Information
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Patent Application
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20040081854
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Publication Number
20040081854
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Date Filed
March 18, 200321 years ago
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Date Published
April 29, 200420 years ago
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Inventors
-
Original Assignees
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CPC
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US Classifications
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International Classifications
Abstract
An organic electroluminescent element having at least one pair of electrodes including an anode and a cathode, at least one of which having light transmissive, and at least one organic compound layer disposed between the electrodes, wherein the at least one organic compound layer contains at least one kind of non-conjugated polymer having terminal groups, and at least one of terminal groups of the non-conjugated polymer contains a fluorescent substance emitting fluorescence in a solid state.
Description
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to an element which emits light by converting electric energy into light, and more particularly to an organic electroluminescent element which can be suitably used in the fields of display elements, back lights of liquid crystals, illumination light sources, exposing apparatus for electrophotography, labels, sign boards and the like.
[0003] 2. Description of the Related Art
[0004] Since an electroluminescent element is a spontaneously emitting wholly solid element, has high visibility, and withstands impacts, wide application thereof is expected. Currently, an electroluminescent element using an inorganic fluorescent substance is popular and is used widely. Since such an electroluminescent element requires alternating current voltage in a range of 200 V or greater and 50 to 1000 Hz for driving, it has a problem in that a running cost thereof is high and luminance is insufficient. On the other hand, study of an electroluminescent element using an organic compound first started using a single crystal of anthracene or the like, but a film thickness of the element is as great as 1 mm, and the element requires a driving voltage of 100 V or greater. For that reason, as reported in Thin Solid Films, 94, 171(1982), thinning by a deposition method has been tried.
[0005] Light emission by these electroluminescent elements is a phenomenon in which electrons are injected from one electrode and holes are injected from another electrode, whereby, a light emitting material in an electroluminescent element is excited to a high energy level, and an excited light emitting substance releases, as light, extra energy produced when returned to a ground state. However, in these electroluminescent elements, a driving voltage is still as high as 30 V, densities of electron carriers and hole carriers present in a film are low, and a probability of production of photons by recombination of carriers is low. Therefore, sufficient luminance cannot be obtained, and these electroluminescent elements have not been put to practical use.
[0006] However, in 1997, Tang et al. reported in Appl. Phys. Lett., 51, 913(1987) and Japanese Patent Application Laid-Open (JP-A) No. 59-194393 that a high luminance of 1000 cd/m2 or larger can be obtained under a low driving voltage of around 10 V by an organic electroluminescent element. This organic electroluminescent element is a function separated-type organic electroluminescent element in which a hole transporting organic low-molecular compound, and a fluorescent organic low-molecular compound having electron transporting ability are successively deposited in order, as an extremely thin film, on a transparent substrate by a vacuum deposition method. Since this study by Tang et al., organic luminescence elements have been actively studied and developed.
[0007] These multilayer electroluminescent elements have a structure in which an organic light emitting substance and a charge transporting organic compound (charge transporting material) are deposited on an electrode, and the light emission by these elements is caused by recombination of holes and electrons, which are generated in both materials and move in the charge transporting material.
[0008] In this case, as the organic light emitting substance, organic dyes emitting fluorescene such as a 8-quinlinol aluminium complex and a coumarin compound are used. In addition, examples of the charge transporting material include diamino compounds such as N,N-di(m-tolyl) N,N′-diphenylbenzidine and 1,1-bis[N,N-di(p-tolyl)aminophenyl]cyclohexane, a 4-(N,N-diphenyl)aminobenzaldehyde-N,N-diphenylhydrazone compound and the like.
[0009] Organic electroluminescent elements using these organic compounds have high light emitting properties, but they have problems with respect to heat stability upon light emission and the storage stability. A thickness of a layer formed of an organic compound in an electroluminescent element is very thin, being as thin as several tens to several hundred of nanometers. Therefore, a voltage applied per unit thickness of a layer composed of this organic compound becomes very high, and the element is driven at a high current density of a few mA/cm2. Therefore, a large amount of Joule heat is generated from this layer. For this reason, a hole transporting low-molecular compound and a fluorescent organic low-molecular compound which are formed into an amorphous film are gradually crystallized as a temperature thereof is elevated and, finally, those compounds are melted, thereby causing a reduction in luminance and dielectric breakdown in many cases. Therefore, there is a problem in that a lifetime of the organic electroluminescent element is reduced. It is considered that the low heat stability of this organic electroluminescent element is derived from a low glass transition temperature of a material used in an organic electroluminescent element. That is, low-molecular compounds used as such a material have a low melting point and have high symmetry.
[0010] Thus, in order to solve the problem regarding heat stability, an organic electroluminescent element using N,N-di(1-naphthyl)N,N′-diphenylbenzidine with an α-naphthyl group introduced therein, as a material which has an improved glass transition temperature and can obtain a stable amorphous state, has been reported in Technical Study Report of the Electronic Information Communication Society, OME95-54(1995) and, for the same purpose, an organic electroluminescent element using a star burst amine has been reported in Proceedings of the 40th Applied Physics Related Associated Seminar 30a-SZK-14(1993). However, when these materials are used alone, since there is an energy barrier derived from ionization potential of a hole transporting material, hole injectability from an anode or hole injectability into a light emitting layer can not be satisfied. Further, in a 2-layered type element in which a hole transporting layer and a light emitting layer are deposited, a mutual diffusion phenomenon is caused. In addition, it is required that a material used in an organic electroluminescent element has heat stability with respect to heat treatment during a step of preparing an organic electroluminescent element, such as deposition, baking, annealing, wiring, sealing and the like, and with respect to change over time due to long term use of the organic electroluminescent element. For this reason, it is desired that a glass transition temperature of a material used in an organic electroluminescent element is even higher.
[0011] On the other hand, an electroluminescent element using a high-molecular material in place of a low-molecular compound has also been studied and developed. For example, in Nature, 357,577(1992) and JP-A No. 10-92576, there has been proposed an element using an electrically conductive polymer such as poly(p-phenylenevinylene) or the like. In addition, in Proceedings of the 42nd Polymer Discussion Meeting 20J21(1993), there has been proposed an element using a polymer in which triphenylamine is introduced on a side chain of polyphosphazene. Further, in Proceedings of the 38th Applied Physics Related Associated Seminar 31p-GI-2(1991), there has been proposed an element using a material in which an electron transporting material and a fluorescent dye are mixed into hole transporting polyvinylcarbazole.
[0012] These high-molecular materials have a comparatively higher glass transition points than that of a low-molecular compound. However, since poly(p-phenylenevinylene) is subjected to heat treatment after spin coating with a soluble precursor, defects are easily generated in a conjugated polymer on a main chain and light emitting properties are remarkably reduced. In addition, phosphazene has a high ionization potential, and thus, charge injecting properties are reduced. Further, polyvinylcarbazole has a high glass transition point, but has a problem due to traps. In addition, when a low-molecular compound is mixed into polyvinylcarbazole, the low-molecular compound acts as a plasticizer. For this reason, an organic electroluminescent element using these high-molecular materials has not yet caught up with the multilayer-type electroluminescent element using an organic low-molecular compound, in luminance, light emitting efficiency and the like.
[0013] In addition, a method of preparing an organic electroluminescent element is desirably a coating method in view of simplification of preparation, processibility, enlargement, cost and the like and, additionally, Proceedings of the 50th Applied Physics Society Seminar, 29p-ZP-5(1989) and Proceeding of the 51th Applied Physics Society Seminar, 28a-PB-7(1990) report that an organic electroluminescent element can also be prepared by a casting method. However, since a charge transporting material has deteriorated solubility in or compatibility with a solvent or a resin, the charge transporting material is easily crystallized and, thus, the above preparation methods lead to defects in preparation and properties of an organic electroluminescent element.
SUMMARY OF THE INVENTION
[0014] An object of the present invention is to solve the various problems of the prior art as described above.
[0015] That is, an object of the invention is to provide an organic electroluminescent element which has high light emitting intensity, has high light emitting efficiency, has a long element life and is easily prepared, using a non-conjugated polymer having a light emitting function which is excellent in the heat stability during light emission, storage stability, and solubility in and compatibility with a solvent and a resin.
[0016] In order to attain the above object, the present inventors intensively studied a non-conjugated polymer having light emitting properties. As a result, the present inventors have found that a non-conjugated polymer having a fluorescent substance emitting fluorescence in a solid state on at least one terminal group has charge injecting properties, charge mobility, thin film forming ability and light emitting properties which are suitable for the organic electroluminescent element, which resulted in completion of the invention.
[0017] That is, a first aspect of the invention provides an electroluminescent element comprising at least one pair of electrodes comprising an anode and a cathode, at least one of which having light transmissive, and at least one organic compound layer disposed between the electrodes, wherein the at least one organic compound layer contains at least one kind of non-conjugated polymer having terminal groups, and at least one terminal group of the non-conjugated polymer contains a fluorescent substance emitting fluorescence in a solid state.
[0018] A second aspect of the invention provides an organic electroluminescent element according to the first aspect, wherein the non-conjugated polymer may be selected from the group consisting of polyester, polyether and polyurethane.
[0019] A third aspect of the invention provides an organic electroluminescent element according to the first aspect, wherein the non-conjugated polymer may be hole transporting polymer.
[0020] A fourth aspect of the invention provides an organic electroluminescent element according to the first aspect, wherein the non-conjugated polymer may comprises a repetition unit containing at least one partial structure selected from the group consisting of the following general formulas (I-1) and (I-2),
1
[0021] wherein, in the general formulas (I-1) and (I-2), Ar represents a group selected from the group consisting of a substituted or unsubstituted monovalent benzene ring, a substituted or unsubstituted monovalent polynuclear aromatic hydrocarbon having an aromatic ring number of 2 to 10, a substituted or unsubstituted monovalent condensed aromatic hydrocarbon having an aromatic ring number of 2 to 10, and a substituted or unsubstituted monovalent aromatic heterocyclic ring; X represents a group selected from the group consisting of a substituted or unsubstituted divalent benzene ring, a substituted or unsubstituted divalent polynuclear aromatic hydrocarbon having an aromatic ring number of 2 to 10, a substituted or unsubstituted divalent condensed aromatic hydrocarbon having an aromatic ring number of 2 to 10, and a substituted or unsubstituted divalent aromatic heterocyclic ring; T represents a group selected from the group consisting of a divalent straight hydrocarbon group having a carbon number of 1 to 6 and a divalent branched hydrocarbon group having a carbon number of 2 to 10; and k, i and j each independently represent an integer selected from 0 to 1.
[0022] A fifth aspect of the invention provides an organic electroluminescent element according to the first aspect, wherein the at least one organic compound layer may comprise 2 or more layers including at least a light emitting layer, and the light emitting layer may contain at least one kind of the non-conjugated polymer.
[0023] A sixth aspect of the invention provides an organic electroluminescent element according to the fifth aspect, wherein the at least one organic compound layer may have a construction selected from the group consisting of a construction comprising the light emitting layer and an electron transporting layer, a construction comprising the light emitting layer and an electron injecting layer, and a construction comprising the light emitting layer, an electron transporting layer and an electron injecting layer.
[0024] A seventh aspect of the invention provides an organic electroluminescent element according to the fifth aspect, wherein the at least one organic compound layer may have a construction selected from the group consisting of a construction comprising the light emitting layer and a hole transporting layer, a construction comprising the light emitting layer and a hole injecting layer, and a construction comprising the light emitting layer, a hole transporting layer and a hole injecting layer.
[0025] An eighth aspect of the invention provides an organic electroluminescent element according to the fifth aspect, wherein the at least one organic compound layer may have a construction selected from the group consisting of a construction comprising the light emitting layer, a hole transporting layer and an electron transporting layer, a construction comprising the light emitting layer, a hole transporting layer and an electron injecting layer, a construction comprising the light emitting layer, a hole transporting layer and an electron injecting layer, a construction comprising the light emitting layer, a hole injecting layer and an electron transporting layer, a construction comprising the light emitting layer, a hole injecting layer and an electron injecting layer, a construction comprising the light emitting layer, a hole injecting layer, an electron transporting layer and an electron injecting layer, a construction comprising the light emitting layer, a hole transporting layer, a hole injecting layer and an electron transporting layer, a construction comprising the light emitting layer, a hole transporting layer, a hole injecting layer and an electron injecting layer, and a construction comprising the light emitting layer, a hole transporting layer, a hole injecting layer, an electron transporting layer and an electron injecting layer.
[0026] A ninth aspect of the invention provides an organic electroluminescent element according to the first aspect, wherein the at least one organic compound layer may be composed only of a light emitting layer having a charge transporting function, and the light emitting layer having the charge transporting function may contain one or more kinds of non-conjugated polymers.
[0027] A tenth aspect of the invention provides an organic selectroluminescent element according to the fourth aspect, wherein the non-conjugated polymer may be a polyester selected from the group consisting of the following general formulas (II-1) and (II-2),
2
[0028] wherein, in the general formulas (II-1) and (II-2), Al represents at least one structure selected from the group consisting of general formulas (I-1) and (I-2), Y1 represents a divalent alcohol residue, Z1 represents a divalent carboxylic acid residue, m represents an integer from 1 to 5, and p represents an integer selected from the range of 5 to 5,000.
[0029] An eleventh aspect of the invention provides an organic electroluminescent element according to the fourth aspect, wherein the non-conjugated polymer may be a polyether represented by the following general formula (III-1),
3
[0030] wherein, in the general formula (III-1), A1 represents at least one structure selected from the group consisting of general formulas (I-1) and (I-2), and p represents an integer from 5 to 5,000.
[0031] A twelfth aspect of the invention provides an organic electroluminescent element according to the fourth aspect, wherein the non-conjugated polymer may be a polyurethane selected from the group consisting of the general formulas (IV-1) and (IV-2),
4
[0032] wherein, in the general formulas (IV-1) and (IV-2), A1 represents at least one structure selected from the group consisting of general formulas (I-1) and (I-2), T represents a group selected from the group consisting of a divalent straight hydrocarbon group having a carbon number of 1 to 6, and a divalent branched hydrocarbon group having a carbon number of 2 to 10; Y2 and Z2 each independently represents a group selected from the group consisting of divalent diisocyanate, alcohol and amine residue; m represents an integer from 1 to 5; and p represents an integer from 5 to 5,000.
[0033] A thirteenth aspect of the invention provides an organic electroluminescent element according to the first aspect, wherein the fluorescent substance may be an organic fluorescent substance.
[0034] A fourteenth aspect of the invention provides an organic electroluminescent element according to the thirteenth aspect, wherein the organic fluorescent substance may be selected from the group consisting of a compound including an aromatic hydrocarbon having an aromatic ring number of 2 or more, and a chelating metal complex.
[0035] A fifteenth aspect of the invention provides an organic electroluminescent element according to the fourteenth aspect, wherein the compound including an aromatic hydrocarbon having an aromatic ring number of 2 or more may be an organic fluorescent substance selected from the group consisting of a polyacene derivative compound, a styrylamine compound, a quinacridone derivative compound, a rubulen derivative compound, a coumarin derivative compound, and a pyran derivative compound.
[0036] A sixteenth aspect of the invention provides an organic electroluminescent element according to the fifteenth aspect, wherein the polyacene derivative compound may be selected from the group consisting of a naphthalene derivative, an anthracene derivative, a tetracene derivative, a perylene derivative, and a pyrne derivative.
[0037] A seventeenth aspect of the invention provides an organic electroluminescent element according to the fourteenth aspect, wherein the chelating metal complex may contain a metal selected from the group consisting of Al, Zn, Be, Mg, Eu, Ga, Pt and Ir.
[0038] An eighteenth aspect of the invention provides an organic electroluminescent element according to the first aspect, wherein a maximum peak wavelength of a fluorescent spectrum of the fluorescent substance may be in the a visible light region.
[0039] A nineteenth aspect of the invention provides an organic electroluminescent element according to the first aspect, wherein both terminal groups of the non-conjugated polymer may contain a fluorescent substance emitting fluorescence in a solid state.
[0040] A twentieth aspect of the invention provides an organic electroluminescent element according to the first aspect, wherein emission colors of fluorescent substances emitting fluorescence in a solid state and respectively contained in the terminal groups may be different from each other.
BRIEF DESCRIPTION OF THE DRAWINGS
[0041]
FIG. 1 is a schematic view showing one example of a layer construction of the organic electroluminescent element of the present invention.
[0042]
FIG. 2 is a schematic view showing another example of a layer construction of the organic electroluminescent element of the invention.
[0043]
FIG. 3 is a schematic view showing another example of a layer construction of the organic electroluminescent element of the invention.
[0044]
FIG. 4 is a schematic view showing another example of a layer construction of the organic electroluminescent element of the invention.
DETAILED DESCRIPTION OF THE INVENTION
[0045] The organic electroluminescent element of the present invention is an electroluminescent element, which comprises at least one pair of electrodes comprising an anode and a cathode, at least one of which having light transmissive, and at least one organic compound layer disposed between the electrodes, wherein the at least one organic compound layer contains at least one kind of non-conjugated polymer having terminal groups, and at least one of terminal groups of the non-conjugated polymer contains a fluorescent substance emitting fluorescence in a solid state.
[0046] In the invention, the “non-conjugated polymer” is a polymer having a repetition structure containing at least one σ bond on a main chain of the polymer, and is not particularly limited as long as at least one of terminal ends of the main chain has a fluorescent substance emitting fluorescence in a solid state (hereinafter, referred to as “fluorescent substance”).
[0047] In a non-conjugated molecule such as a molecule in which a plurality of light emitting compounds such as a fluorescent substance and the like continuously link together, an emitting intensity of the light emitting compound contained in the molecule is remarkably reduced as compared with a light emitting compound unlinked with any compound in some cases. In view of this point, it is preferable that the emitting compound is dispersed in a molecule. Since the non-conjugated polymer used in the invention has at least one non-connected fluorescent substance at terminal ends of a chain of the molecule, the aforementioned reduction in light emitting efficiency can be prevented and, as a result, sufficient light emitting intensity can be obtained.
[0048] Alternatively, a fluorescent substance may be added to any position other than terminal ends of a molecular chain of a polymer. However, when a non-conjugated polymer dose not have a fluorescent substance at terminal ends of the molecular chain, functional groups at terminal ends of the molecular chain may has an adverse effect on light emission of a fluorescent substance added to a part other than the terminal ends in some cases. In addition, when a charge moves on a molecular chain, functional groups at the terminal ends may suppress mobility of the charge in some cases.
[0049] However, since the non-conjugated polymer used in the invention has a fluorescent substance in place of at least one of functional groups at terminal ends of a molecular chain, it can sufficiently exert the light emitting properties of a non-connected fluorescent substance. In addition, when a charge moves on a molecular chain, mobility of the charge may be improved. Further, replacement of a functional group at a terminal end with a fluorescent substance is easy in synthesis of a non-conjugated polymer.
[0050] Further, the non-conjugated polymer used in the invention may have a fluorescent substance on both terminal ends. In this case, an emission color of the non-conjugated polymer can be easily adjusted to a desired color by choosing from combinations of fluorescent substances having different emission colors from each other. Such a non-conjugated polymer can be easily synthesized by copolymerization reaction.
[0051] Since the aforementioned non-conjugated polymer can be synthesized by selecting a structure of a part other than a fluorescent substance and adjusting a molecular weight, it is easy to obtain desired properties (e.g. heat stability, solubility in and compatibility with solvent and resin). For this reason, a non-conjugated polymer having excellent heat stability and film forming ability can be easily obtained.
[0052] As explained above, the non-conjugated polymer used in the invention has a high light emitting intensity, has high light emitting efficiency, has excellent charge moving properties, and is excellent in heat stability, and a film of the polymer can be easily made. Therefore, since in the organic electroluminescent element of the invention, the at least one organic compound layer contains the aforementioned non-conjugated polymer, light emitting intensity is high, the light emitting efficiency is high, a life of the element is long, and it is easy to make the element.
[0053] Examples of a fundamental structure of such a non-conjugated polymer include polymers comprising polyester, polyether, polyurethane, polyimide, polyamide, polyetherketone, polycarbonate, polysulfide, polyethersulfide, a silicon-containing polymer, and a germanium-containing polymer, or copolymers thereof. Among these, it is preferable that a fundamental structure of the non-conjugated polymer is any of polyester, polyether and polyurethane, in view of ease of synthesizing, heat stability, solubility in and the compatibility with a solvent and a resin, and the like.
[0054] In addition, the non-conjugated polymer may have a molecular chain on which a charge can move. In this case, it is preferable that the non-conjugated polymer is a hole transporting polymer.
[0055] It is preferable that the non-conjugated polymer as explained above comprises a repetition unit containing at least one partial structure selected from the group consisting of the following general formulas (I-1) and (I-2).
[0056] Since such a non-conjugated polymer is excellent in the heat stability during light emission, and solubility in and compatibility with a solvent and a resin, it is easy to prepare an organic electroluminescent element and, further, as an organic electroluminescent element, reliability of the light emitting property and a element life can be improved.
5
[0057] Wherein, in the general formulas (I-1) and (I-2), Ar represents a group selected from the group consisting of a substituted or unsubstituted monovalent benzene ring, a substituted or unsubstituted monovalent polynuclear aromatic hydrocarbon having an aromatic ring number of 2 to 10, a substituted or unsubstituted monovalent condensed aromatic hydrocarbon having an aromatic ring number of 2 to 10, and a substituted or unsubstituted monovalent aromatic heterocyclic ring; X represents a group selected from the group consisting of a substituted or unsubstituted divalent benzene ring, a substituted or unsubstituted divalent polynuclear aromatic hydrocarbon having an aromatic ring number of 2 to 10, a substituted or unsubstituted divalent condensed aromatic hydrocarbon having an aromatic ring number of 2 to 10, and a substituted or unsubstituted divalent aromatic heterocyclic ring; T represents a group selected from the group consisting of a divalent straight hydrocarbon group having a carbon number of 1 to 6, and a divalent branched hydrocarbon group having a carbon number of 2 to 10; and k, i and j each independently represent an integer selected from 0 to 1.
[0058] In addition, the polynuclear aromatic hydrocarbon and the condensed aromatic hydrocarbon specifically are compounds defined below in the invention.
[0059] That is, the “polynuclear hydrocarbon” represents hydrocarbon containing 2 or more aromatic rings composed of carbon and hydrogen, in which aromatic rings are connected by a carbon-carbon bond. Examples thereof include biphenyl and terphenyl. In addition, the “condensed aromatic hydrocarbon” represents hydrocarbon containing 2 or more aromatic rings composed of carbon and hydrogen, in which aromatic rings share one pair of carbon atoms. Examples thereof include naphthalene, anthracene, phenanthrene and fluorene.
[0060] In addition, as a heterocyclic ring, heterocyclic rings having the number of atoms (Nr) constituting the ring skeleton of 5 and/or 6 are preferably used. In addition, atoms (hetero atom) other than carbon atoms constituting the ring skeleton are not particularly limited, but for example, a sulfur atom, a nitrogen atom, an oxygen atom and the like are preferably used. In addition, the ring skeleton may contain two or more kinds of and/or two or more hetero atoms. In particular, as a heterocyclic ring having a 5-membered ring structure, thiophene, pyrrole and furan, or heterocyclic rings in which 3- and 4-positional carbon atoms are replaced with nitrogen atoms are preferably used. In addition, as a heterocyclic ring having a 6-membered ring structure, pyridine is preferably used.
[0061] Examples of a substituent of the benzene ring, the polynuclear aromatic hydrocarbon or the condensed aromatic hydrocarbon include a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aralkyl group, a substituted amino group, a halogen atom and the like. As the alkyl group, alkyl groups having a carbon number of 1 to 10 are preferable, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group and the like. As the alkoxy group, alkoxy groups having a carbon number of 1 to 10 are preferable, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group and the like. As the aryl group, aryl groups having a carbon number of 6 to 20 are preferable, and examples thereof include a phenyl group, a toluyl group and the like. As the aralkyl group, aralkyl groups having a carbon number of 7 to 20, and examples thereof include a benzyl group, a phenethyl group and the like. Examples of the substituent of the substituted amino group include an alkyl grouop, an aryl group, an aralkyl group and the like, and specific examples are as described above.
[0062] X represents a substituted or unsubstituted divalent benzene ring, a substituted or unsubstituted divalent polynuclear aromatic hydrocarbon having an aromatic ring number of 2 to 10, a substituted or unsubstituted divalent condensed aromatic hydrocarbon having an aromatic ring number of 2 to 10, or a substituted or unsubstituted divalent aromatic heterocyclic ring, and examples thereof include a group selected from the following formulas (1) to (13).
67
[0063] In the formulas (1) to (13), R1 to R14 represent a hydrogen atom, an alkyl group having a carbon number of 1 to 10, an alkoxy group having a carbon number of 1 to 10, a substituted or unsubstituted phenyl group, a substituted or unsubstituted aralkyl group, or a halogen atom, a means 0 or 1, and b means an integer of 0 to 10. In addition, V represents a group selected from the following formulas (14) to (34).
89
[0064] In formulas (14) to (34), R15 represents a hydrogen atom, an alkyl group or a cyano group, R16 to R17 represent a hydrogen atom, an alkyl group having a carbon number of 1 to 10, an alkoxyl group having a carbon number of 1 to 10, a substituted or unsubstituted phenyl group, a substituted or unsubstituted aralkyl group, or a halogen atom, and c means an integer of 0 to 10.
[0065] In addition, T represents a divalent straight hydrocarbon group having a carbon number of 1 to 6, or a divalent branched hydrocarbon group having a carbon number of 2 to 10, and is preferably selected from a divalent straight hydrocarbon group having a carbon number of 2 to 6, and a divalent branched hydrocarbon group having a carbon number of 3 to 7. Specific structures are shown below.
1011
[0066] In addition, specific examples of the structure represented by the general formulas (I-1) are shown in Table 1 to Table 49, and specific examples of the structure represented by the general formula (I-2) are shown in Table 50 to Table 88. In Table 1 to Table 88, the number described in the “Bonding Point.” column shows that carbon in a benzene ring with this number added thereto is a bonding position, in the general formulas (I-1) and (I-2).
1TABLE 1
|
|
Bonding
StructurekXArPointijT
|
|
101213300—
|
201415411—CH2CH2—
|
301617301—CH2CH2—
|
40181940120
|
50212240123
|
602425401—CH2CH2—
|
702627401—CH2CH2—
|
[0067]
2
TABLE 2
|
|
|
Bonding
|
Structure
k
X
Ar
Point
i
j
T
|
|
|
|
8
0
28
29
4
0
1
—CH2—
|
|
9
0
30
31
4
0
1
—CH2CH2—
|
|
10
0
32
33
4
1
0
—
|
|
11
0
34
35
4
0
1
—CH2—
|
|
12
0
36
37
4
0
1
—CH2CH2—
|
|
13
0
38
39
4
0
1
—CH2—
|
|
14
0
40
41
4
0
1
—CH2CH2—
|
|
[0068]
3
TABLE 3
|
|
|
Bonding
|
Structure
k
X
Ar
Point
i
j
T
|
|
|
15
0
42
43
4
0
1
44
|
|
16
0
45
46
4
0
1
—CH2—
|
|
17
0
47
48
4
0
1
—CH2CH2—
|
|
18
0
49
50
4
0
1
—CH2CH2—
|
|
19
0
51
52
4
0
1
—CH2CH2—
|
|
[0069]
4
TABLE 4
|
|
|
Bonding
|
Structure
k
X
Ar
Point
i
j
T
|
|
|
20
0
53
54
4
0
1
—CH2CH2—
|
|
21
0
55
56
3
0
1
—CH2CH2—
|
|
22
0
57
58
4
0
1
—CH2CH2—
|
|
23
0
59
60
4
0
1
61
|
|
24
0
62
63
4
0
1
—CH2CH2—
|
|
25
0
64
65
4
0
1
—CH2CH2—
|
|
26
0
66
67
4
0
1
—CH2—
|
|
[0070]
5
TABLE 5
|
|
|
Bonding
|
Structure
k
X
Ar
Point
i
j
T
|
|
|
27
0
68
69
4
0
0
—
|
|
28
0
70
71
4
1
0
—
|
|
29
0
72
73
4
0
1
—CH2CH2—
|
|
30
0
74
75
4
1
0
—
|
|
31
0
76
77
4
0
0
—
|
|
32
0
78
79
4
0
0
—
|
|
33
0
80
81
4
0
0
—
|
|
[0071]
6
TABLE 6
|
|
|
Bonding
|
Structure
k
X
Ar
Point
i
j
T
|
|
|
34
0
82
83
4
0
0
—
|
|
35
0
84
85
4
0
0
—
|
|
36
0
86
87
3
1
1
—CH2CH2—
|
|
37
0
88
89
4
1
1
—CH2—
|
|
38
0
90
91
4
1
1
—CH2CH2—
|
|
39
0
92
93
4
1
1
—CH2—
|
|
40
0
94
95
4
1
1
—CH2—
|
|
[0072]
7
TABLE 7
|
|
|
Bonding
|
Structure
k
X
Ar
Point
i
j
T
|
|
|
41
1
96
97
4
0
1
—CH2CH2—
|
|
42
1
98
99
4
0
1
—CH2CH2—
|
|
43
1
100
101
4
0
1
—CH2CH2—
|
|
44
1
102
103
4
0
1
—CH2CH2—
|
|
45
1
104
105
4
0
1
—CH2CH2—
|
|
46
1
106
107
4
0
1
—CH2CH2—
|
|
[0073]
8
TABLE 8
|
|
|
Bonding
|
Structure
k
X
Ar
Point
i
j
T
|
|
|
47
1
108
109
4
0
1
—CH2—
|
|
48
1
110
111
4
0
1
112
|
|
49
1
113
114
4
0
1
115
|
|
50
1
116
117
4
0
1
—CH2CH2—
|
|
51
1
118
119
4
0
1
—CH2CH2—
|
|
52
1
120
121
4
0
1
—CH2CH2—
|
|
[0074]
9
TABLE 9
|
|
|
Bonding
|
Structure
k
X
Ar
Point
i
j
T
|
|
|
53
1
122
123
4
0
1
—CH2CH2—
|
|
54
1
124
125
2
0
1
—CH2CH2—
|
|
55
1
126
127
3
0
1
—CH2CH2—
|
|
56
1
128
129
4
0
1
—CH2—
|
|
57
1
130
131
4
0
1
—CH2CH2—
|
|
58
1
132
133
4
0
1
—(CH2)4—
|
|
[0075]
10
TABLE 10
|
|
|
Bond-
|
Struc-
ing
|
ture
k
X
Ar
Point
i
j
T
|
|
|
59
1
134
135
4
0
1
136
|
|
60
1
137
138
4
0
1
—CH2CH2—
|
|
61
1
139
140
4
0
1
—CH2CH2—
|
|
62
1
141
142
3
0
1
—CH2CH2—
|
|
63
1
143
144
4
0
1
—CH2CH2—
|
|
64
1
145
146
4
0
1
147
|
|
65
1
148
149
3
0
1
—CH2CH2—
|
|
[0076]
11
TABLE 11
|
|
|
Bonding
|
Structure
k
X
Ar
Point
i
j
T
|
|
|
|
66
1
150
151
4
0
1
—CH2CH2—
|
|
67
1
152
153
4
0
1
—(CH2)3—
|
|
68
1
154
155
4
0
1
—CH2CH2—
|
|
69
1
156
157
4
0
1
158
|
|
70
1
159
160
4
0
1
—CH2CH2—
|
|
71
1
161
162
4
0
1
—CH2CH2—
|
|
72
1
163
164
4
0
1
—CH2CH2—
|
|
[0077]
12
TABLE 12
|
|
|
Bond-
|
ing
|
Structure
k
X
Ar
Point
i
j
T
|
|
|
73
1
165
166
3
0
1
—CH2—
|
|
74
1
167
168
3
0
1
—CH2CH2—
|
|
75
1
169
170
4
0
0
—
|
|
76
1
171
172
4
0
0
—
|
|
77
1
173
174
4
0
0
—
|
|
78
1
175
176
4
0
0
—
|
|
[0078]
13
TABLE 13
|
|
|
Bonding
|
Structure
k
X
Ar
Point
i
j
T
|
|
|
|
79
1
177
178
4
0
1
—
|
|
80
1
179
180
4
0
1
—CH2—
|
|
81
1
181
182
4
0
1
—CH2—
|
|
82
1
183
184
4
0
1
—CH2—
|
|
83
1
185
186
4
0
1
—CH2—
|
|
84
1
187
188
4
0
1
—CH2—
|
|
85
1
189
190
4
0
1
—CH2CH2—
|
|
[0079]
14
TABLE 14
|
|
|
Bonding
|
Structure
k
X
Ar
Point
i
j
T
|
|
|
|
86
1
191
192
4
0
1
—CH2CH2—
|
|
87
1
193
194
4
0
1
—CH2CH2—
|
|
88
1
195
196
4
0
1
—CH2CH2—
|
|
89
1
197
198
4
0
1
—CH2CH2—
|
|
90
1
199
200
4
0
1
—CH2CH2—
|
|
91
1
201
202
4
0
1
—CH2CH2—
|
|
[0080]
15
TABLE 15
|
|
|
Bonding
|
Structure
k
X
Ar
Point
i
j
T
|
|
|
|
92
1
203
204
4
0
1
—CH2CH2—
|
|
93
1
205
206
4
0
1
—CH2CH2—
|
|
94
1
207
208
4
0
1
—CH2CH2—
|
|
95
1
209
210
4
0
1
—CH2CH2—
|
|
96
1
211
212
4
0
1
—(CH2)4—
|
|
97
1
213
214
4
0
1
215
|
|
[0081]
16
TABLE 16
|
|
|
Bonding
|
Structure
k
X
Ar
Point
i
j
T
|
|
|
|
98
1
216
217
4
0
1
—CH2CH2—
|
|
99
1
218
219
4
0
1
—CH2CH2—
|
|
100
1
220
221
4
0
1
−CH2
|
|
101
1
222
223
4
0
1
—CH2CH2—
|
|
102
1
224
225
4
0
1
—CH2CH2—
|
|
103
1
226
227
4
0
1
—CH2CH2—
|
|
104
1
228
229
4
0
1
—CH2CH2—
|
|
[0082]
17
TABLE 17
|
|
|
Bonding
|
Structure
k
X
Ar
Point
i
j
T
|
|
|
|
105
1
230
231
4
0
1
—CH2CH2—
|
|
106
1
232
233
4
0
1
234
|
|
107
1
235
236
4
0
1
—CH2CH2—
|
|
108
1
237
238
4
0
1
—CH2—
|
|
109
1
239
240
4
0
1
—CH2CH2—
|
|
110
1
241
242
4
0
0
—
|
|
111
1
243
244
4
0
0
—
|
|
[0083]
18
TABLE 18
|
|
|
Bonding
|
Structure
k
X
Ar
Point
i
j
T
|
|
|
|
112
1
245
246
4
0
0
—
|
|
113
1
247
248
4
0
0
—
|
|
114
1
249
250
4
0
0
—
|
|
115
1
251
252
4
0
1
—CH2—
|
|
116
1
253
254
4
0
1
—CH2—
|
|
117
1
255
256
4
0
1
—CH2—
|
|
118
1
257
258
4
0
1
—CH2—
|
|
[0084]
19
TABLE 19
|
|
|
Bonding
|
Structure
k
X
Ar
Point
i
j
T
|
|
|
|
119
1
259
260
4
0
1
—CH2—
|
|
120
1
261
262
4
0
1
—CH2CH2—
|
|
121
1
263
264
4
0
1
—CH2—
|
|
122
1
265
266
4
0
1
—CH2CH2—
|
|
123
1
267
268
4
0
1
—CH2CH2—
|
|
124
1
269
270
4
0
1
271
|
|
125
1
272
273
4
0
0
—
|
|
[0085]
20
TABLE 20
|
|
|
Bonding
|
Structure
k
X
Ar
Point
i
j
T
|
|
|
|
126
1
274
275
4
0
1
—CH2—
|
|
127
1
276
277
4
0
1
—CH2CH2—
|
|
128
1
278
279
4
0
1
—CH2CH2—
|
|
129
1
280
281
4
0
1
—CH2CH2—
|
|
130
1
282
283
4
0
1
—CH2CH2—
|
|
131
1
284
285
4
0
1
—CH2CH2—
|
|
132
1
286
287
4
0
1
—CH2CH2—
|
|
[0086]
21
TABLE 21
|
|
|
Bonding
|
Structure
k
X
Ar
Point
i
j
T
|
|
|
133
1
288
289
4
0
1
—CH2CH2—
|
|
134
1
290
291
4
0
1
—CH2CH2—
|
|
135
1
292
293
4
0
1
—CH2CH2—
|
|
136
1
294
295
4
0
1
—CH2CH2—
|
|
137
1
296
297
4
0
1
—CH2CH2—
|
|
138
1
298
299
4
0
1
—(CH2)4—
|
|
[0087]
22
TABLE 22
|
|
|
Bonding
|
Structure
k
X
Ar
Point
i
j
T
|
|
|
139
1
300
301
4
0
1
302
|
|
140
1
303
304
4
0
1
—CH2CH2—
|
|
141
1
305
306
4
0
0
—
|
|
142
1
307
308
4
0
1
—CH2—
|
|
143
1
309
310
3
0
0
—
|
|
144
1
311
312
4
0
0
—
|
|
145
1
313
314
4
0
1
—CH2CH2—
|
|
[0088]
23
TABLE 23
|
|
|
Bond-
|
ing
|
Structure
k
X
Ar
Point
i
j
T
|
|
|
146
1
315
316
4
1
0
—
|
|
147
1
317
318
4
0
1
—CH2—
|
|
148
1
319
320
4
0
1
321
|
|
149
1
322
323
4
0
1
—CH2CH2—
|
|
150
1
324
325
4
0
1
—CH2CH2—
|
|
151
1
326
327
4
0
1
—CH2CH2—
|
|
[0089]
24
TABLE 24
|
|
|
Bonding
|
Structure
k
X
Ar
Point
i
j
T
|
|
|
152
1
328
329
4
0
1
—CH2CH2—
|
|
153
1
330
331
4
0
1
—CH2CH2—
|
|
154
1
332
333
4
0
1
—CH2CH2—
|
|
155
1
334
335
4
0
1
—CH2CH2—
|
|
156
1
336
337
4
0
1
—CH2CH2—
|
|
157
1
338
339
4
0
1
—CH2CH2—
|
|
[0090]
25
TABLE 25
|
|
|
Bonding
|
Structure
k
X
Ar
Point
i
j
T
|
|
|
158
1
340
341
4
0
1
—CH2CH2—
|
|
159
1
342
343
4
0
1
—CH2CH2—
|
|
160
1
344
345
4
0
1
—CH2CH2—
|
|
161
1
346
347
4
0
1
—CH2CH2—
|
|
162
1
348
349
4
0
1
—CH2CH2—
|
|
163
1
350
351
4
0
1
—CH2CH2—
|
|
[0091]
26
TABLE 26
|
|
|
Bonding
|
Structure
k
X
Ar
Point
i
j
T
|
|
|
164
1
352
353
4
0
1
—CH2CH2—
|
|
165
1
354
355
4
0
1
—CH2CH2—
|
|
166
1
356
357
4
0
1
—CH2CH2—
|
|
167
1
358
359
4
0
1
—CH2CH2—
|
|
168
1
360
361
4
0
1
—CH2CH2—
|
|
169
1
362
363
4
0
1
—CH2CH2—
|
|
[0092]
27
TABLE 27
|
|
|
Bonding
|
Structure
k
X
Ar
Point
i
j
T
|
|
|
170
1
364
365
4
0
1
—CH2CH2—
|
|
171
1
366
367
4
0
0
—
|
|
172
1
368
369
4
0
1
—CH2—
|
|
173
1
370
371
4
0
0
—
|
|
174
1
372
373
4
1
0
—
|
|
175
1
374
375
4
0
1
—CH2CH2—
|
|
176
1
376
377
4
0
1
—CH2CH2—
|
|
[0093]
28
TABLE 28
|
|
|
Structure
k
X
Ar
|
|
177
1
378
379
|
|
178
1
380
381
|
|
179
1
382
383
|
|
180
1
384
385
|
|
181
1
386
387
|
|
182
1
388
389
|
|
Bond-
|
Structure
Point
i
j
T
|
|
177
4
0
1
—CH2CH2—
|
178
4
0
1
—CH2CH2—
|
179
4
0
1
—CH2CH2—
|
180
4
0
1
—CH2CH2—
|
181
4
0
1
—CH2CH2—
|
182
4
0
1
—CH2CH2—
|
|
[0094]
29
TABLE 29
|
|
|
Bond-
|
Struc-
ing
|
ture
k
X
Ar
Point
i
j
T
|
|
|
183
1
390
391
4
0
1
—CH2CH2—
|
|
184
1
392
393
4
0
1
—CH2CH2—
|
|
185
1
394
395
4
0
1
—CH2—
|
|
186
1
396
397
4
0
1
—CH2CH2—
|
|
187
1
398
399
4
0
1
—CH2CH2—
|
|
188
1
400
401
4
0
1
—CH2CH2—
|
|
189
1
402
403
4
0
0
—
|
|
[0095]
30
TABLE 30
|
|
|
Structure
k
X
Ar
|
|
190
1
404
405
|
|
191
1
406
407
|
|
192
1
408
409
|
|
193
1
410
411
|
|
194
1
412
413
|
|
195
1
414
415
|
|
196
1
416
417
|
|
Bonding
|
Structure
Point
i
j
T
|
|
190
4
0
1
—CH2—
|
191
4
0
1
—CH2—
|
192
4
0
1
—CHCH2—
|
193
4
0
1
418
|
|
194
4
0
1
—CH2CH2—
|
195
4
0
1
—CH2CH2—
|
196
4
0
1
—CH2CH2—
|
|
[0096]
31
TABLE 31
|
|
|
Bonding
|
Structure
k
X
Ar
Point
i
j
T
|
|
|
|
197
1
419
420
4
0
1
—CH2CH2—
|
|
198
1
421
422
4
0
1
—CH2CH2—
|
|
199
1
423
424
4
0
1
—CH2CH2—
|
|
200
1
425
426
4
0
1
—CH2CH2—
|
|
201
1
427
428
4
0
1
—CH2CH2—
|
|
202
1
429
430
4
0
1
—(CH2)3—
|
|
[0097]
32
TABLE 32
|
|
|
Bonding
|
Structure
k
X
Ar
Point
i
j
T
|
|
|
|
203
1
431
432
4
0
1
—CH2CH2—
|
|
204
1
433
434
4
0
1
—CH2CH2—
|
|
205
1
435
436
4
0
0
—
|
|
206
1
437
438
4
0
1
—CH2—
|
|
207
1
439
440
4
0
1
—CH2CH2—
|
|
208
1
441
442
4
0
1
—CH2CH2—
|
|
209
1
443
444
4
0
1
—CH2CH2—
|
|
[0098]
33
TABLE 33
|
|
|
Bonding
|
Structure
k
X
Ar
Point
i
j
T
|
|
|
|
210
1
445
446
4
0
1
—CH2CH2—
|
|
211
1
447
448
4
0
1
—CH2CH2—
|
|
212
1
449
450
4
0
1
—CH2CH2—
|
|
213
1
451
452
4
0
1
—CH2CH2—
|
|
214
1
453
454
4
0
1
—CH2CH2—
|
|
215
1
455
456
4
0
1
—CH2CH2—
|
|
[0099]
34
TABLE 34
|
|
|
Bonding
|
Structure
k
X
Ar
Point
i
j
T
|
|
|
|
216
1
457
458
4
0
1
—CH2CH2—
|
|
217
1
459
460
4
0
1
—CH2CH2—
|
|
218
1
461
462
4
0
0
—
|
|
219
1
463
464
4
0
1
—CH2—
|
|
220
1
465
466
4
0
1
—CH2—
|
|
221
1
467
468
4
0
1
—CH2—
|
|
222
1
469
470
4
0
0
—
|
|
[0100]
35
TABLE 35
|
|
|
Bonding
|
Structure
k
X
Ar
Point
i
j
T
|
|
|
|
223
1
471
472
4
0
1
—(CH2)3—
|
|
224
1
473
474
4
0
1
—CH2CH2—
|
|
225
1
475
476
4
0
1
—CH2CH2—
|
|
226
1
477
478
4
0
1
—CH2CH2—
|
|
227
1
479
480
4
0
1
—CH2CH2—
|
|
228
1
481
482
4
0
1
—CH2—
|
|
[0101]
36
TABLE 36
|
|
|
Bonding
|
Structure
k
X
Ar
Point
i
j
T
|
|
|
|
229
1
483
484
4
0
1
—(CH2)3—
|
|
230
1
485
486
4
0
0
—
|
|
231
1
487
488
4
0
1
—CH2—
|
|
232
1
489
490
4
0
1
—CH2CH2—
|
|
233
1
491
492
4
0
1
—CH2—
|
|
234
1
493
494
4
0
1
—CH2—
|
|
235
1
495
496
4
0
1
—CH2—
|
|
[0102]
37
TABLE 37
|
|
|
Bonding
|
Structure
k
X
Ar
Point
i
j
T
|
|
|
236
1
497
498
4
0
1
—CH2CH2—
|
|
237
1
499
500
4
0
1
—CH2—
|
|
238
1
501
502
4
0
1
—CH2CH2—
|
|
239
1
503
504
4
0
1
—CH2CH2—
|
|
240
1
505
506
4
0
1
—CH2CH2—
|
|
241
1
507
508
4
0
1
—CH2—
|
|
[0103]
38
TABLE 38
|
|
|
Bonding
|
Structure
k
X
Ar
Point
i
j
T
|
|
|
|
242
1
509
510
4
0
1
—(CH2)3—
|
|
243
1
511
512
4
0
1
—CH2CH2—
|
|
244
1
513
514
4
0
1
—CH2—
|
|
245
1
515
516
4
0
1
—CH2—
|
|
246
1
517
518
4
0
1
—CH2—
|
|
247
1
519
520
4
0
1
—CH2CH2—
|
|
[0104]
39
TABLE 39
|
|
|
Bonding
|
Structure
k
X
Ar
Point
i
j
T
|
|
|
|
248
1
521
522
4
0
1
—CH2—
|
|
249
1
523
524
4
0
1
—CH2—
|
|
250
1
525
526
4
0
1
—CH2—
|
|
251
1
527
528
4
0
1
—CH2CH2—
|
|
252
1
529
530
4
0
1
—CH2—
|
|
[0105]
40
TABLE 40
|
|
|
Bonding
|
Structure
k
X
Ar
Point
i
j
T
|
|
|
|
253
1
531
532
4
0
1
—CH2—
|
|
254
1
533
534
4
0
1
—CH2—
|
|
255
1
535
536
4
0
1
—CH2CH2—
|
|
256
1
537
538
4
1
1
—CH2—
|
|
257
1
539
540
4
0
1
—CH2—
|
|
258
1
541
542
4
0
1
—CH2CH2—
|
|
[0106]
41
TABLE 41
|
|
|
Bonding
|
Structure
k
X
Ar
Point
i
j
T
|
|
|
|
259
1
543
544
4
0
1
—CH2—
|
|
260
1
545
546
4
0
1
—CH2CH2—
|
|
261
1
547
548
4
0
1
—(CH2)3—
|
|
262
1
549
550
4
0
1
—CH2CH2—
|
|
263
1
551
552
4
0
1
—CH2CH2—
|
|
[0107]
42
TABLE 42
|
|
|
Bonding
|
Structure
k
X
Ar
Point
i
j
T
|
|
|
|
264
1
553
554
4
0
1
—CH2—
|
|
265
1
555
556
4
0
1
—CH2CH2—
|
|
266
1
557
558
4
0
1
—CH2—
|
|
267
1
559
560
4
0
1
—CH2CH2—
|
|
268
1
561
562
4
0
1
—CH2—
|
|
[0108]
43
TABLE 43
|
|
|
Bonding
|
Structure
k
X
Ar
Point
i
j
T
|
|
|
|
269
1
563
564
4
0
1
—CH2CH2—
|
|
270
1
565
566
4
0
1
—CH2CH2—
|
|
271
1
567
568
4
0
1
—CH2CH2—
|
|
272
1
569
570
4
0
1
—CH2CH2—
|
|
273
1
571
572
4
0
1
—CH2CH2—
|
|
[0109]
44
TABLE 44
|
|
|
Bonding
|
Structure
k
X
Ar
Point
i
j
T
|
|
|
274
1
573
574
4
0
1
—CH2CH2—
|
|
275
1
575
576
4
0
1
—CH2CH2—
|
|
276
1
577
578
4
0
1
—CH2—
|
|
277
1
579
580
4
0
1
—CH2—
|
|
278
1
581
582
4
0
1
—CH2CH2—
|
|
[0110]
45
TABLE 45
|
|
|
Bonding
|
Structure
k
X
Ar
Point
i
j
T
|
|
|
279
1
583
584
4
0
1
—CH2—
|
|
280
1
585
586
4
0
1
—CH2CH2—
|
|
281
1
587
588
4
0
1
—CH2CH2—
|
|
282
1
589
590
4
0
1
—CH2CH2—
|
|
283
1
591
592
4
0
1
—CH2CH2—
|
|
284
1
593
594
4
0
1
—CH2CH2—
|
|
[0111]
46
TABLE 46
|
|
|
Bonding
|
Structure
k
X
Ar
Point
i
j
T
|
|
|
285
1
595
596
4
0
1
—CH2CH2—
|
|
286
1
597
598
4
0
1
—CH2CH2—
|
|
287
1
599
600
4
0
1
—CH2CH2—
|
|
288
1
601
602
4
0
1
—CH2CH2—
|
|
289
1
603
604
4
0
1
—CH2—
|
|
[0112]
47
TABLE 47
|
|
|
Bonding
|
Structure
k
X
Ar
Point
i
j
T
|
|
|
290
1
605
606
4
0
1
—(CH2)3—
|
|
291
1
607
608
4
0
1
—CH2CH2—
|
|
292
1
609
610
4
0
1
—CH2CH2—
|
|
293
1
611
612
4
0
1
—CH2CH2—
|
|
294
1
613
614
4
0
1
—CH2—
|
|
[0113]
48
TABLE 48
|
|
|
Bonding
|
Structure
k
X
Ar
Point
i
j
T
|
|
|
295
1
615
616
4
0
1
—CH2—
|
|
296
1
617
618
4
0
1
—CH2—
|
|
297
1
619
620
4
0
1
—CH2CH2—
|
|
298
1
621
622
4
0
1
—CH2CH2—
|
|
299
1
623
624
4
0
1
—CH2—
|
|
[0114]
49
TABLE 49
|
|
|
Bonding
|
Structure
k
X
Ar
Point
i
j
T
|
|
|
|
300
1
625
626
4
0
1
—(CH2)3—
|
|
301
1
627
628
4
0
1
—CH2CH2—
|
|
302
1
629
630
4
0
1
—CH2CH2—
|
|
[0115]
50
TABLE 50
|
|
|
Bonding
|
Structure
k
X
Ar
Point
i
j
T
|
|
|
303
0
631
632
4, 4′
0
0
—
|
|
304
0
633
634
4, 4′
1
1
—CH2CH2—
|
|
305
0
635
636
4, 4′
0
1
—CH2CH2—
|
|
306
0
637
638
4, 4′
0
1
639
|
|
307
0
640
641
4, 4′
0
1
—CH2CH2—
|
|
308
0
642
643
4, 4′
0
1
644
|
|
309
0
645
646
4, 4′
0
1
—CH2CH2—
|
|
310
0
647
648
4, 4′
0
1
—CH2—
|
|
[0116]
51
TABLE 51
|
|
|
Bonding
|
Structure
k
X
Ar
Point
i
j
T
|
|
|
311
0
649
650
4, 4′
0
1
—CH2CH2—
|
|
312
0
651
652
4, 4′
0
1
—CH2CH2—
|
|
313
0
653
654
4, 4′
0
1
—CH2—
|
|
315
0
655
656
4, 4′
0
1
657
|
|
316
0
658
659
4, 4′
0
1
—CH2—
|
|
317
0
660
661
4, 4′
0
1
—CH2CH2—
|
|
[0117]
52
TABLE 52
|
|
|
Bonding
|
Structure
k
X
Ar
Point
i
j
T
|
|
|
318
0
662
663
4, 4′
0
1
—CH2CH2—
|
|
319
0
664
665
4, 4′
0
1
—CH2CH2—
|
|
320
0
666
667
4, 4′
0
1
—CH2CH2—
|
|
321
0
668
669
4, 4′
0
1
—CH2CH2—
|
|
322
0
670
671
4, 4′
0
1
672
|
|
323
0
673
674
4, 4′
0
1
—CH2CH2—
|
|
324
0
675
676
4, 4′
0
1
—CH2CH2—
|
|
[0118]
53
TABLE 53
|
|
|
Bonding
|
Structure
k
X
Ar
Point
i
j
T
|
|
|
325
0
677
678
4, 4′
0
1
—CH2—
|
|
326
0
679
680
4, 4′
0
0
—
|
|
327
0
681
682
4, 4′
1
0
—
|
|
328
0
683
684
4, 4′
0
1
—CH2CH2—
|
|
329
0
685
686
4, 4′
1
0
—(CH2)4—
|
|
330
0
687
688
4, 4′
0
0
—
|
|
331
0
689
690
4, 4′
0
0
—
|
|
332
0
691
692
4, 4′
0
0
—
|
|
[0119]
54
TABLE 54
|
|
|
Bonding
|
Structure
k
X
Ar
Point
i
j
T
|
|
|
333
0
693
694
4, 4′
0
0
—
|
|
334
0
695
696
4, 4′
0
0
—CH2CH2—
|
|
335
0
697
698
4, 4′
0
0
—CH2—
|
|
336
0
699
700
4, 4′
0
0
—CH2CH2—
|
|
337
0
701
702
4, 4′
0
0
—CH2—
|
|
338
0
703
704
4, 4′
1
1
—CH2—
|
|
339
1
705
706
4, 4′
1
1
—CH2CH2—
|
|
340
1
707
708
4, 4′
1
1
—CH2CH2—
|
|
[0120]
55
TABLE 55
|
|
|
Bonding
|
Structure
k
X
Ar
Point
i
j
T
|
|
|
341
1
709
710
4, 4′
0
1
—CH2CH2—
|
|
342
1
711
712
4, 4′
0
1
—CH2CH2—
|
|
343
1
713
714
4, 4′
0
1
—CH2CH2—
|
|
344
1
715
716
4, 4′
0
1
—CH2CH2—
|
|
345
1
717
718
4, 4′
0
1
—CH2—
|
|
346
1
719
720
4, 4′
0
1
721
|
|
347
1
722
723
4, 4′
0
1
724
|
|
[0121]
56
TABLE 56
|
|
|
Bonding
|
Structure
k
X
Ar
Point
i
j
T
|
|
|
348
1
725
726
4, 4′
0
1
—CH2CH2—
|
|
349
1
727
728
4, 4′
0
1
—CH2CH2—
|
|
350
1
729
730
4, 4′
0
1
—CH2CH2—
|
|
351
1
731
732
4, 4′
0
1
—CH2CH2—
|
|
352
1
733
734
4, 4′
0
1
—CH2CH2—
|
|
353
1
735
736
4, 4′
0
1
—(CH2)4—
|
|
354
1
737
738
4, 4′
0
1
739
|
|
[0122]
57
TABLE 44
|
|
|
Struct-
Bonding
|
ure
k
X
Ar
Point
i
j
T
|
|
|
355
1
740
741
4, 4′
0
1
—CH2CH2—
|
|
356
1
742
743
4, 4′
0
1
—CH2CH2—
|
|
357
1
744
745
4, 4′
0
1
—CH2CH2—
|
|
358
1
746
747
4, 4′
0
1
748
|
|
359
1
749
750
4, 4′
0
1
—CH2CH2—
|
|
360
1
751
752
4, 4′
0
1
—(CH2)3—
|
|
361
1
753
754
4, 4′
0
1
755
|
|
[0123]
58
TABLE 58
|
|
|
Bonding
|
Structure
k
X
Ar
Point
i
j
T
|
|
|
363
1
756
757
4, 4′
0
1
758
|
|
364
1
759
760
4, 4′
0
1
—CH2CH2—
|
|
365
1
761
762
4, 4′
0
1
—CH2CH2—
|
|
366
1
763
764
4, 4′
0
0
—
|
|
367
1
765
766
4, 4′
0
1
—CH2CH2—
|
|
368
1
767
768
4, 4′
0
1
—CH2CH2—
|
|
369
1
769
770
4, 4′
0
1
—CH2CH2—
|
|
[0124]
59
TABLE 59
|
|
|
Bonding
|
Structure
k
X
Ar
Point
i
j
T
|
|
|
370
1
771
772
4, 4′
0
0
—
|
|
371
1
773
774
4, 4′
0
1
—CH2—
|
|
372
1
775
776
4, 4′
0
1
—CH2—
|
|
373
1
777
778
4, 4′
0
1
—CH2—
|
|
374
1
779
780
4, 4′
0
1
—CH2—
|
|
375
1
781
782
4, 4′
0
1
—CH2—
|
|
376
1
783
784
4, 4′
0
1
—CH2CH2—
|
|
377
1
785
786
4, 4′
0
1
—CH2CH2—
|
|
[0125]
60
TABLE 60
|
|
|
Bonding
|
Structure
k
X
Ar
Point
i
j
T
|
|
|
378
1
787
788
4, 4′
1
1
—CH2CH2—
|
|
379
1
789
790
4, 4′
0
1
—CH2CH2—
|
|
380
1
791
792
4, 4′
0
1
—CH2CH2—
|
|
381
1
793
794
4, 4′
0
1
—CH2CH2—
|
|
382
1
795
796
4, 4′
0
1
—CH2CH2—
|
|
383
1
797
798
4, 4′
0
1
—CH2CH2—
|
|
384
1
799
800
4, 4′
0
1
—CH2CH2—
|
|
[0126]
61
TABLE 61
|
|
|
Bond-
|
Struct-
ing
|
ure
k
X
Ar
Point
i
j
T
|
|
|
385
1
801
802
4, 4′
0
1
—CH2CH2—
|
|
386
1
803
804
4, 4′
0
1
—CH2CH2—
|
|
387
1
805
806
4, 4′
0
1
—(CH2)4—
|
|
388
1
807
808
4, 4′
0
1
809
|
|
389
1
810
811
4, 4′
0
1
—CH2CH2—
|
|
390
1
812
813
4, 4′
0
1
—CH2—
|
|
391
1
814
815
4, 4′
0
1
—CH2CH2—
|
|
392
1
816
817
4, 4′
0
1
—CH2CH2—
|
|
[0127]
62
TABLE 62
|
|
|
Structure
k
X
Ar
|
|
393
1
818
819
|
|
394
1
820
821
|
|
395
1
822
823
|
|
396
1
824
825
|
|
307
1
826
827
|
|
398
1
828
829
|
|
399
1
830
831
|
|
400
1
832
833
|
|
Bonding
|
Structure
Point
i
j
T
|
|
393
4,4′
0
1
—CH2CH2—
|
394
4,4′
0
1
—CH2CH2—
|
395
4,4′
0
1
834
|
|
396
4,4′
0
1
—CH2CH2—
|
397
4,4′
0
1
—CH2—
|
398
4,4′
0
1
—CH2CH2—
|
399
4,4′
0
1
—CH2CH2—
|
400
4,4′
0
1
—CH2CH2—
|
|
[0128]
63
TABLE 63
|
|
|
Structure
k
X
Ar
|
|
401
1
835
836
|
|
402
1
837
838
|
|
403
1
839
840
|
|
404
1
841
842
|
|
405
1
843
844
|
|
406
1
845
846
|
|
407
1
847
848
|
|
408
1
849
850
|
|
Bonding
|
Structure
Point
i
j
T
|
|
401
4,4′
0
1
—CH2CH2—
|
402
4,4′
0
1
—CH2CH2—
|
403
4,4′
0
1
—CH2CH2—
|
404
4,4′
0
1
—CH2—
|
405
4,4′
0
1
—CH2—
|
406
4,4′
0
1
—CH2—
|
407
4,4′
0
1
—CH2—
|
408
4,4′
0
1
—CH2—
|
|
[0129]
64
TABLE 64
|
|
|
Bonding
|
Structure
k
X
Ar
Point
i
j
T
|
|
|
409
1
851
852
4,4′
0
1
—CH2CH2—
|
|
410
1
853
854
4,4′
0
1
—CH2—
|
|
411
1
855
856
4,4′
1
1
—CH2CH2—
|
|
412
1
857
858
4,4′
0
1
—CH2CH2—
|
|
413
1
859
860
4,4′
0
1
861
|
|
414
1
862
863
4,4′
0
0
—
|
|
415
1
864
865
4,4′
0
1
—CH2—
|
|
416
1
866
867
4,4′
0
1
—CH2CH2—
|
|
[0130]
65
TABLE 65
|
|
|
Bonding
|
Structure
k
X
Ar
Point
i
j
T
|
|
|
417
1
868
869
4,4′
0
1
—CH2CH2—
|
|
418
1
870
871
4,4′
0
1
—CH2CH2—
|
|
419
1
872
873
4,4′
0
1
—CH2CH2—
|
|
420
1
874
875
4,4′
0
1
—CH2CH2—
|
|
421
1
876
877
4,4′
0
1
—CH2CH2—
|
|
422
1
878
879
4,4′
0
1
—CH2CH2—
|
|
423
1
880
881
4,4′
0
1
—CH2CH2—
|
|
[0131]
66
TABLE 66
|
|
|
Bonding
|
Structure
k
X
Ar
Point
i
j
T
|
|
|
424
1
882
883
4,4′
0
1
—CH2CH2—
|
|
425
1
884
885
4,4′
0
1
—CH2CH2—
|
|
426
1
886
887
4,4′
0
1
—CH2CH2—
|
|
427
1
888
889
4,4′
0
1
—CH2CH2—
|
|
428
1
890
891
4,4′
0
1
892
|
|
429
1
893
894
4,4′
0
1
—CH2CH2—
|
|
430
1
895
896
4,4′
0
1
—CH2—
|
|
431
1
897
898
4,4′
0
1
—CH2CH2—
|
|
[0132]
67
TABLE 67
|
|
|
Struc-
Bonding
|
ture
k
X
Ar
Point
i
j
T
|
|
|
432
1
899
900
4,4′
0
0
—
|
|
433
1
901
902
4,4′
0
1
—CH2CH2—
|
|
434
903
904
4,4′
1
0
—
|
|
435
1
905
906
4,4′
0
1
—CH2—
|
|
436
1
907
908
4,4′
0
1
909
|
|
437
1
910
911
4,4′
0
1
—CH2CH2—
|
|
438
1
912
913
4,4′
0
1
—CH2CH2—
|
|
439
1
914
915
4,4′
0
1
—CH2CH2—
|
|
[0133]
68
TABLE 68
|
|
|
Bonding
|
Structure
k
X
Ar
Point
i
j
T
|
|
|
440
1
916
917
4,4′
0
1
—CH2CH2—
|
|
441
1
918
919
4,4′
0
1
—CH2CH2—
|
|
442
1
920
921
4,4′
0
1
—CH2CH2—
|
|
443
1
922
923
4,4′
0
1
—CH2CH2—
|
|
444
1
924
925
4.4′
0
1
—CH2CH2—
|
|
445
1
926
927
4,4′
0
1
—CH2CH2—
|
|
446
1
928
929
4,4′
0
1
—CH2CH2—
|
|
[0134]
69
TABLE 69
|
|
|
Bonding
|
Structure
k
X
Ar
Point
i
j
T
|
|
|
447
1
930
931
4,4′
0
1
—CH2CH2—
|
|
448
1
932
933
4,4′
0
1
—CH2CH2—
|
|
449
1
934
935
4,4′
0
1
—CH2CH2—
|
|
450
1
936
937
4,4′
0
1
—CH2CH2—
|
|
451
1
938
939
4,4′
0
1
—CH2CH2—
|
|
452
1
940
941
4,4′
0
1
—(CH2)3—
|
|
453
1
942
943
4,4′
0
1
—CH2CH2—
|
|
[0135]
70
TABLE 70
|
|
|
Structure
k
X
Ar
|
|
454
1
944
945
|
|
455
1
946
947
|
|
456
1
948
949
|
|
457
1
950
951
|
|
458
1
952
953
|
|
459
1
954
955
|
|
460
1
956
957
|
|
Bonding
|
Structure
Point
i
j
T
|
|
454
4,4′
0
1
—CH2CH2—
|
|
455
4,4′
0
1
—CH2CH2—
|
|
456
4,4′
0
1
—CH2CH2—
|
|
457
4,4′
0
1
—CH2CH2—
|
|
458
4,4′
0
1
—CH2CH2—
|
|
459
4,4′
0
1
—CH2—
|
|
460
4,4′
0
1
—CH2—
|
|
[0136]
71
TABLE 71
|
|
|
Structure
k
X
Ar
|
|
461
1
958
959
|
|
462
1
960
961
|
|
463
1
962
963
|
|
464
1
964
965
|
|
465
1
966
967
|
|
466
1
968
969
|
|
467
1
970
971
|
|
Bonding
|
Structure
Point
i
j
T
|
|
461
4,4′
1
0
—
|
|
462
4,4′
0
1
—CH2CH2—
|
|
463
4,4′
0
1
—CH2CH2—
|
|
464
4,4′
0
1
—CH2CH2—
|
|
465
4,4′
0
1
—CH2CH2—
|
|
466
4,4′
0
1
—CH2CH2—
|
|
467
4,4′
0
1
—CH2CH2—
|
|
[0137]
72
TABLE 72
|
|
|
Bonding
|
Structure
k
X
Ar
Point
i
j
T
|
|
|
468
1
972
973
4, 41
0
1
—CH2CH2—
|
|
469
1
974
975
4, 41
0
1
—CH2CH2—
|
|
470
1
976
977
4, 41
0
1
—CH2CH2—
|
|
471
1
978
979
4, 41
0
1
—CH2—
|
|
472
1
980
981
4, 41
0
1
—CH2CH2—
|
|
473
1
982
983
4, 41
0
1
—CH2CH2—
|
|
474
1
984
985
4, 41
0
1
—CH2CH2—
|
|
475
1
986
987
4, 41
0
0
—
|
|
[0138]
73
TABLE 73
|
|
|
Bonding
|
Structure
k
X
Ar
Point
i
j
T
|
|
|
476
1
988
989
4, 4′
0
1
—CH2—
|
|
477
1
990
991
4, 4′
0
1
—CH2—
|
|
478
1
992
993
4, 4′
0
1
—CH2CH2—
|
|
479
1
994
995
4, 4′
0
1
996
|
|
480
1
997
998
4, 4′
0
1
—CH2CH2—
|
|
481
1
999
1000
4, 4′
0
1
—CH2CH2—
|
|
482
1
1001
1002
4, 4′
0
1
—CH2CH2—
|
|
483
1
1003
1004
4, 4′
0
1
—CH2CH2—
|
|
[0139]
74
TABLE 74
|
|
|
Bonding
|
Structure
k
X
Ar
Point
i
j
T
|
|
|
484
1
1005
1006
4, 4′
0
1
—CH2—
|
|
485
1
1007
1008
4, 4′
0
1
—CH2—
|
|
486
1
1009
1010
4, 4′
0
1
—CH2—
|
|
487
1
1011
1012
4, 4′
0
1
—CH2—
|
|
488
1
1013
1014
4, 4′
0
1
—(CH2)3—
|
|
489
1
1015
1016
4, 4′
0
1
—CH2—
|
|
490
1
1017
1018
4, 4′
0
1
—CH2—
|
|
[0140]
75
TABLE 75
|
|
|
Bonding
|
Structure
k
X
Ar
Point
i
j
T
|
|
|
491
1
1019
1020
4, 4′
0
0
—
|
|
492
1
1021
1022
4, 4′
0
1
—CH2—
|
|
493
1
1023
1024
4, 4′
0
1
—CH2CH2—
|
|
494
1
1025
1026
4, 4′
0
1
—CH2CH2—
|
|
495
1
1027
1028
4, 4′
0
1
—CH2CH2—
|
|
496
1
1029
1030
4, 4′
0
1
—CH2CH2—
|
|
497
1
1031
1032
4, 4′
0
1
—CH2CH2—
|
|
[0141]
76
TABLE 76
|
|
|
Bonding
|
Structure
k
X
Ar
Point
i
j
T
|
|
|
498
1
1033
1034
4, 4′
0
1
—CH2CH2—
|
|
499
1
1035
1036
4, 4′
0
1
—CH2CH2—
|
|
500
1
1037
1038
4, 4′
0
1
—CH2CH2—
|
|
501
1
1039
1040
4, 4′
0
1
—CH2CH2—
|
|
502
1
1041
1042
4, 4′
0
1
—CH2CH2—
|
|
503
1
1043
1044
4, 4′
0
1
—CH2CH2—
|
|
504
1
1045
1046
4, 4′
0
0
—
|
|
505
1
1047
1048
4, 4′
0
1
—CH2—
|
|
[0142]
77
TABLE 77
|
|
|
Bonding
|
Structure
k
X
Ar
Point
i
j
T
|
|
|
506
1
1049
1050
4, 4′
0
1
—CH2—
|
|
507
1
1051
1052
4, 4′
0
1
—CH2—
|
|
508
1
1053
1054
4, 4′
0
0
—
|
|
509
1
1055
1056
4, 4′
0
1
—(CH2)3—
|
|
510
1
1057
1058
4, 4′
0
1
—CH2CH2—
|
|
511
1
1059
1060
4, 4′
0
1
—CH2CH2—
|
|
512
1
1061
1062
4, 4′
0
1
—(CH2)3—
|
|
[0143]
78
TABLE 78
|
|
|
Bonding
|
Structure
k
X
Ar
Point
i
j
T
|
|
|
513
1
1063
1064
4, 4′
0
1
—CH2CH2—
|
|
514
1
1065
1066
4, 4′
0
1
—CH2—
|
|
515
1
1067
1068
4, 4′
0
1
—(CH2)3—
|
|
516
1
1069
1070
4, 4′
0
0
—
|
|
517
1
1071
1072
4, 4′
0
1
—CH2—
|
|
518
1
1073
1074
4, 4′
0
1
—CH2CH2—
|
|
519
1
1075
1076
4, 4′
0
1
—CH2CH2—
|
|
520
1
1077
1078
4, 4′
0
1
—CH2CH2—
|
|
[0144]
79
TABLE 79
|
|
|
Bonding
|
Structure
k
X
Ar
Point
i
j
T
|
|
|
521
1
1079
1080
4, 4′
0
1
—(CH2)3—
|
|
522
1
1081
1082
4, 4′
0
1
—CH2—
|
|
523
1
1083
1084
4, 4′
0
1
—CH2CH2—
|
|
524
1
1085
1086
4, 4′
0
1
—CH2CH2—
|
|
525
1
1087
1088
4, 4′
0
1
—CH2CH2—
|
|
526
1
1089
1090
4, 4′
0
1
—CH2—
|
|
527
1
1091
1092
4, 4′
0
1
—(CH2)3—
|
|
[0145]
80
TABLE 80
|
|
|
Bonding
|
Structure
k
X
Ar
Point
i
j
T
|
|
|
528
1
1093
1094
4, 4′
0
1
—CH2CH2—
|
|
529
1
1095
1096
4, 4′
0
1
—CH2—
|
|
530
1
1097
1098
4, 4′
0
1
—CH2—
|
|
531
1
1099
1100
4, 4′
0
1
—CH2—
|
|
532
1
1101
1102
4, 4′
0
1
—CH2CH2—
|
|
533
1
1103
1104
4, 4′
0
1
—CH2CH2—
|
|
534
1
1105
1106
4, 4′
0
1
—CH2—
|
|
[0146]
81
TABLE 81
|
|
|
Bonding
|
Structure
k
X
Ar
Point
i
j
T
|
|
|
535
1
1107
1108
4, 4′
0
1
—CH2CH2—
|
|
536
1
1109
1110
4, 4′
0
1
—CH2—
|
|
537
1
1111
1112
4, 4′
0
1
—CH2—
|
|
538
1
1113
1114
4, 4′
0
1
—CH2—
|
|
539
1
1115
1116
4, 4′
0
1
—CH2CH2—
|
|
540
1
1117
1118
4, 4′
0
1
—CH2—
|
|
541
1
1119
1120
4, 4′
0
1
—CH2—
|
|
[0147]
82
TABLE 82
|
|
|
Structure
k
X
Ar
Bonding Point
i
j
T
|
|
|
542
1
1121
1122
4,4′
0
1
—CH2CH2—
|
|
543
1
1123
1124
4,4′
0
1
—CH2—
|
|
544
1
1125
1126
4,4′
0
1
—CH2CH2—
|
|
545
1
1127
1128
4,4′
0
1
—(CH2)3—
|
|
546
1
1129
1130
4,4′
0
1
—CH2CH2—
|
|
547
1
1131
1132
4,4′
0
1
—CH2CH2—
|
|
548
1
1133
1134
4,4′
0
1
—CH2—
|
|
[0148]
83
TABLE 83
|
|
|
Structure
k
X
Ar
Bonding Point
i
j
T
|
|
|
549
1
1135
1136
4,4′
0
1
—CH2CH2—
|
|
550
1
1137
1138
4,4′
0
1
—CH2—
|
|
551
1
1139
1140
4,4′
0
1
—CH2CH2—
|
|
552
1
1141
1142
4,4′
0
1
—CH2—
|
|
553
1
1143
1144
4,4′
0
1
—CH2CH2—
|
|
554
1
1145
1146
4,4′
0
1
—CH2CH2—
|
|
[0149]
84
TABLE 84
|
|
|
Bond-
|
Struc-
ing
|
ture
k
X
Ar
Point
i
j
T
|
|
|
555
1
1147
1148
4,4′
0
1
—CH2CH2—
|
|
556
1
1149
1150
4,4′
0
1
—CH2CH2—
|
|
557
1
1151
1152
4,4′
0
1
—CH2CH2—
|
|
558
1
1153
1154
4,4′
0
1
—CH2CH2—
|
|
559
1
1155
1156
4,4′
0
1
—CH2—
|
|
560
1
1157
1158
4,4′
0
1
—CH2—
|
|
[0150]
85
TABLE 85
|
|
|
Bond-
|
Struc-
ing
|
ture
k
X
Ar
Point
i
j
T
|
|
|
561
1
1159
1160
4,4′
0
1
—CH2CH2—
|
|
562
1
1161
1162
4,4′
0
1
—CH2—
|
|
563
1
1163
1164
4,4′
0
1
—CH2CH2—
|
|
564
1
1165
1166
4,4′
0
1
—CH2CH2—
|
|
565
1
1167
1168
4,4′
0
1
—CH2CH2—
|
|
566
1
1169
1170
4,4′
0
1
—CH2CH2—
|
|
567
1
1171
1172
4,4′
0
1
—(CH2)3—
|
|
[0151]
86
TABLE 86
|
|
|
Structure
k
X
Ar
Bonding Point
i
j
T
|
|
|
568
1
1173
1174
4,4′
0
1
—CH2CH2—
|
|
569
1
1175
1176
4,4′
0
1
—CH2CH2—
|
|
570
1
1177
1178
4,4′
0
1
—CH2CH2—
|
|
571
1
1179
1180
4,4′
0
1
—CH2CH2—
|
|
572
1
1181
1182
4,4′
0
1
—CH2—
|
|
573
1
1183
1184
4,4′
0
1
—(CH2)3—
|
|
[0152]
87
TABLE 87
|
|
|
Bond-
|
Struc-
ing
|
ture
k
X
Ar
Point
i
j
T
|
|
|
574
1
1185
1186
4,4′
0
1
—CH2CH2—
|
|
575
1
1187
1188
4,4′
0
1
—CH2CH2—
|
|
576
1
1189
1190
4,4′
0
1
—(CH2)3—
|
|
577
1
1191
1192
4,4′
0
1
—CH2—
|
|
578
1
1193
1194
4,4′
0
1
—(CH2)3
|
|
579
1
1195
1196
4,4′
0
1
—CH2—
|
|
[0153]
88
TABLE 88
|
|
|
Structure
k
X
Ar
Bonding Point
i
j
T
|
|
|
580
1
1197
1198
4,4′
0
1
—CH2CH2—
|
|
581
1
1199
1200
4,4′
0
1
—CH2CH2—
|
|
582
1
1201
1202
4,4′
0
1
—CH2—
|
|
583
1
1203
1204
4,4′
0
1
—(CH2)3—
|
|
584
1
1205
1206
4,4′
0
1
—CH2CH2—
|
|
[0154] A non-conjugated polymer comprising a repetition unit at least one partial structure selected from the group consisting of the general formulas (I-1) and (I-2) is not particularly limited, but a polyester represented by the following formula (II-1) or (II-2), a polyether represented by the following general formula (III-1), and a polyurethane represented by the following general formula (IV-1) or (IV-2) are suitable.
1207
[0155] In the general formulas (II-1) and (II-2), A1 represents at least one selected from the structures represented by the above general formulas (I-1) and (I-2), Y1 represents a divalent alcohol residue, Z1 represents a divalent carboxylic acid residue, m represents an integer of 1 to 5, and p represents selected from a range of 5 to 5,000.
[0156] In the general formula (III-1), A1 represents at least one selected from the structures represented by the above general formulas (I-1) and (I-2), and p represents an integer from 5 to 5,000.
[0157] In addition, in the general formulas (IV-1) and (IV-2), A1 represents at least one selected from the structures represented by the above general formulas (I-1) and (I-2), T represents a divalent straight hydrocarbon group having a carbon number of 1 to 6, or a divalent branched hydrocarbon group having a carbon number of 2 to 10, Y2 and Z2 represent divalent diisocyanate, alcohol or amine residue, m represents an integer from 1 to 5, and p represents an integer from 5 to 5,000.
[0158] The structure represented by A1 in the general formulas (II-1), (II-2), (III-1), (IV-1) and (IV-4) represents at least one selected from the structures represented by the general formulas (I-1) and (I-2), and two or more structures may be used, if necessary.
[0159] In addition, in the non-conjugated polymer used in the invention as explained above, at least one of terminal groups has a fluorescent substance emitting fluorescence in a solid state. Such a fluorescent substance may be an inorganic fluorescent substance or an organic fluorescent substance, an organic fluorescent substance is preferable in view of a magnitude of light emitting quantum efficiency and diversity of a material, and an organic fluorescent substance which has a further high quantum efficiency, is chemically stable, and has heat resistance is more preferable.
[0160] Examples of such a organic fluorescent substance include a compound having a substituted or unsubstituted monovalent benzene ring or a substituted or unsubstituted monovalent polynuclear aromatic hydrocarbon having an aromatic ring number of 2 to 10, a compound having a substituted or unsubstituted monovalent condensed aromatic hydrocarbon having an aromatic ring number of 2 to 10, and a compound having a substituted or unsubstituted monovalent aromatic heterocyclic ring.
[0161] More specifically, examples thereof include polyacene derivative compounds such as a naphthalene derivative, an anthracene derivative, a tetracene derivative, a perylene derivative, a pyrene derivative and the like, a styrylamine compound, a quinacridone derivative compound, a rubulene derivative compound, a coumarin derivative compound and a pyran derivative compound
[0162] In addition, since chelating metal complexes containing a metal such as Al, Zn, Be, Mg, Eu, Ga, Pt, Ir and the like have high fluorescent quantum efficiency, are chemically stable and have heat resistance, they can be suitably used as a fluorescent substance.
[0163] In addition, it is preferable that a maximum peak wavelength of fluorescent spectrum of a fluorescent substance is in the visible light region (380 nm to 700 nm). When a maximum peak wavelength is outside a range of the visible light region, sufficient light emitting intensity is not obtained in some cases.
[0164] Examples of such a fluorescent substance are shown in Tables 89 to 95, but the fluorescent substance used in the invention is not limited to them.
89TABLE 89
|
|
StructureFluorscent material
|
|
5851208
|
5861209
|
5871210
|
5881211
|
5891212
|
5901213
|
5911214
|
5921215
|
5931216
|
5941217
|
5951218
|
5961219
|
[0165]
90
TABLE 90
|
|
|
Structure
Fluorscent
|
|
|
597
1220
|
|
598
1221
|
|
599
1222
|
|
600
1223
|
|
601
1224
|
|
602
1225
|
|
603
1226
|
|
604
1227
|
|
605
1228
|
|
606
1229
|
|
607
1230
|
|
608
1231
|
|
[0166]
91
TABLE 91
|
|
|
Structure
Fluorscent material
|
|
|
609
1232
|
|
610
1233
|
|
611
1234
|
|
612
1235
|
|
613
1236
|
|
614
1237
|
|
615
1238
|
|
616
1239
|
|
617
1240
|
|
618
1241
|
|
[0167]
92
TABLE 92
|
|
|
Structure
Fluorscent material
|
|
|
619
1242
|
|
620
1243
|
|
621
1244
|
|
622
1245
|
|
623
1246
|
|
624
1247
|
|
625
1248
|
|
626
1249
|
|
627
1250
|
|
628
1251
|
|
[0168]
93
TABLE 93
|
|
|
Structure
Fluorscent material
|
|
|
629
1252
|
|
630
1253
|
|
631
1254
|
|
632
1255
|
|
633
1256
|
|
634
1257
|
|
635
1258
|
|
636
1259
|
|
637
1260
|
|
638
1261
|
|
[0169]
94
TABLE 94
|
|
|
Structure
Fluorscent material
|
|
|
639
1262
|
|
640
1263
|
|
641
1264
|
|
642
1265
|
|
643
1266
|
|
644
1267
|
|
645
1268
|
|
646
1269
|
|
647
1270
|
|
648
1271
|
|
649
1272
|
|
650
1273
|
|
[0170]
95
TABLE 95
|
|
|
Structure
Fluorscent material
|
|
|
651
1274
|
|
652
1275
|
|
653
1276
|
|
654
1277
|
|
655
1278
|
|
656
1279
|
|
657
1280
|
|
658
1281
|
|
659
1282
|
|
660
1283
|
|
[0171] A weight average molecular weight Mw of the non-conjugated polymer used in the invention is not particularly limited, but when the non-conjugated polymer comprises a repetition unit containing at least one partial structure selected from the group consisting of the general formulas (I-1) and (I-2), it is preferable that the weight average molecular weigh Mw is in the range of 5000 to 300000.
[0172] Below, as a non-conjugated polymer, examples of polyester represented by the general formula (I-1) or (II-2) are shown in Tables 96 to 101, examples of polyether represented by the general formula (III-1) are shown in Tables 102 to 103, and examples of polyurethane represented by the general formula (IV-1) or (IV-2) are shown in Tables 104 to 107, but the polyester, the polyether and the polyurethane used in the invention are not limited to these examples.
[0173] Herein, the number in “A1” column of the “monomer” in Tables 96 to 107 corresponds to a compound having the number described in “structure” column in Tables 1 to 88 (specific examples of the above general formulas (I-1) and (I-2)). In addition, “m” means “m” shown in the general formulas (I-1) and (I-2). Hereinafter, an example (compound) with each number added thereto in Tables 96 to 107 is described as an example compound and, for example, an example with number 15 added thereto describes an exemplified compound (15).
[0174] In addition, in Table 96 to Table 101, example compounds, a partial structure of which is described only in “Y1” column, among “Y1” and “Z1” columns, mean polyester represented by the general formula (II-1). In addition, example compounds, a partial structure of which is described in both “Y1” and “Z1” columns, mean polyester represented by the general formula (II-2).
[0175] In addition, in Table 104 to Table 107, example compounds, a partial structure of which is described only in “Y2” column, among “Y2” and “Z2” columns, mean polyurethane represented by the general formula (IV-1). In addition, example compounds, a partial structure of which is described only in “Z2” column, among “Y2” and “Z2” columns, mean polyurethane represented by the general formula (IV-2).
96TABLE 96
|
|
MononerFluorscent
CompoundA1RatioY1Z1materialmp
|
(1)2——CH2CH2——585112
(2)5——CH2CH2——585150
(3)9——CH2CH2——585158
|
(4)9——CH2CH2—1284585162
|
(5)9——CH2CH2—1285585195
|
(6)9——CH2CH2—1286585248
|
(7)13—1287—587135
|
(8)13—1288—(CH2)4—587131
|
(9)19—1289—587125
|
(10)19——CH2CH2——587125
(11)41——CH2CH2——589125
(12)42——CH2CH2——589147
|
(13)42——CH2CH2—1290590275
|
(14)39——CH2CH2——(CH2)4—590189
|
[0176]
97
TABLE 97
|
|
|
Monomer
Fluorscent
|
Compound
A1
Ratio
Y1
Z1
material
m
p
|
|
(15)
46
—
—CH2CH2—
—
594
1
59
|
|
(16)
46
—
—CH2CH2—
1291
594
2
44
|
|
(17)
49
—
1292
—
594
1
78
|
|
(18)
53
—
1293
—
594
1
74
|
|
(19)
80
—
1294
1295
600
1
67
|
|
(20)
80
—
—CH2CH2—
—
603
1
55
|
|
(21)
80
—
—CH2CH2—
1296
609
1
87
|
|
(22)
85
—
1297
—
609
1
48
|
|
(23)
87
—
1298
—
609
1
36
|
|
(24)
87
—
1299
1300
609
1
66
|
|
(25)
88
—
—CH2CH2—
—
616
1
48
|
(26)
92
—
—CH2CH2—
—
616
1
44
|
|
[0177]
98
TABLE 98
|
|
|
Mononer
Fluorscent
|
Compound
A1
Ratio
Y1
Z1
material
m
p
|
|
|
(27)
127
—
—CH2CH2—
1301
616
1
85
|
|
(28)
127
—
1302
—
616
1
66
|
|
(29)
127
—
1303
—
616
1
78
|
|
(30)
127
—
1304
1305
616
1
14
|
|
(31)
137
—
—CH2CH2—
—
626
1
74
|
|
(32)
156
—
—CH2CH2—
1306
629
1
74
|
|
(33)
160
—
—CH2CH2—
—
633
1
56
|
(34)
173
—
—CH2CH2—
—
618
1
63
|
(35)
175
—
—CH2CH2—
—
618
1
78
|
(36)
178
—
—CH2CH2—
—
618
1
75
|
(37)
181
—
—CH2CH2—
—
618
1
25
|
(38)
182
—
—CH2CH2—
—
618
1
65
|
(39)
183
—
—CH2CH2—
—
618
1
45
|
(40)
191
—
—CH2CH2—
—
630
1
42
|
(41)
193
—
—CH2CH2—
—
630
1
85
|
|
[0178]
99
TABLE 99
|
|
|
Monomer
Fluorsoent
|
Compound
A1
Ratio
Y1
Z1
material
m
p
|
|
(42)
233
—
—CH2CH2—
—
630
1
45
|
(43)
234
—
—CH2CH2—
—
630
1
54
|
|
(44)
238
—
—CH2CH2
1307
616
1
86
|
|
(45)
243
—
—(CH2)4—
—(CH2)4—
616
1
65
|
|
(46)
243
—
1308
—
616
1
23
|
|
(47)
243
—
—CH2CH2—
—
606
1
78
|
|
(48)
243
—
—CH2CH2
1309
587
1
92
|
|
(49)
248
—
1310
—
597
1
79
|
|
(50)
249
—
—CH2CH2—
—
597
1
86
|
(51)
251
—
—CH2CH2—
—
604
1
58
|
|
(52)
251
—
1311
—
639
1
98
|
|
(53)
255
—
1312
—
639
1
36
|
|
(54)
262
—
—CH2CH2—
—
639
1
59
|
|
(55)
267
—
—CH2CH2—
1313
645
1
48
|
|
[0179]
100
TABLE 100
|
|
|
Monomer
Fluorscent
|
Compound
A1
Ratio
Y1
Z1
material
m
p
|
|
|
(56)
305
—
1314
—
655
1
18
|
|
(57)
307
—
1315
—
655
1
47
|
|
(58)
305
—
1316
1317
655
1
22
|
|
(59)
267
—
—CH2CH2—
—
655
1
45
|
|
(60)
336
—
—CH2CH2—
1318
656
1
56
|
|
(61)
336
—
1319
—
656
1
44
|
|
(62)
336
—
1320
—
656
1
47
|
|
(63)
352
—
1321
1322
656
1
35
|
|
(64)
352
—
1323
—
656
1
38
|
|
(65)
376
—
1324
—
656
1
75
|
|
[0180]
101
TABLE 101
|
|
|
Monomer
Fluorscent
|
Compound
A1
Ratio
Y1
Z1
material
m
p
|
|
|
(66)
376
—
1325
—
659
1
53
|
|
(67)
379
—
—CH2CH2—
—
659
1
45
|
|
(68)
379
—
—CH2CH2—
1326
658
1
55
|
|
(69)
7/92
1/1
—CH2CH2—
—
658
1
63
|
(70)
7/92
1/1
—CH2CH2—
—
658
2
80
|
|
(71)
7/92
1/1
1327
1328
658
1
45
|
|
(72)
7/92
1/1
—CH2CH2—
—
658
1
43
|
(73)
7/127
1/1
—CH2CH2—
—
618
1
60
|
(74)
7/127
1/1
—CH2CH2—
—
613
2
26
|
(75)
7/175
1/1
—CH2CH2—
—
613
1
24
|
(76)
7/92/17
1/1/1
—CH2CH2—
—
618
1
75
|
(77)
173/220
1/1
—CH2CH2—
—
613
1
63
|
|
(78)
7/311
1/1
—CH2CH2—
1329
613
1
70
|
|
(79)
7/311
1/2
—CH2CH2—
—
618
1
42
|
(80)
311/338
2/1
—CH2CH2—
—
613
1
38
|
|
[0181]
102
TABLE 102
|
|
|
Monomer
Fluorscent
|
Compound
A1
Ratio
material
m
p
|
|
(81)
3
—
585
1
23
|
(82)
5
—
587
2
43
|
(83)
6
—
587
1
45
|
(84)
7
—
587
1
70
|
(85)
12
—
587
2
45
|
(86)
12
—
587
1
65
|
(87)
19
—
587
1
35
|
(88)
20
—
587
0
31
|
(89)
22
—
587
1
45
|
(90)
41
—
587
1
68
|
(91)
43
—
587
1
74
|
(92)
44
—
587
1
35
|
(93)
47
—
600
2
36
|
(94)
49
—
600
1
62
|
(95)
53
—
600
2
33
|
(96)
56
—
600
1
65
|
(97)
88
—
600
1
61
|
(98)
90
—
606
1
39
|
(99)
92
—
606
1
25
|
(100)
93
—
606
1
45
|
(101)
127
—
606
1
35
|
(102)
145
—
606
1
61
|
(103)
175
—
606
1
43
|
(104)
176
—
606
1
58
|
(105)
178
—
616
1
68
|
(106)
179
—
616
1
65
|
(107)
181
—
616
1
35
|
(108)
188
—
616
1
34
|
(109)
221
—
616
1
37
|
(110)
243
—
616
1
62
|
(111)
245
—
616
1
36
|
(112)
247
—
616
1
46
|
(113)
249
—
616
1
38
|
(114)
262
—
616
1
98
|
(115)
265
—
616
1
38
|
|
[0182]
103
TABLE 103
|
|
|
Monomer
Fluorscent
|
Compound
A1
Ratio
material
m
p
|
|
(116)
267
—
616
1
68
|
(117)
273
—
618
1
78
|
(118)
277
—
618
1
88
|
(119)
297
—
618
1
65
|
(120)
304
—
618
1
93
|
(121)
305
—
618
1
75
|
(122)
307
—
618
1
67
|
(123)
311
—
618
1
37
|
(124)
314
—
618
1
68
|
(125)
317
—
652
1
62
|
(126)
319
—
652
2
61
|
(127)
320
—
652
1
37
|
(128)
339
—
652
1
64
|
(129)
340
—
652
1
35
|
(130)
341
—
659
1
78
|
(131)
342
—
639
1
36
|
(132)
347
—
639
1
87
|
(133)
417
—
659
1
45
|
(134)
461
—
639
1
84
|
(135)
462
—
660
1
35
|
(136)
529
—
639
1
84
|
(137)
7/36
1/1
639
1
36
|
(138)
7/43
1/1
639
1
63
|
(139)
7/44
1/2
589
1
47
|
(140)
7/53
1/1
606
2
56
|
(141)
7/85
1/1
600
1
59
|
(142)
20/85
1/2
600
1
65
|
(143)
57/90
1/1
606
1
43
|
(144)
57/92
1/2
589
1
15
|
(145)
57/94
5/1
589
1
34
|
(146)
57/127
1/1
600
1
44
|
(147)
127/196
1/2
606
1
48
|
(148)
176/340
6/1
606
1
37
|
(149)
243/376
2/1
589
1
39
|
(150)
7/20/57
1/2/4
589
1
57
|
|
[0183]
104
TABLE 104
|
|
|
Monomer
Fluorscent
|
Compound
A1
Ratio
Y2
Z2
material
T
m
p
|
|
(151)
2
—
—(CH2)6—
—
585
—CH2—
1
65
|
(152)
2
—
—(CH2)6—
—
587
—CH2CH2—
1
84
|
(153)
4
—
—(CH2)6—
—
587
—CH2—
1
38
|
(154)
6
—
—(CH2)6—
—
587
—CH2—
1
64
|
(155)
7
—
—(CH2)6—
—
587
—CH2CH2—
1
36
|
|
(156)
7
—
1330
—
587
—CH2CH2—
1
55
|
|
(157)
9
—
—(CH2)6—
—
587
—CH2CH2—
1
36
|
|
(158)
9
—
1331
—
587
—CH2CH2—
1
63
|
|
(159)
19
—
1332
—
587
—CH2CH2—
1
65
|
|
(160)
19
—
—
—CH2CH2—
587
—CH2CH2—
1
43
|
(161)
41
—
—(CH2)6—
—
587
—CH2CH2—
1
36
|
(162)
42
—
—(CH2)6—
—
587
—CH2CH2—
1
28
|
|
(163)
44
—
1333
—
600
—CH2—
1
35
|
|
[0184]
105
TABLE 105
|
|
|
Monomer
Fluorscent
|
Compound
A1
Ratio
Y2
Z2
material
T
m
p
|
|
|
(164)
44
—
1334
—
600
—CH2—
1
47
|
|
(165)
46
—
—(CH2)6—
—
600
—CH2—
1
62
|
(166)
53
—
—(CH2)6—
—
600
—CH2—
1
|
(167)
54
—
—(CH2)6—
—
600
—CH2CH2—
1
45
|
|
(168)
54
—
1335
—
606
—CH2—
1
40
|
|
(169)
80
—
—
—CH2CH2—
606
—CH2—
1
75
|
(170)
88
—
—(CH2)6—
—
606
—CH2—
1
61
|
(171)
92
—
—(CH2)6—
—
606
—CH2—
1
43
|
(172)
127
—
—(CH2)6—
—
606
—CH2—
1
88
|
|
(173)
127
—
1336
—
606
—CH2—
1
47
|
|
(174)
156
—
—(CH2)6—
—
606
—CH2—
1
71
|
(175)
175
—
—(CH2)6—
—
616
—CH2—
1
22
|
(176)
176
—
—(CH2)6—
—
616
—CH2CH2—
1
54
|
(177)
178
—
—(CH2)6—
—
616
—CH2CH2—
1
36
|
(178)
182
—
—(CH2)6—
—
616
—CH2CH2—
1
57
|
(179)
183
—
—(CH2)6—
—
616
—CH2CH2—
1
85
|
|
[0185]
106
TABLE 106
|
|
|
Monomer
Fluorscent
|
Compound
A1
Ratio
Y2
Z2
material
T
m
p
|
|
(180)
185
—
—(CH2)6—
—
616
—CH2CH2—
1
63
|
(181)
188
—
—(CH2)6—
—
616
—CH2CH2—
1
41
|
(182)
192
—
—(CH2)6—
—
616
—CH2CH2—
1
52
|
(183)
209
—
—(CH2)6—
—
616
—CH2CH2—
1
67
|
(184)
220
—
—(CH2)6—
—
616
—CH2CH2—
1
52
|
(185)
221
—
—(CH2)6—
—
616
—CH2CH2—
1
36
|
(186)
222
—
—(CH2)6—
—
616
—CH2CH2—
1
78
|
(187)
243
—
—(CH2)6—
—
618
—CH2CH2—
1
45
|
(188)
244
—
—(CH2)6—
—
618
—CH2CH2—
1
74
|
(189)
247
—
—(CH2)6—
—
618
—CH2CH2—
1
98
|
(190)
249
—
—(CH2)6—
—
618
—CH2CH2—
1
78
|
(191)
254
—
—(CH2)6—
—
618
—CH2CH2—
1
58
|
(192)
256
—
—(CH2)6—
—
618
—CH2CH2—
1
98
|
(193)
262
—
—(CH2)6—
—
618
—CH2CH2—
1
62
|
(194)
297
—
—(CH2)6—
—
618
—CH2CH2—
1
85
|
(195)
303
—
—(CH2)6—
—
652
—CH2CH2—
1
47
|
(196)
305
—
—(CH2)6—
—
652
—CH2CH2—
1
65
|
(197)
313
—
—
—CH2CH2—
652
—CH2CH2—
1
69
|
|
[0186]
107
TABLE 107
|
|
|
Monomer
Fluorscent
|
Compound
A1
Ratio
Y2
Z2
material
T
m
p
|
|
(198)
340
—
—(CH2)6—
—
652
—CH2CH2—
1
77
|
(199)
376
—
—
—CH2CH2—
652
—CH2CH2—
1
48
|
(200)
377
—
—(CH2)6—
—
659
—CH2CH2—
1
85
|
(201)
379
—
—(CH2)6—
—
639
—CH2CH2—
1
25
|
(202)
7/43
1/1
—(CH2)6—
—
639
—CH2CH2—
1
76
|
(203)
7/44
1/1
—(CH2)6—
—
659
—CH2CH2—
1
87
|
(204)
7/53
1/1
—(CH2)6—
—
639
—CH2CH2—
1
47
|
(205)
57/127
1/1
—(CH2)6—
—
660
—CH2CH2—
1
74
|
|
[0187] A method of synthesizing the non-conjugated polymer used in the invention is not particularly limited, but the known methods can be utilized by combining them depending on a desired structure, and examples thereof are explained below. The following specific examples explain in detail the cases where a non-conjugated polymer comprising a repetition unit containing at least one partial structure selected from the group consisting of the above general formulas (I-1) and (I-2) is a polyester represented by the above general formula (II-1) or (II-2), a polyether represented by the above general formula (III-1), or a polyurethane represented by the above general formula (IV-1) or (IV-2).
[0188] I) In the Case of Polyester
[0189] When the non-conjugated polymer used in the invention is polyester represented by the above general formula (II-1) or (II-2), the non-conjugated polymer can be synthesized by polymerizing a monomer represented by the following general formula (II-3), for example, by the known method described in 4th edition, Experimental Chemical Course, vol. 28 (Maruzen Co., Ltd., 1992).
A′—A1—A′ (II-3)
[0190] In the general formula (II-3), A1 represents at least one selected from the structures represented by the general formulas (I-1) and (I-2), A′ represents a hydroxyl group, a halogen atom, or a group —O—R18, and R18 represents an alkyl group, a substituted or unsubstituted aryl group, or an aralkyl group.
[0191] That is, polyester represented by the above general formula (II-1) or (II-2) can be synthesized as follows:
[0192] 1) When A′ is a hydroxy group, a divalent alcohol represented by HO—(Y—O)m—H is mixed with a monomer at an approximately equivalent amount, and this is polymerized using an acid catalyst. As an acid catalyst, catalysts which are used for a normal esterification reaction such as sulfuric acid, toluenesulfonic acid, trifluoroacetic acid and the like can be used, and are used in the range of 1/10,000 to 1/10 parts by weight, preferably 1/1,000 to 1/50 parts by weight relative to 1 part by weight of a monomer. In addition, as a solvent, it is preferable to use a solvent which can be azeotroped with water in order to remove water produced during polymerization, toluene, chlorobenzene, 1-chloronaphthalene and the like are effective, and the solvent is used in the range of 1 to 100 parts by weight, preferably 2 to 50 parts by weight relative to 1 part by weight of a monomer. A reaction temperature can be set arbitrarily, but in order to remove water produced during polymerization, it is preferable that a reaction is performed at a boiling point of a solvent.
[0193] After completion of the reaction, when a solvent was not used, the reaction soultion is dissolved in a solvent which can dissolve the reaction solution. When a solvent was used, the reaction solution is added as it is dropwise to a poor solvent in which a polymer is hardly dissolved, such as alcohols such as methanol, ethanol and the like, acetone and the like, to precipitate polyester. Then, precipitated polyester is separated, washed with water or an organic solvent well, and is dried. Further, if necessary, polyester is dissolved in a suitable organic solvent, the solution is added dropwise to a poor solvent, and re-precipitating treatment for precipitating polyester may be repeated. Re-precipitating treatment is preferably performed while effectively stirring with a mechanical stirrer or the like. A solvent which dissolves polyester upon re-precipitating treatment is used in the range of 1 to 100 parts by weight, preferably 2 to 50 parts by weight relative to 1 part by weight of polyester. In addition, a poor solvent is used in the range of 1 to 1,000 parts by weight, preferably 10 to 500 parts by weight relative to 1 part by weight of polyester.
[0194] 2) When A′ is halogen, polymerization is performed by adding an organic basic catalyst such as pyridine and triethylamine to a mixture solution obtained by mixing a monomer and a divalent alcohol represented by HO—(Y—O)m—H at an approximately equivalent amount. An organic basic catalyst is used in the range of 1 to 10 equivalent, preferably 2 to 5 equivalent relative to 1 equivalent of a monomer. As a solvent, methylene chloride, tetrahydrofuran (THF), toluene, chlorobenzene, 1-chloronaphthalene and the like are effective, and the solvent is used in the range of 1 to 100 parts by weight, preferably 2 to 50 parts by weight relative to 1 part by weight of a monomer. A reaction temperature can be set arbitrarily. After polymerization, the reaction is subjected to re-precipitating treatment as described above, and is purified.
[0195] In addition, in the case of a divalent alcohol having the high acidity such as bisphenol, an interface polymerization method may be used. That is, polymerization can be performed by adding a divalent alcohol to water, adding an equivalent amount of a base to dissolve them, and adding a monomer solution at the same equivalent as that of a divalent alcohol while vigorously stirring. Upon this, water is used in the range of 1 to 1,000 parts by weight, preferably 2 to 500 parts by weight relative to 1 part by weight of a divalent alcohol. As a solvent which dissolves a monomer, methylene chloride, dichloroethane, trichloroethane, toluene, chlorobenzene, 1-chloronaphthalene and the like are effective. A reaction temperature can be set arbitrarily and, in order to promote a reaction, it is effective to use a phase transfer catalyst such as ammonium salt, sulfonium salt and the like. A phase transfer catalyst is used in the range of 0.1 to 10 parts by weight, preferably 0.2 to 5 parts by weight relative to 1 part by weight of a monomer.
[0196] 3) When A′ is —O—R18, transesterification is available for polymerization. Such transesterification can be performed by heating a reaction solution which include a monomer, an excessive amount of a divalent alcohol [represented by HO—(Y—O)m—H] relative to the monomer, and a catalyst such as titanium alkoxide, acetate or carbonate of calcium and cobalt, or oxide of zinc or lead. A divalent alcohol is used in the range of 2 to 100 equivalent, preferably 3 to 50 equivalent relative to 1 equivalent of a monomer. A catalyst is used in the range of 1/10,000 to 1 parts by weight, preferably 1/1,000 to I-2 parts by weight relative to 1 part by weight of a monomer. A reaction is performed at a reaction temperature of 200 to 300° C. and, after completion of transesterification from a group —O—R18 to a group —O—(Y—O)m—H, it is preferable to perform a reaction under reduced pressure in order to promote polymerization by leaving of HO—(Y—O)m—H. Alternatively, a reaction may be performed while removing HO—(Y—O)m—H by azeotropy under a normal pressure using a high boiling point solvent such as 1-chloronaphthalene which can be azeotroped with HO—(Y—O)m—H.
[0197] Alternatively, polyester may be synthesized as follows: In aforementioned respective cases, after a compound represented by the following general formula (II-4) is produced by a reaction by adding an excessive amount of a divalent alcohol and, by using this compound in place of a monomer represented by the above general formula (II-3), the compound may be reacted with divalent carboxylic acid or divalent carboxylic halide according to the aforementioned method, whereby, polyester can be obtained.
1337
[0198] In the general formula (II-4), A1 represents at least one selected from the structures represented by the above general formulas (I-1) and (I-2), Y1 represents a divalent alcohol residue, and m represents an integer from 1 to 5.
[0199] 4) Introduction of a fluorescent substance is not particularly limited, but there are following methods. That is, when A′ is a hydroxy group, a fluorescent substance can be introduced in a polymer by copolymerizing monocarboxylic acid of a fluorescent substance, or after a polymerization reaction for a polymer, using monocarboxylic acid of a fluorescent substance to react them. In addition, when A′ is halogen, a fluorescent substance can be introduced into a polymer by copolymerizing monoacid chloride of a fluorescent substance, or after a polymerization reaction for a polymer, using monoacid chloride of a fluorescent substance to react them. When A′ is —O—R18, a fluorescent substance can be introduced into a polymer by copolymerizing monoester of a fluorescent substance, or after a polymerization reaction for a polymer, placing monoester of a fluorescent substance to react them.
[0200] II) In the Case of Polyether
[0201] When the non-conjugated polymer used in the invention is polyether represented by the above general formula (III-1), the non-conjugated polymer can be easily prepared by condensing between molecules of a compound having a hydroxyl group represented by the following general formulas (III-2).
HO—A1—OH (III-2)
[0202] In the general formula (III-2), A1 represents at least one selected from the structures represented by the above general formulas (I-1) and (I-2).
[0203] Polyether represented by the above general formula (III-1) can be specifically synthesized, for example, by the following method.
[0204] 1) The aforementioned polyether can be synthesized by a method of heating and dehydration-condensing a monomer having two hydroxyl groups on both ends of a structure represented by A1, as in the above general formula (III-2). In this case, it is desirable that a monomer is heated to melt without using a solvent, and a reaction is performed under reduced pressure in order to promote a polymerization reaction by leaving of water. In addition, when a solvent is used, in order to remove water, it is effective to use a solvent which is azeotoped with water, for example, trichloroethane, toluene, chlorobenzene, dichlorobenzene, nitrobenzene, 1-chloronaphthalene and the like. In this case, a solvent is used in the range of 1 to 100 equivalent, preferably 2 to 50 equivalent relative to 1 equivalent of a monomer. In addition, a reaction temperature can be set arbitrarily, but in order to remove water produced during polymerization, it is preferable to perform a reaction at a boiling point of a solvent. When polymerization does not proceed, a solvent may be removed from a reaction system, and the reaction may be heated to stir at the viscous state.
[0205] 2) The aforementioned polyether may be synthesized by a method of performing dehydration-condensation using, as an acid catalyst, protonic acids such as p-toluenesulfonic acid, hydrochloric acid, sulfuric acid, trifluoroacetic acid and the like, or Lewis acids such as zinc chloride and the like. In this case, an acid catalyst is used in the range of 1 to 1/10000 to 1/10 equivalent, preferably 1/1000 to 1/50 equivalent relative to 1 equivalent of a monomer. In order to remove water produced during polymerization, it is preferable to use a solvent which can be azeotroped with water. As such a solvent, toluene, chlorobenzene, dichlorobenzene, nitrobenzene, 1-chloronaphthalene and the like are effective, and they are used in the range of 1 to 100 equivalent, preferably 2 to 50 equivalent relative to 1 equivalent of a monomer. A reaction temperature can be set arbitrarily, but in order to remove water during a polymerization, a reaction is preferably performed at a boiling point of a solvent.
[0206] 3) The aforementioned monomer can be also synthesized by a method using a condensing agent such as alkyl isocyanate such as cyclohexyl isocyanate and the like, alkyl cyanate such as cyclohexyl cyanate and the like, cyanate ester such as p-tolyl cyanate, 2,2-bis(4-cyanatophenyl)propane and the like, dichlorohexylcarbodiimide (DCC), trichloroacetonitrile and the like. In this case, a condensing agent is used in the range of I-2 to 10 equivalent, preferably 1 to 3 equivalent relative to 1 equivalent of a monomer. As a solvent, toluene, chlorobenzene, dichlorobenene, 1-chloronaphthalene and the like are effective, and they are used in the range of 1 to 100 equivalent, preferably 2 to 50 equivalent. A reaction temperature can be set arbitrarily, but it is preferable that a reaction is performed at room temperature to a boiling point of a solvent. Among synthesizing methods 1) to 3) explained regarding polyester, the synthesizing method 1) or 3) is preferable because isomerization and side reactions are hardly caused. In particular, the synthesizing method 3) is preferable because the reaction condition is milder.
[0207] After completion of the reaction, when a solvent was not used, the reaction solution is dissolved as it is in a solvent which can dissolve it. When a solvent was used, the reaction solution is added as it is dropwise to a poor solvent which hardly dissolves a non-conjugated polymer, such as alcohols such as methanol, ethanol and the like, acetone or the like, to precipitate polyether, and polyether is separate, washed with water or an organic solvent well, and dried. Further, if necessary, re-precipitating treatment be repeated in which polyether is dissolved in a suitable organic solvent, and the solution is added dropwise to a poor solvent to precipitate a monomer. Upon re-precipitating treatment, it is preferable to perform treatment while stirring effectively with a mechanical stirrer or the like. A solvent which dissolves a monomer upon re-precipitating treatment is used in the range of 1 to 100 equivalent, preferably 2 to 50 equivalent relative to 1 equivalent of polyether. In addition, a poor solvent is used in the range of 1 to 1000 equivalent, preferably 10 to 500 equivalent relative to 1 equivalent of polyether. Further, in the aforementioned reaction, it is possible to copolymerize using two or more kinds of, preferably 2 to 5 kinds of, more preferably 2 to 3 kinds of monomers. By copolymerizing different monomers, the electric property, the film forming property, the solubility and the fluorescent property can be controlled.
[0208] When a polymerization degree of polyether is too low, the film forming property is inferior, and a firm film is hardly obtained. On the other hand, a polymerization degree is too high, solubility in a solvent is reduced, and the processibility is deteriorated in some cases. Therefore, a polymerization degree is preferably in the range of 5 to 5000, more preferably in the range of 10 to 3000, further preferably in the range of 15 to 1000.
[0209] In order to introduce L1, as in a monomer, a hydroxyl group, that is, a terminal group R may be a hydrogen atom. However, when the polymer physical properties such as the solubility, the film forming property, the mobility and the like are adversely influenced, a terminal group R can be modified to control the physical property. For example, a terminal hydroxyl group can be alkyletherized with alkyl sulfate, alkyl iodide or the like. A specific reagent can be arbitrarily selected from dimethyl sulfate, diethyl sulfate, methyl iodide, ethyl iodide and the like, and is used in the range of 1 to 3 equivalent, preferably in the range of 1 to 2 equivalent relative to a terminal hydroxyl group. Upon this, a base catalyst can be used, and can be selected from sodium hydroxide, potassium hydroxide, sodium hydride, sodium metal and the like, and is used in a range of to 3 equivalent, preferably in the range of 1 to 2 equivalent relative to a terminal hydroxyl group.
[0210] A reaction can be performed at 0° C. to a boiling point of a solvent to be used. In addition, as a solvent used thereupon, a single solvent selected from inert solvents such as benzene, toluene, methylene chloride, tetrahydrofuran, N,N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone and the like, or a mixed solvent of 2 to 3 of them can be used. In addition, depending on a reaction, a quaternary ammonium salt such as tetra-n-butylammonium iodide and the like may be used as a phase transfer catalyst. Alternatively, a terminal hydroxyl group may be acylated using acid halide to convert a terminal group R into an acyl group.
[0211] Examples of acid halide are not particularly limited, but include acryoyl chloride, crotonoyl chloride, methacryloyl chloride, n-butyl chloride, 2-furoyl chloride, benzoyl chloride, cyclohexanecarbonyl chloride, enantyl chloride, phenylacethyl chloride, o-toluoyl chloride, m-toluoyl chloride, p-toluoyl chloride and the like. They are used in the range of 1 to 3 equivalent, preferably 1 to 2 equivalent relative to a terminal hydroxyl group. Upon this, a base catalyst can be used, and can be selected arbitrarily from pyridine, dimethylaminopyridine, trimethylamine, triethylamine and the like, and is used in the range of 1 to 3 equivalent, preferably 1 to 2 equivalent relative to acid chloride. Examples of a solvent to be used thereupon include benzene, toluene, methylene chloride, tetrahydrofuran, methyl ethyl ketone and the like.
[0212] A reaction can be performed at 0° C. to a boiling point of the solvent, preferably, in the range of 0° C. to 30° C. Further, acylation may be also performed using acid anhydride such as acetic anhydride and the like. When a solvent is used, specifically, inert solvents such as benzene, toluene, chlorobenzene and the like can be used. A reaction can be performed at 0° C. to a boiling point of the solvent, preferably, 40° C. to a boiling point of a solvent.
[0213] Besides, an urethane residue (—CONH—R′) can be introduced into a terminal end using monoisocyatnate. Specifically, monoisocyanate can be arbitrarily selected from benzyl isocyanate, n-butyl isocyanate, t-butyl isocyanate, cyclohexyl isocianate, 2,6-dimethyl isocyanate, ethyl isocyanate, isopropyl isocyanate, 2-methoxyphenyl isocyanate, 4-methoxyphenyl isocyanate, n-octadecyl isocyanate, phenyl isocyanate, I-propyl isocyanate, m-tolyl isocyanate, p-tolyl isocyanate, 1-naphthyl isocyanate and the like. Monoisocyanate is used in the range of 1 to 3 equivalent, preferably 1 to 2 equivalent relative to a terminal hydroxyl group.
[0214] Examples of a solvent to be used upon this include benzene, toluene, chlorobenzene, dichlorobenzene, methylene chloride, tetrahydrofuran, N,N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone and the like. A reaction can be performed at a temperature of 0° C. to a boiling point of a solvent to be used. When a reaction hardly proceeds, metal compounds such as dibutyltin (II) dilaurate, tin (II) octylate, lead naphthenate and the like, or tertiary amines such as triethylamine, trimethylamine, pyridine, dimethylaminopyridine and the like may be added as a catalyst.
[0215] In addition, introduction of a fluorescent substance is not particularly limited, but the following methods are exemplified. That is, a method of acylating a terminal hydroxyl group by a monoacid salt compound of a fluorescent substance, and a method of introducing an urethane residue into a terminal hydroxyl group by using monoisocyanate of a fluorescent substance can be applied.
[0216] III) In the Case of Polyurethane
[0217] When the non-conjugated polymer used in the invention is polyurethane represented by the above general formula (IV-1) or (IV-2), the non-conjugated polymer can be synthesized by polymerizing monomers represented by the following general formulas (IV-3) to (IV-6) by the known method, for example, described in 4th Experimental Chemical Course, vol. 28 (Maruzen Co., Ltd., 1992), New Polymer Experiment, vol. 2 (Kyouritsushupan) 1995 and the like.
HO—A1—OH (IV-3)
NCO—A1—OCN (IV-4)
[0218]
1338
H2N—A1—NH2 (IV-5)
[0219] In the general formulas (IV-3) to (IV-6), A1 represents at least one selected from the structures represented by the above general formulas (I-1) and (I-2).
[0220] Specifically, for example, when monomers represented by the general formulas (IV-3) and (IV-4) are used, polyurethane can be synthesized as follows.
[0221] When a monomer is a divalent alcohol represented by the general formula (IV-3), the monomer is mixed with diisocyanate represented by the OCN—Y—NCO at an equivalent amount and, when a monomer is diisocyanate represented by the general formula (IV-4), the monomer is mixed with a divalent alcohol represented by HO—Y—OH at an equivalent amount, whereby, polyaddition is performed.
[0222] As the catalyst, catalysts which are used in a reaction of synthesizing polyurethane by normal polyaddition, such as organometal compounds such as dibutyltin (II) dilaurate, dibutyltin (II) diacetate, lead naphthenate and the like can be used. In addition, when aromatic diisocyanate is used in synthesis of polyurethane, tertiary amines such as triethylenediamine and the like can be used as a catalyst. These organometal compounds and tertiary amines may be used by mixing them as a catalyst. An amount of a catalyst is in the range of 1/10,000 to 1/10 parts by weight, preferably 1/1,000 to 1/50 parts by weight relative to 1 part by weight of a monomer. Any solvents may be used as far as they dissolve a monomer and diisocyanate, or divalent alcohols. However, in view of the reactivity, it is preferable to use a solvent having the low polarity or a solvent forming no hydrogen bond to alcohols, and toluene, chlorobenzene, dichlorobenzene, 1-chloronaphthalene are effective. An amount of a solvent is in the range of 1 to 100 parts by weight, preferably 2 to 50 parts by weight relative to 1 part by weight of a monomer. A reaction temperature can be arbitrarily set.
[0223] After completion of the reaction, the reaction solution is added as it is dropwise to a poor solvent in which a polymer is hardly dissolved, such as alcohols such as methanol, ethanol and the like, acetone and the like, and polyurethane is precipitated and separated from the reaction solution, washed with water or an organic solvent well, and is dried. Further, if necessary, re-precipitating treatment may be repeated in which polyurethane is dissolved in a suitable organic solvent, and the solution is added dropwise to a poor solvent, to precipitate polyurethane. Upon re-precipitated treatment, it is preferable to perform the treatment while effectively stirring with a mechanical stirrer or the like. A solvent which dissolves polyurethane upon re-precipitating treatment is used in the range of 1 to 100 parts by weight, preferably 2 to 50 parts by weight relative to 1 part by weight of polyurethane. In addition, a poor solvent is used in the range of 1 to 1,000 parts by weight, preferably 10 to 500 parts by weight relative to 1 part by weight of charge transporting polyurethane.
[0224] On the other hand, when monomers represented by the general formulas (IV-5) and (IV-6) are used, polyurethane can be synthesized as follows:
[0225] That is, when a monomer is bischloroformate represented by the general formula (IV-5), synthesis of polyurethane can be performed by mixing with diamine represented by 2HN—Y2—NH2 at an equivalent amount and conducting polycondensation. In addition, when a monomer is diamine represented by the general formula (IV-6), synthesis of polyurethane can be performed by mixing with bischloroformate represented by ClOCO—Y2—OCOCl at an equivalent amount and conducting polycondensation.
[0226] As a solvent, methylene chloride, dichloroethane, trichloroethane, tetrahydrofuran (THF), toluene, chlorobenzene, 1-chlorohaphthalene and the like are effective, and they are used in the range of 1 to 100 parts by weight, preferably 2 to 50 parts by weight relative to 1 part by weight of a monomer. A reaction temperature can be arbitrarily set. After polymerization, polyurethane is purified by re-precipitating treatment as described above.
[0227] In addition, when basicity of diamine represented by 2HN—Y—NH2 is high, an interface polymerization method may be used. That is, polymerization can be performed by adding water to diamine, adding an equivalent amount of an acid to dissolve the material, and adding diamine and a solution of an equivalent amount of a monomer represented by the aforementioned general formula (IV-5) while vigorously stirring. Upon this, water is used in the range of 1 to 1,000 parts by weight, preferably 10 to 500 parts by weight relative to 1 part by weight of diamine.
[0228] As a solvent which dissolves a monomer, methylene chloride, dichloroethane, trichloroethane, toluene, chlorobenzene, 1-chlorohaphthalene and the like are effective. A reaction temperature can be arbitrarily set. In addition, in order to promote a reaction, it is effective to use a phase transfer catalyst such as ammonium salt, sulfonium salt and the like. A phase transfer catalyst is used in the range of 0.1 to 10 parts by weight, preferably 0.2 to 5 parts by weight relative to 1 part by weight of a monomer.
[0229] In addition, introduction of a fluorescent substance is not particularly limited, but following methods are exemplified. When a monomer represented by the general formula (IV-3) is used, a fluorescent substance can be introduced by copolymerizing a monovalent alcohol of a fluorescent substance, or after a polymerization reaction of a polymer, using a monovalent alcohol of a fluorescent substance to conduct a reaction.s
[0230] When a monomer represented by the general formula (IV-4) is used, a fluorescent substance can be introduced by copolymerizing monoisocyanate of a fluorescent substance, or after a polymerization reaction of a polymer, using monoisocyanate of a fluorescent substance to conduct a reaction.
[0231] When a monomer represented by the general formula (IV-5) is used, a fluorescent substance can be introduced by copolymerizing a monovalent carboxyilic acid of a fluorescent substance, or after a polymerization reaction of a polymer, using monovalent carboxyilic acid of a fluorescent substance to conduct a reaction.
[0232] When a monomer represented by the general formula (IV-6) is used, a fluorescent substance can be introduced by copolymerizing monoamine of a fluorescent substance, or after a polymerization reaction of a polymer, using monoamine of a fluorescent substance to conduct a reaction.
[0233] Then, a layer construction of the organic electroluminescent element of the invention will be described in detail.
[0234] A layer construction of the organic electroluminescent element of the invention is not particularly limited as far as the element comprises at least one pair of electrodes comprising an anode and a cathode, at least one of which having light transmissive, and at least one organic compound layer held by the electrodes, and the aforementioned non-conjugated polymer is contained in the at least one organic compound layer.
[0235] In the organic electroluminescent element of the invention, when the at least one organic compound layer is a single layer, this organic compound layer means a light emitting layer having the charge transporting function, and this light emitting layer having the charge transporting function contains the aforementioned non-conjugated polymer.
[0236] On the other hand, when the at least one organic compound layer is composed of a plurality of layers (that is, when this organic compound layer is function-separated type that functions of respective layers are different), at least one layer comprises a light emitting layer, and this light emitting layer may be a light emitting layer having a charge transporting function. In this case, examples of a layer construction comprising the aforementioned light emitting layer or the light emitting layer having the charge transporting function, and other layers include (1) a layer construction comprising a light emitting layer, an electron transporting layer and/or an electron injecting layer, (2) a layer construction comprising a hole transporting layer and/or a hole injecting layer, a light emitting layer, and an electron transporting layer and/or an electron injecting layer, and (3) a layer construction comprising a hole transporting layer and/or a hole injecting layer, and a light emitting layer having the charge transporting function. Layers other than the light emitting layer and the light emitting layer having the charge transporting function in these layer constructions (1) to (3) have function as a charge transporting layer or a charge injecting layer.
[0237] In addition, in any layer construction of the layer constructions (1) to (3), the non-conjugated polymer may be contained in any one layer, and it is preferable that the non-conjugated polymer is contained in a light emitting layer in the layer construction (1) and (2) and it is preferable that the non-conjugated polymer is contained in a light emitting layer having the electron transporting function in the layer construction (3).
[0238] In addition, the light emitting layer having the charge transporting layer, the hole transporting layer, the hole injecting layer, the electron transporting layer and the electron injecting layer may further contain a charge transporting compound (hole transporting material, electron transporting material) other than the aforementioned non-conjugated polymer. The details of such a charge transporting compound will be described below.
[0239] Hereinafter, the invention will be explained in detail by referring to the drawings, but is not limited to them.
[0240] FIGS. 1 to 4 are schematic cross-sectional views for explaining a layer construction of the organic electroluminescent element of the invention. FIGS. 1-2 and 4 show one example of the case where the organic compound layer comprises a plurality of layers, and FIG. 3 shows an example of the case where the organic compound layer comprises one layer. In FIGS. 1 to 4, the same symbol is given to a member having the same function.
[0241] In the organic electroluminescent element shown in FIG. 1, a transparent electrode 2, a light emitting layer 4, an electron transporting layer and/or an electron injecting layer 5, and a rear surface electrode 7 are deposited in this order on a transparent insulating substrate 1. When a layer shown by the symbol 5 comprising an electron transforming layer and an electron injecting layer, an electron transporting layer, an electron injecting layer and a rear surface electrode 7 are deposited in this order on a side where a rear surface electrode 7 of a light emitting layer 4 is provided.
[0242] In the organic electroluminescent element shown in FIG. 2, a transparent electrode 2, a hole transporting layer and/or a hole injecting layer 3, a light emitting layer 4, an electron transporting layer and/or an electron injecting layer 5, and a rear surface electrode 7 are deposited in this order on transparent insulating substrate 1. When a layer shown by the symbol 3 comprises a hole transporting layer and a hole injecting layer, a hole injecting layer, a hole transporting layer and a light emitting layer 4 are deposited in this order on a side where a rear electrode 7 of a transparent electrode 2 is provided. In addition, when a layer shown by the symbol 5 comprises an electron transporting layer and an electron injecting layer, an electron transporting layer, an electron injecting layer, and a rear surface electrode 7 are deposited in this order on a side where a rear electrode 7 of a light emitting layer 4 is provided.
[0243] In the organic electroluminescent element shown in FIG. 3, a transparent electrode 2, a light emitting layer 6 having the charge transporting function, and a rear surface electrode 7 are deposited in this order on a transparent insulating substrate 1. In the organic electroluminescent element shown in FIG. 4, a transparent electrode 2, a hole transporting layer and/or a hole injecting layer 3, a light emitting layer 6 having the charge transporting function, and a rear electrode 7 are deposited in this order on a transparent insulating substrate 1. When a layer shown by the symbol 3 comprises a hole transporting layer and a hole injecting layer, a hole injecting layer, a hole transporting layer, and a light emitting layer 6 having the charge transporting function are deposited in this order on a side where a rear electrode 7 of a transparent electrode 2 is provided. Each constituent member will be explained in detail below.
[0244] In the case of a layer construction of the organic electroluminescent element shown in FIGS. 1 to 4, a transparent insulating substrate 1 is preferably transparent for taking out the emitted light and glass, plastic film and the like are used. The transparency means that transmittance of the light in a visible region is 10% or more, and further, it is preferable that this transmittance is 75% or more.
[0245] A transparent electrode 2 is transparent for taking out the emitted light as in the transparent insulating substrate, and it is preferable that the electrode has the large work function for carrying out the injection of holes. It is preferable that the value of this work function is 4 eV or more. Examples of the transparent electrode 2 include oxidized films such as tin indium oxide (ITO), tin oxide (NESA), indium oxide, zinc oxide, indium zinc oxide and the like, and gold, platinum, palladium and the like formed by deposition or sputtering. A lower sheet resistance of a transparent electrode 2 is desirable, a few hundreds Ω/□ or less is preferable, further 100 Ω/□ or less is more preferable. In addition, in a transparent electrode 2, transmittance of the light in a visible region is 10% or more as in the transparent insulating substrate, and further, it is preferable that this transmittance is 75% or more.
[0246] In addition, for the purpose of improving the durability or the light emitting efficiency of the organic electroluminescent element, a hole transporting material other than the aforementioned non-conjugated polymer for regulating the hole mobility may be mixed and dispersed in the range of 0.1% by weight to 50% by weight relative to the non-conjugated polymer used in the invention. Examples of such a hole transporting material include a tetraphenylenediamine derivative, a triphenylamine derivative, a carbazole derivative, a stilbine derivative, an arylhydrazone derivative and a porphyrin compound. Among them, a tetraphenylenediamine derivative and a triphenylamine derivative are preferable because they have the better compatibility with the non-conjugated polymer.
[0247] In addition, similarly, when the electron mobility is adjusted, an electron transporting material may be mixed and dispersed in the range of 0.1% by weight to 50% by weight relative to the non-conjugated polymer. Examples of such a electron transporting material include an oxadiazole derivative, a nitro-substituted fluorenone derivative, a diphenoquinone derivative, a thiopyrandioxide derivative, a fluorenylidenmethane derivative and the like.
[0248] In addition, when both of the hole mobility and the electron mobility are required to be adjusted, both of the hole transporting material and the electron transporting material may be mixed into the non-conjugated polymer.
[0249] Further, for the purpose of improvement of the film forming property and prevention of pinhole, a suitable resin (polymer) and additive may be added. As a resin, for example, a polycarbonate resin, polyester resin, a methacryl resin, an acryl resin, a polyvinyl chloride resin, a cellulose resin, an urethane resin, an epoxy resin, a polystyrene resin, a polyvinyl acetate resin, a styrene butadiene copolymer, vinylidene chloride-acrylonitrile copolymer, a vinyl chloride-vinyl acetate-maleic anhydride copolymer, a silicon resin, a poly-N-vinylcarbazole resin, and a polysilane resin, and electrically conducting resins such as polythiophene and polypyrrole can be used. In addition, as an additive, the known antioxidant, ultraviolet ray absorber, plasticizer and the like can be used.
[0250] In addition, for improving the light emitting intensity and adjusting the color purity and the light emitting spectrum, different dye compounds as a guest material may be doped. A dye compound to be doped may be an organic low-molecular compound or an organic high-molecular compound.
[0251] When a dye compound to be doped is an organic low-molecular compound, preferable example of this organic low-molecular compound include a chelating type organic metal complex, a polynuclear aromatic ring compound, a condensation aromatic ring compound, a perylene derivative, a coumarin derivative, a styrylarylene derivative, a silol derivative, an oxazole derivative, a oxathiazole derivative, an oxadiazole derivative and the like. In addition, when a dye compound to be doped is a high-molecular compound, as this high-molecular compound, a polyparaphenylene derivative, a polyparaphenylenevinylene derivative, a polythiophene derivative, a polyacetylene derivative and the like are used. As a suitable example of a dye compound, the following dye compounds (V-1) to (V-15) are used, being not limiting. In addition, in dye compounds (V-13) to (V-15), n and x represent an integer of 1 or more.
133913401341
[0252] A ratio of doping of a dye compound is around 0.001% by weight to 40% by weight, preferably around 0.001% by weight to 10% by weight. As dye compound to be used for such a doping, organic compounds having the better compatibility with a light emitting material and do not prevent better film forming of a light emitting layer are used and, suitably, a DCM derivative, a quinacridone derivative, a rublene derivative, porphyrin and the like are used. Suitable examples include the following dye compounds (VI-1) to (VI-4), being not limiting.
1342
[0253] In the case of a layer construction of the organic electroluminescent element shown in FIGS. 1 to 4, a metal, metal oxide, metal fluoride and the like which can be vacuum-deposited and has small work function for carrying out electron injection are used in a rear surface electrode 7. Examples of the metal include magnesium, aluminum, silver, indium, lithium, calcium and alloys thereof. Examples of the metal oxide include lithium oxide, magnesium oxide and aluminum oxide. In addition, examples of the metal fluoride include lithium fluoride, magnesium fluoride, strontium fluoride, calcium fluoride and aluminum fluoride. Further, in order to prevent deterioration of an organic electroluminescent element due to water or oxide, a protecting layer may be provided on a rear surface electrode 7.
[0254] Examples of a material for the protecting layer include metals such as In, Sn, Pb, Au, Cu, Ag, Al and the like, metal oxides such as MgO, SiO2, TiO2 and the like, and resins such as a polyethylene, a polyurea resin, a polyimide resin and the like. For forming a protecting layer, a vacuum-deposition method, a sputtering method, a plasma polymerization method, a CVD method and a coating method can be applied.
[0255] These organic electroluminescent elements shown in FIGS. 1 to 4 can be prepared by first forming individual layers corresponding to a layer construction of each organic electroluminescent element, in this order, on a transparent electrode 2.
[0256] In addition, a hole transporting layer and/or a hole injecting layer 3, a light emitting layer 4 and an electron transporting layer and/or an electron injecting layer 5, or a light emitting layer 6 having the charge transporting function is formed using the aforementioned respective materials by a vacuum-deposition method, or is formed on a transparent electrode 2 using a coating solution obtained by dissolving or dispersing the aforementioned respective materials in a suitable organic solvent by a spin-coating method, a casting method, a dipping method or the like.
[0257] Thicknesses of a hole transporting layer and/or hole injecting layer 3, a light emitting layer 4, an electron transporting layer and/or an electron injecting layer 5, as well as a light emitting layer 6 having the charge transporting function are preferably in the range of 10 μm or smaller, particularly 0.001 to 5 μm, respectively. The dispersed state for the aforementioned respective materials (non-conjugated polymer, light emitting material etc.) may be the state where materials are dispersed at a molecular level, or the state where fine particles such as fine crystals are dispersed. In the case of a method of forming a film using a coating solution, in order to obtain the state of dispersion at a molecular level, it is necessary to select a dispersing solvent in view of the dispersing property and the solubility of the aforementioned respective materials. In order to obtain dispersion of fine particles, a ball mill, a sand mill, a paint shaker, an attritor, a homogenizer, ultrasound method and the like can be utilized.
[0258] Finally, in the case of the organic electroluminescent element shown in FIG. 1 and FIG. 2, the organic electroluminescent element of the invention is completed by forming a rear electrode 7 on an electron transporting layer and/or an electron injecting layer 5 by a vacuum-deposition method, or a sputtering method or the like. In addition, in the case of the organic electroluminescent element shown in FIGS. 3 and 4, the organic electroluminescent element of the invention is completed by forming a rear electrode 7 on a light emitting layer 6 having the charge transporting function by a vacuum-deposition method, a sputtering method or the like.
EXAMPLES
[0259] The present invention will be explained more specifically by way of Examples below. However, the invention is not limited the following Examples.
Example 1
[0260] By using a substrate (manufactured by Sanyosinku) in which an ITO film is formed on a glass substrate, subjecting this ITO film of a substrate to patterning by photolithography using a photomask on which a strip-like pattern is formed, and subjecting the patterned ITO film to etching treatment, a strip-like ITO electrode (width 2 mm) was formed. Then, this glass substrate equipped with an ITO electrode was washed with neutral detergent, pure water, acetone (for electronic industry, manufactured by Kanto Kagaku) and isopropanol (for electronic industry, manufactured by Kanto Kagaku) by adding ultrasound for each 5 minutes, and dried with a spin coater. Thereafter, the substrate was washed with ultraviolet-ray ozone.
[0261] Then, a solution obtained by filtering dichloroethane containing 5% by weight of a non-conjugated polymer [exemplified compound (11)] with a PTFE filter having an opening of 0.1 μm, was coated on the surface of an ITO electrode of a substrate equipped with the ITO electrode, whereby, a light emitting layer of a thickness of 0.100 μm having the charge transporting layer function was formed.
[0262] Finally, a metal mask on which a strip-like hole is provided was arranged on the surface of a light emitting layer having the charge transporting layer function, and a Mg—Ag alloy was deposited thereon by codeposition to form a rear electrode having a width of 2 mm and a thickness of 0.15 μm so as to cross with the ITO electrode. An effective area of the formed organic electroluminescent element was 0.04 cm2.
Example 2
[0263] Dichloroethane containing 10% by weight of a mixture comprising 1 part by weight of the non-conjugated polymer [exemplified compound (11)] used in Example 1, 4 parts by weight of poly(N-vinylcarbazole) and 0.02 part by weight of the aforementioned dye compound (V-1), was filtered with a PTFE filter having an opening of 0.1 μm to prepare a solution.
[0264] Then, the above solution was coated on a surface of a side where an ITO electrode of a glass substrate equipped with an ITO electrode prepared and washed as in Example 1 was provided, by a spin coater method, to form a light emitting layer of a thickness of about 0.110 μm having the charge transporting function, which was sufficiently dried. Finally, a Mg—Ag alloy was deposited by codeposition on the surface of a light emitting layer having the charge transporting function as in Example 1, to form a rear electrode having a width of 2 mm and a thickness of 0.15 μm so as to cross the ITO electrode. An effective area of the formed organic electroluminescent element was 0.04 cm2.
Example 3
[0265] A non-conjugated polymer [exemplified compound (15)] as a layer functioning as a hole transporting layer and a light emitting layer was formed at a thickness of 0.050 μm, on a surface of a side where an ITO electrode of a glass substrate equipped with an ITO electrode prepared and washed as in Example 1 was provided.
[0266] Then, a light emitting layer of a thickness of 0.065 μm containing the dye compound (V-1) and the dye compound (VI-1) was formed by a vacuum-deposition method and, further, on the surface of a light emitting layer, the following compound (VII-1) as an electron transporting layer was formed at a thickness of 0.030 μm by a vacuum deposition method.
[0267] Finally, a Mg—Ag alloy was deposited by codeposition, on the surface of an electron transporting layer as in Example 1, to form a rear electrode having a width of 2 mm and a thickness of 0.15 μm so as to cross with the ITO electrode. An effective area of the formed organic electroluminescent element was 0.04 cm2.
1343
Example 4
[0268] According to the same manner as that of Example 1 except that an exemplified compound (59) was used in place of an exemplified compound (11) used in Example 1, an organic electroluminescent element was prepared.
Example 5
[0269] According to the same manner as that of Example 2 except that an exemplified compound (87) was used in place of an exemplified compound (11) used in Example 2, an organic electroluminescent element was prepared.
Example 6
[0270] According to the same manner as that of Example 3 except that an exemplified compound (103) was used in place of an exemplified compound (11) used in Example 1, an organic electroluminescent element was prepared.
Example 7
[0271] According to the same manner as that of Example 3 except that an exemplified compound (110) was used in place of an exemplified compound (11) used in Example 1, an organic electroluminescent element was prepared.
Example 8
[0272] According to the same manner as that of Example 3 except that an exemplified compound (165) was used in place of an exemplified compound (11) used in Example 1, an organic electroluminescent element was prepared.
Example 9
[0273] According to the same manner as that of Example 3 except that an exemplified compound (166) was used in place of an exemplified compound (11) used in Example 1, an organic electroluminescent element was prepared.
Example 10
[0274] According to the same manner as that of Example 3 except that an exemplified compound (190) was used in place of an exemplified compound (11) used in Example 1, an organic electroluminescent element was prepared.
Comparative Example 1
[0275] Dichloroethane containing 2% by weight of polyvinylcarbazole (PVK) was filtered with a PTFE filter having an opening of 0.1 μm to prepare a solution. Then, the above solution was coated on the surface of a side where an ITO electrode of a glass substrate equipped with an ITO electrode prepared and washed as in Example 1 was provided, by a dipping method, to form a hole transporting layer having a thickness of 0.06 μm, which was sufficiently dried. Then, a light emitting layer having a thickness of 0.05 μm comprising the dye compound (V-1) as a light emitting material was formed by a vacuum deposition method.
[0276] Finally, a Mg—Ag alloy was deposited by codeposition on the surface of this light emitting layer as in Example 1, to form a rear electrode having a width of 2 mm and a thickness of 0.15 μm so as to cross with the ITO electrode. An effective area of the formed organic EL element was 0.04 cm .
Comparative Example 2
[0277] A dichloroethane solution containing 10% by weight of a mixture obtained by mixing 2 parts by weight of polyvinylcarbazole (PVK), 0.1 part by weight of the dye compound (VI-1) as a light emitting material, and 1 part by weight of the above compound (VII-1) as an electron transporting material, was filtered with a PTFE filter having an opening of 0.1 μm, to prepare a solution.
[0278] Then, the above solution was coated on the surface of a side where an ITO electrode of a glass substrate equipped with an ITO electrode prepared and washed as in Example 1 was provided, by a dipping method, to form a hole transporting layer having a thickness of 0.15 μm, which was sufficiently dried. Finally, a Mg—Ag alloy was deposited by codeposition on the surface of this hole transporting layer as in Example 1, to form a rear electrode having a width of 2 mm and a thickness of 0.15 μm so as to cross with the ITO electrode. An effective area of the formed organic EL element was 0.04 cm2.
[0279] -Assessment-
[0280] A direct voltage was applied to the thus prepared organic EL element in vacuum (133.3×10−3 Pa), in which an ITO electrode side was plus and a Mg—Ag rear electrode side was minus, and light emitting was measured, and the maximum luminance and the emission color were assessed. The results are shown in Table 108. In addition, a light emitting life of the organic EL element was measured in dry nitrogen. In assessment of a light emitting life, a current value was set so that the initial luminance became 100 cd/m2, and a time required for reduction of the luminance from an initial value to half by constant current driving was adopted as an element life (hour). The driving current density upon this is shown together with an element life in Table 108.
108TABLE 108
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Driving
currentElement
EmissionLuminancedensitylife
Color(cd/m2)(mA/m2)(hour)
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Example 1Green11518175
Example 2Green13020230
Example 3Orange15018200
Ecample 4Bluegreen14018170
Example 5Bluegreen18021120
Example 6Blue16520150
Example 7Bluegreen10523210
Example 8Blue20019260
Example 9Green19024120
Example 10Bluegreen15522150
ComparativeGreen853180
Example 1
ComparativeGreen882990
Example 2
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[0281] As explained above, the organic electroluminescent element of the present invention is an electroluminescent element comprising one or more organic compound layers held between one pair of electrodes comprising an anode and a cathode, at least one of which is transparent or translucent, wherein at least one layer of the one or more organic compound layers contains at least one kind of non-conjugated polymer, and at least one of terminal groups of the non-conjugated polymer has a fluorescent substance emitting fluorescence in a solid state.
[0282] Thus, according to the invention, there can be provided an organic electroluminescent element which has the high luminance, the high efficiency and a long element life, and has little defect such as pinhole, and can be easily enlarged, using a light emitting non-conjugated polymer excellent in the heat resistance and solubility in and compatibility with a solvent and a resin.
Claims
- 1. An organic electroluminescent element comprising at least one pair of electrodes comprising an anode and a cathode, at least one of which having light transmissive, and at least one organic compound layer disposed between the electrodes,
wherein the at least one organic compound layer contains at least one kind of non-conjugated polymer having terminal groups, and at least one of terminal groups of the non-conjugated polymer contains a fluorescent substance emitting fluorescence in a solid state.
- 2. An organic electroluminescent element according to claim 1, wherein the non-conjugated polymer is selected from the group consisting of polyester, polyether and polyurethane.
- 3. An organic electroluminescent element according to claim 1, wherein the non-conjugated polymer is a hole transporting polymer.
- 4. An organic electroluminescent element according to claim 1, wherein the non-conjugated polymer comprises a repetition unit containing at least one partial structure selected from the group consisting of -the following general formulas (I-1) and (I-2),
- 5. An organic electroluminescent element according to claim 1, wherein the at least one organic compound layer comprises 2 or more layers including at least a light emitting layer, and the light emitting layer contains at least one kind of the non-conjugated polymer.
- 6. An organic electroluminescent element according to claim 5, wherein the at least one organic compound layer has a construction selected from the group consisting of a construction comprising the light emitting layer and an electron transporting layer, a construction comprising the light emitting layer and an electron injecting layer, and a construction comprising the light emitting layer, an electron transporting layer and an electron injecting layer.
- 7. An organic electroluminescent element according to claim 5, wherein the at least one organic compound layer has a construction selected from the group consisting of a construction comprising the light emitting layer and a hole transporting layer, a construction comprising the light emitting layer and a hole injecting layer, and a construction comprising the light emitting layer, a hole transporting layer and a hole injecting layer.
- 8. An organic electroluminescent element according to claim 5, wherein the at least one organic compound layer has a construction selected from the group consisting of a construction comprising the light emitting layer, a hole transporting layer and an electron transporting layer, a construction comprising the light emitting layer, a hole transporting layer and an electron injecting layer, a construction comprising the light emitting layer, a hole transporting layer, an electron transporting layer and an electron injecting layer, a construction comprising the light emitting layer, a hole injecting layer and an electron transporting layer, a construction comprising the light emitting layer, a hole injecting layer and an electron injecting layer, a construction comprising a light emitting layer, a hole injecting layer, an electron transporting layer and an electron injecting layer, a construction comprising the light emitting layer, a hole transporting layer, a hole injecting layer and an electron transporting layer, a construction comprising the light emitting layer, a hole transporting layer, a hole injecting layer and an electron injecting layer, and a construction comprising the light emitting layer, a hole transporting layer, a hole injecting layer, an electron transporting layer and an electron injecting layer.
- 9. An organic electroluminescent element according to claim 1, wherein the at least one organic compound layer is composed only of a light emitting layer having a charge transporting function, and the light emitting layer having the charge transporting function contains one or more kinds of non-conjugated polymers.
- 10. An organic electroluminescent element according to claim 4, wherein the non-conjugated polymer is a polyester selected from the group consisting of the following general formulas (II-1) and (II-2),
- 11. An organic electroluminescent element according to claim 4, wherein the non-conjugated polymer is a polyether represented by the following general formula (III-1),
- 12. An organic electroluminescent element according to claim 4, wherein the non-conjugated polymer is a polyurethane selected from the group consisting of the following general formulas (IV-1) and (IV-2),
- 13. An organic electroluminescent element according to claim 1, wherein the fluorescent substance is an organic fluorescent substance.
- 14. An organic electroluminescent element according to claim 13, wherein the organic fluorescent substance is selected from the group consisting of a compound including an aromatic hydrocarbon having an aromatic ring number of 2 or more, and a chelating metal complex.
- 15. An organic electroluminescent element according to claim 14, wherein the compound including an aromatic hydrocarbon having an aromatic ring number of 2 or more is an organic fluorescent substance selected from the group consisting of a polyacene derivative compound, a styrylamine compound, a quinacridone derivative compound, a rublene derivative compound, a coumarin derivative compound and a pyran derivative compound.
- 16. An organic electroluminescent element according to claim 15, wherein the polyacene derivative compound is selected from the group consisting of a naphthalene derivative, an anthracene derivative, a tetracene derivative, a perylene derivative and a pyrene derivative.
- 17. An organic electroluminescent element according to claim 14, wherein the chelating metal complex contains a metal selected from the group consisting of Al, Zn, Be, Mg, Eu, Ga, Pt and Ir.
- 18. An organic electroluminescent element according to claim 1, wherein a maximum peak wavelength in a fluorescent spectrum of the fluorescent substance is in the visible light region.
- 19. An organic electroluminescent element according to claim 1, wherein both terminal groups of the non-conjugated polymer contain a fluorescent substance emitting fluorescence in a solid state.
- 20. An organic electroluminescent element according to claim 1, wherein emission colors of the fluorescent substances emitting fluorescence in a solid state and respectively contained in the terminal groups are different from each other.
Priority Claims (1)
Number |
Date |
Country |
Kind |
2002-271831 |
Sep 2002 |
JP |
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