3 , n1, a1, b1, and n3 are the same or different when there are a plurality of each. May be.
  • R 3 represents a monovalent group having a group represented by formula (16), and Ar 2 has a (2 + n5) -valent fragrance with or without a substituent other than R 3.
  • n5 represents an integer of 1 or more, and when there are a plurality of R 3 s , they may be the same or different.
  • R 4 represents a (1 + m3 + m4) -valent organic group.
  • Q 2 , Q 3 , Y 2 , M 2 , Z 2 , Y 3 , n 2, a 2, b 2, and n 3 are described above.
  • m4 each independently represents an integer greater than or equal to 1.
  • Q 2 , Q 3 , Y 2 , M 2 , Z 2 , Y 3 , n 2, a 2, b 2 and n 3 may be the same or different when there are a plurality of each. May be.
  • R 5 represents a monovalent group having a group represented by Formula (18)
  • R 6 represents a monovalent group having a group represented by Formula (19)
  • Ar 3 represents an aromatic group optionally having a substituent other than R 5 and R 6 (2 + n6 + n7) valent
  • each of .R 5 and R 6 represents an integer of 1 or more in each of n6 and n7 independently May be the same or different when there are multiple.
  • R 7 represents a direct bond or a (1 + m5) -valent organic group.
  • Q 1 , Y 1 , M 1 , Z 1 , n1, a1 and b1 have been described above.
  • M5 is an integer of 1 or more.
  • Q 1 , Y 1 , M 1 , Z 1 , n 1 , a 1, and b 1 may be the same or different when there are a plurality of each.
  • R 8 represents a single bond or a (1 + m6) -valent organic group.
  • Y 3 and n3 have been described above.
  • M6 represents an integer of 1 or more, provided that when R 8 is a single bond, m6. Represents 1. When there are a plurality of Q 3 , Y 3 and n3, they may be the same or different.
  • R 9 represents a monovalent group having a group represented by formula (21)
  • R 10 represents a monovalent group having a group represented by formula (22)
  • Ar 4 represents a (2 + n8 + n9) -valent aromatic group having or not having a substituent other than R 9 and R 10.
  • n8 and n9 independently represents an integer of 1 or more, and each of R 9 and R 10 May be the same or different when there are multiple.
  • R 11 represents a single bond or a (1 + m7) -valent organic group.
  • Q 2 , Y 2 , M 2 , Z 2 , n 2, a 2 and b 2 have been described above.
  • M 7 is an integer of 1 or more. Provided that when R 11 is a single bond, m7 is 1. When there are a plurality of Q 2 , Y 2 , M 2 , Z 2 , n 2 , a 2 and b 2 , they may be the same or different. .
  • R 12 represents a single bond or a (1 + m8) -valent organic group.
  • Y 3 and n3 have been described above.
  • M8 represents an integer of 1 or more, provided that when R 12 is a single bond, m8. Represents 1. When there are a plurality of each of Q 3 , Y 3 and n 3, they may be the same or different.
  • the structural unit contained in the ionic polymer may have two or more groups represented by the formula (1), may have two or more groups represented by the formula (2), You may have 2 or more types of group represented by Formula (3).
  • examples of the divalent organic group represented by Q 1 include methylene group, ethylene group, 1,2-propylene group, 1,3-propylene group, 1,2-butylene group, 1, 3-butylene group, 1,4-butylene group, 1,5-pentylene group, 1,6-hexylene group, 1,9-nonylene group, 1,12-dodecylene group, and at least one hydrogen of these groups
  • a divalent cyclic saturated hydrocarbon group having 3 to 50 atoms 1,3-phenylene group, 1,4-phenylene group, 1,4-naphthylene group, 1,5-naphthylene group, 2,6-naphthylene group, 6-5 carbon atoms having or not having a substituent selected from a biphenyl-4,4′-diyl group and a group in which at least one hydrogen atom of these groups is substituted with a substituent.
  • arylene group a methyleneoxy group, an ethyleneoxy group, a propyleneoxy group, a butyleneoxy group, a pentyleneoxy group, a hexyleneoxy group, and a group in which at least one hydrogen atom of these groups is substituted with a substituent
  • raw material monomer a divalent saturated hydrocarbon group, an arylene group, and an alkyleneoxy group are preferable.
  • substituents examples include an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, an arylalkenyl group, an arylalkynyl group, an amino group, and a substituent.
  • C m -C n (m, n is a positive integer satisfying m ⁇ n) indicates that the organic group described together with this term has m to n carbon atoms.
  • a C m -C n alkyl group indicates that the alkyl group has m to n carbon atoms
  • a C m -C n alkyl aryl group indicates that the alkyl group has m carbon atoms of m to n.
  • n represents an aryl-C m -C n alkyl group, the alkyl group has m to n carbon atoms.
  • the alkyl group may be linear or branched, and may be a cycloalkyl group.
  • the alkyl group usually has 1 to 20 carbon atoms, and preferably 1 to 10 carbon atoms.
  • As the alkyl group for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, t-butyl group, pentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, nonyl Groups, decyl groups, and lauryl groups.
  • the hydrogen atom of the alkyl group may be substituted with a fluorine atom.
  • fluorine atom-substituted alkyl group examples include a trifluoromethyl group, a pentafluoroethyl group, a perfluorobutyl group, a perfluorohexyl group, and a perfluorooctyl group.
  • Examples of the C 1 to C 12 alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a s-butyl group, a t-butyl group, a pentyl group, an isoamyl group, a hexyl group, and a cyclohexyl group. , Heptyl group, octyl group, nonyl group, decyl group, and lauryl group.
  • the alkoxy group may be linear or branched, may be a cycloalkyloxy group, and may have a substituent.
  • the alkoxy group usually has 1 to 20 carbon atoms, and preferably 1 to 10 carbon atoms.
  • Examples of alkoxy groups include methoxy, ethoxy, propyloxy, isopropyloxy, butoxy, isobutoxy, s-butoxy, t-butoxy, pentyloxy, hexyloxy, cyclohexyloxy, heptyloxy Group, octyloxy group, nonyloxy group, decyloxy group, and lauryloxy group.
  • the hydrogen atom of the alkoxy group may be substituted with a fluorine atom.
  • Examples of the fluorine atom-substituted alkoxy group include a trifluoromethoxy group, a pentafluoroethoxy group, a perfluorobutoxy group, a perfluorohexyloxy group, and a perfluorooctyloxy group.
  • the alkoxy group also includes a methoxymethyloxy group and a 2-methoxyethyloxy group.
  • Examples of the C 1 -C 12 alkoxy group include a methoxy group, ethoxy group, propyloxy group, isopropyloxy group, butoxy group, isobutoxy group, s-butoxy group, t-butoxy group, pentyloxy group, hexyloxy group, Examples include cyclohexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, 3,7-dimethyloctyloxy group, and lauryloxy group.
  • the alkylthio group may be linear or branched, may be a cycloalkylthio group, and may have a substituent.
  • the alkylthio group usually has 1 to 20 carbon atoms, and preferably 1 to 10 carbon atoms.
  • alkylthio group examples include methylthio group, ethylthio group, propylthio group, isopropylthio group, butylthio group, isobutylthio group, s-butylthio group, t-butylthio group, pentylthio group, hexylthio group, cyclohexylthio group, heptylthio group, octylthio group Group, nonylthio group, decylthio group, and laurylthio group.
  • the hydrogen atom of the alkylthio group may be substituted with a fluorine atom.
  • the fluorine atom-substituted alkylthio group examples include a trifluoromethylthio group.
  • the aryl group is a remaining atomic group obtained by removing one hydrogen atom bonded to a carbon atom constituting an aromatic ring from an aromatic hydrocarbon.
  • a group having a benzene ring, a group having a condensed ring, and two or more benzene rings or condensed rings are bonded to the aryl group via a single bond or a divalent organic group (for example, an alkenylene group such as a vinylene group). Groups are also included.
  • the aryl group usually has 6 to 60 carbon atoms, and preferably 7 to 48 carbon atoms.
  • aryl group examples include a phenyl group, a C 1 to C 12 alkoxyphenyl group, a C 1 to C 12 alkylphenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthracenyl group, a 2-anthracenyl group, and 9- Anthracenyl group may be mentioned.
  • the hydrogen atom of the aryl group may be substituted with a fluorine atom.
  • the fluorine atom-substituted aryl group include a pentafluorophenyl group.
  • aryl group a C 1 -C 12 alkoxyphenyl group and a C 1 -C 12 alkylphenyl group are preferable.
  • Examples of the C 1 -C 12 alkoxyphenyl group include a methoxyphenyl group, an ethoxyphenyl group, a propyloxyphenyl group, an isopropyloxyphenyl group, a butoxyphenyl group, an isobutoxyphenyl group, an s-butoxyphenyl group, and a t-butoxyphenyl group.
  • Pentyloxyphenyl group hexyloxyphenyl group, cyclohexyloxyphenyl group, heptyloxyphenyl group, octyloxyphenyl group, 2-ethylhexyloxyphenyl group, nonyloxyphenyl group, decyloxyphenyl group, 3,7-dimethyloctyloxy A phenyl group and a lauryloxyphenyl group are mentioned.
  • Examples of the C 1 -C 12 alkylphenyl group include, for example, methylphenyl group, ethylphenyl group, dimethylphenyl group, propylphenyl group, mesityl group, methylethylphenyl group, isopropylphenyl group, butylphenyl group, isobutylphenyl group, t- Examples include a butylphenyl group, a pentylphenyl group, an isoamylphenyl group, a hexylphenyl group, a heptylphenyl group, an octylphenyl group, a nonylphenyl group, a decylphenyl group, and a dodecylphenyl group.
  • the aryloxy group usually has 6 to 60 carbon atoms, and preferably 7 to 48 carbon atoms.
  • Examples of the aryloxy group include a phenoxy group, a C 1 -C 12 alkoxyphenoxy group, a C 1 -C 12 alkylphenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, and a pentafluorophenyloxy group.
  • a C 1 -C 12 alkoxyphenoxy group and a C 1 -C 12 alkylphenoxy group are preferable.
  • Examples of the C 1 -C 12 alkoxyphenoxy group include a methoxyphenoxy group, an ethoxyphenoxy group, a propyloxyphenoxy group, an isopropyloxyphenoxy group, a butoxyphenoxy group, an isobutoxyphenoxy group, an s-butoxyphenoxy group, and a t-butoxyphenoxy group.
  • Pentyloxyphenoxy group hexyloxyphenoxy group, cyclohexyloxyphenoxy group, heptyloxyphenoxy group, octyloxyphenoxy group, 2-ethylhexyloxyphenoxy group, nonyloxyphenoxy group, decyloxyphenoxy group, 3,7-dimethyloctyloxy Examples include phenoxy group and lauryloxyphenoxy group.
  • Examples of the C 1 -C 12 alkylphenoxy group include a methylphenoxy group, an ethylphenoxy group, a dimethylphenoxy group, a propylphenoxy group, a 1,3,5-trimethylphenoxy group, a methylethylphenoxy group, an isopropylphenoxy group, and a butylphenoxy group.
  • Isobutylphenoxy group, s-butylphenoxy group, t-butylphenoxy group, pentylphenoxy group, isoamylphenoxy group, hexylphenoxy group, heptylphenoxy group, octylphenoxy group, nonylphenoxy group, decylphenoxy group, and dodecylphenoxy group Can be mentioned.
  • the arylthio group is, for example, a group in which a sulfur element is bonded to the aforementioned aryl group.
  • the arylthio group may have a substituent on the aromatic ring of the aryl group.
  • the arylthio group usually has 6 to 60 carbon atoms, preferably 6 to 30 carbon atoms.
  • Examples of the arylthio group include a phenylthio group, a C 1 -C 12 alkoxyphenylthio group, a C 1 -C 12 alkylphenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, and a pentafluorophenylthio group.
  • the arylalkyl group is, for example, a group in which the above alkyl group is bonded to the above aryl group.
  • the arylalkyl group may have a substituent.
  • the arylalkyl group usually has 7 to 60 carbon atoms, preferably 7 to 30 carbon atoms.
  • arylalkyl group examples include a phenyl-C 1 -C 12 alkyl group, a C 1 -C 12 alkoxyphenyl-C 1 -C 12 alkyl group, a C 1 -C 12 alkylphenyl-C 1 -C 12 alkyl group, -Naphthyl-C 1 -C 12 alkyl group, and 2-naphthyl-C 1 -C 12 alkyl group.
  • the arylalkoxy group is, for example, a group in which the above alkoxy group is bonded to the above aryl group.
  • the arylalkoxy group may have a substituent.
  • the arylalkoxy group usually has 7 to 60 carbon atoms, and preferably 7 to 30 carbon atoms.
  • arylalkoxy group examples include a phenyl-C 1 -C 12 alkoxy group, a C 1 -C 12 alkoxyphenyl-C 1 -C 12 alkoxy group, a C 1 -C 12 alkylphenyl-C 1 -C 12 alkoxy group, 1 -Naphtyl-C 1 -C 12 alkoxy group and 2-naphthyl-C 1 -C 12 alkoxy group are mentioned.
  • the arylalkylthio group is, for example, a group in which the aforementioned alkylthio group is bonded to the aforementioned aryl group.
  • the arylalkylthio group may have a substituent.
  • the arylalkylthio group usually has 7 to 60 carbon atoms, preferably 7 to 30 carbon atoms.
  • arylalkylthio group examples include a phenyl-C 1 -C 12 alkylthio group, a C 1 -C 12 alkoxyphenyl-C 1 -C 12 alkylthio group, a C 1 -C 12 alkylphenyl-C 1 -C 12 alkylthio group, -Naphthyl-C 1 -C 12 alkylthio group, and 2-naphthyl-C 1 -C 12 alkylthio group.
  • the arylalkenyl group is, for example, a group in which an alkenyl group is bonded to the aforementioned aryl group.
  • the arylalkenyl group usually has 8 to 60 carbon atoms, preferably 8 to 30 carbon atoms.
  • Examples of the arylalkenyl group include a phenyl-C 2 -C 12 alkenyl group, a C 1 -C 12 alkoxyphenyl-C 2 -C 12 alkenyl group, a C 1 -C 12 alkylphenyl-C 2 -C 12 alkenyl group, 1 -Naphthyl-C 2 -C 12 alkenyl group, and 2-naphthyl-C 2 -C 12 alkenyl group.
  • a C 1 -C 12 alkoxyphenyl-C 2 -C 12 alkenyl group and a C 2 -C 12 alkylphenyl-C 2 -C 12 alkenyl group are preferred.
  • Examples of the C 2 -C 12 alkenyl group include a vinyl group, 1-propenyl group, 2-propenyl group, 1-butenyl group, 2-butenyl group, 1-pentenyl group, 2-pentenyl group, 1-hexenyl group, 2 -Hexenyl group and 1-octenyl group are mentioned.
  • the arylalkynyl group is, for example, a group in which an alkynyl group is bonded to the aforementioned aryl group.
  • the arylalkynyl group usually has 8 to 60 carbon atoms, preferably 8 to 30 carbon atoms.
  • arylalkynyl group examples include a phenyl-C 2 -C 12 alkynyl group, a C 1 -C 12 alkoxyphenyl-C 2 -C 12 alkynyl group, a C 1 -C 12 alkylphenyl-C 2 -C 12 alkynyl group, 1 -Naphtyl-C 2 -C 12 alkynyl group and 2-naphthyl-C 2 -C 12 alkynyl group.
  • C 1 -C 12 alkoxyphenyl-C 2 -C 12 alkynyl group and a C 1 -C 12 alkylphenyl-C 2 -C 12 alkynyl group are preferred.
  • C 2 -C 12 alkynyl groups include, for example, ethynyl group, 1-propynyl group, 2-propynyl group, 1-butynyl group, 2-butynyl group, 1-pentynyl group, 2-pentynyl group, 1-hexynyl group, 2 -Hexynyl group and 1-octynyl group may be mentioned.
  • an amino group in which at least one hydrogen atom of the amino group is substituted with one or two groups selected from the group consisting of an alkyl group, an aryl group, an arylalkyl group and a monovalent heterocyclic group Groups are preferred.
  • the alkyl group, aryl group, arylalkyl group or monovalent heterocyclic group may have a substituent.
  • the number of carbon atoms of the substituted amino group is usually 1 to 60 excluding the number of carbon atoms of the substituent that the alkyl group, aryl group, arylalkyl group or monovalent heterocyclic group may have, 2 to 48 are preferred.
  • substituted amino groups include methylamino group, dimethylamino group, ethylamino group, diethylamino group, propylamino group, dipropylamino group, isopropylamino group, diisopropylamino group, butylamino group, isobutylamino group, and s-butyl.
  • the alkyl group, aryl group, arylalkyl group or monovalent heterocyclic group may have a substituent.
  • the number of carbon atoms of the substituted silyl group is usually 1 to 60 without including the number of carbon atoms of the substituent that the alkyl group, aryl group, arylalkyl group or monovalent heterocyclic group may have, 3 to 48 are preferred.
  • substituted silyl group examples include trimethylsilyl group, triethylsilyl group, tripropylsilyl group, triisopropylsilyl group, isopropyldimethylsilyl group, isopropyldiethylsilyl group, t-butyldimethylsilyl group, pentyldimethylsilyl group, hexyldimethylsilyl group.
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
  • the acyl group usually has 2 to 20 carbon atoms, and preferably 2 to 18 carbon atoms.
  • Examples of the acyl group include acetyl group, propionyl group, butyryl group, isobutyryl group, pivaloyl group, benzoyl group, trifluoroacetyl group, and pentafluorobenzoyl group.
  • the acyloxy group usually has 2 to 20 carbon atoms, and preferably 2 to 18 carbon atoms.
  • Examples of the acyloxy group include an acetoxy group, a propionyloxy group, a butyryloxy group, an isobutyryloxy group, a pivaloyloxy group, a benzoyloxy group, a trifluoroacetyloxy group, and a pentafluorobenzoyloxy group.
  • the imine residue means a residue obtained by removing one hydrogen atom in this structure from an imine compound having a structure represented by at least one of the formula: HN ⁇ C ⁇ and the formula: —N ⁇ CH—.
  • the imine compound include compounds in which a hydrogen atom bonded to a nitrogen atom in aldimine, ketimine, and aldimine is substituted with an alkyl group, aryl group, arylalkyl group, arylalkenyl group, arylalkynyl group, or the like.
  • the number of carbon atoms in the imine residue is usually 2-20, and preferably 2-18.
  • Examples of the imine residue include the following groups.
  • the amide group usually has 1 to 20 carbon atoms and preferably 2 to 18 carbon atoms.
  • As the amide group for example, formamide group, acetamide group, propioamide group, butyroamide group, benzamide group, trifluoroacetamide group, pentafluorobenzamide group, diformamide group, diacetamide group, dipropioamide group, dibutyroamide group, dibenzamide group, ditriamide Examples include a fluoroacetamide group and a dipentafluorobenzamide group.
  • the acid imide group is a residue obtained by removing a hydrogen atom bonded to the nitrogen atom from an acid imide.
  • the acid imide group usually has 4 to 20 carbon atoms, and preferably 4 to 18 carbon atoms.
  • the acid imide group include the following groups.
  • the monovalent heterocyclic group refers to the remaining atomic group obtained by removing one hydrogen atom from a heterocyclic compound.
  • Heterocyclic compounds are not only carbon atoms but also oxygen atoms, sulfur atoms, nitrogen atoms, phosphorus atoms, boron atoms, silicon atoms, selenium atoms as elements constituting the ring among organic compounds having a cyclic structure.
  • An organic compound containing a heteroatom such as a tellurium atom and an arsenic atom.
  • the monovalent heterocyclic group may have a substituent.
  • the monovalent heterocyclic group usually has 3 to 60 carbon atoms, and preferably 3 to 20 carbon atoms.
  • the number of carbon atoms of the monovalent heterocyclic group does not include the number of carbon atoms of the substituent.
  • Examples of the monovalent heterocyclic group include thienyl group, C 1 -C 12 alkyl thienyl group, pyrrolyl group, furyl group, pyridyl group, C 1 -C 12 alkyl pyridyl group, pyridazinyl group, pyrimidyl group, pyrazinyl group, triazinyl Group, pyrrolidyl group, piperidyl group, quinolyl group, and isoquinolyl group.
  • a thienyl group, a C 1 -C 12 alkyl thienyl group, a pyridyl group and a C 1 -C 12 alkyl pyridyl group are preferable.
  • the monovalent heterocyclic group is preferably a monovalent aromatic heterocyclic group.
  • the substituted carboxyl group is a group in which a hydrogen atom of a carboxyl group is substituted with an alkyl group, an aryl group, an arylalkyl group or a monovalent heterocyclic group, that is, a formula: —C ( ⁇ O) OR * (Wherein R * is an alkyl group, an aryl group, an arylalkyl group, or a monovalent heterocyclic group).
  • the substituted carboxyl group usually has 2 to 60 carbon atoms, and preferably 2 to 48 carbon atoms.
  • the alkyl group, aryl group, arylalkyl group or monovalent heterocyclic group may have a substituent.
  • the number of carbon atoms does not include the number of carbon atoms of the substituent that the alkyl group, aryl group, arylalkyl group or monovalent heterocyclic group may have.
  • the substituted carboxyl group include methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, isopropoxycarbonyl group, butoxycarbonyl group, isobutoxycarbonyl group, s-butoxycarbonyl group, t-butoxycarbonyl group, pentyloxycarbonyl group, Hexyloxycarbonyl group, cyclohexyloxycarbonyl group, heptyloxycarbonyl group, octyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, nonyloxycarbonyl group, decyloxycarbonyl group, 3,7-dimethyloctyloxycarbonyl group, dodecyloxy Carbonyl group, trifluoromethoxycarbon
  • Y 1 represents a monovalent group such as —CO 2 ⁇ , —SO 3 ⁇ , —SO 2 ⁇ , —PO 3 ⁇ , or —B (R a ) 3 — .
  • the Y 1 from the viewpoint of the acidity of the ionic polymer, -CO 2 -, -SO 2 - , and -PO 3 - are preferred, -CO 2 - is more preferable.
  • Y 1 is preferably —CO 2 ⁇ , —SO 3 ⁇ , —SO 2 — or —PO 3 — from the viewpoint of the stability of the ionic polymer.
  • M 1 represents a metal cation or an ammonium cation with or without a substituent.
  • the metal cation is preferably a monovalent, divalent or trivalent cation.
  • metal cations Li, Na, K, Cs, Be, Mg, Ca, Ba, Ag, Al, Bi, Cu, Fe, Ga, Mn, Pb, Sn, Ti, V, W, Y, Yb, Zn, And cations such as Zr, and Li + , Na + , K + , Cs + , Ag + , Mg 2+ , and Ca 2+ are preferable.
  • Examples of the substituent that the ammonium cation may have include, for example, 1 to 10 carbon atoms such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, i-butyl group, and t-butyl group. Of the alkyl group.
  • Z 1 represents F ⁇ , Cl ⁇ , Br ⁇ , I ⁇ , OH ⁇ , R a SO 3 ⁇ , R a COO ⁇ , ClO ⁇ , ClO 2 ⁇ , ClO 3 ⁇ , ClO 4 ⁇ , SCN ⁇ , CN ⁇ , NO 3 ⁇ , SO 4 2 ⁇ , HSO 4 ⁇ , PO 4 3 ⁇ , HPO 4 2 ⁇ , H 2 PO 4 ⁇ , BF 4 ⁇ or PF 6 ⁇ are represented.
  • n1 represents an integer of 0 or more. n1 is preferably an integer of 0 to 8, more preferably an integer of 0 to 2, from the viewpoint of the synthesis of raw material monomers.
  • a1 represents an integer of 1 or more.
  • b1 represents an integer of 0 or more.
  • a1 and b1 are selected such that the charge of the group represented by the formula (1) is zero.
  • Y 1 is —CO 2 ⁇ , —SO 3 ⁇ , —SO 2 ⁇ , —PO 3 ⁇ , or —B (R a ) 3 —
  • M 1 has a monovalent metal cation or substituent.
  • Y 1 is —CO 2 ⁇ , —SO 3 ⁇ , —SO 2 ⁇ , —PO 3 ⁇ , or —B (R a ) 3 —
  • M 1 is a divalent metal cation
  • Z 1 is F ⁇ , Cl ⁇ , Br ⁇ , I ⁇ , OH ⁇ , R a SO 3 ⁇ , R a COO ⁇ , ClO ⁇ , ClO 2 ⁇ , ClO 3 ⁇ , ClO 4 ⁇ , SCN ⁇ , CN ⁇ , NO 3 ⁇
  • Y 1 is —CO 2 ⁇ , —SO 3 ⁇ , —SO 2 ⁇ , —PO 3 ⁇ , or —B (R a ) 3 —
  • M 1 is a trivalent metal cation
  • Z 1 is F ⁇ , Cl ⁇ , Br ⁇ , I ⁇ , OH ⁇ , R a SO 3 ⁇ , R a COO ⁇ , ClO ⁇ , ClO 2 ⁇ , ClO 3 ⁇ , ClO 4 ⁇ , SCN ⁇ , CN ⁇ , NO 3 ⁇
  • Y 1 is —CO 2 ⁇ , —SO 3 ⁇ , —SO 2 ⁇ , —PO 3 ⁇ , or —B (R a ) 3 —
  • a1 is preferably an integer of 1 to 5, more preferably 1 or 2.
  • R a represents an alkyl group having 1 to 30 carbon atoms with or without a substituent or an aryl group having 6 to 50 carbon atoms with or without a substituent.
  • substituents that these groups may have include the same substituents as the substituents exemplified in the aforementioned Q 1 . When a plurality of substituents are present, they may be the same or different.
  • Ra examples include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, C1-C20 alkyl groups such as nonyl, decyl, and lauryl, and phenyl, 1-naphthyl, 2-naphthyl, 1-anthracenyl, 2-anthracenyl, and 9-anthracenyl And aryl groups having 6 to 30 carbon atoms, such as groups.
  • Examples of the group represented by the formula (1) include the following groups.
  • the divalent organic group represented by Q 2 include the groups exemplified as the divalent organic group represented by Q 1.
  • Q 2 is preferably a divalent saturated hydrocarbon group, an arylene group, or an alkyleneoxy group from the viewpoint of ease of synthesis of the raw material monomer.
  • the divalent organic group represented by Q 2 may have a substituent.
  • substituents include a substituent that the divalent organic group represented by Q 1 described above may have. When a plurality of substituents are present, they may be the same or different.
  • Y 2 represents a carbocation, an ammonium cation, a phosphonyl cation, a sulfonyl cation, or an iodonium cation.
  • R represents an alkyl group or an aryl group.
  • a plurality of R may be the same or different from each other).
  • ammonium cations include: -N + R 3 (Wherein, R represents an alkyl group or an aryl group. A plurality of R may be the same or different from each other).
  • Examples of phosphonyl cations include: -P + R 3 (Wherein, R represents an alkyl group or an aryl group. A plurality of R may be the same or different from each other).
  • Examples of the sulfonyl cation include: -S + R 2 (Wherein, R represents an alkyl group or an aryl group. A plurality of R may be the same or different from each other).
  • R represents an alkyl group or an aryl group.
  • a plurality of R may be the same or different from each other).
  • Y 2 is a carbocation, an ammonium cation, a phosphonyl cation, and from the viewpoint of the ease of synthesis of the raw material monomer and the stability of the raw material monomer and the ionic polymer to air, moisture or heat.
  • a sulfonyl cation is preferred, and an ammonium cation is more preferred.
  • Z 2 represents a metal cation or an ammonium cation with or without a substituent.
  • the metal cation is preferably a monovalent, divalent or trivalent cation.
  • metal cations Li, Na, K, Cs, Be, Mg, Ca, Ba, Ag, Al, Bi, Cu, Fe, Ga, Mn, Pb, Sn, Ti, V, W, Y, Yb, Zn, And cations such as Zr.
  • Examples of the substituent that the ammonium cation may have include, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, and the like having 1 to 10 carbon atoms.
  • An alkyl group is mentioned.
  • M 2 represents F ⁇ , Cl ⁇ , Br ⁇ , I ⁇ , OH ⁇ , R b SO 3 ⁇ , R b COO ⁇ , ClO ⁇ , ClO 2 ⁇ , ClO 3 ⁇ , ClO 4 ⁇ , SCN ⁇ , CN ⁇ , NO 3 ⁇ , SO 4 2 ⁇ , HSO 4 ⁇ , PO 4 3 ⁇ , HPO 4 2 ⁇ , H 2 PO 4 ⁇ , BF 4 ⁇ or PF 6 ⁇ are represented.
  • n2 represents an integer of 0 or more. n2 is preferably an integer of 0 to 6, more preferably an integer of 0 to 2.
  • a2 represents an integer of 1 or more.
  • b2 represents an integer of 0 or more.
  • a2 and b2 are selected such that the charge of the group represented by the formula (2) is zero.
  • a2 is preferably an integer from 1 to 3, more preferably 1 or 2.
  • R b represents an alkyl group having 1 to 30 carbon atoms with or without a substituent, or an aryl group having 6 to 50 carbon atoms with or without a substituent.
  • substituents that these groups may have include the same substituents as the substituents exemplified in the aforementioned Q 1 . When a plurality of substituents are present, they may be the same or different.
  • R b examples include a methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, t-butyl group, pentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, C1-C20 alkyl groups such as nonyl, decyl, and lauryl, and phenyl, 1-naphthyl, 2-naphthyl, 1-anthracenyl, 2-anthracenyl, and 9-anthracenyl And aryl groups having 6 to 30 carbon atoms such as a group.
  • Examples of the group represented by the formula (2) include the following groups.
  • examples of the divalent organic group represented by Q 3 include the groups exemplified as the divalent organic group represented by Q 1 .
  • Q 3 is preferably a divalent saturated hydrocarbon group, an arylene group, or an alkyleneoxy group from the viewpoint of ease of synthesis of the raw material monomer.
  • the divalent organic group represented by Q 3 may have a substituent.
  • substituents include a substituent that the divalent organic group represented by Q 1 may have. When a plurality of substituents are present, they may be the same or different.
  • the divalent organic group represented by Q 3 is preferably a group represented by — (CH 2 ) —.
  • N3 represents an integer of 0 or more. n3 is preferably an integer of 0 to 20, more preferably an integer of 0 to 8.
  • Y 3 is represented by —CN or formula (4), (5), (6), (7), (8), (9), (10), (11) or (12). Represents a group.
  • a divalent hydrocarbon group represented by R ′ As, for example, methylene group, ethylene group, 1,2-propylene group, 1,3-propylene group, 1,2-butylene group, 1,3-butylene group, 1,4-butylene group, 1,5- It has a substituent selected from a pentylene group, a 1,6-hexylene group, a 1,9-nonylene group, a 1,12-dodecylene group, and a group in which at least one hydrogen atom of these groups is substituted with a substituent.
  • substituents examples include the substituents exemplified in the description regarding Q 1 described above. When a plurality of substituents are present, they may be the same or different.
  • the group for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, t-butyl group, pentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, nonyl group A decyl group, a lauryl group, and an alkyl group having 1 to 20 carbon atoms with or without a substituent selected from a group in which at least one hydrogen atom of these groups is substituted with a substituent, and the like; Selected from phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthracenyl group, 2-anthracenyl group, 9-anthracenyl group
  • the monovalent hydrocarbon group represented by R ′′ is preferably a methyl group, an ethyl group, a phenyl group, a 1-naphthyl group, or a 2-naphthyl group from the viewpoint of solubility of the ionic polymer.
  • substituents include exemplified substituents such as in the description with respect to Q 1. When a plurality of substituents are present, they may be the same or different.
  • R ′ ′′ as the trivalent hydrocarbon group represented by R ′ ′′, for example, a methanetriyl group, an ethanetriyl group, a 1,2,3-propanetriyl group, a 1,2,4-butanetriyl group, 1,2,5-pentanetriyl group, 1,3,5-pentanetriyl group, 1,2,6-hexanetriyl group, 1,3,6-hexanetriyl group, and at least of these groups
  • R ′′′ As the trivalent hydrocarbon group represented by R ′ ′′, from the viewpoint of solubility of the ionic polymer, methanetriyl group, ethanetriyl group, 1,2,4-benzenetriyl group, and 1,3,5- A benzenetriyl group is preferred.
  • substituents include exemplified substituents such as in the description with respect to Q 1. When a plurality of substituents are present, they may be the same or different.
  • R c is the solubility of the ionic polymer. From the viewpoint, a methyl group, an ethyl group, a phenyl group, a 1-naphthyl group, and a 2-naphthyl group are preferable.
  • a3 represents an integer of 1 or more, and an integer of 3 to 10 is preferable.
  • a4 represents an integer of 0 or more.
  • a4 is preferably an integer of 0 to 30, and more preferably an integer of 3 to 20.
  • a4 is preferably an integer of 0 to 10, and more preferably an integer of 0 to 5.
  • a4 is preferably an integer of 0 to 20, and more preferably an integer of 3 to 20.
  • a4 is preferably an integer of 0 to 20, and more preferably an integer of 0 to 10.
  • Y 3 represents —CN, a group represented by Formula (4), a group represented by Formula (6), a group represented by Formula (10), a group represented by Formula (10), from the viewpoint of ease of synthesis of the raw material monomer. 11) is preferred, the group represented by formula (4), the group represented by formula (6), and the group represented by formula (11) are more preferred, and the following groups are particularly preferred. .
  • the ionic polymer according to this embodiment is represented by the structural unit represented by the formula (13), the structural unit represented by the formula (15), the structural unit represented by the formula (17), and the formula (20). It is preferable that at least one structural unit selected from the group consisting of structural units is included, and it is more preferable that these structural units are included in an amount of 15 to 100 mol% in all the structural units.
  • R 1 represents a monovalent group having a group represented by formula (14), Ar 1 has a substituent other than R 1. Or it shows the (2 + n4) valent aromatic group which does not have, and n4 shows an integer greater than or equal to 1.
  • the group represented by the formula (14) may be directly bonded to Ar 1 , or a methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, nonylene group, dodecylene group, cyclopropylene Group, cyclobutylene group, cyclopentylene group, cyclohexylene group, cyclononylene group, cyclododecylene group, norbornylene group, adamantylene group, a group in which at least one hydrogen atom of these groups is substituted with a substituent, or the like
  • Ar 1 may have a substituent other than R 1 .
  • substituents include exemplified substituents such as in the description with respect to Q 1. When a plurality of substituents are present, they may be the same or different.
  • an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a carboxyl group, and a substituted carboxyl group are preferable from the viewpoint of ease of synthesis of the raw material monomer.
  • n4 represents an integer of 1 or more. n4 is preferably an integer of 1 to 4, more preferably an integer of 1 to 3.
  • Examples of the (2 + n4) -valent aromatic group represented by Ar 1 in the formula (13) include a (2 + n4) -valent aromatic hydrocarbon group and a (2 + n4) -valent aromatic heterocyclic group, preferably A (2 + n4) -valent aromatic group consisting of only carbon atoms, and a (2 + n4) -valent aroma consisting of carbon atoms and one or more atoms selected from the group consisting of hydrogen atoms, nitrogen atoms and oxygen atoms It is a family group.
  • Examples of the (2 + n4) -valent aromatic group include a benzene ring, a pyridine ring, a 1,2-diazine ring, a 1,3-diazine ring, a 1,4-diazine ring, a 1,3,5-triazine ring, A (2 + n4) -valent group obtained by removing (2 + n4) hydrogen atoms from a monocyclic aromatic ring such as a furan ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxazole ring, or an azadiazole ring; consisting of the monocyclic aromatic ring A (2 + n4) -valent group obtained by removing (2 + n4) hydrogen atoms from a condensed polycyclic aromatic ring in which two or more rings selected from the group are condensed; from the monocyclic aromatic ring and the condensed polycyclic aromatic ring A (2 + n4)
  • Examples of monocyclic aromatic rings include the following rings.
  • Examples of the condensed polycyclic aromatic ring include the following rings.
  • aromatic ring assembly include the following rings.
  • Examples of the Aribashi polycyclic aromatic ring include the following rings.
  • (2 + n4) hydrogen atoms are removed from the ring represented by the formulas 1 to 14, 26 to 29, 37 to 39, or 41 from the viewpoint of easy synthesis of the raw material monomer.
  • a group obtained by removing (2 + n4) hydrogen atoms from the ring represented by the formulas 1 to 6, 8, 13, 26, 27, 37, or 41 is more preferred, and the group represented by the formula 1, 37, or 41 is preferred.
  • a group obtained by removing (2 + n4) hydrogen atoms from the ring is more preferred.
  • examples of the (1 + m1 + m2) -valent organic group represented by R 2 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, an s-butyl group, and a t-butyl group.
  • a (1 + m1 + m2) -valent organic group represented by R 2 a group obtained by removing (m1 + m2) hydrogen atoms from an alkyl group and (m1 + m2) hydrogens from an aryl group from the viewpoint of ease of synthesis of the raw material monomer A group in which atoms are removed and a group in which (m1 + m2) hydrogen atoms have been removed from an alkoxy group are preferred.
  • substituents examples include exemplified substituents such as in the description with respect to Q 1. When a plurality of substituents are present, they may be the same or different.
  • R 3 represents a monovalent group having a group represented by formula (16), and Ar 2 has a substituent other than R 3. Or it shows the (2 + n5) valent aromatic group which does not have, and n5 shows an integer greater than or equal to 1.
  • the group represented by the formula (16) may be directly bonded to Ar 2 , or a methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, nonylene group, dodecylene group, cyclopropylene.
  • Ar 2 may have a substituent other than R 3 .
  • substituents include exemplified substituents such as in the description with respect to Q 1. When a plurality of substituents are present, they may be the same or different.
  • an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a carboxyl group, and a substituted carboxyl group are preferable from the viewpoint of ease of synthesis of the raw material monomer.
  • n5 represents an integer of 1 or more. n5 is preferably an integer of 1 to 4, more preferably an integer of 1 to 3.
  • Examples of the (2 + n5) -valent aromatic group represented by Ar 2 in the formula (15) include a (2 + n5) -valent aromatic hydrocarbon group and a (2 + n5) -valent aromatic heterocyclic group, preferably (2 + n5) -valent aromatic group consisting of only carbon atoms, and (2 + n5) -valent aromatics consisting of carbon atoms and one or more atoms selected from the group consisting of hydrogen atoms, nitrogen atoms and oxygen atoms It is a family group.
  • Examples of the (2 + n5) -valent aromatic group include a benzene ring, a pyridine ring, a 1,2-diazine ring, a 1,3-diazine ring, a 1,4-diazine ring, a 1,3,5-triazine ring, A (2 + n5) -valent group obtained by removing (2 + n5) hydrogen atoms from a monocyclic aromatic ring such as a furan ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxazole ring, or an azadiazole ring; consisting of the monocyclic aromatic ring A (2 + n5) -valent group obtained by removing (2 + n5) hydrogen atoms from a condensed polycyclic aromatic ring in which two or more rings selected from the group are condensed; from the monocyclic aromatic ring and the condensed polycyclic aromatic ring A (2 + n5)
  • Examples of the monocyclic aromatic ring include rings represented by formulas 1 to 12 exemplified in the description of the structural unit represented by formula (13).
  • Examples of the condensed polycyclic aromatic ring include rings represented by Formulas 13 to 27 exemplified in the description of the structural unit represented by Formula (13).
  • Examples of the aromatic ring assembly include rings represented by formulas 28 to 36 exemplified in the description of the structural unit represented by formula (13).
  • bridged polycyclic aromatic ring examples include rings represented by the formulas 37 to 44 exemplified in the description of the structural unit represented by the formula (13).
  • (2 + n5) hydrogen atoms are removed from the ring represented by the formulas 1 to 14, 26 to 29, 37 to 39, or 41.
  • a group obtained by removing (2 + n5) hydrogen atoms from the ring represented by the formulas 1 to 6, 8, 13, 26, 27, 37, or 41 is more preferred, and the group represented by the formula 1, 37, or 41 is preferred.
  • a group obtained by removing (2 + n5) hydrogen atoms from the ring is more preferred.
  • n3 and m4 each independently represent an integer of 1 or more.
  • examples of the (1 + m3 + m4) -valent organic group represented by R 4 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, an s-butyl group, and a t-butyl group.
  • a (1 + m3 + m4) -valent organic group represented by R 4 a group obtained by removing (m3 + m4) hydrogen atoms from an alkyl group and (m3 + m4) hydrogens from an aryl group from the viewpoint of ease of synthesis of the raw material monomer.
  • a group in which atoms are removed and a group in which (m3 + m4) hydrogen atoms are removed from an alkoxy group are preferred.
  • substituents examples include exemplified substituents such as in the description with respect to Q 1. When a plurality of substituents are present, they may be the same or different.
  • R 5 represents a monovalent group having a group represented by formula (18)
  • R 6 represents a group represented by formula (19).
  • Ar 3 represents a (2 + n6 + n7) -valent aromatic group having or not having a substituent other than R 5 and R 6 , and n6 and n7 are each independently an integer of 1 or more Indicates.
  • the group represented by the formula (18) and the group represented by the formula (19) may be directly bonded to Ar 3 , or methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene.
  • Ar 3 may have a substituent other than R 5 and R 6 .
  • substituents include exemplified substituents such as in the description with respect to Q 1. When a plurality of substituents are present, they may be the same or different.
  • an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a carboxyl group, and a substituted carboxyl group are preferable from the viewpoint of ease of synthesis of the raw material monomer.
  • n6 represents an integer of 1 or more. n6 is preferably an integer of 1 to 4, more preferably an integer of 1 to 3.
  • n7 represents an integer of 1 or more. n7 is preferably an integer of 1 to 4, more preferably an integer of 1 to 3.
  • Examples of the (2 + n6 + n7) -valent aromatic group represented by Ar 3 in the formula (17) include a (2 + n6 + n7) -valent aromatic hydrocarbon group and a (2 + n6 + n7) -valent aromatic heterocyclic group, preferably (2 + n6 + n7) -valent aromatic group consisting of only carbon atoms, or (2 + n6 + n7) -valent aromatics consisting of carbon atoms and one or more atoms selected from the group consisting of hydrogen atoms, nitrogen atoms and oxygen atoms It is a family group.
  • Examples of the (2 + n6 + n7) -valent aromatic group include a benzene ring, a pyridine ring, a 1,2-diazine ring, a 1,3-diazine ring, a 1,4-diazine ring, a furan ring, a pyrrole ring, a pyrazole ring, and an imidazole.
  • Examples of the monocyclic aromatic ring include rings represented by Formulas 1 to 5 and Formulas 7 to 10 exemplified in the description of the structural unit represented by Formula (13).
  • Examples of the condensed polycyclic aromatic ring include rings represented by Formulas 13 to 27 exemplified in the description of the structural unit represented by Formula (13).
  • Examples of the aromatic ring assembly include rings represented by formulas 28 to 36 exemplified in the description of the structural unit represented by formula (13).
  • bridged polycyclic aromatic ring examples include rings represented by the formulas 37 to 44 exemplified in the description of the structural unit represented by the formula (13).
  • a (2 + n6 + n7) -valent aromatic group from the viewpoint of ease of synthesis of the raw material monomer, hydrogen from a ring represented by the formulas 1 to 5, 7 to 10, 13, 14, 26 to 29, 37 to 39 or 41 A group in which (2 + n6 + n7) atoms are removed is preferred, and a group in which (2 + n6 + n7) hydrogen atoms have been removed from the ring represented by Formula 1, 37 or 41 is more preferred, and from the ring represented by Formula 1, 38 or 42 A group obtained by removing (2 + n6 + n7) hydrogen atoms is more preferable.
  • R 7 represents a single bond or a (1 + m5) -valent organic group, and is preferably a (1 + m5) -valent organic group.
  • the (1 + m5) -valent organic group represented by R 7 for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, t-butyl group A substituent selected from a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a lauryl group, and a group in which at least one hydrogen atom of these groups is substituted with a substituent.
  • the (1 + m5) -valent organic group represented by R 7 is a group obtained by removing m5 hydrogen atoms from an alkyl group and m5 hydrogen atoms from an aryl group from the viewpoint of ease of synthesis of the raw material monomer.
  • a group and a group obtained by removing m5 hydrogen atoms from an alkoxy group are preferred.
  • substituents examples include exemplified substituents such as in the description with respect to Q 1. When a plurality of substituents are present, they may be the same or different.
  • m5 represents an integer of 1 or more. Provided that when R 7 is a single bond m5 is 1.
  • R 8 represents a single bond or a (1 + m6) -valent organic group, and is preferably a (1 + m6) -valent organic group.
  • examples of the (1 + m6) -valent organic group represented by R 8 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, an s-butyl group, and a t-butyl group.
  • the (1 + m6) -valent organic group represented by R 8 is a group obtained by removing m6 hydrogen atoms from an alkyl group and m6 hydrogen atoms from an aryl group from the viewpoint of ease of synthesis of the raw material monomer.
  • a group and a group obtained by removing m6 hydrogen atoms from an alkoxy group are preferred.
  • substituents examples include exemplified substituents such as in the description with respect to Q 1. When a plurality of substituents are present, they may be the same or different.
  • m6 represents an integer of 1 or more. Provided that when R 8 is a single bond m6 represents 1.
  • R 9 represents a monovalent group having a group represented by formula (21)
  • R 10 represents a group represented by formula (22).
  • Ar 4 represents a (2 + n8 + n9) -valent aromatic group with or without a substituent other than R 9 and R 10
  • n8 and n9 are each independently an integer of 1 or more Indicates.
  • the group represented by the formula (21) and the group represented by the formula (22) may be directly bonded to Ar 4 , or methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene.
  • Ar 4 may have a substituent other than R 9 and R 10 .
  • substituents include exemplified substituents such as in the description with respect to Q 1. When a plurality of substituents are present, they may be the same or different.
  • an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a carboxyl group, and a substituted carboxyl group are preferable from the viewpoint of ease of synthesis of the raw material monomer.
  • n8 represents an integer of 1 or more. n8 is preferably an integer of 1 to 4, more preferably an integer of 1 to 3.
  • n9 represents an integer of 1 or more. n9 is preferably an integer of 1 to 4, more preferably an integer of 1 to 3.
  • Examples of the (2 + n8 + n9) -valent aromatic group represented by Ar 4 in the formula (20) include a (2 + n8 + n9) -valent aromatic hydrocarbon group and a (2 + n8 + n9) -valent aromatic heterocyclic group.
  • Examples of the (2 + n8 + n9) -valent aromatic group include a benzene ring, a pyridine ring, a 1,2-diazine ring, a 1,3-diazine ring, a 1,4-diazine ring, a furan ring, a pyrrole ring, a pyrazole ring, And a (2 + n8 + n9) -valent group obtained by removing (2 + n8 + n9) hydrogen atoms from a monocyclic aromatic ring such as an imidazole ring; a condensed polycycle in which two or more rings selected from the group consisting of the monocyclic aromatic rings are condensed A (2 + n8 + n9) -valent group obtained by removing (2 + n8 + n9) hydrogen atoms from the formula aromatic ring; two or more aromatic rings selected from the group consisting of the monocyclic aromatic ring and the condensed polycyclic aromatic ring are bonded to a
  • Examples of the monocyclic aromatic ring include rings represented by Formulas 1 to 5 and Formulas 7 to 10 exemplified in the description of the structural unit represented by Formula (13).
  • Examples of the condensed polycyclic aromatic ring include rings represented by Formulas 13 to 27 exemplified in the description of the structural unit represented by Formula (13).
  • Examples of the aromatic ring assembly include rings represented by formulas 28 to 36 exemplified in the description of the structural unit represented by formula (13).
  • bridged polycyclic aromatic ring examples include rings represented by the formulas 37 to 44 exemplified in the description of the structural unit represented by the formula (13).
  • a (2 + n8 + n9) -valent aromatic group from the viewpoint of ease of synthesis of the raw material monomer, hydrogen from a ring represented by the formulas 1 to 5, 7 to 10, 13, 14, 26 to 29, 37 to 39 or 41
  • a group in which (2 + n8 + n9) atoms are removed is preferred, and a group in which (2 + n8 + n9) hydrogen atoms have been removed from the ring represented by formulas 1 to 6, 8, 14, 27, 28, 38 or 42 is more preferred.
  • 37 or 41 a group obtained by removing (2 + n8 + n9) hydrogen atoms from the ring is more preferred.
  • R 11 represents a single bond or a (1 + m7) -valent organic group, and is preferably a (1 + m7) -valent organic group.
  • examples of the (1 + m7) -valent organic group represented by R 11 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, an s-butyl group, and a t-butyl group.
  • the (1 + m7) -valent organic group represented by R 11 is a group in which m7 hydrogen atoms are removed from an alkyl group and m7 hydrogen atoms are removed from an aryl group from the viewpoint of ease of synthesis of the raw material monomer. And a group obtained by removing m7 hydrogen atoms from an alkoxy group.
  • substituents examples include exemplified substituents such as in the description with respect to Q 1. When a plurality of substituents are present, they may be the same or different.
  • m7 represents an integer of 1 or more. Provided that when R 11 is a single bond m7 represents 1.
  • R 12 represents a single bond or a (1 + m8) valent organic group, and is preferably a (1 + m8) valent organic group.
  • examples of the (1 + m8) -valent organic group represented by R 12 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, an s-butyl group, and a t-butyl group.
  • the (1 + m8) -valent organic group represented by R 12 from the viewpoint of ease of synthesis of the raw material monomer, a group in which m8 hydrogen atoms are removed from the alkyl group, and m8 hydrogen atoms are removed from the aryl group. A group and a group obtained by removing m8 hydrogen atoms from an alkoxy group are preferred.
  • substituents examples include exemplified substituents such as in the description with respect to Q 1. When a plurality of substituents are present, they may be the same or different.
  • m8 represents an integer of 1 or more. Provided that when R 12 is a single bond m8 represents 1.
  • R 13 represents a (1 + m9 + m10) valent organic group
  • R 14 represents a monovalent organic group.
  • Q 1 , Q 3 , Y 1 , M 1 , Z 1 , Y 3 , n1 , A1, b1, and n3 are as described above, and m9 and m10 each independently represents an integer of 1 or more, Q 1 , Q 3 , Y 1 , M 1 , Z 1 , Y 3 , n1, a1, b1, and n3.
  • m9 and m10 each independently represents an integer of 1 or more, Q 1 , Q 3 , Y 1 , M 1 , Z 1 , Y 3 , n1, a1, b1, and n3.
  • examples of the (1 + m9 + m10) -valent organic group represented by R 13 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, an s-butyl group, and a t-butyl group.
  • the (1 + m9 + m10) -valent organic group represented by R 13 is a group obtained by removing (m9 + m10) hydrogen atoms from an alkyl group and (m9 + m10) hydrogen atoms from an aryl group from the viewpoint of ease of synthesis of the raw material monomer.
  • a group in which atoms are removed and a group in which (m9 + m10) hydrogen atoms have been removed from an alkoxy group are preferred.
  • examples of the monovalent organic group represented by R 14 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a s-butyl group, a t-butyl group, and pentyl.
  • the monovalent organic group represented by R 14 is a group obtained by removing one hydrogen atom from an alkyl group, a group obtained by removing one hydrogen atom from an aryl group, from the viewpoint of ease of synthesis of the raw material monomer, And a group obtained by removing one hydrogen atom from an alkoxy group is preferred.
  • Examples of the structural unit represented by the formula (23) include the following structural units.
  • R 13 represents a (1 + m11 + m12) -valent organic group.
  • Q 1 , Q 3 , Y 1 , M 1 , Z 1 , Y 3 , n1, a1, b1, and n3 are described above.
  • m12 each independently represents an integer greater than or equal to 1.
  • Each of R 13 , m11, m12, Q 1 , Q 3 , Y 1 , M 1 , Z 1 , Y 3 , n1, a1, b1, and n3 is plural. In some cases, they may be the same or different.
  • examples of the (1 + m11 + m12) -valent organic group represented by R 13 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, an s-butyl group, and a t-butyl group.
  • the (1 + m11 + m12) -valent organic group represented by R 13 is a group obtained by removing (m11 + m12) hydrogen atoms from an alkyl group and (m11 + m12) hydrogen atoms from an aryl group from the viewpoint of ease of synthesis of the raw material monomer.
  • a group in which atoms are removed and a group in which (m11 + m12) hydrogen atoms have been removed from an alkoxy group are preferred.
  • Examples of the structural unit represented by the formula (24) include the following structural units.
  • the structural unit represented by the formula (13) is preferably a structural unit represented by the formula (25) from the viewpoint of durability of the obtained ionic polymer.
  • R 15 represents a (1 + m13 + m14) -valent organic group.
  • Q 1 , Q 3 , Y 1 , M 1 , Z 1 , Y 3 , n1, a1, b1, and n3 are described above.
  • M14 and m15 each independently represents an integer greater than or equal to 1.
  • R 15 , m13, m14, Q 1 , Q 3 , Y 1 , M 1 , Z 1 , Y 3 , n1, a1, b1 and n3 are each When there are a plurality, they may be the same or different.
  • examples of the (1 + m13 + m14) -valent organic group represented by R 15 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, an s-butyl group, and a t-butyl group.
  • the (1 + m13 + m14) -valent organic group represented by R 15 is a group obtained by removing (m13 + m14) hydrogen atoms from an alkyl group and (m13 + m14) hydrogen atoms from an aryl group from the viewpoint of ease of synthesis of the raw material monomer.
  • a group in which atoms are removed and a group in which (m13 + m14) hydrogen atoms have been removed from an alkoxy group are preferred.
  • Examples of the structural unit represented by the formula (25) include the following structural units.
  • the structural unit represented by formula (15) is the structural unit represented by formula (26) and the formula from the viewpoint of electron transport properties of the obtained ionic polymer.
  • the structural unit represented by (27) is preferred, and the structural unit represented by formula (27) is more preferred.
  • R 16 represents a (1 + m16 + m17) valent organic group
  • R 17 represents a monovalent organic group.
  • Q 3 indicating an integer of 1 or more, respectively m17 independently, Q 3, Y 2, M 2, Z 2, Y 3, n2, a2, b2 , and n3
  • examples of the (1 + m16 + m17) -valent organic group represented by R 16 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, an s-butyl group, and a t-butyl group.
  • the (1 + m16 + m17) -valent organic group represented by R 16 is a group obtained by removing (m16 + m17) hydrogen atoms from an alkyl group and (m16 + m17) hydrogen atoms from an aryl group from the viewpoint of ease of synthesis of the raw material monomer.
  • a group in which atoms are removed and a group in which (m16 + m17) hydrogen atoms have been removed from an alkoxy group are preferred.
  • examples of the monovalent organic group represented by R 17 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a s-butyl group, a t-butyl group, and pentyl.
  • a group in which one hydrogen atom is removed from an alkyl group having 1 to 20 carbon atoms which is not present phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthracenyl group, 2-anthracenyl group, 9-anthracenyl 1 hydrogen from an aryl group having 6 to 30 carbon atoms, with or without a substituent selected from a group, a group in which at least one hydrogen atom of these groups is substituted with a substituent, and the like
  • the monovalent organic group represented by R 17 is a group obtained by removing one hydrogen atom from an alkyl group, a group obtained by removing one hydrogen atom from an aryl group, from the viewpoint of ease of synthesis of the raw material monomer, And a group obtained by removing one hydrogen atom from an alkoxy group is preferred.
  • Examples of the structural unit represented by the formula (26) include the following structural units.
  • R 16 represents a (1 + m16 + m17) valent organic group.
  • Q 2 , Q 3 , Y 2 , M 2 , Z 2 , Y 3 , n 2, a 2, b 2, and n 3 are described above.
  • m17 each independently represents an integer of 1 or more, and each of R 16 , m16, m17, Q 2 , Q 3 , Y 2 , M 2 , Z 2 , Y 3 , n 2, a 2, b 2 and n 3 is plural. In some cases, they may be the same or different.
  • examples of the (1 + m16 + m17) -valent organic group represented by R 16 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, an s-butyl group, and a t-butyl group.
  • the (1 + m16 + m17) -valent organic group represented by R 16 is a group obtained by removing (m16 + m17) hydrogen atoms from an alkyl group and (m16 + m17) hydrogen atoms from an aryl group from the viewpoint of ease of synthesis of the raw material monomer.
  • a group in which atoms are removed and a group in which (m16 + m17) hydrogen atoms have been removed from an alkoxy group are preferred.
  • Examples of the structural unit represented by the formula (27) include the following structural units.
  • the structural unit represented by the formula (15) is preferably a structural unit represented by the formula (28) from the viewpoint of durability of the obtained ionic polymer.
  • R 18 represents a (1 + m18 + m19) -valent organic group.
  • Q 2 , Q 3 , Y 2 , M 2 , Z 2 , Y 3 , n 2, a 2, b 2 and n 3 are the same as described above.
  • M19 and m20 each independently represents an integer greater than or equal to 1.
  • R 18 , m18, m19, Q 2 , Q 3 , Y 2 , M 2 , Z 2 , Y 3 , n 2, a 2, b 2 and n 3 are each When there are a plurality, they may be the same or different.
  • examples of the (1 + m18 + m19) -valent organic group represented by R 18 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, an s-butyl group, and a t-butyl group.
  • the (1 + m18 + m19) -valent organic group represented by R 18 is a group obtained by removing (m18 + m19) hydrogen atoms from an alkyl group and (m18 + m19) hydrogen atoms from an aryl group from the viewpoint of ease of synthesis of the raw material monomer.
  • a group in which atoms are removed and a group in which (m18 + m19) hydrogen atoms have been removed from an alkoxy group are preferred.
  • Examples of the structural unit represented by the formula (28) include the following structural units.
  • the structural unit represented by formula (17) is preferably a structural unit represented by formula (29) from the viewpoint of electron transport properties of the obtained ionic polymer.
  • R 19 represents a single bond or a (1 + m21) -valent organic group
  • R 20 represents a single bond or a (1 + m22) -valent organic group.
  • Q 1 , Q 3 , Y 1 , M 1 , Z 1, Y 3, n1 , a1, the b1 and n3 represents an integer of 1 or more in each .m21 and m22 described above independently.
  • m21 when R 19 is a single bond indicates 1
  • R 20 is In the case of a single bond
  • m22 represents 1.
  • Q 1 , Q 3 , Y 1 , M 1 , Z 1 , Y 3 , n1, a1, b1, and n3 are plural, they may be the same or different. .
  • examples of the (1 + m21) -valent organic group represented by R 19 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, an s-butyl group, and a t-butyl group.
  • the (1 + m21) -valent organic group represented by R 19 is a group obtained by removing (m21) hydrogen atoms from an alkyl group and (m21) hydrogen atoms from an aryl group from the viewpoint of ease of synthesis of the raw material monomer.
  • a group in which atoms are removed and a group in which (m21) hydrogen atoms have been removed from an alkoxy group are preferred.
  • examples of the (1 + m22) -valent organic group represented by R 20 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, an s-butyl group, and a t-butyl group.
  • the (1 + m22) -valent organic group represented by R 20 is a group obtained by removing (m22) hydrogen atoms from an alkyl group and (m22) hydrogen atoms from an aryl group from the viewpoint of ease of synthesis of the raw material monomer.
  • a group in which atoms are removed and a group in which (m22) hydrogen atoms have been removed from an alkoxy group are preferred.
  • Examples of the structural unit represented by the formula (29) include the following structural units.
  • the structural unit represented by the formula (17) is preferably a structural unit represented by the formula (30) from the viewpoint of durability of the obtained ionic polymer.
  • R 21 represents a single bond or a (1 + m23) -valent organic group
  • R 22 represents a single bond or a (1 + m24) -valent organic group
  • the b1 and n3 represents an integer of 1 or more in each .m23 and m24 described above independently.
  • m23 when R 21 is a single bond indicates 1
  • R 22 is In the case of a single bond
  • m24 represents 1.
  • n25 and m26 each independently represents an integer of 1 or more, m23, m24, R 21 , R 22 , Q 1 , Q 3 , Y 1 , M 1 , Z 1 , Y 3 , n1, a1, b1, and n3 may be the same or different when there are a plurality of each.
  • examples of the (1 + m23) -valent organic group represented by R 21 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, an s-butyl group, and a t-butyl group.
  • Group in which (m23) hydrogen atoms have been removed from the alkyl group methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, nonyloxy group, dodecyloxy group, cyclopropyloxy group, cyclobutyl An oxy group, a cyclopentyloxy group, a cyclohexyloxy group, a
  • the (1 + m23) -valent organic group represented by R 21 is a group obtained by removing (m23) hydrogen atoms from an alkyl group and (m23) hydrogen atoms from an aryl group from the viewpoint of ease of synthesis of the raw material monomer.
  • a group in which atoms are removed and a group in which (m23) hydrogen atoms have been removed from an alkoxy group are preferred.
  • examples of the (1 + m24) -valent organic group represented by R 22 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, an s-butyl group, and a t-butyl group.
  • the (1 + m24) -valent organic group represented by R 22 is a group obtained by removing (m24) hydrogen atoms from an alkyl group and (m24) hydrogen atoms from an aryl group from the viewpoint of ease of synthesis of the raw material monomer.
  • a group in which atoms are removed and a group in which (m24) hydrogen atoms have been removed from an alkoxy group are preferred.
  • Examples of the structural unit represented by the formula (30) include the following structural units.
  • the structural unit represented by formula (20) is preferably a structural unit represented by formula (31) from the viewpoint of the obtained electron transport property.
  • R 23 represents a single bond or a (1 + m27) valent organic group
  • R 24 represents a single bond or a (1 + m28) valent organic group.
  • Q 2 , Q 3 , Y 2 , M 2 , Z 2 , Y 3 , n 2, a 2, b 2 and n 3 are as described above
  • m 27 and m 28 each independently represent an integer of 1 or more, provided that when R 23 is a single bond, m 27 represents 1 and R 24 represents In the case of a single bond, m28 represents 1.
  • Q 2 , Q 3 , Y 2 , M 2 , Z 2 , Y 3 , n 2, a 2, b 2 and n 3 they may be the same or different. .
  • examples of the (1 + m27) -valent organic group represented by R 23 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, an s-butyl group, and a t-butyl group.
  • Group in which (m27) hydrogen atoms have been removed from the alkyl group methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, nonyloxy group, dodecyloxy group, cyclopropyloxy group, cyclobutyl
  • R 23 (1 + m27) valent organic group, from the viewpoint of easy synthesis of the raw material monomer, the alkyl group (m27) number of groups other than hydrogen atoms, the aryl group (m27) number of hydrogen A group in which atoms are removed and a group in which (m27) hydrogen atoms have been removed from an alkoxy group are preferred.
  • examples of the (1 + m28) -valent organic group represented by R 24 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, an s-butyl group, and a t-butyl group.
  • the (1 + m28) -valent organic group represented by R 24 is a group obtained by removing (m28) hydrogen atoms from an alkyl group and (m28) hydrogen atoms from an aryl group from the viewpoint of ease of synthesis of the raw material monomer.
  • a group in which atoms are removed and a group in which (m28) hydrogen atoms have been removed from an alkoxy group are preferred.
  • Examples of the structural unit represented by the formula (31) include the following structural units.
  • the structural unit represented by the formula (20) is preferably a structural unit represented by the formula (32) from the viewpoint of durability of the obtained ionic polymer.
  • R 25 represents a single bond or a (1 + m29) -valent organic group
  • R 26 represents a single bond or a (1 + m30) -valent organic group.
  • Q 2 , Q 3 , Y 2 , M 2 , Z 2 , Y 3 , n 2, a 2, b 2 and n 3 are as described above
  • m 29 and m 30 each independently represent an integer of 1 or more, provided that when R 25 is a single bond, m 29 represents 1 and R 26 represents In the case of a single bond, m30 represents 1.
  • n31 and m32 each independently represent an integer of 1 or more m29, m30, R 25 , R 26 , Q 2 , Q 3 , Y 2 , M 2 , Z 2 , Y 3 , n2, a2, b2 and n3 may be the same or different when there are a plurality of each.
  • examples of the (1 + m29) -valent organic group represented by R 25 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, an s-butyl group, and a t-butyl group.
  • the (1 + m29) -valent organic group represented by R 25 is a group obtained by removing (m29) hydrogen atoms from an alkyl group and (m29) hydrogen atoms from an aryl group from the viewpoint of ease of synthesis of the raw material monomer.
  • a group in which atoms are removed and a group in which (m29) hydrogen atoms have been removed from an alkoxy group are preferred.
  • examples of the (1 + m30) -valent organic group represented by R 26 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, an s-butyl group, and a t-butyl group.
  • the (1 + m30) -valent organic group represented by R 26 is a group obtained by removing (m30) hydrogen atoms from an alkyl group and (m30) hydrogen atoms from an aryl group from the viewpoint of ease of synthesis of the raw material monomer.
  • a group in which atoms are removed and a group in which (m30) hydrogen atoms have been removed from an alkoxy group are preferred.
  • Examples of the structural unit represented by the formula (32) include the following structural units.
  • the ionic polymer which concerns on this embodiment may further have 1 or more types of structural units represented by Formula (33).
  • Ar 5 represents a divalent aromatic group having or not having a substituent, or a divalent aromatic amine residue having or not having a substituent
  • X ′ represents a substituted group.
  • An imino group with or without a group, a silylene group with or without a substituent, an ethenylene group with or without a substituent, or an ethynylene group, and m33 and m34 are each independently 0 or 1 And at least one of m33 and m34 is 1.
  • Examples of the divalent aromatic group represented by Ar 5 in formula (33) include a divalent aromatic hydrocarbon group and a divalent aromatic heterocyclic group.
  • Examples of the divalent aromatic group include a benzene ring, a pyridine ring, a 1,2-diazine ring, a 1,3-diazine ring, a 1,4-diazine ring, a 1,3,5-triazine ring, a furan ring, A divalent group obtained by removing two hydrogen atoms from a monocyclic aromatic ring selected from a pyrrole ring, a thiophene ring, a pyrazole ring, an imidazole ring, an oxazole ring, an oxadiazole ring and an azadiazole ring; A divalent group obtained by removing two hydrogen atoms from a condensed polycyclic aromatic ring in which two or more selected from the group consisting of rings are condensed; from the
  • the condensed polycyclic aromatic ring is preferably one in which 2 to 4 monocyclic aromatic rings are condensed from the viewpoint of solubility of the ionic polymer.
  • the number of condensed monocyclic aromatic rings is more preferably 2 to 3, and further preferably 2.
  • the aromatic ring assembly is preferably one in which 2 to 4 aromatic rings are linked from the viewpoint of solubility of the ionic polymer.
  • the number of linked aromatic rings is more preferably 2 to 3, and still more preferably 2.
  • the bridged polycyclic aromatic ring is preferably one in which 2 to 4 aromatic rings are crosslinked from the viewpoint of solubility of the ionic polymer.
  • the number of aromatic rings to be bridged is more preferably 2 to 3, and even more preferably 2.
  • Examples of the monocyclic aromatic ring include the following rings.
  • Examples of the condensed polycyclic aromatic ring include the following rings.
  • Examples of the aromatic ring assembly include the following rings.
  • Examples of the Aribashi polycyclic aromatic ring include the following rings.
  • the divalent aromatic group represented by Ar 5 is represented by the formulas 45 to 60, 61 to 71, 77 to 80, 91. , 92, 93 or 96 is preferably a divalent group obtained by removing two hydrogen atoms from the ring represented by formulas 45 to 50, 59, 60, 77, 80, 91, 92 or 96.
  • a divalent group in which two hydrogen atoms are removed is more preferable.
  • the above divalent aromatic group may have a substituent.
  • substituent group and substituted groups exemplified in the description with respect to Q 1.
  • Examples of the divalent aromatic amine residue represented by Ar 5 in formula (33) include a group represented by formula (34).
  • Ar 6 , Ar 7 , Ar 8 and Ar 9 are each independently an arylene group with or without a substituent or a divalent heterocyclic ring with or without a substituent.
  • Ar 10 , Ar 11 and Ar 12 each independently represent an aryl group with or without a substituent, or a monovalent heterocyclic group with or without a substituent, and n10 and m35 independently represents 0 or 1.
  • Examples of the substituent that the arylene group, aryl group, divalent heterocyclic group, and monovalent heterocyclic group may have include, for example, a halogen atom, an alkyl group, an alkyloxy group, an alkylthio group, an aryl group, and an aryl group.
  • the substituent is vinyl group, acetylene group, butenyl group, acrylic group, acrylate group, acrylamide group, methacryl group, methacrylate group, methacrylamide group, vinyl ether group, vinylamino group, silanol group, small ring (cyclopropyl group) , A cyclobutyl group, an epoxy group, an oxetane group, a diketene group, an episulfide group, etc.), a lactone group, a lactam group, or a cross-linking group such as a group containing a siloxane derivative structure.
  • the carbon atom in Ar 6 and the carbon atom in Ar 8 may be directly bonded, or may be bonded through a divalent group such as —O— or —S—. Good.
  • Examples of the aryl group represented by Ar 10 , Ar 11 , and Ar 12 and the monovalent heterocyclic group include the aryl groups described and exemplified as the above-described substituents, and monovalent heterocyclic groups.
  • arylene group represented by Ar 6 , Ar 7 , Ar 8 , and Ar 9 a group composed of the remaining atomic group obtained by removing two hydrogen atoms bonded to a carbon atom constituting an aromatic ring from an aromatic hydrocarbon.
  • an arylene group for example, a group having a benzene ring, a group having a condensed ring, two or more benzene rings or condensed rings are bonded via a single bond or a divalent organic group (for example, an alkenylene group such as a vinylene group).
  • Groups. Arylene group has usually 6 to 60 carbon atoms, and preferably 7 to 48..
  • the arylene group include, for example, a phenylene group, a biphenylene group, a C 1 to C 17 alkoxyphenylene group, a C 1 to C 17 alkylphenylene group, a 1-naphthylene group, a 2-naphthylene group, a 1-anthracenylene group, 2- Anthracenylene group and 9-anthracenylene group may be mentioned.
  • the hydrogen atom of the aryl group may be substituted with a fluorine atom.
  • the fluorine atom-substituted aryl group include a tetrafluorophenylene group.
  • a phenylene group, a biphenylene group, a C 1 to C 12 alkoxyphenylene group, and a C 1 to C 12 alkylphenylene group are preferable.
  • Examples of the divalent heterocyclic group represented by Ar 6 , Ar 7 , Ar 8 , and Ar 9 include groups composed of the remaining atomic groups obtained by removing two hydrogen atoms from a heterocyclic compound.
  • a heterocyclic compound is an organic compound having a cyclic structure, and as an element constituting the ring, in addition to carbon atoms, oxygen atoms, sulfur atoms, nitrogen atoms, phosphorus atoms, boron atoms, silicon atoms, selenium atoms , An organic compound containing one or more heteroatoms selected from the group consisting of tellurium atoms and arsenic atoms.
  • the divalent heterocyclic group may have a substituent.
  • the divalent heterocyclic group usually has 4 to 60 carbon atoms, and preferably 4 to 20 carbon atoms.
  • the number of carbon atoms of the divalent heterocyclic group does not include the number of carbon atoms of the substituent.
  • the divalent heterocyclic group for example, thiophenediyl group, C 1 ⁇ C 12 alkyl thiophenediyl group, pyrrolediyl group, furandiyl group, pyridinediyl group, C 1 ⁇ C 12 alkyl pyridinediyl group, pyridazine-diyl group, pyrimidine
  • Examples include diyl group, pyrazinediyl group, triazinediyl group, pyrrolidinediyl group, piperidinediyl group, quinolinediyl group, and isoquinolinediyl group.
  • the ionic polymer containing a divalent aromatic amine residue as a structural unit may further have another structural unit.
  • other structural units include arylene groups such as a phenylene group and a fluorenediyl group.
  • ionic polymers those containing a crosslinking group are preferred.
  • Examples of the divalent aromatic amine residue represented by the formula (34) include groups in which two hydrogen atoms have been removed from the aromatic amine represented by the following formulas 101 to 110.
  • the aromatic amines represented by Formulas 101 to 110 may have a substituent as long as a divalent aromatic amine residue can be generated.
  • substituents include the substituents exemplified in the description regarding Q 1 described above. When a plurality of substituents are present, they may be the same or different.
  • X ′ represents an imino group with or without a substituent, a silylene group with or without a substituent, an ethenylene group with or without a substituent, or an ethynylene group.
  • Examples of the substituent that the imino group, silyl group or ethenylene group may have include, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, t-butyl group, pentyl
  • An alkyl group having 1 to 20 carbon atoms such as a group, hexyl group, cyclohexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, 3,7-dimethyloctyl group, and lauryl group;
  • Examples thereof include aryl groups having 6 to 30 carbon atoms such as phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthracenyl group, 2-anthracenyl group, and 9-anthracenyl group.
  • X ′ is preferably an imino group, an ethenylene group, or an ethynylene group.
  • m33 is preferably 1 and m34 is preferably 0.
  • the structural unit represented by the formula (33) is preferable from the viewpoint of electron accepting property of the ionic polymer.
  • Ar 13 is a pyridinediyl group with or without a substituent, a pyrazinediyl group with or without a substituent, a pyrimidinediyl group with or without a substituent, A pyridazine diyl group with or without a group or a triazinediyl group with or without a substituent is shown.
  • Examples of the substituent that the pyridinediyl group may have include the substituents exemplified in the description regarding Q 1 described above. When a plurality of substituents are present, they may be the same or different.
  • Examples of the substituent that the pyrazinediyl group may have include the substituents exemplified in the description of Q 1 described above. When a plurality of substituents are present, they may be the same or different.
  • Examples of the substituent that the pyrimidinediyl group may have include the substituents exemplified in the description of Q 1 described above. When a plurality of substituents are present, they may be the same or different.
  • Examples of the substituent that the pyridazinediyl group may have include the substituents exemplified in the description regarding Q 1 described above. When a plurality of substituents are present, they may be the same or different.
  • Examples of the substituent that the triazinediyl group may have include the substituents exemplified in the description regarding Q 1 described above. When a plurality of substituents are present, they may be the same or different.
  • the total number of structural units represented by the formula (20) is 30 to 100 mol% in all structural units contained in the ionic polymer excluding the terminal structural unit. It is more preferable that
  • terminal structural unit terminal structural unit of the ionic polymer according to the present embodiment for example, a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, butyl group, isobutyl group, s- butyl Group, t-butyl group, pentyl group, isoamyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, nonyl group, decyl group, lauryl group methoxy group, ethoxy group, propyloxy group, isopropyloxy group, butoxy group, Isobutoxy group, s-butoxy group, t-butoxy group, pentyloxy group, hexyloxy group, cyclohexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group,
  • the ionic polymer according to this embodiment is preferably a conjugated compound.
  • the “conjugated compound” refers to an unshared electron pair possessed by a multiple bond (for example, a double bond or a triple bond) or a nitrogen atom and an oxygen atom in the main chain of the ionic polymer. It means that there is a region that is continuous with one single bond.
  • the ionic polymer is a conjugated compound
  • ⁇ (Number of atoms on the main chain in a region where multiple bonds or unshared electron pairs are connected via a single bond) / (Number of all atoms on the main chain) ⁇ ⁇ 100% Is preferably 50% or more, more preferably 60% or more, more preferably 70% or more, further preferably 80% or more, and 90% or more. Even more preferably.
  • the ionic polymer according to this embodiment is preferably a polymer compound, more preferably a conjugated polymer compound.
  • the “polymer compound” refers to a compound having a polystyrene-equivalent number average molecular weight of 1 ⁇ 10 3 or more.
  • the ionic polymer is a conjugated polymer compound means that the ionic polymer is a conjugated compound and a polymer compound.
  • the number average molecular weight in terms of polystyrene of the ionic polymer is preferably 1 ⁇ 10 3 to 1 ⁇ 10 8 , and preferably 2 ⁇ 10 3 to 1 ⁇ 10 7 . More preferably, it is more preferably 3 ⁇ 10 3 to 1 ⁇ 10 7 , and still more preferably 5 ⁇ 10 3 to 1 ⁇ 10 7 .
  • the weight average molecular weight in terms of polystyrene is preferably 1 ⁇ 10 3 to 5 ⁇ 10 7 , more preferably 1 ⁇ 10 3 to 1 ⁇ 10 7 , and more preferably 1 ⁇ 10 7.
  • the number average molecular weight in terms of polystyrene is 1 ⁇ 10 3 ⁇ 5 ⁇ 10 5, more preferably 1 ⁇ 10 3 ⁇ 5 ⁇ 10 4, 1 ⁇ More preferably, it is 10 3 to 3 ⁇ 10 3 .
  • the polystyrene-equivalent number average molecular weight and weight average molecular weight of the ionic polymer can be determined using, for example, gel permeation chromatography (GPC).
  • the number of all structural units (that is, the degree of polymerization) contained in the ionic polymer excluding the terminal structural unit is preferably 1 or more and 20 or less, and preferably 1 or more and 10 or less. it is more preferable, and more preferably 1 to 5.
  • the orbital energy of the lowest unoccupied molecular orbital (LUMO) of the ionic polymer is preferably ⁇ 5.0 eV or more and ⁇ 2.0 eV or less, and ⁇ 4.5 eV. More preferably, it is -2.0 eV or less.
  • the orbital energy of the highest occupied molecular orbital (HOMO) of the ionic polymer is preferably ⁇ 6.0 eV or more and ⁇ 3.0 eV or less, and more preferably ⁇ 5.5 eV or more and ⁇ 3.0 eV or less.
  • the orbital energy of HOMO is lower than that of LUMO.
  • the orbital energy of the highest occupied molecular orbital (HOMO) of the ionic polymer can be obtained by measuring the ionization potential of the ionic polymer and using the obtained ionization potential as the orbital energy of HOMO.
  • the orbital energy of the lowest unoccupied molecular orbital (LUMO) of an ionic polymer is obtained by calculating the energy difference between HOMO and LUMO and using the sum of the energy difference value and the ionization potential as the LUMO orbital energy. Can do.
  • a photoelectron spectrometer is used to measure the ionization potential.
  • the energy difference between HOMO and LUMO can be obtained from the absorption terminal by measuring the absorption spectrum of the ionic polymer using an ultraviolet / visible / near infrared spectrophotometer.
  • the polymer (ionic polymer) according to this embodiment is used as an electroluminescent device, it is preferable that the polymer is substantially non-luminescent.
  • the polymer is substantially non-luminescent.
  • “the polymer is substantially non-luminescent” has the following meaning. First, an electroluminescent element A having a layer containing a certain polymer is produced. The electroluminescent element 2 which does not have a layer containing a polymer is produced. Although the electroluminescent element A has a layer containing a polymer, the electroluminescent element 2 is different from the electroluminescent element 2 only in that it does not have a layer containing a polymer.
  • a forward voltage of 10 V is applied to the electroluminescent element A and the electroluminescent element 2 to measure an emission spectrum.
  • the wavelength ⁇ that gives the maximum peak in the emission spectrum obtained for the electroluminescent element 2 is obtained.
  • the emission spectrum at the wavelength ⁇ is set to 1, the emission spectrum obtained for the electroluminescent element 2 is normalized, and the normalized emission amount S 0 is calculated by integrating with respect to the wavelength.
  • the emission intensity at the wavelength ⁇ is 1, the emission spectrum obtained for the electroluminescent element A is also normalized, and the normalized emission amount S is calculated by integrating the wavelength.
  • the polymer When the value calculated by (S ⁇ S 0 ) / S 0 ⁇ 100% is 30% or less, that is, compared with the normalized light emission amount of the electroluminescent element 2 having no polymer-containing layer, the polymer When the increase in the normalized luminescence amount of the electroluminescent element A having a layer containing is 30% or less, the polymer used is substantially non-luminescent.
  • the value calculated by (S ⁇ S 0 ) / S 0 ⁇ 100 is preferably 15% or less, and more preferably 10% or less.
  • an ionic polymer containing a group represented by the formula (1) and a group represented by the formula (3), an ionic polymer comprising only the structural unit represented by the formula (23), represented by the formula (23) And one type selected from the group consisting of groups represented by formulas 45 to 50, 59, 60, 77, 80, 91, 92, 96, and 101 to 110, in which two hydrogen atoms are removed.
  • An ionic polymer comprising the above group, an ionic polymer comprising only the structural unit represented by formula (24), a structural unit represented by formula (24), and formulas 45 to 50, 59, 60, 77 80, 91, 92, 96, and an ionic polymer comprising one or more groups selected from the group consisting of groups obtained by removing two hydrogen atoms from the groups represented by 101 to 110, the formula (25)
  • An ionic polymer comprising one or more groups selected from the group, an ionic polymer comprising only a structural unit represented by formula (29), a structural unit represented by formula (29), and formulas 45 to 50 59, 60, 77, 80, 91, 92, 96, and one or more groups selected from the group consisting of groups obtained by removing two hydrogen atoms from groups 101 to 110 A polymer, an ionic polymer consisting only of the structural unit represented by formula (30), a structural unit represented by formula (30), and formulas 45 to 50, 59, 60, 77, 80, 91, 92, 96, And 2 hydrogen atoms from the groups represented by 101 to 110 And one or more groups selected from the group consisting of excluding groups include ionic polymer consisting of.
  • Examples of the ionic polymer containing a group represented by the formula (1) and a group represented by the formula (3) include the following polymer compounds.
  • the proportion of the structural unit on the left is p mol% and the proportion of the structural unit on the right is (100-p) mol%. , and the these structural units are arranged at random.
  • n represents the degree of polymerization.
  • an ionic polymer containing a group represented by the formula (2) and a group represented by the formula (3), an ionic polymer comprising only a structural unit represented by the formula (26), represented by the formula (26) And one type selected from the group consisting of groups represented by formulas 45 to 50, 59, 60, 77, 80, 91, 92, 96, and 101 to 110, in which two hydrogen atoms are removed.
  • An ionic polymer comprising the above group, an ionic polymer comprising only a structural unit represented by formula (27), a structural unit represented by formula (27), and formulas 45 to 50, 59, 60, 77 80, 91, 92, 96, and an ionic polymer comprising one or more groups selected from the group consisting of groups obtained by removing two hydrogen atoms from the groups represented by 101 to 110, the formula (28)
  • An ionic polymer comprising at least one group selected from the group, an ionic polymer comprising only a structural unit represented by formula (31), a structural unit represented by formula (31), and formulas 45 to 50 59, 60, 77, 80, 91, 92, 96, and one or more groups selected from the group consisting of groups obtained by removing two hydrogen atoms from groups 101 to 110 A polymer, an ionic polymer consisting only of the structural unit represented by formula (32), a structural unit represented by formula (32), and formulas 45 to 50, 59, 60, 77, 80, 91, 92, 96, and 2 hydrogen atoms from a group represented by 101-110 And one or more groups selected from the group consisting of excluding groups include ionic polymer consisting of.
  • Examples of the ionic polymer containing a group represented by the formula (2) and a group represented by the formula (3) include the following polymer compounds.
  • the proportion of the structural unit on the left is p mol% and the proportion of the structural unit on the right is (100-p) mol%. , and the these structural units are arranged at random.
  • n represents the degree of polymerization.
  • a method for producing the ionic polymer according to this embodiment will be described.
  • a method in which a compound represented by the following general formula (36) is used as one of the raw materials and condensation polymerization is performed can be mentioned.
  • a compound in which —A a — is a structural unit represented by the formula (13)
  • a formula (17 It is preferable to use at least one selected from the group consisting of a compound which is a structural unit represented by formula (20) and a compound which is a structural unit represented by formula (20).
  • a a is represented by the formula (3) and one or more groups selected from the group consisting of the group represented by the formula (1) and the group represented by the formula (2).
  • a structural unit having one or more groups is shown, and Y 4 and Y 5 each independently represent a group involved in condensation polymerization.
  • the ionic polymer according to the present embodiment contains a structural unit other than -A a- together with the structural unit represented by -A a- in the above formula (36), other than -A a- A compound having another structural unit and two groups involved in condensation polymerization may be subjected to condensation polymerization together with the compound represented by formula (36).
  • a compound represented by the formula (37) is exemplified.
  • An ionic polymer further having a structural unit represented by —A b — can be produced by condensation polymerization of the compound represented by formula (37) together with the compound represented by formula (36).
  • a b represents a general formula (33) a structural unit represented by the structural unit or the general formula (35) represented by, Y 6 and Y 7 are each independently a condensation polymerization Indicates the group involved.
  • Examples of the group (Y 4 , Y 5 , Y 6 and Y 7 ) involved in the condensation polymerization include a hydrogen atom, a halogen atom, an alkyl sulfonate group, an aryl sulfonate group, an aryl alkyl sulfonate group, a borate ester residue, and a sulfonium methyl group.
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
  • alkyl sulfonate group examples include a methane sulfonate group, an ethane sulfonate group, and a trifluoromethane sulfonate group
  • aryl sulfonate group examples include a benzene sulfonate group and a p-toluene sulfonate group.
  • arylalkyl sulfonate groups examples include benzyl sulfonate groups.
  • boric acid ester residue examples include a group represented by the following formula.
  • phosphonate methyl group the following formula: —CH 2 PO (OR d ) 2 (Wherein, R d represents an alkyl group, an aryl group, or an arylalkyl group).
  • Examples of the monohalogenated methyl group include a methyl fluoride group, a methyl chloride group, a methyl bromide group, and a methyl iodide group.
  • a group suitable as a group involved in condensation polymerization varies depending on the type of polymerization reaction.
  • a polymerization reaction using a zerovalent nickel complex such as a Yamamoto coupling reaction
  • a halogen atom such as a Yamamoto coupling reaction
  • an alkyl sulfonate group, an aryl sulfonate group, And arylalkyl sulfonate groups such as a Suzuki coupling reaction
  • an alkyl sulfonate group, a halogen atom, a boric acid ester residue, and —B (OH) 2 may be mentioned.
  • oxidative polymerization with an oxidizing agent or electrochemically a hydrogen atom may be mentioned.
  • the compound (monomer) represented by the general formula (36) or (37) is dissolved in an organic solvent as necessary, and an alkali or an appropriate catalyst is obtained.
  • a polymerization method in which the reaction is carried out at a temperature between the melting point and the boiling point of the organic solvent may be employed.
  • a polymerization method for example, “Organic Reactions”, Vol. 14, pages 270-490, John Wiley & Sons, Inc., 1965, “Organic Synthesis”. ”, Collective Volume 6 (Collective Volume VI), 407-411, John Wiley & Sons, Inc., 1988, Chemical Review, Vol. 95, 2457 (1995). Journal of Organometallic Chemistry (J.
  • a known condensation polymerization reaction may be employed depending on the type of group involved in the condensation polymerization.
  • Examples of such a polymerization method include a method of polymerizing an appropriate monomer by a Suzuki coupling reaction, a method of polymerizing by a Grignard reaction, a method of polymerizing by a nickel zero-valent complex (Ni (0) complex), FeCl 3 and the like.
  • Examples thereof include a method of polymerizing with an oxidizing agent, a method of electrochemically oxidatively polymerizing, and a method of decomposing an intermediate polymer having an appropriate leaving group.
  • a method of polymerizing an appropriate monomer by a Suzuki coupling reaction a method of polymerizing by a Grignard reaction, and a method of polymerizing by a nickel zero-valent complex are preferable because the structure of the resulting ionic polymer can be easily controlled.
  • One aspect of a preferred method for producing an ionic polymer according to the present embodiment has a group selected from the group consisting of a halogen atom, an alkyl sulfonate group, an aryl sulfonate group, and an arylalkyl sulfonate group as a group involved in condensation polymerization.
  • an ionic polymer is produced by condensation polymerization of at least one raw material monomer in the presence of a nickel zero-valent complex.
  • raw material monomers in this case include dihalogenated compounds, bis (alkyl sulfonate) compounds, bis (aryl sulfonate) compounds, bis (aryl alkyl sulfonate) compounds, halogen-alkyl sulfonate compounds, halogen-aryl sulfonate compounds, and halogen-aryl.
  • Examples include alkyl sulfonate compounds, alkyl sulfonate-aryl sulfonate compounds, alkyl sulfonate-aryl alkyl sulfonate compounds, and aryl sulfonate-aryl alkyl sulfonate compounds.
  • a halogen atom as a group involved in the condensation polymerization, a halogen atom, an alkyl sulfonate group, an aryl sulfonate group, an arylalkyl sulfonate group, —B (OH) 2 , and A group selected from the group consisting of boric acid ester residues, and the total number (J) of moles of halogen atoms, alkyl sulfonate groups, aryl sulfonate groups and arylalkyl sulfonate groups in the raw material monomer; A raw material monomer in which the ratio of the total number of moles (K) of B (OH) 2 and boric acid ester residues (K) is substantially 1 (usually, K / J is in the range of 0.7 to 1.2)
  • the organic solvent varies depending on the type of raw material monomer and the type of reaction, but an organic solvent that has been sufficiently deoxygenated to suppress side reactions is preferred.
  • the organic solvent is preferably dehydrated in the same manner as the deoxygenation treatment. However, this is not the case when a two-phase reaction with water such as a Suzuki coupling reaction is performed.
  • saturated hydrocarbons such as pentane, hexane, heptane, octane, cyclohexane
  • unsaturated hydrocarbons such as benzene, toluene, ethylbenzene, xylene, carbon tetrachloride, chloroform, dichloromethane, chlorobutane, bromobutane, chloropentane
  • Halogenated saturated hydrocarbons such as bromopentane, chlorohexane, bromohexane, chlorocyclohexane, and bromocyclohexane
  • halogenated unsaturated hydrocarbons such as chlorobenzene, dichlorobenzene, and trichlorobenzene, methanol, ethanol, propanol, isopropanol, butanol
  • alcohols such as t-butyl alcohol, carboxylic acids such as formic acid, acetic acid and
  • organic solvents ethers are more preferable from the viewpoint of reactivity, and tetrahydrofuran and diethyl ether are more preferable.
  • organic solvents toluene and xylene are preferable from the viewpoint of reaction rate.
  • an alkali or an appropriate catalyst to the reaction solution in order to react the raw material monomers more efficiently. What is necessary is just to select an alkali or a catalyst according to the superposition
  • the alkali or catalyst those which are sufficiently dissolved in the solvent used in the reaction are preferable.
  • a method of mixing an alkali or a catalyst a method of slowly adding an alkali or catalyst solution while stirring the reaction solution under an inert atmosphere such as argon or nitrogen, and a method of slowly adding the reaction solution to an alkali or catalyst solution. The method of adding is illustrated.
  • the terminal group is protected with a stable group. May be.
  • the stable group that protects the terminal group has a conjugated bond and forms a structure that is continuously conjugated with the conjugated structure of the main chain of the ionic polymer. It is preferable.
  • the structure include a structure in which an aryl group or a heterocyclic group is bonded via a carbon-carbon bond.
  • the stable group for protecting the terminal group include substituents such as a monovalent aromatic compound group represented by the structural formula of Chemical Formula 10 in JP-A-9-45478.
  • an ionic polymer having no cation is polymerized in the first step, and then from the ionic polymer in the second step.
  • the method of manufacturing the ionic polymer containing a cation is mentioned.
  • the above-mentioned condensation polymerization reaction may be mentioned.
  • the reaction in the second step include a hydrolysis reaction with a metal hydroxide or an alkyl ammonium hydroxide.
  • an ionic polymer having no ions is polymerized in the first step, and ions are generated from the ionic polymer in the second step.
  • the method of manufacturing the ionic polymer containing this is mentioned.
  • the above-mentioned condensation polymerization reaction may be mentioned.
  • the reaction in the second step include a quaternary ammonium salification reaction of an amine using an alkyl halide or a halogen abstraction reaction with SbF 5 .
  • the ionic polymer according to this embodiment is excellent in charge injection and transportability. For this reason, the light emitting element which has the layer containing the ionic polymer which concerns on this embodiment light-emits with high brightness
  • Examples of a method for forming a layer containing an ionic polymer include a method of forming a film containing a solution containing an ionic polymer.
  • Solvents used in the film formation include alcohols other than water, ethers, esters, nitrile compounds, nitro compounds, halogenated alkyls, halogenated aryls, thiols, sulfides, sulfoxides, Of the solvents such as thioketones, amides, and carboxylic acids, a solvent having a solubility parameter of 9.3 or more is preferable.
  • Solvents include, for example, methanol (12.9), ethanol (11.2), 2-propanol (11.5), 1-butanol (9.9), t-butyl alcohol (10.5), acetonitrile (11.8), 1,2-ethanediol (14.7), N, N-dimethylformamide (11.5), dimethyl sulfoxide ( 12.8), acetic acid (12.4), nitrobenzene (11.1), nitromethane (11.0), 1,2-dichloroethane (9.7), dichloromethane (9.6), chlorobenzene (9.6) , Bromobenzene (9.9), dioxane (9.8), propylene carbonate (13.3), pyridine (10.4), carbon disulfide (10.0), and mixed solvents thereof.
  • the thickness of the electron injection layer varies depending on the ionic polymer used, and is appropriately selected so that the drive voltage and the light emission efficiency become appropriate values.
  • the electron injection layer needs to have a thickness that does not cause pinholes. From the viewpoint of lowering the driving voltage of the element, the thickness of the electron injection layer is preferably 1 nm to 1 ⁇ m, more preferably 2 nm to 500 nm, and further preferably 2 nm to 200 nm. From the viewpoint of protecting the light emitting layer, the thickness of the electron injection layer is preferably 5 nm to 1 ⁇ m.
  • a material for the cathode As a material for the cathode, a material having a small work function, easy electron injection into the light emitting layer, and high electrical conductivity is preferable. In the case of an organic EL device configured to extract light from the anode side, a material having a high visible light reflectivity is preferable as the cathode material in order to reflect light emitted from the light emitting layer to the anode side at the cathode.
  • the material for the cathode for example, alkali metals, alkaline earth metals, transition metals, and Group 13 metals of the periodic table can be used.
  • cathode materials include lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium, terbium, ytterbium, and the like. 1 or more selected from gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten and tin, and an alloy containing two or more metals selected from these metals, one or more selected from the above metals Alloys with seeds or more, or graphite or graphite intercalation compounds are used.
  • alloys include magnesium-silver alloys, magnesium-indium alloys, magnesium-aluminum alloys, indium-silver alloys, lithium-aluminum alloys, lithium-magnesium alloys, lithium-indium alloys, and calcium-aluminum alloys.
  • a transparent conductive electrode made of a conductive metal oxide, a conductive organic material, or the like can be used as the cathode.
  • the conductive metal oxide include indium oxide, zinc oxide, tin oxide, ITO, and IZO
  • examples of the conductive organic substance include polyaniline or a derivative thereof and polythiophene or a derivative thereof.
  • the cathode may be composed of a laminate in which two or more layers are laminated. In some cases, the electron injection layer is used as a cathode.
  • the thickness of the cathode is appropriately designed in consideration of required characteristics and process simplicity, and is, for example, 10 nm to 10 ⁇ m, preferably 20 nm to 1 ⁇ m, more preferably 50 nm to 500 nm.
  • Examples of the method for producing the cathode include a vacuum deposition method, a sputtering method, and a lamination method in which a metal thin film is thermocompression bonded.
  • the above organic EL device can be used as a lighting device, a surface light source device, or a display device by adding predetermined components.
  • a first film was produced using the production apparatus shown in FIG. That is, a biaxially stretched polyethylene naphthalate film (PEN film, thickness: 100 ⁇ m, width: 350 mm, manufactured by Teijin DuPont Films, trade name “Teonex Q65FA”) is used as a base material (base material 6), and this is sent out. Mounted on a roll 701. And while applying a magnetic field between the film-forming roll 31 and the film-forming roll 32 and supplying electric power to each of the film-forming roll 31 and the film-forming roll 32, Was discharged to generate plasma.
  • PEN film thickness: 100 ⁇ m, width: 350 mm
  • Teijin DuPont Films trade name “Teonex Q65FA”
  • a film-forming gas (mixed gas of hexamethyldisiloxane (HMDSO) as a source gas and oxygen gas (which also functions as a discharge gas) as a source gas) is supplied to the formed discharge region under the following conditions
  • a thin film was formed by a plasma CVD method to obtain a first film.
  • ⁇ Film formation conditions Supply amount of source gas: 50 sccm (Standard Cubic Centimeter per Minute converted to zero and 1 atm. The same applies hereinafter) Supply amount of oxygen gas: 500 sccm Degree of vacuum in the vacuum chamber: 3Pa Applied power from the power source for plasma generation: 0.8 kW Frequency of power source for plasma generation: 70 kHz Film conveyance speed: 0.5 m / min.
  • the thickness of the gas barrier layer in the obtained first film was 0.3 ⁇ m. Further, the water vapor permeability of the obtained first film was 3.1 ⁇ 10 ⁇ 4 g / (m under the conditions of a temperature of 40 ° C., a humidity of 0% RH on the low humidity side, and a humidity of 90% RH on the high humidity side. 2 ⁇ day), a value below the detection limit under the conditions of a temperature of 40 ° C., a humidity of 10% RH on the low humidity side, and a humidity of 100% RH on the high humidity side.
  • the water vapor transmission rate under the conditions of a temperature of 40 ° C., a low humidity side humidity of 10% RH, and a high humidity side humidity of 100% RH after bending the first film under the condition of a curvature radius of 8 mm is below the detection limit. It was confirmed that even when the first film was bent, the decrease in gas barrier properties was sufficiently suppressed.
  • Etching ion species Argon (Ar + ) Etching rate (SiO 2 thermal oxide equivalent value): 0.05 nm / sec Etching interval (SiO 2 equivalent value): 10 nm
  • Etching ion species Argon (Ar + ) Etching rate (SiO 2 thermal oxide equivalent value): 0.05 nm / sec Etching interval (SiO 2 equivalent value): 10 nm
  • X-ray photoelectron spectrometer Model “VG Theta Probe” manufactured by Thermo Fisher Scientific Irradiation X-ray: Single crystal spectroscopy AlK ⁇ X-ray spot and size: 800 ⁇ 400 ⁇ m oval.
  • the obtained silicon distribution curve, oxygen distribution curve and carbon distribution curve are shown in FIG. Regarding the obtained silicon distribution curve, oxygen distribution curve, carbon distribution curve and oxygen-carbon distribution curve, the atomic ratio (atomic concentration) and the distance from the surface of the gas barrier layer (atomic concentration) and the relationship between the etching time and the surface ( together relationship between nm) shown in the graph of FIG. “Distance (nm)” described on the horizontal axis of the graph of FIG. 6 is a value obtained by calculation from the etching time and the etching rate.
  • the obtained carbon distribution curve has a plurality of distinct extreme values, and the difference between the maximum value and the minimum value of the atomic ratio of carbon is 5 at. %, And in the region of 90% or more in the thickness direction of the gas barrier layer, the atomic ratio of silicon, the atomic ratio of oxygen, and the atomic ratio of carbon satisfy the conditions represented by the above formula (1). It was confirmed.
  • Reference Example A2 The first film having a gas barrier layer having a thickness of 0.3 ⁇ m obtained in Reference Example A1 was mounted on a delivery roll 701, and a gas barrier layer was newly formed on the surface of the gas barrier layer. Otherwise in the same manner as in Reference Example A1, a first film (A) was obtained. The thickness of the gas barrier layer on the base material (PEN film) in the first film (A) was 0.6 ⁇ m.
  • the first film (A) was mounted on a delivery roll 701, and a gas barrier layer was newly formed on the surface of the gas barrier layer. Otherwise in the same manner as in Reference Example A1, a first film (B) was obtained.
  • the thickness of the gas barrier layer in the first film (B) was 0.9 ⁇ m.
  • the first film (B) has a water vapor transmission rate of 6.9 ⁇ 10 ⁇ 4 g / (m 2 ⁇ m at a temperature of 40 ° C., a humidity of 0% RH on the low humidity side and a humidity of 90% RH on the high humidity side. day), a value below the detection limit under the conditions of a temperature of 40 ° C., a humidity of 10% RH on the low humidity side, and a humidity of 100% RH on the high humidity side.
  • the water vapor transmission rate is detected under conditions of a temperature of 40 ° C., a humidity of 10% RH on the low humidity side, and a humidity of 100% RH on the high humidity side after the first film (B) is bent under the condition of a curvature radius of 8 mm. It was a value below the limit, and it was confirmed that even when the first film (B) was bent, the gas barrier property was sufficiently suppressed.
  • a silicon distribution curve, an oxygen distribution curve, a carbon distribution curve, and an oxygen carbon distribution curve were prepared by the same method as in Reference Example A1.
  • the obtained results are shown in FIG. Regarding the silicon distribution curve, oxygen distribution curve, carbon distribution curve and oxygen carbon distribution curve, the relationship between the atomic ratio (atomic concentration) and the etching time, as well as the atomic ratio (atomic concentration) and the distance (nm) from the surface of the gas barrier layer.
  • the relationship is also shown in the graph of FIG. “Distance (nm)” described on the horizontal axis of the graph of FIG. 8 is a value obtained by calculation from the etching time and the etching rate.
  • the obtained carbon distribution curve has a plurality of distinct extreme values, and the difference between the maximum value and the minimum value of the atomic ratio of carbon is 5 at. %, And in the region of 90% or more in the thickness direction of the gas barrier layer, the atomic ratio of silicon, the atomic ratio of oxygen, and the atomic ratio of carbon satisfy the conditions represented by the above formula (1). It was confirmed.
  • Reference Example A3 A first film was obtained in the same manner as in Reference Example A1, except that the supply amount of the source gas was changed to 100 sccm.
  • the thickness of the gas barrier layer in the first film was 0.6 ⁇ m.
  • the water vapor permeability of the first film is 3.2 ⁇ 10 ⁇ 4 g / (m 2 ⁇ day) under the conditions of a temperature of 40 ° C., a humidity of 0% RH on the low humidity side, and a humidity of 90% RH on the high humidity side. Yes, the value was below the detection limit under the conditions of a temperature of 40 ° C., a humidity of 10% RH on the low humidity side, and a humidity of 100% RH on the high humidity side.
  • the water vapor transmission rate under the conditions of a temperature of 40 ° C., a low humidity side humidity of 10% RH, and a high humidity side humidity of 100% RH after bending the first film under the condition of a curvature radius of 8 mm is below the detection limit. It was confirmed that even when the first film was bent, the decrease in gas barrier properties was sufficiently suppressed.
  • a silicon distribution curve, an oxygen distribution curve, a carbon distribution curve, and an oxygen carbon distribution curve were prepared by the same method as in Reference Example A1.
  • the obtained silicon distribution curve, oxygen distribution curve and carbon distribution curve are shown in FIG. Regarding the obtained silicon distribution curve, oxygen distribution curve, carbon distribution curve and oxygen-carbon distribution curve, the atomic ratio (atomic concentration) and the distance from the surface of the gas barrier layer (nm) as well as the relationship between the atomic ratio (atomic concentration) and etching time. 10 is shown in the graph of FIG. “Distance (nm)” described on the horizontal axis of the graph of FIG. 10 is a value obtained by calculation from the etching time and the etching rate.
  • the obtained carbon distribution curve has a plurality of distinct extreme values, and the difference between the maximum value and the minimum value of the atomic ratio of carbon is 5 at. %, And in the region of 90% or more in the thickness direction of the gas barrier layer, the atomic ratio of silicon, the atomic ratio of oxygen, and the atomic ratio of carbon satisfy the conditions represented by the above formula (1). It was confirmed.
  • the thickness of the gas barrier layer in the first film was 100 nm.
  • the water vapor transmission rate of the first film is 1.3 g / (m 2 ⁇ day) under the conditions of a temperature of 40 ° C., a humidity of 10% RH on the low humidity side, and a humidity of 100% RH on the high humidity side.
  • the gas barrier property was insufficient.
  • a silicon distribution curve, an oxygen distribution curve, a carbon distribution curve, and an oxygen carbon distribution curve were prepared by the same method as in Reference Example A1.
  • the obtained silicon distribution curve, oxygen distribution curve and carbon distribution curve are shown in FIG. Regarding the obtained silicon distribution curve, oxygen distribution curve, carbon distribution curve and oxygen-carbon distribution curve, the atomic ratio (atomic concentration) and the distance from the surface of the gas barrier layer (nm) as well as the relationship between the atomic ratio (atomic concentration) and etching time. ) the relationship conjunction with shown in the graph of FIG. 12.
  • “Distance (nm)” described on the horizontal axis of the graph of FIG. 12 is a value obtained by calculation from the etching time and the etching rate. As is clear from the results shown in FIGS. 11 and 12, it was confirmed that the obtained carbon distribution curve has no extreme value.
  • the first film having the gas barrier layer used in the organic EL device according to the present invention has a sufficient gas barrier property, and even when bent, the gas barrier property is sufficiently lowered. It is possible to suppress it.
  • an ionic polymer was produced, and an organic EL device was produced using the produced ionic polymer.
  • the weight average molecular weight (Mw) and number average molecular weight (Mn) of the polymer were determined by using gel permeation chromatography (GPC) (manufactured by Tosoh Corporation: HLC-8220 GPC), polystyrene equivalent weight average molecular weight and number average molecular weight. As sought.
  • the sample to be measured was dissolved in tetrahydrofuran so as to have a concentration of about 0.5% by weight, and 50 ⁇ L was injected into GPC. Tetrahydrofuran was used for the mobile phase of GPC and flowed at a flow rate of 0.5 mL / min.
  • the structural analysis of the polymer was performed by 1 H-NMR analysis using a 300 MHz NMR spectrometer manufactured by Varian. The measurement was performed by dissolving the sample in a soluble heavy solvent (a solvent in which a hydrogen atom in a solvent molecule was replaced with a deuterium atom) so as to have a concentration of 20 mg / mL.
  • a soluble heavy solvent a solvent in which a hydrogen atom in a solvent molecule was replaced with a deuterium atom
  • the orbital energy of the highest occupied molecular orbital (HOMO) of the polymer was determined by measuring the ionization potential of the polymer and using the obtained ionization potential as the HOMO orbital energy.
  • the orbital energy of the lowest unoccupied molecular orbital (LUMO) of the polymer was obtained by calculating the energy difference between HOMO and LUMO and using the sum of the value and the ionization potential measured above as the LUMO orbital energy.
  • a photoelectron spectrometer manufactured by Riken Keiki Co., Ltd .: AC-2
  • the energy difference between HOMO and LUMO was determined from the absorption terminal by measuring the absorption spectrum of the polymer using an ultraviolet / visible / near infrared spectrophotometer (Varian: Cary 5E).
  • the obtained solution was dropped into a mixed solvent of 120 ml of methanol and 50 ml of 3% by weight acetic acid aqueous solution and stirred for 1 hour, and then the deposited precipitate was filtered, and the precipitate was dissolved in 20 ml of tetrahydrofuran.
  • the solution thus obtained was dropped into 200 ml of methanol and stirred for 30 minutes, and then the deposited precipitate was filtered to obtain a solid.
  • the obtained solid was dissolved in tetrahydrofuran and purified by passing through an alumina column and a silica gel column.
  • the number average molecular weight in terms of polystyrene of the polymer A was 5.2 ⁇ 10 4 .
  • the polymer A consists of a structural unit represented by the formula (A).
  • Conjugated polymer compound 1 is composed of a structural unit represented by formula (B) ("selected from the group consisting of a group represented by formula (1) and a group represented by formula (2) in all structural units).
  • the conjugated polymer compound 1 had an orbital energy of HOMO of ⁇ 5.5 eV and an orbital energy of LUMO of ⁇ 2.7 eV.
  • Conjugated polymer compound 2 is composed of a structural unit represented by formula (C) ("selected from the group consisting of a group represented by formula (1) and a group represented by formula (2) in all structural units).
  • the conjugated polymer compound 2 had an orbital energy of HOMO of ⁇ 5.5 eV and an orbital energy of LUMO of ⁇ 2.7 eV.
  • Conjugated polymer compound 3 is composed of a structural unit represented by formula (D) ("selected from the group consisting of a group represented by formula (1) and a group represented by formula (2) in all structural units).
  • the conjugated polymer compound 3 had a HOMO orbital energy of ⁇ 5.6 eV and a LUMO orbital energy of ⁇ 2.8 eV.
  • the conjugated polymer compound 4 is composed of a structural unit represented by the formula (E) (“selected from the group consisting of a group represented by the formula (1) and a group represented by the formula (2) in all structural units).
  • the conjugated polymer compound 4 had a HOMO orbital energy of ⁇ 5.6 eV and a LUMO orbital energy of ⁇ 2.8 eV.
  • reaction was allowed to react for 3.5 hours. Thereafter, parabromotoluene (0.68 g) was added thereto, and the mixture was further reacted for 2.5 hours. After the reaction, the reaction solution was cooled to room temperature, 50 ml of ethyl acetate / 50 ml of distilled water were added, and the aqueous layer was removed. After adding 50 ml of distilled water again to remove the aqueous layer, magnesium sulfate was added as a desiccant to the organic solvent layer. Insoluble matter was filtered to remove the organic solvent to obtain a residue.
  • the number average molecular weight in terms of polystyrene of the polymer B was 2.0 ⁇ 10 3 .
  • the polymer B is represented by the formula (F).
  • the obtained polymer B cesium salt is referred to as a conjugated polymer compound 5.
  • the conjugated polymer compound 5 is represented by the formula (G) (“one type selected from the group consisting of the group represented by the formula (1) and the group represented by the formula (2) in all structural units).
  • the conjugated polymer compound 5 had a HOMO orbital energy of ⁇ 5.6 eV and a LUMO orbital energy of ⁇ 2.6 eV.
  • the obtained solution was dropped into a mixed solvent of 120 ml of methanol and 50 ml of 3% by weight acetic acid aqueous solution and stirred for 1 hour, and then the deposited precipitate was filtered and dissolved in 20 ml of tetrahydrofuran.
  • the solution thus obtained was dropped into 200 ml of methanol and stirred for 30 minutes, and then the deposited precipitate was filtered to obtain a solid.
  • the obtained solid was dissolved in tetrahydrofuran and purified by passing through an alumina column and a silica gel column. The tetrahydrofuran solution collected from the column was concentrated and then added dropwise to methanol (200 mL), and the precipitated solid was filtered and dried.
  • the yield of the obtained polymer C was 526 mg.
  • the number average molecular weight in terms of polystyrene of the polymer C was 3.6 ⁇ 10 4 .
  • the polymer C consists of a structural unit represented by the formula (H).
  • N, N′-bis (4-bromophenyl) -N, N′-bis (4-tert-butyl-2,6-dimethylphenyl) 1,4-phenylenediamine is disclosed in, for example, JP-A-2008-74017. It can be synthesized by the method described.
  • Conjugated polymer compound 6 is composed of a structural unit represented by formula (I) ("selected from the group consisting of a group represented by formula (1) and a group represented by formula (2) in all structural units).
  • the conjugated polymer compound 6 had a HOMO orbital energy of ⁇ 5.3 eV and a LUMO orbital energy of ⁇ 2.6 eV.
  • the mixed solution was dropped into 300 mL of methanol and stirred for 1 hour, and then the deposited precipitate was filtered, dried under reduced pressure for 2 hours, and dissolved in 20 mL of tetrahydrofuran.
  • the obtained solution was dropped into a mixed solvent of 120 ml of methanol and 50 ml of 3% by weight acetic acid aqueous solution and stirred for 1 hour, and then the deposited precipitate was filtered and dissolved in 20 ml of tetrahydrofuran.
  • the solution thus obtained was dropped into 200 ml of methanol and stirred for 30 minutes, and then the deposited precipitate was filtered to obtain a solid.
  • the obtained solid was dissolved in tetrahydrofuran and purified by passing through an alumina column and a silica gel column.
  • the tetrahydrofuran solution collected from the column was concentrated and then added dropwise to methanol (200 mL), and the precipitated solid was filtered and dried.
  • the yield of the obtained polymer D was 590 mg.
  • the number average molecular weight in terms of polystyrene of the polymer D was 2.7 ⁇ 10 4 .
  • the polymer D consists of a structural unit represented by the formula (J). 3,7-Dibromo-N- (4-n-butylphenyl) phenoxazine was synthesized by the method described in JP2004137456.
  • the resulting solid was washed with water and dried under reduced pressure to obtain a pale yellow solid (210 mg). From the NMR spectrum, it was confirmed that the signal derived from the ethyl group at the ethyl ester site in the polymer D had completely disappeared.
  • the resulting cesium salt of polymer D is referred to as conjugated polymer compound 7.
  • the conjugated polymer compound 7 is composed of a structural unit represented by the formula (K) (“selected from the group consisting of a group represented by the formula (1) and a group represented by the formula (2) in all structural units).
  • the conjugated polymer compound 7 had a HOMO orbital energy of ⁇ 5.3 eV and a LUMO orbital energy of ⁇ 2.4 eV.
  • Phenylboronic acid (0.002 g) was added to the reaction solution and refluxed for 10 hours. Next, an aqueous sodium diethyldithiacarbamate solution (10 mL, concentration: 0.05 g / mL) was added and stirred for 1 hour. The mixed solution was dropped into 300 mL of methanol and stirred for 1 hour, and then the deposited precipitate was filtered, dried under reduced pressure for 2 hours, and dissolved in 20 mL of tetrahydrofuran.
  • the obtained solution was dropped into a mixed solvent of 120 ml of methanol and 50 ml of 3% by weight acetic acid aqueous solution and stirred for 1 hour, and then the deposited precipitate was filtered and dissolved in 20 ml of tetrahydrofuran.
  • the solution thus obtained was dropped into 200 ml of methanol and stirred for 30 minutes, and then the deposited precipitate was filtered to obtain a solid.
  • the obtained solid was dissolved in tetrahydrofuran and purified by passing through an alumina column and a silica gel column. The tetrahydrofuran solution collected from the column was concentrated and then added dropwise to methanol (200 mL), and the precipitated solid was filtered and dried.
  • the yield of the obtained polymer E was 293 mg.
  • the number average molecular weight in terms of polystyrene of the polymer E was 1.8 ⁇ 10 4 .
  • the polymer E consists of a structural unit represented by the formula (L).
  • conjugated polymer compound 8 is composed of a structural unit represented by the formula (M) (“selected from the group consisting of a group represented by the formula (1) and a group represented by the formula (2) in all structural units).
  • the conjugated polymer compound 8 had a HOMO orbital energy of ⁇ 5.6 eV and a LUMO orbital energy of ⁇ 2.6 eV.
  • Phenylboronic acid (0.002 g) was added to the reaction solution and refluxed for 4 hours. Next, an aqueous sodium diethyldithiacarbamate solution (10 mL, concentration: 0.05 g / mL) was added and stirred for 1 hour. The mixed solution was dropped into 300 mL of methanol and stirred for 1 hour, and then the deposited precipitate was filtered, dried under reduced pressure for 2 hours, and dissolved in 20 mL of tetrahydrofuran.
  • the obtained solution was dropped into a mixed solvent of 120 ml of methanol and 50 ml of 3% by weight acetic acid aqueous solution and stirred for 1 hour, and then the deposited precipitate was filtered and dissolved in 20 ml of tetrahydrofuran.
  • the solution thus obtained was dropped into 200 ml of methanol and stirred for 30 minutes, and then the deposited precipitate was filtered to obtain a solid.
  • the obtained solid was dissolved in a mixed solvent of tetrahydrofuran / ethyl acetate (1/1 (volume ratio)) and purified by passing through an alumina column and a silica gel column.
  • the tetrahydrofuran solution collected from the column was concentrated and then added dropwise to methanol (200 mL), and the precipitated solid was filtered and dried.
  • the yield of the obtained polymer E was 343 mg.
  • the polystyrene equivalent number average molecular weight of the polymer F was 6.0 ⁇ 10 4 .
  • the polymer F consists of a structural unit represented by the formula (N).
  • the resulting solid was washed with water and dried under reduced pressure to obtain a pale yellow solid (130 mg). From the NMR spectrum, it was confirmed that the signal derived from the ethyl group at the ethyl ester site in the polymer E completely disappeared.
  • the resulting cesium salt of polymer F is referred to as conjugated polymer compound 9.
  • the conjugated polymer compound 9 is composed of a structural unit represented by the formula (O) (“selected from the group consisting of a group represented by the formula (1) and a group represented by the formula (2) in all structural units).
  • the conjugated polymer compound 9 had a HOMO orbital energy of ⁇ 5.9 eV and a LUMO orbital energy of ⁇ 2.8 eV.
  • the resulting precipitate was collected by filtration and redissolved in tetrahydrofuran.
  • the solution was added dropwise to a mixture of methanol (200 mL) and 15% aqueous ammonia (100 mL), and the resulting precipitate was collected by filtration.
  • the precipitate was redissolved in tetrahydrofuran, added dropwise to a mixture of methanol (200 mL) and water (100 mL), and the resulting precipitate was collected by filtration.
  • the collected precipitate was dried under reduced pressure to obtain a polymer G (360 mg).
  • the number average molecular weight in terms of polystyrene of the polymer G was 6.0 ⁇ 10 4 .
  • the polymer G consists of a structural unit represented by the formula (P).
  • Conjugated polymer compound 10 is composed of a structural unit represented by formula (Q) ("selected from the group consisting of a group represented by formula (1) and a group represented by formula (2) in all structural units).
  • the conjugated polymer compound 10 had a HOMO orbital energy of ⁇ 5.7 eV and a LUMO orbital energy of ⁇ 2.9 eV.
  • the obtained precipitate was filtered off to obtain a solid (18 g). Under an inert atmosphere, the obtained solid (1 g), 2- [2- (2-methoxyethoxy) ethoxy] -p-toluenesulfonate (1.5 g), potassium carbonate (0.7 g), DMF (15 mL) were added. The mixture was mixed and stirred at 100 ° C. for 4 hours. After allowing to cool, chloroform was added to perform liquid separation and extraction, and the solution was concentrated. The concentrate was dissolved in chloroform and purified by passing through a silica gel column. The solution was concentrated to give 1,3-dibromo-5-ethoxycarbonyl-6- [2- [2- (2-methoxyethoxy) ethoxy] ethoxy] benzene (1.0 g).
  • Phenylboronic acid (6 mg) was added to the reaction solution and refluxed for 14 hours. Then, a sodium diethyldithiacarbamate aqueous solution (10 mL, concentration: 0.05 g / mL) was added, and the mixture was stirred for 2 hours. The aqueous layer was removed, the organic layer was washed with distilled water, and the solid obtained by concentration was dissolved in chloroform and purified by passing through an alumina column and a silica gel column. The eluate from the column was concentrated and dried. The yield of the obtained polymer H was 0.44 g.
  • the number average molecular weight in terms of polystyrene of the polymer H was 3.6 ⁇ 10 4 .
  • the polymer H consists of a structural unit represented by the formula (R).
  • the resulting solid was washed with water and dried under reduced pressure to obtain a pale yellow solid (190 mg). From the NMR spectrum, it was confirmed that the signal derived from the ethyl group at the ethyl ester site in the polymer H had completely disappeared.
  • the resulting cesium salt of polymer H is referred to as conjugated polymer compound 11.
  • the conjugated polymer compound 11 is composed of a structural unit represented by the formula (S) (“selected from the group consisting of a group represented by the formula (1) and a group represented by the formula (2) in all structural units).
  • the conjugated polymer compound 11 had a HOMO orbital energy of ⁇ 5.6 eV and a LUMO orbital energy of ⁇ 2.8 eV.
  • the number average molecular weight in terms of polystyrene of the polymer I was 2.0 ⁇ 10 3 .
  • the polymer I is represented by the formula (T).
  • 2- (4,4,5,5-tetramethyl-1,2,3-dioxaboran-2-yl) -9,9-dioctylfluorene is obtained by a method described in, for example, JP-A-2008-74017. Can be synthesized.
  • the obtained polymer I cesium salt is referred to as a conjugated polymer compound 12.
  • the conjugated polymer compound 12 is represented by the formula (U) (“one type selected from the group consisting of a group represented by the formula (1) and a group represented by the formula (2) in all structural units).
  • the conjugated polymer compound 12 had a HOMO orbital energy of ⁇ 5.6 eV and a LUMO orbital energy of ⁇ 2.8 eV.
  • PEDOT PSS solution (poly (3,4-ethylenedioxythiophene) / polystyrene sulfonic acid, product name: “Baytron”) manufactured by Stark Vitec Co., Ltd. was used as the hole injection material solution.
  • a hole transporting polymer material and xylene were mixed to obtain a composition for forming a hole transporting layer containing 0.7 wt% of the hole transporting polymer material.
  • the hole transporting polymer material was synthesized by the following method. To a 1 liter three-necked round bottom flask equipped with a reflux condenser and an overhead stirrer was added 2,7-bis (1,3,2-dioxyborol) -9,9-di (1-octyl) fluorene (3.863 g). 7.283 mmol), N, N-di (p-bromophenyl) -N- (4- (butan-2-yl) phenyl) amine (3.177 g, 6.919 mmol) and di (4-bromophenyl) Benzocyclobutanamine (156.3 mg, 0.364 mmol) was added.
  • the aqueous layer was removed and the organic layer was washed with 50 mL of water.
  • the organic layer was returned to the reaction flask and 0.75 g of sodium diethyldithiocarbamate and 50 mL of water were added.
  • the resulting mixture was stirred in an 85 ° C. oil bath for 16 hours.
  • the aqueous layer was removed and the organic layer was washed 3 times with 100 mL of water and then passed through a column of silica gel and basic alumina.
  • toluene as an eluent, a toluene solution containing the eluted polymer was recovered. Next, the recovered toluene solution was poured into methanol to precipitate a polymer.
  • the precipitated polymer was dissolved again in toluene, and the obtained toluene solution was poured into methanol to precipitate the polymer again.
  • the precipitated polymer was vacuum-dried at 60 ° C. to obtain 4.2 g of a hole transporting polymer material.
  • the obtained hole transporting polymer material had a polystyrene equivalent weight average molecular weight of 1.24 ⁇ 10 5 and a molecular weight distribution index (Mw / Mn) of 2.8. It was.
  • the composition for forming a hole transport layer was applied by a spin coating method to obtain a coating film having a thickness of 20 nm.
  • the substrate provided with this coating film was heated at 190 ° C. for 20 minutes in an inert atmosphere (in a nitrogen atmosphere) to insolubilize the coating film, and then naturally cooled to room temperature to form a substrate on which the hole transport layer was formed. Obtained.
  • a light emitting polymer material (“Lumation BP361” manufactured by Summation Co., Ltd.) and xylene were mixed to obtain a composition for forming a light emitting layer containing 1.4% by weight of the light emitting polymer material.
  • the composition for light emitting layer formation was apply
  • the substrate provided with this coating film was heated at 130 ° C. for 15 minutes in an inert atmosphere (nitrogen atmosphere) to evaporate the solvent and then naturally cooled to room temperature to obtain a substrate on which a light emitting layer was formed.
  • the substrate on which the layer containing the conjugated polymer compound 1 obtained above was formed was inserted into a vacuum apparatus, and an Al film was formed on the layer by vacuum vapor deposition to form a cathode, thereby forming a laminated structure. 1 was produced.
  • the laminated structure 1 obtained above was taken out from the vacuum apparatus and sealed with sealing glass and a two-component mixed epoxy resin in an inert atmosphere (in a nitrogen atmosphere) to obtain an organic EL element 1.
  • Example 29 Methanol and conjugated polymer compound 1 were mixed to obtain a composition containing 0.2% by weight of conjugated polymer compound 1.
  • the composition was applied by spin coating in the air on an ITO cathode (film thickness: 45 nm) patterned on the surface of a glass substrate to obtain a coating film having a film thickness of 10 nm.
  • the substrate provided with this coating film was heated in an inert atmosphere (nitrogen atmosphere) at 130 ° C. for 10 minutes to evaporate the solvent, and then naturally cooled to room temperature. A formed substrate was obtained.
  • a light emitting polymer material (“Lumation BP361” manufactured by Summation Co., Ltd.) and xylene were mixed to obtain a composition for forming a light emitting layer containing 1.4% by weight of the light emitting polymer material.
  • a composition for forming a light-emitting layer is applied in the air by a spin coating method on the layer containing the conjugated polymer compound 1 of the substrate on which the layer containing the conjugated polymer compound 1 obtained above is formed. Coating film was obtained.
  • the substrate provided with this coating film was heated at 130 ° C. for 15 minutes in an inert atmosphere (nitrogen atmosphere) to evaporate the solvent and then naturally cooled to room temperature to obtain a substrate on which a light emitting layer was formed.
  • the hole injection material solution was applied in the air by a spin coating method on the light emitting layer of the substrate on which the light emitting layer obtained above was formed, to obtain a coating film having a film thickness of 60 nm.
  • the substrate provided with this coating film was heated in an inert atmosphere (nitrogen atmosphere) at 130 ° C. for 15 minutes to evaporate the solvent and then naturally cooled to room temperature to obtain a substrate on which a hole injection layer was formed.
  • PEDOT PSS solution (poly (3,4-ethylenedioxythiophene) / polystyrenesulfonic acid, product name: “Baytron”) manufactured by Starck Vitec Co., Ltd. was used as the hole injection material solution.
  • the substrate on which the hole injection layer formed above was formed was inserted into a vacuum apparatus, Au was deposited on the layer by 80 nm by a vacuum deposition method, and an anode was formed, whereby the laminated structure 1 was manufactured. .
  • the laminated structure 2 obtained above was taken out from the vacuum apparatus and sealed with sealing glass and a two-component mixed epoxy resin in an inert atmosphere (in a nitrogen atmosphere) to obtain an organic EL element 17.

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  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

La présente invention concerne un élément électroluminescent (EL) organique, comprenant un premier film et un élément EL organique disposé sur le premier film. L'élément EL organique comprend une paire d'électrodes, une couche électroluminescente disposée entre les électrodes, et une couche d'injection d'électrons disposée entre les électrodes. La couche d'injection d'électrons contient un polymère ionique. Le premier film comprend une couche barrière contre les gaz contenant un atome de silicium, un atome d'oxygène, et un atome de carbone. La courbe de répartition de silicium, la courbe de répartition d'oxygène, et la courbe de répartition de carbone, obtenues à partir de la couche barrière contre les gaz, satisfont aux conditions suivantes : (i) entre le rapport du nombre d'atomes de silicium, le rapport du nombre d'atomes d'oxygène, et le rapport du nombre d'atomes de carbone, le rapport du nombre d'atomes de silicium est le deuxième plus grand dans une région représentant 90 % ou plus dans la direction de l'épaisseur de la couche barrière contre les gaz ; (ii) la courbe de répartition de carbone présente au moins une valeur extrême ; et (iii) la différence entre la valeur maximum et la valeur minimum du rapport du nombre d'atomes de carbone est supérieure ou égale à 5 % atomiques dans la courbe de répartition de carbone.
PCT/JP2011/072882 2010-10-08 2011-10-04 Élément électroluminescent organique, et son procédé de production WO2012046736A1 (fr)

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US20160005997A1 (en) * 2013-03-08 2016-01-07 Konica Minolta, Inc. Organic electroluminescent element and method of manufacturing organic electroluminescent element
CN111032339A (zh) * 2017-08-25 2020-04-17 住友化学株式会社 层叠膜

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WO2014103756A1 (fr) * 2012-12-25 2014-07-03 コニカミノルタ株式会社 Film barrière aux gaz
JPWO2015029732A1 (ja) * 2013-08-27 2017-03-02 コニカミノルタ株式会社 ガスバリアフィルムおよびガスバリアフィルムの製造方法
JP6409258B2 (ja) * 2013-09-03 2018-10-24 Jnc株式会社 ガスバリアフィルム積層体とそれを用いた電子部品
JP6705170B2 (ja) * 2013-12-26 2020-06-03 住友化学株式会社 積層フィルムおよびフレキシブル電子デバイス
TWI747382B (zh) * 2020-07-15 2021-11-21 友達光電股份有限公司 發光裝置

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