WO2017018328A1 - Additif pour couche électroluminescente de cellule électrochimiluminescente, composition pour la formation d'une couche électroluminescente dans une cellule électrochimiluminescente, et cellule électrochimiluminescente - Google Patents

Additif pour couche électroluminescente de cellule électrochimiluminescente, composition pour la formation d'une couche électroluminescente dans une cellule électrochimiluminescente, et cellule électrochimiluminescente Download PDF

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WO2017018328A1
WO2017018328A1 PCT/JP2016/071490 JP2016071490W WO2017018328A1 WO 2017018328 A1 WO2017018328 A1 WO 2017018328A1 JP 2016071490 W JP2016071490 W JP 2016071490W WO 2017018328 A1 WO2017018328 A1 WO 2017018328A1
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light emitting
general formula
emitting layer
atom
represented
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PCT/JP2016/071490
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English (en)
Japanese (ja)
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文広 米川
洋平 水口
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日本化学工業株式会社
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Priority claimed from JP2016142758A external-priority patent/JP6797586B2/ja
Application filed by 日本化学工業株式会社 filed Critical 日本化学工業株式会社
Priority to US15/739,837 priority Critical patent/US10439143B2/en
Priority to KR1020187000225A priority patent/KR20180034382A/ko
Priority to EP16830433.5A priority patent/EP3331043A4/fr
Priority to CN201680040328.3A priority patent/CN107851725B/zh
Publication of WO2017018328A1 publication Critical patent/WO2017018328A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
    • C07C69/80—Phthalic acid esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/09—Esters of phosphoric acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C08K5/19—Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
    • C08K5/3445—Five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/41—Compounds containing sulfur bound to oxygen
    • C08K5/42—Sulfonic acids; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
    • 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
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers

Definitions

  • the present invention relates to an additive for a light emitting layer in an electrochemiluminescence cell.
  • the present invention also relates to a composition for forming a light emitting layer of an electrochemiluminescence cell.
  • the present invention also relates to an electrochemiluminescence cell using an additive for light emitting layer.
  • organic electroluminescence (organic EL) elements which are self-luminous elements using electrons and holes as carriers, has been rapidly progressing.
  • Organic EL has features such as being thinner and lighter than a liquid crystal element that does not emit light and requires a backlight, and has excellent visibility.
  • An organic EL element generally includes a pair of substrates on which electrodes are formed on the surfaces facing each other, and a light emitting layer disposed between the pair of substrates.
  • the light emitting layer is made of an organic thin film containing a light emitting material that emits light when a voltage is applied.
  • a voltage is applied to the organic thin film from the anode and the cathode to inject holes and electrons.
  • holes and electrons are recombined in the organic thin film, and the excitons generated by the recombination return to the ground state, whereby light emission is obtained.
  • the organic EL device in addition to the light emitting layer, a hole injection layer and an electron injection layer for increasing the injection efficiency of holes and electrons between the light emitting layer and the electrode, and recombination of holes and electrons. It is necessary to provide a hole transport layer and an electron transport layer for improving efficiency. As a result, the organic EL element has a multi-layered structure, which complicates the structure and increases the manufacturing process. In organic EL, there are many limitations because it is necessary to consider the work function when selecting the electrode material used for the anode and the cathode.
  • An electrochemiluminescence cell generally has a light emitting layer containing an ionic compound and a light emitting material.
  • Various inorganic salts or organic salts are used as the ionic compound, and organic polymers and metal complexes are used as the light emitting material.
  • cations and anions derived from the ionic compound move in the light emitting layer toward the cathode and the anode, respectively, which results in a large electric field gradient (electric double layer) at the electrode interface.
  • the formed electric double layer facilitates the injection of electrons and holes in the cathode and the anode, respectively. Therefore, the electrochemiluminescence cell does not require a multilayer structure like an organic EL. In addition, since there is no need to consider the work function of the material used as the cathode and anode in the electrochemiluminescence cell, there are few restrictions on the material. For these reasons, the electrochemiluminescence cell is expected as a self-luminous element that can significantly reduce the manufacturing cost as compared with the organic EL.
  • JP 2011-103234 A International Publication WO2010 / 085180 Pamphlet
  • an organic polymer light emitting material similar to the light emitting material used for organic EL, particularly a ⁇ -conjugated polymer is often used.
  • organic polymers also have the function of transporting holes and electrons.
  • a thin film using an organic polymer light-emitting material as a light-emitting material has high mobility of holes and electrons, but low mobility of ions (also referred to as ion transport) has been a problem. .
  • a light emitting material a combination of a light emitting substance such as a metal complex, a small organic molecule, or a quantum dot and an organic polymer conductive material that transports holes and electrons to these may be used.
  • the problem is that the ion mobility is low.
  • the low mobility of ions in the light-emitting layer of the electrochemiluminescence cell is due to the low-polarity light-emitting material (specifically, when an organic polymer light-emitting material is used as the light-emitting material, In the case of using a combination of a metal complex, a small organic molecule, or a quantum dot, and an organic polymer conductive material, this is due to the low compatibility between the organic polymer conductive material) and a highly polar ionic compound. It is said that.
  • the low mobility of ions especially the low mobility of ions due to low compatibility between the luminescent material and the ionic compound, reduces the reorientation rate at the electrode interface described above, Electron injection efficiency is reduced.
  • Patent Documents 1 and 2 In order to increase the compatibility between the luminescent material and the ionic compound and to increase the ion mobility in the luminescent layer, Patent Documents 1 and 2 also disclose organic salts instead of conventional inorganic salts as ionic compounds. The use of an ionic liquid, and the addition of a polymer compound such as polyethylene oxide are described. However, development of a technique capable of further improving the compatibility between the light emitting material and the ionic compound has been awaited.
  • the present inventor has added a specific compound having an ester bond to a light-emitting layer containing a light-emitting material and an ionic compound. It has been found that the compatibility of the two can be improved in combination, and the film quality of the organic thin film forming the light emitting layer can be improved, and the present invention has been completed.
  • this invention solves the said subject by providing the additive for light emitting layers of the electrochemiluminescence cell containing the compound represented by following General formula (1).
  • X is a phosphorus atom, a carbon atom or a sulfur atom
  • A is a hydrogen atom, a direct bond, an aromatic hydrocarbon group, a chain aliphatic hydrocarbon group, an alicyclic hydrocarbon group or a heterocyclic group
  • R is a hydrogen atom or a branched, linear or cyclic alkyl group, and a plurality of R may be the same or different, and a plurality of R bonded to the same X via O.
  • Rs may be connected to each other to form a ring.
  • At least one R is an alkyl group, m is 0 or 1, r is 1 when X is a phosphorus atom or a carbon atom, and 2 when X is a sulfur atom, n is a number represented by 3-m when X is a phosphorus atom, and is a number represented by 2-m when X is a carbon atom or a sulfur atom.
  • p is 1 when m is 0 or when m is 1 and A is a hydrogen atom
  • p is 2 when m is 1 and A is a direct bond
  • m is 1 and A is A number that can be substituted in A when not a hydrogen atom or a direct bond.
  • A is not a direct bond.
  • X is a sulfur atom, A is not a hydrogen atom.
  • this invention solved the said subject by providing the composition for electroluminescent cell formation of the electrochemiluminescent cell containing the compound represented by the said General formula (1), an ionic compound, and a luminescent material. Is.
  • this invention is an electrochemiluminescence cell which has a light emitting layer and the electrode distribute
  • the said light emitting layer is a luminescent material, an ionic compound, and the compound represented by the said General formula (1).
  • an additive capable of obtaining a light emitting layer having high light emission efficiency and excellent light emission luminance when added to a light emitting layer in an electrochemiluminescence cell.
  • a composition for forming a light emitting layer having high light emission efficiency and excellent light emission luminance is provided.
  • an electrochemiluminescence cell using the additive or the composition for forming a light emitting layer in a light emitting layer.
  • FIG. 1 is a schematic cross-sectional view of an electrochemiluminescence cell according to an embodiment of the present invention.
  • FIG. 2 is a conceptual diagram showing a light emission mechanism of the electrochemiluminescence cell.
  • FIG. 2A shows an electrochemiluminescence cell before voltage application
  • FIG. 2B shows an electrochemiluminescence cell after voltage application.
  • the electrochemiluminescence cell 10 used in this embodiment includes a light emitting layer 12 and electrodes 13 and 14 disposed on each surface thereof.
  • the electrochemiluminescence cell 10 includes a first electrode 13 and a second electrode 14 that are a pair of electrodes facing each other, and a light emitting layer 12 sandwiched between the pair of electrodes 13 and 14.
  • the light emitting layer emits light when a voltage is applied.
  • the electrochemiluminescence cell 10 is used as various displays. FIG.
  • the first electrode 13 is connected to the anode of the DC power source, and the second electrode 14 is connected to the cathode.
  • the first electrode 13 may be connected to the cathode and the second electrode 14 may be connected to the anode.
  • an AC power source as a power source instead of a DC power source.
  • the first electrode 13 and the second electrode 14 may be transparent electrodes having translucency, or may be translucent or opaque electrodes.
  • the transparent electrode having translucency include those made of metal oxides such as indium-doped tin oxide (ITO) and fluorine-doped tin oxide (FTO). Further, there can be mentioned those made of a polymer having transparency such as poly (3,4-ethylenedioxythiophene) (PEDOT) doped with impurities.
  • the translucent or opaque electrode include aluminum (Al), silver (Ag), gold (Au), platinum (Pt), tin (Sn), bismuth (Bi), copper (Cu), and chromium (Cr). And metal materials such as
  • the first electrode 13 and the second electrode 14 are used as a transparent electrode because light emitted from the light emitting layer 12 can be easily extracted to the outside. Further, when one is a transparent electrode and the other is an opaque metal electrode, it is preferable because light emitted from the light emitting layer 12 can be taken out while being reflected by the metal electrode. Moreover, it is good also as a see-through light-emitting body by making both the 1st electrode 13 and the 2nd electrode 14 into a transparent electrode.
  • both the first electrode 13 and the second electrode 14 are metal electrodes made of Ag or the like having a high reflectivity, and the thickness of the light emitting layer 12 is controlled, so that the electrochemiluminescence cell 10 is laser-oscillated. It can also be an element.
  • the first electrode 13 is a transparent electrode and the second electrode 14 is an opaque or translucent metal electrode
  • the first electrode 13 is, for example, 10 nm or more and 500 nm or less from the viewpoint of realizing appropriate resistivity and light transmittance. It is preferable to have a thickness of
  • the second electrode 14 preferably has a thickness of, for example, 10 nm or more and 500 nm or less from the viewpoint of realizing an appropriate resistivity and light transmittance in the same manner as the first electrode 13.
  • the light emitting layer 12 is a mixture of a light emitting material and an ionic compound.
  • the light emitting layer 12 may be either solid or liquid.
  • the light emitting layer 12 can maintain a certain shape and can resist the force applied from the outside, or can be expanded and contracted by combining a flexible material such as an expandable electrode with the light emitting layer 12. This is preferable because possible electrochemiluminescence cells can be produced.
  • the light-emitting material functions as an electron and hole carrier body (having a hole and electron transport function) by being doped with anions and cations, and emits light when excited by the combination of electrons and holes. It means (has a light emitting function). Therefore, in the present invention, the simple term “luminescent material” means a conductive luminescent material.
  • the light emitting material may be a material having both a hole and electron transport function and a light emission function, or a material having a hole and / or electron transport function and a positive It may be a combination with a material that receives holes and electrons and emits light.
  • examples of the material having both a hole and electron transport function and a light emitting function include organic polymer light emitting materials described later.
  • examples of the material having a function of transporting holes and / or electrons include organic polymer conductive materials such as polyvinyl carbazole described later.
  • materials other than organic polymers are usually used as a material having a function of receiving holes and electrons from a material that transports holes and / or electrons and emitting light. A dot etc. can be mentioned.
  • an organic polymer conductive material that does not have a light-emitting function or has a low light-emitting function is used in combination with a light-emitting material other than an organic polymer such as a metal complex, a small organic molecule, or a quantum dot.
  • a light-emitting material other than an organic polymer such as a metal complex, a small organic molecule, or a quantum dot.
  • light emitting material therefore, for example, “compatibility with a light emitting material” to be described later is used when the combination of the organic polymer conductive material and the metal complex, organic low molecule or quantum dot is used as the light emitting material. Including compatibility.
  • the light emitting layer 12 contains a specific additive in addition to the light emitting material and the ionic compound.
  • the additive of this embodiment contains a compound represented by the following general formula (1).
  • X is a phosphorus atom, a carbon atom or a sulfur atom
  • A is a hydrogen atom, a direct bond, an aromatic hydrocarbon group, a chain aliphatic hydrocarbon group, an alicyclic hydrocarbon group or a heterocyclic group
  • R is a hydrogen atom or a branched, linear or cyclic alkyl group, and a plurality of R may be the same or different, and a plurality of R bonded to the same X via O.
  • Rs may be connected to each other to form a ring.
  • At least one R is an alkyl group, m is 0 or 1, r is 1 when X is a phosphorus atom or a carbon atom, and 2 when X is a sulfur atom, n is a number represented by 3-m when X is a phosphorus atom, and is a number represented by 2-m when X is a carbon atom or a sulfur atom.
  • p is 1 when m is 0 or when m is 1 and A is a hydrogen atom
  • p is 2 when m is 1 and A is a direct bond
  • m is 1 and A is A number that can be substituted in A when not a hydrogen atom or a direct bond.
  • A is not a direct bond.
  • X is a sulfur atom, A is not a hydrogen atom.
  • the additive used in the present invention includes a compound having an ester bond which is a group represented by [—X ( ⁇ O) r (—O—) n ].
  • the compatibility also referred to as dispersibility
  • the emission brightness of the electrochemiluminescence cell can be increased at a low voltage, so that high brightness can be achieved while suppressing power consumption.
  • the inventor presumes the reason for this as follows.
  • the ester bond portion represented by [—X ( ⁇ O) r (—O—) n ] has polarity
  • the alkyl group represented by R or the alkyl group and The group represented by A is a site with low polarity.
  • the polar part of the compound of the general formula (1) dispersed in the light emitting material has high compatibility with the ionic compound, the compatibility between the light emitting material and the ionic compound, or the ionicity to the light emitting material.
  • the dispersibility of the compound can be increased. As described above, the dispersibility of the ionic compound in the light-emitting material is improved, so that the ion transport property is improved.
  • the compound of the general formula (1) dispersed in the light-emitting material has a transfer point of the ionic compound. Thus, an ion transport property is imparted to the light emitting material.
  • the additive of the present invention when added to the light emitting layer, the ion transport property in the light emitting layer is increased, so that the emission luminance of the electrochemiluminescent cell can be increased at a low voltage.
  • the ester bond includes any of a phosphate ester bond, a phosphonate ester bond, a carbonate ester bond, a carboxylic acid ester bond, and a sulfate ester bond.
  • P which is the number of ester bonds in the general formula (1), is 1 when m is 0 or m is 1 and A is a hydrogen atom, and when m is 1 and A is a direct bond, , 2 on the condition that X is a carbon atom.
  • m is 1 and A is an aromatic hydrocarbon group, a chain aliphatic hydrocarbon group, an alicyclic hydrocarbon group, or a heterocyclic group, these groups represented by A are substituted. Any group is possible.
  • the preferable lower limit of the number of p is a general formula It is preferable that it is 1 or more from a compatible viewpoint with the ionic compound of the compound represented by (1), and the viewpoint of the availability of the compound represented by General formula (1).
  • Examples of the aromatic hydrocarbon group represented by A in the general formula (1) include a group in which one hydrogen atom on the aromatic ring in the aromatic hydrocarbon compound is removed, that is, an aryl group.
  • Specific examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthracenyl group, and a group in which one or more hydrogen atoms bonded to these aromatic rings are substituted with a chain aliphatic hydrocarbon group. Examples thereof include a tolyl group and a xylyl group.
  • the aromatic hydrocarbon group preferably has 6 to 22 carbon atoms in consideration of the compatibility of the compound represented by the general formula (1) with the luminescent material and the ionic compound, and more preferably 6 or more.
  • the number of carbon atoms here includes the number of carbon atoms of the chain aliphatic hydrocarbon group when the aromatic ring is substituted with a chain aliphatic hydrocarbon group.
  • Examples of the chain aliphatic hydrocarbon group include groups exemplified as the chain aliphatic hydrocarbon group represented by A described later.
  • Examples of the chain aliphatic hydrocarbon group represented by A in the general formula (1) include a chain saturated aliphatic hydrocarbon group and a chain unsaturated aliphatic hydrocarbon group.
  • Examples of the chain saturated aliphatic hydrocarbon group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, s-butyl group, t-butyl group, isobutyl group, n-amyl group, and isoamyl group.
  • T-amyl group n-hexyl group, n-heptyl group, isoheptyl group, t-heptyl group, n-octyl group, isooctyl group, 2-ethylhexyl group, t-octyl group, nonyl group, isononyl group, decyl group And branched or straight chain alkyl groups such as isodecyl group, undecyl group, dodecyl group, tridecyl group, isotridecyl group, tetradecyl group, hexadecyl group, octadecyl group, icosyl group.
  • Examples of the chain unsaturated aliphatic hydrocarbon group include groups in which one or more carbon-carbon single bonds in the chain saturated aliphatic hydrocarbon group are replaced with carbon-carbon double bonds or triple bonds.
  • Alkenyl group and alkynyl group examples include vinyl, allyl, isopropenyl, 2-butenyl, 2-methylallyl, 1,1-dimethylallyl, 3-methyl-2-butenyl, and 3-methyl-3-butenyl.
  • straight-chain or branched alkenyl groups such as 4-pentenyl group, hexenyl group, octenyl group, nonenyl group and decenyl group.
  • alkynyl group examples include ethynyl group and prop-2-yn-1-yl group.
  • the chain aliphatic hydrocarbon group represented by A has 2 to 16 carbon atoms in consideration of the compatibility of the compound represented by the general formula (1) with the light emitting material and the ionic compound. It is preferable that it is 4 or more and 8 or less.
  • Examples of the alicyclic hydrocarbon group represented by A in the general formula (1) include a saturated alicyclic hydrocarbon group and an unsaturated alicyclic hydrocarbon group.
  • Examples of the saturated alicyclic hydrocarbon group include a cyclopentyl group, a cyclohexyl group, and a group in which one or more of these hydrogen atoms are substituted with any of the above-mentioned chain aliphatic hydrocarbon groups.
  • Examples of the unsaturated alicyclic hydrocarbon group include a cyclopentynyl group, a cyclohexynyl group, a cyclohexyldienyl group, and one or more hydrogen atoms in these groups are any of the chain aliphatic hydrocarbon groups.
  • Examples include substituted groups. These alicyclic hydrocarbon groups represented by A have 4 to 20 carbon atoms in consideration of the compatibility of the compound represented by the general formula (1) with the luminescent material and the ionic compound. It is preferable that it is 5 or more and 18 or less.
  • the number of carbon atoms here includes the number of carbon atoms of the chain aliphatic hydrocarbon group when the alicyclic ring is substituted with a chain aliphatic hydrocarbon group.
  • heterocyclic group represented by A in the general formula (1) examples include monovalent groups derived from pyridine, pyrrole, furan, imidazole, pyrazole, oxazole, imidazoline, pyrazine and the like.
  • the heterocyclic group represented by A preferably has 3 to 8 carbon atoms in consideration of the compatibility of the compound represented by the general formula (1) with the luminescent material and the ionic compound, More preferably, it is 4 or more and 6 or less.
  • the number of carbon atoms here does not include the number of carbon atoms of the chain aliphatic hydrocarbon group when the heterocyclic group is substituted with a chain aliphatic hydrocarbon group.
  • the number of carbon atoms of the heterocyclic group including the number of carbon atoms of the chain aliphatic hydrocarbon group is preferably 4 or more and 20 or less, and more preferably 6 or more and 16 or less.
  • one or two or more of the hydrogen atoms contained therein may be substituted with a functional group.
  • the functional group include an amino group, a nitrile group, a phenyl group, a benzyl group, a carboxyl group, and an alkoxy group having 1 to 12 carbon atoms.
  • the functional group is substituted for the above-mentioned aromatic hydrocarbon group, chain aliphatic hydrocarbon group, alicyclic hydrocarbon group or heterocyclic group, aromatic hydrocarbon group, chain aliphatic hydrocarbon group.
  • the preferred number of carbon atoms described above for the alicyclic hydrocarbon group or heterocyclic group does not include the number of carbon atoms of the functional group.
  • the alkyl group represented by R in the general formula (1) may be branched, linear or cyclic, but is preferably branched or linear.
  • Examples of the branched or straight chain alkyl group represented by R include the groups listed above as examples of the chain saturated aliphatic hydrocarbon group represented by A.
  • Examples of the cyclic alkyl group represented by R include the groups listed above as examples of the saturated alicyclic hydrocarbon group represented by A.
  • a plurality of R bonded to the same X through O may be connected to each other to form a ring.
  • examples of the compound of the general formula (1) in which two Rs are connected to each other to form a ring include cyclic carbonates and cyclic phosphates.
  • R is an alkyl group.
  • the number of Rs that are alkyl groups is preferably 1 or more, and more preferably 2 or more.
  • n R bonded to one X via an oxygen atom O it is preferable that one or more Rs are alkyl groups among n Rs bonded to one X via an oxygen atom O, and two or more Rs are alkyl groups. More preferably.
  • the number of Rs that are alkyl groups is particularly preferably 3 or more.
  • the number of carbon atoms of the alkyl group represented by R maintains a high compatibility with the ionic compound of the additive of the present invention, the viewpoint of obtaining the effect of the present invention more reliably, and dissolution in a solvent From the viewpoint of property, it is preferably 16 or less, more preferably 14 or less, still more preferably 10 or less, and particularly preferably 8 or less. In addition, if the number of carbon atoms of the alkyl group represented by R is 1 or more, the effect of the present invention can be sufficiently obtained. However, when an additive is added to the light emitting layer, it is easy to obtain high luminance at a lower voltage. Therefore, it is preferably 2 or more, more preferably 3 or more, and particularly preferably 4 or more.
  • one or more of the hydrogen atoms contained therein may be substituted with a functional group.
  • the functional group include an amino group and a nitrile group.
  • a compound represented by General formula (1) it is preferable from viewpoints of the availability of a compound that X is a phosphorus atom or a carbon atom.
  • X is a phosphorus atom
  • p is 1 from the viewpoint of easy availability and ease of handling.
  • m is 1 from the viewpoint of more reliably obtaining the effect of obtaining high emission luminance at a low voltage.
  • the compound represented by the general formula (2) is a phosphate ester.
  • X is a phosphorus atom, m is 0, and p is 1.
  • the compound represented by the following general formula (3) is a carboxylic acid ester, and in the general formula (1), X is a carbon atom and m is 1.
  • A is preferably an aromatic hydrocarbon group, a chain aliphatic hydrocarbon group, an alicyclic hydrocarbon group, or a heterocyclic group.
  • the compound represented by the general formula (1) when X is a sulfur atom, the compound represented by the following general formula (A) is used in terms of withstand voltage and compatibility with a light emitting material. To preferred.
  • R and p are the same as those in the general formula (1), and A is an aromatic hydrocarbon group, a chain aliphatic hydrocarbon group, an alicyclic hydrocarbon group or a heterocyclic group.
  • a compound represented by the following general formula (b) in which X is a carbon atom and m is 0 is also suitable for withstand voltage and light emitting materials. It is preferable from the viewpoint of solubility.
  • the compound represented by the general formula (b) described above a compound in which two Rs are both alkyl groups, or two Rs bonded to the same C via O are connected to each other to form a ring.
  • the formed compound represented by the following general formula (c) is preferable from the viewpoints of voltage endurance and compatibility with a light emitting material.
  • Ra, Rb, Rc and Rd are hydrogen atoms or alkyl groups, which may be the same or different from each other, and q is a number of 1 or more and 3 or less.
  • the alkyl group represented by Ra, Rb, Rc and Rd is preferably linear or branched, and the number of carbon atoms of Ra, Rb, Rc and Rd is the availability of the compound and the ease of handling. Is preferably 1 or more and 8 or less, more preferably 1 or more and 4 or less.
  • q is preferably a number from 1 to 2.
  • the most preferable compound represented by the general formula (c) is a compound in which q is 1, or Ra, Rb, Rc and Rd are all hydrogen atoms, or Ra, Rb, Rc.
  • Rd is a compound in which one group is an alkyl group and the remainder is a hydrogen atom.
  • the molecular weight of the compound represented by the general formula (1) is preferably 70 or more and 1000 or less, more preferably 120 or more and 1000 or less, particularly preferably 150 or more and 800 or less, and particularly preferably 200 or more and 500 or less.
  • the compound represented by the general formula (1) and the additive of the present invention containing the compound may be solid or liquid at normal temperature (25 ° C.).
  • the method for producing the compound represented by the general formula (1) is not particularly limited.
  • the phosphate ester compound represented by the general formula (2) can be obtained by dehydration condensation of phosphoric acid and alcohol, or by condensing phosphate compound and alcohol by the action of a base.
  • the carboxylic acid ester compound represented by the general formula (3) can be produced by dehydration condensation of carboxylic acids and alcohol.
  • the sulfonic acid ester compound represented by the general formula (I) can be obtained, for example, by reacting a sulfonic acid chloride with an alcohol.
  • the carbonate ester compound represented by the general formula (b) can be produced, for example, by transesterifying dimethyl carbonate and alcohol.
  • a commercially available compound can also be used as a compound represented by General formula (1).
  • the additive of the present invention may contain only the compound represented by the general formula (1), or may contain other components. Other components include surfactants other than the solvent and the compound represented by the general formula (1).
  • the additive of the present invention preferably contains 90% by mass or more of the compound represented by the general formula (1) from the viewpoint of ease of use when used by being added to the ionic compound and the light emitting material, and 95% by mass. It is more preferable to contain above. The upper limit of the preferable content is 100% by mass.
  • the compound represented by the general formula (1) is contained in the light emitting layer in an amount of 1% by mass or more, and the effect of improving the light emission efficiency and light emission luminance of the electrochemiluminescence cell is obtained more reliably. This is preferable.
  • the compound represented by the general formula (1) is contained in the light emitting layer in an amount of 20% by mass or less from the viewpoint of suppressing a decrease in emission luminance due to dilution. From these viewpoints, the compound represented by the general formula (1) is more preferably contained in the light emitting layer in an amount of 2% by mass or more and 18% by mass or less, and more preferably 3% by mass or more and 15% by mass or less.
  • the content of the compound represented by the general formula (1) in the light emitting layer 12 is preferably 2 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the light emitting material.
  • the amount of the light emitting material here is the amount of the organic polymer light emitting material when an organic polymer light emitting material is used as the light emitting material, and the light emitting material is a light emitting property such as a metal complex, an organic small molecule or a quantum dot.
  • the total amount of a metal complex, a light emitting substance such as an organic low molecule or a quantum dot, and an organic polymer conductive material is 2 to 30 parts by mass with respect to 100 parts by mass of the organic polymer light emitting material when the light emitting material is an organic polymer light emitting material described later. It is particularly preferred that the amount is not more than parts.
  • the light emitting material to be described later is a combination of a metal complex, a light emitting substance such as an organic low molecule or quantum dot, and an organic polymer conductive material
  • the content of the compound represented by the general formula (1) in the light emitting layer 12 Is particularly preferably 2 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the total amount of the light emitting substance such as the metal complex, the organic low molecule or the quantum dot, and the organic polymer conductive material.
  • the ionic compound is a substance for ensuring mobility of ions, forming an electric double layer easily, and facilitating injection of holes and electrons.
  • an ionic compound it is a compound containing a cation and an anion, and both the salt of an organic cation and the salt of an inorganic cation are employable.
  • the salt of the organic cation one in which the cation is a phosphonium cation, an ammonium cation, a pyridinium cation, an imidazolium cation, or a pyrrolidinium cation can be used.
  • the inorganic cation salt include salts of metal cations belonging to Group 1 or Group 2.
  • the ionic compound may be either an organic salt or an inorganic salt.
  • examples include the above-described organic cation salt and a salt composed of an inorganic cation and an organic anion.
  • Metal cations such as those that are lithium ions or potassium ions can be used. Among them, it is preferable from the viewpoint of compatibility with the light emitting material that the cation is at least one selected from a phosphonium cation, an ammonium cation and an imidazolium cation.
  • the additive of the present invention when added, it is preferable to use at least one cation selected from a phosphonium cation and an ammonium cation as the ionic compound used in the light emitting layer from the viewpoint of easily obtaining high luminance at a low voltage. .
  • Examples of the ionic compound whose cation is a phosphonium cation or an ammonium cation include a compound represented by the following general formula (4).
  • R 1 , R 2 , R 3 and R 4 are each an alkyl group, an alkoxyalkyl group, a trialkylsilylalkyl group, an alkenyl group, an alkynyl group, an aryl group, which may be substituted with a functional group, or Represents a heterocyclic group, R 1 , R 2 , R 3 and R 4 may be the same or different from each other, M represents N or P, and X ⁇ represents an anion.
  • examples of the ionic compound whose cation is an imidazolium cation include a compound represented by the following general formula (5).
  • R 5 and R 6 each represents an alkyl group, an alkoxyalkyl group, a trialkylsilylalkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group, which may be substituted with a functional group.
  • R 5 and R 6 may be the same or different from each other, and X ⁇ represents an anion.
  • the alkyl group represented by R 1 , R 2 , R 3 , R 4 , R 5 and R 6 may be branched, linear or cyclic, but is branched or linear. preferable.
  • Examples of the branched or straight chain alkyl group include the groups mentioned above as examples of the chain saturated aliphatic hydrocarbon group represented by A in the general formula (1).
  • Examples of the cyclic alkyl group include the groups listed above as examples of the saturated alicyclic hydrocarbon group represented by A.
  • Examples of the alkoxyalkyl group represented by R 1 , R 2 , R 3 , R 4 , R 5 and R 6 include the alkoxides of the alkyl groups described above.
  • Examples of the alkyl group in the alkoxyalkyl group include the groups listed above as examples of the chain saturated aliphatic hydrocarbon group represented by A in the general formula (1).
  • Examples of the alkyl group in the trialkylsilylalkyl group represented by R 1 , R 2 , R 3 , R 4 , R 5 and R 6 include a chain saturated fat represented by A in the general formula (1)
  • Examples of the group hydrocarbon group include the groups mentioned above.
  • Examples of the alkenyl group and alkynyl group represented by R 1 , R 2 , R 3 , R 4 , R 5 and R 6 include the alkenyl group and alkynyl group represented by A in the general formula (1) as described above. The groups mentioned are mentioned.
  • Examples of the aryl group represented by R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are as described above as examples of the aromatic hydrocarbon group represented by A in the general formula (1).
  • Examples of the heterocyclic group represented by R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are the examples of the heterocyclic group represented by A in the general formula (1). The groups mentioned are mentioned.
  • Each group mentioned above as the group represented by R 1 , R 2 , R 3 , R 4 , R 5 and R 6 is substituted with one or more of the hydrogen atoms contained therein with a functional group.
  • a functional group include a halogen atom, an amino group, a nitrile group, a phenyl group, a benzyl group, a carboxyl group, and an alkoxy group having 1 to 12 carbon atoms.
  • Each group mentioned above as a group represented by R 1 , R 2 , R 3 , R 4 , R 5 and R 6 is such that a hydrogen atom contained in these groups is partially substituted with a fluorine atom. Also good. By introducing fluorine atoms, the withstand voltage is improved, which leads to stability and long life of the electrochemiluminescence cell.
  • the compatibility with the compound of the general formula (1) is good, a high luminance is obtained, and the compatibility with the light emitting material and the voltage resistance are viewpoints.
  • R 1, R 2, R 3 and R1 4 that one or more of the groups is an alkyl group is preferably, R 1, R 2, also R 3 and R 4 are both an alkyl group It is more preferable.
  • the number of carbon atoms of the alkyl group represented by R 1 , R 2 , R 3 and R 4 Is preferably from 2 to 18, more preferably from 4 to 8.
  • R 1 , R 2 , R 3 and R 4 are alkyl groups having the same number of carbon atoms, from the same viewpoint as described above,
  • These alkyl groups having the same number of carbon atoms preferably have 2 or more and 18 or less carbon atoms, and more preferably 4 or more and 8 or less.
  • examples of the ionic compound in which the cation is a phosphonium cation or an ammonium cation include R 1 , R 2 , R 3 and R 4 . It is preferable that one or more, particularly three or more groups of the above are alkyl groups having a carbon atom difference of 5 or less with respect to the alkyl group represented by R in the compound represented by the general formula (1). In particular, one or more of R 1 , R 2 , R 3, and R 4 , particularly 3 or more groups, is a carbon with an alkyl group represented by R in the compound represented by the general formula (1).
  • the difference in the number of atoms is an alkyl group having 3 or less.
  • R 1 , R 2 , R 3 and R 4 are represented by R in the general formula (1). It is preferably an alkyl group having the same number of carbon atoms as the alkyl group represented.
  • R in any compound when a plurality of types of compounds represented by the general formula (1) are added (or added) to the light emitting layer. .
  • the compound What is necessary is just to be materialized between any of R inside.
  • the molecular weight of the phosphonium cation or ammonium cation in the general formula (4) is 150 or more and 750 or less, particularly 200 or more and 500 or less, and particularly 250 or more and 350 or less. Is preferable because it is more excellent.
  • R 5 and / or R 6 is an alkyl group from the viewpoint of good compatibility with the compound represented by the general formula (1) and high brightness. Preferably there is.
  • the number of carbon atoms of the alkyl group represented by R 5 is 1 or more and 8 or less. It is preferably 1 or more and 4 or less.
  • the number of carbon atoms of the alkyl group represented by R 6 is 1 or more and 8 or less from the viewpoint of further improving the compatibility with the compound represented by the general formula (1) and the light emitting material. Preferably, it is 2 or more and 6 or less.
  • R 6 is represented by the general formula ( It is preferable that the difference in the number of carbon atoms with respect to the alkyl group represented by R of the compound represented by 1) is an alkyl group having 5 or less, and that the difference in the number of carbon atoms is an alkyl group having 3 or less. preferable.
  • R 6 is preferably an alkyl group having the same number of carbon atoms as the alkyl group represented by R in the general formula (1).
  • R 5 represents the general formula (1) contained in the light emitting layer. It is preferable that the difference of the carbon atom number with respect to the alkyl group represented by R of the compound represented by is an alkyl group of 8 or less.
  • the above relationship may be established with R in any compound when a plurality of types of compounds represented by the general formula (1) are added (or added) to the light emitting layer. .
  • the compound What is necessary is just to be materialized between any of R inside.
  • the molecular weight of the imidazolium cation is 90 or more and 300 or less, particularly 100 or more and 260 or less, and particularly 120 or more and 240 or less, the emission luminance of the electrochemiluminescence cell is further increased and the emission luminance is further improved. preferable.
  • Polymer compounds used for improving ion transport properties such as polyethylene oxide are usually inferior in voltage resistance compared to the additive of the present invention. Therefore, by using the additive of the present invention in addition to or as a substitute for a polymer compound such as polyethylene oxide, it is possible to obtain a certain luminance while maintaining or improving the voltage resistance of the light emitting layer. Although the reason why the additive of the present invention has such an action although it is not a polymer is not clear, the present inventor believes that the additive of the present invention is compatible with the luminescent material and the ionic compound, or One of the reasons for this is that the dispersibility of the ionic compound in the light-emitting material can be improved efficiently.
  • the metal ion is preferably a cation of a metal belonging to Group 1 or Group 2
  • the cation of a metal belonging to Group 1 is preferably a cation of Li, Na, K, or Cs.
  • Preferred examples of the metal cation belonging to Group 2 include Mg and Ca cations.
  • Li, Na, and K are particularly preferable from the viewpoint of ion transportability.
  • Examples of the organic cation salt and the inorganic cation salt, the anion in the organic salt and the inorganic salt, and the anion represented by X ⁇ in the general formulas (5) and (6) include, for example, fluorine and bromine.
  • Halogen ions such as iodine and chlorine, tetrafluoroborate (BF 4 ), benzotriazolate (N 3 (C 6 H 4 )), tetraphenyl borate (B (C 6 H 5 ) 4 ), hexafluorophosphate (PF 6 ), bis (trifluoromethylsulfonyl) imide (N (CF 3 SO 2 ) 2 ), bis (fluorosulfonyl) imide (N (SO 2 F) 2 ), trifluoromethanesulfonate (SO 3 CF 3 ), methanesulfonate (SO 3 CH 3), tris (pentafluoroethyl) trifluoro phosphate ((C 2 H 5) 3 PF 3), triflic B acetate (CF 3 COO), amino acids, Bisuo Kisara oxalatoborate (B (C 2 O 4) 2), p- toluenesulfonate (CH 3 C 6
  • R 7 is an alkyl group having 1 to 20 carbon atoms, and two R 7 may be the same or different.
  • R 8 is an alkyl group having 1 to 20 carbon atoms.
  • R 9 is an alkyl group having 1 to 20 carbon atoms, and two R 9 may be the same or different.
  • R 10 CO 2 (10) (In the formula, R 10 is an alkyl group having 1 to 20 carbon atoms.)
  • the anion in the ionic compound it is preferable to use an anion that does not contain a halogen atom, because an electrochemiluminescence cell having high luminance can be easily obtained. This is because an anion containing no halogen atom is more compatible with the light-emitting material than an anion containing a halogen atom.
  • an anion containing no halogen atom is more compatible with the light-emitting material than an anion containing a halogen atom.
  • the additive of the present invention is added to a light emitting layer containing an ionic compound having an anion containing a halogen atom, high emission luminance is obtained at a lower voltage. The effect that it is obtained can be produced.
  • the ionic compound containing the anion has a better compatibility with many light emitting materials. Therefore, it is preferable in that an electrochemiluminescence cell having higher luminance is easily obtained.
  • the compound represented by the general formula (1) added to the light emitting layer as an anion in the ionic compound from the viewpoint of obtaining an electrochemiluminescent cell having high compatibility with the additive of the present invention and high brightness. It is preferable to use an anion having an alkyl group having a carbon atom difference of 5 or less from the alkyl group represented by R, and to use an anion having an alkyl group having a carbon atom difference of 3 or less. More preferred. In particular, it is preferable to use an anion having an alkyl group having the same number of carbon atoms as the alkyl group represented by any R in any compound represented by the general formula (1) added to the light emitting layer.
  • the difference in the number of carbon atoms between R 7 to R 10 in the general formulas (7) to (10) and R in the general formula (1) is preferably in the above range, and R 7 to R 10 and R It is most preferable that the number of carbon atoms is the same.
  • the above relationship may be established with R in any compound when a plurality of types of compounds represented by the general formula (1) are added (or added) to the light emitting layer. .
  • the compound What is necessary is just to be materialized between any of R inside.
  • the ionic compound may be solid at room temperature (25 ° C.) or liquid.
  • the ionic compound is in a solid or liquid state depending on the combination of the selected cation and anion and the structure of the cation.
  • an ionic compound can be used 1 type or in combination of 2 or more types.
  • An ionic compound can be produced, for example, as follows.
  • a quaternary phosphonium halide obtained by reacting a tertiary phosphine compound corresponding to the target phosphonium cation and a halogenated hydrocarbon compound is used, and an ionic liquid in which the anion is halogen is prepared.
  • An anionic component other than halogen can be obtained by reacting the quaternary phosphonium halide with a metal salt of the anionic component to exchange anions.
  • the cation is an ammonium ion, it can be similarly obtained using a quaternary ammonium halide obtained by reacting a tertiary amine compound and a halogenated hydrocarbon compound.
  • the cation is an imidazolium ion, it can be obtained in the same manner by using an imidazolium halide obtained by reacting an imidazole compound corresponding to the target imidazolium cation with a halogenated hydrocarbon compound.
  • the cation is a phosphonium or ammonium ion and the anion is a phosphoric acid ester bond or an ionic compound having a sulfate ester bond, a tertiary phosphine compound or a tertiary amine compound and PO (OR X) 3 or SO 2 (by reacting oR X) compounds represented by compounds represented by 2, it is possible to obtain an ionic compound with a halogen-free manufacturing process.
  • Rx is an alkyl group having 1 to 20 carbon atoms.
  • the content ratio of the ionic compound in the light emitting layer 12 is preferably 1% by mass or more and 20% by mass or less from the viewpoint of ensuring ion mobility and improving the film forming property of the light emitting layer 12. It is more preferable that the amount is not more than mass%.
  • the content of the ionic compound in the light emitting layer 12 is preferably 1 part by mass or more and 25 parts by mass or less with respect to 100 parts by mass of the light emitting material.
  • the amount of the light emitting material here is the amount of the organic polymer light emitting material when an organic polymer light emitting material is used as the light emitting material, and the light emitting material is a light emitting property such as a metal complex, an organic small molecule or a quantum dot.
  • the total amount of a metal complex, a light emitting substance such as an organic low molecule or a quantum dot, and an organic polymer conductive material is 1 part by mass or more and 25 parts by mass or less with respect to 100 parts by mass of the organic polymer light emitting material.
  • the content of the ionic compound in the light emitting layer 12 is such metal complex, organic small molecule or quantum dot, and It is preferably 1 part by mass or more and 25 parts by mass or less with respect to 100 parts by mass of the total amount of the organic polymer conductive material.
  • the light-emitting material included in the light-emitting layer 12 include an organic polymer light-emitting material, or a combination of a light-emitting substance such as a metal complex, an organic small molecule, or a quantum dot, and an organic polymer conductive material.
  • the organic polymer light emitting material include organic polymers that are various ⁇ -conjugated polymers. Specific examples include paraphenylene vinylene, fluorene, 1,4-phenylene, thiophene, pyrrole, paraphenylene sulfide, benzothiadiazole, biothiophine, or a derivative polymer having a substituent introduced thereto, or a copolymer containing these.
  • Examples of such a substituent include an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 18 carbon atoms, [(—CH 2 CH 2 O—) n CH 3 ] (n is an integer of 1 or more and 10 or less) and the like.
  • Examples of the copolymer include those obtained by bonding each repeating unit of two or more kinds of the above-mentioned ⁇ -conjugated polymers.
  • Examples of the arrangement of each repeating unit in the copolymer include a random arrangement, an alternating arrangement, a block arrangement, or a combination thereof.
  • fluorene paraphenylene vinylene
  • a derivative polymer having a substituent introduced thereto or a copolymer containing these polymers.
  • a commercial item can also be used as an organic polymer light-emitting material.
  • Such commercial products include, for example, Poly [(9,9-dioctylfluorenyl-2,7-diyl) -alt-co- (9,9'-spirobifluorene), a compound available from Solaris Chem under the name SOL2412.
  • PDY-132 a compound available from Merck & Co., Phenylene substitutedpoly (para-phenylenevinylene), Poly [(9,9-di- n-octylfluorenyl-2,7-diyl) -alt- (benzo [2,1,3] thiadiazol-4,8-diyl)].
  • metal complex known ones conventionally used as a light emitting material in organic EL can be used.
  • tris (8-quinolinolato) aluminum complex tris (4-methyl-8-quinolinolato) aluminum complex, bis (8 -Quinolinolato) zinc complex, tris (4-methyl-5-trifluoromethyl-8-quinolinolato) aluminum complex, tris (4-methyl-5-cyano-8-quinolinolato) aluminum complex, bis (2-methyl-5- Trifluoromethyl-8-quinolinolato) [4- (4-cyanophenyl) phenolate] aluminum complex, bis (2-methyl-5-cyano-8-quinolinolato) [4- (4-cyanophenyl) phenolate] aluminum complex, Tris (8-quinolinolato) scandium complex, [8- (para-tosyl) aminoquinoline] zinc complexes, cadmium complexes, phosphorescent emitters such as Ir complexes, bipyridyl (
  • organic low molecule known ones conventionally used as light emitting materials in organic EL can be used. 9,10-diarylanthracene derivatives, pyrene, coronene, perylene, rubrene, 1,1,4,4-tetra Phenylbutadiene, 1,2,3,4-tetraphenylcyclopentadiene, pentaphenylcyclopentadiene, poly-2,5-diheptyloxy-para-phenylene vinylene, coumarin phosphor, perylene phosphor, pyran phosphor Fluorescence of anthrone phosphor, porphyrin phosphor, quinacridone phosphor, N, N′-dialkyl substituted quinacridone phosphor, naphthalimide phosphor, N, N′-diaryl substituted pyrrolopyrrole phosphor, etc. Illuminant etc. are mentioned.
  • quantum dot examples include Si, Ge, GaN, GaP, CdS, CdSe, CdTe, InP, InN, ZnS, In 2 S 3 , ZnO, CdO, or a mixture thereof.
  • Examples of the organic polymer conductive material for transporting electrons and / or holes include polyvinylcarbazole, polyphenylene, polyfluorene, polyaniline, polythiophene, polypyrrole, polyphenylene vinylene, polythienylene vinylene, polyquinoline, polyquinoxaline, and the like.
  • the organic polymer light emitting material described above can also be used because it has a function of transporting electrons and / or holes.
  • the content ratio in the light emitting layer 12 is preferably 60% by mass or more and 99% by mass or less when the organic polymer light emitting material is used, and 70% by mass. More preferably, it is 98 mass% or less.
  • the ratio of these total amounts in the light emitting layer 12 is 60 mass% or more 99.
  • the content is preferably not more than mass%, more preferably not less than 70 mass% and not more than 98 mass%.
  • the organic high molecular weight relative to 100 parts by weight of the light emitting substance such as a metal complex, a small organic molecule or a quantum dot is used.
  • the proportion of the molecular conductive material is preferably 5 parts by mass or more and 25 parts by mass or less.
  • the light emitting layer 12 may contain a substance other than the light emitting material and the ionic compound.
  • examples of such substances include surfactants and polymer components (polystyrene, polymethyl methacrylate (PMMA), etc.) for improving film forming properties.
  • an organic polymer light emitting material is used as the light emitting material
  • an organic polymer conductive material such as polyvinyl carbazole is also included in the other components.
  • the amount of the components other than the light emitting material, the ionic compound and the compound represented by the general formula (1) (excluding the solvent) in the light emitting layer 12 is 30 parts by mass when the entire light emitting layer 12 is 100 parts by mass.
  • the content is preferably set to the following, more preferably 20 parts by mass or less, and particularly preferably 10 parts by mass or less.
  • a polymer compound that has been conventionally used for improving charge transportability may be used.
  • a polymer compound include a compound having a polyether skeleton such as polyethylene oxide and polypropylene oxide, a compound having a polyester skeleton such as polyethylene succinate and poly- ⁇ -propiolactone, and a polyamine skeleton such as polyethyleneimine.
  • examples thereof include compounds and compounds having a polysulfide skeleton such as polyalkylene sulfide.
  • the amount of these polymer compounds in the light emitting layer is preferably 50% by mass or less, more preferably 40% by mass or less, and particularly preferably 30% by mass or less. It is.
  • the amount may be smaller than that, and a polymer compound such as polyethylene oxide may not be used.
  • a polymer compound such as polyethylene oxide
  • the fact that these polymer compounds are not used in the light emitting layer means, for example, that the amount of these polymer compounds in the light emitting layer is 0% by mass.
  • the film thickness of the light-emitting layer 12 thus configured is preferably 20 nm or more and 300 nm or less, and more preferably 50 nm or more and 150 nm or less.
  • the film thickness of the light emitting layer 12 is within this range, it is preferable from the viewpoints that light emission can be sufficiently and efficiently obtained from the light emitting layer 12, defects in a light emission scheduled portion can be suppressed, and short circuit prevention can be achieved.
  • the electrochemiluminescence cell 10 of this embodiment can be manufactured by the following manufacturing method, for example.
  • a substrate provided with the first electrode 13 is prepared.
  • the first electrode 13 is formed from, for example, ITO, by forming a deposited ITO film in a pattern on the surface of a glass substrate or the like by using a photolithography method or a combination of the photolithography method and the lift-off method, A first electrode 13 made of ITO can be formed on the surface.
  • an ionic compound, a luminescent material, and a compound represented by the general formula (1) are dissolved or dispersed in an organic solvent to prepare a composition for forming a luminescent layer of an electrochemiluminescence cell.
  • the organic solvent is selected from the group consisting of toluene, benzene, tetrahydrofuran, dimethyl chloride, cyclohexanone, chlorobenzene and chloroform from the viewpoint of efficiently mixing the ionic compound, the light emitting material and the compound represented by the general formula (1). It is preferable to contain at least one organic solvent. In this case, only one of these compounds or a combination of two or more of these compounds can be used as the organic solvent.
  • the organic solvent for dissolving or dispersing the ionic compound, the luminescent material, and the compound represented by the general formula (1) is at least one selected from the group consisting of toluene, benzene, tetrahydrofuran, dimethyl chloride, cyclohexanone, chlorobenzene, and chloroform.
  • a seed organic solvent and other organic solvents can be contained.
  • the compounding ratio (mass ratio) of the ionic compound and the light emitting material in the composition for forming a light emitting layer is preferably 1: 4 to 100 in the former: latter.
  • the compounding ratio (mass ratio) of the compound represented by the general formula (1) and the light emitting material in the light emitting layer forming composition is preferably 1: 3 to 50 in the former: latter.
  • the amount of the light emitting material here is the amount of the organic polymer light emitting material when an organic polymer light emitting material is used as the light emitting material, and the light emitting material is a light emitting property such as a metal complex, an organic small molecule or a quantum dot.
  • the total amount of the light emitting substance such as a metal complex, an organic low molecule, or a quantum dot, and the organic polymer conductive material is used. Furthermore, the ratio of the compound represented by the general formula (1) in the composition for forming a light emitting layer is 0.0001% by mass to 10% by mass, particularly 0.0005% by mass to 5% by mass. This is preferable from the viewpoint of easily forming a light emitting layer in which the effects of the present invention can be obtained more reliably.
  • This composition for forming a light emitting layer is applied onto the first electrode 13 of the substrate by a spin coating method or the like.
  • the preparation of the light emitting layer forming composition and the formation of the light emitting layer 12 are preferably performed in an inert gas atmosphere having a moisture content of 100 ppm or less.
  • the inert gas include argon, nitrogen, helium and the like.
  • the second electrode 14 is formed on the formed light emitting layer 12.
  • an electrode having a predetermined pattern is formed on the light emitting layer 12 by evaporating aluminum (Al) into a film shape by, for example, a vacuum evaporation method through a mask.
  • Al aluminum
  • the second electrode 14 is formed on the light emitting layer 12.
  • the electrochemiluminescence cell 10 of the present embodiment emits light by the following light emission mechanism.
  • a voltage is applied to the light emitting layer 12 so that the first electrode 13 serves as an anode and the second electrode 14 serves as a cathode.
  • ions in the light emitting layer 12 move along the electric field, and a layer in which anion species are collected in the vicinity of the interface between the light emitting layer 12 and the first electrode 13 is formed.
  • a layer in which cationic species are collected in the vicinity of the interface with the second electrode 14 in the light emitting layer 12 is formed. In this way, an electric double layer is formed at the interface of each electrode.
  • the p-doped region 16 is spontaneously formed in the vicinity of the first electrode 13 that is the anode
  • the n-doped region 17 is spontaneously formed in the vicinity of the second electrode 14 that is the cathode.
  • These doped regions constitute a pin junction with a high carrier density.
  • the composition for forming a light emitting layer, and the electrochemiluminescence cell using the compound represented by the general formula (1), the light emitting material in the light emitting layer is combined with the ionic compound in the general formula (1)
  • the compatibility between the luminescent material and the ionic compound is improved as compared with the case where the compound represented by the general formula (1) is not added.
  • the mobility of the compound is greatly improved. For this reason, it is possible to obtain an electrochemiluminescence cell having high emission luminance at a low voltage and suppressed resistance increase in a low resistance state as compared with the case where the compound represented by the general formula (1) is not added. it can.
  • the first electrode of the electrochemiluminescence cell is connected to the anode of the direct current, the second electrode is connected to the cathode, and a voltage is applied up to 15 V at a sweep rate of 1 V / sec. did. Moreover, the voltage at that time was measured. The measurement was performed with CS-2000 (manufactured by Konica Minolta).
  • Example 1 A commercially available glass substrate with an ITO film (manufactured by Geomatic Co., Ltd., ITO film thickness 200 nm) was used as the first electrode 13.
  • PFO-spiro (Poly [(9,9-dioctylfluorenyl-2,7-diyl) -alt-co- (9,9'-spirobifluorene-2,7-diyl)], Solaris Chem)
  • These mixed solutions were prepared using the product, model number SOL2412), the phosphonium phosphate ester salt shown in Table 1 as an ionic compound, and the additive which is the compound shown in Table 1.
  • a glove in an argon atmosphere In a box, a toluene solution (concentration: 9 g / L) of an organic polymer light emitting material, a toluene solution of an ionic compound (concentration: 9 g / L), and a toluene solution of an additive (concentration: 9 g / L) at room temperature.
  • a toluene solution concentration: 9 g / L
  • ionic compound solution concentration: 9 g / L
  • additive solution 8: 1: 1 to prepare a light emitting layer forming composition.
  • the composition for forming a light emitting layer prepared above is applied by spin coating on the first electrode 13 of the glass substrate at room temperature in a glove box under an argon atmosphere, and is further heated at 50 ° C. The organic solvent was evaporated by heating on the plate for 30 minutes. Thus, the solid light emitting layer 12 having a thickness of 100 nm was formed. Further, a second electrode 14 made of aluminum (Al) having a thickness of 50 nm was formed on the formed light emitting layer 12 by the method described above. In this manner, an electrochemiluminescence cell 10 having an area of 2 mm ⁇ 2 mm square of a light emission scheduled portion was produced. Table 1 shows the results of measuring the light emission characteristics of the obtained electrochemiluminescence cell 10.
  • Example 1-1 The same procedure as in Example 1 was performed except that no additive was added. Table 1 shows the results of measuring the light emission characteristics of the obtained electrochemiluminescence cell 10.
  • Examples 2-1 to 2-5> A commercially available glass substrate with an ITO film (manufactured by Geomatic Co., Ltd., ITO film thickness 200 nm) was used as the first electrode 13.
  • Organic polymer light emitting material Super Yellow Phenylene substituted poly (para-phenylenevinylene), manufactured by Merck & Co., product name: PDY-132), phosphonium phosphate ester salts shown in Table 2 as ionic compounds, and additions that are compounds shown in Table 2 These mixed solutions were prepared using an agent.
  • a toluene solution (concentration: 9 g / L) of an organic polymer light emitting material, a toluene solution of an ionic compound (concentration: 9 g / L), and an additive in a glove box in an argon atmosphere at room temperature.
  • the composition for forming a light emitting layer prepared above is applied by spin coating on the first electrode 13 of the glass substrate at room temperature in a glove box under an argon atmosphere, and is further heated at 50 ° C. The organic solvent was evaporated by heating on the plate for 30 minutes. Thus, the solid light emitting layer 12 having a thickness of 100 nm was formed. Further, a second electrode 14 made of aluminum (Al) having a thickness of 50 nm was formed on the formed light emitting layer 12 by the method described above. In this manner, an electrochemiluminescence cell 10 having an area of 2 mm ⁇ 2 mm square of a light emission scheduled portion was produced. Table 2 shows the results of measuring the light emission characteristics of the obtained electrochemiluminescence cell 10.
  • Example 3 The same procedure as in Example 1 was performed except that the ammonium phosphate ester salt shown in Table 3 was used as the ionic compound. Table 3 shows the results of measuring the light emission characteristics of the obtained electrochemiluminescence cell 10.
  • Example 3 The same procedure as in Example 3 was performed except that no additive was added. Table 3 shows the results of measuring the light emission characteristics of the obtained electrochemiluminescence cell 10.
  • Examples 4-1 to 4-4> A commercially available glass substrate with an ITO film (manufactured by Geomatic Co., Ltd., ITO film thickness 200 nm) was used as the first electrode 13.
  • Super yellow Phenylene substituted poly (para-phenylenevinylene), manufactured by Merck, product name: PDY-132) as an organic polymer light-emitting material, ammonium phosphate ester salts shown in Table 4 as ionic compounds, and compounds shown in Table 4
  • These mixed solutions were prepared using additives.
  • a toluene solution (concentration: 9 g / L) of an organic polymer light emitting material, a toluene solution of an ionic compound (concentration: 9 g / L), and an additive in a glove box in an argon atmosphere at room temperature.
  • the composition for forming a light emitting layer prepared above is applied by spin coating on the first electrode 13 of the glass substrate at room temperature in a glove box under an argon atmosphere, and is further heated at 50 ° C. The organic solvent was evaporated by heating on the plate for 30 minutes. Thus, the solid light emitting layer 12 having a thickness of 100 nm was formed. Further, a second electrode 14 made of aluminum (Al) having a thickness of 50 nm was formed on the formed light emitting layer 12 by the method described above. In this manner, an electrochemiluminescence cell 10 having an area of 2 mm ⁇ 2 mm square of a light emission scheduled portion was produced. Table 4 shows the results of measuring the light emission characteristics of the obtained electrochemiluminescence cell 10.
  • Examples 5-1 to 5-7> A commercially available glass substrate with an ITO film (manufactured by Geomatic Co., Ltd., ITO film thickness 200 nm) was used as the first electrode 13.
  • PFO-spiro (Poly [(9,9-dioctylfluorenyl-2,7-diyl) -alt-co- (9,9'-spirobifluorene-2,7-diyl)], Solaris Chem)
  • These mixed solutions were prepared using the product, model number SOL2412), an imidazolium phosphate ester salt shown in Table 5 as an ionic compound, and an additive which is a compound shown in Table 5.
  • a toluene solution (concentration: 9 g / L) of an organic polymer light emitting material, a toluene solution of an ionic compound (concentration: 9 g / L), and a toluene solution of an additive (concentration: 9 g / L) at room temperature.
  • an organic polymer light emitting material solution: ionic compound solution: additive solution 8: 1: 1 in a volume ratio to prepare a composition for forming a light emitting layer.
  • the composition for forming a light emitting layer prepared above is applied by spin coating on the first electrode 13 of the glass substrate at room temperature in a glove box under an argon atmosphere, and is further heated at 50 ° C. The organic solvent was evaporated by heating on the plate for 30 minutes. Thus, the solid light emitting layer 12 having a thickness of 100 nm was formed. Further, a second electrode 14 made of aluminum (Al) having a thickness of 50 nm was formed on the formed light emitting layer 12 by the method described above. In this manner, an electrochemiluminescence cell 10 having an area of 2 mm ⁇ 2 mm square of a light emission scheduled portion was produced. Table 5 shows the results of measuring the light emission characteristics of the obtained electrochemiluminescence cell 10.
  • Examples 6-1 to 6-8> A commercially available glass substrate with an ITO film (manufactured by Geomatic Co., Ltd., ITO film thickness 200 nm) was used as the first electrode 13.
  • Super yellow Phenylene substituted poly (para-phenylenevinylene), manufactured by Merck, product name: PDY-132) as an organic polymer light-emitting material, imidazolium phosphate ester salts shown in Table 6 as ionic compounds, and compounds shown in Table 6
  • These mixed solutions were prepared using an additive.
  • a toluene solution (concentration: 9 g / L) of an organic polymer light emitting material, a toluene solution of an ionic compound (concentration: 9 g / L), and an additive in a glove box in an argon atmosphere at room temperature.
  • the composition for forming a light emitting layer prepared above is applied by spin coating on the first electrode 13 of the glass substrate at room temperature in a glove box under an argon atmosphere, and is further heated at 50 ° C. The organic solvent was evaporated by heating on the plate for 30 minutes. Thus, the solid light emitting layer 12 having a thickness of 100 nm was formed. Further, a second electrode 14 made of aluminum (Al) having a thickness of 50 nm was formed on the formed light emitting layer 12 by the method described above. In this manner, an electrochemiluminescence cell 10 having an area of 2 mm ⁇ 2 mm square of a light emission scheduled portion was produced. Table 6 shows the results of measuring the light emission characteristics of the obtained electrochemiluminescence cell 10.
  • Examples 7-1 and 7-2> A commercially available glass substrate with an ITO film (manufactured by Geomatic Co., Ltd., ITO film thickness 200 nm) was used as the first electrode 13.
  • PFO-spiro (Poly [(9,9-dioctylfluorenyl-2,7-diyl) -alt-co- (9,9'-spirobifluorene-2,7-diyl)], Solaris Chem)
  • a mixed solution of these was prepared using the product No. SOL2412), a phosphonium (p-toluenesulfonyl) salt shown in Table 7 as an ionic compound, and an additive which is a compound shown in Table 7.
  • argon was used.
  • a toluene solution of organic polymer light emitting material (concentration: 9 g / L)
  • a toluene solution of ionic compound (concentration: 9 g / L)
  • a toluene solution of additive (concentration: 9 g) at room temperature.
  • the composition for forming a light emitting layer prepared above is applied by spin coating on the first electrode 13 of the glass substrate at room temperature in a glove box under an argon atmosphere, and is further heated at 50 ° C. The organic solvent was evaporated by heating on the plate for 30 minutes. Thus, the solid light emitting layer 12 having a thickness of 100 nm was formed. Further, a second electrode 14 made of aluminum (Al) having a thickness of 50 nm was formed on the formed light emitting layer 12 by the method described above. In this manner, an electrochemiluminescence cell 10 having an area of 2 mm ⁇ 2 mm square of a light emission scheduled portion was produced. Table 7 shows the results of measuring the light emission characteristics of the obtained electrochemiluminescence cell 10.
  • Examples 8-1 to 8-2> A commercially available glass substrate with an ITO film (manufactured by Geomatic Co., Ltd., ITO film thickness 200 nm) was used as the first electrode 13.
  • Super Yellow Phenylene substituted poly (para-phenylenevinylene), manufactured by Merck, product name: PDY-132) as an organic polymer light-emitting material, phosphonium (p-toluenesulfonyl) salts shown in Table 8 as ionic compounds, and Table 8
  • These mixed solutions were prepared using the additive which is a compound.
  • a toluene solution (concentration: 9 g / L) of an organic polymer light emitting material, a toluene solution of an ionic compound (concentration: 9 g / L), and an additive in a glove box in an argon atmosphere at room temperature.
  • the composition for forming a light emitting layer prepared above is applied by spin coating on the first electrode 13 of the glass substrate at room temperature in a glove box under an argon atmosphere, and is further heated at 50 ° C. The organic solvent was evaporated by heating on the plate for 30 minutes. Thus, the solid light emitting layer 12 having a thickness of 100 nm was formed. Further, a second electrode 14 made of aluminum (Al) having a thickness of 50 nm was formed on the formed light emitting layer 12 by the method described above. In this manner, an electrochemiluminescence cell 10 having an area of 2 mm ⁇ 2 mm square of a light emission scheduled portion was produced. Table 8 shows the results of measuring the emission characteristics of the obtained electrochemiluminescence cell 10.
  • Example 9 A commercially available glass substrate with an ITO film (manufactured by Geomatic Co., Ltd., ITO film thickness 200 nm) was used as the first electrode 13.
  • PFO-spiro (Poly [(9,9-dioctylfluorenyl-2,7-diyl) -alt-co- (9,9'-spirobifluorene-2,7-diyl)], Solaris Chem)
  • These mixed solutions were prepared using the product, model number SOL2412), a phosphonium (bis (oxalato) borate) salt shown in Table 9 as an ionic compound, and an additive which is a compound shown in Table 9.
  • the composition for forming a light emitting layer prepared above is applied by spin coating on the first electrode 13 of the glass substrate at room temperature in a glove box under an argon atmosphere, and is further heated at 50 ° C.
  • Example 9 The same procedure as in Example 9 was performed except that no additive was added. Table 9 shows the results of measuring the light emission characteristics of the obtained electrochemiluminescence cell 10.
  • Example 10 A commercially available glass substrate with an ITO film (manufactured by Geomatic Co., Ltd., ITO film thickness 200 nm) was used as the first electrode 13.
  • Super Yellow Phenylene substituted poly (para-phenylenevinylene), manufactured by Merck, product name: PDY-132) as an organic polymer light-emitting material, phosphonium (bis (oxalato) borate) salts shown in Table 10 as ionic compounds, and Table 10
  • These mixed solutions were prepared using additives which are the compounds shown.
  • a toluene solution (concentration: 9 g / L) of an organic polymer light emitting material, a toluene solution of an ionic compound (concentration: 9 g / L), and an additive in a glove box in an argon atmosphere at room temperature.
  • the composition for forming a light emitting layer prepared above is applied by spin coating on the first electrode 13 of the glass substrate at room temperature in a glove box under an argon atmosphere, and is further heated at 50 ° C. The organic solvent was evaporated by heating on the plate for 30 minutes. Thus, the solid light emitting layer 12 having a thickness of 100 nm was formed. Further, a second electrode 14 made of aluminum (Al) having a thickness of 50 nm was formed on the formed light emitting layer 12 by the method described above. In this manner, an electrochemiluminescence cell 10 having an area of 2 mm ⁇ 2 mm square of a light emission scheduled portion was produced. Table 10 shows the results of measuring the light emission characteristics of the obtained electrochemiluminescence cell 10.
  • Example 10 The same method as in Example 10 was performed except that the additive was not added. Table 10 shows the results of measuring the light emission characteristics of the obtained electrochemiluminescence cell 10.
  • Example 11 A commercially available glass substrate with an ITO film (manufactured by Geomatic Co., Ltd., ITO film thickness 200 nm) was used as the first electrode 13.
  • PFO-spiro (Poly [(9,9-dioctylfluorenyl-2,7-diyl) -alt-co- (9,9'-spirobifluorene-2,7-diyl)], Solaris Chem)
  • These mixed solutions were prepared using a product, model number SOL2412), a phosphonium (bistrifluoromethylsulfonylimide) salt shown in Table 11 as an ionic compound, and an additive which is a compound shown in Table 11.
  • the composition for forming a light emitting layer prepared above is applied by spin coating on the first electrode 13 of the glass substrate at room temperature in a glove box under an argon atmosphere, and is further heated at 50 ° C.
  • the organic solvent was evaporated by heating on the plate for 30 minutes.
  • the solid light emitting layer 12 having a thickness of 100 nm was formed.
  • Al aluminum
  • Table 11 shows the results of measuring the luminescence properties of the obtained electrochemiluminescence cell 10.
  • Example 11 The same procedure as in Example 11 was performed except that no additive was added. Table 11 shows the results of measuring the luminescence properties of the obtained electrochemiluminescence cell 10.
  • Examples 12-1 to 12-2> A commercially available glass substrate with an ITO film (manufactured by Geomatic Co., Ltd., ITO film thickness 200 nm) was used as the first electrode 13.
  • Super Yellow Phenylene substituted poly (para-phenylenevinylene), manufactured by Merck, product name: PDY-132) as an organic polymer light-emitting material, phosphonium (bistrifluoromethylsulfonylimide) salt shown in Table 12 as an ionic compound, and Table 12
  • These mixed solutions were prepared using additives which are the compounds shown.
  • a toluene solution (concentration: 9 g / L) of an organic polymer light emitting material, a toluene solution of an ionic compound (concentration: 9 g / L), and an additive in a glove box in an argon atmosphere at room temperature.
  • the composition for forming a light emitting layer prepared above is applied by spin coating on the first electrode 13 of the glass substrate at room temperature in a glove box under an argon atmosphere, and is further heated at 50 ° C. The organic solvent was evaporated by heating on the plate for 30 minutes. Thus, the solid light emitting layer 12 having a thickness of 100 nm was formed. Further, a second electrode 14 made of aluminum (Al) having a thickness of 50 nm was formed on the formed light emitting layer 12 by the method described above. In this manner, an electrochemiluminescence cell 10 having an area of 2 mm ⁇ 2 mm square of a light emission scheduled portion was produced. Table 12 shows the results of measuring the light emission characteristics of the obtained electrochemiluminescence cell 10.
  • Examples 13-1 to 13-2> A commercially available glass substrate with an ITO film (manufactured by Geomatic Co., Ltd., ITO film thickness 200 nm) was used as the first electrode 13.
  • PFO-spiro (Poly [(9,9-dioctylfluorenyl-2,7-diyl) -alt-co- (9,9'-spirobifluorene-2,7-diyl)], Solaris Chem)
  • These mixed solutions were prepared using the product, model number SOL2412), a phosphonium (tetrafluoroborate) salt shown in Table 13 as an ionic compound, and an additive which is a compound shown in Table 13.
  • a toluene solution (concentration: 9 g / L) of an organic polymer light emitting material, a toluene solution of an ionic compound (concentration: 9 g / L), and a toluene solution of an additive (concentration: 9 g / L) at room temperature.
  • the composition for forming a light emitting layer prepared above is applied by spin coating on the first electrode 13 of the glass substrate at room temperature in a glove box under an argon atmosphere, and is further heated at 50 ° C. The organic solvent was evaporated by heating on the plate for 30 minutes. Thus, the solid light emitting layer 12 having a thickness of 100 nm was formed. Further, a second electrode 14 made of aluminum (Al) having a thickness of 50 nm was formed on the formed light emitting layer 12 by the method described above. In this manner, an electrochemiluminescence cell 10 having an area of 2 mm ⁇ 2 mm square of a light emission scheduled portion was produced. Table 13 shows the results of measuring the luminescence properties of the obtained electrochemiluminescence cell 10.
  • Examples 14-1 to 14-2> A commercially available glass substrate with an ITO film (manufactured by Geomatic Co., Ltd., ITO film thickness 200 nm) was used as the first electrode 13.
  • These mixed solutions were prepared using an additive which is: Specifically, a toluene solution (concentration: 9 g / L) of an organic polymer light emitting material, a toluene solution of an ionic compound (concentration: 9 g / L), and an additive in a glove box in an argon atmosphere at room temperature.
  • the composition for forming a light emitting layer prepared above is applied by spin coating on the first electrode 13 of the glass substrate at room temperature in a glove box under an argon atmosphere, and is further heated at 50 ° C. The organic solvent was evaporated by heating on the plate for 30 minutes. Thus, the solid light emitting layer 12 having a thickness of 100 nm was formed.
  • a second electrode 14 made of aluminum (Al) having a thickness of 50 nm was formed on the formed light emitting layer 12 by the method described above. In this manner, an electrochemiluminescence cell 10 having an area of 2 mm ⁇ 2 mm square of a light emission scheduled portion was produced. Table 14 shows the results of measuring the light emission characteristics of the obtained electrochemiluminescence cell 10.
  • Examples 15-1 to 15-6> A commercially available glass substrate with an ITO film (manufactured by Geomatic Co., Ltd., ITO film thickness 200 nm) was used as the first electrode 13.
  • These mixed solutions were prepared using Specifically, a cyclohexanone solution (concentration: 9 g / L) of an organic polymer light emitting material, a cyclohexanone solution (concentration: 9 g / L) of a metal salt, and an additive cyclohexanone in a glove box in an argon atmosphere at room temperature.
  • the composition for forming a light-emitting layer prepared above is applied by spin coating on the first electrode 13 of the glass substrate at room temperature in a glove box in an argon atmosphere, and further heated at 80 ° C.
  • the cyclohexanone was evaporated by heating on the plate for 60 minutes.
  • the solid light emitting layer 12 having a thickness of 100 nm was formed.
  • a second electrode 14 made of aluminum (Al) having a thickness of 50 nm was formed on the formed light emitting layer 12 by the method described above. In this manner, an electrochemiluminescence cell 10 having an area of 2 mm ⁇ 2 mm square of a light emission scheduled portion was produced.
  • Table 15 shows the results of measuring the light emission characteristics of the obtained electrochemiluminescence cell 10.
  • Example 16 A commercially available glass substrate with an ITO film (manufactured by Geomatic Co., Ltd., ITO film thickness 200 nm) was used as the first electrode 13.
  • Super Yellow Phenylene substituted poly (para-phenylenevinylene), manufactured by Merck & Co., product name: PDY-132) as an organic polymer light emitting material, an ionic compound (metal salt) shown in Table 16, and an additive which is a compound shown in Table 16
  • These mixed solutions were prepared using Specifically, a cyclohexanone solution (concentration: 9 g / L) of an organic polymer light emitting material, a cyclohexanone solution (concentration: 9 g / L) of a metal salt, and an additive cyclohexanone in a glove box in an argon atmosphere at room temperature.
  • the composition for forming a light-emitting layer prepared above is applied by spin coating on the first electrode 13 of the glass substrate at room temperature in a glove box in an argon atmosphere, and further heated at 80 ° C.
  • the cyclohexanone was evaporated by heating on the plate for 60 minutes.
  • the solid light emitting layer 12 having a thickness of 100 nm was formed.
  • a second electrode 14 made of aluminum (Al) having a thickness of 50 nm was formed on the formed light emitting layer 12 by the method described above. In this manner, an electrochemiluminescence cell 10 having an area of 2 mm ⁇ 2 mm square of a light emission scheduled portion was produced.
  • Table 15 shows the results of measuring the light emission characteristics of the obtained electrochemiluminescence cell 10.
  • Example 16 The same procedure as in Example 16 was performed except that no additive was added. Table 16 shows the results of measuring the light emission characteristics of the obtained electrochemiluminescence cell 10.
  • Examples 17-1 to 17-2> A commercially available glass substrate with an ITO film (manufactured by Geomatic Co., Ltd., ITO film thickness 200 nm) was used as the first electrode 13.
  • PFO-spiro Poly [(9,9-dioctylfluorenyl-2,7-diyl) -alt-co- (9,9,9'-spirobifluorene-2,7-diyl)]
  • Solaris Chem as an organic polymer light-emitting material
  • a cyclohexanone solution (concentration: 9 g / L) of an organic polymer light emitting material, a cyclohexanone solution (concentration: 9 g / L) of a metal salt, and an additive cyclohexanone in a glove box in an argon atmosphere at room temperature.
  • the composition for forming a light-emitting layer prepared above is applied by spin coating on the first electrode 13 of the glass substrate at room temperature in a glove box in an argon atmosphere, and further heated at 80 ° C.
  • the cyclohexanone was evaporated by heating on the plate for 60 minutes.
  • the solid light emitting layer 12 having a thickness of 100 nm was formed.
  • a second electrode 14 made of aluminum (Al) having a thickness of 50 nm was formed on the formed light emitting layer 12 by the method described above. In this manner, an electrochemiluminescence cell 10 having an area of 2 mm ⁇ 2 mm square of a light emission scheduled portion was produced.
  • Table 15 shows the results of measuring the light emission characteristics of the obtained electrochemiluminescence cell 10.
  • Electrochemiluminescence cell 12 Light emitting layer 13 1st electrode 14 2nd electrode 16 p doped area

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Abstract

La présente invention concerne un additif pour couche électroluminescente dans une cellule électrochimiluminescente, qui contient un composé représenté par la formule générale (1). Dans la formule : X est un atome de phosphore (P), de carbone (C) ou de soufre (S) ; A est un groupe hydrocarboné cyclique qui peut être un atome d'hydrogène (H), une liaison directe, un groupe hydrocarboné en chaîne, ou un hétéroatome ; R est H ou un groupe alkyle, et une pluralité de R peuvent se lier ensemble pour former un cycle, et si ledit cycle est formé, au moins un R est un groupe alkyle ; m vaut 0 ou 1 ; r vaut 1 quand X est un atome de phosphore ou un atome de carbone et 2 quand X est un atome de soufre ; n est un nombre représenté par 3-m quand X est un atome de phosphore, et un nombre représenté par 2-m si X est un atome de carbone ou un atome de soufre ; et p vaut 1 quand m vaut 0, au moins 1 quand m vaut 1, et est un nombre substituable dans A.
PCT/JP2016/071490 2015-07-27 2016-07-22 Additif pour couche électroluminescente de cellule électrochimiluminescente, composition pour la formation d'une couche électroluminescente dans une cellule électrochimiluminescente, et cellule électrochimiluminescente WO2017018328A1 (fr)

Priority Applications (4)

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US15/739,837 US10439143B2 (en) 2015-07-27 2016-07-22 Additive for light-emitting layer in light-emitting electrochemical cell, composition for forming light-emitting layer in light-emitting electrochemical cell, and light-emitting electrochemical cell
KR1020187000225A KR20180034382A (ko) 2015-07-27 2016-07-22 전기 화학 발광 셀의 발광층용 첨가제, 전기 화학 발광 셀의 발광층 형성용 조성물 및 전기 화학 발광 셀
EP16830433.5A EP3331043A4 (fr) 2015-07-27 2016-07-22 Additif pour couche électroluminescente de cellule électrochimiluminescente, composition pour la formation d'une couche électroluminescente dans une cellule électrochimiluminescente, et cellule électrochimiluminescente
CN201680040328.3A CN107851725B (zh) 2015-07-27 2016-07-22 电化学发光单元发光层用添加剂、电化学发光单元发光层形成用组合物和电化学发光单元

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WO2021084701A1 (fr) * 2019-10-31 2021-05-06 シャープ株式会社 Élément électroluminescent, dispositif électroluminescent et procédé de fabrication d'élément électroluminescent

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JP2011103234A (ja) * 2009-11-11 2011-05-26 Dainippon Printing Co Ltd 有機固体膜、電気化学発光素子、および電気化学発光装置、並びに電気化学発光素子の製造方法および駆動方法
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JP2006339010A (ja) * 2005-06-01 2006-12-14 Toshiba Corp 電気化学デバイス用電解液
JP2011103234A (ja) * 2009-11-11 2011-05-26 Dainippon Printing Co Ltd 有機固体膜、電気化学発光素子、および電気化学発光装置、並びに電気化学発光素子の製造方法および駆動方法
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WO2021084701A1 (fr) * 2019-10-31 2021-05-06 シャープ株式会社 Élément électroluminescent, dispositif électroluminescent et procédé de fabrication d'élément électroluminescent

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