WO2006025612A1 - Material composition for conductive layers in electronic devices - Google Patents

Material composition for conductive layers in electronic devices Download PDF

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Publication number
WO2006025612A1
WO2006025612A1 PCT/JP2005/016573 JP2005016573W WO2006025612A1 WO 2006025612 A1 WO2006025612 A1 WO 2006025612A1 JP 2005016573 W JP2005016573 W JP 2005016573W WO 2006025612 A1 WO2006025612 A1 WO 2006025612A1
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Prior art keywords
substituent
composition
linking agent
epoxy
conductive materials
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PCT/JP2005/016573
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French (fr)
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Koichi Terao
Yuji Shinohara
Takashi Shinohara
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Seiko Epson Corporation
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Publication of WO2006025612A1 publication Critical patent/WO2006025612A1/en

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/141—Organic polymers or oligomers comprising aliphatic or olefinic chains, e.g. poly N-vinylcarbazol, PVC or PTFE
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H10K85/633—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising polycyclic condensed aromatic hydrocarbons as substituents on the nitrogen atom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H10K85/636—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising heteroaromatic hydrocarbons as substituents on the nitrogen atom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
    • H10K10/40—Organic transistors
    • H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
    • H10K10/462—Insulated gate field-effect transistors [IGFETs]
    • H10K10/466—Lateral bottom-gate IGFETs comprising only a single gate
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/655—Aromatic compounds comprising a hetero atom comprising only sulfur as heteroatom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/656—Aromatic compounds comprising a hetero atom comprising two or more different heteroatoms per ring
    • H10K85/6565—Oxadiazole compounds
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene

Definitions

  • the present invention relates to a composition for conductivematerials, a conductivematerial, a conductive layer, an electronic device, and electronic equipment, and more specifically to a composition for conductive materials from which a conductive layerhaving ahigh carrier transport ability can be made, a conductive material formed of the composition and having a high carrier transport ability, a conductive layer formed using the conductive material as a main material, an electronic device providedwith the conductive layer and having high reliability, and electronic equipment provided with the electronic device.
  • Electroluminescent devices using organic materials have been extensively developed in expectation of their use as solid-state luminescent devices or emitting devices for use in inexpensive large full-color displays.
  • such an organic EL device has a structure in which a light emitting layer is provided between a cathode and an anode.
  • a light emitting layer is provided between a cathode and an anode.
  • the injected electrons and holes are recombined in the light emitting layer, which then causes their energy level to return from the conduction band to the valence band. At this time, excitation energy is released as light energy so that the light emitting layer emits light.
  • organic layers For this purpose, it is necessary to laminate a light emitting layer and organic layers having different carrier transport properties fromeach other (hereinafter, these layers are collectively referred to as "organic layers") on the electrode.
  • organic layers organic layers having different carrier transport properties fromeach other
  • composition for conductive materials which comprises a compound represented by the following general formula (Al) :
  • R may be the same or different and each independently represents a hydrogen atom, a methyl group or an ethyl group
  • Y represents a group containing at least one substituted or unsubstituted aromatic hydrocarbon ring or substituted or unsubstituted heterocycle
  • X 1 , X 2 , X 3 and X 4 may be the same or different and each independently represents a substituent represented by the following general formula (A2):
  • n 1 is an integer of 2 to 8.
  • the group Y contains at least one substituted or unsubstituted aromatic hydrocarbon ring.
  • the substituent X 1 and the substituent X 3 are identical with each other.
  • composition described above it is also possible to make variation in intervals between the main skeletons of the compounds smaller in aresultant polymer. This also makes it possible to further improve a hole transport ability of the polymer.
  • the substituent X 1 , the substituent X 2 , the substituent X 3 and the substituent X 4 are identical with each other.
  • composition described above it is also possible to make variation in intervals between the main skeletons of the compounds smaller in aresultant polymer. This also makes it possible to further improve a hole transport ability of the polymer.
  • each of the substituent X 1 , the substituent X 2 , the substituent X 3 and the substituent X 4 is bonded to the 3-, 4- or 5-position of the benzene ring.
  • the group Y consists of carbon atoms and hydrogen atoms.
  • the group Y contains 6 to 30 carbon atoms in total.
  • the group Y contains 1 to 5 aromatic hydrocarbon rings.
  • the group Y is a biphenylene group or a derivative thereof.
  • composition further comprises an epoxy-based cross-linking agent in addition to the compound represented by the above-mentioned general formula (AX).
  • the epoxy-based cross-linking agent contains a (meth)acrylic ester-based epoxy cross-linking agent.
  • the epoxy based cross-linking agent contains a bisphenol epoxy cross-linking agent.
  • the epoxy-based cross-linking agent contains at least one cross-linking agent selected from the group comprising a glycidyl ester-based epoxy cross-linking agent, an alicyclic epoxy cross-linking agent, an urethane modified epoxy cross-linking agent and a silicon-containing epoxy cross-linking agent.
  • the epoxy-based cross-linking agent contains at least one of a polyfunctional phenol-based epoxy cross-linking agent and a glycidyl amine-based epoxy cross-linking agent.
  • the substituent X 1 and the substituent X 3 are identical with each other. This makes it possible to properly prevent or suppress the electron density in a resultant polymer from being biased, and thereby enabling to improve a hole transport ability of the polymer.
  • This also makes it possible to properly prevent or suppress the electron density in a resultant polymer from being biased, and thereby enabling to improve a hole transport ability of the polymer.
  • the substituent X 1 , the substituent X 2 , the substituent X 3 and the substituent X 4 are identical with each other.
  • This also makes it possible to properly prevent or suppress the electron density in a resultant polymer from being biased, and thereby enabling to further improve ahole transport ability of the polymer.
  • each of the substituent X 1 , the substituent X 2 , the substituent X 3 and the substituent X 4 is bonded to the 3-, 4- or 5-position of the benzene ring. This allows the main skeletons to exist at a suitable interval more reliably in a resultant polymer.
  • the group Y consists of carbon atoms andhydrogen atoms.
  • the groupY contains 6 to 30 carbon atoms in total.
  • the group Y contains 1 to 5 aromatic hydrocarbon rings.
  • the group Y is a biphenylene group or a derivative thereof.
  • the group Y contains at least one substituted orunsubstitutedheterocycle.
  • composition described above it is possible to make variation in intervals between the main skeletons of the compounds small in a resultant polymer, thereby enabling to improve a carrier transport ability of the polymer.
  • composition described above it is also possible to make variation in intervals between the main skeletons of the compounds small in a resultant polymer, thereby enabling to further improve a carrier transport ability of the polymer.
  • substituent X 1 , the substituent X 2 , the substituent X 3 and the substituent X 4 are identical with each other.
  • composition described above it is also possible to make variation in intervals between the main skeletons of the compounds small in a resultant polymer, thereby enabling to further improve a carrier transport ability of the polymer.
  • each of the substituent X 1 , the substituent X 2 , the substituent X 3 and the substituent X 4 is bonded to the 3-, 4- or 5-position of the benzene ring.
  • the heterocycle contains at least one heteroatom selected from the group comprising nitrogen, oxygen, sulfur, selenium and tellurium.
  • the energy level of the valence and conductionbands or the size of the band gap of thepolymereasily changes, so that it is possible to change the characteristics of the carrier transport ability of the polymer.
  • the heterocycle may be either of an aromatic heterocycle or a nonaromatic heterocycle, but the aromatic heterocycle is more preferable.
  • the group Y contains 1 to 5 heterocycles.
  • the group Y By allowing the group Y to have such a number of heterocyclic rings, it is possible to change the energy level of the valence and conduction bands or the size of the band gap of the polymer sufficiently.
  • the group Y contains at least one substituted or unsubstituted aromatic hydrocarbon ring in addition to the heterocycle.
  • the group Y contains two aromatic hydrocarbon rings respectively bonded to each N in the general formula (Al) directly and at least one heterocycle existing between these aromatic hydrocarbon rings.
  • the group Y contains 2 to 75 carbon atoms in total.
  • the solubility of the compound represented by the general formula (Al) in a solvent tends to be increased, so that there is a possibility that the range of the choices of solvents to be used in preparing the composition for conductive materials becomes wide.
  • the above composition further comprises an epoxy-based cross-linking agent.
  • the epoxy-based cross-linking agent contains a (meth)acrylic ester-based epoxy cross-linking agent.
  • the epoxy based cross-linking agent contains a bisphenol epoxy cross-linking agent.
  • the epoxy-based cross-linking agent contains at least one cross-linking agent selected from the group comprising a glycidyl ester-based epoxy cross-linking agent, an alicyclic epoxy cross-linking agent, an urethane modified epoxy cross-linking agent and a silicon-containing epoxy cross-linking agent.
  • the epoxy-based cross-linking agent contains at least one of a polyfunctional phenol-based epoxy cross-linking agent and a glycidyl amine-based epoxy cross-linking agent.
  • This also makes it possible to properly prevent or suppress the electron density in a resultant polymer from being biased, and thereby enabling to further improve a carrier transport ability of the polymer.
  • the substituent X 1 , the substituent X 2 , the substituent X 3 and the substituent X 4 are identical with each other.
  • This also makes it possible to properly prevent or suppress the electron density in a resultant polymer from being biased, and thereby enabling to further improve a carrier transport ability of the polymer.
  • each of the substituent X 1 , the substituent X 2 , the substituent X 3 and the substituent X 4 is bonded to the 3-, 4- or 5-position of the benzene ring.
  • the heterocycle contains at least one heteroatom selected from the group comprising nitrogen, oxygen, sulfur, selenium and tellurium.
  • the energy level of the valence and conductionbands or the size of the band gap of the polymer easily changes, so that it is possible to change the characteristics of the carrier transport ability of the polymer.
  • the heterocycle may be either of an aromatic heterocycle or a nonaromatic heterocycle, but the aromatic heterocycle is more preferable.
  • the group Y contains 1 to 5 heterocycles.
  • the group Y By allowing the group Y to have such a number of heterocyclic rings, it is possible to change the energy level of the valence and conduction bands or the size of the band gap of the polymer sufficiently.
  • the group Y contains at least one substituted or unsubstituted aromatic hydrocarbon ring in addition to the heterocycle.
  • the group Y contains two aromatic hydrocarbon rings respectively bonded to each N in the general formula (Al) directly and at least one hetero ⁇ ycle existing between these aromatic hydrocarbon rings.
  • the groupY contains 2 to 75 carbon atoms in total.
  • the solubility of the compound represented by the general formula (Al) in a solvent tends to be increased, so that there is a possibility that the range of the choices of solvents to be used in preparing the composition for conductive materials becomes wide.
  • Another aspect of the present invention is directed to a conductive material obtained by direct polymerization reaction or polymerization reaction via an epoxy-based cross-linking agent of substituents X 1 , substituents X 2 , substituents X 3 and substituents X 4 of compounds each represented by the following general formula (Al), each compound being contained in the composition for conductive materials defined in claim 1:
  • R may be the same or different and each independently represents a hydrogen atom, a methyl group or an ethyl group
  • Y represents a group containing at least one substituted or unsubstituted aromatic hydrocarbon ring or substituted or unsubstituted heterocycle
  • X 1 , X 2 , X 3 and X 4 may be the same or different and each independently represents a substituent represented by the following general formula (A2):
  • n 1 is an integer of 2 to 8.
  • the compounds are polymerized by light irradiation.
  • both the compound and the epoxy-based cross-linking agent are polymerized by light irradiation.
  • a conductive layer mainly comprising the conductive material as described above.
  • This conductive layer can have a high hole transport ability.
  • the conductive layer is used for a hole transport layer.
  • This hole transport layer can also have a high hole transport ability.
  • the average thickness of the hole transport layer is in the range of 10 to 150 nm.
  • the conductive layer of the present invention described above may be used for an electron transport layer.
  • Such an electron transport layer can also have a high electron transport ability.
  • the average thickness of the electron transport layer is in the range of 10 to 150 nm.
  • the conductive layer of the present invention described above may be used for an organic semiconductor layer.
  • Such an organic semiconductor layer can exhibit excellent semiconductor characteristics.
  • the average thickness of the organic semiconductor layer is in the range of 0.1 to 1,000 nm.
  • the other aspect of the present invention is directed to an electronic device comprising a laminated bodywhich includes the conductive layer as described above.
  • Such an electronic device can have high reliability.
  • Examples of the electronic device may include a light emitting device and a photoelectric transducer. These light emitting device and photoelectric transducer can also have high reliability.
  • the light emitting device includes an organic EL device.
  • Such an organic EL device can also have high reliability.
  • examples of the electronic device may also include a switching element.
  • a switching element can also have high reliability.
  • the switching element includes an organic thin film transistor.
  • Such an organic thin film transistor can also have high reliability.
  • Yet other aspect of the present invention is directed to electronic equipment comprising the electronic device described above.
  • Such electronic equipment can also have high reliability.
  • FIG. 1 is a cross-sectional view which shows an example of an organic EL device
  • FIG. 2(a) is a cross-sectional view of an organic TFT
  • FIG. 2(b) is a plan view of the organic TFT
  • FIG. 3(a) to FIG. 3(d) are illustrations which explain the manufacturing method of the organic TFT shown in FIG. 2;
  • FIG. 4(a) to FIG. 4(d) are illustrations which explain the manufacturing method of the organic TFT shown in FIG. 2;
  • FIG. 5 is a perspective view which shows the structure of a personal mobile computer (or a personal notebook computer) to which the electronic equipment according to the present invention is applied;
  • FIG. 6 is a perspective view which shows the structure of a mobile phone (including the personal handyphone system (PHS)) to which the electronic equipment according to the present invention is applied; and
  • PHS personal handyphone system
  • FIG. 7 is a perspective view which shows the structure of a digital still camera to which the electronic equipment according to the present invention is applied.
  • a conductive layer obtained by using a conductive material according to the present invention as its mainmaterial that is, a conductive layer according to the present invention
  • a conductive material according to the present invention contains as its main ingredient a polymer obtained by direct polymerization reaction at substituents X 1 , X 2 , X 3 and X 4 of compounds (which are an arylamine derivative) each represented by the following general formula (Al) (hereinafter, each of these substituents X 1 , X 2 , X 3 and X 4 will be referred to as “substituent X” and all of these substituents will be collectively referred to as “the substituents X” depending on the occasions).
  • R may be the same or different and each independently represents a hydrogen atom, a methyl group, or an ethyl group
  • Y represents a group containing at least one substituted or unsubstituted aromatic hydrocarbon ring or substituted or unsubstituted hetero ⁇ ycle
  • X 1 , X 2 , X 3 and X 4 may be the same or different and each independently represents a substituent represented by the following general formula (A2):
  • n 1 is an integer of 2 to 8.
  • first link structure a two-dimensional network of the main skeletons becomes easily to be formed.
  • each main skeleton has a conjugated chemical structure, and because of its unique spread of the electron cloud, the main skeletons contribute to smooth transport of carriers (holes or electrons) in the polymer.
  • the main skeletons are linked via the first link structure so that the adjacent main skeletons exist at a predetermined interval therebetween. Therefore, the interaction between the adjacent main skeletons decreases, so that transfer of the carriers between the main skeletons can be carried out smoothly.
  • the main skeletons are linked to form the two-dimensional network as described above. Therefore, even in the case where the network has a portion in which the link structure between the main skeletons is cut off, carriers are smoothly transported through other routes.
  • the network having two-dimensional expansion is likely to be formed as described above, and such a network makes it possible to prevent or suppress polymers frombeing interwoven to each other effectively.
  • interval between the adjacent main skeletons is shortened and thereby the interaction between the adjacent main skeletons becomes too large to decrease the carrier transport ability.
  • carriers can be smoothly transported.
  • the polymer of the present invention which is the main ingredient of the composition for conductive materials of the present invention has the structure in which the main skeletons are linked via the first link structure so that the adjacent main skeletons exist at a predetermined interval therebetween as well as the characteristic by which the two-dimensional network of the main skeletons are likely to be formed.
  • the conductive material of the present invention can exhibit an especially high carrier transport ability.
  • a conductive layer which is formed using the conductive material of the present invention as its major material can also have an especially high carrier transport ability.
  • each substituent X represented by the general formula (A2) has a straight-chain carbon-carbon link (i.e. , an alkylene group) in which n 1 is 2 to 8, in particular 3 to 6.
  • n 1 is 2 to 8, in particular 3 to 6.
  • the substituent X 1 and the substituent X 3 are identical with each other. Namely, it is preferred that the substituent X 1 and the substituent X 3 have substantially the same number of carbon atoms and more preferably the same number of carbon atoms.
  • the substituent X 2 and the substituent X 4 are identical with each other. Namely, it is also preferred that the substituent X 2 and the substituent X 4 have substantially the same number of carbon atoms andmore preferably the same number of carbon atoms. This makes it possible to improve the above-described effect further, thereby enabling to further improve the carrier transport ability of the polymer.
  • the substituent X 1 , the substituent X 2 , the substituent X 3 and the substituent X 4 are identical with each other. Namely, it is also preferred that the substituent X 1 , the substituent X 2 , the substituent X 3 and the substituent X 4 have substantially the same number of carbon atoms and more preferably the same number of carbon atoms. This makes it possible to exhibit the above-described effect conspicuously. Further, in this case, since the length of each of the substituents X which protrudes from the main skeleton is substantially the same (or exactly the same) with each other, it is possible to decrease a possibility of steric hindrance caused by the substituent X. This makes it possible that polymerization reaction is carried out reliably between the substituents X, that is the polymer is produced reliably. With this result, it is possible to further improve the carrier transport ability of the polymer.
  • each substituent X has an epoxy group as its functional group. Since the epoxy group has high reactivity and bonding stability, it is relatively easy to polymerize substituents X directly to form a network having a large two-dimensional expansion.
  • the first link structure that is, each of the substituents X
  • the first link structure has a structure havingmany conjugated ⁇ bonds such as a benzene ring
  • interaction occurs between the adjacent main skeletons through such a structure, which cancels the effect obtained by allowing the adjacent main skeletons to exist at a suitable interval.
  • the substituent X may be bonded to the 2-, 3-, A-, 5- or 6-position of the benzene ring, but preferably bonded to the 3-, 4- or 5-position. This makes it possible to conspicuously exhibit the effect obtained by linking the adjacent main skeletons via the first link structure. Namely, it is possible for the adjacent main skeletons to exist at a suitable interval more reliably.
  • the group Y contains at least one substituted or unsubstituted aromatic hydrocarbon ring or at least one substituted or unsubstituted heterocyclic ring.
  • the group Y has 6 to 30 carbon atoms, more preferably 10 to 25 carbon atoms, and even more preferably 10 to 20 carbon atoms, in total.
  • the number of aromatic hydrocarbon ring is 1 to 5, more preferably 2 to 5, and even more preferably 2 to 3.
  • the hole transport ability of the resultant polymer becomes excellent, and thus the resultant conductive layer can also have an excellent hole transport ability.
  • such a heterocyclic ring contains at least one heteroatom selected from among nitrogen, oxygen, sulfur, selenium, and tellurium.
  • the heterocyclic ring may be either an aromatic heterocycle or a nonaromatic heterocycle, but an aromatic heterocycle is preferably used.
  • an aromatic heterocycle it is possible to properly prevent the electron density of the main skeleton with a conjugated chemical structure frombeing biased, that is, it is possible to properly prevent localization of ⁇ electrons. As a result, the carrier transport ability of the polymer is prevented from being impaired.
  • the group Y preferably contains 1 to 5 heterocyclic rings, more preferably 1 to 3 heterocyclic rings. In the case where the group Y contains 2 or more heterocyclic rings, these rings may be the same or different. By allowing the group Y to have such a number of heterocyclic rings, it is possible to sufficiently change the energy level of the valence and conduction bands or the size of the band gap of the polymer.
  • the group Y may further contain at least one aromatic hydrocarbon ring in addition to the at least one heterocyclic ring.
  • the group Y contains two aromatic hydrocarbon rings each bonded to each N in the general formula (1) directly and at least one heterocyclic ring which exists between these aromatic hydrocarbon rings.
  • the group Y has 2 to 75 carbon atoms, more preferably 2 to 50 carbon atoms, in total. If the group Y has too many carbon atoms in total, the solubility of the compound represented by the general formula (Al) in a solvent tends to be lowered depending on the kind of substituent X, creating a possibility that the range of the choices of solvents to be used in preparing the composition for conductive materials according to the present invention becomes narrow.
  • each Q 1 may be the same or different and each independently represent N-T 1 , S, O, Se, or Te (where T 1 represents H, CH 3 , or Ph)
  • each Q 2 may be the same or different and each independently represent S or O
  • each Q 3 may be the same or different and each independently represent N-T 3 , S, O, Se, or Te (where T 3 represents H, CH 3 , C 2 H 5 or Ph) .
  • a polymer obtained by selecting, for example, any one of the chemical formula (D2), (D16), (D18) and (D20) as the groupY can exhibit ahighhole transport ability as compared to a polymer obtained by selecting the chemical formula (Dl7) and can exhibit an especially high hole transport ability as compared to a polymer obtained by selecting the chemical formula (D8) or (D19).
  • a polymer obtained by selecting any one of the chemical formulas (D8), (D17) and (D19) as the group Y can exhibit a high electron transport ability as compared to a polymer obtained by the chemical formulas (D2) or (D16). Further, the polymer obtained by selecting any one of the chemical formulas (D8), (Dl7) and (Dl9) as the group Y can also exhibit an especially high electron transport ability as compared with a polymer obtained by selecting the chemical formulas (D18) or (D20).
  • the unsubstituted heterocyclic ring and/or the unsubstituted aromatic hydrocarbon ring contained in the group Y may introduce a substituent so long as the planarity of the main skeleton is not greatly affected.
  • a substituent include an alkyl group having a relatively small number of carbon atoms such as a methyl group or an ethyl group or and a halogen group and the like.
  • each of the substituents R is a hydrogen atom, a methyl group, or an ethyl group, and each substituent R is selected in accordance with the number of carbon atoms of the substituent X.
  • a hydrogen atom is selected as the substituent R
  • a methyl group or an ethyl group is selected as the substituent R.
  • the polymer contains a second link structure produced by polymerization reaction(s) of a substituent X and a substituent X via an epoxy-based cross-linking agent in addition to the first link structure produced by the direct polymerization reaction of the substituents X (which are any one of the substituents X 1 , X 2 , X 3 and X 4 ) as described above.
  • a polymer since an interval between the main skeletons is maintained at a suitable interval, interaction between the main skeletons can be further decreased. As a result, the polymer containing the second link structure can exhibit a sufficiently high hole transport ability.
  • the substituent X represented by the general formula (A2) has a straight-chain carbon-carbon link (i.e., an alkylene group) in which n 1 is 2 to 8, in particular 2 to 6.
  • n 1 is 2 to 8, in particular 2 to 6.
  • the substituent X 1 and the substituent X 3 contain substantially the same number of carbon atoms, more preferably the same number of carbon atoms.
  • substituents X it is possible to adequately prevent the electrical affects to the main skeleton which would be given by the substituents X (the substituent X 1 and/or the substituent X 3 ) from varying, and as a result thereof the electron density in the polymer from being biased. This makes it possible to improve the carrier transport ability of the polymer.
  • the substituent X 2 and the substituent X 4 have substantially the same number of carbon atoms and more preferably the same number of carbon atoms. This makes it possible to improve the above-described effect further, thereby enabling to further improve the carrier transport ability of the polymer.
  • the substituent X 1 , the substituent X 2 , the substituent X 3 and the substituent X 4 have substantially the same number of carbon atoms and more preferably the same number of carbon atoms. This makes it possible to exhibit the above-described effect conspicuously. Further, in this case, since the interval between the main skeletons in the polymer can be made larger than a certain distance in spite of the case where the first link structure is formed and/or the second link structure is formed, occurrence of the interaction between the main skeletons can be further prevented. With this result, it is possible to further improve the carrier transport ability of the polymer.
  • the epoxy-based cross-linking agent used in the present invention has an epoxy group as a group to be bonded to the substituent X (hereinbelow, simply referred to as "bonding radical") .
  • bonding radical the substituent X
  • the epoxy group since the epoxy grouphas highbonding stability, the epoxy-based cross-linking agent exhibits superior adhesiveness, water-resisting property, chemical resistance andheat resistance.
  • a conductive layer formed from the conductive material (polymer) of the present invention can exhibit superior adhesiveness for the primary layer (lower layer) on which the conductive layer is to be formed and also exhibit excellent water-resisting property, chemical resistance and heat resistance. For these reasons, it is possible to improve characteristics of an electronic device provided with the conductive layer.
  • such a conductive material formed of the composition mentioned above has a high solubility for various solvents. Therefore, the range of the choices of solvents to be used in preparing the composition for conductive materials of the present invention becomes wide, and thus there is an advantage that it is possible to improve a process for forming the conductive layer.
  • the epoxy group has a stable photopolymerization reaction characteristic, the epoxy group reacts with the substituent X effectively and thereby it is possible to effectively prevent unreacted substituents X and epoxy-based cross-linking agent from remaining as they are. Therefore, it is possible to prevent formation of a polymer in which a portion where the substituents X are directly bonded to each other and a portion where the substituents X are bonded via the epoxy-based cross-linking agent are unevenly distributed, thereby enabling a conductive layer having a uniform membrane property to be formed.
  • the epoxy-based cross-linking agent to be used is not particularly limited so long as a substituent X and a substituent X can be linked (bonded) together via the epoxy-based cross-linking agent.
  • examples of such an epoxy-based cross-linking agent include a (meth)acrylic ester-based epoxy cross-linking agent, a bisphenol epoxy cross-linking agent, a glycidyl ester-based epoxy cross-linking agent, an alicyclic epoxy cross-linking agent, an urethane modified epoxy cross-linking agent, a silicon-containing epoxy cross-linking agent, a polyfunctional phenol-based epoxy cross-linking agent, and a glycidyl amine-based epoxy cross-linking agent.
  • These epoxy-based cross-linking agents may be used singly or in combination of two or more of them.
  • an epoxy-based cross-linking agent which contains at least one of the (meth)acrylic ester-based epoxy cross-linking agent, the bisphenol epoxy cross-linking agent, the glycidyl ester-based epoxy cross-linking agent, the alicyclic epoxy cross-linking agent, the urethane modified epoxy cross-linking agent, the silicon-containing epoxy cross-linking agent, the polyfunctional phenol-based epoxy cross-linking agent and the glycidyl amine-based epoxy cross-linking agent is particularly preferable.
  • the (meth)acrylic ester-based epoxy cross-linking agent has as its bonding radicals an epoxy group and a (meth)acryloyl group in its molecular structure. Therefore, by using the (meth)acrylic ester-based epoxy cross-linking agent as the epoxy-based cross-linking agent, when a substituent X and a substituent X are to be bonded or linked together via the epoxy-based cross-linking agent, it becomes possible to react the epoxygroup and the (meth)acryloyl groupwith the respective substituents X separately. Namely, it is possible to react one of the epoxy.
  • the density of polymer in a conductive layer to be formed can also have a high density, and thus the conductive layer is capable of exhibiting sufficient strength.
  • Such an epoxy-based cross-linking agent is particularly helpful when it is used in combination with the compounds each represented by the above-mentioned general formula (Al) in which the number of n 1 of the substituent X is large, that is the compounds each represented by the above-mentioned general formula (Al) and having a relatively flexible structure.
  • the density of polymer becomes high, it is possible to prevent the material for forming an upper layer from entering, into a portion of the conductive layer which is in the vicinity of the upper surface thereof. This makes it possible to clearly define the boundary between the conductive layer and the upper layer to be formed on the conductive layer. Further, this also makes it possible to transfer the carriers from the conductive layer to the upper layer smoothly. For these reasons, it becomes possible to improve characteristics of electronic devices such as organic EL devices and organic thin film transistors which will be described later in details.
  • cross-linking agent represented by the following chemical formula (Bl) can be mentioned.
  • a 1 represents a hydrogen atom or a methyl group.
  • cross-linking agent represented by the following chemical formulas (B2) to (B6) can be mentioned.
  • n 6 in these formulas it is possible to form an epoxy cross-linking agent of the type of monomer and low molecular polymer.
  • an epoxy cross-linking agent By using such an epoxy cross-linking agent, it is possible to obtain a link structure that allows the main skeletons to exist at a more appropriate interval.
  • n is an integer of 0 to 10.
  • the bisphenol F epoxy cross-linking agent representedby the above-mentionedchemical formula (B3) it becomes possible to decrease the viscosity of the obtained composition for conductive materials. This makes it possible to apply the conductive material formed of the composition onto the lower layer (primary layer) when forming a conductive layer. As a result, it is possible to form conductive layers having even (uniform) characteristics. Furthermore, by using the biphenyl epoxy cross-linking agent representedby the above-mentioned chemical formula (B4) , it becomes possible to improve moisture resistance and thermal conductivity of a polymer to be formed and to lower a stress generated therein.
  • Each of the glycidyl ester-based epoxy cross-linking agent, the alicyclic epoxy cross-linking agent, the urethane modified epoxy cross-linking agent and the silicon-containing epoxy cross-linking agent has a molecular structure having excellent flexibility as compared to the benzene rings contained in the epoxy-based cross-linking agents such as the bisphenol epoxy cross-linking agent and the polyfunctional phenole-based epoxy cross-linking agent. Therefore, polymers that are formed using these epoxy-based cross-linking agents can exhibit excellent flexibility. This also makes it possible to impart flexibility to a conductive layer to be formed with maintaining sufficient strength. As a result, electronic devices provided with conductive layers formed using these epoxy-based cross-linking agents can have excellent flexibility.
  • epoxy-based cross-linking agents are advantageous when used in combination with the compound represented by the above-mentioned general formula (Al) and having a small number of n 1 in the substituent X, that is the compound represented by the above-mentioned general formula (Al) which has a relatively solid structure.
  • cross-linking agents represented by the following chemical formulas (B7) and (B8) can be mentioned.
  • cross-linking agents represented by the following chemical formulas (B9) to (Bl2) can be mentioned.
  • cross-linking agent representedby the following chemical formula (B13) can be mentioned.
  • a 2 represents a group obtained by eliminating two isocyanate groups from a di-isocyanate compound
  • two A 3 S may be the same or different and each independently represents a group obtained by eliminating two hydroxyl groups from a diol compound.
  • the total number of carbon atoms of A 2 and A 3 S are not particularly limited to any specific value so long as an interval between the main skeletons can be maintained at a suitable distance in the link structure formed using such an epoxy-based cross-linking agent, but preferably it is set to 10 to 30. This allows to set the interval between themain skeletons at amore suitable distance.
  • diol compound examples include, but are not limited thereto, alkylene diol such as ethylene glycol, propylene glycol, trimethylene glycol, butylenes glycol, tetramethylene glycol, pentamethylene glycol, buten diol, and hexamethylene glycol; polycarbonate diol; carboxylic acid; and polyoxy alkylene diol, and the like.
  • alkylene diol such as ethylene glycol, propylene glycol, trimethylene glycol, butylenes glycol, tetramethylene glycol, pentamethylene glycol, buten diol, and hexamethylene glycol
  • polycarbonate diol such as ethylene glycol, propylene glycol, trimethylene glycol, butylenes glycol, tetramethylene glycol, pentamethylene glycol, buten diol, and hexamethylene glycol
  • polycarbonate diol such as ethylene glycol, propylene glycol, trimethylene glycol,
  • di-isocyanate compound examples include, but are not limited thereto, aromatic diisocyanate compound such as tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), naphthalene diisocyanate (NDI), p-phenylene diisocyanate, 1,3-bis-(isocyanatomethyl)-benzene (XDI), tetramethylkylylene diisocyanate,
  • aromatic diisocyanate compound such as tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), naphthalene diisocyanate (NDI), p-phenylene diisocyanate, 1,3-bis-(isocyanatomethyl)-benzene (XDI), tetramethylkylylene diisocyanate,
  • alicyclic diisocyanate compound such as trans-1,4-cyclohexane diisocyanate (CHDI), 4,4' -dicyclohexylmethane di-isocyanate (H12MDI), 1,3-bis- (isocyanatomethyl) -cyclohexane (H6XDI), and 3-isocyanatomethyl-3,5,5' -trimethylcyclohexylisocyanate (IPDI) and the like; and aliphatic diisocyanate compound such as hexamethylene diisocyanate (HDI) , dimer diisocyanate (DDI) , and norbornene diisocyanate (NBDI) and the like.
  • HDI hexamethylene diisocyanate
  • DDI dimer diisocyanate
  • NBDI norbornene diisocyanate
  • cross-linking agent representedby the following chemical formula (B14) can be mentioned.
  • Each of the polyfunctional phenol-based epoxy cross-linking agent and glycidyl " amine-based epoxy cross-linking agent has three or more epoxy groups (bonding radicals) in its molecular structure. Therefore, by using such an epoxy-based cross-linking agent, it is possible to bond or link three or more substituents X and three ormore substituents X together. This mean that it is possible to increase the cross-linking density of the substituents Xvia the epoxy-based cross-linking agent. As a result, it is possible to obtain a conductive layer formed from polymer having high density, so that the same effects as those of the (meth)acrylic ester-based epoxy cross-linking agent can be obtained.
  • the low molecular type cross-linking agents represented by the following chemical formulas (Bl5) to (B18) and the.monomer type cross-linking agents represented by the following chemical formulas (B19) to (B22) canbementioned.
  • n 9 i .s an integer of 1 to 20 and n ,10 is an integer of 1 to 30.
  • n .11 is an integer of 0 to 8 .
  • the epoxy-based cross-linking agent obtained by setting n .11 in the formula to the range mentioned above allows the main skeletons to exist at a more suitable interval.
  • epoxy-based cross-linking agents represented by the chemical formulas (B15) to (B17) it is possible to improve moisture resistance of the polymer to be formed and decrease a stress generated in a conductive layer to be formed from the polymer.
  • the above-mentioned epoxy-based cross-linking agents may ⁇ be usedbycombining two ormore of themarbitrarily. This makes it possible to exhibit the characteristics of the respective epoxy-based cross-linking agents synergistically. As a result, a conductive layer to be formed has compositive characteristics given by the respective epoxy-based cross-linking agents.
  • epoxy-based cross-linking agents which contain a benzene ring having a conjugated bond in its chemical structure.
  • cross-linking agents also contain as its essential structure a non-conjugated chemical structure such as a methylene group, an ether bonding, C-CH 3 bonding, and cyclic hydrocarbon, the characteristics of such non-conjugated chemical structures appear in preference to those of the benzene ring structure. Therefore, it is possible to prevent or suppress interaction between the main skeletons through the benzene ring in a resultant polymer from occurring appropriately.
  • the conductive layer also has excellent solvent resistance, because it is formed of a polymer as its main material which is obtained by direct polymerization reaction of the compounds each represented by the above-mentioned general formula (Al) or polymerization reaction of the compounds via the epoxy-based cross-linking agent.
  • Al general formula
  • the upper layer is formed onto the conductive layer in contact therewith, it is possible to reliably prevent the conductive layer from being swelled up or dissolved by the solvent or dispersant contained in a material for forming the upper layer.
  • the polymer is obtained by the reaction or bonding between the substituents X or between the substituent X and the epoxy group of the epoxy-based cross-linking agent. Since such an epoxy bonding exhibits a particularly excellent bonding stability, it is possible to prevent the conductive layer from being swelled up or dissolved reliably.
  • the electronic device of the present invention is embodied as an organic electroluminescent device (hereinafter, simply referred to as an "organic EL device") that is a light emitting device.
  • organic EL device organic electroluminescent device
  • FIG. 1 is a cross-sectional view which shows an example of the organic EL device.
  • the organic EL device 1 shown in FIG. 1 includes a transparent substrate 2, an anode 3 provided on the substrate 2, an organic EL layer 4 provided on the anode 3, a cathode 5 provided on the organic EL layer 4 and a protection layer 6 provided so as to cover these layers 3, 4 and 5.
  • the substrate 2 serves as a support for the organic EL device 1, and the layers described above are formed on the substrate 2.
  • a material having a light-transmitting property and a good optical property can be used as a constituent material of the substrate 2.
  • Such a material examples include various resins such as polyethylene terephthalate, polyethylene naphthalate, polypropylene, cycloolefin polymer, polyamide, polyethersulfone, polymethylmethacrylate, polycarbonate, and polyarylate, and various glass materials, and the like. At least one of these materials can be used as a constituent material of the substrate 2.
  • the thickness of the substrate 2 is not particularly limited, but is preferably in the range of about 0.1 to 30 mm, more preferably in the range of about 0.1 to 10 mm.
  • the anode 3 is an electrode which injects holes into the organic EL layer 4 (that is, into a hole transport layer 41 described later) .
  • This anode 3 is made substantially transparent (which includes transparent and colorless, colored and transparent, or translucent) so that light emission from the organic EL layer 4 (that is, from a light emitting layer 42 described later) can be visually identified.
  • anode material a material having a high work function, excellent conductivity, and a light transmitting property is preferably used as the constituent material of the anode 3 (hereinafter, referred to as "anode material").
  • anode material examples include oxides such as ITO (Indium Tin Oxide), SnO 2 , Sb-containing SnO 2 , and Al-containing ZnO, Au, Pt, Ag, Cu, and alloys containing two or more of them. At least one of these materials can be used as an anode material.
  • oxides such as ITO (Indium Tin Oxide), SnO 2 , Sb-containing SnO 2 , and Al-containing ZnO, Au, Pt, Ag, Cu, and alloys containing two or more of them. At least one of these materials can be used as an anode material.
  • the thickness of the anode 3 is not limited to any specific value, but is preferably in the range of about 10 to 200 nm, more preferably in the range of about 50 to 150 nm. If the thickness of the anode 3 is too thin, there is a case that a function of the anode 3 will not be sufficiently exhibited. On the other hand, if the anode 3 is too thick, there is a case that the light transmittance will be significantly lowered depending on, for example, the kind of anode material used, thus resulting in an organic EL device that is not suitable for practical use. It is to be noted that conductive resins such as polythiophene, polypyrrole, and the like can also be used as the anode material.
  • the cathode 5 is an electrode which injects electrons into the organic EL layer 4 (that is, into an electron transport layer 43 described later) .
  • cathode material As a constituent material of the cathode 5 (hereinafter, referred to as "cathode material”) , amaterial having a lowwork function is preferably used.
  • cathode material examples include Li, Mg, Ca, Sr, La, Ce, Er, Eu, Sc, Y, Yb, Ag, Cu, Al, Cs, Rb, and alloys containing two or more of them. At least one of these materials can be used as a cathode material.
  • an alloy containing a stable metallic element such as Ag, Al, or Cu specifically an alloy such as MgAg, AlLi, or CuLi is preferablyused.
  • an alloy containing a stable metallic element such as Ag, Al, or Cu
  • an alloy such as MgAg, AlLi, or CuLi is preferablyused.
  • the use of such an alloy as a cathode material makes it possible to improve the electron injection efficiency and stability of the cathode 5.
  • the thickness of the cathode 5 is preferably in the range of about 1 nm to 1 ⁇ m, more preferably in the range of about 100 to 400 nm. If the thickness of the cathode 5 is too thin, there is a case that a function of the cathode 5 will not be sufficiently exhibited. On the other hand, if the cathode 5 is too thick, there is a case that the light emitting efficiency of the organic EL device 1 will be lowered.
  • the organic EL layer 4 is provided between the anode 3 and the cathode 5.
  • the organic EL layer 4 includes the hole transport layer 41, the light emitting layer 42, and the electron transport layer 43. These layers 41, 42 and 43 are formed on the anode 3 in this order.
  • the hole transport layer 41 has the function of transporting holes, which are injected from the anode 3, to the light emitting layer 42.
  • the electron transport layer 43 has the function of transporting electrons, which are injected from the cathode 5, to the light emitting layer 42.
  • the conductive material according to the present invention can be used as a constituent material for one of the hole transport layer 41 and the electron transport layer 43 or for both the layers 41, 43.
  • a compound having a chemical structure of the group Y which is constituted from a substituted or unsubstituted aromatic hydrocarbon ring can be used.
  • compounds having chemical structures of the group Y represented by the above-mentioned chemical formulas (Cl) to (C-16) can be used.
  • the constituent material of the electron transport layer 43 are not limited to specific materials, and various materials can be used for the electron transport layer 43.
  • benzene-based compounds starburst-based compounds
  • TPQl 1,3,5-tris[ (3-phenyl-6-tri-fluoromethyl)quinoxaline-2-yl] benzene
  • TPQ2 1,3,5-tris[ ⁇ 3-(4-t-butylphenyl) -6-trisfluoromethyl ⁇ quinoxal ine-2-yl]benzene
  • naphthalene-based compounds such as naphthalene
  • phenanthrene-based compounds such as phenanthrene
  • chrysene-based compounds such as chrysene
  • perylene-based compounds such as perylene
  • anthracene-based compounds such as anthracene
  • pyrene-based compounds such as pyrene
  • acridine-based compounds such as acridine
  • stilbene-based compounds such as stilbene
  • thiophene-based compounds such as BBOT
  • butadiene-based compounds such as butadiene
  • coumarin-based compounds such as coumarin
  • quinoline-based compounds such as quinoline
  • bistyryl-based compounds such as bistyryl
  • a constituent material of the hole transport layer 41 and a constituent material of the electron transport layer 43 are selected in consideration of their hole transport ability and electron transport ability.
  • these constituent materials are selected so that the hole transport ability of the hole transport layer 41 becomes relativelyhigher than that of the electron transport layer 43 and the electron transport ability of the hole transport layer 41 becomes relatively lower than that of the electron transport layer 43.
  • these constituent materials are selected so that the electron transport ability of the electron transport layer 43 becomes relatively higher than that of the hole transport layer 41 and the hole transport ability of the electron transport layer 43 becomes relatively lower than that of the hole transport layer 41.
  • a conductive material for forming an electron transport layer 43 is preferably a polymer of a compound represented by the general formula (1) in which the group Y has a chemical structure represented by the chemical formula (D7) or (D19).
  • a polymer of a compound represented by the general formula (1) in which the group Y has a chemical structure represented by the chemical formula (D17) may also be used as a conductive material for forming the electron transport layer 43.
  • the conductive material for forming the hole transport layer 41 may also be a polymer of a compound represented by the general formula (1) in which the group Y has a chemical structure represented by the chemical formula (D2) or (D16).
  • the volume resistivity of the hole transport layer 41 is preferably 10 ⁇ -cm or larger, more preferably 10 2 ⁇ -cm or larger. This makes it possible to provide an organic EL device 1 having a higher light emitting efficiency.
  • the thickness of thehole transport layer 41 is not limited to any specific value, but is preferably in the range of about 10 to 150 nm, more preferably in the range of about 50 to 100 nm. If the thickness of the hole transport layer 41 is too thin, there is a case that a pin hole may be produced. On the other hand, if the thickness of the hole transport layer 41 is too thick, there is a case that the transmittance of the hole transport layer 41 may be lowered so that the chromaticity (hue) of luminescent color of the organic EL device 1 is changed.
  • the thickness of the electron transport layer 43 is not limited to any specific value, but is preferably in the range of about 1 to 100 nm, more preferably in the range of about 20 to 50 nm. If the thickness of the electron transport layer 43 is too thin, there is a case that a pin hole may be produced, thereby causing a short-circuit. On the other hand, if the electron transport layer 43 is too thick, there is a case that the value of resistance may become high.
  • the conductive material according to the present invention is particularly useful for forming a relatively thin hole transport layer 41 or electron transport layer 43.
  • any material can be used as a constituent material of the light emitting layer 42 (hereinafter, referred to as "light emittingmaterial” ) so long as it can provide a fieldwhere holes can be injected from the anode 3 and electrons can be injected from the cathode 5 during the application of a voltage to allow the holes and the electrons to be recombined.
  • Such light emitting materials include various low-molecular light emitting materials and various high-molecular light emitting materials (which will be mentioned below) . At least one of these materials can be used as a light emitting material.
  • the use of a low-molecular light emitting material makes it possible to obtain a dense light emitting layer 42, thereby improving the light emitting efficiency of the light emitting layer 42. Further, since a high-molecular light emitting material is relatively easily dissolved in a solvent, the use of such a high-molecular light emitting material makes it easy to form a light emitting layer 42 by means of various application methods such as an ink-jet method and the like.
  • the low-molecular light emitting material and the high-molecular light emitting material are used together, it is possible to obtain the synergistic effect resulting from the effect of the low-molecular light emitting material and the effect of the high-molecular light emittingmaterial. That is, it is possible to obtain the effect that a dense light emitting layer 42 having excellent light emitting efficiency can be easily formed by means of various application methods such as the ink-jet method and the like.
  • Examples of such a low-molecular light emitting material include: benzene-based compounds such as distyrylbenzene (DSB) , and diaminodistyrylbenzene (DADSB) ; naphthalene-based compounds such as naphthalene and Nile red; phenanthrene-based compounds such as phenanthrene; chrysene-based compounds such as chrysene and 6-nitrochrysene; perylene-based compounds such as perylene and
  • benzene-based compounds such as distyrylbenzene (DSB) , and diaminodistyrylbenzene (DADSB)
  • naphthalene-based compounds such as naphthalene and Nile red
  • phenanthrene-based compounds such as phenanthrene
  • chrysene-based compounds such as chrysene and 6-nitrochrysene
  • perylene-based compounds such as perylene
  • BPPC N,N' -bis(2,5-di-t-butylphenyl)-3,4,9,10-perylene-di-carboxy imide
  • coronene-based compounds such as coronene
  • anthracene-based compounds such as anthracene and bisstyrylanthracene
  • pyrene-based compounds such as pyrene
  • pyran-based compounds such as
  • acridine-based compounds such as acridine
  • stilbene-based compounds such as stilbene
  • thiophene-based compounds such as 2,5-dibenzooxazolethiophene
  • benzooxazole-based compounds such as benzooxazole
  • benzoimidazole-based compounds such as benzoimidazole
  • benzothiazole-based compounds such as 2,2' - (para-phenylenedivinylene) -bisbenzothiazole
  • butadiene-based compounds such as bistyryK1,4-diphenyl-l,3-butadiene) and tetraphenylbutadiene
  • naphthalimide-based compounds such as naphthalimide
  • coumarin-based compounds such as coumarin
  • perynone-based compounds such as perynone
  • Examples of a high-molecular light emitting material include polyacetylene-based compounds such as trans-type polyacetylene, cis-type polyacetylene, poly(di-phenylacetylene) (PDPA) , and poly(alkyl, phenylacetylene) (PAPA); polyparaphenylenevinylene-based compounds such as poly(para-phenylenevinylene) (PPV) , poly(2,5-dialkoxy-para-phenylenevinylene) (RO-PPV) , cyano-substituted-poly(para-phenylenevinylene) (CN-PPV) , poly(2-dimethyloctylsilyl-para-phenylenevinylene) (DMOS-PPV), .
  • polyacetylene-based compounds such as trans-type polyacetylene, cis-type polyacetylene, poly(di-phenylacetylene) (PDPA) , and poly(al
  • poly(2-methoxy-5-(2 ' -ethylhexoxy)-para-phenylenevinylene)_ MH-PPV
  • polythiophene-based compounds such as poly(3-alkylthiophene) (PAT), and poly(oxypropylene)triol (POPT)
  • polyfluorene-based compounds such as poly(9,9-dialkylfluorene) (PDAF) , ⁇ , ⁇ -bis[N,N' -di(methylphenyl)aminophenyl] -poly[9, 9-bis(2- ethylhexyl)fluorene-2,7-diyl] (PF2/6am4) , poly(9,9-dioctyl-2,7-divinylenefluorenyl) -alt-co(anthracene -9,10-diyl); polyparaphenylene-based compounds such as poly(para-phenylene) (PPP)
  • the conductive material according to the present invention can also be used as the light emitting material depending on the combination of constituent materials used for forming a hole transport layer 41 and an electron transport layer 43.
  • poly(thiophene/styrenesulfonic acid) such as poly(3,4-ethylenedioxythiophene/styrenesulfonic acid) or an arylamine compound such as N,N'-bis(l-naphthyl)-N,N'-diphenyl-benzidine( ⁇ -NPD) is used as a constituent material of the hole transport layer 41 and a triazole-based compound such as 3,4,5-triphenyl-l,2,4-triazole or an oxadiazole compound such as 2-(4-t-butylphenyl) -5-(biphenyl-4-yl) -1,3,5-oxadiazole (PBD) is used as a constituent material of the electron transport layer 43, a polymer of the compound represented by the general formula (1) in which the group Y has a chemical structure represented by the chemical formula (D12) or (D14) can be usedas a conductivematerial for forming a
  • the thickness of the light emitting layer 42 is not limited to any specific value, but is preferably in the range of about 10 to 150 nm, more preferably in the range of about 50 to 100 nm. By setting the thickness of the light emitting layer to a value within the above range, recombination of holes and electrons efficiently occurs, thereby enabling the light emitting efficiency of the light emitting layer 42 to be further improved.
  • any one of the electron transport layer 41, the light emitting layer 42, and the electron transport layer 43 in the organic EL device 1 may be formed using the conductive material according to the present invention or all the layers 41, 42, and 43 may be formed using the conductive material according to the present invention.
  • each of the light emitting layer 42, the hole transport layer 41, and the electron transport layer 43 is separately provided, they may be formed into a hole-transportable light emitting layer which combines the hole transport layer 41 with the light emitting layer 42 or an electron-transportable light emitting layer which combines the electron transport layer 43 with the light emitting layer 42.
  • an area in the vicinity of the boundary between the hole-transportable light emitting layer and the electron transport layer 43 or an area in the vicinity of the boundary between the electron-transportable light emitting layer and the hole transport layer 41 functions as the light emitting layer 42.
  • holes injected from an anode into the hole-transportable light emitting layer are trapped by the electron transport layer
  • electrons injected from a cathode into the electron-transportable light emitting layer are trapped in the electron-transportable light emitting layer.
  • any additional layer may be provided according to its purpose.
  • a hole injecting layer for improving the injection efficiency of holes from the anode 3 may be provided between the hole transport layer 41 and the anode 3, or an electron injecting layer for improving the injection efficiency of electrons from the cathode 5 may be provided between the electron transport layer 43 and the cathode 5.
  • the conductive material according to the present invention can be used as a constituent material of the hole injecting layer and/or the electron injecting layer.
  • a constituent material of a hole injecting layer other than the conductivematerial according to the present invention for example, copper phthalo ⁇ yanine, 4,4' ,4' ' -tris(N,N-phenyl-3-methylphenylamino)triphenylamine (M-MTDATA), or the like can be used.
  • M-MTDATA 4,4' ,4' ' -tris(N,N-phenyl-3-methylphenylamino)triphenylamine
  • the protection layer 6 is provided so as to cover the layers 3, 4 and 5 constituting the organic EL device 1.
  • This protection layer 6 has the function of hermetically sealing the layers 3, 4 and 5 constituting the organic EL device 1 to shut off oxygen and moisture.
  • Examples of a constituent material of the protection layer 6 include Al, Au, Cr, Nb, Ta and Ti, alloys containing them, silicon oxide, various resin materials, and the like.
  • a conductive material is used as a constituent material of the protection layer 6, it is preferred that an insulating film is provided between the protection layer 6 and each of the layers 3, 4 and 5 to prevent a short circuit therebetween, if necessary.
  • the organic EL device 1 can be used for a display, for example, but it can also be used for various optical purposes such as a light source and the like.
  • the drive system thereof is not particularly limited, and either of an active matrix system or a passive matrix system may be employed.
  • the organic EL device 1 as described above can be manufactured in the following manner, for example.
  • a substrate 2 is prepared, and then an anode 3 is formed on the substrate 2.
  • the anode 3 can be formed by, for example, chemical vapor deposition (CVD) such as plasma CVD, thermal CVD, and laser CVD, vacuum deposition, sputtering, dry plating such as ion plating, wet plating such as electrolytic plating, immersion plating, and electroless plating, thermal spraying, a sol-gel method, a MOD method, bonding of a metallic foil, or the like.
  • CVD chemical vapor deposition
  • thermal CVD thermal CVD
  • laser CVD vacuum deposition
  • vacuum deposition sputtering
  • dry plating such as ion plating
  • wet plating such as electrolytic plating, immersion plating, and electroless plating
  • thermal spraying a sol-gel method, a MOD method, bonding of a metallic foil, or the like.
  • a composition for conductive materials of the present invention (hereinafter, also referred to as a "hole transport material”) is applied or supplied onto the anode 3.
  • the mixing ratio between the compoundrepresentedby the general formula (Al) and the epoxy-based cross-linking agent in the composition for conductive materials is preferably 9: 1 to 3: 2, more preferably 4: 1 to 7: 3, in terms of mole ratio.
  • various application methods such as a spin coating method, a casting method, a micro gravure coating method, a gravure coating method, a bar coating method, a roll coating method, a wire-bar coating method, a dip coating method, a spray coating method, a screen printing method, a flexographic printing method, an offset printing method, an ink-jet method, and the like can be employed. According to such an application method, it is possible to relatively easily supply the hole transport material onto the anode 3.
  • examples of such a solvent or dispersion medium include: inorganic solvents such as nitric acid, sulfuric acid, ammonia, hydrogen peroxide, water, carbon disulfide, carbon tetrachloride, and ethylene carbonate; and various organic solvents such as ketone-based solvents e.g., methyl ethyl ketone (MEK), acetone, diethyl ketone, methyl isobutyl ketone (MIBK), methyl isopropyl ketone (MIPK), and cyclohexanone, alcohol-based, solvents e.g., methanol, ethanol, isopropanol, ethylene glycol, diethylene glycol (DEG), and glycerol, ether-based solvents e.g., diethyl ether, diisopropyl ether, 1,2-dimethoxy ethane (DMEK), methyl ethyl ketone (MEK), acetone, die
  • methyl cellosolve, ethyl cellosolve, and phenyl cellosolve aliphatic hydrocarbon-based solvents e.g, hexane, pentane, heptane, and cyclohexane, aromatic hydrocarbon-based solvents e.g., toluene, xylene, and benzene, aromatic heterocyclic compound-based solvents e.g., pyridine, pyrazine, furan, pyrrole, thiophene, and methyl pyrrolidone, amide-based solvents e.g., N,N-dimethylformamide (DMF) and N,N-dimethylacetamide (DMA), halogen compound-based solvents e.g., dichloromethane, chloroform, and 1,2-dichloroethane, ester-based solvents e.g., ethyl acetate, methyl acetate, and ethyl
  • the composition for conductive materials preferably contains a polymerization initiator.
  • a polymerization initiator By adding a polymerization initiator to the composition for conductive materials, it is possible to promote direct polymerization of substituents X or polymerization of substituents X via the epoxy-based cross-linking agent when predetermined treatment such as heating or light irradiation is carried out in the next step [A2-2].
  • Examples of a polymerization initiator include, but are not limited thereto, photopolymerization initiators such as radical photopolymerization initiators and cationic photopolymerization initiators, heat polymerization initiators, and anaerobic polymerization initiators. Among them, radical photopolymerization initiators are particularly preferably used. By using a radical photopolymerization initiator, it is possible to promote direct polymerization of substituents X or polymerization of substituents X via the epoxy-based cross-linking agent in the next step [A2-2] relatively easily.
  • photopolymerization initiators such as radical photopolymerization initiators and cationic photopolymerization initiators, heat polymerization initiators, and anaerobic polymerization initiators.
  • radical photopolymerization initiators are particularly preferably used.
  • cationic photopolymerization initiator various cationic photopolymerization initiators can be used.
  • cationic photopolymerization initiators include onium salt-based cationic photopolymerization initiators such as aromatic sulfouium salt-based cationic photopolymerization initiator, aromatic iodonium salt-based cationic photopolymerization initiator, aromatic diazonium cationic photopolymerization initiator, pyridium suit-based cationic photopolymerization initiator, and aromatic phosphonium salt-based cationic photopolymerization initiator.
  • nonionic photopolymerization initiators such as iron arene complex and sulfonate ester may be used.
  • a sensitizer suitable for the photopolymerization initiator may be added to the composition for conductive materials.
  • the hole transport material supplied onto the anode 3 is irradiated with light.
  • substituents X of the compounds each represented by the general formula (Al) and contained in the hole transport material are polymerized directly or via the epoxy-based cross-linking agent to obtain a polymer having a network structure (that is, a conductive material according to the present invention).
  • a hole transport layer 41 mainly comprised of the conductive material according to the present invention is formed on the anode 3.
  • a hole transport layer 41 By forming a hole transport layer 41 using the conductive material according to the present invention as its mainmaterial, it is possible to prevent the hole transport layer 41 from swelling and being dissolved due to a solvent or dispersion medium contained in a light emitting layer material to be supplied onto the hole transport layer 41 in the next step [A3] . As aresult, mutual dissolution between the hole transport layer 41 and the light emitting layer 42 is reliably prevented.
  • a hole transport layer 41 using the conductive material (that is, the polymer) according to the present invention as its main material, it is also possible to reliably prevent the mixing of the constituent materials of the hole transport layer 41 and the light emitting layer 42 from occurring near the boundary between these layers 41 and 42 in a resultant organic EL device 1 with the lapse of time.
  • the conductive material that is, the polymer
  • the weight-average molecular weight of the polymer is not particularly limited, but is preferably in the range of about 1,000 to 1,000,000, more preferably in the range of about 10,000 to 300,000. By setting the weight-average molecular weight of the polymer to a value within the above range, it is possible to suppress or prevent the swelling and dissolution of the polymer more reliably.
  • the hole transport layer 41 may contain a monomer or oligomer of the compound represented by the general formula (Al) and/or a monomer or oligomer of the epoxy-based cross-linking agent to the extent that mutual dissolution between the hole transport layer 41 and the light emitting layer 42 can be prevented.
  • the hole transport material for example, infrared rays, visible light, ultraviolet rays, or X-rays can be used. These types of light can be used singly or in combination of two or more of them. Among them, ultraviolet rays are particularly preferably used. By using ultraviolet rays, it is possible to easily and reliably polymerize the substituents X directly or via the epoxy-based cross-linking agent.
  • the wavelength of ultraviolet rays to be used for light irradiation is preferably in the range of about 100 to 420 nm, more preferably in the range of about 150 to 400 nm.
  • the irradiation intensity of ultraviolet rays is preferably in the range of about 1 to 60 )00 mW/cm 2 , more preferably in the range of about 1 to 300 mW/cm 2 .
  • the irradiation time of ultraviolet rays is preferably in the range of about 60 to 600 seconds, more preferably in the range of about 90 to 500 seconds.
  • each of the wavelength, irradiation intensity, and irradiation time of ultraviolet rays is set to a value within the above range, it is possible to relatively easily control the progress of polymerization reaction of the hole transport material supplied onto the anode 3.
  • the resultant hole transport layer 41 may be subjected to heat treatment in the atmosphere or an inert atmosphere or under reduced pressure (or under vacuum) when necessary. By doing so, it is possible to dry (that is, it is possible to remove a solvent or a dispersion medium) or solidify the hole transport layer 41.
  • the hole transport layer 41 may be dried by means other than heat treatment.
  • predetermined treatment for polymerizing the substituents X directly orvia the epoxy-based cross-linking agent other than light irradiation include heating and anaerobic treatment.
  • light irradiation as described above is preferably employed. By employing light irradiation, it is possible to relatively easily select the area where a polymerization reaction is carried out and the degree of polymerization.
  • a light emitting layer 42 is formed on the hole transport layer 41.
  • the light emitting layer 42 can be formed by, for example, applying onto the hole transport layer 41, a light emitting layermaterial (that is, amaterial for forming a light emitting layer) obtained by dissolving the light emitting material as described above in a solvent or dispersing the light emitting material in a dispersion medium.
  • a light emitting layermaterial that is, amaterial for forming a light emitting layer
  • solvents or dispersion media in which the light emitting material is to be dissolved or dispersed the same solvents or dispersion media that have been mentioned with reference to the step of forming the hole transport layer [A2] can be used.
  • an electron transport layer 43 is formedon the light emitting layer 42.
  • the electron transport layer 43 can be formed using the composition for conductive materials according to the present invention in the same manner that has been described with reference to the step of forming the hole transport layer [A2].
  • the electron transport layer 43 can be formed using the known electron transport materials described above in the same manner that has been described with reference to the step of forming the light emitting layer [A3].
  • a solvent or dispersion medium in which the composition for conductive materials for use in forming the electron transport layer 43 is to be dissolved or dispersed is selected from among those which do not cause swelling and dissolution of the light emitting layer 42.
  • a cathode 5 is formedon the electron transport layer 43.
  • the cathode 5 can be formed by, for example, vacuum deposition, sputtering, bonding of ametallic foil, or the like.
  • a protection layer 6 is formed so as to cover the anode 3, the organic EL layer 4, and the cathode 5.
  • the protection layer 6 can be formed or provided by, for example, bonding a box-like protection cover made of the material as mentioned above by the use of various curable resins (adhesives) .
  • thermosetting resins As for such curable resins, all of thermosetting resins, photocurable resins, reactive curable resins, and anaerobic curable resins can be used.
  • the organic EL device 1 is manufactured through these steps as described above.
  • the electronic device of the present invention is embodied as an organic thin film transistor that is a switching element (hereinafter, simply referred to as an "organic TFT") .
  • FIG. 2(a) is a cross-sectional view of an organic TFT 10
  • FIG. 2(b) is a plan view of the organic TFT 10. It is to be noted that in the following description, the upper side and the lower side in FIG. 2(a) will be referred to as “upper side” and “lower side", respectively.
  • the organic TFT 10 shown in FIG. 2 is provided on a substrate 20.
  • a source electrode 30, a drain electrode 40, an organic semiconductor layer (that is, a conductive layer according to the present invention) 50, a gate insulating layer 60, and a gate electrode 70 are laminated in this order from the side of the substrate 20.
  • the source electrode 30 and the drain electrode 40 are separately provided on the substrate 20, and the organic semiconductor layer 50 is provided so as to cover these electrodes 30 and 40.
  • the gate insulating layer 60 is provided on the organic semiconductor layer 50.
  • the gate electrode 70 is provided so as to overlap with at least a region between the source electrode 30 and the drain electrode 40.
  • the region in the organic semiconductor layer 50 which is existed between the source electrode 30 and the drain electrode 40 functions as a channel region 510 where carriers are moved.
  • channel length L the length of the channel region 510 in a direction that carriers are moved, that is, the distance between the source electrode 30 and the drain electrode 40
  • channel width W the length of the channel region 510 in a direction orthogonal to the direction of the channel length L.
  • the organic TFT 10 is an organic TFT having a structure in which the source electrode 30 and the drain electrode 40 are provided so as to be closer to the substrate 20 than the gate electrode 70 provided through the gate insulating layer 60. That is, the organic TFT 10 is an organic TFT having a top gate structure.
  • the substrate 20 supports the layers (or the components) constituting the organic TFT 10.
  • a substrate 20 for example, the same substrate that has been described with reference to the substrate 2 of the organic EL device 1 can be used.
  • a silicon substrate or a gallium arsenide substrate may be used as the substrate 20.
  • the source electrode 30 and the drain electrode 40 are provided side by side at a predetermined distance in the direction of the channel length L.
  • the constituent material of the source electrode 30 and the drain electrode 40 is not particularly limited so long as it has conductivity.
  • Examples of such a constituent material include metallic materials such as Pd, Pt, Au, W, Ta, Mo, Al, Cr, Ti, Cu, and alloys containing two ormore of them, conductive oxidematerials such as ITO, FTO, ATO, and SnO 2 , carbonmaterials such as carbon black, carbon nanotube, and fullerene, and conductive polymeric materials such as polyacetylene, polypyrrole, .
  • polythiophene e.g., PEDOT (poly-ethylenedioxythiophene) , polyaniline, poly(p-phenylene) , poly(p-phenylenevinylene) , polyfluorene, polycarbazole, polysilane, and derivatives thereof.
  • the conductive polymeric materials are usually dopedwith iron chloride, iodine, strong acid, organic acid, or a polymer such as polystyrenesulfonic acid so as to have conductivitywhen used. These conductive materials can be used singly or in combination of two or more of them.
  • each of the source electrode 30 and the drain electrode 40 is not particularly limited, but is preferably in the range of about 30 to 300 nm, more preferably in the range of about 50 to 200 nm.
  • the distance between the source electrode 30 and the drain electrode 40, that is, the channel length L is preferably in the range of about 2 to 30 ⁇ m, more preferably in the range of about 2 to 20 ⁇ m.
  • the channel width W is preferably in the range of about 0.1 to 5 mm, more preferably in the range of about 0.3 to 3 mm.
  • the organic semiconductor layer 50 is provided on the substrate 20 so as to cover the source electrode 30 and the drain electrode 40.
  • the conductive material according to the present invention can be used as a constituent material of the organic semiconductor layer 50.
  • the conductive material according to the present invention is useful for forming an organic semiconductor layer 50 because it is possible to impart good semiconductivity to the polymer by appropriately setting the chemical structure of the group Y.
  • a polymer of the compound represented by the general formula (Al) in which the group Y has a chemical structure represented by the chemical formula (D2), (D3), (D16), (D17), or (D20) is preferably selected.
  • the thickness of the organic semiconductor layer 50 is preferably in the range of about 0.1 to 1,000 nm, more preferably in the range of about 1 to 500 nm, and even more preferably in the range of about 10 to 100 nm.
  • the thickness of the organic semiconductor layer 50 is preferably in the range of about 0.1 to 1,000 nm, more preferably in the range of about 1 to 500 nm, and even more preferably in the range of about 10 to 100 nm.
  • the organic semiconductor layer 50 is not limited to one provided so as to cover the source electrode 30 and the drain electrode 40.
  • the organic semiconductor layer 50 should be provided in at least the region between the source electrode 30 and the drain electrode 40 (that is, in at least the channel region 510) .
  • the gate insulating layer 60 is provided on the organic semiconductor layer 50.
  • the gate insulating layer 60 is provided to insulate the gate electrode 70 from the source electrode 30 and the drain electrode 40.
  • the gate insulating layer 60 is preferably formed using an organicmaterial (especially, an organic polymericmaterial) as its main material.
  • an organic polymeric material especially, an organic polymericmaterial
  • organic polymeric material include polystyrene, polyimide, polyamideimide, polyvinylphenylene, polycarbonate.
  • PC polymethylmethacrylate
  • PTFE polytetrafluoroethylene
  • phenolic resins such as polyvinyl phenol and novola ⁇ resins
  • olefin-based resins such as polyethylene, polypropylene, polyisobutylene, and polybutene.
  • the thickness of the gate insulating layer 60 is not particularly limited, but is preferably in the range of about 10 to 5,000 nm, more preferably in the range of about 100 to 1,000 nm. By setting the thickness of the gate insulating layer 60 to a value within the above range, it is possible to prevent the size of the organic TFT 10 frombeing increased (especially, an increase in thickness of the organic TFT 10) while reliably insulating the gate electrode 70 from the source electrode 3 and the drain electrode 40.
  • the gate insulating layer 60 is not limited to one comprised of a single layer and may have two or more layers.
  • the gate electrode 70 is provided on the gate insulating layer 60.
  • constituent materials of the gate electrode 70 the same constituent materials that have been mentioned with reference to the source electrode 30 and the drain electrode 40 can be used.
  • the thickness of the gate electrode 70 is not particularly limited, but is preferably in the range of about 0.1 to 5,000 nm, more preferably in the range of about 1 to 5,000 nm, even more preferably in the range of about 10 to 5,000 nm.
  • the amount of current flowing between the source electrode 30 and the drain electrode 40 is controlled by changing voltage applied to the gate electrode 70.
  • FIGs. 3 and 4 are drawings (cross-sectional views) to be used for explaining a manufacturing method of the organic TFT 10 shown in FIG. 2. It is to be noted that, in the following description, the upper side and lower side in FIGs. 3 and 4 will be referred to as the "upper side” and the “lower side", respectively.
  • a substrate 20 as shown in FIG. 3 (a) is prepared.
  • the substrate 20 is washed with, for example, water (e.g. , pure water) and/or organic solvents.
  • Water and organic solvents may be used singly or in combination of two or more of them.
  • a photoresist is supplied onto the substrate 20 to form a film 80' (see FIG. 3 (b)).
  • a photoresist to be supplied onto the substrate 20 either a negative-type photoresist or a positive-type photoresist may be used.
  • the negative-type photoresist an area irradiated with light (that is, an area exposed to light) is cured and then an area other than the area exposed to light is dissolved by development to be removed.
  • the positive-type photoresist an area exposed to light is dissolved by development to be removed.
  • Examples of such a negative-type photoresist include water-soluble photoresists such as rosin-dichromate. polyvinyl alcohol (PVA) -dichromate, shellac-dichromate, casein-di ⁇ hromate, PVA-diazo, and acrylic photoresists and oil-soluble photoresists such as polyvinyl cinnamate, cyclized rubber-azide,. polyvinyl cinnamylidene acetate, and polycinnamic acid ⁇ -vinyloxyethyl ester.
  • water-soluble photoresists such as rosin-dichromate. polyvinyl alcohol (PVA) -dichromate, shellac-dichromate, casein-di ⁇ hromate, PVA-diazo, and acrylic photoresists and oil-soluble photoresists such as polyvinyl cinnamate, cyclized rubber-azide,. polyviny
  • Examples of a positive-type photoresist include oil-soluble photoresists such as o-naphthoquinonediazide.
  • Any method can be used for supplying a photoresist onto the substrate 20, but various application methods are preferably employed.
  • the film 80' is exposed to light through a photomask and is then developed to form a resist layer 80 having openings 820 where a source electrode 30 and a drain electrode 40 are to be formed (see FIG. 3(C)).
  • a predetermined amount of a liquid material 90 containing a constituent material of a source electrode 30 and a drain electrode 40 to be formed or a precursor thereof is supplied to the openings 820 provided on the substrate 20.
  • solvents or dispersion media in which a constituent material of a source electrode 30 and a drain electrode 40 or a precursor thereof is dissolved or dispersed for preparing a liquid material 90 the same solvents or dispersion media that have been mentioned with reference to the step of forming hole transport layer [A2] can be used.
  • an inkjet method that is, a liquid droplet ejecting method
  • a liquid droplet ejecting method By employing the inkjet method, it is possible to eject the liquid material 90 in the form of liquid droplets from a nozzle of a liquid droplet ejecting head, thereby enabling the liquid material 90 to be reliably supplied to the openings 820. As a result, adhesion of the liquid material 90 to the resist layer 80 is reliably prevented.
  • the solvent or dispersion medium contained in the liquid material 90 supplied to the openings 820 is removed to form a source electrode 30 and a drain electrode 40.
  • the temperature at which the solvent or dispersion medium is removed is not particularly limited, and slightly varies depending on the kind of solvent or dispersion medium used. However, the temperature at which the solvent or dispersion medium is removed is preferably in the range of about 20 to 200 0 C, more preferably in the range of about 50 to 100°C. By removing the solvent or dispersion medium at a temperature within the above range, it is possible to reliably remove the solvent or dispersion medium from the liquid material 90.
  • the solvent or dispersion medium contained in the liquid material 90 may be removed by heating under reduced pressure. By doing so, it is possible to more reliably remove the solvent or dispersion medium from the liquid material 90.
  • the resist layer 80 provided on the substrate 20 is removed to obtain the substrate 20 on which the source electrode 30 and the drain electrode 40 are formed (see FIG. 4(a)).
  • Amethod for removing the resist layer 80 is appropriately selected depending on the kind of resist layer 80.
  • ashing such as plasma treatment or ozone treatment, irradiation with ultraviolet rays, or irradiation with a laser such as a Ne-He laser, an Ar laser, a CO 2 laser, a ruby laser, a semiconductor laser, a YAG laser, a glass laser, a YVO 4 laser, or an excimer laser may be carried out.
  • the resist layer 80 may removed by being brought into contact with a solvent capable of dissolving or decomposing the resist layer 80 by, for example, immersing the resist layer 80 in such a solvent.
  • an organic semiconductor layer 50 is formed on the substrate 20 so as to cover the source electrode 30 and the drain electrode 40 provided on the substrate 20.
  • a channel region 510 is formed between the source electrode 30 and the drain electrode 40 (that is, in an area corresponding to an area where a gate electrode 70 is to be formed) .
  • the organic semiconductor layer 50 can be formed using the composition for conductive materials according to the present invention by the same method that has been described with reference to the step of forming the hole transport layer [A2] in the manufacturing method of the organic EL device 1.
  • the organic semiconductor layer 50 is formed using the conductive material (that is, the polymer) according to the present invention as its main material. Therefore, when a gate insulating layer material is supplied onto the organic semiconductor layer 50 in the next step [B3], swelling and dissolution of the polymer due to a solvent or dispersion medium contained in the gate insulating layer material is properly inhibited or prevented. As a result, mutual dissolution between the organic semiconductor layer 50 and a gate insulating layer 60 is reliably prevented.
  • the conductive material that is, the polymer
  • an organic semiconductor layer 50 By forming an organic semiconductor layer 50 using a polymer such as the conductive material according to the present invention as its main material, it is possible to reliably prevent the mixing of the constituent materials of the organic semiconductor layer 50 and the gate insulating layer 60 from occurring near the boundary between these layers 50 and 60 with the lapse of time.
  • a gate insulating layer 60 is formed on the organic semiconductor layer 50 by an application method.
  • the gate insulating layer 60 can be formed by applying or supplying a solution containing an insulating material or a precursor thereof onto the organic semiconductor layer 50 by the application method described above.
  • the thus obtained layer is subjected to aftertreatment such as heating, irradiationwith infraredrays, or exposure to ultrasound.
  • a gate electrode 70 is formed on the gate insulating layer 60 by an application method.
  • the gate electrode 70 can be formed by applying or supplying a solution containing an electrode material or a precursor thereof onto the gate insulating layer 60 bythe applicationmethod.
  • the thus obtained layer is subjected to aftertreatment such as heating, irradiation with infrared rays, or exposure to ultrasound.
  • an inkjet method is preferably employed.
  • the inkjet method it is possible to eject a solution containing an electrode material or a precursor thereof in the form of liquid droplets from a nozzle of a liquid droplet ejecting head to carry out patterning.
  • a gate electrode 70 having a predetermined shape is easily and reliably formed on the gate insulating layer 60.
  • the organic TFT 10 is manufactured through the steps described above.
  • the electronic devices according to the present invention such as the organic EL device (which is a light emitting device) 1 and the organic TFT (which is a switching element) 10 as described above can be used for various electronic equipment.
  • FIG. 5 is a perspective view which shows the structure of a personal mobile computer (or a personal notebook computer) to which the electronic equipment according to the present invention is applied.
  • a personal computer 1100 is comprised of a main body 1104 provided with a keyboard 1102 and a display unit 1106 provided with a display.
  • the display unit 1106 is rotatably supported by the main body 1104 via a hinge structure.
  • the display unit 1106 includes the organic EL device (which is a light emitting device) 1 and the organic TFT (which is a switching element) 10 described above.
  • FIG. 6 is a perspective view which shows the structure of a mobile phone (including the personal handyphone system (PHS)) to which the electronic equipment according to the present invention is applied.
  • PHS personal handyphone system
  • the mobile phone 1200 shown in FIG. 6 includes a plurality of operation buttons 1202, an earpiece 1204, a mouthpiece 1206, and a display.
  • the display includes the organic EL device (which is a light emitting device) 1 and the organic TFT (which is a switching element) 10 described above.
  • FIG. 7 is a perspective view which shows the structure of a digital still camera to which the electronic equipment according to the present invention is applied. In this drawing, interfacing to external devices is simply illustrated.
  • an image pickup device such as a CCD (Charge Coupled Device) generates an image pickup signal (or an image signal) by photoelectric conversion of the optical image of an object.
  • CCD Charge Coupled Device
  • a display which provides an image based on the image pickup signal generated by the CCD. That is, the display functions as a finder which displays the object as an electronic image.
  • the display includes the organic EL device (which is a light emitting device) 1 and the organic TFT (which is a switching element) 10 described above.
  • the circuit board 1308 has a memory capable of storing an image pickup signal.
  • a light receiving unit 1304 including an optical lens (an image pickup optical system) and a CCD.
  • an image pickup signal generated by the CCD at that time is transferred to the memory in the circuit board 1308 and then stored therein.
  • a video signal output terminal 1312 and an input-output terminal for data communication 1314 there are provided a video signal output terminal 1312 and an input-output terminal for data communication 1314.
  • a television monitor 1430 and a personal computer 1440 are connected to the video signal output terminal 1312 and the input-output terminal for data communication 1314, respectively.
  • an image pickup signal stored in the memory of the circuit board 1308 is outputted to the television monitor 1430 or the personal computer 1440 by carrying out predetermined operation.
  • the electronic equipment according to the present invention can be applied not only to the personal computer (which is apersonalmobile computer) shown in FIG.5, the mobile phone shown in FIG. 6, and the digital still camera shown in FIG. 7 but also to a television set, a video ' camera, a view-finer or monitor type of video tape recorder, a laptop-type personal computer, a car navigation device, a pager, an electronic notepad (which may have communication facility) , an electronic dictionary, an electronic calculator, a computerized game machine, a word processor, a workstation, a videophone, a security television monitor, an electronic binocular, a POS terminal, an apparatus providedwith a touch panel (e.g., a cash dispenser located on a financial institute, a ticket vending machine), medical equipment (e.g., an electronic thermometer, a sphygmomanometer, a blood glucose meter, an electrocardiograph monitor, ultrasonic diagnostic equipment, an endoscope monitor), a fish detector, various measuring instruments, gages (e
  • composition for conductive materials, the conductive material, the conductive layer, the electronic device, and the electronic equipment according to the present invention have been described based on the embodiments shown in the drawings, but the present invention is not limited thereto.
  • the electronic device according to the present invention has a hole transport layer as a conductive layer
  • such an electronic device can be used for, for example, a solar cell that is an example of light receiving devices (or photoelectric transducers) as well as the organic EL device as described above that is an example of display devices (or light emitting devices) .
  • the electronic device according to the present invention has an organic semiconductor layer as a conductive layer
  • such an electronic device can be used for, for example, a semiconductor device as well as the organic TFT as described above that is an example of switching elements.
  • the conductive layer according to the present invention can be used as, for example, wiring or an electrode as well as the hole transport layer as described above.
  • a resultant electronic device according to the present invention can be used for a wiring board and the like.
  • 6-(p-aminophenyl)he ⁇ anol was treated with 4-methoxybenzylbromide and sodium hydride in anhydrous dimethylformamide to transformhydroxy1 group into benzyl ether group and then it was protected.
  • 6-(p-bromophenyl)hexanol was subjected to the same treatment as that for 6-(p-aminophenyl)hexanol to transform hydroxyl group into benzyl ether group and then it was protected to obtain a dry substance (benzyl ether derivative) .
  • the thus obtained compound was reduced by hydrogen gas under Pd-C catalyst so that transformation was made from the benzyl ether group to the hydroxyl group to carry out deprotection.
  • the thus obtained compound was confirmed to be the following compound (AI) bymeans of amass spectrum (MS) method, a ⁇ -nuclear magnetic resonance ( 1 H-NMR) spectrum method, a 13 C-nuclear magnetic resonance ( 13 C-NMR) spectrum method, and a Fourier transform infrared absorption (FT-IR) spectrum method.
  • MS amass spectrum
  • 1 H-NMR ⁇ -nuclear magnetic resonance
  • 13 C-NMR 13 C-nuclear magnetic resonance
  • FT-IR Fourier transform infrared absorption
  • a compound (BI) was obtained in the same manner as the compound (AI) except that 4,4' -diiodobiphenyl was changed to 4,4' -diiodo-2,2' -dimethylbiphenyl.
  • a compound (CI) was obtained in the same manner as the compound (AI) except that 6-(p-aminophenyl)hexanolwas changed to 2-(p-aminophenyl)ethanol and 6-(p-bromophen ⁇ l)hexanol was changed to 2-(p-bromophenyl)ethanol, respectively.
  • a compound (EI) was obtained in the same manner as the compound (AI) except that 6-(p-aminophenyl)hexanol was changed to 8- (p-aminophenyl)octanol and 6-(p-bromophenyl)hexanol was changed to 8-(p-bromophenyl)octanol, respectively.
  • a compound (FI) was obtained in the same manner as the compound (AI) except that 6- (p-aminophenyl)hexanol was changed to 8-(p-aminophenyl)octanol.
  • a compound (GI) was obtained in the same manner as the compound (AI) except that 6-(p-aminophenyl)hexanol was changed to l-(p-aminophenyl)methanol and 6-(p-bromophenyl)hexanol was changed to l-(p-bromophenyl)methanol, respectively.
  • a compound (All) was obtained in the same manner as the compound (AI) except that 4,4 ' -diiodobiphenyl was changed to 2,5-bis(4-iodophenyl) -thiophene.
  • a compound (BII) was obtained in the same manner as the compound (All) except that 2,5-bis(4-iodophen ⁇ l) -thiophene was changed to 2,5-bis(2-methyl-4-iodophenyl) -thiophene.
  • a compound (CII) was obtained in the same manner as the compound (All) except that 6-(p-aminophenyl)hexanol was changed to 2-(p-aminophenyl)ethanol and 6-(p-bromophenyl)hexanol was changed to 2-(p-bromophenyl)ethanol, respectively.
  • a compound (DII) was obtained in the same manner as the compound (CII) except that 2-(p-aminophen ⁇ l)ethanol was changed to 2- (2' ,6' -dimethyl-4' -aminophenyl)ethanol.
  • a compound (EII) was obtained in the same manner as the compound (All) except that 6-(p-aminophenyl)hexanol was changed to 8-(p-aminophenyl)octanol and 6-(p-bromophenyl)hexanol was changed to 8-(p-bromophenyl)octanol, respectively.
  • a compound (FII) was obtained in the same manner as the compound (All) except that 6- (p-aminophenyl)hexanol was changed to 8- (p-aminophenyl)octanol.
  • a compound (GII) was obtained in the same manner as the compound (All) except that 6-(p-aminophenyl)hexanol was changed . to l-(p-aminophenyl)methanol and 6-(p-bromophenyl)hexanol was changed to 1-(p-bromophenyl)methanol, respectively.
  • a compound (HII) was obtained in the same manner as the compound (All) except that 2,5-bis(4-iodophenyl) -thiophene was changed to
  • a compound (III) was obtained in the same manner as the compound (All) except that 2,5-bis(4-iodophenyl)-thiophene was changed to 3,5-diiodo-l,2,4-triazole.
  • a compound (KII) was obtained in the same manner as the compound (All) except that 2,5-bis(4-iodophenyl)-thxophene was changed to 3,3' -diiodo-1,1' -biisobenzothiophene.
  • a compound (LII) was obtained in the same manner as the compound (KII) except that 6-(p-aminophenyl)hexanol was changed to 2-(p-aminophenyl)ethanol and 6-(p-bromophenyl)hexanol was changed to 2-(p-bromophenyl)ethanol, respectively.
  • a compound (Mil) was obtained in the same manner as the compound (KII) except that 6- (p-aminophenyl)hexanol was changed to 8- (p-aminophenyl)octanol and 6-(p-bromophenyl)hexanol was changed to 8-(p-bromophenyl)octanol, respectively.
  • a compound (Nil) was obtained in the same manner as the compound (KII) except that 6- (p-aminophenyl)hexanol was changed to 8-(p-aminophenyl)octanol.
  • a compound (Oil) was obtained in the same manner as the compound (KII) except that 6-(p-aminophen ⁇ l)hexanol was changed to 1-(p-aminophenyl)methanol and 6-(p-bromophenyl)hexanol was changed to 1-(p-bromophenyl)methanol, respectively.
  • a compound (PII) was obtained in the same manner as the compound (All) except that 2,5-bis(4-iodophenyl) -thiophene was changed to
  • the obtained compound was found to be the following compound (SII) by means of a mass spectrum (MS) method, a 1 H-nuclear magnetic resonance ( 1 H-NMR) spectrum method, a 13 C-nuclear magnetic resonance ( 13 C-NMR) spectrum method, and a Fourier transform infrared absorption (FT-IR) spectrum method.
  • MS mass spectrum
  • 1 H-NMR 1 H-nuclear magnetic resonance
  • 13 C-NMR 13 C-nuclear magnetic resonance
  • FT-IR Fourier transform infrared absorption
  • a compound (UII) was obtained in the same manner as the compound (SII) except that 2,5-bis(4-iodophenyl) -thiophene was changed to 3,5-diiodo-l,2,4-triazole.
  • the compound (AI) was used as an arylamine derivative, and the compound (AI) and a cationic photopolymerization initiator ("FC-508" producedby Sumitomo 3MLimited) in aweight ratio of 99:1 were mixed with dichloroethane to obtain a hole transport material (that is, a composition for conductive materials) .
  • an ITO electrode that is, an anode
  • a transparent glass substrate having an average thickness of 0.5 mmbyvacuumevaporation so as to have an average thickness of 100 nm.
  • the hole transport material was applied onto the ITO electrode by a spin coating method, and was then dried.
  • the hole transport material was irradiated with ultraviolet rays having a wavelength of 365 nm from a mercury lamp ("UM-452", USHIO Inc.) through a filter at an intensity of irradiation of 500 mW/cm 2 for 15 seconds in the dry atmosphere and then heated for 60 minutes at temperature of 110°C to polymerize the compound (AI), so that a hole transport layer having an average thickness of 50 nm was formed.
  • UM-452 ultraviolet rays having a wavelength of 365 nm from a mercury lamp ("UM-452", USHIO Inc.) through a filter at an intensity of irradiation of 500 mW/cm 2 for 15 seconds in the dry atmosphere and then heated for 60 minutes at temperature of 110°C to polymerize the compound (AI), so that a hole transport layer having an average thickness of 50 nm was formed.
  • an electron transport layer having an average thickness of 20 nm was formed on the light emitting layer by a vacuum evaporation of 3,4,5-triphenyl-l,2,4-triazole.
  • an AlLi electrode that is, a cathode
  • an AlLi electrode that is, a cathode
  • a protection cover made of polycarbonate was provided so as to cover these layers described above, and was then secured and sealed with an ultraviolet curable resin to obtain an organic EL device.
  • Organic EL devices were manufactured in the same manner as in Example IA except that the hole transport material prepared in the step 2A was used and the irradiation of ultraviolet rays from the mercury lamp was omitted.
  • the compound (TII) was dispersed in water to prepare a
  • Organic EL devices were manufactured in the same manner as in Comparative Example IA except that the hole transport material was changed to the hole transport material prepared in this Comparative Example 2A.
  • the compound (HI) was used as an afylamine derivative, and a bifunctional epoxy compound ("DENACOL EX-212" produced by Nagase chemteX Corporation) was used as a photocrosslinking agent, and the compound (HI) , the epoxy compound and a cationic photopolymerization initiator ("FC-508" produced by Sumitomo 3M Limited) in a weight ratio of 50:49:1 were mixed with dichloroethane to obtain a hole transport material.
  • a bifunctional epoxy compound (“DENACOL EX-212" produced by Nagase chemteX Corporation) was used as a photocrosslinking agent
  • FC-508 cationic photopolymerization initiator
  • Organic EL devices were manufactured in the same manner as in Comparative Example IA except that the hole transport material was changed to the hole transport material prepared in this Comparative Example 3A.
  • Organic EL devices were manufactured after a hole transport material was prepared in the same manner as in Example IA except that the compound (GI) was used as an arylamine derivative.
  • Example IB preparation of hole transport material>
  • the compound (AI) was used as an arylamine derivative, a bisphenol A epoxy compound represented by the above-mentioned chemical formula (B2) (where n 6 is 0 to 1) (hereinafter, this cross-linking agent will be referred to as "cross-linking agent B2") was used as an epoxy-based cross-linking agent, and a cationic photopolymerization initiator ("FC-508" produced by Sumitomo 3M Limited) was used as a photopolymerization initiator, and then they were dissolved with dichloroethane to obtain a hole transport material (that is, a composition for conductive materials) .
  • a hole transport material that is, a composition for conductive materials
  • the mixing ratio of the compound (AI) and the cross-linking agent B2 was 3:1 in a mole ratio, and the weight ratio of the total weight of the compound (AI) and the cross-linking agent B2 with respect to the cationic photopolymerization initiator was 99:1.
  • an ITO electrode that is, an anode
  • a transparent glass substrate having an average thickness of 100 nm in the same manner as the step IA described above.
  • the prepared hole transport material was applied onto the ITO electrode by a spin coating method, and was then dried.
  • the hole transport material was irradiated with ultraviolet rays having a wavelength of 365 nm from a mercury lamp ("UM-452", USHIO Inc.) through a filter at an intensity of irradiation of 400 mW/cm 2 for 10 seconds in the dry atmosphere and then heated for 60 minutes at temperature of 110 0 C to polymerize the compound (AI) and the cross-linking agent B2, so that a hole transport layer having an average thickness of 50 nm was formed.
  • UM-452 ultraviolet rays having a wavelength of 365 nm from a mercury lamp ("UM-452", USHIO Inc.) through a filter at an intensity of irradiation of 400 mW/cm 2 for 10 seconds in the dry atmosphere and then heated for 60 minutes at temperature of 110 0 C to polymerize the compound (AI) and the cross-linking agent B2, so that a hole transport layer having an average thickness of 50 nm was formed.
  • an AlLi electrode that is, a cathode having an average thickness of 300. nm was formed on the electron transport layer in the same manner as the step 5A described above.
  • a protection cover made of polycarbonate was provided so as to cover these layers described above, and was then secured and sealed in the same manner as the step 6A described above to obtain an organic EL device.
  • Organic EL devices were manufactured after a hole transport material was prepared in the same manner as in Example IB except that a biphenyl epoxy compound represented by the above-mentioned chemical formula (B4) (where n 6 is 0 to 2) was used instead of the cross-linking agent B2.
  • B4 a biphenyl epoxy compound represented by the above-mentioned chemical formula (B4) (where n 6 is 0 to 2) was used instead of the cross-linking agent B2.
  • Organic EL devices were manufactured after a hole transport material was prepared in the same manner as in Example IB except that the compound (BI) was used as an arylamine derivative and that a bisphenol S epoxy compound represented by the above-mentioned chemical formula (B5) (where n 6 is 0 to 1) was used instead of the cross-linking agent B2.
  • Organic EL devices were manufactured after a hole transport material was prepared in the same manner as in Example IB except that the compound (BI) was used as an arylamine derivative and that a bisphenylether epoxy compoundrepresented by the above-mentioned chemical formula (B6) (where n 6 is 0) was used instead of the cross-linking agent B2.
  • Organic EL devices were manufactured after a hole transport material was prepared in the same manner as in Example IB except that the compound (CI) was used as an arylamine derivative and that a glycidyl ester-based phthalic acid epoxy compound represented by the above-mentioned chemical formula (B8) was used instead of the cross-linking agent B2.
  • Organic EL devices were manufactured after a hole transport material was prepared in the same manner as in Example IB except that the compound (CI) was used as an arylamine derivative and that an alicyclic epoxy compound represented by the above-mentioned chemical formula (B9) was used instead of the cross-linking agent B2.
  • Organic EL devices were manufactured after a hole transport material was prepared in the same manner as in Example IB except that the compound (CI) was used as an arylamine derivative and that an urethane modified epoxy compound represented by the above-mentioned chemical formula (B13) (where A 2 represents a group obtained by eliminating two isocyanate groups from tolylene diisocyanate and two A 2 S represent a group obtained by eliminating two hydroxyl groups from ethylene glycol) was used instead of the cross-linking agent B2.
  • Organic EL devices were manufactured after a hole transport material was prepared in the same manner as in Example IB except that the compound (DI) was used as an arylamine derivative and that a silicon-containing epoxy compound represented by the above-mentioned chemical formula (B14) was used instead of the cross-linking agent B2.
  • Organic EL devices were manufactured after a hole transport material was prepared in the same manner as in Example IB except that the compound (DI) was used as arylamine derivative and that an acrylic ester compound represented by the above-mentioned chemical formula (Bl) (where A 1 is hydrogen atom) was used instead of the cross-linking agent B2.
  • Organic EL devices were manufactured after a hole transport material was prepared in the same manner as in Example IB except that the compound (DI) was used as an arylamine derivative and that a polyfunctional phenol-based epoxy compound represented by the above-mentioned chemical formula (B15) (where n 9 is 2 to 5) was used instead of the cross-linking agent B2.
  • the compound (DI) was used as an arylamine derivative and that a polyfunctional phenol-based epoxy compound represented by the above-mentioned chemical formula (B15) (where n 9 is 2 to 5) was used instead of the cross-linking agent B2.
  • Organic EL devices were manufactured after a hole transport material was prepared in the same manner as in Example IB except that the compound (EI) was used as an arylamine derivative and that a polyparaphenylenevinylene(PPV) -based epoxy compound represented by the above-mentioned chemical formula (B18) (where n 10 is 5 to 10) was used instead of the cross-linking agent B2.
  • the compound (EI) was used as an arylamine derivative and that a polyparaphenylenevinylene(PPV) -based epoxy compound represented by the above-mentioned chemical formula (B18) (where n 10 is 5 to 10) was used instead of the cross-linking agent B2.
  • Organic EL devices were manufactured after a hole transport material was prepared in the samemanner as in Example IB except that the compound (EI) was used as an arylamine derivative and that a polyfunctional phenol-based epoxy compound represented by the above-mentioned chemical formula (B19) was used instead of the cross-linking agent B2.
  • Organic EL devices were manufactured after a hole transport material was prepared in the samemanner as in Example IB except that the compound (EI) was used as an arylamine derivative and that a glycidyl amine-based epoxy compound represented by the above-mentioned chemical formula (B23) was used instead of the cross-linking agent B2.
  • Organic EL devices were manufactured after a hole transport material was prepared in the samemanner as in Example IB except that the compound (FI) was used as an arylamine derivative and that a mixture of a bisphenol A epoxy compound representedbythe above-mentionedchemical formula (B2) (where n 6 is 0 to 3) and a glycidyl ester-based dimmer acid epoxy compound represented by the above-mentioned chemical formula (B7) was used instead of the cross-linking agent B2.
  • the compound (FI) was used as an arylamine derivative
  • a mixture of a bisphenol A epoxy compound representedbythe above-mentionedchemical formula (B2) (where n 6 is 0 to 3) and a glycidyl ester-based dimmer acid epoxy compound represented by the above-mentioned chemical formula (B7) was used instead of the cross-linking agent B2.
  • Organic EL devices were manufactured after a hole transport material was prepared in the same manner as in Example IB except that the compound (FI) was used as an arylamine derivative and that a mixture of a bisphenol A epoxy compound representedby the above-mentioned chemical formula (B2) (where n 6 is 0 to 1) and a polyfunctional phenol-based epoxy compound represented by the above-mentioned chemical formula (B19) was used instead of the cross-linking agent B2.
  • Organic EL devices were manufactured after a hole transport material was prepared in the same manner as in Example IB except that the addition of the cross-liking agent B2 to the hole transport material was omitted and that the arylamine derivatives for use in the hole transport material were changed to those shown in Table 2.
  • Organic EL devices were manufactured in the same manner as in Comparative Example IA except that the hole transport material was changed to the hole transport material prepared in this Comparative Example 3B.
  • Organic EL devices were manufactured after a hole transport material was prepared in the same manner as in Example IB except that the compound (HI) was used as an arylamine derivative.
  • Organic EL devices were manufactured after a hole transport material was prepared in the same manner as in Example IB except that the compound (AI) was used as an arylamine derivative.
  • Example 1C preparation of hole transport material>
  • the compound (All) was used as an arylamine derivative, and the compound (All) and a cationic photopolymerization initiator ("FC-508" producedby Sumitomo 3MLimited) in aweight ratio of 99:1 were mixed with dichloroethane to obtain a hole transport material (that is, a composition for conductive materials) .
  • an ITO electrode that is, an anode
  • a transparent glass substrate having an average thickness of 100 nm in the same manner as the step IA described above.
  • the prepared hole transport material was applied onto the ITO electrode by a spin coating method, and was then dried.
  • the hole transport material was irradiated with ultraviolet rays having a wavelength of 365 nm from a mercury lamp ("UM-452", USHIO Inc.) through a filter at an intensity of irradiation of 500mW/cm 2 for 15 seconds in dry atmosphere and then heated for 60 minutes at temperature of 110 0 C to polymerize the compound (All), so that a hole transport layer having an average thickness of 50 nm was formed.
  • a mercury lamp "UM-452", USHIO Inc.
  • a light emitting layer having an average thickness of 50 nm was formed on the hole transport layer in the same manner as the step 3A described above.
  • an electron transport layer having an average thickness of 20 nm was formed on the light emitting layer by the polymerization of the compound (III) in the same manner as the step 2C described above except that the prepared electron transport material was used instead of the hole transport material.
  • an AlLi electrode (that is, a cathode) having an average thickness of 300 nm was formed on the electron transport layer in the same manner as the step 5A described above.
  • a protection cover made of polycarbonate was provided so as to cover these layers described above, and was then secured and sealed in the same manner as the step 6A described above to obtain an organic EL device.
  • a hole transport material was obtained by dissolving the compound (SII) in dichloroethane.
  • Organic EL devices were manufactured in the same manner as in Example 1C except that a hole transport layer was formed using the prepared hole transport material but omitting the irradiation of ultraviolet rays at the step 2C and that an electron transport layer was formed using the compound (UII) by vacuum evaporation at the step 4C.
  • a hole transport layer was formed using the prepared hole transport material but omitting the irradiation of ultraviolet rays at the step 2C and that an electron transport layer was formed using the compound (UII) by vacuum evaporation at the step 4C.
  • the compound (TII) was dispersed in water to prepare a
  • Organic EL devices were manufactured in the same manner as in Comparative Example 1C except that the hole transport material was changed to the hole transport material prepared in this Comparative Example.
  • the compound (SII) was used as an arylamine derivative, and a bifunctional epoxy compound ("DENACOL EX-212" produced by Nagase chemteX Corporation) was used as a photocrosslinking agent, and the compound (SII) , the epoxy compound and a cationic photopolymerization initiator ("FC-508" produced by Sumitomo 3M Limited) in a weight ratio of 50:49:1 were mixed with dichloroethane to obtain a hole transport material.
  • a bifunctional epoxy compound (“DENACOL EX-212" produced by Nagase chemteX Corporation) was used as a photocrosslinking agent
  • FC-508 cationic photopolymerization initiator
  • Organic EL devices were manufactured in the same manner as in Comparative Example 1C except that the hole transport material was changed to the hole transport material prepared in the above-mentioned step 2C and that an electron transport layer was formed using the compound (UII) by vacuum evaporation in the step 4C.
  • the hole transport material was changed to the hole transport material prepared in the above-mentioned step 2C and that an electron transport layer was formed using the compound (UII) by vacuum evaporation in the step 4C.
  • Organic EL devices were manufactured after a hole transport material was prepared in the same manner as in Example 3C except that the compound (GII) was used as an arylamine derivative for use in the hole transport material.
  • Example ID preparation of hole transport material>
  • the compound (All) was used as an arylamine derivative
  • the cross-linking agent B2 was used as an epoxy-based cross-linking agent
  • a cationic photopolymerization initiator (“FC-508" produced by Sumitomo 3M Limited) was used as aphotopolimerization initiator, respectively, and then they were mixed with dichloroethane to obtain a hole transport material (that is, a composition for conductive materials).
  • the mixing ratio of the compound (All) and the cross-linking agent B2 was 3:1 in a mole ratio, and the weight ratio of the total weight of the compound (All) and the cross-linking agent B2 with respect to the cationic photopolymerization initiator was 99:1.
  • An electron transport material (that is, a composition for conductive materials) was obtained in the same manner as the hole transport material prepared in this Example except that the compound (III) was used as an arylamine derivative.
  • an ITO electrode that is, an anode having an average thickness of 100 nm was formed on a transparent glass substrate in the same manner as the step IA described above.
  • the hole transport material was applied onto the ITO electrode by a spin coating method, " and was then dried.
  • the hole transport material was irradiated with ultraviolet rays having a wavelength of 365 nm from a mercury lamp ("UM-452", USHIO Inc.) through a filter at an intensity of irradiation of 400 mW/cm 2 for 10 seconds in dry atmosphere and then heated for 60 minutes at temperature of 110 0 C to polymerize the compound (All) and the cross-linking agent B2, so that a hole transport layer having an average thickness of 50 nm was formed.
  • UM-452 ultraviolet rays having a wavelength of 365 nm from a mercury lamp ("UM-452", USHIO Inc.) through a filter at an intensity of irradiation of 400 mW/cm 2 for 10 seconds in dry atmosphere and then heated for 60 minutes at temperature of 110 0 C to polymerize the compound (All) and the cross-linking agent B2, so that a hole transport layer having an average thickness of 50 nm was formed.
  • a light emitting layer having an average thickness of 50 nm was formed on the hole transport layer in the same manner as the step 3A described above.
  • an electron transport layer having an average thickness of 20 nm was formed on the light emitting layer by polymerizing the compound (III) and the cross-linking agent B2 in the same manner as the step 2D described above except that the prepared electron transport material was used instead of the hole transport material.
  • an AlLi electrode that is, a cathode was formed on the electron transport layer so as to have an average thickness of 300 nm in the same manner as the step 5A described above.
  • a protection cover made of polycarbonate was provided so as to cover these layers described above, and was then secured and sealed with an ultraviolet curable resin to obtain an organic EL device.
  • Organic EL devices were manufactured after a hole transport material and an electron transport material were prepared in the same manner as in Example ID except that a bisphenol F epoxy compound represented by the above-mentioned chemical formula (B3) (where n 6 is 0 to 1) was used as an epoxy-based cross-linking agent for use in the hole transport material and the electron transport material.
  • B3 bisphenol F epoxy compound represented by the above-mentioned chemical formula (B3) (where n 6 is 0 to 1) was used as an epoxy-based cross-linking agent for use in the hole transport material and the electron transport material.
  • Example 20D Organic EL devices were manufactured after a hole transport material and an electron transport material were prepared in the same manner as in Example ID except that a biphenyl epoxy compound represented by the above-mentioned chemical formula (B4) (where n 6 is 0 to 2) was used as an epoxy-based cross-linking agent for use in the hole transport material and the electron transport material.
  • B4 a biphenyl epoxy compound represented by the above-mentioned chemical formula (B4) (where n 6 is 0 to 2) was used as an epoxy-based cross-linking agent for use in the hole transport material and the electron transport material.
  • Organic EL devices were manufactured after a hole transport material and an electron transport material were prepared in the same manner as in Example ID except that a bisphenol S epoxy compound represented by the above-mentioned chemical formula (B5) (where n 6 is 0 to 1) was used as an eppxy-based cross-linking agent for use in the hole transport material and the electron transport material.
  • B5 bisphenol S epoxy compound represented by the above-mentioned chemical formula (B5) (where n 6 is 0 to 1) was used as an eppxy-based cross-linking agent for use in the hole transport material and the electron transport material.
  • Organic EL devices were manufactured after a hole transport material and an electron transport material were prepared in the same manner as in Example ID except that a bisphenylether epoxy compound represented by the above-mentioned chemical formula (B6) (where n 6 is 0) was used as an epoxy-based cross-linking agent for use in the hole transport material and the electron transport material.
  • B6 bisphenylether epoxy compound represented by the above-mentioned chemical formula (B6) (where n 6 is 0) was used as an epoxy-based cross-linking agent for use in the hole transport material and the electron transport material.
  • Organic EL devices were manufactured after a hole transport material and an electron transport material were prepared in the same manner as in.
  • Example ID except that a glycidyl ester-based dimmer acid epoxy compound represented by the above-mentioned chemical formula (B7) was used as an epoxy-based cross-linking agent for use in the hole transport material and the electron transport material.
  • B7 a glycidyl ester-based dimmer acid epoxy compound represented by the above-mentioned chemical formula (B7) was used as an epoxy-based cross-linking agent for use in the hole transport material and the electron transport material.
  • Organic EL devices were manufactured after a hole transport material and an electron transport material were prepared in the same manner as in Example ID except that a glycidyl ester-based phthalic acid epoxy compound represented by the above-mentioned chemical formula (B8) was used as an epoxy-based cross-linking agent for use in the hole transport material and the electron transport material.
  • a glycidyl ester-based phthalic acid epoxy compound represented by the above-mentioned chemical formula (B8) was used as an epoxy-based cross-linking agent for use in the hole transport material and the electron transport material.
  • Organic EL devices were manufactured after a hole transport material and an electron transport material were prepared in the same manner as in Example ID except that an alicyclic epoxy compound represented by the above-mentioned chemical formula (B9) was used as an epoxy-based cross-linking agent for use in the hole transport material and the electron transport material.
  • an alicyclic epoxy compound represented by the above-mentioned chemical formula (B9) was used as an epoxy-based cross-linking agent for use in the hole transport material and the electron transport material.
  • Organic EL devices were manufactured after a hole transport material and an electron transport material were prepared in the same manner as in Example ID except that an urethane modified epoxy compound represented by the above-mentioned chemical formula (B13) (where A2 represents a group obtained by eliminating two isocyanate groups from tolylene diisocyanate and two A 2 S represent a group obtained by eliminating two hydroxyl groups from ethylene glycol) was used as an epoxy-based cross-linking agent for use in the hole transport material and the electron transport material.
  • B13 an urethane modified epoxy compound represented by the above-mentioned chemical formula (B13) (where A2 represents a group obtained by eliminating two isocyanate groups from tolylene diisocyanate and two A 2 S represent a group obtained by eliminating two hydroxyl groups from ethylene glycol) was used as an epoxy-based cross-linking agent for use in the hole transport material and the electron transport material.
  • Organic EL devices were manufactured after a hole transport material and an electron transport material were prepared in the same manner as in Example ID except that the compound (EII) was used as an arylamine derivative for use in the hole transport material and that a silicon-containing epoxy compound represented by the above-mentioned chemical formula (B14) was used as an epoxy-based cross-linking agent for use in the hole transport material and the electron transport material.
  • the compound (EII) was used as an arylamine derivative for use in the hole transport material and that a silicon-containing epoxy compound represented by the above-mentioned chemical formula (B14) was used as an epoxy-based cross-linking agent for use in the hole transport material and the electron transport material.
  • Organic EL devices were manufactured after a hole transport material and an electron transport material were prepared in the same manner as in Example 27D except that an acrylic ester compound represented by the above-mentioned chemical formula (Bl) (where A 1 is hydrogen atom) was used as an epoxy-based cross-linking agent for use in the hole transport material and the electron transport material.
  • Bl an acrylic ester compound represented by the above-mentioned chemical formula (Bl) (where A 1 is hydrogen atom) was used as an epoxy-based cross-linking agent for use in the hole transport material and the electron transport material.
  • Organic EL devices were manufactured after a hole transport material and an electron transport material were prepared in the same manner as in Example 27D except that a polyfunctional phenol-based epoxy compound represented by the above-mentioned chemical formula (Bl5) (where n 9 is 2 to 5) was used as an epoxy-based cross-linking agent for use in the hole transport material and the electron transport material.
  • a polyfunctional phenol-based epoxy compound represented by the above-mentioned chemical formula (Bl5) (where n 9 is 2 to 5) was used as an epoxy-based cross-linking agent for use in the hole transport material and the electron transport material.
  • Organic EL devices were manufactured after a hole transport material and an electron transport material were prepared in the same manner as in Example 27D except that a polyparaphenylenevinylene(PPV)-based epoxy compound represented by the above-mentioned chemical formula (B18) (where n 10 is 5 to 10) was used as an epoxy-based cross-linking agent for use in the hole transport material and the electron transport material.
  • a polyparaphenylenevinylene(PPV)-based epoxy compound represented by the above-mentioned chemical formula (B18) (where n 10 is 5 to 10) was used as an epoxy-based cross-linking agent for use in the hole transport material and the electron transport material.
  • Organic EL devices were manufactured after a hole transport material and an electron transport material were prepared in the same manner as in Example 27D except that a polyfunctional phenol-based epoxy compound represented by the above-mentioned chemical formula (B19) was used as an epoxy-based cross-linking agent for use in the hole transport material and the electron transport material.
  • a polyfunctional phenol-based epoxy compound represented by the above-mentioned chemical formula (B19) was used as an epoxy-based cross-linking agent for use in the hole transport material and the electron transport material.
  • Organic EL devices were manufactured after a hole transport material and an electron transport material were prepared in the same manner as in Example 27D except that a glycidyl amine-based epoxy compound represented by the above-mentioned chemical formula (B23) was used as an epoxy-based cross-linking agent for use in the hole transport material and the electron transport material.
  • a glycidyl amine-based epoxy compound represented by the above-mentioned chemical formula (B23) was used as an epoxy-based cross-linking agent for use in the hole transport material and the electron transport material.
  • Organic EL devices were manufactured after a hole transport material and an electron transport material were prepared in the same manner as in Example 27D except that a mixture of a bisphenol A epoxy compound represented by the above-mentioned chemical formula (B2) (where n 6 is 0 to 3) and a gly ⁇ idyl ester-based dimmer acid epoxy compound represented by the above-mentioned chemical formula (B7) was used as an epoxy-based cross-linking agent for use in the hole transport material and the electron transport material.
  • B2 bisphenol A epoxy compound represented by the above-mentioned chemical formula (B2) (where n 6 is 0 to 3)
  • a gly ⁇ idyl ester-based dimmer acid epoxy compound represented by the above-mentioned chemical formula (B7) was used as an epoxy-based cross-linking agent for use in the hole transport material and the electron transport material.
  • Organic EL devices were manufactured after a hole transport material and an electron transport material were prepared in the same manner as in Example 27D except that a mixture of a bisphenol A epoxy compound represented by the above-mentioned chemical formula (B2) (where n 6 is 0 to 1) and apolyfunctional phenol-basedepoxy compoundrepresentedby the above-mentioned chemical formula (Bl9) was used as an epoxy-based cross-linking agent for use in the hole transport material and the electron transport material.
  • B2 bisphenol A epoxy compound represented by the above-mentioned chemical formula (B2) (where n 6 is 0 to 1) and apolyfunctional phenol-basedepoxy compoundrepresentedby the above-mentioned chemical formula (Bl9) was used as an epoxy-based cross-linking agent for use in the hole transport material and the electron transport material.
  • the compound (All) was used as an arylamine derivative, and the compound (All) and a polycarbonate resin ("PANLITE-1250" produced by TEIJIN CHEMICALS LTD. ) in a weight ratio of 3:7 were mixed with dichloroethane to obtain a hole transport material.
  • a polycarbonate resin ("PANLITE-1250" produced by TEIJIN CHEMICALS LTD. ) in a weight ratio of 3:7 were mixed with dichloroethane to obtain a hole transport material.
  • Organic EL devices were manufactured in the same manner as in Comparative Example ID except that the hole transport material was changed to the hole transport material prepared in this Comparative Example 3D.
  • Organic EL devices were manufactured after a hole transport material and an electron transport material were prepared in the same manner as in Example ID' except that the compound (GII) was used as an arylamine derivative for use in the hole transport material and that the compound (UII) was used as an arylamine derivative for use in the electron transport material.
  • the luminous brightness (cd/m 2 ) , the maximum luminous efficiency (lm/W) , and the time that elapsedbefore the luminous brightness became half of the initial value (that is, a half-life) of each of the organic EL devices obtained in Examples andComparative Examples mentioned above weremeasured. Based on the measurement values for the five organic EL devices, an average was calculated.
  • the luminous brightness was measured by applying a voltage of 6V across the ITO electrode and the AlLi electrode.
  • Themeasurement values (that is, the luminous brightness, the maximum luminous efficiency, and the half-life) of each of the Examples IA to 6A and the Comparative Examples 2A to 4A were evaluated based on the measurement values of the Comparative Example IA according to the following four criteria, respectively.
  • the measurement values (that is, the luminous brightness, the maximum luminous efficiency, and the half-life) of each of the Examples IB to 2IB, the Examples IB' to 6B' and the Comparative Examples 2B to 8B were evaluated based on the measurement values of the Comparative Example IB according to the following four criteria, respectively.
  • each of the organic EL devices of the Examples IB to 2IB shows a tendency that the maximum luminous efficiency was improved as compared to the organic EL devices of the Examples IB 1 to 6B' .
  • Such a result suggests that in the organic EL devices of the Examples IB to 2IB the interval between the adjacent main skeletons could be maintained at a more suitable distance due to the addition of the epoxy-based cross-linking agent.
  • the organic EL devices of the Examples IB, 2B, and 3B which were formed from the hole transport material in which the compound represented by the above-mentioned general formula (Al) and the epoxy-based cross-linking agent were mixed with a particularly preferable mixing ratio show a tendency that the luminous brightness and the maximum luminous efficiency were further improved and the half-life was also further prolonged as compared to the organic EL devices of the Examples 4B and 5B.
  • compositions of the Examples whichwere formed of the compounds containing the substituents X each having an appropriate n 1 value in the general formula (A2) that is the compositions formed of the compounds containing the substituents X by which the adjacent main skeletons are allowed to exist at a suitable interval, could have more superior luminous brightness, maximum luminous efficiency, and half-life as compared to the compositions which do not have such a substituent X.
  • Themeasurement values (that is, the luminous brightness, the maximum luminous efficiency, and the half-life) of each of the Examples 1C to 14C and the Comparative Examples 2C to 4C were evaluated based on the measurement values of the Comparative Example 1C according to the following four criteria, respectively.
  • compositions of the Examples whichwere formed of the compounds containing the substituents X each having an appropriate n 1 value in the general formula (A2) that is the compositions which were formed of the compounds containing the substituents X by which the adjacent main skeletons are allowed to exist at a suitable interval, could have more superior luminous brightness, maximum luminous efficiency, and half-life as compared with the compositions which do not have such a substituent X.
  • the organic EL devices in the Examples each obtained by appropriately selecting conductive materials for respectively constituting the hole transport material and the electron transport material namely, the organic EL devices in the Examples each having a preferred combination of the hole transport layer and the electron transport layer by appropriately selecting the group Y of the compound represented by the above-mentioned general formula (Al) couldhave superior luminous brightness, maximum luminous efficiency, and half-life.
  • Themeasurement values (that is, the luminous brightness, the maximum luminous efficiency, and the half-life) of each of the Examples ID to 34D, the Examples ID' to 14D' and the Comparative Examples 2D to 7D were evaluated based on the measurement values of the Comparative Example ID according to the following four criteria, respectively.
  • each of the organic EL devices of the Examples ID to 34D shows a tendency that the maximum luminous efficiency was improved as compared to the organic EL devices of the Examples ID' to 14D'.
  • Such a tendency was recognized more conspicuously as the organic EL devices which were formed of the hole transport materials each having a particularly preferable mixing ratio of the compound represented by the general formula (IA) and the epoxy-based cross-linking agent. This result suggests that the interval between the adjacent main skeletons could be maintained at a more suitable interval due to the addition of the epoxy-based cross-linking agent.
  • the luminous brightness, the maximum luminous efficiency and the half-life were superior irrespective of the kind of epoxy-based cross-linking agent used. This result suggests that the adjacent main skeletons are allowed to exist at a suitable interval even in the case where any epoxy-based cross-linking agent is used.
  • compositions of the Examples which contain substituents Xeachhaving an appropriate n 1 value in the general formula (A2), that is the compositions containing the substituents X by which the adjacent main skeletons are allowed to exist at a suitable interval could have more superior luminous brightness, maximum luminous efficiency, and half-life as compared to the compositions which do not have such a substituent X.
  • the organic EL devices in the Examples each obtained by appropriately selecting conductive materials for respectively constituting the hole transport material and the electron transport material namely, the organic EL devices in the Examples each having a preferred combination of the hole transport layer and the electron transport layer by appropriately selecting the group Y of the compound represented by the above-mentioned general formula (Al) couldhave superior luminous brightness, maximum luminous efficiency, and half-life.
  • the compound (KII) was used as an arylamine derivative, and the compound (KII) and a cationic photopolymerization initiator ("FC-508" producedby Sumitomo 3MLimited) in aweight ratio of 99:1 were mixed with di ⁇ hloroethane to obtain an organic semiconductor material (that is, a composition for conductive materials) .
  • a glass substrate having an average thickness of 1 mm was prepared, and it was then washedwith water (that is, with a cleaning fluid).
  • a photoresist was applied onto the glass substrate by a spin coating method, and then the photoresist was prebaked to form a film.
  • the film was irradiated with (or exposed to) ultraviolet rays through a photomask to develop it. In this way, a resist layer having openings where a source electrode and a drain electrode were to be provided was formed.
  • an aqueous gold colloidal solution was supplied to the openings by an InkJet method. Then, the glass substrate to which the aqueous gold colloidal solution had been supplied was dried by heating to obtain a source electrode and a drain electrode.
  • the resist layer was removed by oxygen plasma treatment. Then, the glass substrate on which the source electrode and the drain electrode had been formed was washed with water, and was then washed with methanol.
  • the prepared organic semiconductor material was applied onto the substrate by a spin coating method and then it was dried.
  • the organic semiconductor material was irradiated with ultraviolet rays having a wavelength of 365 nm from a mercury lamp ("UM-452", USHIO Inc.) through a filter at an intensity of irradiation of 500 mW/cm 2 for 15 seconds in dry atmosphere to polymerize the compound (KII) and then heated for 60 minutes at temperature of 110°C, so that an organic semiconductor layer having an average thickness of 50 nm was formed on the glass substrate.
  • a butyl acetate solution of polymethylmethacrylate (PMMA) was applied onto the organic semiconductor layer by a spin coating method, andwas then dried to form a gate insulating layer having an average thickness of 500 nm.
  • PMMA polymethylmethacrylate
  • a water dispersion of polyethylenedioxythiophene was applied to an area on the gate insulating layer corresponding to the area between the source electrode and the drain electrode by an inkjet method, and was then dried to form a gate electrode having an average thickness of 100 nm.
  • organic TFTs were manufactured after the organic semiconductor material was prepared in the same manner as in Example IE except that as for an arylamine derivative for use in preparing the organic semiconductor material, those shown in Table 5 were used.
  • Organic TFTs were manufactured in the same manner as in Example IE except that the organic semiconductor material was changed to the organic semiconductor material prepared in the step 4E and the organic semiconductor material was not irradiatedwith ultraviolet rays from amercury lamp in the step 4E .
  • the compound (SII) was used as an arylamine derivative, and a bifunctional epoxy compound ("DENACOL EX-212" produced by Nagase chemteX Corporation) was used as a photocrosslinking agent, and the compound (SII) , the epoxy compound and a cationic photopolymerization initiator ("FC-508" produced by Sumitomo 3M Limited) in a weight ratio of 50:49:1 were mixed with dichloroethane to obtain an organic semiconductor material.
  • a bifunctional epoxy compound (“DENACOL EX-212" produced by Nagase chemteX Corporation) was used as a photocrosslinking agent
  • FC-508 cationic photopolymerization initiator
  • Organic TFTs were manufactured in the same manner as in Example IE except that the organic semiconductor material prepared in this Comparative Example was used as the organic semiconductor material.
  • Organic TFTs were manufactured after the organic semiconductor material was prepared in the same manner as in Example IE except that the compound (Oil) was used as an arylamine derivative for use in preparing the organic semiconductor material.
  • the mixing ratio of the compound (KII) and the cross-linking agent B2 was 3:1 in a molar ratio, and the weight ratio of the total weight of the compound (KII) and the cross-linking agent B2 with respect to the cationic polymerization initiator was 991:1.
  • a resist layer having openings where a source electrode and a drain electrode were to be provided was formed on a glass substrate.
  • the prepared organic semiconductor material was applied onto the substrate by a spin coatingmethodand then it was dried. Then, the organic semiconductor material was irradiated with ultraviolet rays having a wavelength of 365 nm from a mercury lamp ("UM-452", USHIO Inc.) through a filter at an intensity of irradiation of 400 mW/cm 2 for 10 seconds in dry atmosphere and thenheatedfor 60 minutes at temperature of 110 0 C to polymerize the compound (KII) and the cross-linking agent B2, so that an organic semiconductor layer having an average thickness of 50 nm was formed on the glass substrate.
  • a mercury lamp "UM-452", USHIO Inc.
  • a gate insulating layer having an average thickness of 500 nm was formed on the organic semiconductor layer.
  • a gate electrode having an average thickness of 100 nm was formed on an area on the gate insulating layer corresponding to the area between the source electrode and the drain electrode.
  • organic TFTs were manufactured after the organic semiconductor material was prepared in the same manner as in Example IF except that the arylamine derivative for use in preparing the organic semiconductor material and the mixing ratio (mole ratio) of the arylamine derivative and the cross-linking agent B2 were changed to those shown in Table 6 were used.
  • Example 13F Organic TFTs were manufactured after the organic semiconductor material was prepared in the same manner as in Example IF except that a glycidyl ester-based dimmer acid epoxy compound represented by the above-mentioned chemical formula (B7) was used as an epoxy-based cross-linking agent for use in preparing the organic semiconductor material.
  • a glycidyl ester-based dimmer acid epoxy compound represented by the above-mentioned chemical formula (B7) was used as an epoxy-based cross-linking agent for use in preparing the organic semiconductor material.
  • Organic TFTs were manufactured after the organic semiconductor material was prepared in the same manner as in Example IF except that an alicyclic epoxy compound represented by the above-mentioned chemical formula (B9) was used as an epoxy-based cross-linking agent for use in preparing the organic semiconductor material.
  • an alicyclic epoxy compound represented by the above-mentioned chemical formula (B9) was used as an epoxy-based cross-linking agent for use in preparing the organic semiconductor material.
  • Organic TFTs were manufactured after the organic semiconductor material was prepared in the same manner as in Example IF except that an acrylic ester compound represented by the above-mentioned chemical formula (Bl) (where A 1 is hydrogen atom) was used as an epoxy-based cross-linking agent for use in preparing the organic semiconductor material.
  • an acrylic ester compound represented by the above-mentioned chemical formula (Bl) (where A 1 is hydrogen atom) was used as an epoxy-based cross-linking agent for use in preparing the organic semiconductor material.
  • Organic TFTs were manufactured after the organic semiconductor material was prepared in the same manner as in Example IF except that a polyfunctional phenol-based epoxy compound represented by the above-mentioned chemical formula (B15) (where n 9 is 2 to 5) was used as an epoxy-based cross-linking agent for use in preparing the organic semiconductor material.
  • a polyfunctional phenol-based epoxy compound represented by the above-mentioned chemical formula (B15) (where n 9 is 2 to 5) was used as an epoxy-based cross-linking agent for use in preparing the organic semiconductor material.
  • TFTs were manufactured after the organic semiconductor material was prepared in the same manner as in Example IF except that a glycidyl amine-based epoxy compound represented by the above-mentioned chemical formula (B23) was used as an epoxy-based cross-linking agent for use in preparing the organic semiconductor material.
  • organic TFTs were manufactured after the organic semiconductor material was prepared in the same manner as in Example IF except that the arylamine derivative for use in preparing the organic semiconductor material was changed to those shown in Table 6. 5. Evaluation of organic TFT
  • the word “OFF-state current” means the value of current flowing between the source electrode and the drain electrode when a gate voltage is not applied
  • the word “ON-state current” means the value of current flowing between the source electrode and the drain electrode when a gate voltage is applied.
  • a larger value of ratio of the absolute value of the ON-state current to the absolute value of the OFF-state current means that an organic TFT has better characteristics.
  • the OFF-state current was measured at a potential difference between the source electrode and the drain electrode of 30 V
  • the ON-state current was measured at a potential difference between the source electrode and the drain electrode of 30 V and an absolute value of gate voltage of 40 V.
  • A The value of ON/OFF ratio was 10 4 or more.
  • compositions of Examples which were formed of the compounds containing the substituents X each having an appropriate n 1 value in the general formula (A2) that is the compositions formed of the compounds having the substituents X by which the adjacent main skeletons are allowed to exist at a suitable interval, could have more increased value of ON/OFF ratio, that is, the characteristics of the organic TFT were further improved.
  • the compound (AI) was used as an arylamine derivative
  • the cross-linking agent B2 was used as the epoxy-based cross-linking agent
  • a cationic photopolymerization initiator (“FC-508" produced by Sumitomo 3M Limited) was used as a photopolymerization initiator, and they were mixed with dichloroethane to prepare a conductive material.
  • the mixing ratio of the compound (AI) and the cross-linking agent B2 was 3:1 in a mole ratio, and the weight ratio of the total of the compound (AI) and the cross-linking agent B2 with respect to the cationic photopolymerization initiator was 99:1.
  • the prepared the conductive material was applied onto a silicon substrate having an average thickness of 1.2mm by a spin coating method, and was then dried.
  • the conductive material was irradiated with ultraviolet rays having a wavelength of 365 nm from a mercury lamp ("UM-452", USHIO Inc.) through a filter at an intensity of irradiation of 400 mW/cm 2 for 10 seconds in the dry atmosphere and then heated for 60 minutes at temperature of 110 0 C to polymerize the compound (AI) and the cross-linking agent B2, so that a conductive layer having an average thickness of 50 nm was formed on the substrate.
  • UM-452 ultraviolet rays having a wavelength of 365 nm from a mercury lamp ("UM-452", USHIO Inc.) through a filter at an intensity of irradiation of 400 mW/cm 2 for 10 seconds in the dry atmosphere and then heated for 60 minutes at temperature of 110 0 C to polymerize the compound (AI) and the cross-linking agent B2, so that a conductive layer having an average thickness of 50 nm was formed on the substrate.
  • conductive layers were manufactured in the same manner as in Example IG except that the hole transport materials used in the Examples 2B to 2IB were used for the respective conductive materials.
  • Conductive layers were manufactured in the same manner as in Example IG except that the hole transport material used in the Example 8B was used for the conductive material and that irradiation of ultraviolet rays by a mercury lamp and heat treatment were omitted.
  • ⁇ Preparation of conductive layer> The compound (All) was used as an arylamine derivative, the cross-linking agent B2 was used as the epoxy-based cross-linking agent, and a cationic photopolymerization initiator ("F.C-508" produced by Sumitomo 3M Limited) was used as a photopolymerization initiator, and they were mixed with dichloroethane to prepare a conductive material.
  • a cationic photopolymerization initiator (“F.C-508" produced by Sumitomo 3M Limited
  • the mixing ratio of the compound (All) and the cross-linking agent B2 was 3:1 in a molar ratio, and the weight ratio of the total of the compound (All) and the cross-linking agent B2 with respect to the cationic photopolymerization initiator was 99:1.
  • the prepared the conductive material was applied onto a silicon substrate having an average thickness of 1.2mm by a spin coating method, and was then dried.
  • the conductive material was irradiated with ultraviolet rays having a wavelength of 365 nm from a mercury lamp ("UM-452", USHIO Inc.) through a filter at an intensity of irradiation of 400 mW/cm 2 for 10 seconds in the dry atmosphere and then heated for 60 minutes at temperature of 110 0 C to polymerize the compound (All) and the cross-linking agent B2, so that a conductive layer having an average thickness of 50 nm was formed on the substrate.
  • UM-452 ultraviolet rays having a wavelength of 365 nm from a mercury lamp ("UM-452", USHIO Inc.) through a filter at an intensity of irradiation of 400 mW/cm 2 for 10 seconds in the dry atmosphere and then heated for 60 minutes at temperature of 110 0 C to polymerize the compound (All) and the cross-linking agent B2, so that a conductive layer having an average thickness of 50 nm was formed on the substrate.
  • Example 2H to 17H conductive layers were manufactured in the same manner as in Example IH except that the hole transport materials used in the Examples 19D to 34D were used for the respective conductive materials.
  • Conductive layers were manufactured in the same manner as in Example IH except that the hole transport material used in the Example 4D was used for the conductive material and that irradiation of ultraviolet rays by a mercury lamp and heat treatment were omitted.
  • the hardness of the thin film was measured using a scanning type nanoindenter (Hysitron Inc.).
  • the hardness was obtained from the average values for the five thin films.
  • the scanning type nanoindenter is an apparatus provided with a diamond tip as a detecting section.
  • this apparatus by repeating addition of a load to the surface of a thin film and removal of the load therefrom, displacements at the surface of the thin film are detected successively to obtain a load-displacement curve, and based on the thus obtained load-displacement curve the hardness of the thin film and the like are calculated.
  • each of the conductive layers of the Examples and the Comparative Examples was immersed in an acetone solution for ten days at room temperature, and then the surface condition of each conductive layerwas observed with naked eyes.
  • the chemical resistance test was carried out for five conductive layers in each case.
  • A There was no change in the surface condition.
  • B There was a minor color change in the surface.
  • C Slight swelling was observed at the surface.
  • D Considerable swelling and peeling-off were observed at the surface.
  • the conductive layer (that is, a layer formed using the conductive material according to the present invention as its main material) of each of the Examples shows the superior results in not only the hardness test but also the chemical resistance test as compared to those of the Comparative Example G.
  • the conductive material of the present invention makes it possible to impart sufficient hardness and chemical resistance to a resultant conductive layer due to the fact that the conductive material is obtained by cross-linking the compounds each represented by the above-mentioned general formula (Al) via the epoxy-based cross-linking agent.
  • the conductive layers in the Examples which use any of a glycidyl ester-based epoxy cross-linking agent, an alicycli ⁇ epoxy cross-linking agent, an urethane modified epoxy cross-linking agent, and a silicon-containing epoxy cross-linking agent as their epoxy-based cross-linking agent can have sufficient flexibility as compared to the conductive layers of the other Examples.
  • the conductive layers in the Examples which use any of a (meth)acrylic ester-based epoxy cross-linking agent, a polyfun ⁇ tional phenol-based epoxy compound, and a glycidyl amine-based epoxy cross-linking agent as their epoxy-based cross-linking agent tend to exhibit more superior hardness.
  • the conductive layer of each of the Example 2OG and the Example 21G which uses the cross-linking agent in which two kinds of epoxy-based cross-linking agents are mixed exhibits synergistic effect obtained from the respective epoxy-based cross-linking agents.
  • the conductive layer that is, a layer formed using the conductive material according to the present invention as its mainmaterial
  • the conductive layer of each of the Examples exhibits superiorresults in not only the hardness test but also the chemical resistance test as compared to the conductive layer of the Comparative Example H.
  • the conductive material of the present invention makes it possible to impart sufficient hardness and chemical resistance to a resultant conductive layer due to the fact that the conductive material is obtained by cross-linking the compounds each represented by the above-mentioned general formula (Al) via the epoxy-based cross-linking agent.
  • the conductive layers in the Examples which use any of a glycidyl ester-based epoxy cross-linking agent, an alicyclic epoxy cross-linking agent, an urethane modified epoxy cross-linking agent, and a silicon-containing epoxy cross-linking agent as their epoxy-based cross-linking agent can have sufficient flexibility as compared to the conductive layers of the other Examples.
  • the conductive layers in the Examples which use any of a (meth)acrylic ester-based epoxy cross-linking agent, a polyfunctional phenol-based epoxy compound, and a glycidyl amine-based epoxy cross-linking agent as their epoxy-based cross-linking agent tend to exhibit more superior hardness.
  • the conductive layer of each of the Example 16H and the Example 17H which uses the cross-linking agent in which two kinds of epoxy-based cross-linking agents are mixed exhibits synergistic effect obtained from the respective epoxy-based cross-linking agents.
  • the polymer contained in the conductive material has a structure in which adjacent main skeletons of compounds are repeatedly linked through a chemical structure which is produced by the direct polymerization reaction between any one or more of the respective substituents X 1 , X 2 , X 3 and X 4 of the compounds or a chemical structure which is produced by the polymerization reaction between the respective substituents X of the compounds via an epoxy-based cross-linking agent, that is, a structure in which adjacent main skeletons repeatedly exist at a suitable interval. Therefore, it is possible to decrease the interaction between the adjacent main skeletons in the polymer.
  • the constituent material of the conductive layer from such a polymer, when an upper layer is formed on the conductive layer using a liquid material, it is possible to properly suppress or prevent the polymer from being swelled or dissolved by the solvent or dispersion medium contained in the liquid material. As a result, it is possible to prevent mutual dissolution from occurring between the conductive layer and the upper layer to be formed.
  • the polymer can exhibit a high carrier transport ability, and thus a conductive material constituted from the polymer as its main material can also have a high carrier transport ability. Consequently, both an electronic device provided with such a conductive layer and electronic equipment provided such an electronic device can have high reliability. Therefore, the present invention has industrial adaptability required by PCT.

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Abstract

The object of the present invention is to provide a composition for conductive materials from which a conductive layer having a high carrier transport ability can be made, a conductive material formed of the composition and having a high carrier transport ability, a conductive layer formed using the conductive material as a main material, an electronic device provided with the conductive layer and having high reliability, and electronic equipment provided with the electronic device. The composition for conductive materials of the present invention contains a compound represented by the following general formula (Al): wherein eight Rs may be the same or different and each independently represents a hydrogen atom, a methyl group or an ethyl group, Y represents a group containing at least one substituted or unsubstituted aromatic hydrocarbon ring or substituted or unsubstituted heterocycle, and X1, X2, X3 and X4 may be the same or different and each independently represents a substituent represented by the following general formula wherein n1 is an integer of 2 to 8.

Description

DESCRIPTION
COMPOSITION FOR CONDUCTIVE MATERIALS, CONDUCTIVE MATERIAL, CONDUCTIVE LAYER, ELECTRONIC DEVICE, AND ELECTRONIC EQUIPMENT
Technical Field
The present invention relates to a composition for conductivematerials, a conductivematerial, a conductive layer, an electronic device, and electronic equipment, and more specifically to a composition for conductive materials from which a conductive layerhaving ahigh carrier transport ability can be made, a conductive material formed of the composition and having a high carrier transport ability, a conductive layer formed using the conductive material as a main material, an electronic device providedwith the conductive layer and having high reliability, and electronic equipment provided with the electronic device.
Background Art
Electroluminescent devices using organic materials (hereinafter, simplyreferredto as an "organic EL device" ) have been extensively developed in expectation of their use as solid-state luminescent devices or emitting devices for use in inexpensive large full-color displays.
In general, such an organic EL device has a structure in which a light emitting layer is provided between a cathode and an anode. When an electric field is applied between the cathode and the anode, electrons are injected into the light emitting layer from the cathode side, and holes are injected into the light emitting layer from the anode side.
The injected electrons and holes are recombined in the light emitting layer, which then causes their energy level to return from the conduction band to the valence band. At this time, excitation energy is released as light energy so that the light emitting layer emits light.
In such organic EL devices, it has" been known that a layered device structure, in which organic layers formed of organic materials having different carrier transport properties for electrons or holes are provided between a light emitting layer and a cathode and/or an anode, is effective in obtaining a high-efficiency organic EL device with high luminance.
For this purpose, it is necessary to laminate a light emitting layer and organic layers having different carrier transport properties fromeach other (hereinafter, these layers are collectively referred to as "organic layers") on the electrode. However, in the conventional manufacturing method using an application method, when such organic layers are laminated, mutual dissolution occurs between the adjacent organic layers, thereby causing the problem of deterioration in the light emitting efficiency of a resultant organic EL device, the color purity of emitted light, and/or the pattern precision.
For this reason, in the case where organic layers are laminated, these organic layers have to be formed using organic materials having different solubilities.
In order to solve such a problem, a method for improving the durability of a lower organic layer, that is, the solvent resistance of the lower organic layer has been disclosed (see, for example, JP-A No. 9-255774). In this method, organic materials constituting the lower organic layer are polymerized to improve the solvent resistance of the lower organic layer.
Another method for improving the solvent resistance of a lower organic layer is found in the JP-A No. 2000-208254 that discloses amethod in which a curing resin is added to an organic material constituting the lower organic layer to cure the organic material together with the curing resin.
However, even in the case where such a method is employed in manufacturing an organic EL device, the characteristics of a resultant organic EL device are not so improved as to meet expectations in actuality.
The problem described above has also been raised in thin film transistors using organic materials.
Disclosure of Invention
It is therefore the object of the present invention to provide a composition for conductive materials from which a conductive layer having a high carrier transport ability can be made, a conductive material having a high carrier transport ability obtained by using the composition for conductive materials, a conductive layer obtained by using the conductive material as a main material, a high-reliability electronic device provided with the conductive layer, and electronic equipment provided with the electronic device.
In order to achieve the above object, the present invention is directed to a composition for conductive materials, which comprises a compound represented by the following general formula (Al) :
Figure imgf000005_0001
wherein eight Rs may be the same or different and each independently represents a hydrogen atom, a methyl group or an ethyl group, Y represents a group containing at least one substituted or unsubstituted aromatic hydrocarbon ring or substituted or unsubstituted heterocycle, and X1, X2, X3 and X4 may be the same or different and each independently represents a substituent represented by the following general formula (A2):
Figure imgf000005_0002
wherein n1 is an integer of 2 to 8
According to the present invention described above, it is possible to provide a composition for conductive materials from which a conductive layer having a high carrier transport ability can be made.
In the composition for conductive materials according to the present invention, it is preferred that the group Y contains at least one substituted or unsubstituted aromatic hydrocarbon ring.
By using such a composition, it is possible for a polymer obtained by polymerization reaction of the compounds each represented by the above-mentioned general formula (Al) with each other at any one or more of their respective substituents X1, X2, X3 and X4 (hereinafter, each of these substituents will be referred to as "substituent X" and all of these substituents will be collectively referred to as "the substituents X" depending on the occasions) to exhibit ahole transport ability.
Further, in the composition for conductive materials according to the present invention, it is also preferred that the substituent X1 and the substituent X3 are identical with each other.
According to the composition described above, it is possible to make variation in intervals between "the main skeletons of the compounds each represented by the above-mentioned general formula (Al) small in a resultant polymer (here, "main skeleton" means a portion of each compound other than its substituents X) . This makes it possible to improve a hole transport ability of the polymer. Further, in the composition for conductive materials according to the present invention, it is also preferred that the substituent X2 and the substituent X4 are identical with each other.
According to the composition described above, it is also possible to make variation in intervals between the main skeletons of the compounds smaller in aresultant polymer. This also makes it possible to further improve a hole transport ability of the polymer.
Further, in the composition for conductive materials according to the present invention, it is also preferred that the substituent X1, the substituent X2, the substituent X3 and the substituent X4 are identical with each other.
According to the composition described above, it is also possible to make variation in intervals between the main skeletons of the compounds smaller in aresultant polymer. This also makes it possible to further improve a hole transport ability of the polymer.
Furthermore, in the composition for conductive materials according to. the present invention, it is also preferred that each of the substituent X1, the substituent X2, the substituent X3 and the substituent X4 is bonded to the 3-, 4- or 5-position of the benzene ring.
This allows the main skeletons to exist at a suitable interval more reliably in a resultant polymer.
Moreover, in the composition for conductive materials according to the present invention, it is also preferred that the group Y consists of carbon atoms and hydrogen atoms.
This makes it possible for a resultant polymer to have a high hole transport ability, and therefore a conductive layer to be formed of the polymer can also have a high hole transport ability.
Moreover, in the composition for conductive materials according to the present invention, it is also preferred that the group Y contains 6 to 30 carbon atoms in total.
This also makes it possible for the resultant polymer to have ahigherhole transport ability, and therefore a conductive layer to be formed of the polymer can also have a higher hole transport ability.
Moreover, in the composition for conductive materials according to the present invention, it is also preferred that the group Y contains 1 to 5 aromatic hydrocarbon rings.
This also makes it possible for the resultant polymer to have ahigher hole transport ability, and therefore a conductive layer to be formed of the polymer can also have a higher hole transport ability.
Moreover, in the composition for conductive materials according to the present invention, it is also preferred that the group Y is a biphenylene group or a derivative thereof.
This also makes it possible for the resultant polymer to have ahigherhole transport ability, and therefore a conductive layer to be formed of the polymer can also have a higher hole transport ability.
Moreover, in the present invention, it is also preferred that the composition further comprises an epoxy-based cross-linking agent in addition to the compound represented by the above-mentioned general formula (AX).
This makes it possible to obtain a polymer having a link structure produced by polymerization reaction of a substituent X and a substituent X via an epoxy-based cross-linking agent. According to such a polymer, since an interval between the main skeletons is maintained at a more suitable interval, interaction between the main skeletons can be further decreased. As a result, the polymer can exhibit a sufficiently high hole transport ability.
In the composition described above, it is preferred that the epoxy-based cross-linking agent contains a (meth)acrylic ester-based epoxy cross-linking agent.
By using such a composition, it is possible to produce a conductive layer that can exhibit sufficient strength.
Further, in the composition described above, it is also preferred that the epoxy based cross-linking agent contains a bisphenol epoxy cross-linking agent.
By using such a composition, it is possible to produce a conductive layer having an improved chemical resistance.
Furthermore, in the composition described above, it is also preferred that the epoxy-based cross-linking agent contains at least one cross-linking agent selected from the group comprising a glycidyl ester-based epoxy cross-linking agent, an alicyclic epoxy cross-linking agent, an urethane modified epoxy cross-linking agent and a silicon-containing epoxy cross-linking agent.
By using such a composition, it is possible to produce a conductive layer having flexibility with maintaining sufficient strength.
Moreover, in the composition described above, it is also preferred that the epoxy-based cross-linking agent contains at least one of a polyfunctional phenol-based epoxy cross-linking agent and a glycidyl amine-based epoxy cross-linking agent.
By using such a composition, it is possible to produce a conductive layer having sufficient strength.
Further, in the composition described above, it is preferred that the substituent X1 and the substituent X3 are identical with each other. This makes it possible to properly prevent or suppress the electron density in a resultant polymer from being biased, and thereby enabling to improve a hole transport ability of the polymer.
Further, in the composition described above, it is also preferred that the substituent X2 and the substituent X4 are identical with each other.
This also makes it possible to properly prevent or suppress the electron density in a resultant polymer from being biased, and thereby enabling to improve a hole transport ability of the polymer.
Furthermore, in the composition described above, it is preferred that the substituent X1, the substituent X2, the substituent X3 and the substituent X4 are identical with each other.
This also makes it possible to properly prevent or suppress the electron density in a resultant polymer from being biased, and thereby enabling to further improve ahole transport ability of the polymer.
Moreover, in the composition for conductive materials according to the present invention, it is also preferred that each of the substituent X1, the substituent X2, the substituent X3 and the substituent X4 is bonded to the 3-, 4- or 5-position of the benzene ring. This allows the main skeletons to exist at a suitable interval more reliably in a resultant polymer.
Further., in the composition descried above, it is also preferred that the group Y consists of carbon atoms andhydrogen atoms.
This makes it possible for a resultant polymer to have a high hole transport ability, and therefore a conductive layer to be formed of the polymer can also have a high hole transport ability.
Moreover, in the composition described above, it is also preferredthat the groupY contains 6 to 30 carbon atoms in total.
This also makes it possible for the resultant polymer to have ahigherhole transport ability, and therefore a conductive layer to be formed of the polymer can also have a higher hole transport ability.
Moreover, in the composition described above, it is also preferred that the group Y contains 1 to 5 aromatic hydrocarbon rings.
This also makes it possible for the resultant polymer to have ahigher hole transport ability, and therefore a conductive layer to be formed of the polymer can also have a higher hole transport ability.
Moreover, in the composition described above, it is also preferred that the group Y is a biphenylene group or a derivative thereof.
This also makes it possible for the resultant polymer to have ahigherhole transport ability, and therefore a conductive layer to be formed of the polymer can also have a higher hole transport ability.
In the composition for conductive materials according to the present invention, it is also preferred that the group Y contains at least one substituted orunsubstitutedheterocycle.
This makes it possible to adjust characteristics of a hole transport ability easily in a resultant polymer.
Further, in the composition described above, it is also preferred that the substituent X1 and the substituent X3 are identical with each other.
According to the composition described above, it is possible to make variation in intervals between the main skeletons of the compounds small in a resultant polymer, thereby enabling to improve a carrier transport ability of the polymer.
Further, in the composition described above, it is also preferred that the substituent X2 and the substituent X4 are identical with each other.
According to the composition described above, it is also possible to make variation in intervals between the main skeletons of the compounds small in a resultant polymer, thereby enabling to further improve a carrier transport ability of the polymer.
Further, in the composition described above, it is also preferred that the substituent X1, the substituent X2, the substituent X3 and the substituent X4 are identical with each other.
According to the composition described above, it is also possible to make variation in intervals between the main skeletons of the compounds small in a resultant polymer, thereby enabling to further improve a carrier transport ability of the polymer.
Furthermore, in the composition described above, it is also preferred that each of the substituent X1, the substituent X2, the substituent X3 and the substituent X4 is bonded to the 3-, 4- or 5-position of the benzene ring.
This allows the adjacent main skeletons to exist at a suitable interval more reliably in a resultant polymer.
Further, in the composition descried above, it is also preferred that the heterocycle contains at least one heteroatom selected from the group comprising nitrogen, oxygen, sulfur, selenium and tellurium.
By selecting such a heterocyclic ring which contains such a kind of heteroatom, the energy level of the valence and conductionbands or the size of the band gap of thepolymereasily changes, so that it is possible to change the characteristics of the carrier transport ability of the polymer.
Further, in the composition descried above, the heterocycle may be either of an aromatic heterocycle or a nonaromatic heterocycle, but the aromatic heterocycle is more preferable.
By using such an aromatic heterocycle, it is possible to properly prevent the electron density of the main skeleton with a conjugated chemical structure from being biased, that is, it is possible to properlyprevent the localization of π electrons. As a result, it is possible to prevent the carrier transport ability of the polymer from being impaired.
Further, in the composition descried above, it is preferred that the group Y contains 1 to 5 heterocycles.
By allowing the group Y to have such a number of heterocyclic rings, it is possible to change the energy level of the valence and conduction bands or the size of the band gap of the polymer sufficiently.
Further, in the composition descried above, it is preferred that the group Y contains at least one substituted or unsubstituted aromatic hydrocarbon ring in addition to the heterocycle.
By selecting such a group containing a heterocycle and an aromatic hydrocarbon ring as the group Y, it is possible to impart a desired carrier transport property to the polymer more reliably.
Further, in the composition descried above, it is preferred that the group Y contains two aromatic hydrocarbon rings respectively bonded to each N in the general formula (Al) directly and at least one heterocycle existing between these aromatic hydrocarbon rings.
This makes it possible to prevent reliably the electron density in the polymer from being biased , and thereby enabling each polymer to have an even carrier transport ability.
Furthermore, in the composition described above, it is preferred that the group Y contains 2 to 75 carbon atoms in total.
According to this composition, the solubility of the compound represented by the general formula (Al) in a solvent tends to be increased, so that there is a possibility that the range of the choices of solvents to be used in preparing the composition for conductive materials becomes wide.
In the present invention, it is also preferred that the above composition further comprises an epoxy-based cross-linking agent.
This makes it possible to obtain a polymer having a link structure produced by polymerization reaction of a substituent X and a substituent X with an epoxy-based cross-linking agent. According to such a polymer, since an interval between the main skeletons is maintained at a more suitable interval, interaction between the main skeletons can be further decreased. As a result, the polymer can exhibit a sufficiently high carrier transport ability.
In the composition described above, it is preferred that the epoxy-based cross-linking agent contains a (meth)acrylic ester-based epoxy cross-linking agent.
By using such a composition, it is possible to produce a conductive layer that can exhibit sufficient strength.
Further, in the composition described above, it is also preferred that the epoxy based cross-linking agent contains a bisphenol epoxy cross-linking agent.
By using such a composition, it is possible to produce a conductive layer having an improved chemical resistance.
Furthermore, in the composition described above, it is also preferred that the epoxy-based cross-linking agent contains at least one cross-linking agent selected from the group comprising a glycidyl ester-based epoxy cross-linking agent, an alicyclic epoxy cross-linking agent, an urethane modified epoxy cross-linking agent and a silicon-containing epoxy cross-linking agent.
By using such a composition, it is possible to produce a conductive layer having flexibility with maintaining sufficient strength.
Moreover, in the composition described above, it is also preferred that the epoxy-based cross-linking agent contains at least one of a polyfunctional phenol-based epoxy cross-linking agent and a glycidyl amine-based epoxy cross-linking agent.
By using such a composition, it is possible to produce a conductive layer having sufficient strength.
Further, in the composition described above, it is preferred that the substituent X1 and the substituent X3 are identical with each other.
This makes it possible to properly prevent or suppress the electron density in a resultant polymer from being biased, and thereby enabling to improve a carrier transport ability of the polymer.
Further, in the composition described above, it is also preferred that the substituent X2 and the substituent X4 are identical with each other.
This also makes it possible to properly prevent or suppress the electron density in a resultant polymer from being biased, and thereby enabling to further improve a carrier transport ability of the polymer.
Furthermore, in the composition described above, it is preferred that the substituent X1, the substituent X2, the substituent X3 and the substituent X4 are identical with each other.
This also makes it possible to properly prevent or suppress the electron density in a resultant polymer from being biased, and thereby enabling to further improve a carrier transport ability of the polymer.
Moreover, in the composition for conductive materials according to the present invention, it is also preferred that each of the substituent X1, the substituent X2, the substituent X3 and the substituent X4 is bonded to the 3-, 4- or 5-position of the benzene ring.
This allows the main skeletons to exist at a suitable interval more reliably in a resultant polymer.
Further, in the composition descried above, it is also preferred that the heterocycle contains at least one heteroatom selected from the group comprising nitrogen, oxygen, sulfur, selenium and tellurium.
By selecting such a heterocyclic ring which contains such a kind of heteroatom, the energy level of the valence and conductionbands or the size of the band gap of the polymer easily changes, so that it is possible to change the characteristics of the carrier transport ability of the polymer.
Further, in the composition descried "above, the heterocycle may be either of an aromatic heterocycle or a nonaromatic heterocycle, but the aromatic heterocycle is more preferable.
By using such an aromatic heterocycle, it is possible to properly prevent the electron density of the main skeleton with a conjugated chemical structure from being biased, that is, it is possible to prevent the localization of π electrons properly. As a result, the carrier transport ability of the polymer is prevented from being impaired.
Further, in the composition descried above, it is preferred that the group Y contains 1 to 5 heterocycles.
By allowing the group Y to have such a number of heterocyclic rings, it is possible to change the energy level of the valence and conduction bands or the size of the band gap of the polymer sufficiently.
Further, in the composition descried above, it is preferred that the group Y contains at least one substituted or unsubstituted aromatic hydrocarbon ring in addition to the heterocycle.
By selecting such a group containing a heterocycle and an aromatic hydrocarbon ring as the group Y, it is possible to impart a desired carrier transport property to the polymer more reliably.
Further, in the composition descried above, it is preferred that the group Y contains two aromatic hydrocarbon rings respectively bonded to each N in the general formula (Al) directly and at least one heteroσycle existing between these aromatic hydrocarbon rings.
This makes it possible to prevent the electron density in the polymer from being biased reliably, and thereby enabling each polymer to have an even carrier transport ability.
Furthermore, in the composition described above, it is preferred that the groupY contains 2 to 75 carbon atoms in total.
According to this composition, the solubility of the compound represented by the general formula (Al) in a solvent tends to be increased, so that there is a possibility that the range of the choices of solvents to be used in preparing the composition for conductive materials becomes wide.
Another aspect of the present invention is directed to a conductive material obtained by direct polymerization reaction or polymerization reaction via an epoxy-based cross-linking agent of substituents X1, substituents X2, substituents X3 and substituents X4 of compounds each represented by the following general formula (Al), each compound being contained in the composition for conductive materials defined in claim 1:
Figure imgf000021_0001
wherein eight Rs may be the same or different and each independently represents a hydrogen atom, a methyl group or an ethyl group, Y represents a group containing at least one substituted or unsubstituted aromatic hydrocarbon ring or substituted or unsubstituted heterocycle, and X1, X2, X3 and X4 may be the same or different and each independently represents a substituent represented by the following general formula (A2):
H2C--CH-CH2-O-[CH2-^1
(A2)
wherein n1 is an integer of 2 to 8.
According to the conductive material described above, it is. possible to produce a conductive layer (polymer) having a high carrier transport ability.
In the conductive material described above, it is preferred that the compounds are polymerized by light irradiation.
By employing light irradiation, it is possible to relatively easily select the areawhere polymerization reaction of the compounds each represented by the above-mentioned general formula (Al) occurs as well as the degree of the polymerization in a resultant conductive layer.
In the conductive material described above, it is preferred that both the compound and the epoxy-based cross-linking agent are polymerized by light irradiation. In this case, it is also possible to relatively easily select the area where polymerization reaction of the compounds each represented by the above-mentioned general formula (Al) and the epoxy-based cross-linking agent occurs as well as the degree of the polymerization in a resultant conductive layer.
Other aspect of the present invention is directed to a conductive layer mainly comprising the conductive material as described above. This conductive layer can have a high hole transport ability.
In this case, it is preferred that the conductive layer is used for a hole transport layer. This hole transport layer can also have a high hole transport ability.
In this case, it is preferred that the average thickness of the hole transport layer is in the range of 10 to 150 nm.
When such a hole transport layer is used in an organic EL device, it is possible to increase the reliability of the organic EL device.
Further, the conductive layer of the present invention described above may be used for an electron transport layer. Such an electron transport layer can also have a high electron transport ability.
In this case, it is preferred that the average thickness of the electron transport layer is in the range of 10 to 150 nm.
When such an electron transport layer is used in an organic EL device, it .is possible to increase the reliability of the organic EL device.
Furthermore, the conductive layer of the present invention described above may be used for an organic semiconductor layer. Such an organic semiconductor layer can exhibit excellent semiconductor characteristics.
In this case, it is preferred that the average thickness of the organic semiconductor layer is in the range of 0.1 to 1,000 nm.
When such an organic semiconductor layer is used in an organic thin film transistor, it is possible to increase the reliability of the organic thin film transistor.
The other aspect of the present invention is directed to an electronic device comprising a laminated bodywhich includes the conductive layer as described above. Such an electronic device can have high reliability.
Examples of the electronic device may include a light emitting device and a photoelectric transducer. These light emitting device and photoelectric transducer can also have high reliability.
In this case, it is preferred that the light emitting device includes an organic EL device. Such an organic EL device can also have high reliability.
In the present invention, examples of the electronic device may also include a switching element. Such a switching element can also have high reliability.
In this case, it is preferred that the switching element includes an organic thin film transistor. Such an organic thin film transistor can also have high reliability.
Yet other aspect of the present invention is directed to electronic equipment comprising the electronic device described above. Such electronic equipment can also have high reliability.
Brief Description of Drawings
FIG. 1 is a cross-sectional view which shows an example of an organic EL device;
FIG. 2(a) is a cross-sectional view of an organic TFT, and FIG. 2(b) is a plan view of the organic TFT;
FIG. 3(a) to FIG. 3(d) are illustrations which explain the manufacturing method of the organic TFT shown in FIG. 2;
FIG. 4(a) to FIG. 4(d) are illustrations which explain the manufacturing method of the organic TFT shown in FIG. 2;
FIG. 5 is a perspective view which shows the structure of a personal mobile computer (or a personal notebook computer) to which the electronic equipment according to the present invention is applied;
FIG. 6 is a perspective view which shows the structure of a mobile phone (including the personal handyphone system (PHS)) to which the electronic equipment according to the present invention is applied; and
FIG. 7 is a perspective view which shows the structure of a digital still camera to which the electronic equipment according to the present invention is applied.
Best Mode for Carrying Out the Invention
Hereinbelow, a composition for conductive materials, a conductive material, a conductive layer, ah electronic device, and electronic equipment according to the present invention will be described in detail with reference to preferred embodiments shown in the accompanying drawings.
(Conductive Layer)
First, a conductive layer obtained by using a conductive material according to the present invention as its mainmaterial (that is, a conductive layer according to the present invention) will be described.
A conductive material according to the present invention contains as its main ingredient a polymer obtained by direct polymerization reaction at substituents X1, X2, X3 and X4 of compounds (which are an arylamine derivative) each represented by the following general formula (Al) (hereinafter, each of these substituents X1, X2, X3 and X4 will be referred to as "substituent X" and all of these substituents will be collectively referred to as "the substituents X" depending on the occasions).
Figure imgf000027_0001
wherein eight Rs may be the same or different and each independently represents a hydrogen atom, a methyl group, or an ethyl group, Y represents a group containing at least one substituted or unsubstituted aromatic hydrocarbon ring or substituted or unsubstituted heteroσycle, and X1, X2, X3 and X4 may be the same or different and each independently represents a substituent represented by the following general formula (A2):
(A2 ) HgCr ~CH CH2 O-rCH2 "Xj1I
V
wherein n1 is an integer of 2 to 8.
In such a polymer, adjacent main skeletons which are portions of the compounds other than the substituents X (that is, arylamine skeletons) are linked via a chemical structure formed by the direct reaction between the respective substituents. X (hereinafter, this chemical structure will be referred to as "first link structure"), and thus a two-dimensional network of the main skeletons becomes easily to be formed.
Here, it is to be noted that each main skeleton has a conjugated chemical structure, and because of its unique spread of the electron cloud, the main skeletons contribute to smooth transport of carriers (holes or electrons) in the polymer.
In particular, in the polymer of the present invention, the main skeletons are linked via the first link structure so that the adjacent main skeletons exist at a predetermined interval therebetween. Therefore, the interaction between the adjacent main skeletons decreases, so that transfer of the carriers between the main skeletons can be carried out smoothly.
Further, in the polymer of the present invention, the main skeletons are linked to form the two-dimensional network as described above. Therefore, even in the case where the network has a portion in which the link structure between the main skeletons is cut off, carriers are smoothly transported through other routes.
Furthermore, in the polymer of the present invention, the network having two-dimensional expansion is likely to be formed as described above, and such a network makes it possible to prevent or suppress polymers frombeing interwoven to each other effectively. In other words, if polymers are interwoven complicatedly, interval between the adjacent main skeletons is shortened and thereby the interaction between the adjacent main skeletons becomes too large to decrease the carrier transport ability. For these reasons, in a conductive layer formed of the polymer of the present invention, carriers can be smoothly transported. As described above, the polymer of the present invention which is the main ingredient of the composition for conductive materials of the present invention has the structure in which the main skeletons are linked via the first link structure so that the adjacent main skeletons exist at a predetermined interval therebetween as well as the characteristic by which the two-dimensional network of the main skeletons are likely to be formed. Because of the synergistic effect of these factors, the conductive material of the present invention can exhibit an especially high carrier transport ability. As a result, a conductive layer which is formed using the conductive material of the present invention as its major material can also have an especially high carrier transport ability.
In this regard, it is to be noted that if the interval between the adjacent main skeletons in the polymer is too small, interaction between the adjacent main skeletons tends to be strong. On the other hand, if the interval between the adjacent main skeletons in the polymer is too large, it becomes difficult to transfer carriers between the main skeletons, causing the carrier transport ability of the polymer to be impaired.
The structure of each substituent X should be determined in view of these facts. Specifically, it is preferred that each substituent X represented by the general formula (A2) has a straight-chain carbon-carbon link (i.e. , an alkylene group) in which n1 is 2 to 8, in particular 3 to 6. This makes it possible for the adjacent main skeletons to exist at a suitable interval, thereby reliably decreasing the interaction between the adjacent main skeletons in a resultant polymer. In addition. it is also possible to transfer carriers between the main skeletons more reliably, so that the resultant polymer can have a high carrier transport ability.
In the composition for conductive materials of the present invention, it is preferred that the substituent X1 and the substituent X3 are identical with each other. Namely, it is preferred that the substituent X1 and the substituent X3 have substantially the same number of carbon atoms and more preferably the same number of carbon atoms. This makes it possible for the adjacent main skeletons of the compounds which are to be linked by the polymerization reaction between the respective substituents X (that is, the substituent X1 or the substituent X3) to make variation in their intervals small. Namely, it is possible to make variation in the intervals between the main skeletons small in a resultant polymer. As a result, it is possible to prevent the electron density from being biased in the resultant polymer effectively, thereby enabling to improve a hole transport ability of the polymer.
In view of the above, it is also preferred that the substituent X2 and the substituent X4 are identical with each other. Namely, it is also preferred that the substituent X2 and the substituent X4 have substantially the same number of carbon atoms andmore preferably the same number of carbon atoms. This makes it possible to improve the above-described effect further, thereby enabling to further improve the carrier transport ability of the polymer.
Further, it is also preferred that the substituent X1, the substituent X2, the substituent X3 and the substituent X4 are identical with each other. Namely, it is also preferred that the substituent X1, the substituent X2, the substituent X3 and the substituent X4 have substantially the same number of carbon atoms and more preferably the same number of carbon atoms. This makes it possible to exhibit the above-described effect conspicuously. Further, in this case, since the length of each of the substituents X which protrudes from the main skeleton is substantially the same (or exactly the same) with each other, it is possible to decrease a possibility of steric hindrance caused by the substituent X. This makes it possible that polymerization reaction is carried out reliably between the substituents X, that is the polymer is produced reliably. With this result, it is possible to further improve the carrier transport ability of the polymer.
As shown in the general formula (A2), each substituent X has an epoxy group as its functional group. Since the epoxy group has high reactivity and bonding stability, it is relatively easy to polymerize substituents X directly to form a network having a large two-dimensional expansion.
Further, in the case of epoxy group, upon polymerization reaction of a substituent X and a substituent X, that is polymerization reaction (bonding) of an epoxy group and an epoxy group, by-product other than a product obtained by bonding of these substituents X is difficult to be produced. Therefore, it is possible to prevent impurities from entering into a resultant conductive material. Furthermore, in the first link structure obtained by- polymerization reaction of the epoxy groups, an ether link (bond) and a straight-chain carbon to carbon link (i.e., an alkylene group) exist. In such a link structure having the above structure, transfer of carriers is suppressed. Therefore, even in the case where the interval between the adjacent main skeletons is relatively small, it is possible to prevent or suppress the interaction between the main skeletons from being enhanced.
In this connection, it is to be noted that if the first link structure (that is, each of the substituents X) has a structure havingmany conjugated π bonds such as a benzene ring, interaction occurs between the adjacent main skeletons through such a structure, which cancels the effect obtained by allowing the adjacent main skeletons to exist at a suitable interval.
Furthermore, it is to be noted that the substituent X may be bonded to the 2-, 3-, A-, 5- or 6-position of the benzene ring, but preferably bonded to the 3-, 4- or 5-position. This makes it possible to conspicuously exhibit the effect obtained by linking the adjacent main skeletons via the first link structure. Namely, it is possible for the adjacent main skeletons to exist at a suitable interval more reliably.
Next, a description will be made with regard to the main skeletons which contribute to carrier transportation in a polymer.
In the compound represented by the above-mentioned general formula (Al) (hereinafter, simply referred to as "compound (Al) " ) , it is possible to change the carrier transport properties of the polymer by appropriately setting the chemical structure of a group (or a linking group) Y. The reason for this can be considered as follows. In the polymer, the energy level of the valence and conduction bands or the size of the band gap is changed according to changes in the spread of the electron cloud (i.e., distribution of electrons) in the main skeleton which contributes to carrier transportation.
In the compound (Al), the group Y contains at least one substituted or unsubstituted aromatic hydrocarbon ring or at least one substituted or unsubstituted heterocyclic ring. By selecting kinds of the aromatic hydrocarbon ring and/or heterocyclic ring appropriately, it is possible to adjust carrier transport properties in a resultant polymer relatively easily.
For example, by selecting a structure constituted from unsubstituted aromatic hydrocarbon ring as the group Y, it is possible to obtain a polymer which can exhibit a hole transport ability. In particular, by selecting a structure consisting of carbon atoms and hydrogen atoms as the group Y, it is also possible to obtain a polymer which can exhibit a higher hole transport ability.
In more details, as for the structure constituted from the unsubstituted aromatic hydrocarbon ring, those represented by the following chemical formulas (Cl) to (Cl6) can be mentioned. (Cl) to (C16)
Figure imgf000034_0001
Figure imgf000034_0002
Figure imgf000034_0003
Figure imgf000034_0004
( C16 ) ( C17 )
Figure imgf000035_0001
In this case, it is preferred that the group Y has 6 to 30 carbon atoms, more preferably 10 to 25 carbon atoms, and even more preferably 10 to 20 carbon atoms, in total.
Further, in the group Y, it is preferred that the number of aromatic hydrocarbon ring is 1 to 5, more preferably 2 to 5, and even more preferably 2 to 3.
Taking the above-mentioned factors into account, in the compound (Al) a biphenylene group represented by the chemical formula (Cl) or its derivative is considered to be a particularly preferable structure as the group Y.
By selecting such a group, the hole transport ability of the resultant polymer becomes excellent, and thus the resultant conductive layer can also have an excellent hole transport ability.
Further, by selecting a structure which contains at least one substituted or unsubstituted heterocyclic ring as the group Y, it is possible to control the carrier transport ability of the resultant polymer relatively easily. In this connection, it is preferred that such a heterocyclic ring contains at least one heteroatom selected from among nitrogen, oxygen, sulfur, selenium, and tellurium. By selecting such a heterocyclic ring that contains such a kind of heteroatom, it is easy to change the energy level of the valence and conduction bands or the size of the band gap of the polymer.
The heterocyclic ring may be either an aromatic heterocycle or a nonaromatic heterocycle, but an aromatic heterocycle is preferably used. By using an aromatic heterocycle, it is possible to properly prevent the electron density of the main skeleton with a conjugated chemical structure frombeing biased, that is, it is possible to properly prevent localization of π electrons. As a result, the carrier transport ability of the polymer is prevented from being impaired.
The group Ypreferably contains 1 to 5 heterocyclic rings, more preferably 1 to 3 heterocyclic rings. In the case where the group Y contains 2 or more heterocyclic rings, these rings may be the same or different. By allowing the group Y to have such a number of heterocyclic rings, it is possible to sufficiently change the energy level of the valence and conduction bands or the size of the band gap of the polymer.
In the case where the group Y contains at least one substituted or unsubstituted heterocyclic ring, the group Y may further contain at least one aromatic hydrocarbon ring in addition to the at least one heterocyclic ring. By selecting a group containing a heterocycle and an aromatic hydrocarbon ring as the group Y, it is possible to impart a desired carrier transport property to the polymer more reliably.
Particularly, it is preferred that the group Y contains two aromatic hydrocarbon rings each bonded to each N in the general formula (1) directly and at least one heterocyclic ring which exists between these aromatic hydrocarbon rings. By using such a group Y, it is possible to reliably prevent the electron density of the polymer from being biased. As a result, the polymer can have an even (uniform) carrier transport ability.
Further, it is also preferred that the group Y has 2 to 75 carbon atoms, more preferably 2 to 50 carbon atoms, in total. If the group Y has too many carbon atoms in total, the solubility of the compound represented by the general formula (Al) in a solvent tends to be lowered depending on the kind of substituent X, creating a possibility that the range of the choices of solvents to be used in preparing the composition for conductive materials according to the present invention becomes narrow.
On the other hand, by setting a total number of carbon atoms contained in the group Y to a value within the above range, it is possible to maintain the planarity of the main skeleton. As a result, the carrier transport ability of the polymer is reliably prevented from being impaired.
Taking these factors into account, as a structure constituted from unsubstituted heterocyclic rings, such structures as represented by any one of the following chemical formulas (Dl) to (D20) are considered to be preferable structures.
)
Figure imgf000038_0001
Figure imgf000039_0001
Figure imgf000039_0002
Figure imgf000039_0003
Figure imgf000040_0001
Figure imgf000040_0002
Figure imgf000040_0003
Figure imgf000040_0004
Figure imgf000040_0005
Figure imgf000040_0006
Figure imgf000041_0001
(D20)
Note that in these chemical formulas each Q1 may be the same or different and each independently represent N-T1, S, O, Se, or Te (where T1 represents H, CH3, or Ph), each Q2 may be the same or different and each independently represent S or O, and each Q3 may be the same or different and each independently represent N-T3, S, O, Se, or Te (where T3 represents H, CH3, C2H5 or Ph) .
By appropriately determining the chemical structure of the group Y as described above, a polymer obtained by selecting, for example, any one of the chemical formula (D2), (D16), (D18) and (D20) as the groupY can exhibit ahighhole transport ability as compared to a polymer obtained by selecting the chemical formula (Dl7) and can exhibit an especially high hole transport ability as compared to a polymer obtained by selecting the chemical formula (D8) or (D19).
On the contrary, a polymer obtained by selecting any one of the chemical formulas (D8), (D17) and (D19) as the group Y can exhibit a high electron transport ability as compared to a polymer obtained by the chemical formulas (D2) or (D16). Further, the polymer obtained by selecting any one of the chemical formulas (D8), (Dl7) and (Dl9) as the group Y can also exhibit an especially high electron transport ability as compared with a polymer obtained by selecting the chemical formulas (D18) or (D20).
Further, the unsubstituted heterocyclic ring and/or the unsubstituted aromatic hydrocarbon ring contained in the group Y may introduce a substituent so long as the planarity of the main skeleton is not greatly affected. Examples of such a substituent include an alkyl group having a relatively small number of carbon atoms such as a methyl group or an ethyl group or and a halogen group and the like.
Furthermore, in the main skeleton, each of the substituents R is a hydrogen atom, a methyl group, or an ethyl group, and each substituent R is selected in accordance with the number of carbon atoms of the substituent X. For example, in the case where the number of carbon atoms is large, a hydrogen atom is selected as the substituent R, and in the case where the number of carbon atoms is small, a methyl group or an ethyl group is selected as the substituent R.
Now, in the present invention, it is preferred that the polymer contains a second link structure produced by polymerization reaction(s) of a substituent X and a substituent X via an epoxy-based cross-linking agent in addition to the first link structure produced by the direct polymerization reaction of the substituents X (which are any one of the substituents X1, X2, X3 and X4) as described above. According to such a polymer, since an interval between the main skeletons is maintained at a suitable interval, interaction between the main skeletons can be further decreased. As a result, the polymer containing the second link structure can exhibit a sufficiently high hole transport ability.
In such a polymer, it is preferred that the substituent X represented by the general formula (A2) has a straight-chain carbon-carbon link (i.e., an alkylene group) in which n1 is 2 to 8, in particular 2 to 6. This makes it possible for adjacent main skeletons to exist at a suitable interval, therebyreliably decreasing the interaction between the adjacent main skeletons in a resultant polymer in spite of the case where the first link structure and/or the second link structure is produced. In addition, it is also possible to transfer carriers between the main skeletons more reliably so that the resultant polymer has a high carrier transport ability.
Preferably, the substituent X1 and the substituent X3 contain substantially the same number of carbon atoms, more preferably the same number of carbon atoms. By selecting such substituents X, it is possible to adequately prevent the electrical affects to the main skeleton which would be given by the substituents X (the substituent X1 and/or the substituent X3) from varying, and as a result thereof the electron density in the polymer from being biased. This makes it possible to improve the carrier transport ability of the polymer.
In view of the above, it is also preferred that the substituent X2 and the substituent X4 have substantially the same number of carbon atoms and more preferably the same number of carbon atoms. This makes it possible to improve the above-described effect further, thereby enabling to further improve the carrier transport ability of the polymer.
Further, it is also preferred that the substituent X1, the substituent X2, the substituent X3 and the substituent X4 have substantially the same number of carbon atoms and more preferably the same number of carbon atoms. This makes it possible to exhibit the above-described effect conspicuously. Further, in this case, since the interval between the main skeletons in the polymer can be made larger than a certain distance in spite of the case where the first link structure is formed and/or the second link structure is formed, occurrence of the interaction between the main skeletons can be further prevented. With this result, it is possible to further improve the carrier transport ability of the polymer.
On the other hand, the epoxy-based cross-linking agent used in the present invention has an epoxy group as a group to be bonded to the substituent X (hereinbelow, simply referred to as "bonding radical") . As described above, since the epoxy grouphas highbonding stability, the epoxy-based cross-linking agent exhibits superior adhesiveness, water-resisting property, chemical resistance andheat resistance. Therefore, by using the epoxy-based cross-linking agent as a cross-linking agent for bonding a substituent X and a substituent X, a conductive layer formed from the conductive material (polymer) of the present invention can exhibit superior adhesiveness for the primary layer (lower layer) on which the conductive layer is to be formed and also exhibit excellent water-resisting property, chemical resistance and heat resistance. For these reasons, it is possible to improve characteristics of an electronic device provided with the conductive layer.
Further, such a conductive material formed of the composition mentioned above has a high solubility for various solvents. Therefore, the range of the choices of solvents to be used in preparing the composition for conductive materials of the present invention becomes wide, and thus there is an advantage that it is possible to improve a process for forming the conductive layer.
Furthermore, since the epoxy group has a stable photopolymerization reaction characteristic, the epoxy group reacts with the substituent X effectively and thereby it is possible to effectively prevent unreacted substituents X and epoxy-based cross-linking agent from remaining as they are. Therefore, it is possible to prevent formation of a polymer in which a portion where the substituents X are directly bonded to each other and a portion where the substituents X are bonded via the epoxy-based cross-linking agent are unevenly distributed, thereby enabling a conductive layer having a uniform membrane property to be formed.
The epoxy-based cross-linking agent to be used is not particularly limited so long as a substituent X and a substituent X can be linked (bonded) together via the epoxy-based cross-linking agent. Examples of such an epoxy-based cross-linking agent include a (meth)acrylic ester-based epoxy cross-linking agent, a bisphenol epoxy cross-linking agent, a glycidyl ester-based epoxy cross-linking agent, an alicyclic epoxy cross-linking agent, an urethane modified epoxy cross-linking agent, a silicon-containing epoxy cross-linking agent, a polyfunctional phenol-based epoxy cross-linking agent, and a glycidyl amine-based epoxy cross-linking agent. These epoxy-based cross-linking agents may be used singly or in combination of two or more of them.
Among these epoxy-based cross-linking agents, an epoxy-based cross-linking agent which contains at least one of the (meth)acrylic ester-based epoxy cross-linking agent, the bisphenol epoxy cross-linking agent, the glycidyl ester-based epoxy cross-linking agent, the alicyclic epoxy cross-linking agent, the urethane modified epoxy cross-linking agent, the silicon-containing epoxy cross-linking agent, the polyfunctional phenol-based epoxy cross-linking agent and the glycidyl amine-based epoxy cross-linking agent is particularly preferable.
Hereinbelow, a detailed description will be made with regard to each of these epoxy-based cross-linking agents.
(I) (meth)acrylic ester-based epoxy cross-linking agent
The (meth)acrylic ester-based epoxy cross-linking agent has as its bonding radicals an epoxy group and a (meth)acryloyl group in its molecular structure. Therefore, by using the (meth)acrylic ester-based epoxy cross-linking agent as the epoxy-based cross-linking agent, when a substituent X and a substituent X are to be bonded or linked together via the epoxy-based cross-linking agent, it becomes possible to react the epoxygroup and the (meth)acryloyl groupwith the respective substituents X separately. Namely, it is possible to react one of the epoxy. group and the (meth)acryloyl group with a substituent X and then react the other of the epoxy group and the (meth)acryloyl groupwitha substituent X. This means that, in the example case where the (meth)acryloyl group is reacted with a substituent X after the epoxy group has been reacted with a substituent X, there is an advantage in that after the reaction of the epoxy group with substituent X has been fullyprogressed, the (meth)aσryloyl groupwhich is different from the epoxy group can be made to react with the remaining substituent X. In other words, by using the epoxy group and the (meth)acryloyl group having different reaction paths to progress the reactions, it is possible to reduce the number of unreacted substituents X remaining in the resultant polymer.
This in turn makes it possible to increase the cross-linking density of the substituents X via the epoxy-based cross-linking agent. As a result, the density of polymer in a conductive layer to be formed can also have a high density, and thus the conductive layer is capable of exhibiting sufficient strength.
Such an epoxy-based cross-linking agent is particularly helpful when it is used in combination with the compounds each represented by the above-mentioned general formula (Al) in which the number of n1 of the substituent X is large, that is the compounds each represented by the above-mentioned general formula (Al) and having a relatively flexible structure. Further, since the density of polymer becomes high, it is possible to prevent the material for forming an upper layer from entering, into a portion of the conductive layer which is in the vicinity of the upper surface thereof. This makes it possible to clearly define the boundary between the conductive layer and the upper layer to be formed on the conductive layer. Further, this also makes it possible to transfer the carriers from the conductive layer to the upper layer smoothly. For these reasons, it becomes possible to improve characteristics of electronic devices such as organic EL devices and organic thin film transistors which will be described later in details.
Practically, as for such an epoxy-based cross-linking agent, the cross-linking agent represented by the following chemical formula (Bl) can be mentioned.
H2C^A1
(B1> C=O
C)CH2CH-CH2 XO where A1 represents a hydrogen atom or a methyl group.
(II) bisphenol epoxy cross-linking agent
When a bisphenol epoxy cross-linking agent is used as the epoxy-based cross-linking agent, it becomes possible to improve chemical resistance of a polymer (conductive material) to be formed and a conductive layer to be formed from the polymer due to the characteristics of its molecular structure (in particular, bisphenol structure). This makes it possible to select various types of solvents or dispersants which can be used in preparation of the materials for forming the upper layer. This means that more appropriate constituent materials can be selected for a conductive layer. As a result, it becomes possible to manufacture electronic devices capable of exhibiting sufficient characteristics.
Practically, as for such a bisphenol epoxy cross-linking agent, the cross-linking agent represented by the following chemical formulas (B2) to (B6) can be mentioned.
In this regard, it is to be noted that by setting n6 in these formulas to the below mentioned ranges, it is possible to form an epoxy cross-linking agent of the type of monomer and low molecular polymer. By using such an epoxy cross-linking agent, it is possible to obtain a link structure that allows the main skeletons to exist at a more appropriate interval.
Figure imgf000049_0001
Figure imgf000050_0001
Note that in each of these formulas, n is an integer of 0 to 10.
Among these bisphenol epoxy-based cross-linking agents, by using the bisphenol A epoxy cross-linking agent represented by the above-mentioned chemical formula (B2), it becomes possible to improve the reactivity between the substituent X and the epoxy-based cross-linking agent when forming a conductive layer by polymerization reaction of the substituent X and the epoxy-based cross-linking agent by light radiation. As a result, a polymer to be formed can have a high percentage of chemical structure in which the substituents X are bonded together via the epoxy-based cross-linking agent. This means that in the resultant polymer most of the main skeletons are allowed to exist at an appropriate interval therebetween, and thus the polymer can have a higher carrier transport ability.
Further, by using the bisphenol F epoxy cross-linking agent representedby the above-mentionedchemical formula (B3) , it becomes possible to decrease the viscosity of the obtained composition for conductive materials. This makes it possible to apply the conductive material formed of the composition onto the lower layer (primary layer) when forming a conductive layer. As a result, it is possible to form conductive layers having even (uniform) characteristics. Furthermore, by using the biphenyl epoxy cross-linking agent representedby the above-mentioned chemical formula (B4) , it becomes possible to improve moisture resistance and thermal conductivity of a polymer to be formed and to lower a stress generated therein.
Moreover, by using the bisphenol S epoxy cross-linking agent representedby the above-mentionedchemical formula (B5) , it becomes possible to improve moisture resistance of a polymer to be formed. As a result, electronic devices to be manufactured can maintain superior characteristics even though they are exposed to high temperature and high moisture environment.
(Ill) glycidyl ester-based epoxy cross-linking agent, alicyclic epoxy cross-linking agent, urethane modified epoxy cross-linking agent and silicon-containing epoxy cross-linking agent
Each of the glycidyl ester-based epoxy cross-linking agent, the alicyclic epoxy cross-linking agent, the urethane modified epoxy cross-linking agent and the silicon-containing epoxy cross-linking agent has a molecular structure having excellent flexibility as compared to the benzene rings contained in the epoxy-based cross-linking agents such as the bisphenol epoxy cross-linking agent and the polyfunctional phenole-based epoxy cross-linking agent. Therefore, polymers that are formed using these epoxy-based cross-linking agents can exhibit excellent flexibility. This also makes it possible to impart flexibility to a conductive layer to be formed with maintaining sufficient strength. As a result, electronic devices provided with conductive layers formed using these epoxy-based cross-linking agents can have excellent flexibility.
In this regard, it is to be noted that these epoxy-based cross-linking agents are advantageous when used in combination with the compound represented by the above-mentioned general formula (Al) and having a small number of n1 in the substituent X, that is the compound represented by the above-mentioned general formula (Al) which has a relatively solid structure.
Practically, as for such a glycidyl ester-based epoxy cross-linking agent, the cross-linking agents represented by the following chemical formulas (B7) and (B8) can be mentioned.
Figure imgf000052_0001
Figure imgf000052_0002
In this regard, it is to be noted that byusing the glycidyl ester-based epoxy cross-linking agent containing phthalic acid represented by the chemical formula (B8), it is possible to improve reactivity between the substituent X and the epoxy-based cross-linking agent when a conductive layer is to be formed by the polymerization reaction between the substituent X.and the epoxy-based cross-linking agent by light irradiation. As a result, due to the same reason as that describedwith reference to the bisphenol A epoxy cross-linking agent, it is possible to obtain a polymer having a high carrier transport ability.
Further, by using this type of glycidyl ester-based epoxy cross-linking agent, there is an advantage in that it is possible to improve UV resistance and transparency of the polymer to be formed.
Further, practically, as for the alicyclic epoxy cross-linking agent, the cross-linking agents represented by the following chemical formulas (B9) to (Bl2) can be mentioned.
Figure imgf000053_0001
Figure imgf000053_0002
( B12 )
Figure imgf000053_0003
By using such an alicyclic epoxy cross-linking agent, it is possible to obtain the same results as those of the glycidyl ester-based epoxy cross-linking agent containing phthalic acid described above.
Further, in the case where such an alicyclic epoxy cross-linking agent is used, it is possible to decrease the viscosity of the conductive material ' obtained from the conductive composition. As a result, it is possible to improve applicability of the conductivematerialwhen it is applied onto the lower layer.
Furthermore, as for the urethane modified epoxy cross-linking agent, the cross-linking agent representedby the following chemical formula (B13) can be mentioned.
(Bl3) H2C--HCH2C-OA3OCNH-A2-NHCOA3O-CH2CH-CH2 O o O U
wherein A2 represents a group obtained by eliminating two isocyanate groups from a di-isocyanate compound, and two A3S may be the same or different and each independently represents a group obtained by eliminating two hydroxyl groups from a diol compound.
In this regard, it is to be noted that the total number of carbon atoms of A2 and A3S are not particularly limited to any specific value so long as an interval between the main skeletons can be maintained at a suitable distance in the link structure formed using such an epoxy-based cross-linking agent, but preferably it is set to 10 to 30. This allows to set the interval between themain skeletons at amore suitable distance.
Examples of the diol compound include, but are not limited thereto, alkylene diol such as ethylene glycol, propylene glycol, trimethylene glycol, butylenes glycol, tetramethylene glycol, pentamethylene glycol, buten diol, and hexamethylene glycol; polycarbonate diol; carboxylic acid; and polyoxy alkylene diol, and the like.
Examples of the di-isocyanate compound include, but are not limited thereto, aromatic diisocyanate compound such as tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), naphthalene diisocyanate (NDI), p-phenylene diisocyanate, 1,3-bis-(isocyanatomethyl)-benzene (XDI), tetramethylkylylene diisocyanate,
3,3' -dimethyldiphenylmethane-4,4' -diisocyanate, and 4,4'-methylenebis(phenyl isocyanate) and the like; alicyclic diisocyanate compound such as trans-1,4-cyclohexane diisocyanate (CHDI), 4,4' -dicyclohexylmethane di-isocyanate (H12MDI), 1,3-bis- (isocyanatomethyl) -cyclohexane (H6XDI), and 3-isocyanatomethyl-3,5,5' -trimethylcyclohexylisocyanate (IPDI) and the like; and aliphatic diisocyanate compound such as hexamethylene diisocyanate (HDI) , dimer diisocyanate (DDI) , and norbornene diisocyanate (NBDI) and the like.
Moreover, as for the silicon-containing epoxy cross-linking agent, the cross-linking agent representedby the following chemical formula (B14) can be mentioned.
Figure imgf000056_0001
(IV) polyfunctional phenol-based epoxy cross-linking agent and glycidyl amine-based epoxy cross-linking agent
Each of the polyfunctional phenol-based epoxy cross-linking agent and glycidyl "amine-based epoxy cross-linking agent has three or more epoxy groups (bonding radicals) in its molecular structure. Therefore, by using such an epoxy-based cross-linking agent, it is possible to bond or link three or more substituents X and three ormore substituents X together. This mean that it is possible to increase the cross-linking density of the substituents Xvia the epoxy-based cross-linking agent. As a result, it is possible to obtain a conductive layer formed from polymer having high density, so that the same effects as those of the (meth)acrylic ester-based epoxy cross-linking agent can be obtained.
As for the polyfunctional phenol-based epoxy cross-linking agent, the low molecular type cross-linking agents represented by the following chemical formulas (Bl5) to (B18) and the.monomer type cross-linking agents represented by the following chemical formulas (B19) to (B22) canbementioned.
In this regard, it is to be noted that when any one of the low molecular type cross-linking agents is used, it is possible to control the number of the substituents X to be bonded to this epoxy-based cross -linking agent, that is the number of the compound represented by the above-mentioned general formula (Al), by setting the value of n9 and the value of n10 in each formula to the below-mentioned ranges, respectively.
Figure imgf000057_0001
Figure imgf000057_0002
Note that in each of these chemical formulas, n 9 i .s an integer of 1 to 20 and n ,10 is an integer of 1 to 30.
Figure imgf000057_0003
Figure imgf000058_0001
Figure imgf000058_0002
where n .11 is an integer of 0 to 8 .
Figure imgf000058_0003
The epoxy-based cross-linking agent obtained by setting n .11 in the formula to the range mentioned above allows the main skeletons to exist at a more suitable interval.
Further, in the case where the epoxy-based cross-linking agents represented by the chemical formulas (B15) to (B17), it is possible to improve moisture resistance of the polymer to be formed and decrease a stress generated in a conductive layer to be formed from the polymer.
Furthermore, by using the polyparaphenylenevinylene(PPV)-based epoxy cross-linking agent representedby the above-mentionedchemical formula (B18) , it is possible to lower resistance value of the polymer to be formed.
Finally, as for the glycidyl amine-based epoxy cross-linking agent, the monomer type cross-linking agents represented by the following chemical formulas (B23) to (B25) can be mentioned.
Figure imgf000059_0001
Figure imgf000059_0002
The above-mentioned epoxy-based cross-linking agents may¬ be usedbycombining two ormore of themarbitrarily. This makes it possible to exhibit the characteristics of the respective epoxy-based cross-linking agents synergistically. As a result, a conductive layer to be formed has compositive characteristics given by the respective epoxy-based cross-linking agents.
Further, in the above-mentioned epoxy-based cross-linking agents, there are some epoxy-based cross-linking agents which contain a benzene ring having a conjugated bond in its chemical structure. However, in the case where such cross-linking agents also contain as its essential structure a non-conjugated chemical structure such as a methylene group, an ether bonding, C-CH3 bonding, and cyclic hydrocarbon, the characteristics of such non-conjugated chemical structures appear in preference to those of the benzene ring structure. Therefore, it is possible to prevent or suppress interaction between the main skeletons through the benzene ring in a resultant polymer from occurring appropriately.
The conductive layer also has excellent solvent resistance, because it is formed of a polymer as its main material which is obtained by direct polymerization reaction of the compounds each represented by the above-mentioned general formula (Al) or polymerization reaction of the compounds via the epoxy-based cross-linking agent. As a result, in the case where the upper layer is formed onto the conductive layer in contact therewith, it is possible to reliably prevent the conductive layer from being swelled up or dissolved by the solvent or dispersant contained in a material for forming the upper layer.
Further., the polymer is obtained by the reaction or bonding between the substituents X or between the substituent X and the epoxy group of the epoxy-based cross-linking agent. Since such an epoxy bonding exhibits a particularly excellent bonding stability, it is possible to prevent the conductive layer from being swelled up or dissolved reliably.
Furthermore, in the case where electronic devices (which will be described later in detail) are manufactured using a laminated body having such a conductive layer, it is possible to prevent the constituent material of the conductive layer and the constituent material of a contacting layer which is in contact with the conductive layer frombeing mutually dissolved with the elapse of time at the boundary between the conductive layer and the contacting layer assuredly since the conductive layer is mainly formed of the polymer described above. As a result, it is possible to prevent the characteristics of the electronic devices from being deteriorated with the elapse of time.
(Organic Electroluminescent Device)
Next, an embodiment of the electronic device according to the present inventionwill be described. In this embodiment, the electronic device of the present invention is embodied as an organic electroluminescent device (hereinafter, simply referred to as an "organic EL device") that is a light emitting device.
FIG. 1 is a cross-sectional view which shows an example of the organic EL device.
The organic EL device 1 shown in FIG. 1 includes a transparent substrate 2, an anode 3 provided on the substrate 2, an organic EL layer 4 provided on the anode 3, a cathode 5 provided on the organic EL layer 4 and a protection layer 6 provided so as to cover these layers 3, 4 and 5.
The substrate 2 serves as a support for the organic EL device 1, and the layers described above are formed on the substrate 2.
As a constituent material of the substrate 2, a material having a light-transmitting property and a good optical property can be used.
Examples of such a material include various resins such as polyethylene terephthalate, polyethylene naphthalate, polypropylene, cycloolefin polymer, polyamide, polyethersulfone, polymethylmethacrylate, polycarbonate, and polyarylate, and various glass materials, and the like. At least one of these materials can be used as a constituent material of the substrate 2.
The thickness of the substrate 2 is not particularly limited, but is preferably in the range of about 0.1 to 30 mm, more preferably in the range of about 0.1 to 10 mm. The anode 3 is an electrode which injects holes into the organic EL layer 4 (that is, into a hole transport layer 41 described later) . This anode 3 is made substantially transparent (which includes transparent and colorless, colored and transparent, or translucent) so that light emission from the organic EL layer 4 (that is, from a light emitting layer 42 described later) can be visually identified.
From such a viewpoint, a material having a high work function, excellent conductivity, and a light transmitting property is preferably used as the constituent material of the anode 3 (hereinafter, referred to as "anode material").
Examples of such an anode material include oxides such as ITO (Indium Tin Oxide), SnO2, Sb-containing SnO2, and Al-containing ZnO, Au, Pt, Ag, Cu, and alloys containing two or more of them. At least one of these materials can be used as an anode material.
The thickness of the anode 3 is not limited to any specific value, but is preferably in the range of about 10 to 200 nm, more preferably in the range of about 50 to 150 nm. If the thickness of the anode 3 is too thin, there is a case that a function of the anode 3 will not be sufficiently exhibited. On the other hand, if the anode 3 is too thick, there is a case that the light transmittance will be significantly lowered depending on, for example, the kind of anode material used, thus resulting in an organic EL device that is not suitable for practical use. It is to be noted that conductive resins such as polythiophene, polypyrrole, and the like can also be used as the anode material.
On the other hand, the cathode 5 is an electrode which injects electrons into the organic EL layer 4 (that is, into an electron transport layer 43 described later) .
As a constituent material of the cathode 5 (hereinafter, referred to as "cathode material") , amaterial having a lowwork function is preferably used.
Examples of such a cathode material include Li, Mg, Ca, Sr, La, Ce, Er, Eu, Sc, Y, Yb, Ag, Cu, Al, Cs, Rb, and alloys containing two or more of them. At least one of these materials can be used as a cathode material.
Particularly, in the case where an alloy is used as a cathode material, an alloy containing a stable metallic element such as Ag, Al, or Cu, specifically an alloy such as MgAg, AlLi, or CuLi is preferablyused. The use of such an alloy as a cathode material makes it possible to improve the electron injection efficiency and stability of the cathode 5.
The thickness of the cathode 5 is preferably in the range of about 1 nm to 1 μm, more preferably in the range of about 100 to 400 nm. If the thickness of the cathode 5 is too thin, there is a case that a function of the cathode 5 will not be sufficiently exhibited. On the other hand, if the cathode 5 is too thick, there is a case that the light emitting efficiency of the organic EL device 1 will be lowered.
The organic EL layer 4 is provided between the anode 3 and the cathode 5. The organic EL layer 4 includes the hole transport layer 41, the light emitting layer 42, and the electron transport layer 43. These layers 41, 42 and 43 are formed on the anode 3 in this order.
The hole transport layer 41 has the function of transporting holes, which are injected from the anode 3, to the light emitting layer 42. The electron transport layer 43 has the function of transporting electrons, which are injected from the cathode 5, to the light emitting layer 42.
As a constituent material for one of the hole transport layer 41 and the electron transport layer 43 or for both the layers 41, 43, the conductive material according to the present invention can be used.
For example, in the case where the conductive material of the present invention is used as the constituent material of the hole transport layer 41, a compound having a chemical structure of the group Y which is constituted from a substituted or unsubstituted aromatic hydrocarbon ring can be used.
In more detail, compounds having chemical structures of the group Y represented by the above-mentioned chemical formulas (Cl) to (C-16) can be used. In this regard, it is to be noted that the constituent material of the electron transport layer 43 are not limited to specific materials, and various materials can be used for the electron transport layer 43.
Examples of such materials that can be used for the electron transport layer 43 include: benzene-based compounds (starburst-based compounds) such as 1,3,5-tris[ (3-phenyl-6-tri-fluoromethyl)quinoxaline-2-yl] benzene (TPQl), " and
1,3,5-tris[{3-(4-t-butylphenyl) -6-trisfluoromethyl}quinoxal ine-2-yl]benzene (TPQ2); naphthalene-based compounds such as naphthalene; phenanthrene-based compounds such as phenanthrene; chrysene-based compounds such as chrysene; perylene-based compounds such as perylene; anthracene-based compounds such as anthracene; pyrene-based compounds such as pyrene; acridine-based compounds such as acridine; stilbene-based compounds such as stilbene; thiophene-based compounds such as BBOT; butadiene-based compounds such as butadiene; coumarin-based compounds such as coumarin; quinoline-based compounds such as quinoline; bistyryl-based compounds such as bistyryl; pyrazine-based compounds such as pyrazine and distyrylpyrazine; quinoxaline-based compounds such as quinoxaline; benzoquinone-based compounds such as benzoquinone, and 2, 5-diphenyl-para-benzoquinone; naphthoquinone-based compounds such as naphthoquinone; anthraquinone-based compounds such as anthraquinone; oxadiazole-based compounds such as oxadiazole, 2-(4-biphenylyl)-5-(4-t-butylphenyl)-l,3,4-oxadiazole (PBD) , BMD, BND, BDD, and BAPD; triazole-based compounds such as triazole, and 3,4,5-triphenyl-l,2,4-triazole; oxazole-based compounds; anthrone-based compounds such as anthrone; fluorenone-based compounds such as fluorenone, and 1,3,8-trinitr.o-fluorenone (TNF); diphenoquinone-based compounds such as diphenoguinone, and MBDQ; stilbenequinone-based compounds such as stilbenequinone, and MBSQ; anthraquinodimethane-based compounds; thiopyran dioxide-based compounds; fluorenylidenemethane-based compounds; diphenyldicyanoethylene-based compounds; florene-based compounds such as florene; metallic or non-metallic phthalocyanine-based compounds such as phthalocyanine, copper phthalocyanine, and iron phthalocyanine; and various metal complexes such as 8-hydroxyquinoline aluminum (AIq3) , and complexes having benzooxazole or benzothiazole as a ligand. These compounds may be used singly or in combination of two or more of them.
In the case where both of the hole transport layer 41 and the electron transport layer 43 are formed using the conductive material according to the present invention as a main material, a constituent material of the hole transport layer 41 and a constituent material of the electron transport layer 43 are selected in consideration of their hole transport ability and electron transport ability.
Specifically, these constituent materials are selected so that the hole transport ability of the hole transport layer 41 becomes relativelyhigher than that of the electron transport layer 43 and the electron transport ability of the hole transport layer 41 becomes relatively lower than that of the electron transport layer 43. In other words, these constituent materials are selected so that the electron transport ability of the electron transport layer 43 becomes relatively higher than that of the hole transport layer 41 and the hole transport ability of the electron transport layer 43 becomes relatively lower than that of the hole transport layer 41.
For example, in the case where a polymer of a compound represented by the general formula (1) in which the group Y has a chemical structure represented by the chemical formula (D18) or (D20) is used as a conductive material for forming a hole transport layer 41, a conductive material for forming an electron transport layer 43 is preferably a polymer of a compound represented by the general formula (1) in which the group Y has a chemical structure represented by the chemical formula (D7) or (D19). In this case, a polymer of a compound represented by the general formula (1) in which the group Y has a chemical structure represented by the chemical formula (D17) may also be used as a conductive material for forming the electron transport layer 43. In the case where a polymer of a compound represented by the general formula (1) in which the group Y has a chemical structure represented by the chemical formula (D7), (D19), or (D17) is used as a conductive material for forming an electron transport layer 43, the conductive material for forming the hole transport layer 41 may also be a polymer of a compound represented by the general formula (1) in which the group Y has a chemical structure represented by the chemical formula (D2) or (D16).
Further, the volume resistivity of the hole transport layer 41 is preferably 10 Ω-cm or larger, more preferably 102 Ω-cm or larger. This makes it possible to provide an organic EL device 1 having a higher light emitting efficiency.
The thickness of thehole transport layer 41 is not limited to any specific value, but is preferably in the range of about 10 to 150 nm, more preferably in the range of about 50 to 100 nm. If the thickness of the hole transport layer 41 is too thin, there is a case that a pin hole may be produced. On the other hand, if the thickness of the hole transport layer 41 is too thick, there is a case that the transmittance of the hole transport layer 41 may be lowered so that the chromaticity (hue) of luminescent color of the organic EL device 1 is changed.
The thickness of the electron transport layer 43 is not limited to any specific value, but is preferably in the range of about 1 to 100 nm, more preferably in the range of about 20 to 50 nm. If the thickness of the electron transport layer 43 is too thin, there is a case that a pin hole may be produced, thereby causing a short-circuit. On the other hand, if the electron transport layer 43 is too thick, there is a case that the value of resistance may become high.
Further, the conductive material according to the present invention is particularly useful for forming a relatively thin hole transport layer 41 or electron transport layer 43.
When a current flows between the anode 3 and the cathode 5 (that is, a voltage is applied across the anode 3 and the cathode 5) , holes are moved in the hole transport layer 41 and electrons are moved in the electron transport layer 43, and the holes and the electrons are then recombined in the light emitting layer 42. Then, in the light emitting layer 42, excitons are produced by energy released upon the recombination, and the excitons release energy (in the form of fluorescence or phosphorescence) or emit light when returning to the ground state.
Any material can be used as a constituent material of the light emitting layer 42 (hereinafter, referred to as "light emittingmaterial" ) so long as it can provide a fieldwhere holes can be injected from the anode 3 and electrons can be injected from the cathode 5 during the application of a voltage to allow the holes and the electrons to be recombined.
Such light emitting materials include various low-molecular light emitting materials and various high-molecular light emitting materials (which will be mentioned below) . At least one of these materials can be used as a light emitting material.
In this regard, it is to be noted that the use of a low-molecular light emitting material makes it possible to obtain a dense light emitting layer 42, thereby improving the light emitting efficiency of the light emitting layer 42. Further, since a high-molecular light emitting material is relatively easily dissolved in a solvent, the use of such a high-molecular light emitting material makes it easy to form a light emitting layer 42 by means of various application methods such as an ink-jet method and the like. Furthermore, if the low-molecular light emitting material and the high-molecular light emitting material are used together, it is possible to obtain the synergistic effect resulting from the effect of the low-molecular light emitting material and the effect of the high-molecular light emittingmaterial. That is, it is possible to obtain the effect that a dense light emitting layer 42 having excellent light emitting efficiency can be easily formed by means of various application methods such as the ink-jet method and the like.
Examples of such a low-molecular light emitting material include: benzene-based compounds such as distyrylbenzene (DSB) , and diaminodistyrylbenzene (DADSB) ; naphthalene-based compounds such as naphthalene and Nile red; phenanthrene-based compounds such as phenanthrene; chrysene-based compounds such as chrysene and 6-nitrochrysene; perylene-based compounds such as perylene and
N,N' -bis(2,5-di-t-butylphenyl)-3,4,9,10-perylene-di-carboxy imide (BPPC) ; coronene-based compounds such as coronene; anthracene-based compounds such as anthracene and bisstyrylanthracene; pyrene-based compounds such as pyrene; pyran-based compounds such as
4-(di-cyanomethylene) -2-methyl-6- (para-dimethylaminostyryl) -4H-pyran (DCM); acridine-based compounds such as acridine; stilbene-based compounds such as stilbene; thiophene-based compounds such as 2,5-dibenzooxazolethiophene; benzooxazole-based compounds such as benzooxazole; benzoimidazole-based compounds such as benzoimidazole; benzothiazole-based compounds such as 2,2' - (para-phenylenedivinylene) -bisbenzothiazole; butadiene-based compounds such as bistyryK1,4-diphenyl-l,3-butadiene) and tetraphenylbutadiene; naphthalimide-based compounds such as naphthalimide; coumarin-based compounds such as coumarin; perynone-based compounds such as perynone; oxadiazole-based compounds such as oxadiazole; aldazine-based compounds; cyclopentadiene-based compounds such as 1,2,3,4,5-pentaphenyl-1,3-cyclopentadiene (PPCP) ; quinacridone-based compounds such as quinacridone and quinacridone red; pyridine-based compounds such as pyrrolopyridine and thiadiazolopyridine; spiro compounds such as 2,2 ' ,7,7' -tetraphenyl-9,9 '-spirobifluorene; metallic or non-metallic phthalocyanine-based compounds such as phthalocyanine (H2Pc) and copper phthalocyanine; florene-based compounds such as florene; and various metallic complexes such as 8-hydroxyquinoline aluminum (AIq3), tris(4-methyl-8-quinolinolate) aluminum(III) (Almq3), (8-hydroxyquinoline) zinc (Znq2),
(1,10-phenanthroline)-tris-(4,4,4-trifluoro-1-(2-thienyl)-b utane-l,3-dionate) europium(III) (Eu(TTA)3(phen) ) , fac-tris(2-phenylpγridine) iridium (Ir(ppy)3), and (2,3,7,8,12,13,17, 18-octaethyl-21H, 23H-porphin) platinum(II) .
Examples of a high-molecular light emitting material include polyacetylene-based compounds such as trans-type polyacetylene, cis-type polyacetylene, poly(di-phenylacetylene) (PDPA) , and poly(alkyl, phenylacetylene) (PAPA); polyparaphenylenevinylene-based compounds such as poly(para-phenylenevinylene) (PPV) , poly(2,5-dialkoxy-para-phenylenevinylene) (RO-PPV) , cyano-substituted-poly(para-phenylenevinylene) (CN-PPV) , poly(2-dimethyloctylsilyl-para-phenylenevinylene) (DMOS-PPV), . and poly(2-methoxy-5-(2 ' -ethylhexoxy)-para-phenylenevinylene)_ (MEH-PPV) ; polythiophene-based compounds such as poly(3-alkylthiophene) (PAT), and poly(oxypropylene)triol (POPT); polyfluorene-based compounds such as poly(9,9-dialkylfluorene) (PDAF) , α,ω-bis[N,N' -di(methylphenyl)aminophenyl] -poly[9, 9-bis(2- ethylhexyl)fluorene-2,7-diyl] (PF2/6am4) , poly(9,9-dioctyl-2,7-divinylenefluorenyl) -alt-co(anthracene -9,10-diyl); polyparaphenylene-based compounds such as poly(para-phenylene) (PPP) , and poly(l,5-dialkoxy-para-phenylene) (RO-PPP) ; polycarbazole-based compounds such as poly(N-vinylcarbazole) (PVK); and polysilane-based compounds such as poly(methylphenylsilane) (PMPS), poly(naphthylphenylsilane) (PNPS), and poly(biphenylylphenylsilane) (PBPS).
Further, the conductive material according to the present invention can also be used as the light emitting material depending on the combination of constituent materials used for forming a hole transport layer 41 and an electron transport layer 43.
For example, in the case where poly(thiophene/styrenesulfonic acid) such as poly(3,4-ethylenedioxythiophene/styrenesulfonic acid) or an arylamine compound such as N,N'-bis(l-naphthyl)-N,N'-diphenyl-benzidine(α-NPD) is used as a constituent material of the hole transport layer 41 and a triazole-based compound such as 3,4,5-triphenyl-l,2,4-triazole or an oxadiazole compound such as 2-(4-t-butylphenyl) -5-(biphenyl-4-yl) -1,3,5-oxadiazole (PBD) is used as a constituent material of the electron transport layer 43, a polymer of the compound represented by the general formula (1) in which the group Y has a chemical structure represented by the chemical formula (D12) or (D14) can be usedas a conductivematerial for forming a light emitting layer 42.
The thickness of the light emitting layer 42 is not limited to any specific value, but is preferably in the range of about 10 to 150 nm, more preferably in the range of about 50 to 100 nm. By setting the thickness of the light emitting layer to a value within the above range, recombination of holes and electrons efficiently occurs, thereby enabling the light emitting efficiency of the light emitting layer 42 to be further improved.
It is to be noted here that any one of the electron transport layer 41, the light emitting layer 42, and the electron transport layer 43 in the organic EL device 1 may be formed using the conductive material according to the present invention or all the layers 41, 42, and 43 may be formed using the conductive material according to the present invention.
Although, in the present embodiment, each of the light emitting layer 42, the hole transport layer 41, and the electron transport layer 43 is separately provided, they may be formed into a hole-transportable light emitting layer which combines the hole transport layer 41 with the light emitting layer 42 or an electron-transportable light emitting layer which combines the electron transport layer 43 with the light emitting layer 42. In this case, an area in the vicinity of the boundary between the hole-transportable light emitting layer and the electron transport layer 43 or an area in the vicinity of the boundary between the electron-transportable light emitting layer and the hole transport layer 41 functions as the light emitting layer 42.
Further, in the case where the hole-transportable light emitting layer is used, holes injected from an anode into the hole-transportable light emitting layer are trapped by the electron transport layer, and in the case where the electron-transportable light emitting layer is used, electrons injected from a cathode into the electron-transportable light emitting layer are trapped in the electron-transportable light emitting layer. In both cases, there is an advantage in that the recombination efficiency of holes and electrons can be improved.
In this regard, it is to be noted that between the adjacent layers in the layers 3, 4 and 5, any additional layer may be provided according to its purpose. For example, a hole injecting layer for improving the injection efficiency of holes from the anode 3 may be provided between the hole transport layer 41 and the anode 3, or an electron injecting layer for improving the injection efficiency of electrons from the cathode 5 may be provided between the electron transport layer 43 and the cathode 5. In such a case where the organic EL device 1 includes a hole injecting layer and/or an electron injecting layer, the conductive material according to the present invention can be used as a constituent material of the hole injecting layer and/or the electron injecting layer.
As a constituent material of a hole injecting layer other than the conductivematerial according to the present invention, for example, copper phthaloσyanine, 4,4' ,4' ' -tris(N,N-phenyl-3-methylphenylamino)triphenylamine (M-MTDATA), or the like can be used.
As described above, the protection layer 6 is provided so as to cover the layers 3, 4 and 5 constituting the organic EL device 1. This protection layer 6 has the function of hermetically sealing the layers 3, 4 and 5 constituting the organic EL device 1 to shut off oxygen and moisture. By providing such a protection layer 6, it is possible to obtain the effect of improving the reliability of the organic EL device 1 and the effect of preventing the alteration and deterioration of the organic EL device 1.
Examples of a constituent material of the protection layer 6 include Al, Au, Cr, Nb, Ta and Ti, alloys containing them, silicon oxide, various resin materials, and the like. In this regard, it is to be noted that in the case where a conductive material is used as a constituent material of the protection layer 6, it is preferred that an insulating film is provided between the protection layer 6 and each of the layers 3, 4 and 5 to prevent a short circuit therebetween, if necessary.
The organic EL device 1 can be used for a display, for example, but it can also be used for various optical purposes such as a light source and the like.
In the case where the organic EL device 1 is used for a display, the drive system thereof is not particularly limited, and either of an active matrix system or a passive matrix system may be employed.
The organic EL device 1 as described above can be manufactured in the following manner, for example.
[Al] Step of forming anode
First, a substrate 2 is prepared, and then an anode 3 is formed on the substrate 2.
The anode 3 can be formed by, for example, chemical vapor deposition (CVD) such as plasma CVD, thermal CVD, and laser CVD, vacuum deposition, sputtering, dry plating such as ion plating, wet plating such as electrolytic plating, immersion plating, and electroless plating, thermal spraying, a sol-gel method, a MOD method, bonding of a metallic foil, or the like.
[A2] Step of forming hole transport layer
[A2-1]
First, a composition for conductive materials of the present invention (hereinafter, also referred to as a "hole transport material") is applied or supplied onto the anode 3. In the case where the composition for conductive materials contains an epoxy-based cross-linking agent in addition to a compound represented by the general formula (Al) , the mixing ratio between the compoundrepresentedby the general formula (Al) and the epoxy-based cross-linking agent in the composition for conductive materials is preferably 9: 1 to 3: 2, more preferably 4: 1 to 7: 3, in terms of mole ratio. By setting the mixing ratio of the epoxy-based cross-linking agent within the above range, it is possible for adjacent main skeletons to exist at a more suitable interval in a resultant polymer.
In the application of the hole transport material, various application methods such as a spin coating method, a casting method, a micro gravure coating method, a gravure coating method, a bar coating method, a roll coating method, a wire-bar coating method, a dip coating method, a spray coating method, a screen printing method, a flexographic printing method, an offset printing method, an ink-jet method, and the like can be employed. According to such an application method, it is possible to relatively easily supply the hole transport material onto the anode 3.
In the case where the composition for conductive materials are prepared using a solvent or dispersion medium, examples of such a solvent or dispersion medium include: inorganic solvents such as nitric acid, sulfuric acid, ammonia, hydrogen peroxide, water, carbon disulfide, carbon tetrachloride, and ethylene carbonate; and various organic solvents such as ketone-based solvents e.g., methyl ethyl ketone (MEK), acetone, diethyl ketone, methyl isobutyl ketone (MIBK), methyl isopropyl ketone (MIPK), and cyclohexanone, alcohol-based, solvents e.g., methanol, ethanol, isopropanol, ethylene glycol, diethylene glycol (DEG), and glycerol, ether-based solvents e.g., diethyl ether, diisopropyl ether, 1,2-dimethoxy ethane (DME), 1,4-dioxane, tetrahydrofuran (THF), tetrahydropyran (THP), anisole, diethylene glycol dimethyl ether (diglyme) , and diethylene glycol ethyl ether (Carbitol), cellosolve-based solvents e.g". , methyl cellosolve, ethyl cellosolve, and phenyl cellosolve, aliphatic hydrocarbon-based solvents e.g, hexane, pentane, heptane, and cyclohexane, aromatic hydrocarbon-based solvents e.g., toluene, xylene, and benzene, aromatic heterocyclic compound-based solvents e.g., pyridine, pyrazine, furan, pyrrole, thiophene, and methyl pyrrolidone, amide-based solvents e.g., N,N-dimethylformamide (DMF) and N,N-dimethylacetamide (DMA), halogen compound-based solvents e.g., dichloromethane, chloroform, and 1,2-dichloroethane, ester-based solvents e.g., ethyl acetate, methyl acetate, and ethyl formate, sulfur compound-based solvents e.g., dimethyl sulfoxide (DMSO) and sulfolane, nitrile-based solvents e.g., acetonitrile, propionitrile, and acrylonitrile, organic acid-based solvents e.g., formic acid, acetic acid, trichloroacetic acid, and trifluoroacetic acid, and mixed solvents containing them.
It is to be noted that the composition for conductive materials preferably contains a polymerization initiator. By adding a polymerization initiator to the composition for conductive materials, it is possible to promote direct polymerization of substituents X or polymerization of substituents X via the epoxy-based cross-linking agent when predetermined treatment such as heating or light irradiation is carried out in the next step [A2-2].
Examples of a polymerization initiator include, but are not limited thereto, photopolymerization initiators such as radical photopolymerization initiators and cationic photopolymerization initiators, heat polymerization initiators, and anaerobic polymerization initiators. Among them, radical photopolymerization initiators are particularly preferably used. By using a radical photopolymerization initiator, it is possible to promote direct polymerization of substituents X or polymerization of substituents X via the epoxy-based cross-linking agent in the next step [A2-2] relatively easily.
As such a cationic photopolymerization initiator, various cationic photopolymerization initiators can be used. Examples of such cationic photopolymerization initiators include onium salt-based cationic photopolymerization initiators such as aromatic sulfouium salt-based cationic photopolymerization initiator, aromatic iodonium salt-based cationic photopolymerization initiator, aromatic diazonium cationic photopolymerization initiator, pyridium suit-based cationic photopolymerization initiator, and aromatic phosphonium salt-based cationic photopolymerization initiator. Further, nonionic photopolymerization initiators such as iron arene complex and sulfonate ester may be used. Further, in the case where a photopolymerization initiator is used as a polymerization initiator, a sensitizer suitable for the photopolymerization initiator may be added to the composition for conductive materials.
[A2-2]
Next, the hole transport material supplied onto the anode 3 is irradiated with light.
By this light irradiation, substituents X of the compounds each represented by the general formula (Al) and contained in the hole transport material are polymerized directly or via the epoxy-based cross-linking agent to obtain a polymer having a network structure (that is, a conductive material according to the present invention). As a result, a hole transport layer 41 mainly comprised of the conductive material according to the present invention is formed on the anode 3.
By forming a hole transport layer 41 using the conductive material according to the present invention as its mainmaterial, it is possible to prevent the hole transport layer 41 from swelling and being dissolved due to a solvent or dispersion medium contained in a light emitting layer material to be supplied onto the hole transport layer 41 in the next step [A3] . As aresult, mutual dissolution between the hole transport layer 41 and the light emitting layer 42 is reliably prevented.
In addition, by forming a hole transport layer 41 using the conductive material (that is, the polymer) according to the present invention as its main material, it is also possible to reliably prevent the mixing of the constituent materials of the hole transport layer 41 and the light emitting layer 42 from occurring near the boundary between these layers 41 and 42 in a resultant organic EL device 1 with the lapse of time.
The weight-average molecular weight of the polymer is not particularly limited, but is preferably in the range of about 1,000 to 1,000,000, more preferably in the range of about 10,000 to 300,000. By setting the weight-average molecular weight of the polymer to a value within the above range, it is possible to suppress or prevent the swelling and dissolution of the polymer more reliably.
It is to be noted that the hole transport layer 41 may contain a monomer or oligomer of the compound represented by the general formula (Al) and/or a monomer or oligomer of the epoxy-based cross-linking agent to the extent that mutual dissolution between the hole transport layer 41 and the light emitting layer 42 can be prevented.
As light with which the hole transport material is irradiated, for example, infrared rays, visible light, ultraviolet rays, or X-rays can be used. These types of light can be used singly or in combination of two or more of them. Among them, ultraviolet rays are particularly preferably used. By using ultraviolet rays, it is possible to easily and reliably polymerize the substituents X directly or via the epoxy-based cross-linking agent. The wavelength of ultraviolet rays to be used for light irradiation is preferably in the range of about 100 to 420 nm, more preferably in the range of about 150 to 400 nm.
The irradiation intensity of ultraviolet rays is preferably in the range of about 1 to 60 )00 mW/cm2, more preferably in the range of about 1 to 300 mW/cm2.
Further, the irradiation time of ultraviolet rays is preferably in the range of about 60 to 600 seconds, more preferably in the range of about 90 to 500 seconds.
By setting each of the wavelength, irradiation intensity, and irradiation time of ultraviolet rays to a value within the above range, it is possible to relatively easily control the progress of polymerization reaction of the hole transport material supplied onto the anode 3.
It is to be noted that the resultant hole transport layer 41 may be subjected to heat treatment in the atmosphere or an inert atmosphere or under reduced pressure (or under vacuum) when necessary. By doing so, it is possible to dry (that is, it is possible to remove a solvent or a dispersion medium) or solidify the hole transport layer 41. The hole transport layer 41 may be dried by means other than heat treatment.
Further, examples of predetermined treatment for polymerizing the substituents X directly orvia the epoxy-based cross-linking agent other than light irradiation include heating and anaerobic treatment. Among these treatment methods, light irradiation as described above is preferably employed. By employing light irradiation, it is possible to relatively easily select the area where a polymerization reaction is carried out and the degree of polymerization.
[A3] Step of forming light emitting layer Next, a light emitting layer 42 is formed on the hole transport layer 41.
The light emitting layer 42 can be formed by, for example, applying onto the hole transport layer 41, a light emitting layermaterial (that is, amaterial for forming a light emitting layer) obtained by dissolving the light emitting material as described above in a solvent or dispersing the light emitting material in a dispersion medium.
As solvents or dispersion media in which the light emitting material is to be dissolved or dispersed, the same solvents or dispersion media that have been mentioned with reference to the step of forming the hole transport layer [A2] can be used.
Further, as methods for applying the light emitting layer material onto the hole transport layer 41, the same application methods that have been mentioned with reference to the step of forming the hole transport layer [2A] can be employed.
[A4] Step of forming electron transport layer
Next, an electron transport layer 43 is formedon the light emitting layer 42.
In the case where a constituent material of the electron transport layer 43 is formed of the conductive material according to the present invention, the electron transport layer 43 can be formed using the composition for conductive materials according to the present invention in the same manner that has been described with reference to the step of forming the hole transport layer [A2].
On the otherhand, in the casewhere a constituentmaterial of the electron transport layer 43 is not formed of the conductive material according to the present invention, the electron transport layer 43 can be formed using the known electron transport materials described above in the same manner that has been described with reference to the step of forming the light emitting layer [A3].
It is to be noted that in the case where the light emitting layer 42 is not formed using a polymer such as the conductive material according to the present invention, a solvent or dispersion medium in which the composition for conductive materials for use in forming the electron transport layer 43 is to be dissolved or dispersed is selected from among those which do not cause swelling and dissolution of the light emitting layer 42. By using such a solvent or a dispersion medium, it is possible to reliably prevent mutual dissolution between the light emitting layer 42 and the electron transport layer 43. [A5] Step of forming cathode
Next, a cathode 5 is formedon the electron transport layer 43.
The cathode 5 can be formed by, for example, vacuum deposition, sputtering, bonding of ametallic foil, or the like.
[A6] Step of forming protection layer Next, a protection layer 6 is formed so as to cover the anode 3, the organic EL layer 4, and the cathode 5.
The protection layer 6 can be formed or provided by, for example, bonding a box-like protection cover made of the material as mentioned above by the use of various curable resins (adhesives) .
As for such curable resins, all of thermosetting resins, photocurable resins, reactive curable resins, and anaerobic curable resins can be used.
The organic EL device 1 is manufactured through these steps as described above.
(Organic Thin Film Transistor)
Next, another embodiment of the electronic device according to the present invention will be described. In this embodiment, the electronic device of the present invention is embodied as an organic thin film transistor that is a switching element (hereinafter, simply referred to as an "organic TFT") . FIG. 2(a) is a cross-sectional view of an organic TFT 10, and FIG. 2(b) is a plan view of the organic TFT 10. It is to be noted that in the following description, the upper side and the lower side in FIG. 2(a) will be referred to as "upper side" and "lower side", respectively.
The organic TFT 10 shown in FIG. 2 is provided on a substrate 20. On the substrate 20, a source electrode 30, a drain electrode 40, an organic semiconductor layer (that is, a conductive layer according to the present invention) 50, a gate insulating layer 60, and a gate electrode 70 are laminated in this order from the side of the substrate 20.
Specifically, in the organic TFT 10, the source electrode 30 and the drain electrode 40 are separately provided on the substrate 20, and the organic semiconductor layer 50 is provided so as to cover these electrodes 30 and 40. On the organic semiconductor layer 50, the gate insulating layer 60 is provided. On the gate insulating layer 60, the gate electrode 70 is provided so as to overlap with at least a region between the source electrode 30 and the drain electrode 40.
In the organic TFT 10, the region in the organic semiconductor layer 50 which is existed between the source electrode 30 and the drain electrode 40 functions as a channel region 510 where carriers are moved. Hereinafter, the length of the channel region 510 in a direction that carriers are moved, that is, the distance between the source electrode 30 and the drain electrode 40 is referred to as "channel length L", and the length of the channel region 510 in a direction orthogonal to the direction of the channel length L is referred to as "channel width W".
The organic TFT 10 is an organic TFT having a structure in which the source electrode 30 and the drain electrode 40 are provided so as to be closer to the substrate 20 than the gate electrode 70 provided through the gate insulating layer 60. That is, the organic TFT 10 is an organic TFT having a top gate structure.
Hereinbelow, components of the organic TFT 10 will be described one by one.
The substrate 20 supports the layers (or the components) constituting the organic TFT 10. As such a substrate 20, for example, the same substrate that has been described with reference to the substrate 2 of the organic EL device 1 can be used. Alternatively, a silicon substrate or a gallium arsenide substrate may be used as the substrate 20.
On the substrate 20, the source electrode 30 and the drain electrode 40 are provided side by side at a predetermined distance in the direction of the channel length L.
The constituent material of the source electrode 30 and the drain electrode 40 is not particularly limited so long as it has conductivity. Examples of such a constituent material include metallic materials such as Pd, Pt, Au, W, Ta, Mo, Al, Cr, Ti, Cu, and alloys containing two ormore of them, conductive oxidematerials such as ITO, FTO, ATO, and SnO2, carbonmaterials such as carbon black, carbon nanotube, and fullerene, and conductive polymeric materials such as polyacetylene, polypyrrole, . polythiophene e.g., PEDOT (poly-ethylenedioxythiophene) , polyaniline, poly(p-phenylene) , poly(p-phenylenevinylene) , polyfluorene, polycarbazole, polysilane, and derivatives thereof. Among them, the conductive polymeric materials are usually dopedwith iron chloride, iodine, strong acid, organic acid, or a polymer such as polystyrenesulfonic acid so as to have conductivitywhen used. These conductive materials can be used singly or in combination of two or more of them.
The thickness of each of the source electrode 30 and the drain electrode 40 is not particularly limited, but is preferably in the range of about 30 to 300 nm, more preferably in the range of about 50 to 200 nm.
The distance between the source electrode 30 and the drain electrode 40, that is, the channel length L is preferably in the range of about 2 to 30 μm, more preferably in the range of about 2 to 20 μm.
The channel width W is preferably in the range of about 0.1 to 5 mm, more preferably in the range of about 0.3 to 3 mm.
As described above, the organic semiconductor layer 50 is provided on the substrate 20 so as to cover the source electrode 30 and the drain electrode 40. As a constituent material of the organic semiconductor layer 50, the conductive material according to the present invention can be used.
As described above, by appropriately setting the chemical structure of the group Y of the compound represented by the general formula (1) , it is possible to impart a desired carrier transport property to a resultant polymer (that is, to a conductive material according to the present invention) .
Therefore, the conductive material according to the present invention is useful for forming an organic semiconductor layer 50 because it is possible to impart good semiconductivity to the polymer by appropriately setting the chemical structure of the group Y.
As a conductive material constituting such an organic semiconductor layer 50, for example, a polymer of the compound represented by the general formula (Al) in which the group Y has a chemical structure represented by the chemical formula (D2), (D3), (D16), (D17), or (D20) is preferably selected.
The thickness of the organic semiconductor layer 50 is preferably in the range of about 0.1 to 1,000 nm, more preferably in the range of about 1 to 500 nm, and even more preferably in the range of about 10 to 100 nm. By setting the thickness of the organic semiconductor layer 50 to a value within the above range, it is possible to prevent an increase in size of the organic TFT 10 (especially, an increase in thickness of the organic TFT 10) while maintaining a high carrier transport ability of the organic TFT 10. By using the organic semiconductor layer 50 which is obtained by using a polymer such as the conductive material according to the present invention as its main material, it is possible to obtain an organic TFT 10 having reduced size and weight. In addition, it is also possible for the organic TFT 10 to have excellent flexibility. Such an organic TFT 10 is suitably used for a switching element of a flexible display provided with the organic EL devices described above.
The organic semiconductor layer 50 is not limited to one provided so as to cover the source electrode 30 and the drain electrode 40. The organic semiconductor layer 50 should be provided in at least the region between the source electrode 30 and the drain electrode 40 (that is, in at least the channel region 510) .
As described above, the gate insulating layer 60 is provided on the organic semiconductor layer 50.
The gate insulating layer 60 is provided to insulate the gate electrode 70 from the source electrode 30 and the drain electrode 40.
The gate insulating layer 60 is preferably formed using an organicmaterial (especially, an organic polymericmaterial) as its main material. By using an organic polymeric material as amainmaterial of the gate insulating layer 60, it is possible to form the gate insulating layer 60 easily as well as to bring the gate insulating layer 60 into closer contact with the organic semiconductor layer 50. Examples of such an organic polymeric material include polystyrene, polyimide, polyamideimide, polyvinylphenylene, polycarbonate. (PC) , acrylic resins such as polymethylmethacrylate (PMMA) , fluorinated resins such as polytetrafluoroethylene (PTFE) , phenolic resins such as polyvinyl phenol and novolaσ resins, and olefin-based resins such as polyethylene, polypropylene, polyisobutylene, and polybutene. These organic polymeric materials may be used singly or in combination of two or more of them.
The thickness of the gate insulating layer 60 is not particularly limited, but is preferably in the range of about 10 to 5,000 nm, more preferably in the range of about 100 to 1,000 nm. By setting the thickness of the gate insulating layer 60 to a value within the above range, it is possible to prevent the size of the organic TFT 10 frombeing increased (especially, an increase in thickness of the organic TFT 10) while reliably insulating the gate electrode 70 from the source electrode 3 and the drain electrode 40.
It is to be noted that the gate insulating layer 60 is not limited to one comprised of a single layer and may have two or more layers.
As described above, the gate electrode 70 is provided on the gate insulating layer 60.
As constituent materials of the gate electrode 70, the same constituent materials that have been mentioned with reference to the source electrode 30 and the drain electrode 40 can be used.
The thickness of the gate electrode 70 is not particularly limited, but is preferably in the range of about 0.1 to 5,000 nm, more preferably in the range of about 1 to 5,000 nm, even more preferably in the range of about 10 to 5,000 nm.
In the organic TFT 10 as described above, the amount of current flowing between the source electrode 30 and the drain electrode 40 is controlled by changing voltage applied to the gate electrode 70.
Namely, in the OFF-state where voltage is not applied to the gate electrode 70, only a little current flows even by applying voltage across the source electrode 30 and the drain electrode 40 because carriers hardly exist in the organic semiconductor layer 50. On the other hand, in the ON-state where voltage is applied to the gate electrode 70, an electric charge is induced in the surface of the organic semiconductor layer 50 that is in contact with the gate insulating layer 60 so that a channel for carriers is formed in the channel region 510. In such a state, by applying voltage across the source electrode 30 and the drain electrode 40, it is possible to allow carriers (holes or electrons) to pass through the channel region 510.
Such an organic TFT 10 as described above can be manufactured in the following manner, for example. FIGs. 3 and 4 are drawings (cross-sectional views) to be used for explaining a manufacturing method of the organic TFT 10 shown in FIG. 2. It is to be noted that, in the following description, the upper side and lower side in FIGs. 3 and 4 will be referred to as the "upper side" and the "lower side", respectively.
[Bl] Step of forming source electrode and drain electrode
[Bl-I]
First, a substrate 20 as shown in FIG. 3 (a) is prepared. The substrate 20 is washed with, for example, water (e.g. , pure water) and/or organic solvents. Water and organic solvents may be used singly or in combination of two or more of them.
Next, a photoresist is supplied onto the substrate 20 to form a film 80' (see FIG. 3 (b)).
As a photoresist to be supplied onto the substrate 20, either a negative-type photoresist or a positive-type photoresist may be used. When the negative-type photoresist is used, an area irradiated with light (that is, an area exposed to light) is cured and then an area other than the area exposed to light is dissolved by development to be removed. When the positive-type photoresist is used, an area exposed to light is dissolved by development to be removed.
Examples of such a negative-type photoresist include water-soluble photoresists such as rosin-dichromate. polyvinyl alcohol (PVA) -dichromate, shellac-dichromate, casein-diσhromate, PVA-diazo, and acrylic photoresists and oil-soluble photoresists such as polyvinyl cinnamate, cyclized rubber-azide,. polyvinyl cinnamylidene acetate, and polycinnamic acid β-vinyloxyethyl ester.
Examples of a positive-type photoresist include oil-soluble photoresists such as o-naphthoquinonediazide.
Any method can be used for supplying a photoresist onto the substrate 20, but various application methods are preferably employed.
As such application methods, the same methods that have been mentioned with reference to the step of forming the hole transport layer [A2] in the manufacturing method of the organic EL device 1 can be employed.
Next, the film 80' is exposed to light through a photomask and is then developed to form a resist layer 80 having openings 820 where a source electrode 30 and a drain electrode 40 are to be formed (see FIG. 3(C)).
[Bl-2]
Next, as shown in FIG. 3 (d), a predetermined amount of a liquid material 90 containing a constituent material of a source electrode 30 and a drain electrode 40 to be formed or a precursor thereof is supplied to the openings 820 provided on the substrate 20. As solvents or dispersion media in which a constituent material of a source electrode 30 and a drain electrode 40 or a precursor thereof is dissolved or dispersed for preparing a liquid material 90, the same solvents or dispersion media that have been mentioned with reference to the step of forming hole transport layer [A2] can be used.
As methods for supplying the liquid material 90 to the openings 820, the same application methods that have been mentioned above can be employed. Among these application methods, an inkjet method (that is, a liquid droplet ejecting method) is preferably employed. By employing the inkjet method, it is possible to eject the liquid material 90 in the form of liquid droplets from a nozzle of a liquid droplet ejecting head, thereby enabling the liquid material 90 to be reliably supplied to the openings 820. As a result, adhesion of the liquid material 90 to the resist layer 80 is reliably prevented.
[Bl-3]
Next, the solvent or dispersion medium contained in the liquid material 90 supplied to the openings 820 is removed to form a source electrode 30 and a drain electrode 40.
The temperature at which the solvent or dispersion medium is removed is not particularly limited, and slightly varies depending on the kind of solvent or dispersion medium used. However, the temperature at which the solvent or dispersion medium is removed is preferably in the range of about 20 to 2000C, more preferably in the range of about 50 to 100°C. By removing the solvent or dispersion medium at a temperature within the above range, it is possible to reliably remove the solvent or dispersion medium from the liquid material 90.
In this.connection, it is to be noted that the solvent or dispersion medium contained in the liquid material 90 may be removed by heating under reduced pressure. By doing so, it is possible to more reliably remove the solvent or dispersion medium from the liquid material 90.
[Bl-4]
Next, the resist layer 80 provided on the substrate 20 is removed to obtain the substrate 20 on which the source electrode 30 and the drain electrode 40 are formed (see FIG. 4(a)).
Amethod for removing the resist layer 80 is appropriately selected depending on the kind of resist layer 80. For example, ashing such as plasma treatment or ozone treatment, irradiation with ultraviolet rays, or irradiation with a laser such as a Ne-He laser, an Ar laser, a CO2 laser, a ruby laser, a semiconductor laser, a YAG laser, a glass laser, a YVO4 laser, or an excimer laser may be carried out. Alternatively, the resist layer 80 may removed by being brought into contact with a solvent capable of dissolving or decomposing the resist layer 80 by, for example, immersing the resist layer 80 in such a solvent.
[B2] Step of forming organic semiconductor layer Next, as shown in FIG. 4(b), an organic semiconductor layer 50 is formed on the substrate 20 so as to cover the source electrode 30 and the drain electrode 40 provided on the substrate 20.
At this.time, a channel region 510 is formed between the source electrode 30 and the drain electrode 40 (that is, in an area corresponding to an area where a gate electrode 70 is to be formed) .
The organic semiconductor layer 50 can be formed using the composition for conductive materials according to the present invention by the same method that has been described with reference to the step of forming the hole transport layer [A2] in the manufacturing method of the organic EL device 1.
The organic semiconductor layer 50 is formed using the conductive material (that is, the polymer) according to the present invention as its main material. Therefore, when a gate insulating layer material is supplied onto the organic semiconductor layer 50 in the next step [B3], swelling and dissolution of the polymer due to a solvent or dispersion medium contained in the gate insulating layer material is properly inhibited or prevented. As a result, mutual dissolution between the organic semiconductor layer 50 and a gate insulating layer 60 is reliably prevented.
By forming an organic semiconductor layer 50 using a polymer such as the conductive material according to the present invention as its main material, it is possible to reliably prevent the mixing of the constituent materials of the organic semiconductor layer 50 and the gate insulating layer 60 from occurring near the boundary between these layers 50 and 60 with the lapse of time.
[B3] Step of forming gate insulating layer
Next, as shown in FIG. 4(c), a gate insulating layer 60 is formed on the organic semiconductor layer 50 by an application method.
Specifically, the gate insulating layer 60 can be formed by applying or supplying a solution containing an insulating material or a precursor thereof onto the organic semiconductor layer 50 by the application method described above. When necessary, the thus obtained layer is subjected to aftertreatment such as heating, irradiationwith infraredrays, or exposure to ultrasound.
[B4] Step of forming gate electrode
Next, as shown in FIG. 4(d) , a gate electrode 70 is formed on the gate insulating layer 60 by an application method.
Specifically, the gate electrode 70 can be formed by applying or supplying a solution containing an electrode material or a precursor thereof onto the gate insulating layer 60 bythe applicationmethod. When necessary, the thus obtained layer is subjected to aftertreatment such as heating, irradiation with infrared rays, or exposure to ultrasound.
As application methods to be used, the same methods that have been mentioned above can be employed. Particularly, an inkjet method is preferably employed. By employing the inkjet method, it is possible to eject a solution containing an electrode material or a precursor thereof in the form of liquid droplets from a nozzle of a liquid droplet ejecting head to carry out patterning. As a result, a gate electrode 70 having a predetermined shape is easily and reliably formed on the gate insulating layer 60.
The organic TFT 10 is manufactured through the steps described above.
(Electronic equipment)
The electronic devices according to the present invention such as the organic EL device (which is a light emitting device) 1 and the organic TFT (which is a switching element) 10 as described above can be used for various electronic equipment.
FIG. 5 is a perspective view which shows the structure of a personal mobile computer (or a personal notebook computer) to which the electronic equipment according to the present invention is applied.
In FIG. 5, a personal computer 1100 is comprised of a main body 1104 provided with a keyboard 1102 and a display unit 1106 provided with a display. The display unit 1106 is rotatably supported by the main body 1104 via a hinge structure.
In the personal computer 1100, for example, the display unit 1106 includes the organic EL device (which is a light emitting device) 1 and the organic TFT (which is a switching element) 10 described above.
FIG. 6 is a perspective view which shows the structure of a mobile phone (including the personal handyphone system (PHS)) to which the electronic equipment according to the present invention is applied.
The mobile phone 1200 shown in FIG. 6 includes a plurality of operation buttons 1202, an earpiece 1204, a mouthpiece 1206, and a display.
In this mobile phone 1200, for example, the display includes the organic EL device (which is a light emitting device) 1 and the organic TFT (which is a switching element) 10 described above.
FIG. 7 is a perspective view which shows the structure of a digital still camera to which the electronic equipment according to the present invention is applied. In this drawing, interfacing to external devices is simply illustrated.
In a conventional camera, a silver salt film is exposed to the optical image of an object. On the other hand, in the digital still camera 1300, an image pickup device such as a CCD (Charge Coupled Device) generates an image pickup signal (or an image signal) by photoelectric conversion of the optical image of an object.
In the rear surface of a case (or a body) 1302 of the digital still camera 1300, there is provided a display which provides an image based on the image pickup signal generated by the CCD. That is, the display functions as a finder which displays the object as an electronic image.
In this digital still camera 1300, for example, the display includes the organic EL device (which is a light emitting device) 1 and the organic TFT (which is a switching element) 10 described above.
In the inside of the case, there is" provided a circuit board 1308. The circuit board 1308 has a memory capable of storing an image pickup signal.
In the front surface of the case 1302 (in FIG. 7, the front surface of the case 1302 is on the back side) , there is provided a light receiving unit 1304 including an optical lens (an image pickup optical system) and a CCD.
When a photographer presses a shutter button 1306 after checking an object image on the display, an image pickup signal generated by the CCD at that time is transferred to the memory in the circuit board 1308 and then stored therein.
Further, in the side surface of the case 1302 of the digital still camera 1300, there are provided a video signal output terminal 1312 and an input-output terminal for data communication 1314. As shown in FIG. 7, when necessary, a television monitor 1430 and a personal computer 1440 are connected to the video signal output terminal 1312 and the input-output terminal for data communication 1314, respectively. In this case, an image pickup signal stored in the memory of the circuit board 1308 is outputted to the television monitor 1430 or the personal computer 1440 by carrying out predetermined operation.
The electronic equipment according to the present invention can be applied not only to the personal computer (which is apersonalmobile computer) shown in FIG.5, the mobile phone shown in FIG. 6, and the digital still camera shown in FIG. 7 but also to a television set, a video'camera, a view-finer or monitor type of video tape recorder, a laptop-type personal computer, a car navigation device, a pager, an electronic notepad (which may have communication facility) , an electronic dictionary, an electronic calculator, a computerized game machine, a word processor, a workstation, a videophone, a security television monitor, an electronic binocular, a POS terminal, an apparatus providedwith a touch panel (e.g., a cash dispenser located on a financial institute, a ticket vending machine), medical equipment (e.g., an electronic thermometer, a sphygmomanometer, a blood glucose meter, an electrocardiograph monitor, ultrasonic diagnostic equipment, an endoscope monitor), a fish detector, various measuring instruments, gages (e.g., gages for vehicles, aircraft, and boats and ships), a flight simulator, various monitors, and a projection display such as a projector.
The composition for conductive materials, the conductive material, the conductive layer, the electronic device, and the electronic equipment according to the present invention have been described based on the embodiments shown in the drawings, but the present invention is not limited thereto.
For example, in the case where the electronic device according to the present invention has a hole transport layer as a conductive layer, such an electronic device can be used for, for example, a solar cell that is an example of light receiving devices (or photoelectric transducers) as well as the organic EL device as described above that is an example of display devices (or light emitting devices) .
Further, in the case where the electronic device according to the present invention has an organic semiconductor layer as a conductive layer, such an electronic device can be used for, for example, a semiconductor device as well as the organic TFT as described above that is an example of switching elements.
Furthermore, the conductive layer according to the present invention can be used as, for example, wiring or an electrode as well as the hole transport layer as described above. In this case, a resultant electronic device according to the present invention can be used for a wiring board and the like.
Examples
Next, the present invention will be described with reference to Examples.
1. Synthesis of compound
First, compounds (AI) to (UII) described below were prepared. <Compound (AI)>
6-(p-aminophenyl)heχanol was treated with 4-methoxybenzylbromide and sodium hydride in anhydrous dimethylformamide to transformhydroxy1 group into benzyl ether group and then it was protected.
Next, 1 mol of thus obtained compound was dissolved in 150 mL of acetic acid, and acetic anhydride was dropped therein at room temperature and then they were stirred. After the completion of the reaction, solidmatterprecipitatedwas filtered and then dried after washingwithwater to obtain a dry substance (benzyl ether derivative) .
Next, 6-(p-bromophenyl)hexanol was subjected to the same treatment as that for 6-(p-aminophenyl)hexanol to transform hydroxyl group into benzyl ether group and then it was protected to obtain a dry substance (benzyl ether derivative) .
Next, 0.37 mol of benzyl ether derivative obtained from 6-(p-aminophenylhexanol, 0.66 mol of benzyl ether derivative obtained from 6- (p-bromophenyl)hexanol, 1.1 mol of potassium carbonate, copper powder, and iodine were mixed and heated at 200°C. After the mixture was allowed to cool, 130 mL of isoamyl alcohol, 50 mL of pure water, and 0.73 mol of potassiumhydroxide were added to the mixture, and then they were stirred and dried.
Further, 130 mmol of the thus obtained compound, 62 mmol of 4,4' -diiodobiphenyl, 1.3 mmol of palladium acetate, 5.2 mmol of t-butylphosphine, 260 mmol of sodium t-butoxide, and 700 mL of xylene were mixed, and then they were stirred at 1200C. Thereafter, the mixture was allowed to cool for crystallization.
The thus obtained compound was reduced by hydrogen gas under Pd-C catalyst so that transformation was made from the benzyl ether group to the hydroxyl group to carry out deprotection.
Next, 100 mmol of the compound" and 2000 mmol of epichlorohydrinwere added to a 50% of sodiumhydroxide solution to which a small amount of tetra-n-butylammonium hydrogen sulphate (phase transfer catalyst) hadbeen added, and then they were stirred for 10 hours at room temperature. Thereafter, the mixture was allowed to cool for crystallization to obtain a compound.
Then, the thus obtained compound was confirmed to be the following compound (AI) bymeans of amass spectrum (MS) method, a ^-nuclear magnetic resonance (1H-NMR) spectrum method, a 13C-nuclear magnetic resonance (13C-NMR) spectrum method, and a Fourier transform infrared absorption (FT-IR) spectrum method.
Figure imgf000107_0001
<Compound (BI)>
A compound (BI) was obtained in the same manner as the compound (AI) except that 4,4' -diiodobiphenyl was changed to 4,4' -diiodo-2,2' -dimethylbiphenyl.
(BI)
Figure imgf000107_0002
<Compound (CI)>
A compound (CI) was obtained in the same manner as the compound (AI) except that 6-(p-aminophenyl)hexanolwas changed to 2-(p-aminophenyl)ethanol and 6-(p-bromophenγl)hexanol was changed to 2-(p-bromophenyl)ethanol, respectively.
Figure imgf000108_0001
<Compound (DI)>
A compound (DI) was obtained in the same manner as the compound (CI) except that 2-(p-aminophenyl)ethanolwas changed to 2-(2' ,6'-dimethyl-4'-aminophenyl)ethanol. (DI)
Figure imgf000109_0001
<Compound (EI)>
A compound (EI) was obtained in the same manner as the compound (AI) except that 6-(p-aminophenyl)hexanol was changed to 8- (p-aminophenyl)octanol and 6-(p-bromophenyl)hexanol was changed to 8-(p-bromophenyl)octanol, respectively.
(EI)
Figure imgf000110_0001
< Compound (FI )>
A compound (FI) was obtained in the same manner as the compound (AI) except that 6- (p-aminophenyl)hexanol was changed to 8-(p-aminophenyl)octanol.
(FI)
Figure imgf000110_0002
<Compound (GI)>
A compound (GI) was obtained in the same manner as the compound (AI) except that 6-(p-aminophenyl)hexanol was changed to l-(p-aminophenyl)methanol and 6-(p-bromophenyl)hexanol was changed to l-(p-bromophenyl)methanol, respectively.
(GI)
Figure imgf000111_0001
<Compound (HI) .
As for the following compound (HI), N,N,N',N'- tetrakis(4-methylphenyl)- benzidine ("OSA 6140" provided by TOSCO CO., LTD.) was prepared. (HI)
Figure imgf000112_0001
<Compound (AII)>
A compound (All) was obtained in the same manner as the compound (AI) except that 4,4 ' -diiodobiphenyl was changed to 2,5-bis(4-iodophenyl) -thiophene.
(All)
Figure imgf000112_0002
<Compound (BII)>
A compound (BII) was obtained in the same manner as the compound (All) except that 2,5-bis(4-iodophenγl) -thiophene was changed to 2,5-bis(2-methyl-4-iodophenyl) -thiophene.
Ill (BII)
Figure imgf000113_0001
<Compound (CII)>
A compound (CII) was obtained in the same manner as the compound (All) except that 6-(p-aminophenyl)hexanol was changed to 2-(p-aminophenyl)ethanol and 6-(p-bromophenyl)hexanol was changed to 2-(p-bromophenyl)ethanol, respectively.
(CII)
Figure imgf000113_0002
<Compound (DII)>
A compound (DII) was obtained in the same manner as the compound (CII) except that 2-(p-aminophenγl)ethanol was changed to 2- (2' ,6' -dimethyl-4' -aminophenyl)ethanol.
Figure imgf000114_0001
<Compound (EII)>
A compound (EII) was obtained in the same manner as the compound (All) except that 6-(p-aminophenyl)hexanol was changed to 8-(p-aminophenyl)octanol and 6-(p-bromophenyl)hexanol was changed to 8-(p-bromophenyl)octanol, respectively.
(EII)
Figure imgf000115_0001
< Compound (FII) >
A compound (FII) was obtained in the same manner as the compound (All) except that 6- (p-aminophenyl)hexanol was changed to 8- (p-aminophenyl)octanol.
Figure imgf000115_0002
<Compound (GII)>
A compound (GII) was obtained in the same manner as the compound (All) except that 6-(p-aminophenyl)hexanol was changed . to l-(p-aminophenyl)methanol and 6-(p-bromophenyl)hexanol was changed to 1-(p-bromophenyl)methanol, respectively.
(GII)
Figure imgf000116_0001
<Compound (HII)>
A compound (HII) was obtained in the same manner as the compound (All) except that 2,5-bis(4-iodophenyl) -thiophene was changed to
5,5' '-bis(4-iodophenyl)-2,2' :5' ,2' ' -ter-thiophene.
(HII)
Figure imgf000117_0001
< Compound ( III ) >
A compound (III) was obtained in the same manner as the compound (All) except that 2,5-bis(4-iodophenyl)-thiophene was changed to 3,5-diiodo-l,2,4-triazole.
Figure imgf000117_0002
<Compound (JII)> A compound (JII) was obtained in the same manner as the compound (All) except that 2,5-bis(4-iodophenyl)-thiophene was changed to 2,5-bis(4-iodophenyl) -1,3,4-oxadiazole.
(JII)
Figure imgf000118_0001
<Compound (KII)>
A compound (KII) was obtained in the same manner as the compound (All) except that 2,5-bis(4-iodophenyl)-thxophene was changed to 3,3' -diiodo-1,1' -biisobenzothiophene.
(KII)
Figure imgf000119_0001
<Compound (LII)>
A compound (LII) was obtained in the same manner as the compound (KII) except that 6-(p-aminophenyl)hexanol was changed to 2-(p-aminophenyl)ethanol and 6-(p-bromophenyl)hexanol was changed to 2-(p-bromophenyl)ethanol, respectively.
(LII)
Figure imgf000119_0002
<Compound (MII)>
A compound (Mil) was obtained in the same manner as the compound (KII) except that 6- (p-aminophenyl)hexanol was changed to 8- (p-aminophenyl)octanol and 6-(p-bromophenyl)hexanol was changed to 8-(p-bromophenyl)octanol, respectively.
(Mil)
Figure imgf000120_0001
<Compound (NII)>
A compound (Nil) was obtained in the same manner as the compound (KII) except that 6- (p-aminophenyl)hexanol was changed to 8-(p-aminophenyl)octanol.
(Nil)
Figure imgf000121_0001
<Compound (OII)>
A compound (Oil) was obtained in the same manner as the compound (KII) except that 6-(p-aminophenγl)hexanol was changed to 1-(p-aminophenyl)methanol and 6-(p-bromophenyl)hexanol was changed to 1-(p-bromophenyl)methanol, respectively.
(Oil)
Figure imgf000121_0002
<Compound (PII)>
A compound (PII) was obtained in the same manner as the compound (All) except that 2,5-bis(4-iodophenyl) -thiophene was changed to
5,5' -diiodo-2,2' -bi(3,4-dioxyethyleneselenophene) .
Figure imgf000122_0001
<Compound (QII)>
A compound (QII) was obtained in the same manner as the compound (All) except that 2,5-bis(4-iodophenyl) -thiophene was changed to 5,5' ' -diiodo-2,2' : 5 ' ,2 ' ' -ter-selenophene. (QII)
Figure imgf000123_0001
<Compound (RII)>
A compound (RII) was obtained in the same manner as the compound (All) except that 2,5-bis(4-iodophenyl)-thiophene was changed to
5,5' '-diiodo-3,3' :5' ,3' ' -ter- (4-phenyl-l ,2, 4-triazole) . (RID
Figure imgf000123_0002
<Compound (SII)>
1 mol of l-amino-4-methylbenzene was dissolved in 150 mL of acetic acid, and acetic anhydride was dropped therein at room temperature, and then they were stirred. After the completion of the reaction, solid matter precipitated was filtered, and was then dried after washing with water.
Next, 0.37 mol of the thus obtained substance, 0.66 mol of l-bromo-4-methylbenzene, 1.1 mol of potassium carbonate, copper powder, and iodine were mixed and heated at 200°C. After the mixture was allowed to cool, 130 mL of isoamyl alcohol, 50 mL of pure water, and 0.73 mol of potassium hydroxide were added to the mixture, and then they were stirred and dried.
Further, 130 mmol of the thus obtained compound, 62 mmol of 2,5-bis(4-iodophenyl)-thiophene, 1.3 mmol of palladium acetate, 5.2 mmol of t-butylphosphine, 260 mmol of sodium t-butoxide, and 700 mL of xylene were mixed, and then they were stirred at 120°C.
Thereafter, the mixture was allowed to cool for crystallization to obtain a compound.
Then, the obtained compound was found to be the following compound (SII) by means of a mass spectrum (MS) method, a 1H-nuclear magnetic resonance (1H-NMR) spectrum method, a 13C-nuclear magnetic resonance (13C-NMR) spectrum method, and a Fourier transform infrared absorption (FT-IR) spectrum method.
Figure imgf000125_0001
<Compound (TII)>
Poly(3,4-ethylenedioxythiophene/styrenesulfonic acid) ("BAYTRON P CH800", Bayer) was prepared as the following compound (TII).
(TII)
Figure imgf000125_0002
<Compound (UII)>
A compound (UII) was obtained in the same manner as the compound (SII) except that 2,5-bis(4-iodophenyl) -thiophene was changed to 3,5-diiodo-l,2,4-triazole.
(UII)
Figure imgf000126_0001
2. Manufacture of organic EL device
Five organic EL devices were manufactured in each of the following Examples and Comparative Examples.
(Example IA)
<Preparation of hole transport material> The compound (AI) was used as an arylamine derivative, and the compound (AI) and a cationic photopolymerization initiator ("FC-508" producedby Sumitomo 3MLimited) in aweight ratio of 99:1 were mixed with dichloroethane to obtain a hole transport material (that is, a composition for conductive materials) .
Manufacture of organic EL device>
IA First, an ITO electrode (that is, an anode) was formed on a transparent glass substrate having an average thickness of 0.5 mmbyvacuumevaporation so as to have an average thickness of 100 nm.
2A Next, the hole transport material was applied onto the ITO electrode by a spin coating method, and was then dried.
Then, the hole transport material was irradiated with ultraviolet rays having a wavelength of 365 nm from a mercury lamp ("UM-452", USHIO Inc.) through a filter at an intensity of irradiation of 500 mW/cm2 for 15 seconds in the dry atmosphere and then heated for 60 minutes at temperature of 110°C to polymerize the compound (AI), so that a hole transport layer having an average thickness of 50 nm was formed.
3A Next, a 1.7 wt% xylene solution of poly(9,9-dioctyl-2,7-divinylenefluoreny1-alt-co(anthracene- 9,10-diyl) (Weight average molecular weight: 200,000) was applied onto the hole transport layer by a spin coating method, and was then dried to form a light emitting layer having an average thickness of 50 nm.
4A Next, an electron transport layer having an average thickness of 20 nm was formed on the light emitting layer by a vacuum evaporation of 3,4,5-triphenyl-l,2,4-triazole.
5A Next, an AlLi electrode (that is, a cathode) was formed on the electron transport layer by vacuum evaporation so as to have an average thickness of 300 nm.
6A Next, a protection cover made of polycarbonate was provided so as to cover these layers described above, and was then secured and sealed with an ultraviolet curable resin to obtain an organic EL device.
(Examples 2A to 5A)
In each of Examples 2A to 5A, organic EL devices were manufactured after a hole transport material was prepared in the same manner as in Example IA except that as for the arylamine derivatives for use in the hole transport material were changed to those shown in Table 1.
(Comparative Example IA) preparation of hole transport material> A hole transport material was obtained by dissolving the compound (Hl) .
<Manufacture of organic EL device>
Organic EL devices were manufactured in the same manner as in Example IA except that the hole transport material prepared in the step 2A was used and the irradiation of ultraviolet rays from the mercury lamp was omitted.
(Comparative Example 2A)
Preparation of hole transport material>
The compound (TII) was dispersed in water to prepare a
2.0 wt% water dispersion of the compound (TII), thereby obtaining a hole transport material.
In this regard, it is to be noted that the weight ratio of 3,4-ethylenedioxythiophene to styrenesulfonic acid in the compound (TII) was 1: 20. <Manufacture of organic EL device>
Organic EL devices were manufactured in the same manner as in Comparative Example IA except that the hole transport material was changed to the hole transport material prepared in this Comparative Example 2A.
(Comparative Example 3A)
<Preparation of hole transport material> The compound (HI) was used as an afylamine derivative, and a bifunctional epoxy compound ("DENACOL EX-212" produced by Nagase chemteX Corporation) was used as a photocrosslinking agent, and the compound (HI) , the epoxy compound and a cationic photopolymerization initiator ("FC-508" produced by Sumitomo 3M Limited) in a weight ratio of 50:49:1 were mixed with dichloroethane to obtain a hole transport material.
<Manufaσture of organic EL device>
Organic EL devices were manufactured in the same manner as in Comparative Example IA except that the hole transport material was changed to the hole transport material prepared in this Comparative Example 3A.
(Comparative Example 4A)
Organic EL devices were manufactured after a hole transport material was prepared in the same manner as in Example IA except that the compound (GI) was used as an arylamine derivative.
(Example IB) preparation of hole transport material> The compound (AI) was used as an arylamine derivative, a bisphenol A epoxy compound represented by the above-mentioned chemical formula (B2) (where n6 is 0 to 1) (hereinafter, this cross-linking agent will be referred to as "cross-linking agent B2") was used as an epoxy-based cross-linking agent, and a cationic photopolymerization initiator ("FC-508" produced by Sumitomo 3M Limited) was used as a photopolymerization initiator, and then they were dissolved with dichloroethane to obtain a hole transport material (that is, a composition for conductive materials) .
In this regard, it is to be noted that the mixing ratio of the compound (AI) and the cross-linking agent B2 was 3:1 in a mole ratio, and the weight ratio of the total weight of the compound (AI) and the cross-linking agent B2 with respect to the cationic photopolymerization initiator was 99:1.
<Manufacture of organic EL device>
IB First, an ITO electrode (that is, an anode) was formed on a transparent glass substrate having an average thickness of 100 nm in the same manner as the step IA described above.
2B Next, the prepared hole transport material was applied onto the ITO electrode by a spin coating method, and was then dried.
Then, the hole transport material was irradiated with ultraviolet rays having a wavelength of 365 nm from a mercury lamp ("UM-452", USHIO Inc.) through a filter at an intensity of irradiation of 400 mW/cm2 for 10 seconds in the dry atmosphere and then heated for 60 minutes at temperature of 1100C to polymerize the compound (AI) and the cross-linking agent B2, so that a hole transport layer having an average thickness of 50 nm was formed.
3B Next, a light emitting layer having an average thickness of 50 nm was formed on the hole transport layer in the same manner as the step 3A described above. '
4B Next, an electron transport layer having an average thickness of 20 nm was formed on the light emitting layer in the same manner as the step 4A described above.
5B Next, an AlLi electrode (that is, a cathode) having an average thickness of 300. nm was formed on the electron transport layer in the same manner as the step 5A described above.
6B Next, a protection cover made of polycarbonate was provided so as to cover these layers described above, and was then secured and sealed in the same manner as the step 6A described above to obtain an organic EL device.
(Examples 2B to 5B)
In each of Examples 2B to 5B, organic EL devices were manufactured after a hole transport material was prepared in the same manner as in Example IB except the mixing ratio (mole ratio) of the compound (AI) and the cross-linking agent B2 was changed to those shown in Table 2.
(Example 6B)
Organic. EL devices were manufactured after a hole transport material was prepared in the same manner as in Example IB except that a bisphenol F epoxy compound represented by the above-mentioned chemical formula (B3) (where n6 is 0 to 1) was used instead of the cross-linking agent B2.
(Example 7B)
Organic EL devices were manufactured after a hole transport material was prepared in the same manner as in Example IB except that a biphenyl epoxy compound represented by the above-mentioned chemical formula (B4) (where n6 is 0 to 2) was used instead of the cross-linking agent B2.
(Example 8B)
Organic EL devices were manufactured after a hole transport material was prepared in the same manner as in Example IB except that the compound (BI) was used as an arylamine derivative and that a bisphenol S epoxy compound represented by the above-mentioned chemical formula (B5) (where n6 is 0 to 1) was used instead of the cross-linking agent B2.
(Example 9B)
Organic EL devices were manufactured after a hole transport material was prepared in the same manner as in Example IB except that the compound (BI) was used as an arylamine derivative and that a bisphenylether epoxy compoundrepresented by the above-mentioned chemical formula (B6) (where n6 is 0) was used instead of the cross-linking agent B2.
(Example 10B)
Organic. EL devices were manufactured after a hole transport material was prepared in the same manner as in Example IB except that the compound (BI) was used as an arylamine derivative and that a glycidyl ester-based dimmer acid epoxy compound represented by the above-mentioned chemical formula (B7) was used instead of the cross-linking agent B2.
(Example HB)
Organic EL devices were manufactured after a hole transport material was prepared in the same manner as in Example IB except that the compound (CI) was used as an arylamine derivative and that a glycidyl ester-based phthalic acid epoxy compound represented by the above-mentioned chemical formula (B8) was used instead of the cross-linking agent B2.
(Example 12B)
Organic EL devices were manufactured after a hole transport material was prepared in the same manner as in Example IB except that the compound (CI) was used as an arylamine derivative and that an alicyclic epoxy compound represented by the above-mentioned chemical formula (B9) was used instead of the cross-linking agent B2.
(Example 13B)
Organic EL devices were manufactured after a hole transport material was prepared in the same manner as in Example IB except that the compound (CI) was used as an arylamine derivative and that an urethane modified epoxy compound represented by the above-mentioned chemical formula (B13) (where A2 represents a group obtained by eliminating two isocyanate groups from tolylene diisocyanate and two A2S represent a group obtained by eliminating two hydroxyl groups from ethylene glycol) was used instead of the cross-linking agent B2.
(Example 14B)
Organic EL devices were manufactured after a hole transport material was prepared in the same manner as in Example IB except that the compound (DI) was used as an arylamine derivative and that a silicon-containing epoxy compound represented by the above-mentioned chemical formula (B14) was used instead of the cross-linking agent B2.
(Example 15B)
Organic EL devices were manufactured after a hole transport material was prepared in the same manner as in Example IB except that the compound (DI) was used as arylamine derivative and that an acrylic ester compound represented by the above-mentioned chemical formula (Bl) (where A1 is hydrogen atom) was used instead of the cross-linking agent B2.
(Example 16B)
Organic EL devices were manufactured after a hole transport material was prepared in the same manner as in Example IB except that the compound (DI) was used as an arylamine derivative and that a polyfunctional phenol-based epoxy compound represented by the above-mentioned chemical formula (B15) (where n9 is 2 to 5) was used instead of the cross-linking agent B2.
(Example 17B)
Organic EL devices were manufactured after a hole transport material was prepared in the same manner as in Example IB except that the compound (EI) was used as an arylamine derivative and that a polyparaphenylenevinylene(PPV) -based epoxy compound represented by the above-mentioned chemical formula (B18) (where n10 is 5 to 10) was used instead of the cross-linking agent B2.
(Example 18B)
Organic EL devices were manufactured after a hole transport material was prepared in the samemanner as in Example IB except that the compound (EI) was used as an arylamine derivative and that a polyfunctional phenol-based epoxy compound represented by the above-mentioned chemical formula (B19) was used instead of the cross-linking agent B2.
(Example 19B)
Organic EL devices were manufactured after a hole transport material was prepared in the samemanner as in Example IB except that the compound (EI) was used as an arylamine derivative and that a glycidyl amine-based epoxy compound represented by the above-mentioned chemical formula (B23) was used instead of the cross-linking agent B2.
(Example 20B)
Organic EL devices were manufactured after a hole transport material was prepared in the samemanner as in Example IB except that the compound (FI) was used as an arylamine derivative and that a mixture of a bisphenol A epoxy compound representedbythe above-mentionedchemical formula (B2) (where n6 is 0 to 3) and a glycidyl ester-based dimmer acid epoxy compound represented by the above-mentioned chemical formula (B7) was used instead of the cross-linking agent B2.
(Example 21B)
Organic EL devices were manufactured after a hole transport material was prepared in the same manner as in Example IB except that the compound (FI) was used as an arylamine derivative and that a mixture of a bisphenol A epoxy compound representedby the above-mentioned chemical formula (B2) (where n6 is 0 to 1) and a polyfunctional phenol-based epoxy compound represented by the above-mentioned chemical formula (B19) was used instead of the cross-linking agent B2.
(Examples IB' to 6B' )
Organic EL devices were manufactured after a hole transport material was prepared in the same manner as in Example IB except that the addition of the cross-liking agent B2 to the hole transport material was omitted and that the arylamine derivatives for use in the hole transport material were changed to those shown in Table 2.
(Comparative Example IB)
Organic EL devices were manufactured in the same manner as in Comparative Example IA. (Comparative Example 2B)
Organic EL devices were manufactured in the same manner as in Comparative Example 2A.
(Comparative Example 3B) Preparation of hole transport material> The compound (AI) and a polycarbonate resin ( "PANLITE-1250" produced by TEIJIN CHEMICALS LTD. ) in a weight ratio of 3:7 were mixed with dicloethane to obtain a hole transport material.
Manufacture of organic EL device>
Organic EL devices were manufactured in the same manner as in Comparative Example IA except that the hole transport material was changed to the hole transport material prepared in this Comparative Example 3B.
(Comparative Example 4B)
Organic EL devices were manufactured after a hole transport material was prepared in the same manner as in Example IB except that the compound (HI) was used as an arylamine derivative.
(Comparative Examples 5B and 6B)
In each of Comparative Examples 5B and 6B, organic EL devices were manufactured after a hole transport material was prepared in the same manner as in Example IB except that the compound (GI) was used as an arylamine derivative for use in the hole transport material and that the mixing ratio (mole ratio) of the compound (GI) and the cross-linking agent B2 were changed to those shown in Table 2.
(Comparative Example 7B)
Organic. EL devices were manufactured after a hole transport material was prepared in the same manner as in Example IB except that the addition of the cross-liking agent B2 to the hole transport material was omitted and that the compound (GI) was used as an arylamine derivative foruse in the hole transport material.
(Comparative Example 8B)
Organic EL devices were manufactured after a hole transport material was prepared in the same manner as in Example IB except that the compound (AI) was used as an arylamine derivative.
(Example 1C) preparation of hole transport material> The compound (All) was used as an arylamine derivative, and the compound (All) and a cationic photopolymerization initiator ("FC-508" producedby Sumitomo 3MLimited) in aweight ratio of 99:1 were mixed with dichloroethane to obtain a hole transport material (that is, a composition for conductive materials) .
<Preparation of electron transport material> An electron transport material (that is, a composition for conductive materials) was obtained in the same manner as the hole transport material prepared in this example except that the compound (III) was used as an arylamine derivative. <Manufacture of organic EL device>
1C First, an ITO electrode (that is, an anode) was formed on a transparent glass substrate having an average thickness of 100 nm in the same manner as the step IA described above.
2C Next, the prepared hole transport material was applied onto the ITO electrode by a spin coating method, and was then dried.
Then, the hole transport material was irradiated with ultraviolet rays having a wavelength of 365 nm from a mercury lamp ("UM-452", USHIO Inc.) through a filter at an intensity of irradiation of 500mW/cm2 for 15 seconds in dry atmosphere and then heated for 60 minutes at temperature of 1100C to polymerize the compound (All), so that a hole transport layer having an average thickness of 50 nm was formed.
3C Next, a light emitting layer having an average thickness of 50 nm was formed on the hole transport layer in the same manner as the step 3A described above.
4C Next, an electron transport layer having an average thickness of 20 nm was formed on the light emitting layer by the polymerization of the compound (III) in the same manner as the step 2C described above except that the prepared electron transport material was used instead of the hole transport material. 5C Next, an AlLi electrode (that is, a cathode) having an average thickness of 300 nm was formed on the electron transport layer in the same manner as the step 5A described above.
6C Next, a protection cover made of polycarbonate was provided so as to cover these layers described above, and was then secured and sealed in the same manner as the step 6A described above to obtain an organic EL device.
(Examples 2C to 14C)
In each of Examples 2C to 13C, organic EL devices were manufactured after a hole transport material was prepared in the same manner as in Example 1C except that as for the arylamine derivatives for use in the hole transport material and the electron transport material, those shown in Table 3 are used, respectively.
(Comparative Example 1C)
<Preparation of hole transport material> A hole transport material was obtained by dissolving the compound (SII) in dichloroethane.
Manufacture of organic EL device>
Organic EL devices were manufactured in the same manner as in Example 1C except that a hole transport layer was formed using the prepared hole transport material but omitting the irradiation of ultraviolet rays at the step 2C and that an electron transport layer was formed using the compound (UII) by vacuum evaporation at the step 4C. (Comparative Example 2C)
Preparation of hole transport material>
The compound (TII) was dispersed in water to prepare a
2.0 wt% water dispersion of the compound (TII), thereby obtaining a hole transport material.
In this regard, it is to be noted that the weight ratio of 3, 4-ethylenedioxythiophene to styrenesulfonic acid in the compound (TII) was 1: 20.
<Manufacture of organic EL device>
Organic EL devices were manufactured in the same manner as in Comparative Example 1C except that the hole transport material was changed to the hole transport material prepared in this Comparative Example.
(Comparative Example 3C)
<Preparation of hole transport material> The compound (SII) was used as an arylamine derivative, and a bifunctional epoxy compound ("DENACOL EX-212" produced by Nagase chemteX Corporation) was used as a photocrosslinking agent, and the compound (SII) , the epoxy compound and a cationic photopolymerization initiator ("FC-508" produced by Sumitomo 3M Limited) in a weight ratio of 50:49:1 were mixed with dichloroethane to obtain a hole transport material.
<Manufacture of organic EL device>
Organic EL devices were manufactured in the same manner as in Comparative Example 1C except that the hole transport material was changed to the hole transport material prepared in the above-mentioned step 2C and that an electron transport layer was formed using the compound (UII) by vacuum evaporation in the step 4C.
(Comparative Example 4C)
Organic EL devices were manufactured after a hole transport material was prepared in the same manner as in Example 3C except that the compound (GII) was used as an arylamine derivative for use in the hole transport material.
(Example ID) preparation of hole transport material> The compound (All) was used as an arylamine derivative, the cross-linking agent B2 was used as an epoxy-based cross-linking agent and a cationic photopolymerization initiator ("FC-508" produced by Sumitomo 3M Limited) was used as aphotopolimerization initiator, respectively, and then they were mixed with dichloroethane to obtain a hole transport material (that is, a composition for conductive materials).
In this regard, it is to be noted that the mixing ratio of the compound (All) and the cross-linking agent B2 was 3:1 in a mole ratio, and the weight ratio of the total weight of the compound (All) and the cross-linking agent B2 with respect to the cationic photopolymerization initiator was 99:1.
preparation of electron transport material> An electron transport material (that is, a composition for conductive materials) was obtained in the same manner as the hole transport material prepared in this Example except that the compound (III) was used as an arylamine derivative.
Manufacture of organic EL device>
ID First, an ITO electrode (that is, an anode) having an average thickness of 100 nmwas formed on a transparent glass substrate in the same manner as the step IA described above.
2D Next, the hole transport material was applied onto the ITO electrode by a spin coating method," and was then dried.
Then, the hole transport material was irradiated with ultraviolet rays having a wavelength of 365 nm from a mercury lamp ("UM-452", USHIO Inc.) through a filter at an intensity of irradiation of 400 mW/cm2 for 10 seconds in dry atmosphere and then heated for 60 minutes at temperature of 1100C to polymerize the compound (All) and the cross-linking agent B2, so that a hole transport layer having an average thickness of 50 nm was formed.
3D Next, a light emitting layer having an average thickness of 50 nm was formed on the hole transport layer in the same manner as the step 3A described above.
4D Next, an electron transport layer having an average thickness of 20 nm was formed on the light emitting layer by polymerizing the compound (III) and the cross-linking agent B2 in the same manner as the step 2D described above except that the prepared electron transport material was used instead of the hole transport material. 5D Next, an AlLi electrode (that is, a cathode) was formed on the electron transport layer so as to have an average thickness of 300 nm in the same manner as the step 5A described above.
6D Next, a protection cover made of polycarbonate was provided so as to cover these layers described above, and was then secured and sealed with an ultraviolet curable resin to obtain an organic EL device.
(Examples 2D to 18D)
In each of Examples 2D to 18D, organic EL devices were manufactured after a hole transport material and an electron transport material were prepared in the same manner as in Example ID except that the arylamine derivatives for use in the hole transport material and the electron transport material and themolar ratio of the arylamine derivative to the cross-linking agent B2 were changed to those shown in Table 4 (Table A).
(Example 19D)
Organic EL devices were manufactured after a hole transport material and an electron transport material were prepared in the same manner as in Example ID except that a bisphenol F epoxy compound represented by the above-mentioned chemical formula (B3) (where n6 is 0 to 1) was used as an epoxy-based cross-linking agent for use in the hole transport material and the electron transport material.
(Example 20D) Organic EL devices were manufactured after a hole transport material and an electron transport material were prepared in the same manner as in Example ID except that a biphenyl epoxy compound represented by the above-mentioned chemical formula (B4) (where n6 is 0 to 2) was used as an epoxy-based cross-linking agent for use in the hole transport material and the electron transport material.
(Example 21D)
Organic EL devices were manufactured after a hole transport material and an electron transport material were prepared in the same manner as in Example ID except that a bisphenol S epoxy compound represented by the above-mentioned chemical formula (B5) (where n6 is 0 to 1) was used as an eppxy-based cross-linking agent for use in the hole transport material and the electron transport material.
(Example 22D)
Organic EL devices were manufactured after a hole transport material and an electron transport material were prepared in the same manner as in Example ID except that a bisphenylether epoxy compound represented by the above-mentioned chemical formula (B6) (where n6 is 0) was used as an epoxy-based cross-linking agent for use in the hole transport material and the electron transport material.
(Example 23D)
Organic EL devices were manufactured after a hole transport material and an electron transport material were prepared in the same manner as in. Example ID except that a glycidyl ester-based dimmer acid epoxy compound represented by the above-mentioned chemical formula (B7) was used as an epoxy-based cross-linking agent for use in the hole transport material and the electron transport material.
(Example 24D)
Organic EL devices were manufactured after a hole transport material and an electron transport material were prepared in the same manner as in Example ID except that a glycidyl ester-based phthalic acid epoxy compound represented by the above-mentioned chemical formula (B8) was used as an epoxy-based cross-linking agent for use in the hole transport material and the electron transport material.
(Example 25D)
Organic EL devices were manufactured after a hole transport material and an electron transport material were prepared in the same manner as in Example ID except that an alicyclic epoxy compound represented by the above-mentioned chemical formula (B9) was used as an epoxy-based cross-linking agent for use in the hole transport material and the electron transport material.
(Example 26D)
Organic EL devices were manufactured after a hole transport material and an electron transport material were prepared in the same manner as in Example ID except that an urethane modified epoxy compound represented by the above-mentioned chemical formula (B13) (where A2 represents a group obtained by eliminating two isocyanate groups from tolylene diisocyanate and two A2S represent a group obtained by eliminating two hydroxyl groups from ethylene glycol) was used as an epoxy-based cross-linking agent for use in the hole transport material and the electron transport material.
(Example 27D)
Organic EL devices were manufactured after a hole transport material and an electron transport material were prepared in the same manner as in Example ID except that the compound (EII) was used as an arylamine derivative for use in the hole transport material and that a silicon-containing epoxy compound represented by the above-mentioned chemical formula (B14) was used as an epoxy-based cross-linking agent for use in the hole transport material and the electron transport material.
(Example 28D)
Organic EL devices were manufactured after a hole transport material and an electron transport material were prepared in the same manner as in Example 27D except that an acrylic ester compound represented by the above-mentioned chemical formula (Bl) (where A1 is hydrogen atom) was used as an epoxy-based cross-linking agent for use in the hole transport material and the electron transport material.
(Example 29D)
Organic EL devices were manufactured after a hole transport material and an electron transport material were prepared in the same manner as in Example 27D except that a polyfunctional phenol-based epoxy compound represented by the above-mentioned chemical formula (Bl5) (where n9 is 2 to 5) was used as an epoxy-based cross-linking agent for use in the hole transport material and the electron transport material.
(Example 30D)
Organic EL devices were manufactured after a hole transport material and an electron transport material were prepared in the same manner as in Example 27D except that a polyparaphenylenevinylene(PPV)-based epoxy compound represented by the above-mentioned chemical formula (B18) (where n10 is 5 to 10) was used as an epoxy-based cross-linking agent for use in the hole transport material and the electron transport material.
(Example 31D)
Organic EL devices were manufactured after a hole transport material and an electron transport material were prepared in the same manner as in Example 27D except that a polyfunctional phenol-based epoxy compound represented by the above-mentioned chemical formula (B19) was used as an epoxy-based cross-linking agent for use in the hole transport material and the electron transport material.
(Example 32D)
Organic EL devices were manufactured after a hole transport material and an electron transport material were prepared in the same manner as in Example 27D except that a glycidyl amine-based epoxy compound represented by the above-mentioned chemical formula (B23) was used as an epoxy-based cross-linking agent for use in the hole transport material and the electron transport material.
(Example 33D)
Organic EL devices were manufactured after a hole transport material and an electron transport material were prepared in the same manner as in Example 27D except that a mixture of a bisphenol A epoxy compound represented by the above-mentioned chemical formula (B2) (where n6 is 0 to 3) and a glyσidyl ester-based dimmer acid epoxy compound represented by the above-mentioned chemical formula (B7) was used as an epoxy-based cross-linking agent for use in the hole transport material and the electron transport material.
(Example 34D)
Organic EL devices were manufactured after a hole transport material and an electron transport material were prepared in the same manner as in Example 27D except that a mixture of a bisphenol A epoxy compound represented by the above-mentioned chemical formula (B2) (where n6 is 0 to 1) and apolyfunctional phenol-basedepoxy compoundrepresentedby the above-mentioned chemical formula (Bl9) was used as an epoxy-based cross-linking agent for use in the hole transport material and the electron transport material.
(Examples ID' to 14D')
In each of Examples ID' to 14D' , organic EL devices were manufactured after a hole transport material was prepared in the same mariner as in Example ID except that the addition of the cross-liking agent B2 to the hole transport material was omitted and that the arylamine derivatives for use in the hole transport material were changed to those shown in Table 4 (C) .
(Comparative Example ID)
Organic.EL devices were manufactured in the same manner as in Comparative Example 1C.
(Comparative Example 2D)
Organic EL devices were manufactured in the same manner as Comparative Example 2C.
(Comparative Example 3D)
Preparation of hole transport material> The compound (All) was used as an arylamine derivative, and the compound (All) and a polycarbonate resin ("PANLITE-1250" produced by TEIJIN CHEMICALS LTD. ) in a weight ratio of 3:7 were mixed with dichloroethane to obtain a hole transport material.
<Manufacture of organic EL device>
Organic EL devices were manufactured in the same manner as in Comparative Example ID except that the hole transport material was changed to the hole transport material prepared in this Comparative Example 3D.
(Comparative Example 4D)
Organic EL devices were manufactured after a hole transport material was prepared in the same manner as in Comparative Example ID except that the compound (All) was used as an arylamine derivative for use in the hole transport material. (Comparative Example 5D)
Organic EL devices were manufactured after a hole transport material and an electron transport material were prepared in the same manner as in Example ID' except that the compound (GII) was used as an arylamine derivative for use in the hole transport material and that the compound (UII) was used as an arylamine derivative for use in the electron transport material.
(Comparative Examples 6D and 7D)
In each of Comparative Examples 6D and 7D, organic EL devices were manufactured after a hole transport material and an electron transport material were prepared in the same manner as in Example ID except that the arylamine derivatives for use in the hole transport material and the electron transport material were changed to those shown in Table 4(C).
3. Evaluation of organic EL device
The luminous brightness (cd/m2) , the maximum luminous efficiency (lm/W) , and the time that elapsedbefore the luminous brightness became half of the initial value (that is, a half-life) of each of the organic EL devices obtained in Examples andComparative Examples mentioned aboveweremeasured. Based on the measurement values for the five organic EL devices, an average was calculated.
In this regard, it is to be noted that the luminous brightness was measured by applying a voltage of 6V across the ITO electrode and the AlLi electrode.
Themeasurement values (that is, the luminous brightness, the maximum luminous efficiency, and the half-life) of each of the Examples IA to 6A and the Comparative Examples 2A to 4A were evaluated based on the measurement values of the Comparative Example IA according to the following four criteria, respectively.
A: The measurement value was 1.5 times or more that of Comparative Example IA.
B: The measurement value was 1.25 times or more but less than 1.5 times that of Comparative Example IA.
C: The measurement value was 1.00 times or more but less than 1.25 times that of Comparative Example IA.
D: The measurement value was 0.75 times or more but less than 1.00 times that of Comparative Example IA.
The evaluation results are shown in the attached Table 1.
As shown in Table 1, all the organic EL devices of the Examples (that is, organic EL devices including ahole transport layer which was formed using the conductive material according to the present invention as its main material) were superior to the organic EL devices of the Comparative Examples in their luminous brightness, maximum luminous efficiency, and half-life.
From the result, it has been found that in the organic EL device according to the present invention interaction between the adjacent main skeletons was properly decreased. In addition, it has also been found that in the organic EL device according to the present invention mutual dissolution between the hole transport layer and the light emitting layer was properly prevented.
Further, it has been also foundthat the organic EL devices of the Examples which were formed of the compositions each having the adjacent main skeletons which are allowed to exist at a more suitable interval, the luminous brightness and the maximum luminous efficiency were further improved and the half-life was also further prolonged.
The measurement values (that is, the luminous brightness, the maximum luminous efficiency, and the half-life) of each of the Examples IB to 2IB, the Examples IB' to 6B' and the Comparative Examples 2B to 8B were evaluated based on the measurement values of the Comparative Example IB according to the following four criteria, respectively.
A: The measurement value was 1.5 times or more that of Comparative Example IB.
B: The measurement value was 1.25 times or more but less than 1.5 times that of Comparative Example IB.
C: The measurement value was 1.00 times or more but less than 1.25 times that of Comparative Example IB.
D: The measurement value was 0.75 times or more but less than 1.00 times that of Comparative Example IB. The evaluation results are shown in the attached Table 2.
As shown in Table 2, all the organic EL devices of the Examples (that is, organic EL devices including ahole transport layer which was formed using the conductive material according to the present invention as a main material) were superior to the organic EL devices of the Comparative Examples in their luminous brightness, maximum luminous efficiency, and half-life.
From the result, it has been found that in the organic EL device according to the present invention interaction between the adjacent main skeletons was properly decreased. In addition, it has also been found that in the organic EL device according to the present invention mutual dissolution between the hole transport layer and the light emitting layer was properly prevented.
Further, each of the organic EL devices of the Examples IB to 2IB shows a tendency that the maximum luminous efficiency was improved as compared to the organic EL devices of the Examples IB1 to 6B' . Such a result suggests that in the organic EL devices of the Examples IB to 2IB the interval between the adjacent main skeletons could be maintained at a more suitable distance due to the addition of the epoxy-based cross-linking agent.
Furthermore, the organic EL devices of the Examples IB, 2B, and 3B which were formed from the hole transport material in which the compound represented by the above-mentioned general formula (Al) and the epoxy-based cross-linking agent were mixed with a particularly preferable mixing ratio show a tendency that the luminous brightness and the maximum luminous efficiency were further improved and the half-life was also further prolonged as compared to the organic EL devices of the Examples 4B and 5B.
Moreover, in the case where the evaluation results are reviewed from the view point of the substituent X, there is a tendency that the compositions of the Examples whichwere formed of the compounds containing the substituents X each having an appropriate n1 value in the general formula (A2), that is the compositions formed of the compounds containing the substituents X by which the adjacent main skeletons are allowed to exist at a suitable interval, could have more superior luminous brightness, maximum luminous efficiency, and half-life as compared to the compositions which do not have such a substituent X.
Themeasurement values (that is, the luminous brightness, the maximum luminous efficiency, and the half-life) of each of the Examples 1C to 14C and the Comparative Examples 2C to 4C were evaluated based on the measurement values of the Comparative Example 1C according to the following four criteria, respectively.
A: The measurement value was 1.5 times or more that of Comparative Example 1C.
B: The measurement value was 1.25 times or more but less than 1.5 times that of Comparative Example 1C.
C: The measurement value was 1.00 times or more but less than 1.25 times that of Comparative Example 1C.
D: The measurement value was 0.75 times or more but less than 1.00 times that of Comparative Example 1C.
The evaluation results are shown in the attached Table 3.
As shown in Table 3, all the organic EL devices of the Examples (that is, organic EL devices including ahole transport layer and a electron transport layer which were formed using the conductive material according to the present invention as amain material thereof) were superior to the organic EL devices of the Comparative Examples in their luminous brightness, maximum luminous efficiency, and half-life.
From the results, it has been found that in the organic EL device according to the present invention interaction between the adjacent main skeletons was properly decreased. In addition, it has also been found that in the organic EL device according to the present invention mutual dissolution between the hole transport layer and the light emitting layer was properly prevented.
Further, in the case where the evaluation results are reviewed from the view point of the substituent X, there is a tendency that the compositions of the Examples whichwere formed of the compounds containing the substituents X each having an appropriate n1 value in the general formula (A2), that is the compositions which were formed of the compounds containing the substituents X by which the adjacent main skeletons are allowed to exist at a suitable interval, could have more superior luminous brightness, maximum luminous efficiency, and half-life as compared with the compositions which do not have such a substituent X.
Furthermore, the organic EL devices in the Examples each obtained by appropriately selecting conductive materials for respectively constituting the hole transport material and the electron transport material, namely, the organic EL devices in the Examples each having a preferred combination of the hole transport layer and the electron transport layer by appropriately selecting the group Y of the compound represented by the above-mentioned general formula (Al) couldhave superior luminous brightness, maximum luminous efficiency, and half-life.
Themeasurement values (that is, the luminous brightness, the maximum luminous efficiency, and the half-life) of each of the Examples ID to 34D, the Examples ID' to 14D' and the Comparative Examples 2D to 7D were evaluated based on the measurement values of the Comparative Example ID according to the following four criteria, respectively.
A: The measurement value was 1.5 times or more that of Comparative Example ID.
B: The measurement value was 1.25 times or more but less than 1.5 times that of Comparative Example ID.
C: The measurement value was 1.00 times or more but less than 1.25 times that of Comparative Example ID.
D: The measurement value was 0.75 times or more but less than 1.00 times that of Comparative Example ID.
The evaluation results are respectively shown in the attached Tables 4(A) to 4(C).
As shown in Tables 4(A) to 4(C) , all the organic EL devices of the Examples (that is, the organic EL devices including a hole transport layer which was formed using the conductive material according to the present invention as its main material) were superior to the organic EL devices of the Comparative Examples in their luminous brightness, maximum luminous efficiency, and half-life.
From the result, it has been found that in the organic EL device according to the present invention interaction between the adjacent main skeletons was properly decreased. In addition, it has also been found that in the organic EL device according to the present invention mutual dissolution between the hole transport layer and the light emitting layer was properly prevented.
Further, each of the organic EL devices of the Examples ID to 34D shows a tendency that the maximum luminous efficiency was improved as compared to the organic EL devices of the Examples ID' to 14D'. Such a tendency was recognized more conspicuously as the organic EL devices which were formed of the hole transport materials each having a particularly preferable mixing ratio of the compound represented by the general formula (IA) and the epoxy-based cross-linking agent. This result suggests that the interval between the adjacent main skeletons could be maintained at a more suitable interval due to the addition of the epoxy-based cross-linking agent.
Furthermore, as shown in the Examples 19D to 34D, the luminous brightness, the maximum luminous efficiency and the half-life were superior irrespective of the kind of epoxy-based cross-linking agent used. This result suggests that the adjacent main skeletons are allowed to exist at a suitable interval even in the case where any epoxy-based cross-linking agent is used.
Moreover, in the case where the evaluation results are reviewed from the view point of the substituent X, there is a tendency that the compositions of the Examples which contain substituents Xeachhaving an appropriate n1value in the general formula (A2), that is the compositions containing the substituents X by which the adjacent main skeletons are allowed to exist at a suitable interval, could have more superior luminous brightness, maximum luminous efficiency, and half-life as compared to the compositions which do not have such a substituent X.
Moreover, the organic EL devices in the Examples each obtained by appropriately selecting conductive materials for respectively constituting the hole transport material and the electron transport material, namely, the organic EL devices in the Examples each having a preferred combination of the hole transport layer and the electron transport layer by appropriately selecting the group Y of the compound represented by the above-mentioned general formula (Al) couldhave superior luminous brightness, maximum luminous efficiency, and half-life.
4. Manufacture of organic TFT
Five organic TFTs were manufactured in each of the following Examples and Comparative Examples.
(Example IE)
Preparation of organic semiconductor material> The compound (KII) was used as an arylamine derivative, and the compound (KII) and a cationic photopolymerization initiator ("FC-508" producedby Sumitomo 3MLimited) in aweight ratio of 99:1 were mixed with diσhloroethane to obtain an organic semiconductor material (that is, a composition for conductive materials) .
<Manufacture of organic TFT>
IE First, a glass substrate having an average thickness of 1 mmwas prepared, and it was then washedwith water (that is, with a cleaning fluid).
Next, a photoresist was applied onto the glass substrate by a spin coating method, and then the photoresist was prebaked to form a film.
Next, the film was irradiated with (or exposed to) ultraviolet rays through a photomask to develop it. In this way, a resist layer having openings where a source electrode and a drain electrode were to be provided was formed.
2E Next, an aqueous gold colloidal solution was supplied to the openings by an InkJet method. Then, the glass substrate to which the aqueous gold colloidal solution had been supplied was dried by heating to obtain a source electrode and a drain electrode.
3E Next, the resist layer was removed by oxygen plasma treatment. Then, the glass substrate on which the source electrode and the drain electrode had been formed was washed with water, and was then washed with methanol.
4E Next, the prepared organic semiconductor material was applied onto the substrate by a spin coating method and then it was dried.
Then, the organic semiconductor material was irradiated with ultraviolet rays having a wavelength of 365 nm from a mercury lamp ("UM-452", USHIO Inc.) through a filter at an intensity of irradiation of 500 mW/cm2 for 15 seconds in dry atmosphere to polymerize the compound (KII) and then heated for 60 minutes at temperature of 110°C, so that an organic semiconductor layer having an average thickness of 50 nm was formed on the glass substrate.
5E Next, a butyl acetate solution of polymethylmethacrylate (PMMA) was applied onto the organic semiconductor layer by a spin coating method, andwas then dried to form a gate insulating layer having an average thickness of 500 nm.
6E Next, a water dispersion of polyethylenedioxythiophene was applied to an area on the gate insulating layer corresponding to the area between the source electrode and the drain electrode by an inkjet method, and was then dried to form a gate electrode having an average thickness of 100 nm.
By way of these steps, an organic TFT was manufactured.
(Examples 2E to 7E)
In each of Examples 2E to 8E, organic TFTs were manufactured after the organic semiconductor material was prepared in the same manner as in Example IE except that as for an arylamine derivative for use in preparing the organic semiconductor material, those shown in Table 5 were used.
(Comparative Example IE)
<Preparation of organic semiconductor material> The compound (SII) was dissolved in dichloroethane to prepare an organic semiconductor material.
Manufacture of organic TFT>
Organic TFTs were manufactured in the same manner as in Example IE except that the organic semiconductor material was changed to the organic semiconductor material prepared in the step 4E and the organic semiconductor material was not irradiatedwith ultraviolet rays from amercury lamp in the step 4E .
(Comparative Example 2E)
Preparation of organic semiconductor material> The compound (SII) was used as an arylamine derivative, and a bifunctional epoxy compound ("DENACOL EX-212" produced by Nagase chemteX Corporation) was used as a photocrosslinking agent, and the compound (SII) , the epoxy compound and a cationic photopolymerization initiator ("FC-508" produced by Sumitomo 3M Limited) in a weight ratio of 50:49:1 were mixed with dichloroethane to obtain an organic semiconductor material.
Manufacture of organic TFT>
Organic TFTs were manufactured in the same manner as in Example IE except that the organic semiconductor material prepared in this Comparative Example was used as the organic semiconductor material.
(Comparative Example 3E)
Organic TFTs were manufactured after the organic semiconductor material was prepared in the same manner as in Example IE except that the compound (Oil) was used as an arylamine derivative for use in preparing the organic semiconductor material.
(Example IF)
<Preparation of organic semiconductor material> The compound (KII) was used as an arylamine derivative, the cross-linking agent B2 was used as the epoxy-based cross-linking agent, and a cationic photopolymerization initiator ("FC-508" produced by Sumitomo 3M Limited) was used as a photopolymerization initiator, and then they were dissolved with dichloroethane to obtain an organic semiconductor material (that is, a composition for conductive materials) .
In this regard, it is to be noted that the mixing ratio of the compound (KII) and the cross-linking agent B2 was 3:1 in a molar ratio, and the weight ratio of the total weight of the compound (KII) and the cross-linking agent B2 with respect to the cationic polymerization initiator was 991:1.
Manufacture of organic TFT>
IF First, in the same manner as the step IE described above, a resist layer having openings where a source electrode and a drain electrode were to be provided was formed on a glass substrate.
2F Next, in the same manner as the step 2E described above, a source electrode and a drain electrode were formed on the substrate.
3F Next, in the same manner as the step 3E described above, the resist layer was removed, and then the glass substrate on which the source electrode and the drain electrode had been formed was washed with water.
4F Next, in the same manner as the step 4E described above, the prepared organic semiconductor material was applied onto the substrate by a spin coatingmethodand then it was dried. Then, the organic semiconductor material was irradiated with ultraviolet rays having a wavelength of 365 nm from a mercury lamp ("UM-452", USHIO Inc.) through a filter at an intensity of irradiation of 400 mW/cm2 for 10 seconds in dry atmosphere and thenheatedfor 60 minutes at temperature of 1100C to polymerize the compound (KII) and the cross-linking agent B2, so that an organic semiconductor layer having an average thickness of 50 nm was formed on the glass substrate.
5F Next, in the same manner as the step 5E described above, a gate insulating layer having an average thickness of 500 nm was formed on the organic semiconductor layer.
6F Next, in the same manner as the step 6E described above, a gate electrode having an average thickness of 100 nm was formed on an area on the gate insulating layer corresponding to the area between the source electrode and the drain electrode.
(Examples 2F to 12F)
In each of Examples 2F to 12F, organic TFTs were manufactured after the organic semiconductor material was prepared in the same manner as in Example IF except that the arylamine derivative for use in preparing the organic semiconductor material and the mixing ratio (mole ratio) of the arylamine derivative and the cross-linking agent B2 were changed to those shown in Table 6 were used.
(Example 13F) Organic TFTs were manufactured after the organic semiconductor material was prepared in the same manner as in Example IF except that a glycidyl ester-based dimmer acid epoxy compound represented by the above-mentioned chemical formula (B7) was used as an epoxy-based cross-linking agent for use in preparing the organic semiconductor material.
(Example 14F)
Organic TFTs were manufactured after the organic semiconductor material was prepared in the same manner as in Example IF except that an alicyclic epoxy compound represented by the above-mentioned chemical formula (B9) was used as an epoxy-based cross-linking agent for use in preparing the organic semiconductor material.
(Example 15F)
Organic TFTs were manufactured after the organic semiconductor material was prepared in the same manner as in Example IF except that an acrylic ester compound represented by the above-mentioned chemical formula (Bl) (where A1 is hydrogen atom) was used as an epoxy-based cross-linking agent for use in preparing the organic semiconductor material.
(Example 16F)
Organic TFTs were manufactured after the organic semiconductor material was prepared in the same manner as in Example IF except that a polyfunctional phenol-based epoxy compound represented by the above-mentioned chemical formula (B15) (where n9 is 2 to 5) was used as an epoxy-based cross-linking agent for use in preparing the organic semiconductor material.
(Example 17F)
Organic. TFTs were manufactured after the organic semiconductor material was prepared in the same manner as in Example IF except that a glycidyl amine-based epoxy compound represented by the above-mentioned chemical formula (B23) was used as an epoxy-based cross-linking agent for use in preparing the organic semiconductor material.
(Examples IF' to 8F' )
In each of Examples IF' to 7F' , organic TFTs were manufactured after the organic semiconductor material was prepared in the same manner as in Example IF except that the addition of the cross-linking agent B2 to the organic semiconductormaterialwas omitted and the arylamine derivative for use in preparing the organic semiconductor material was changed to those shown in Table 6.
(Comparative Example IF)
Organic TFTs were manufactured in the same manner as Comparative Example IE.
(Comparative Examples 2F and 3F)
In each of Examples 2F and 3F, organic TFTs were manufactured after the organic semiconductor material was prepared in the same manner as in Example IF except that the arylamine derivative for use in preparing the organic semiconductor material was changed to those shown in Table 6. 5. Evaluation of organic TFT
The OFF-state current and the ON-state current of each of the organic TFTs manufactured in Examples and Comparative Examples were measured.
Here, the word "OFF-state current" means the value of current flowing between the source electrode and the drain electrode when a gate voltage is not applied, and the word "ON-state current" means the value of current flowing between the source electrode and the drain electrode when a gate voltage is applied.
Therefore, a larger value of ratio of the absolute value of the ON-state current to the absolute value of the OFF-state current (hereinafter, simply referred to as a "value of ON/OFF ratio") means that an organic TFT has better characteristics.
The OFF-state current was measured at a potential difference between the source electrode and the drain electrode of 30 V, and the ON-state current was measured at a potential difference between the source electrode and the drain electrode of 30 V and an absolute value of gate voltage of 40 V.
The value of ON/OFF ratio of each of the Examples and the Comparative Examples was evaluated according to the following four criteria.
A: The value of ON/OFF ratio was 104 or more.
B: The value of ON/OFF ratio was 103 or more but less than 104 .
C: The value of ON/OFF ratio was 102 or more but less than
10^
D: The value of ON/OFF ratio was less than 10'
The evaluation results are shown in the following Table 5 and Table 6.
As shown in Table 5, the values of ON/OFF ratio of all the organic TFTs obtained in the Examples were larger than those of the organic TFTs obtained in the Comparative Examples. This means that all the organic TFTs of the Examples had better characteristics.
From the result, it has been found that interaction between the adjacent main skeletons was properly decreased. In addition, it has been also found that in the organic EL device according to the present invention mutual dissolution between the organic semiconductor layer and the gate insulating layer was properly prevented.
Further, in the case where the evaluation results are reviewed from the view point of the substituent X, there is a tendency that in the compositions of the Examples which were formed of the compounds containing the substituents X each having an appropriate n1 value in the general formula (A2) , that is the compositions formed of the compounds containing the substituents X by which the adjacent main skeletons are allowed to exist at a suitable interval, the value of ON/OFF ratio was more increased, that is, the characteristics of the organic TFT were further improved.
Further, as shown in Table 6, the values of ON/OFF ratio of all the organic TFTs obtained in the Examples were larger than those of the organic TFTs obtained in the Comparative Examples. This means that all the organic TFTs of the Examples had better characteristics.
From the result, it has been found that interaction between the adjacent main skeletons was properly decreased. In addition, it has been also found that in the organic TFTs according to the present invention mutual dissolution between the organic semiconductor layer and the gate insulating layer was properly prevented.
Further, there is a tendency that the organic TFTs of the Examples IF to 17F were improved in the value of ON/OFF ratio as compared to the organic TFTs of the Examples IF' to 8F' . This suggests that the addition of the epoxy-based cross-linking agent allowed the adjacent main skeletons to exist at a more suitable interval.
In this regard, it should be noted that as shown in each of the Examples 13F to 17F the value of ON/OFF ratio was improved irrespective of the kind of epoxy-based cross-linking agent used. This suggests that the addition of the epoxy-based cross-linking agent allowed the adjacent main skeletons to exist at a more suitable interval even in the case where any epoxy-based cross-linking agent was used. Further, in the case where the evaluation results are reviewed from the view point of the substituent X, there is a tendency that the compositions of Examples which were formed of the compounds containing the substituents X each having an appropriate n1 value in the general formula (A2), that is the compositions formed of the compounds having the substituents X by which the adjacent main skeletons are allowed to exist at a suitable interval, could have more increased value of ON/OFF ratio, that is, the characteristics of the organic TFT were further improved.
6. Manufacture of Conductive Layer
Five conductive layers were manufactured in each of the following Examples and Comparative Examples.
(Example IG)
Preparation of conductive layer>
The compound (AI) was used as an arylamine derivative, the cross-linking agent B2 was used as the epoxy-based cross-linking agent, and a cationic photopolymerization initiator ("FC-508" produced by Sumitomo 3M Limited) was used as a photopolymerization initiator, and they were mixed with dichloroethane to prepare a conductive material.
In this regard, it is to be noted that the mixing ratio of the compound (AI) and the cross-linking agent B2 was 3:1 in a mole ratio, and the weight ratio of the total of the compound (AI) and the cross-linking agent B2 with respect to the cationic photopolymerization initiator was 99:1. Manufacture of conductive layer>
First, the prepared the conductive material was applied onto a silicon substrate having an average thickness of 1.2mm by a spin coating method, and was then dried.
Then, the conductive material was irradiated with ultraviolet rays having a wavelength of 365 nm from a mercury lamp ("UM-452", USHIO Inc.) through a filter at an intensity of irradiation of 400 mW/cm2 for 10 seconds in the dry atmosphere and then heated for 60 minutes at temperature of 1100C to polymerize the compound (AI) and the cross-linking agent B2, so that a conductive layer having an average thickness of 50 nm was formed on the substrate.
(Examples 2G to 21G)
In each of Examples 2G to 2IG, conductive layers were manufactured in the same manner as in Example IG except that the hole transport materials used in the Examples 2B to 2IB were used for the respective conductive materials.
(Comparative Example G)
Conductive layers were manufactured in the same manner as in Example IG except that the hole transport material used in the Example 8B was used for the conductive material and that irradiation of ultraviolet rays by a mercury lamp and heat treatment were omitted.
(Example IH)
<Preparation of conductive layer> The compound (All) was used as an arylamine derivative, the cross-linking agent B2 was used as the epoxy-based cross-linking agent, and a cationic photopolymerization initiator ("F.C-508" produced by Sumitomo 3M Limited) was used as a photopolymerization initiator, and they were mixed with dichloroethane to prepare a conductive material.
In this regard, it is to be noted that the mixing ratio of the compound (All) and the cross-linking agent B2 was 3:1 in a molar ratio, and the weight ratio of the total of the compound (All) and the cross-linking agent B2 with respect to the cationic photopolymerization initiator was 99:1.
<Manufacture of conductive layer>
First, the prepared the conductive material was applied onto a silicon substrate having an average thickness of 1.2mm by a spin coating method, and was then dried.
Then, the conductive material was irradiated with ultraviolet rays having a wavelength of 365 nm from a mercury lamp ("UM-452", USHIO Inc.) through a filter at an intensity of irradiation of 400 mW/cm2 for 10 seconds in the dry atmosphere and then heated for 60 minutes at temperature of 1100C to polymerize the compound (All) and the cross-linking agent B2, so that a conductive layer having an average thickness of 50 nm was formed on the substrate.
(Examples 2H to 17H)
In each of Examples 2H to 17H, conductive layers were manufactured in the same manner as in Example IH except that the hole transport materials used in the Examples 19D to 34D were used for the respective conductive materials.
(Comparative Example H)
Conductive layers were manufactured in the same manner as in Example IH except that the hole transport material used in the Example 4D was used for the conductive material and that irradiation of ultraviolet rays by a mercury lamp and heat treatment were omitted.
7. Evaluation of conductive layers
7-1 Hardness test
In each of the conductive layers of the Examples and the Comparative Examples, the hardness of the thin filmwas measured using a scanning type nanoindenter (Hysitron Inc.).
In each case, the hardness was obtained from the average values for the five thin films.
In this regard, it should be noted that the scanning type nanoindenter is an apparatus provided with a diamond tip as a detecting section. In this apparatus, by repeating addition of a load to the surface of a thin film and removal of the load therefrom, displacements at the surface of the thin film are detected successively to obtain a load-displacement curve, and based on the thus obtained load-displacement curve the hardness of the thin film and the like are calculated.
The values of hardness measured in each of the Examples IG to 21G were evaluated based on the measurement value of the Comparative Example G according to the following four criteria, respectively.
A: The measurement value was 2.0 times or more that of Comparative Example G.
B: The measurement value was 1.5 times or more but less than 2.0 times that of Comparative Example G.
C: The measurement value was 1.00 times or more but less than 1.5 times that of Comparative Example G.
D: The measurement value was less than 1.00 times that of Comparative Example G.
The values of hardness measured in each of the Examples IH to 17H were evaluated based on the measurement value of the Comparative Example H according to the following four criteria, respectively.
A: The measurement value was 2.0 times or more that of Comparative Example H.
B: The measurement value was 1.5 times or more but less than 2.0 times that of Comparative Example H.
C: The measurement value was 1.00 times or more but less than 1.5 times that of Comparative Example H.
D: The measurement value was less than 1.00 times that of Comparative Example H.
7-2 Chemical resistance test
In this chemical resistance test, each of the conductive layers of the Examples and the Comparative Examples was immersed in an acetone solution for ten days at room temperature, and then the surface condition of each conductive layerwas observed with naked eyes. The chemical resistance test was carried out for five conductive layers in each case.
The results of the observations for the conductive layers of the Examples and the Comparative Example were evaluated according to the following four criteria, respectively.
A: There was no change in the surface condition. B: There was a minor color change in the surface. C: Slight swelling was observed at the surface. D: Considerable swelling and peeling-off were observed at the surface.
These evaluation results are shown in the following Table 7 and Table 8, respectively.
As shown in Table 7, the conductive layer (that is, a layer formed using the conductive material according to the present invention as its main material) of each of the Examples shows the superior results in not only the hardness test but also the chemical resistance test as compared to those of the Comparative Example G.
This means that the conductive material of the present invention makes it possible to impart sufficient hardness and chemical resistance to a resultant conductive layer due to the fact that the conductive material is obtained by cross-linking the compounds each represented by the above-mentioned general formula (Al) via the epoxy-based cross-linking agent.
Further, it has been found that the conductive layers in the Examples which use a bisphenol epoxy cross-linking agent as their epoxy-based cross-linking agent exhibit superior chemical resistance in particular.
Furthermore, it has also been found that the conductive layers in the Examples which use any of a glycidyl ester-based epoxy cross-linking agent, an alicycliσ epoxy cross-linking agent, an urethane modified epoxy cross-linking agent, and a silicon-containing epoxy cross-linking agent as their epoxy-based cross-linking agent can have sufficient flexibility as compared to the conductive layers of the other Examples.
Moreover, it has also been found that the conductive layers in the Examples which use any of a (meth)acrylic ester-based epoxy cross-linking agent, a polyfunσtional phenol-based epoxy compound, and a glycidyl amine-based epoxy cross-linking agent as their epoxy-based cross-linking agent tend to exhibit more superior hardness.
Moreover, it has also been found that the conductive layer of each of the Example 2OG and the Example 21G which uses the cross-linking agent in which two kinds of epoxy-based cross-linking agents are mixed exhibits synergistic effect obtained from the respective epoxy-based cross-linking agents.
Moreover, it has also been found that it is possible to adjust the chemical resistance of the conductive layers byusing a different epoxy-based cross-linking agent (see Example 9G and Example 10G) as well as the flexibility (see Example 15G and Example 16G), See the following Table 8.
Further, it has also been found that, as shown in Table 8, the conductive layer (that is, a layer formed using the conductive material according to the present invention as its mainmaterial) of each of the Examples exhibits superiorresults in not only the hardness test but also the chemical resistance test as compared to the conductive layer of the Comparative Example H.
This means that the conductive material of the present invention makes it possible to impart sufficient hardness and chemical resistance to a resultant conductive layer due to the fact that the conductive material is obtained by cross-linking the compounds each represented by the above-mentioned general formula (Al) via the epoxy-based cross-linking agent.
Further, it has been found that the conductive layers in the Examples which use a bisphenol epoxy cross-linking agent as their epoxy-based cross-linking agent exhibit superior chemical resistance in particular.
Furthermore, it has also been found that the conductive layers in the Examples which use any of a glycidyl ester-based epoxy cross-linking agent, an alicyclic epoxy cross-linking agent, an urethane modified epoxy cross-linking agent, and a silicon-containing epoxy cross-linking agent as their epoxy-based cross-linking agent can have sufficient flexibility as compared to the conductive layers of the other Examples.
Moreover, it has also been found that the conductive layers in the Examples which use any of a (meth)acrylic ester-based epoxy cross-linking agent, a polyfunctional phenol-based epoxy compound, and a glycidyl amine-based epoxy cross-linking agent as their epoxy-based cross-linking agent tend to exhibit more superior hardness.
Moreover, it has also been found that the conductive layer of each of the Example 16H and the Example 17H which uses the cross-linking agent in which two kinds of epoxy-based cross-linking agents are mixed exhibits synergistic effect obtained from the respective epoxy-based cross-linking agents.
Moreover, it has also been found that it is possible to adjust the chemical resistance of the conductive layers byusing a different epoxy-based cross-linking agent (see Example 5H and Example 6H) as well as the flexibility (see Example HH and Example 12H) .
Industrial Applicability
According to the present invention, the polymer contained in the conductive material has a structure in which adjacent main skeletons of compounds are repeatedly linked through a chemical structure which is produced by the direct polymerization reaction between any one or more of the respective substituents X1, X2, X3 and X4 of the compounds or a chemical structure which is produced by the polymerization reaction between the respective substituents X of the compounds via an epoxy-based cross-linking agent, that is, a structure in which adjacent main skeletons repeatedly exist at a suitable interval. Therefore, it is possible to decrease the interaction between the adjacent main skeletons in the polymer. Further, by forming the constituent material of the conductive layer from such a polymer, when an upper layer is formed on the conductive layer using a liquid material, it is possible to properly suppress or prevent the polymer from being swelled or dissolved by the solvent or dispersion medium contained in the liquid material. As a result, it is possible to prevent mutual dissolution from occurring between the conductive layer and the upper layer to be formed. For these reasons, the polymer can exhibit a high carrier transport ability, and thus a conductive material constituted from the polymer as its main material can also have a high carrier transport ability. Consequently, both an electronic device provided with such a conductive layer and electronic equipment provided such an electronic device can have high reliability. Therefore, the present invention has industrial adaptability required by PCT.
Table 1
Figure imgf000181_0001
Table 2
Figure imgf000182_0001
No epoxy-based cross -linking agent was added . Table 3
CD
Figure imgf000183_0001
Figure imgf000184_0001
Table 4(B)
Figure imgf000185_0001
Table 4(C)
Figure imgf000186_0001
-: No epoxy-based cross-linking agent was added.
Table 5
Figure imgf000187_0001
Table 6
Figure imgf000188_0001
No epoxy-based cross-linking agent was added. Table 7
Figure imgf000189_0001
-: No epoxy-based cross-linking agent was added. Table 8
Figure imgf000190_0001
- : No epoxy-based cross-linking agent was added.

Claims

CLAIMSWHAT IS CLAIMED IS:
1. A composition for conductive materials, comprising a compound represented by the following general formula (Al):
Figure imgf000191_0001
wherein eight Rs may be the same or different and each independently represents a hydrogen atom, a methyl group or an ethyl group, Y represents a group containing at least one substituted or unsubstituted aromatic hydrocarbon ring or substituted or unsubstituted heterocycle, and X1, X2, X3 and X4 may be the same or different and each independently represents a substituent represented by the following general formula (A2):
(A2) H2C-,CH-CH2-O-^CH2 -^Ϊ 0 wherein n1 is an integer of 2 to 8.
2. The composition for conductive materials as claimed in claim 1, wherein the group Y contains at least one substituted or unsubstituted aromatic hydrocarbon ring.
3. The composition for conductive materials as claimed in claim 2, wherein the substituent X1 and the substituent X3 are identical with each other.
4. The composition for conductive materials as claimed in claim 2, wherein the substituent X2 and the substituent X4 are identical with each other.
5. The composition for conductive materials as claimed in claim 2, wherein the substituent X1, the substituent X2, the substituent X3 and the substituent X4 are identical with each other.
6. The composition for conductive materials as claimed in claim 2, wherein each of the substituent X1, the substituent X2, the substituent X3 and the substituent X4 is bonded to the 3-, 4- or 5-position of the benzene ring.
7. The composition for conductive materials as claimed in claim 2, wherein the group Y consists of carbon atoms and hydrogen atoms.
8. The composition for conductive materials as claimed in claim 2, wherein the group Y contains 6 to 30 carbon atoms in total.
9. The composition for conductive materials as claimed in claim 2, wherein the group Y contains 1 to 5 aromatic hydrocarbon rings.
10. The composition for conductive materials as claimed in claim 2, wherein the group Y is a biphenylene group or a derivative thereof.
11. The composition for conductive materials as claimed in claim 2, further comprising an epoxy-based cross-linking agent.
12. The composition for conductive materials as claimed in claim 11, wherein the epoxy-based cross-linking agent contains a (meth)acrylic ester-based epoxy cross-linking agent.
13. The composition for conductive materials as claimed in claim 11, wherein the epoxy based cross-linking agent contains a bisphenol epoxy cross-linking agent.
14. The composition for conductive materials as claimed in claim 11, wherein the epoxy-based cross-linking agent contains at least one cross-linking agent selected from the group comprising a glycidyl ester-based epoxy cross-linking agent, an alicycliσ epoxy cross-linking agent, an urethane modified epoxy cross-linking agent and a silicon-containing epoxy cross-linking agent.
15. The composition for conductive materials as claimed in claim 11, wherein the epoxy-based cross-linking agent contains at least one of a polyfunctional phenol-based epoxy cross-linking agent and a glycidyl amine-based epoxy cross-linking agent.
16. The composition for conductive materials as claimed in claim 11, wherein the substituent X1 and the substituent X3 are identical with each other.
17. The composition for conductive materials as claimed in claim 11, wherein the substituent X2 and the substituent X4 are identical with each other.
18. The composition for conductive materials as claimed in claim 11, wherein the substituent X1, the substituent X2, the substituent X3 and the substituent X4 are identical with each other.
19. The composition for conductive materials as claimed in claim 11, wherein each of the substituent X1, the substituent X2, the substituent X3 and the substituent X4 is bonded to the 3-, 4- or 5-position of the benzene ring.
20. The composition for conductive materials as claimed in claim 11, wherein the group Y consists of carbon atoms and hydrogen atoms.
21. The composition for conductive materials as claimed in claim 11, wherein the group Y contains 6 to 30 carbon atoms in total.
22. The composition for conductive materials as claimed in claim 11, wherein the group Y contains 1 to 5 aromatic hydrocarbon rings.
23. The composition for conductive materials as claimed in claim 11, wherein the group Y is a biphenylene group or a derivative thereof.
24. The composition for conductive materials as claimed in claim 1, wherein the group Y contains at least one substituted or unsubstituted heterocycle.
25. The composition for conductive materials as claimed in claim 24, wherein the substituent X1 and the substituent X3 are identical with each other.
26. The composition for conductive materials as claimed in claim 24, wherein the substituent X2 and the substituent X4 are identical with each other.
27. The composition for conductive materials as claimed in claim 24, wherein the substituent X1, the substituent X2, the substituent X3 and the substituent X4 are identical with each other.
28. The composition for conductive materials as claimed in claim 24, wherein each of the substituent X1, the substituent X2, the substituent X3 and the substituent X4 is bonded to the 3-, 4- or 5-position of the benzene ring.
29. The composition for conductive materials as claimed in claim 24, wherein the heterocycle contains at least one heteroatom selected from the group comprisingnitrogen, oxygen, sulfur, selenium and tellurium.
30. The composition for conductive materials as claimed in claim 24, wherein the heterocycle is an aromatic heterocycle.
31. The composition for conductive materials as claimed in claim 24, wherein the group Y contains 1 to 5 heterocycles.
32. The composition for conductive materials as claimed in claim 24, wherein the group Y contains at least one substituted or unsubstituted aromatic hydrocarbon ring in addition to the heterocycle.
33. The composition for conductive materials as claimed in claim 32, wherein the group Y contains two aromatic hydrocarbon rings respectively bonded to each N in the general formula (Al) directly and at least one heterocycle existing between these aromatic hydrocarbon rings.
34. The composition for conductive materials as claimed in claim 24, wherein the group Y contains 2 to 75 carbon atoms in total.
35. The composition for conductive materials as claimed in claim 24, further comprising an epoxy-based cross-linking agent.
36. The composition for conductive materials as claimed in claim 35, wherein the epoxy-based cross-linking agent contains a (meth)acrylic ester-based epoxy cross-linking agent.
37. The composition for conductive materials as claimed in claim 35, wherein the epoxy-based cross-linking agent contains a bisphenol epoxy cross-linking agent.
38. The composition for conductive materials as claimed in claim 35, wherein the epoxy-based cross-linking agent contains at least one cross-linking agent selected from the group comprising a glycidyl ester-based epoxy cross-linking agent, an alicyclic epoxy cross-linking agent, an urethane modified epoxy cross-linking agent and a silicon-containing epoxy cross-linking agent.
39. The composition for conductive materials as claimed in claim 35, wherein the epoxy-based cross-linking agent contains at least one of a polyfunctional phenol-based epoxy cross-linking agent and a glycidyl amine-based epoxy cross-linking agent.
40. The composition for conductive materials as claimed in claim 35, wherein the two substituents X1 are identical with each other.
41. The composition for conductive materials as claimed in claim 35, wherein the substituent X2 and the substituent X4 are identical with each other.
42. The composition for conductive materials as claimed in claim 35, wherein the substituent X1, the substituent X2, the substituent X3 and the substituent X4 are identical with each other.
43. The composition for conductive materials as claimed in claim 35, wherein each substituent X1 is bonded to the 3-, 4- or 5-position of the benzene ring.
44. The composition for conductive materials as claimed in claim 35, wherein the heteroσycle contains at least one heteroatom selected fromthe group comprising nitrogen, oxygen, sulfur, selenium and tellurium.
45. The composition for conductive materials as claimed in claim 35, wherein the heterocycle is an aromatic heterocycle.
46. The composition for conductive materials as claimed in claim 35, wherein the group Y contains 1 to 5 heterocycles.
47. The composition for conductive materials as claimed in claim 35, wherein the group Y contains at least one substituted or unsubstituted aromatic hydrocarbon ring in addition to the heterocycle.
48. The composition for conductive materials as claimed in claim 47, wherein the group Y contains two aromatic hydrocarbon rings respectively bonded to each N in the general formula (Al) directly and at least one heterocycle existing between these aromatic hydrocarbon rings .
49. The composition for conductive materials as claimed in claim 35, wherein the group Y contains 2 to 75 carbon atoms in total.
50. A conductive material obtained by direct polymerization reaction or polymerization reaction via an epoxy-based cross-linking agent of substituents X1, substituents X2, substituents X3 and substituents X4 of compounds each represented by the following general formula (Al), each compound being contained in the composition for conductive materials defined in claim 1:
Figure imgf000199_0001
wherein eight Rs may be the same or different and each independently represents a hydrogen atom, a methyl group or an ethyl group, Y represents a group containing at least one substituted or unsubstituted aromatic hydrocarbon ring or substituted or unsubstituted heterocycle, and X1, X2, X3 and X4 may be the same or different and each independently represents a substituent represented by the following general formula (A2):
H2C-CH-CH2-O-[CH2 -^i
(A2) O
wherein n1 is an integer of 2 to 8.
51. The conductive material as claimed in claim 50, wherein the compounds are polymerized by light irradiation.
52. The conductive material as claimed in claim 50, wherein the compounds and the epoxy-based cross-linking agent are polymerized by light irradiation.
53. A conductive layer mainly comprising the conductive material defined in claim 50.
54. The conductive layer as claimed in claim 53, wherein the conductive layer is a hole transport layer.
55. The conductive layer as claimed in claim 54, wherein the average thickness of the hole transport layer is in the range of 10 to 150 nm.
56. The conductive layer as claimed in claim 53, wherein the conductive layer is an electron transport layer.
57. The conductive layer as claimed in claim 56, wherein the average thickness of the electron transport layer is in the range of 1 to 100 nm.
58. The conductive layer as claimed in claim 53, wherein the conductive layer is an organic semiconductor layer.
59. The conductive layer as claimed in claim 58, wherein the average thickness of the organic semiconductor layer is in the range of 0.1 to 1,000 nm.
60. An electronic device comprising a laminated body which includes the conductive layer defined in claim 53.
61. The electronic device as claimed in claim 60, which is a light emitting device or a photoelectric transducer.
62. The electronic device as claimed in claim 61, wherein the light emitting device is an organic electroluminescent device.
63. The electronic device as claimed in claim 60, wherein the electronic device is a switching element.
64. The electronic device as claimed in claim 63, wherein the switching element is an organic thin film transistor.
65. Electronic equipment comprising the electronic device as claimed in claim 60.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0637899A1 (en) * 1993-08-02 1995-02-08 BASF Aktiengesellschaft Electroluminescent arrangement
US6391471B1 (en) * 1999-03-29 2002-05-21 Kabushiki Kaisha Toshiba Functional device and multi-component multi-phase type polymeric shaped material
WO2004028216A1 (en) * 2002-09-17 2004-04-01 International Business Machines Corporation Organic electroluminescent display and method for manufacturing organic electroluminescent display

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0637899A1 (en) * 1993-08-02 1995-02-08 BASF Aktiengesellschaft Electroluminescent arrangement
US6391471B1 (en) * 1999-03-29 2002-05-21 Kabushiki Kaisha Toshiba Functional device and multi-component multi-phase type polymeric shaped material
WO2004028216A1 (en) * 2002-09-17 2004-04-01 International Business Machines Corporation Organic electroluminescent display and method for manufacturing organic electroluminescent display

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