Cycloalkyl-substituted polycyclic aromatic compounds

Abstract

Novel cycloalkyl-substituted polycyclic aromatic compounds and organic EL devices using the same provide. [Solution] Novel polycyclic aromaticization by linking multiple aromatic rings with boron atoms and oxygen atoms, etc. By introducing a cycloalkyl group into the compound, materials for organic devices such as organic EL elements can be produced. This will increase the options available. In addition, novel cycloalkyl-substituted polycyclic aromatic compounds will be used for organic EL elements. By using it as a material, it is possible to provide organic EL elements with excellent luminous efficiency and element lifespan, for example.

Description

[Technical Field]

[0001] The present invention relates to a cycloalkyl-substituted polycyclic aromatic compound and an organic electroluminescent device using the same. Organic field-effect transistors and organic thin-film solar cells, as well as display devices and lighting devices. Regarding this. In this specification, "organic electroluminescent element" is referred to as "organic EL element" or simply It is sometimes written as "element". [Background technology]

[0002] Conventionally, display devices using electroluminescent light-emitting elements have been made possible by their low power consumption and thin design. Various studies have been conducted, and furthermore, organic electroluminescent devices made of organic materials are easily made lighter and larger. For this reason, it has been actively studied. In particular, the emission characteristics of blue light, one of the three primary colors of light Development of organic materials possessing charge transport capabilities such as holes and electrons (potential for semiconductors and superconductors). Regarding the development of organic materials possessing the ability to do so, whether polymer compounds or low molecular weight compounds... This has been actively researched up until now.

[0003] An organic EL element consists of a pair of electrodes, an anode and a cathode, and an electrode placed between the pair of electrodes. The structure consists of one or more layers containing an organic compound. These include light-emitting layers and charge transport / injection layers that transport or inject charges such as holes and electrons. However, various organic materials suitable for these layers have been developed.

[0004] For example, benzofluorene compounds have been developed as materials for the light-emitting layer (International (Publication No. 2004 / 061047). Furthermore, examples of hole transport materials include triphenylamine. Compounds of this type have been developed (Japanese Patent Publication No. 2001-172232). Also, as an electron transport material... For example, anthracene-based compounds have been developed (Japanese Patent Publication No. 2005-170911).

[0005] Furthermore, in recent years, triphenylamine has been used as a material for organic EL elements and organic thin-film solar cells. Materials with improved mine derivatives have also been reported (International Publication No. 2012 / 118164). The material was N,N'-diphenyl-N,N'-bis(3-methylphenyl) Referencing )-1,1'-biphenyl-4,4'-diamine (TPD), triphenyl A material characterized by its enhanced planarity achieved by linking the aromatic rings that make up the amine. This document, for example, evaluates the charge transport properties of NO-linked compounds (compound 1 on page 63). Although it is valued, the method of producing materials other than NO-linked compounds is not described. Furthermore, if the linking elements are different, the overall electronic state of the compound will be different, therefore NO-linked compounds and The properties obtained from external materials are still unknown. Other examples of such compounds can be found. (International Publication No. 2011 / 107186). For example, when the energy (T1) of a triplet exciton is large Compounds with a tightly conjugated structure can emit phosphorescence at shorter wavelengths, thus producing blue light. It is useful as a material for light-emitting layers. It can also be used as an electron transport material or hole transport material sandwiching the light-emitting layer. There is a need for new conjugated compounds with a large T1.

[0006] The host material for organic EL elements is generally an existing aromatic ring such as benzene or carbazole. These molecules are linked by single bonds or multiple phosphorus or silicon atoms. This is a relatively small conjugated system. By linking together numerous aromatic rings, the large HOMO-LUMO rings required for the host material are formed. This is because the band gap (Eg in thin films) is guaranteed. Furthermore, phosphorescent materials For host materials of organic EL devices using thermally activated delayed fluorescence materials, high triplet excitation energy is required. Ghee (E T ) is also necessary, but the molecule must have a donor or acceptor aromatic ring or substituent. By linking them together, SOMO1 and SOMO2 of the triplet excited state (T1) are localized. By reducing the exchange interaction between the two orbitals, the triplet excitation energy (E T ) improve This becomes possible. However, the small aromatic rings in the conjugated system do not have sufficient redox stability. Devices that use molecules formed by linking existing aromatic rings as host materials do not have a sufficient lifespan. On the other hand, polycyclic aromatic compounds with extended π-conjugated systems generally exhibit excellent redox stability. However, the HOMO-LUMO gap (band gap Eg in thin films) and triple-term excitation Electromotive force (E T Because of its low ) ratio, it has been considered unsuitable as a host material. [Prior art documents] [Patent Documents]

[0007] [Patent Document 1] International Publication No. 2004 / 061047 [Patent Document 2] Japanese Patent Publication No. 2001-172232 [Patent Document 3] Japanese Patent Publication No. 2005-170911 [Patent Document 4] International Publication No. 2012 / 118164 [Patent Document 5] International Publication No. 2011 / 107186 [Patent Document 6] International Publication No. 2015 / 102118 [Overview of the project] [Problems that the invention aims to solve]

[0008] As mentioned above, various materials have been developed for use in organic EL elements. However, in order to increase the options for materials for organic EL elements, materials made of compounds different from conventional ones are being developed. Development is desired. In particular, materials other than NO-linked compounds reported in Patent Documents 1-4. The organic EL properties obtained from this and the methods for manufacturing it are still unknown.

[0009] Furthermore, Patent Document 6 describes a polycyclic aromatic compound containing boron and an organic EL element using the same. As has been reported, in order to further improve the device characteristics, the luminous efficiency and device lifespan are being improved. There is a need for light-emitting layer materials, particularly dopant materials, that can achieve this. [Means for solving the problem]

[0010] The present inventors, after diligently studying to solve the above problems, have introduced a cycloalkyl group. A layer containing a polycyclic aromatic compound is placed between a pair of electrodes to constitute, for example, an organic EL element. By doing so, we discovered that superior organic EL elements can be obtained, and thus completed the present invention. The present invention relates to the following cycloalkyl-substituted polycyclic aromatic compounds or their polymers, Furthermore, organic E compounds containing cycloalkyl-substituted polycyclic aromatic compounds or their polymers are included below. We provide materials for organic devices, such as materials for L elements.

[0011] In this specification, chemical structures and substituents may be represented by the number of carbon atoms, but in the case of chemical structures... The number of carbon atoms in cases where a substitution group is substituted, or where a substituent is further substituted, is determined by the chemical formula. This refers to the number of carbon atoms in the chemical structure and each substituent, as well as the total number of carbon atoms in the chemical structure and substituents. This does not mean the total number of carbon atoms in the substituents. For example, "substituted with substituent A having X carbon atoms." A substituent B with a carbon number of Y is a substituent A with a carbon number of X on a substituent B with a carbon number of Y. This means substitution, and the number of carbon atoms Y is not the total number of carbon atoms of substituents A and B. For example, "substituent B with carbon number Y substituted with substituent A" means "substituent B with carbon number Y". This means that substituent A (without carbon number restrictions) is substituted, and the carbon number Y is equal to substituent A. This is not the total number of carbon atoms in substituent B.

[0012] Section 1. A polycyclic aromatic compound represented by the following general formula (1), or a compound represented by the following general formula (1) A polymer of polycyclic aromatic compounds having multiple structures. [ka] (In the above formula (1), Rings A, B, and C are each independently an aryl ring or a heteroaryl ring. Furthermore, at least one hydrogen in these rings may be substituted. Y 1 These are B, P, P=O, P=S, Al, Ga, As, Si-R, or Ge-R. In the Si-R and Ge-R, R is either aryl or alkyl. X 1 and X 2 These are, independently, >O, >NR, >C(-R)2, >S or >Se, and the R in the above >NR is an aryl that may be substituted, even if substituted A heteroaryl, optionally substituted alkyl, or optionally substituted cycloaryl It is a lucyl, and the R in >C(-R)2 is hydrogen, or may be substituted with an aryl or a It is a lukil, and the R of >NR and / or the R of >C(-R)2 are linking groups or may be bonded to the A ring, B ring and / or C ring by a single bond, at least one hydrogen in the compound or structure represented by formula (1) may be deuterium, cyano or halogen, and at least one hydrogen in the compound or structure represented by formula (1) is cycloalkyl substituted. )

[0013] Item 2. The A ring, B ring and C ring are each independently an aryl ring or a heteroaryl ring, and at least one hydrogen in these rings is substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted diarylamino, substituted or unsubstituted diheteroarylamino, substituted or unsubstituted arylheteroarylamino, substituted or unsubstituted diarylboryl (the two aryls may be bonded via a single bond or a linking group ), substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy or substituted or <00​​​​​​​​​​​​​​​​​​​​​​​​​​A heteroaryl, alkyl, or cycloalkyl which may be substituted with the above > In C(-R)2, R is hydrogen, or an aryl or alkyl which may be substituted with an alkyl group. Furthermore, the R of >NR and / or the R of >C(-R)2 are -O-, -S-, -C(-R)2- or single bonds are bonded to the A, B and / or C rings. Also, the R in -C(-R)2- is hydrogen or alkyl. At least one hydrogen in the compound or structure represented by formula (1) is deuterium, cyano Alternatively, it may be substituted with a halogen. In the case of a polymer, it is a dimer or trimer having two or three structures represented by general formula (1). And, At least one hydrogen in the compound or structure represented by formula (1) is cycloalkyl It is replaced by A polycyclic aromatic compound or its polymer as described in item 1.

[0014] Section 3. A polycyclic aromatic compound as described in item 1, represented by the following general formula (2). [ka] (In the above formula (2), R 1 ~R 11 These are, independently, hydrogen, aryl, heteroaryl, and diarylia. Mino, diheteroarylamino, arylheteroarylamino, diarylboryl(2 (the aryl group may be linked by a single bond or via a linking group), alkyl, alkoxy It is either aryloxy or aryloxy, and at least one hydrogen in these is aryl, heterooxy. It may be substituted with a loaryl or alkyl, and R 1 ~R 11 Among the adjacent The groups bond together to form an aryl ring or heteroaryl ring with the a, b, or c ring. It may be formed, and at least one hydrogen in the formed ring is aryl, heteroaryl. Diarylamino, Diheteroarylamino, Arylheteroarylamino, Di Arylboryl (the two aryls may be linked by a single bond or a linking group), They may be substituted with alkyl, alkoxy or aryloxy, and in small amounts At the very least, one hydrogen atom may be substituted with an aryl, heteroaryl, or alkyl group. , Y 1 These are B, P, P=O, P=S, Al, Ga, As, Si-R, or Ge-R. The R in the Si-R and Ge-R is an aryl or a aryl with 6 to 12 carbon atoms. It is Lukil, X 1 and X 2 These are, independently, >O, >NR, >C(-R)2, >S or >Se, and the R in >NR is an aryl with 6 to 12 carbon atoms, and a hetero with 2 to 15 carbon atoms. The aryl, C1-C6 alkyl, or C3-C4 cycloalkyl, and the above >In C(-R)2, R is hydrogen, and it is either an aryl group with 6 to 12 carbon atoms or an alkyl group with 1 to 6 carbon atoms. Yes, and also, the R of >NR and / or the R of >C(-R)2 are -O-, -S- , bonded to the a, b and / or c rings by -C(-R)2- or single bonds It is also possible that the R in -C(-R)2- is an alkyl group having 1 to 6 carbon atoms. In the compound represented by formula (2), at least one hydrogen is deuterium, cyano or halo It may be substituted with Gen, and, In the compound represented by formula (2), at least one hydrogen atom is substituted with a cycloalkyl group. (It is.)

[0015] Section 4. R 1 ~R 11 These are, independently, hydrogen, aryl atoms with 6 to 30 carbon atoms, and aryl atoms with 2 to 3 carbon atoms. 0 heteroaryl and diarylamino (where aryl is an aryl with 6 to 12 carbon atoms) diarylboryl (however, aryl is an aryl with 6 to 12 carbon atoms, and two aryl (The atoms may be bonded via single bonds or linking groups) or alkyl groups having 1 to 24 carbon atoms. And also, R 1 ~R 11 Adjacent groups among them bond together to form an a-ring, b-ring, or c-ring. They both form an aryl ring with 9 to 16 carbon atoms or a heteroaryl ring with 6 to 15 carbon atoms. It is also possible that at least one hydrogen in the formed ring is an aryl group having 6 to 10 carbon atoms. It may be substituted with an alkyl group having 1 to 12 carbon atoms. Y 1 The elements are B, P, P=O, P=S, or Si-R, where R in Si-R represents the number of carbon atoms (6). It is an aryl group with ~10 carbon atoms or an alkyl group with 1 to 4 carbon atoms. X 1 and X 2 These are independent of each other, >O, >NR, >C(-R)2, or >S. Yes, the R in >NR above is an aryl with 6 to 10 carbon atoms, an alkyl with 1 to 4 carbon atoms, or a carbon atom. It is a cycloalkyl group with 5 to 10 prime numbers, where R in >C(-R)2 is hydrogen and the number of carbon atoms is 6 to 10. It is an aryl or C1-C4 alkyl group. In the compound represented by formula (2), at least one hydrogen is deuterium, cyano or halo It may be substituted with Gen, and, In the compound represented by formula (2), at least one hydrogen atom is substituted with a cycloalkyl group. It is Polycyclic aromatic compounds as described in item 3.

[0016] Section 5. R 1 ~R 11 These are, independently, hydrogen, aryl atoms with 6 to 16 carbon atoms, and aryl atoms with 2 to 2 carbon atoms. 0 heteroaryl and diarylamino (where aryl is an aryl with 6 to 10 carbon atoms) or alkyl groups with 1 to 12 carbon atoms, Y 1 B, P, P=O or P=S, X 1 and X 2 These are independently >O, >NR, or >C(-R)2, In the above >NR, R represents an aryl group with 6 to 10 carbon atoms, an alkyl group with 1 to 4 carbon atoms, or a group with 5 carbon atoms. It is a cycloalkyl with ~10 carbon atoms, where R in >C(-R)2 is hydrogen, and it is an ali with 6 to 10 carbon atoms. It is an alkyl group or an alkyl group having 1 to 4 carbon atoms, and In the compound represented by formula (2), at least one hydrogen atom is substituted with a cycloalkyl group. It is Polycyclic aromatic compounds as described in item 3.

[0017] Section 6. R 1 ~R 11 These are, independently, hydrogen, aryl and diarylar atoms with 6 to 16 carbon atoms. Mino (however, aryls must have 6 to 10 carbon atoms) or alkyls with 1 to 12 carbon atoms can be, Y 1 is B, X 1 and X 2 Both are >NR, or X 1 is >NR and X 2 is>O And the R in >NR is an aryl with 6 to 10 carbon atoms, an alkyl with 1 to 4 carbon atoms, or It is a cycloalkyl group with 5 to 10 carbon atoms, and, In the compound represented by formula (2), at least one hydrogen atom is substituted with a cycloalkyl group. It is Polycyclic aromatic compounds as described in item 3.

[0018] Section 7. Diarylamino groups substituted with cycloalkyl groups, carba groups substituted with cycloalkyl groups Substituted with a benzocarbazolyl group substituted with a zolyl group or a cycloalkyl group, A polycyclic aromatic compound or a polymer thereof as described in any of 1 to 6.

[0019] Section 8. R 2 is a diarylamino group substituted with a cycloalkyl group or a cycloalkyl group A polycyclic aromatic compound as described in any of sections 3 to 6, which has a modified carbazolyl group.

[0020] Section 9. The cycloalkyl is a cycloalkyl having 3 to 20 carbon atoms, as specified in any of items 1 to 8. The polycyclic aromatic compounds described.

[0021] Section 10. The halogen is fluorine, or a polycyclic aromatic compound as described in any of items 1 to 9 or The polymer.

[0022] Section 11. A polycyclic aromatic compound as described in item 1, represented by one of the following structural formulas. [ka] [ka] (In each of the above structural formulas, "Me" represents a methyl group and "tBu" represents a t-butyl group.)

[0023] Section 12. A polycyclic aromatic compound or its polymer described in any of items 1 to 11 has a reactive substituent. A substituted, reactive compound.

[0024] Section 13. A polymer compound obtained by polymerizing the reactive compound described in item 12 as a monomer, or , a polymer crosslinked material obtained by further crosslinking the polymer compound.

[0025] Section 14. Pendant-type polymer compounds obtained by substituting the reactive compounds described in item 12 into the main chain polymer. , or a pendant-type polymer crosslinked product obtained by further crosslinking the said pendant-type polymer compound. .

[0026] Section 15. Organic compounds containing polycyclic aromatic compounds or their polymers as described in any of items 1 to 11. Materials for devices.

[0027] Section 16. A material for organic devices containing the reactive compounds described in item 12.

[0028] Section 17. Materials for organic devices containing the polymer compounds or polymer crosslinks described in item 13.

[0029] Section 18. Contains the pendant-type polymer compound or pendant-type polymer crosslinked material described in item 14. Materials for organic devices.

[0030] Section 19. The aforementioned organic device material is an organic electroluminescent device material, an organic field-effect transistor material Organic devices described in any of items 15 to 18, which are materials for organic thin-film solar cells or organic devices Materials for use.

[0031] Section 20. The organic device according to item 19, wherein the material for the organic electroluminescent element is a material for a light-emitting layer Material.

[0032] Item 21. An ink composition comprising a polycyclic aromatic compound or a multimer thereof according to any one of items 1 to 11 and an organic solvent Ink composition.

[0033] Item 22. An ink composition comprising the reactive compound according to item 12 and an organic solvent

[0034] Item 23. An ink composition comprising a main-chain polymer, the reactive compound according to item 12, and an organic solvent .

[0035] Item 24. An ink composition comprising the polymer compound or polymer crosslinked body according to item 13 and an organic solvent Ink composition.

[0036] Item 25. An ink composition comprising the pendant-type polymer compound or pendant-type polymer crosslinked body according to item 14 and an organic solvent Ink composition.

[0037] Item 26. An organic electroluminescent device having a pair of electrodes composed of an anode and a cathode, and an organic layer disposed between the pair of electrodes and containing a polycyclic aromatic compound or a multimer thereof according to any one of items 1 to 11, the reactive compound according to item 12, the polymer compound or polymer crosslinked body according to item 13, or the pendant-type polymer compound or pendant-type polymer crosslinked body according to item 14 Ink composition. Ink composition. Ink composition. Organic electroluminescent device.

[0038] Item 27. A pair of electrodes composed of an anode and a cathode, and an organic layer disposed between the pair of electrodes and containing a polycyclic aromatic compound or a multimer thereof according to any one of items 1 to 11 The polycyclic aromatic compound or its multimer described in any of them, the reactive compound described in item 12, the polymer compound or polymer crosslinked body described in item 13, or the pendant type polymer compound or pendant type polymer crosslinked body described in item 14, and has a light-emitting layer containing an organic electroluminescent device.

[0039] Item 28. The light-emitting layer is a host, and the polycyclic aromatic compound as a dopant, its multimer, reactive compound, polymer compound, polymer crosslinked body, pendant type polymer compound or pendant type polymer crosslinked body, and the organic electroluminescent device described in item 27.

[0040] Item 29. The host is an anthracene-based compound, a fluorene-based compound or a dibenzocrisene-based compound, and the organic electroluminescent device described in item 28.

[0041] Item 30. It has an electron transport layer and / or an electron injection layer disposed between the cathode and the light-emitting layer, and at least one of the electron transport layer and the electron injection layer is at least one selected from the group consisting of a borane derivative, a pyridine derivative, a fluoranthene derivative, a BO-based derivative, an anthracene derivative, a benzofluorene derivative, a phosphine oxide derivative, a pyrimidine derivative, a carbazole derivative, a triazine derivative, a benzimidazole derivative, a phenanthroline derivative and a quinolinol-based metal complex and contains, and the organic electroluminescent device described in any of items 26 to 29.

[0042] Item 31. The electron transport layer and / or the electron injection layer further contains an alkali metal, an alkaline earth metal ​Groups, rare earth metals, alkali metal oxides, alkali metal halides, alkaline earth metals Oxides of the genus, halides of alkaline earth metals, oxides of rare earth metals, halides of rare earth metals Alkali metal oxidides, alkali metal organic complexes, alkaline earth metal organic complexes, and rare earth metal organic complexes The organic field generator according to claim 30, comprising at least one selected from the group consisting of organic complexes. Optical element.

[0043] Section 32. At least one of the following: hole injection layer, hole transport layer, light emission layer, electron transport layer, and electron injection layer Each layer is a polymer compound formed by polymerizing low-molecular-weight compounds that can form each layer as monomers. Alternatively, a polymer crosslinked polymer obtained by further crosslinking the polymer compound, or forming each layer The resulting low molecular weight compound is reacted with a main chain polymer to form a pendant-type polymer compound, or Item 2 includes a pendant-type polymer crosslinked product obtained by further crosslinking the pendant-type polymer compound. An organic electroluminescent device as described in any of 6 to 31.

[0044] Section 33. Display device or lighting device equipped with an organic electroluminescent element as described in any of items 26 to 32 . [Effects of the Invention]

[0045] According to a preferred embodiment of the present invention, for example, an organic device material such as an organic EL element material and To provide a novel cycloalkyl-substituted polycyclic aromatic compound that can be used in this way. By using this cycloalkyl-substituted polycyclic aromatic compound, excellent organic EL elements and other applications can be achieved. We can provide organic devices.

[0046] Specifically, the inventors have found that the aromatic ring is composed of heterogens such as boron, phosphorus, oxygen, nitrogen, and sulfur. A polycyclic aromatic compound (basic skeleton part) connected in a simple form has a large HOMO-LUMO gap (band gap Eg in a thin film) and high triplet excitation energy (E T ). It was found that since the 6-membered ring containing hetero elements has low aromaticity, the decrease in the HOMO-LUMO gap accompanying the extension of the conjugated system is suppressed, and due to the electronic perturbation of the hetero elements , the SOMO1 and SOMO2 in the triplet excited state (T1) are localized. It is considered that this is the cause. In addition, the polycyclic aromatic compound (basic skeleton part) containing hetero elements according to the present invention has localization of SOMO1 and SOMO2 in the triplet excited state (T1) . As a result, the exchange interaction between the two orbitals becomes small, so the energy difference between the triplet excited state (T1) and the singlet excited state (S1) is small, and thermally activated delayed fluorescence is exhibited. Therefore, it is also useful as a fluorescent material for organic EL devices. In addition, a material having high triplet excitation energy (E ) is useful as an electron transport layer or a hole transport layer of a phosphorescent organic EL device or an organic EL device using thermally activated delayed fluorescence. Furthermore, since the energy of the HOMO and LUMO of these polycyclic aromatic compounds (basic skeleton part) can be arbitrarily moved by introducing substituents, the ionization potential and electron affinity can be optimized according to the surrounding materials. T In addition to the characteristics of such a basic skeleton part, the compound of the present invention can be expected to lower the melting point and sublimation temperature by introducing a cycloalkyl group. This means that in sublimation purification, which is almost essential as a purification method for materials for organic devices such as organic EL devices that require high purity, purification can be performed at a relatively low temperature, so thermal decomposition of the material can be avoided.

[0047] In addition to the characteristics of such a basic skeleton part, by introducing a cycloalkyl group into the compound of the present invention, a decrease in the melting point and sublimation temperature can be expected. This means that in sublimation purification, which is almost essential as a purification method for materials for organic devices such as organic EL devices that require high purity, purification can be performed at a relatively low temperature, so thermal decomposition of the material can be avoided. This means that in sublimation purification, which is almost essential as a purification method for materials for organic devices such as organic EL devices that require high purity, purification can be performed at a relatively low temperature, so thermal decomposition of the material can be avoided. This means that in sublimation purification, which is almost essential as a purification method for materials for organic devices such as organic EL devices that require high purity, purification can be performed at a relatively low temperature, so thermal decomposition of the material can be avoided. This means that in sublimation purification, which is almost essential as a purification method for materials for organic devices such as organic EL devices that require high purity, purification can be performed at a relatively low temperature, so thermal decomposition of the material can be avoided. Also​​​ This is a powerful method for fabricating organic devices such as organic light-emitting diodes (OLEDs), specifically the vacuum deposition process. The same applies to this as well; the process can be carried out at relatively low temperatures, thus avoiding thermal decomposition of the material. This allows for the creation of high-performance organic devices. Many compound polymers have high sublimation temperatures due to factors such as molecular weight and flatness. Furthermore, the reduction in sublimation temperature by introducing cycloalkyl groups becomes more effective. The introduction of a chloroalkyl group improves solubility in organic solvents, so the coating process is utilized. This can also be applied to the fabrication of such elements. However, the present invention is not particularly limited to these principles. It's not that it's possible. [Brief explanation of the drawing]

[0048] [Figure 1] This is a schematic cross-sectional view showing an organic EL element according to this embodiment. [Modes for carrying out the invention]

[0049] 1. Cycloalkyl-substituted polycyclic aromatic compounds and their polymers The present invention relates to a polycyclic aromatic compound represented by the following general formula (1), or the following general formula (1) A polymer of polycyclic aromatic compounds having multiple structures represented by the following general formula, preferably a polymer of polycyclic aromatic compounds having multiple structures represented by the following general formula (2) A polycyclic aromatic compound represented by, or having multiple structures represented by the following general formula (2) It is a polymer of polycyclic aromatic compounds, and at least one of these compounds or structures The hydrogen atoms are substituted with cycloalkyl groups. [ka]

[0050] In general formula (1), rings A, B, and C are each independently an aryl ring or It is a heteroaryl ring, and at least one hydrogen in these rings is substituted with a substituent. This substituent may be a substituted or unsubstituted aryl or a substituted or unsubstituted hetero. Aryl, substituted or unsubstituted diarylamino, substituted or unsubstituted diheteroaryl amino, substituted or unsubstituted aryl heteroarylaminos (aryl and heteroaryl (An amino group having), substituted or unsubstituted diarylboryl (the two aryls are single-bonded) (or may be bonded via a linking group), substituted or unsubstituted alkyl, substituted or unsubstituted Substituted alkoxy or substituted or unsubstituted aryloxy is preferred. Examples of substituents in the case of a substitution group include aryl, heteroaryl, or alkyl groups. Furthermore, the above aryl ring or heteroaryl ring is Y 1 , X 1 and X 2 Composed of The general formula (1) has a central fused two-ring structure and a five-membered or six-membered ring that shares a bond with it. This is preferable.

[0051] Here, the "condensed two-ring structure" refers to the Y shown in the center of general formula (1). 1 , X 1 and X 2 This refers to a structure in which two saturated hydrocarbon rings, which include [a specific compound], are condensed. A "six-membered ring sharing structure and bonding" refers, for example, to the fused two-ring as shown in the general formula (2) above. It refers to a condensed α-ring (benzene ring (6-membered ring)) in the structure. Also, "(an ant that is an A-ring)" "Having an A ring or heteroaryl ring in this 6-membered ring" means that the A ring is formed by this 6-membered ring alone. Either this is achieved, or other rings are condensed into this six-membered ring to include it. This means that an A-ring is formed. In other words, "having a 6-membered ring (with an A-ring)" is what is meant here. An aryl ring or heteroaryl ring is a six-member ring that makes up all or part of an A ring. This means that the ring is condensed into the aforementioned condensed two-ring structure. "B ring (b ring)", "C ring (c The same explanation applies to "rings" and also to "5-membered rings."

[0052] The ring A (or ring B, ring C) in general formula (1) is the same as the ring a in general formula (2) and Substituent R 1 ~R 3 (or the b-ring and its substituent R) 4 ~R 7 , the c ring and its substituent R 8 ~R 11 ) corresponds to the same thing. In other words, general formula (2) has a "six-membered ring" as rings A to C of general formula (1). The rings A-C correspond to the selected structure. In that sense, each ring in general formula (2) is lowercase. This was expressed using a to c.

[0053] In general formula (2), substituents R of the a, b, and c rings 1 ~R 11 Among adjacent bases The atoms combine to form an aryl ring or heteroaryl ring with the a, b, or c ring. It may be present, and at least one hydrogen in the formed ring is aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, diary Ruboryl (the two aryls may be linked by a single bond or via a linking group), Alky They may be substituted with alkoxy or aryloxy, and in at least these, The other hydrogen may be substituted with an aryl, heteroaryl, or alkyl group. Therefore, polycyclic aromatic compounds represented by general formula (2) have a ring a, a ring b, and a ring c. Depending on the combination of the recombinant groups, as shown in formulas (2-1) and (2-2) below, The ring structure that makes up the compound changes. The A' ring, B' ring, and C' ring in each formula are given by the general formula (1 These correspond to ring A, ring B, and ring C in ) respectively.

[0054] [ka]

[0055] The rings A', B', and C' in the above equations (2-1) and (2-2) are the same as those in the general formula (2 To explain it using ), substituent R 1 ~R 11 Adjacent groups among them bond together, forming ring a. , showing an aryl ring or heteroaryl ring formed together with the b ring and c ring (a ring, b ring) Alternatively, it can be described as a fused ring formed by the fusion of another ring structure with a c-ring. Note that this is not shown in the formula. However, there are also compounds in which all of the a, b, and c rings have been transformed into A', B', and C' rings. Yes. Also, as can be seen from equations (2-1) and (2-2) above, for example, the R of ring b. 8 and the R of the c ring 7 , the R of ring b 11 and the R of ring a 1 , the R of the c ring 4 and the R of ring a 3 These are examples of "adjacent" These do not fall under the category of "groups together," and they do not bond. In other words, they are not the same as "adjacent groups." It means adjacent bases on a ring.

[0056] The compounds represented by formulas (2-1) and (2-2) above are, for example, the a-ring (or b-ring or benzene rings (c rings), indole rings, pyrrole rings, benzofuran rings, etc. A' ring (or B' ring or C' ring) formed by the condensation of a ring or a benzothiophene ring. A compound having a fused ring A' (or fused ring B' or fused ring C) formed thereon. ') represents the naphthalene ring, carbazole ring, indole ring, dibenzofuran ring, or It is a dibenzothiophene ring.

[0057] Y in general formula (1) 1 is B, P, P=O, P=S, Al, Ga, As, Si-R Alternatively, it is Ge-R, where R in Si-R and Ge-R is aryl or alkyl. In the case of P=O, P=S, Si-R, or Ge-R, it bonds with the A, B, or C ring. The atoms involved are P, Si, or Ge. 1 These are B, P, P=O, P=S, or Si-R B is preferred, and B is particularly preferred. This explanation is for Y in general formula (2). 1 But it's the same.

[0058] X in general formula (1) 1 and X 2 These are, independently, >O, >NR, >C( -R)2, >S or >Se, where R in >NR may be substituted with an aryl. , optionally substituted heteroaryl, optionally substituted alkyl or substituted It is a cycloalkyl that may be substituted, and R in >C(-R)2 is hydrogen, even if it is substituted. A good aryl or alkyl, and the R and / or the C(-R) of >NR R in 2 may be linked to the B ring and / or C ring by a linking group or a single bond. The linking group is preferably -O-, -S-, or -C(-R)2-. In (-R)2-, R is either hydrogen or alkyl. This explanation is related to X in general formula (2). 1 and X 2 But it's the same.

[0059] Here, in general formula (1), ">R of NR and / or R of ">C(-R)2" The term states that "it is bonded to the A, B, and / or C rings by a linking group or a single bond." The definition is that in general formula (2), "R of NR and / or R of C(-R)2 is -O- The a, b and / or c rings are bonded by -S-, -C(-R)2-, or single bonds. This corresponds to the provision that "they are in agreement."

[0060] This provision is represented by the following formula (2-3-1), X 1 Ya X 2 is a fused ring B' and a fused ring It can be represented by a compound having a ring structure incorporated into C'. That is, for example, general formula (2) For the benzene ring which is the b-ring (or c-ring) in the above, X 1 (or X 2 ) will be incorporated. It is a compound having a B' ring (or C' ring) formed by the condensation of other rings. The resulting fused ring B' (or fused ring C') is, for example, a phenoxazine ring or phenotia. It is a zinc ring or an acridine ring.

[0061] Furthermore, the above provisions are expressed by the following formulas (2-3-2) and (2-3-3), X 1 and / or X 2 It can also be represented by compounds having a ring structure in which is incorporated into the fused ring A'. For example, for the benzene ring which is ring a in general formula (2), X 1 (and / or X 2 It is a compound having an A' ring formed by the condensation of other rings, incorporating the A' ring. The resulting fused ring A' is, for example, a phenoxazine ring, a phenothiazine ring, or an acridi ring. It is a ring.

[0062] [ka]

[0063] Examples of "aryl rings" which are the A, B, and C rings of general formula (1) include, for example, the number of carbon atoms. Examples include aryl rings with 6 to 30 carbon atoms, with aryl rings having 6 to 16 carbon atoms being preferred, and those with 6 to 30 carbon atoms. A 12-carat aryl ring is more preferred, and an aryl ring having 6 to 10 carbon atoms is particularly preferred. This "aryl ring" is defined by the "R" in general formula (2). 1 ~R 11 Among adjacent bases This corresponds to "an aryl ring formed by the bonding of a ring with an a-ring, a-ring, or a-ring," and also to "an aryl ring." (or ring b, ring c) is already composed of a benzene ring with 6 carbon atoms, so it has 5 members The lower limit for the number of carbon atoms is 9, which is the total number of carbon atoms in the fused ring formed by the fusion of two rings.

[0064] Specific examples of "aryl rings" include the monocyclic benzene ring and the bicyclic biphenyl ring. The ring, the condensed bicyclic naphthalene ring, the tricyclic terphenyl ring (m-terphenyl, o-terphenyl, p-terphenyl), a condensed tricyclic system, acenaphthylene ring, fluorine Lenne ring, phenalene ring, phenanthrene ring, condensed tetracyclic triphenylene ring, pyrene Examples include rings, naphthacene rings, and condensed pentacyclic systems such as perylene rings and pentacene rings.

[0065] Examples of heteroaryl rings, which are the A, B, and C rings of general formula (1), include: Examples include heteroaryl rings with 2 to 30 carbon atoms, with heteroaryl rings with 2 to 25 carbon atoms being preferred. More preferably, heteroaryl rings having 2 to 20 carbon atoms are preferred, and heteroaryl rings having 2 to 15 carbon atoms are preferred. A reel ring is more preferred, and a heteroaryl ring having 2 to 10 carbon atoms is particularly preferred. Examples of "heteroaryl rings" include, for example, oxygen, sulfur, and nitrogen in addition to carbon as ring constituent atoms. Examples include heterocycles containing one to five heteroatoms selected from the elements. A "heteroaryl ring" is defined by the general formula (2) "R 1 ~R 11 Among adjacent bases This corresponds to a heteroaryl ring formed by the bonding of two rings together with an a-ring, a-ring, or a-ring. Furthermore, since ring a (or ring b, or ring c) is already composed of a benzene ring with 6 carbon atoms, The lower limit of carbon numbers is 6, which is the total number of carbon atoms in the fused ring formed by the condensation of a 5-membered ring.

[0066] Specific examples of "heteroaryl rings" include, for example, pyrrole rings, oxazole rings, and iso Oxazole ring, thiazole ring, isothiazole ring, imidazole ring, oxadiazole Ring, thiadiazole ring, triazole ring, tetrazol ring, pyrazole ring, pyridine ring, Pyrimidine ring, pyridazine ring, pyrazine ring, triazine ring, indole ring, isoindo 1H-indazole ring, benzimidazole ring, benzoxazole ring, benzoth Azole ring, 1H-benzotriazole ring, quinoline ring, isoquinoline ring, synnoline ring , quinazoline ring, quinoxaline ring, phthalazine ring, naphthyridine ring, purine ring, pteridine phenoxathiine ring, carbazole ring, acridine ring, phenoxathiine ring, phenoxazine ring, phenox Thiazine ring, phenazine ring, indoridine ring, furan ring, benzofuran ring, isobenzof Lan ring, dibenzofuran ring, thiophene ring, benzothiophene ring, dibenzothiophene ring Examples include the furazan ring, oxadiazole ring, and thianthlene ring.

[0067] At least one hydrogen in the above "aryl ring" or "heteroaryl ring" is The substituents of 1 are substituted or unsubstituted "aryl" and substituted or unsubstituted "heteroaryl". "diarylamino", substituted or unsubstituted "diarylamino", substituted or unsubstituted "diheteramino" "arylamino", substituted or unsubstituted "arylheteroarylamino", substituted or unsubstituted The substitution "diarylboryl (the two aryls are linked by a single bond or a linking group)" (Good), substituted or unsubstituted "alkyl", substituted or unsubstituted "alkoxy", and This may be substituted with a substituted or unsubstituted "aryloxy", but this first substitution The aryl and diaryl groups as bases, and the aryl and diarylamino groups as in "aryl" and "heteroaryl". "heteroarylamino" heteroaryl, "arylheteroarylamino" aryl The aryl in "diarylboryl" and the aryl in "aryloxy" Examples of rings include the monovalent group of the aforementioned "aryl ring" or "heteroaryl ring". ru.

[0068] Furthermore, the "alkyl" as the first substituent can be either a straight chain or a branched chain. Examples include linear alkyl groups with 1 to 24 carbon atoms or branched alkyl groups with 3 to 24 carbon atoms. It is possible. C1-C18 alkyl (C3-C18 branched alkyl) is preferred, Alkyl groups with prime numbers 1 to 12 (branched-chain alkyl groups with 3 to 12 carbon atoms) are more preferred, and C1 ~6 alkyl groups (branched alkyl groups with 3 to 6 carbon atoms) are more preferred, and C1 to C4 alkyl groups are also preferred. Lukyl (branched alkyl group with 3-4 carbon atoms) is particularly preferred.

[0069] Specific alkyl groups include methyl, ethyl, n-propyl, isopropyl, and n-butyl. Isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl, neopentyl t-pentyl, n-hexyl, 1-methylpentyl, 4-methyl-2-pentyl, 3, 3-Dimethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl, n-oc Tyl, t-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl n-nonyl, 2,2-dimethylheptyl, 2,6-dimethyl-4-heptyl, 3,5, 5-Trimethylhexyl, n-decyl, n-undecyl, 1-methyldecyl, n-dodecyl n-Tridecyl, 1-Hexylheptyl, n-Tetradecyl, n-Pentadecyl, n Examples include hexadecyl, n-heptadecyl, n-octadecyl, and n-eicosyl. ru.

[0070] Furthermore, as the first substituent, "alkoxy" can be, for example, a linear chain with 1 to 24 carbon atoms. Examples include branched chain alkoxys with 3 to 24 carbon atoms. Also, alkoxys with 1 to 18 carbon atoms ( Branched alkoxys with 3 to 18 carbon atoms are preferred, and alkoxys with 1 to 12 carbon atoms are preferred. A branched alkoxy with 3 to 12 carbon atoms is more preferred, and an alkoxy with 1 to 6 carbon atoms is more preferred. A branched chain alkoxy with 3 to 6 carbon atoms is more preferable, and an alkoxy with 1 to 4 carbon atoms (3 carbon atoms) is even more preferable. ~4 branched chain alkoxys are particularly preferred.

[0071] Specific alkoxys include methoxy, ethoxy, propoxy, isopropoxy, and b Toxy, isobutoxy, s-butoxy, t-butoxy, pentyloxy, hexyloxy Examples include heptyloxy and octyloxy.

[0072] Furthermore, the "aryl" in the first substituent "diarylboryl" is the aforementioned aryl You can quote the explanation of aryl. Also, these two aryls are single bonds or linking groups (for example, >C( -R)2, >O, >S or >NR) may be joined via. Here, >C(- R)2 and >NR's R stands for aryl, heteroaryl, diarylamino, alkyl , cycloalkyl, alkoxy or aryloxy (the above are the first substituents), The first substituent may further be an aryl, heteroaryl, alkyl, or cycloalkyl (or more) The group may also be substituted with a second substituent, and specific examples of these groups include the first substitutions mentioned above. The groups used are aryl, heteroaryl, diarylamino, alkyl, and cycloalkyl. You can cite explanations of alkoxys or aryloxys.

[0073] The first substituent is a substituted or unsubstituted "aryl" or a substituted or unsubstituted "hetero" "aryl", substituted or unsubstituted "diarylamino", substituted or unsubstituted "dihetero" "Arylamino", substituted or unsubstituted "arylheteroarylamino", substituted or Unsubstituted "diarylboryl" (the two aryls are linked by a single bond or a linking group) (may be), substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy, Alternatively, substituted or unsubstituted "aryloxy" is described as substituted or unsubstituted. As such, at least one hydrogen atom in them may be substituted with a second substituent. Examples of this second substituent include aryl, heteroaryl, or alkyl compounds. These specific examples are the monovalent base of the "aryl ring" or "heteroaryl ring" mentioned above. You can also refer to the explanation of "alkyl" as the first substituent. In aryl and heteroaryl substituents, at least one hydrogen atom is present. Aryl groups such as phenyl (specific examples are the groups mentioned above) and alkyl groups such as methyl (specific examples are mentioned above) Structures substituted with the (substituted) group are also included in the category of aryl or heteroaryl as the second substituent. One example is when the second substituent is a carbazolyl group, at least at the 9-position Another hydrogen atom is substituted with an aryl group such as phenyl or an alkyl group such as methyl in a carbazolitic group. The 'L' group is also included in heteroaryl groups as a second substituent.

[0074] R in general formula (2) 1 ~R 11 Aryl, heteroaryl, and diarylamino in aryl, diheteroarylammonium heteroaryl, arylheteroarylammonium Aryl and heteroaryl, diarylboryl, or aryloxy As a ring, it is one of the "aryl rings" or "heteroaryl rings" explained in general formula (1). The basis of the value can be listed. Also, R 1 ~R 11 The alkyl or alkoxy in this context is: In the explanation of general formula (1) above, the first substituents are "alkyl" and "alkoxy". You can refer to the explanation of ". Furthermore, aryl and he as substituents on these groups. The same applies to teloaryl or alkyl groups. Also, R 1 ~R 11 Among adjacent bases In the field where the rings are bonded together to form an aryl ring or heteroaryl ring with the a, b, or c rings The substituents on these rings are heteroaryl, diarylamino, and diheteroaryl arylamino, arylheteroarylamino, diarylboryl (the two aryls are single bonds) (or may be bonded via a linking group), alkyl, alkoxy or aryl oxy The same applies to the cy, and the further substituents aryl, heteroaryl, or alkyl. It is the same.

[0075] Specifically, the luminescence is caused by the steric hindrance, electron-donating, and electron-withdrawing properties of the structure of the first substituent. The wavelength can be adjusted, preferably a group represented by the following structural formula, and more preferably methyl, t-butyl, phenyl, o-tolyl, p-tolyl, 2,4-xylyl, 2, 5-Xylyl, 2,6-Xylyl, 2,4,6-Mesityl, Diphenylamino, Di-p- Tolylamino, bis(p-(t-butyl)phenyl)amino, carbazolyl, 3,6-di These are methylcarbazolyl, 3,6-di-t-butylcarbazolyl, and phenoxy, More preferably, methyl, t-butyl, phenyl, o-tolyl, 2,6-xylyl, 2, 4,6-Mesityl, Diphenylamino, Di-p-Tolylamino, Bis(p-(t-butyl )phenyl)amino, carbazolyl, 3,6-dimethylcarbazol and 3,6-di- This is t-butylcarbazolyl. From the standpoint of ease of synthesis, a compound with greater steric hindrance is preferred. Preferably for synthesis, specifically t-butyl, o-tolyl, p-tolyl, 2,4 -Xylyl, 2,5-Xylyl, 2,6-Xylyl, 2,4,6-Mesityl, Di-p-T Lylamino, bis(p-(t-butyl)phenyl)amino, 3,6-dimethylcarbazoli Lu and 3,6-di-t-butylcarbazol are preferred.

[0076] In the structural formula below, "Me" represents methyl and "tBu" represents t-butyl. [ka] [Chemical] [Chemical] [Chemical] [Chemical]

[0077] Y in the general formula (1) 1 The R in Si-R and Ge-R is aryl or alkyl, and examples of such aryl and alkyl include the groups described above. Particularly, aryl having 6 to 10 carbon atoms (such as phenyl, naphthyl, etc.), alkyl having 1 to 4 carbon atoms (such as methyl, ethyl, etc.) are preferred. This explanation also applies to Y in the general formula (2). 1 This is the same for Y in the general formula (2).

[0078] X in the general formula (1) 1 and X 2 The R in >N-R in is aryl, heteroaryl, alkyl or cycloalkyl which may be substituted with the above-mentioned second substituent, and at least one hydrogen in the aryl, heteroaryl, alkyl or cycloalkyl may be substituted with, for example, alkyl. Examples of such aryl, heteroaryl and alkyl include the groups described above. Also, for cycloalkyl, the description to be described later can be cited. Particularly, aryl having 6 to 10 carbon atoms (such as phenyl, naphthyl, etc.), heteroaryl having 2 to 15 carbon atoms (such as carbazolyl, etc.), alkyl having 1 to 4 carbon atoms ( such as methyl, ethyl, etc.) are preferred. This explanation also applies to X in the general formula (2). heteroaryl having 2 to 15 carbon atoms (such as carbazolyl, etc.), alkyl having 1 to 4 carbon atoms ( such as methyl, ethyl, etc.) are preferred. This explanation also applies to X and X in the general formula (2). 1 and X 2 ​​​It is the same as well.

[0079] X in the general formula (1) 1 and X 2 For >C(-R)2 in, R is hydrogen, aryl or alkyl which may be substituted with the above-mentioned second substituent, and at least one hydrogen in the aryl may be substituted with, for example, alkyl. Examples of this aryl and alkyl include the groups described above. Particularly preferred are aryl having 6 to 10 carbon atoms (such as phenyl, naphthyl, etc.) and alkyl having 1 to 4 carbon atoms (such as methyl, ethyl, etc.). This explanation also applies to X in the general formula (2) and X 1 and X 2 It is the same as well.

[0080] R of "-C(-R)2-", which is the linking group in the general formula (1), is hydrogen or alkyl, and examples of this alkyl include the groups described above. Particularly preferred is alkyl having 1 to 4 carbon atoms such as methyl, ethyl, etc.). This explanation also applies to the linking group "-C(-R)2-" in the general formula (2) It is the same as well.

[0081] In addition, the present invention relates to a multimer of a polycyclic aromatic compound having a plurality of unit structures represented by the general formula (1), preferably a multimer of a polycyclic aromatic compound having a plurality of unit structures represented by the general formula (2). The multimer is preferably a dimer to hexamer, more preferably a dimer to trimer, and particularly preferably a dimer. The multimer may be in a form having a plurality of the above unit structures in one compound. For example, in addition to a form in which the above unit structures are linked by a linking group such as a single bond, an alkylene group having 1 to 3 carbon atoms, a phenylene group, a naphthylene group, etc., any ring (ring A, ring B or ring C, ring a, ring b or ring c) contained in the above unit structure is shared by a plurality of unit structures It is okay, and in addition to the form in which the above unit structures are linked by a linking group such as a single bond, an alkylene group having 1 to 3 carbon atoms, a phenylene group, a naphthylene group, etc., any ring (ring A, ring B or ring C, ring a, ring b or ring c) contained in the above unit structure is shared by a plurality of unit structures It may be in a bonded form, and any ring (ring A, ring B or The rings (C, a, b, or c) may be bonded together by condensation. .

[0082] Examples of such polymers include those shown in equations (2-4), (2-4-1), and (2- 4-2) Multimerization represented by equations (2-5-1) to (2-5-4) or (2-6) A compound is an example. The polymer compound represented by the following formula (2-4) is explained by general formula (2). Therefore, by sharing the benzene ring which is the a-ring, multiple units represented by general formula (2) are formed. It is a polymer compound that has the structure within a single compound. It is also represented by the following formula (2-4-1). The resulting polymeric compound, as explained by general formula (2), shares a benzene ring, which is the α ring. Therefore, a polymer compound having two unit structures represented by general formula (2) in a single compound. Furthermore, the polymer compound represented by the following formula (2-4-2) is explained by general formula (2). Then, by sharing the benzene ring which is the α ring, three units represented by general formula (2) are formed. It is a polymer compound that has the structure within a single compound. Also, the following formulas (2-5-1) to formula ( The polymer compound represented by 2-5-4) can be described by general formula (2) as having a b-ring (or c-ring). ) by sharing a benzene ring, multiple unit structures represented by general formula (2) It is a polymer compound found in one compound. Furthermore, the polymerization represented by the following formula (2-6) Compounds, as explained by general formula (2), are formed, for example, in a b-ring (or a-ring, c-ring) of a certain unit structure. A benzene ring condenses with a benzene ring that is a b-ring (or a-ring, c-ring) of a certain unit structure. In this way, a polymer having multiple unit structures represented by general formula (2) in a single compound It is a compound.

[0083] [ka]

[0084] The polymeric compounds are represented by formula (2-4), formula (2-4-1), or formula (2-4-2). In a multi-quantification form, one of equations (2-5-1) to (2-5-4) or equation (2-6) It may also be a polymer formed by a combination of the expressed multimerized forms, as shown in equations (2-5-1) to equation (2-5-1). The multi-quantification form expressed by any of (2-5-4) and the multi-quantification form expressed by equation (2-6) It may also be a polymer formed by a combination of morphologies, such as formula (2-4), formula (2-4-1), or The multi-quantified form expressed by equation (2-4-2) and equations (2-5-1) to (2-5-4) A combination of the multi-quantification form expressed by either of the above and the multi-quantification form expressed by equation (2-6) It may also be a polymer.

[0085] Furthermore, the chemistry of polycyclic aromatic compounds represented by general formula (1) or (2) and their polymers. The hydrogen in the structure may consist of all or part of deuterium, cyanohydrogen, or halogen. For example, in formula (1), ring A, ring B, and ring C (rings A to C are aryl rings or heteroaryl rings) (Lille ring), substituents on rings A-C, Y 1 When R is Si-R or Ge-R, then R(=A Lukil, Ariel), and X 1 and X 2 When >NR or >C(-R)2 The hydrogen atoms in the R (=alkyl, aryl) are substituted with deuterium, cyano, or halogen. However, among these, all or some of the hydrogen in aryl and heteroaryl forms heavy water Examples include embodiments substituted with fluorine, cyano or halogen. Halogens include fluorine, chlorine, It is bromine or iodine, preferably fluorine, chlorine or bromine, more preferably fluorine It is chlorine.

[0086] Furthermore, the polycyclic aromatic compound and its polymer according to the present invention can be used as a material for organic devices. Organic devices can be used, for example, organic electroluminescent devices and organic field-effect devices. Examples include transistors and organic thin-film solar cells. In particular, organic electroluminescent devices Therefore, as the dopant material for the light-emitting layer, Y 1 B, X 1 and X 2 The compound is >NR Object, Y 1 B, X 1 ga>O,X 2 Compounds where >NR, Y 1 B, X 1 and X 2 but A compound containing >O is preferred, and as the host material for the light-emitting layer, Y 1 B, X 1 ga>O,X 2 Compounds where >NR, Y 1 B, X 1 and X 2 Compounds in which >O are preferred, As a transport material, Y 1 B, X 1 and X 2 Compounds where >O, Y 1 P=O, X 1 and X 2 Compounds in which >O are preferably used.

[0087] Furthermore, the chemistry of polycyclic aromatic compounds represented by general formula (1) or (2) and their polymers. At least one hydrogen in the structure is cycloalkyl-substituted, and all or some of the hydrogens are substituted. The hydrogen atom may be a cycloalkyl group.

[0088] Other forms of cycloalkyl substitution include polycyclic aromatics represented by general formula (1) or (2). Fragrance compounds and their polymers, for example, cycloalkyl-substituted diarylamino groups , cycloalkyl-substituted carbazolyl group or cycloalkyl-substituted benzocal Examples of substitution with a bazolyl group include those described in "1st" above. The groups described as "substituted groups" include diarylamino groups, carbazolyl groups, and As for the substitution forms of cycloalkyl groups on the benzocarbazolyl group, these groups have ali Examples include cases where some or all of the hydrogen atoms in a benzene ring or a cycloalkyl group are substituted with cycloalkyl groups. It is possible.

[0089] Furthermore, more specific examples include polycyclic aromatic compounds represented by general formula (2) and so R in the polymer 2 However, cycloalkyl-substituted diarylamino groups or cycloalkyl An example is a carbazolyl group substituted with a lukyl group.

[0090] As an example, a polycyclic aromatic compound represented by the following general formula (2-A), or the following general Examples include polycyclic aromatic compounds having multiple structures represented by formula (2-A). is a cycloalkyl group, and n is an integer from 1 to 5 (preferably 1) independently, and the structure The definitions of each sign in the formula are the same as the definitions of each sign in general formula (2). [ka]

[0091] Furthermore, specific examples of the cycloalkyl-substituted polycyclic aromatic compounds and their polymers according to the present invention. One example is when at least one hydrogen atom in one or more aromatic rings in a compound is 1 Examples include compounds substituted with one or more cycloalkyl groups, for example, one or two cycloalkyl groups. Examples include compounds substituted with chloroalkyl groups.

[0092] Specifically, the compounds represented by the following formulas (1-1-Cy) to (1-4401-Cy). The following are examples. In the following equations, n can be independently 0 to 2 (however, it is not possible for all n to be 0). (and not), preferably 1. Note that "Cy" in the following structural formula is a cycloalkyl group. "OPh" indicates a phenoxy group, and "Me" indicates a methyl group.

[0093] [ka]

[0094] [ka]

[0095] [ka]

[0096] [ka]

[0097] [ka]

[0098] [ka]

[0099] [ka]

[0100] [ka]

[0101] [ka]

[0102] Cycloalkyls include cycloalkyls with 3 to 24 carbon atoms and cycloalkyls with 3 to 20 carbon atoms. Alkyl, cycloalkyl with 3-16 carbon atoms, cycloalkyl with 3-14 carbon atoms, carbon number 5-10 cycloalkyl groups, 5-8 cycloalkyl groups, 5-6 cycloalkyl groups Examples include cycloalkyl groups with 5 carbon atoms.

[0103] Examples of cycloalkyl groups include cyclopropyl, cyclobutyl, and cyclopentyl , cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, And these alkyl (especially methyl) substituted derivatives having 1 to 4 carbon atoms, norborneyl, bicyl Clo[1.0.1]butyl, Bicyclo[1.1.1]pentyl, Bicyclo[2.0.1] Pentyl, bicyclo[1.2.1]hexyl, bicyclo[3.0.1]hexyl, bicyclo [2.1.2]heptyl, bicyclo[2.2.2]octyl, adamantyl, diamane Examples include til, decahydronaphthalenyl, and decahydroazurenyl.

[0104] More specific examples of the cycloalkyl-substituted polycyclic aromatic compounds of the present invention include, Examples of compounds represented by the structural formulas below include: In the structural formulas below, "D" represents deuterium, and "M" represents deuterium. "e" indicates a methyl group, "tBu" indicates a t-butyl group, and "Ph" indicates a phenyl group.

[0105]

change

[0106]

change

[0107]

change

[0108]

change

[0109]

change

[0110]

change

[0111]

change

[0112]

change

[0113]

change

[0114]

change

[0115]

change

[0116] [ka]

[0117] [ka]

[0118] [ka]

[0119] [ka]

[0120] [ka]

[0121] [ka]

[0122] [ka]

[0123] [ka]

[0124] [ka]

[0125] The polycyclic aromatic compound represented by general formula (1) according to the present invention and its polymers are provided for these purposes. A polymer compound obtained by polymerizing a reactive compound with a reactive substituent substituted as a monomer ( The monomer for obtaining the polymer compound has a polymerizable substituent, or the polymer A polymer crosslinked polymer obtained by further crosslinking the subcomponents (the polymerization process for obtaining this polymer crosslinked polymer) The compound has a crosslinkable substituent, or the main chain polymer is reacted with the reactive compound. pendant-type polymer compound (the reactivity required to obtain this pendant-type polymer compound) The compound has reactive substituents, or the pendant-type polymer compound is further crosslinked. A pendant-type polymer crosslinked material (the pendant used to obtain this pendant-type polymer crosslinked material) Even if the polymer compound has crosslinkable substituents, it can be used as a material for organic devices, for example, Materials for organic field-effect light-emitting devices, materials for organic field-effect transistors, or materials for organic thin-film solar cells It can be used as a food ingredient.

[0126] The above-mentioned reactive substituents (the polymerizable substituent, the crosslinkable substituent, and pendant type) (Includes reactive substituents for obtaining polymers, and hereafter also simply referred to as "reactive substituents") This refers to substituents that can increase the molecular weight of the above polycyclic aromatic compound or its polymer, and thus Substituents that can further crosslink the obtained polymer compound, and pendant reaction of the main chain polymer While there are no particular limitations as long as the substituent is suitable, substituents with the following structures are preferred. Each structural formula The asterisk (*) inside indicates the bond location. [ka]

[0127] L is independent of each other, a single bond, -O-, -S-, >C=O, -OC(=O)-, Alkylenes with 1 to 12 carbon atoms, oxyalkylenes with 1 to 12 carbon atoms, and C1-12 It is a polyoxyalkylene. Among the substituents above, formula (XLS-1), formula (XLS- 2) Formula (XLS-3), Formula (XLS-9), Formula (XLS-10), or Formula (XLS-1 7) The group represented by formula (XLS-1), formula (XLS-3), or formula (XLS- The group represented by 17) is more preferred.

[0128] Such polymer compounds, polymer crosslinks, pendant-type polymer compounds and pendants Detailed information on the uses of cross-linked polymer compounds (hereinafter also simply referred to as "polymer compounds and cross-linked polymer compounds") Details will be discussed later.

[0129] 2. Method for producing cycloalkyl-substituted polycyclic aromatic compounds and their polymers Polycyclic aromatic compounds represented by general formulas (1) and (2), and their polymers, are basically, First, the A ring (a ring), B ring (b ring), and C ring (c ring) are bonded together by a bonding group (X 1 Ya X 2 (including the base) An intermediate is produced by bonding the rings (first reaction), and then the A ring (a ring) and the B ring (b ring) are bonded together. ) and the C ring (c ring) are bonded by a Y group 1 The final product is produced by bonding with a group containing ( ). This is possible (second reaction). In the first reaction, for example, in the case of an etherification reaction, nucleophilic substitution can occur. Common reactions such as the Ullmann reaction can be used, and for amination reactions, the Buchwald reaction can be used. - Common reactions such as the Hartwig reaction can be used. Also, in the second reaction, tandem The hetero-Friedel-Crafts reaction (a series of electrophilic aromatic substitution reactions, hereafter the same) can be used. Furthermore, at some point in these reaction steps, cycloalkyl-substituted raw materials may be used, or By adding a step to introduce a cycloalkyl group, the desired position can be changed to a cycloalkyl group. The modified compound of the present invention can be produced.

[0130] The second reaction is as shown in schemes (1) and (2) below: ring A (a-ring), ring B (b-ring) and Y which connects the C ring (c ring) 1 This is a reaction that introduces Y 1 is a boron atom, X 1 and X 2 The case where X is an oxygen atom is shown below. First, X 1 and X 2 The hydrogen atom between them is n- Orthometallation with butyllithium, sec-butyllithium, or t-butyllithium, etc. Next, boron trichloride or boron tribromide is added to perform lithium-boron metal exchange. After that, by adding a Brønsted base such as N,N-diisopropylethylamine, The target product can be obtained by carrying out a tandem Boraf Friedelcrafts reaction. Second reaction odor In order to accelerate the reaction, a Lewis acid such as aluminum trichloride may be added. The structure in schemes (1) and (2), and further in schemes (3) to (28) thereafter. The definition of the sign in the formula is the same as the definition described above.

[0131] [ka] [ka]

[0132] Furthermore, schemes (1) and (2) above are polycyclic aromaticizations represented by general formulas (1) and (2). The method for producing the compound is mainly shown, but the polymer consists of multiple A rings (a rings) and B rings. It can be manufactured using an intermediate having a (b-ring) and a C-ring (c-ring). Details This will be explained in the following schemes (3) to (5). In this case, the butyllithium and other test materials used will be... The desired substance can be obtained by doubling or tripling the amount of the drug.

[0133] [ka] [ka] [ka]

[0134] In the above scheme, lithium was introduced to the desired location by orthometallation, As shown in schemes (6) and (7) below, introduce bromine atoms, etc., at the desired location for lithium. Furthermore, lithium can be introduced to the desired position by halogen-metal replacement.

[0135] [ka] [ka]

[0136] Furthermore, the method for producing the polymer described in scheme (3) is also described in scheme (6) above. As shown in (7), introduce halogens such as bromine or chlorine atoms at the position where you want to introduce lithium. Furthermore, lithium can be introduced to the desired position by halogen-metal replacement (below) See schemes (8), (9), and (10).

[0137] [ka] [ka] [ka]

[0138] This method allows for the formation of the target product even in cases where orthometalation is not possible due to the influence of substituents. It is useful because it can be synthesized.

[0139] By appropriately selecting the above synthesis method and the raw materials used, the desired position can be cyclo Alkyl-substituted, having substituents at desired positions, Y 1 X is a boron atom. 1 and X 2 is acid It is possible to synthesize polycyclic aromatic compounds, which are elementary atoms, and their polymers.

[0140] Next, as an example, Y 1 X is a boron atom. 1 and X 2 The following scheme applies when it is a nitrogen atom ( As shown in 11) and (12). X 1 and X 2 As with the case where is an oxygen atom, first X 1 and X 2 The hydrogen atoms in between are orthometalated with n-butyllithium, etc. Then, tribromide After adding boron and performing lithium-boron metal exchange, N,N-diisopropylethyl By adding a Brønsted base such as an amine, the tandem bora-Friedel-Crafts reaction can be performed. Then, the target product can be obtained. Here, aluminum trichloride, etc. are used to promote the reaction. A Lewis acid may be added. Also, at some point in these reaction steps, a cycloalkyl-substituted compound may be added. By using specially selected raw materials or by adding a process to introduce cycloalkyl groups, the desired The compounds of the present invention, in which the positions are cycloalkyl-substituted, can be produced.

[0141] [ka] [ka]

[0142] Also, Y 1 X is a boron atom. 1 and X 2 The same applies to the polymer when nitrogen is the atom. As in schemes (6) and (7), bromine atoms, chlorine atoms, etc. can be introduced at the desired location. By introducing halogens and by replacing the halogen-metal element, lithium can also be introduced to the desired position. This is possible (see schemes (13), (14), and (15) below).

[0143] [ka] [ka] [ka]

[0144] Next, as an example, Y 1 is a phosphorus sulfide, phosphorus oxide, or phosphorus atom, and X 1 oh Call X 2 The case where is an oxygen atom is shown in the following schemes (16) to (19). First, X 1 and X 2 The hydrogen atoms in between are orthometalated with n-butyllithium, etc. Next Next, phosphorus trichloride and sulfur are added in that order, and finally a Lewis acid such as aluminum trichloride and N By adding a Brønsted base such as N-diisopropylethylamine, tandem heating is achieved. The Sphafridel-Crafts reaction is carried out, Y 1 It is possible to obtain a compound in which the phosphorus sulfide is obtained. Furthermore, the obtained phosphorus sulfide compound can be treated with m-chloroperbenzoic acid (m-CPBA). By processing Y1 A compound in which phosphorus oxide can be obtained, and triethylphosphorus By processing with Y 1 Compounds in which the atom is a phosphorus atom can be obtained. At some point in the reaction process, cycloalkyl-substituted starting materials are used, or cycloalkyl groups are introduced. By adding a step to the process, the desired position can be substituted with a cycloalkyl compound, thus fulfilling the present invention. It is possible to manufacture a compound.

[0145] [ka] [ka] [ka] [ka]

[0146] Also, Y 1 is a phosphorus sulfide, X 1 and X 2 Even for the polymer when it is an oxygen atom, As in schemes (6) and (7) above, bromine atoms or chlorine atoms can be introduced at the desired location to introduce lithium. By introducing halogens, lithium can also be introduced to the desired position through halogen-metal replacement. This is possible (see schemes (20), (21), and (22) below). Also, in this way Y was created by doing this. 1 is phosphorus sulfide, X 1 and X 2 The polymer when it is an oxygen atom is also as described above. As shown in schemes (18) and (19), m-chloroperbenzoic acid (m-CPBA) By processing with Y 1 A compound in which phosphorus oxide is obtained can be obtained, and triethylphosphorus By processing with fins, Y 1 A compound in which the atom is a phosphorus atom can be obtained.

[0147] [ka] [ka] [ka]

[0148] Here, Y 1 However, B, P, P=O or P=S, and X 1 and X 2 O or N An example of R is given, but by appropriately changing the raw materials, Y can be used. 1 However, Al, Ga, As, Si -R or Ge-R, or X 1 and X 2 Compounds in which S can also be synthesized. ru.

[0149] Specific examples of solvents used in the above reactions include t-butylbenzene and xylene.

[0150] Furthermore, in general formula (2), the substituents R of the a, b, and c rings 1 ~R 11 Among the adjacent The groups bond together to form an aryl ring or heteroaryl ring with the a, b, or c ring. It may be formed, and at least one hydrogen in the formed ring is aryl or hetero It may be substituted with an aryl group. Therefore, the polycyclic aromatic compound represented by general formula (2) The substance is determined by the relative bonding configuration of substituents in the a, b, and c rings, according to the following scheme ( As shown in formulas (2-1) and (2-2) of 23) and (24), the compound is composed of The ring structure changes. These compounds are intermediates shown in schemes (23) and (24) below. It can be synthesized by applying the synthesis methods shown in schemes (1) to (19) above. Furthermore, at some point in these reaction steps, cycloalkyl-substituted raw materials may be used, or By adding a step to introduce a cycloalkyl group, the desired position can be changed to a cycloalkyl group. The modified compound of the present invention can be produced.

[0151] [ka] [ka]

[0152] In formulas (2-1) and (2-2) above, the A', B', and C' rings are substituents R 1 ~R 11 Adjacent groups bond together to form rings a, b, and c, respectively. This shows an aryl ring or heteroaryl ring (where another ring structure is contracted to the a, b, or c ring). (It can also be described as a fused ring formed by the combination of rings.) Although not shown in the formula, rings a, b and c Some compounds have all of their rings transformed into A', B', and C' rings.

[0153] Furthermore, in general formula (2), the R of ">NR and / or the R of ">C(-R)2" -O-, -S-, -C(-R)2- or single bonds connect the a-ring, b-ring and / or c The provision that it is "bonded to a ring" is expressed by equation (2-3-1) in scheme (25) below. X 1 Ya X 2 Compounds having a ring structure in which the fused ring B' and fused ring C' are incorporated, or formula ( X, which can be expressed in equations (2-3-2) or (2-3-3). 1 Ya X2 The ring incorporated into the fused ring A' These compounds can be represented by compounds having a structure. These compounds are shown in the scheme (25) below. The intermediate shown can be synthesized by applying the synthesis methods shown in schemes (1) to (19) above. This can be done. Also, at some point in these reaction steps, cycloalkyl-substituted raw materials can be used. By adding a step to introduce a cycloalkyl group, the desired position can be changed to a cycloalkyl group. The compound of the present invention can be produced by substituted with lucyl.

[0154] [ka]

[0155] Furthermore, in the synthesis methods of schemes (1) to (17) and (20) to (25) above, trichloride Before adding boron or boron tribromide, X 1 and X 2 Hydrogen atoms (or halogen atoms) between them By orthometalating ) with butyllithium, etc., tandem hetero-Friedelcrafts Although an example of the reaction was shown, it is possible to perform trichloride without orthometallation using butyllithium, etc. The reaction can also be accelerated by adding boron, boron tribromide, or other compounds.

[0156] Also, Y 1 If it is phosphorus-based, as shown in schemes (26) and (27) below, X 1 and X 2 (In the formula below, the hydrogen atoms between O are n-butyllithium and sec-butyllithium) Alternatively, orthometallation with t-butyllithium, etc., and then bis-diethylaminochlorophosphate After adding sphingo and performing lithium-phosphorus metal exchange, Lewis plates such as aluminum trichloride are added. By adding acid, the tandem phosphine-Friedel-Crafts reaction can be carried out to obtain the desired product. Yes, it is possible. This reaction method is also described in International Publication No. 2010 / 104047 (for example, page 27). It is stated. Also, at some point in these reaction steps, the cycloalkyl-substituted starting material is used. By using or adding a step to introduce a cycloalkyl group, the desired position can be achieved. The compounds of the present invention, which are substituted with rhalkyl compounds, can be produced.

[0157] [ka] [ka]

[0158] Furthermore, in schemes (26) and (27) above, butyllithium and other orthometals are also used. By using two or three times the molar amount of the chemical reagent relative to the molar amount of intermediate 1, the polymer compound can be produced. It can be synthesized. Also, bromine can be introduced in advance at the location where you want to introduce metals such as lithium. By introducing halogens such as chlorine atoms and performing halogen-metal exchange, the desired position can be achieved. Hemetal can be introduced.

[0159] For other polycyclic aromatic compounds represented by general formula (2-A), see scheme (2) below. As shown in 8), a cycloalkyl-substituted intermediate is synthesized and then cyclized to obtain the desired result. Polycyclic aromatic compounds can be synthesized in which the position is substituted with a cycloalkyl group. Scheme (28 In formula (2), X represents a halogen or hydrogen, and the definitions of the other signs are the same as the definitions of the signs in formula (2). It is the same as righteousness.

[0160] [ka]

[0161] The intermediates before cyclization in scheme (28) are also synthesized using the method shown in scheme (1), etc. This is possible, namely the Buchwald-Hartwig reaction and the Suzuki coupling reaction. The reaction, or etherification reaction such as nucleophilic substitution or Ullmann reaction, is combined as appropriate. By combining these reactions, intermediates having the desired substituents can be synthesized. In this process, commercially available raw materials can be used as cycloalkyl-substituted precursors. .

[0162] Compounds of general formula (2-A) having a cycloalkyl-substituted diphenylamino group are, For example, it can also be synthesized by the following method: namely, cycloalkyl-substituted bromobenzene and Aniline trihalides are reacted with amination reactions such as the Buchwald-Hartwig reaction. After introducing a cycloalkyl-substituted diphenylamino group by the response, X 1 , X 2 is N If it is -R, an amination reaction such as the Buchwald-Hartwig reaction will occur. X 1 , X 2 If O, intermediate (M-3) is obtained by etherification using phenol. This is then induced, and subsequently, a metalling reagent such as butyllithium is applied to the transmolecular structure. After tarrification, the mixture is treated with a boron halide such as boron tribromide, followed by diethylisoprazole. Tandem borage by applying a Brønsted base such as lopyruamine Compounds of general formula (2-A) can be synthesized by the Lucrafts reaction. The reaction can also be applied to other cycloalkyl-substituted compounds.

[0163] The orthometalation reagent used in the above schemes (1) to (28) is methyl Lithium, n-butyllithium, sec-butyllithium, t-butyllithium, etc. Lithium, lithium diisopropylamide, lithium tetramethylpiperidide, lith Organic alkali compounds such as potassium hexamethyldisilazide and potassium hexamethyldisilazide Items can be listed.

[0164] Note that Metal-Y used in schemes (1) to (28) above. 1 As a metal exchange reagent , Y 1 trifluoride, Y 1 trichloride, Y 1 Tribromide of Y 1 Y such as triiodide 1 of Halides, such as CIPN(NEt2)2, and Y 1 Amination halogens, Y 1 Al Coxylate, Y 1 Examples include aryl oxy compounds.

[0165] The Brønsted bases used in the above schemes (1) to (28) are N,N -Diisopropylethylamine, Triethylamine, 2,2,6,6-Tetramethylpiper Lysine, 1,2,2,6,6-pentamethylpiperidine, N,N-dimethylaniline, N N-dimethyltoluidine, 2,6-lutidine, sodium tetraphenylborate, tetra Potassium laphenylborate, triphenylborane, tetraphenylsilane, Ar4BNa Examples include Ar4BK, Ar3B, and Ar4Si (where Ar is an aryl group such as phenyl). It can be done.

[0166] The Lewis acids used in the above schemes (1) to (28) are AlCl3 and AlBr3. , AlF3, BF3·OEt2, BCl3, BBr3, GaCl3, GaBr3, InC l3, InBr3, In(OTf)3, SnCl4, SnBr4, AgOTf, ScCl 3, Sc(OTf)3, ZnCl2, ZnBr2, Zn(OTf)2, MgCl2, Mg Br2, Mg(OTf)2, LiOTf, NaOTf, KOTf, Me3SiOTf, C u(OTf)2, CuCl2, YCl3, Y(OTf)3, TiCl4, TiBr4, Z Examples include rCl4, ZrBr4, FeCl3, FeBr3, CoCl3, and CoBr3. It can be done.

[0167] In the above schemes (1) to (28), the promotion of the tandem hetero-Friedel-Crafts reaction A Brønsted base or Lewis acid may be used for this purpose. However, Y 1 trifluoride , Y 1 trichloride, Y 1 Tribromide of Y 1 Y such as triiodide 1 Using the halogenated compounds If this occurs, as the aromatic electrophilic substitution reaction progresses, hydrogen fluoride, hydrogen chloride, hydrogen bromide, and yogurt will be produced. Since acids such as hydrogen citrate are produced, the use of Brønsted bases to capture the acids is effective. Yes. On the other hand, Y 1 Amination halogens, Y 1 When an alkoxy compound is used, the aroma As group electrophilic substitution reactions proceed, amines and alcohols are produced, and therefore in many cases, Brønsted bases are not necessary, but they have low leaving ability for amino and alkoxy groups. Therefore, the use of Lewis acids to promote their elimination is effective.

[0168] Furthermore, the polycyclic aromatic compounds and their polymers of the present invention contain at least some hydrogen atoms that are heavy water. Compounds substituted with elements or cyano compounds, or compounds substituted with halogens such as fluorine and chlorine While substances are included, such compounds can undergo deuteration, cyanation, or fluorination at the desired position. Alternatively, it can be synthesized in the same manner as described above by using chlorinated raw materials.

[0169] 3. Organic devices The cycloalkyl-substituted polycyclic aromatic compound according to the present invention is used as a material for organic devices. It can be used as an organic device, for example, an organic electroluminescent device, an organic electroluminescent device. Examples include transistors and organic thin-film solar cells.

[0170] 3-1. Organic electroluminescent element The organic EL element according to this embodiment will be described in detail below with reference to the drawings. Figure 1 This is a schematic cross-sectional view showing an organic EL element according to this embodiment.

[0171] <Structure of Organic Field-Emitting Light> The organic EL element 100 shown in Figure 1 consists of a substrate 101 and an anode provided on the substrate 101. 102, a hole injection layer 103 provided on the anode 102, and a hole injection layer 103 provided on the hole injection layer 103 A hole transport layer 104 is provided, and a light-emitting layer 105 is provided on the hole transport layer 104, and light emission An electron transport layer 106 provided on top of layer 105, and an electron transport layer 106 provided on top of electron transport layer 106 It has an injection layer 107 and a cathode 108 provided on the electron injection layer 107.

[0172] Furthermore, the organic EL element 100 can be manufactured in the reverse order, for example, using substrate 101 and substrate 10 A cathode 108 provided on 1, an electron injection layer 107 provided on the cathode 108, and electron An electron transport layer 106 provided on top of the injection layer 107, and an electron transport layer 106 provided on top of the electron transport layer 106 A light-emitting layer 105, a hole transport layer 104 provided on the light-emitting layer 105, and a hole transport layer 104 A hole injection layer 103 provided on top of and an anode 102 provided on top of the hole injection layer 103 A configuration having the following characteristics is also possible.

[0173] Not all of the above layers are necessarily required; the minimum constituent unit consists of the anode 102 and the light-emitting layer. The structure consists of 105 and cathode 108, with a hole injection layer 103, a hole transport layer 104, and electron The transport layer 106 and the electron injection layer 107 are optional layers. Each layer may consist of a single layer or multiple layers.

[0174] The configuration of the layers constituting the organic EL element is as described above: "substrate / anodote / hole injection layer / hole In addition to the configuration of "transport layer / light-emitting layer / electron transport layer / electron injection layer / cathode", there is also "substrate / anode / positive Pore ​​transport layer / Emitting layer / Electron transport layer / Electron injection layer / Cathode, Substrate / Anode / Hole injection layer / Emitting Layer / Electron transport layer / Electron injection layer / Cathode, Substrate / Anode / Hole injection layer / Hole transport layer / Emitting layer / Electron injection layer / Cathode", "Substrate / Anode / Hole injection layer / Hole transport layer / Emitting layer / Electron transport layer / " Cathode, Substrate / Anode / Emitting Layer / Electron Transport Layer / Electron Injection Layer / Cathode, Substrate / Anode / Hole Transport layer / emissive layer / electron injection layer / cathode, substrate / anode / hole transport layer / emissive layer / electron transport layer / cathode", "substrate / anode / hole injection layer / emissive layer / electron injection layer / cathode", "substrate / anode / positive "Pore injection layer / light-emitting layer / electron transport layer / cathode", "Substrate / anode / light-emitting layer / electron transport layer / cathode", The configuration may also consist of "substrate / anode / light-emitting layer / electron injection layer / cathode".

[0175] <Substrates for organic electroluminescent devices> The substrate 101 is a support for the organic EL element 100, and is typically made of quartz, glass, metal, or plastic. Materials such as plastic are used. The substrate 101 can be in the form of a plate, film, or sheet depending on the purpose. Formed in a t shape, for example, glass plate, metal plate, metal foil, plastic film, plastic Sheets such as glass and polyester / polymetallic are used. A transparent synthetic resin sheet such as rilate, polycarbonate, or polysulfone is preferred. For lath substrates, soda-lime glass or alkali-free glass are used, and the thickness It only needs to be thick enough to maintain mechanical strength, for example, 0.2 mm or more. i. The upper limit of the thickness is, for example, 2 mm or less, preferably 1 mm or less. glass Regarding the material, it is better to use alkali-free glass as it has fewer ions leached from the glass. While this is preferable, soda-lime glass with a barrier coating such as SiO2 is also commercially available. Therefore, this can be used. In addition, the substrate 101 is designed to enhance gas barrier properties. Furthermore, a gas barrier film such as a dense silicon oxide film may be provided on at least one side, and in particular, gas When using a board, film, or sheet made of synthetic resin with low barrier properties as the substrate 101. It is preferable to provide a gas barrier film.

[0176] <Anode in an organic electroluminescent element> The anode 102 plays the role of injecting holes into the light-emitting layer 105. If a hole injection layer 103 and / or a hole transport layer 104 are provided between layer 105 In this case, holes will be injected into the light-emitting layer 105 via these.

[0177] Materials that can form the anode 102 include inorganic compounds and organic compounds. Examples of compounds include metals (aluminum, gold, silver, nickel, palladium, chromium). (etc.), metal oxides (indium oxide, tin oxide, indium-tin oxide (I TO), indium zinc oxide (IZO), metal halides (copper iodide, etc.), Examples include copper sulfide, carbon black, ITO glass, and NESA glass. Organic compounds and For example, polythiophenes such as poly(3-methylthiophene), polypyrrole, Examples include conductive polymers such as polyaniline. Other examples include those used as anodes in organic EL elements. It can be appropriately selected and used from among the substances currently in use.

[0178] The resistance of the transparent electrode is not limited, as long as it can supply enough current for the light-emitting element to emit light. However, from the standpoint of the power consumption of the light-emitting element, low resistance is desirable. For example, 300Ω / □The following ITO substrates will function as element electrodes, but currently, substrates with an impedance of approximately 10Ω / □ are available. Since it is also possible to supply such as, for example, 100~5Ω / □, preferably 50~5Ω / It is especially desirable to use low-resistance components marked with a square. The thickness of the ITO can be arbitrarily selected according to the resistance value. It can be used in a wider range, but it is usually used in the 50-300nm range.

[0179] <Hole injection layer and hole transport layer in organic electroluminescent devices> The hole injection layer 103 efficiently delivers holes moving from the anode 102 into the light-emitting layer 105. Alternatively, it plays the role of injecting into the hole transport layer 104. The hole transport layer 104 is from the anode 102 The injected holes or holes injected from the anode 102 through the hole injection layer 103 are efficiently The hole injection layer 103 and hole transport layer 104 play a role in transporting the holes to the light-emitting layer 105. Each involves laminating or mixing one or more types of hole injection / transport materials, or hole injection / transport materials. It is formed from a mixture of transport material and polymer binder. Additionally, iron chloride is used as the hole injection / transport material. (III) An inorganic salt may be added to form a layer.

[0180] As a hole-injecting and transporting material, it efficiently transports holes from the positive electrode between electrodes under an applied electric field. It is necessary to inject and transport the holes efficiently, and the hole injection efficiency is high, and the injected holes are transported efficiently. It is desirable to do so. For this to happen, the ionization potential must be small and the hole mobility must be It is large, highly stable, and less likely to generate trapping impurities during manufacturing and use. It is preferable that the substance is fine.

[0181] The material used to form the hole injection layer 103 and the hole transport layer 104 is a photoconductive material. Compounds, p-type semiconductors, and organic EL elements have been conventionally used as charge transport materials for holes. Select any compound from among the known compounds used in the hole injection layer and hole transport layer. They can be selected and used. Specific examples include carbazole derivatives (N-phenylacetate). Lubazole, polyvinylcarbazole, etc.), bis(N-arylcarbazole) or Biscarbazole derivatives such as bis(N-alkylcarbazole), triarylamines Derivatives (polymers having aromatic tertiary amino acids in the main chain or side chain, 1,1-bis(4-di- p-Tolylaminophenyl)cyclohexane, N,N'-diphenyl-N,N'-di(3 -methylphenyl)-4,4'-diaminobiphenyl,N,N'-diphenyl-N,N' -Dinaphthyl-4,4'-diaminobiphenyl, N,N'-diphenyl-N,N'-di( 3-methylphenyl)-4,4'-diphenyl-1,1'-diamine, N,N'-dinaph Tyl-N,N'-diphenyl-4,4'-diphenyl-1,1'-diamine, N4 ,N 4 ’ -diphenyl-N 4 ,N 4’ -Bis(9-phenyl-9H-carbazole-3-yl) -[1,1'-biphenyl]-4,4'-diamine, N 4 ,N 4 ,N 4’ ,N 4’ -Teto Ra[1,1'-biphenyl]-4-yl)-[1,1'-biphenyl]-4,4'-dia Min, 4,4',4”-Tris(3-methylphenyl(phenyl)amino)triphenyl Triphenylamine derivatives such as amines, starburst amine derivatives, etc., stilbe Pyrazoline derivatives, phthalocyanine derivatives (metal-free, copper phthalocyanine, etc.), pyrazoline derivatives , hydrazone compounds, benzofuran derivatives and thiophene derivatives, oxadiazole derivatives The body, quinoxaline derivatives (e.g., 1,4,5,8,9,12-hexaazatriphenyl (e.g., 2,3,6,7,10,11-hexacarbonitride), porphyrin derivatives These are heterocyclic compounds, polysilanes, etc. In polymer systems, the monomer is found in the side chain. Recarbonates, styrene derivatives, polyvinylcarbazoles, and polysilanes are preferred. However, it is possible to form a thin film necessary for fabricating a light-emitting element, and to inject holes from the anode, and further holes The compound is not particularly limited as long as it can transport the substance.

[0182] Furthermore, it is known that the conductivity of organic semiconductors is strongly affected by doping. Such organic semiconductor matrix materials are compounds with good electron-donating properties, or It is composed of compounds with good electron-accepting properties. For doping with electron-donating substances, Tetracyanoquinone dimethane (TCNQ) or 2,3,5,6-tetrafluorotetra Strong electron acceptors such as cyano-1,4-benzoquinone dimethane (F4TCNQ) are known. (For example, see the reference "M. Pfeiffer, A. Beyer, T. Fritz, K. Leo, Appl. Phys. Lett., 73(22), 32 02-3204(1998)" and the document "J. Blochwitz, M. Pheiffer, T. Fritz, K. Leo, Appl. Phys. Lett., See 73(6), 729-731(1998). These are electron-donating base materials (hole transport materials). The electron transfer process in ) generates so-called holes. The number and mobility of holes This significantly alters the conductivity of the base material. Examples of the compound include benzidine derivatives (such as TPD) or starburst amino acids. Derivatives of phosphates (such as TDATA), or certain metal phthalocyanines (especially zinc phthalocyanines). Anine (ZnPc, etc.) is known (Japanese Patent Publication No. 2005-167175).

[0183] The hole injection layer material and hole transport layer material described above are provided by substituting reactive substituents therein. A polymer compound obtained by polymerizing a reactive compound as a monomer, or a polymer crosslink thereof. A body, or a pendant-type polymer compound obtained by reacting a main-chain polymer with the reactive compound. Alternatively, it can be used as a material for the hole layer, either as a pendant-type polymer crosslinked material or as such. In this case, the reactive substituent is explained using the polycyclic aromatic compound represented by formula (1). It can be used. Details of the applications of such polymer compounds and polymer crosslinks will be described later.

[0184] <Emitting layer in organic electroluminescent element> The light-emitting layer 105 emits holes injected from the anode 102 between electrodes to which an electric field is applied. This is a light-emitting layer that emits light by recombining with electrons injected from cathode 10⁸. The material that forms 105 is a compound that emits light when excited by the recombination of holes and electrons. Any substance (luminescent compound) will suffice, and it must be able to form a stable thin film shape and be in a solid state. It is preferable that the compound exhibits strong luminescence (fluorescence) efficiency in its state. In the present invention, the material for the luminescent layer As materials, a host material and, for example, a multiplier represented by the above general formula (1) as a dopant material. A cyclic aromatic compound can be used.

[0185] The light-emitting layer can consist of a single layer or multiple layers, and each layer is made of a material for the light-emitting layer (phosphorus). It is formed from a host material and a dopant material. The host material and the dopant material are, respectively It can be one type or a combination of multiple types. The dopant material is H It may be included in the entire material or in part. As for the coating method, it can be formed by co-deposition with a host material, but The materials may be mixed beforehand and then deposited simultaneously.

[0186] The amount of host material used varies depending on the type of host material, and should be adjusted according to the characteristics of that host material. You can decide based on that. The guideline for the amount of host material to use is preferably 50% of the total amount of material for the light-emitting layer. It is 99.999% by weight, more preferably 80-99.95% by weight, and even more preferably It is more accurately 90-99.9% by weight.

[0187] The amount of dopant material used varies depending on the type of dopant material. The amount of dopant to use should be determined according to its characteristics. Preferably, the amount of dopant to use is determined by the light-emitting layer material. It is 0.001 to 50% by weight of the total, more preferably 0.05 to 20% by weight, More preferably, the concentration is 0.1 to 10% by weight. Within this range, for example, concentration quenching phenomenon It is preferable in that it can prevent this.

[0188] As host materials, anthracene, pyrene, and gibberellin have long been known as luminescent materials. Condensed ring derivatives such as nzocrycene or fluorene, bis-styrylanthracene derivatives, and Bistyryl derivatives such as distyrylbenzene derivatives, tetraphenylbutadiene derivatives Examples include cyclopentadiene derivatives. In particular, anthracene compounds and fluorescein compounds. A dibenzo-based compound or a dibenzo-chrycene compound is preferred.

[0189] <Anthracene compounds> Anthracene compounds used as hosts include, for example, compounds represented by the following general formula (3). be. [ka]

[0190] In formula (3), X and Ar 4 These are, independently, hydrogen, an aryl that may be substituted, and a substituted A heteroaryl that may be substituted, a diarylamino that may be substituted A diheteroarylamino which may be substituted, or an arylheteroarylamino which may be substituted. , optionally substituted alkyl, optionally substituted cycloalkyl, substituted A potentially substituted alkenyl, a potentially substituted alkoxy, or a potentially substituted aryl. The oxy, optionally substituted arylthio, or optionally substituted silyl, All X and Ar 4 They do not become hydrogen at the same time. In the compound represented by formula (3), at least one hydrogen is a halogen, cyano, or deuterium. Alternatively, it may be substituted with a heteroaryl that may be substituted.

[0191] Furthermore, the structure represented by formula (3) is used as a unit structure to form a polymer (preferably a dimer). This is also acceptable. In this case, for example, the unit structures represented by equation (3) are joined together via X. Examples include single bonds, arylenes (phenylene, biphenylene, and naphthium), and X is a single bond. (Chiene, etc.) and heteroarylenes (pyridine ring, dibenzofuran ring, dibenzothiophene) Examples include benzocarbazole rings, carbazole rings, and phenyl-substituted carbazole rings. Examples include groups with a divalent bonding valency.

[0192] The above aryl, heteroaryl, diarylamino, diheteroarylamino, aryl Heteroarylamino, alkyl, cycloalkyl, alkenyl, alkoxy, alley Details of luoxy, arylthio, or silyl are described in the Preferred Embodiments section below. Furthermore, substituents on these include aryl, heteroaryl, diarylamino, and dihetamine. Loarylamino, arylheteroarylamino, alkyl, cycloalkyl, alke Examples include nyl, alkoxy, aryloxy, arylthio or silyl, and these Further details will be explained in the section on preferred embodiments below.

[0193] Preferred embodiments of the above anthracene compounds are described below. The symbols in the following structure The definition is the same as the definition described above. [ka]

[0194] In general formula (3), X is independently expressed in the above formulas (3-X1), (3-X2), or It is a group represented by formula (3-X3), and is also represented by formula (3-X1), formula (3-X2), or formula (3-X The group represented by 3) bonds with the anthracene ring of formula (3) in *. Preferably, two X cannot simultaneously be the basis represented by equation (3-X3). More preferably, two X are At the same time, it does not serve as a base represented by the equation (3-X²).

[0195] Furthermore, the structure represented by formula (3) is used as a unit structure to form a polymer (preferably a dimer). This is also acceptable. In this case, for example, the unit structures represented by equation (3) are joined together via X. Examples include single bonds, arylenes (phenylene, biphenylene, and naphthium), and X is a single bond. (Chiene, etc.) and heteroarylenes (pyridine ring, dibenzofuran ring, dibenzothiophene) Examples include benzocarbazole rings, carbazole rings, and phenyl-substituted carbazole rings. Examples include groups with a divalent bonding valency.

[0196] In formulas (3-X1) and (3-X2), the naphthylene moiety is condensed by a single benzene ring. They may be combined. The resulting condensed structure is as follows: [ka]

[0197] Ar 1 and Ar 2 These are, independently, hydrogen, phenyl, biphenylyl, and terphenyl. Niryl, quaterpheniryl, naphthyl, phenanthryl, fluorenyl, benzofluor Renyl, crisenyl, triphenylenyl, pyrenyl, or represented by the above formula (A) Groups (including carbazolyl groups, benzocarbazolyl groups, and phenyl-substituted carbazolyl groups) That is. Also, Ar 1 or Ar 2 If the base is represented by formula (A), then it is expressed by formula (A). The group being bonded in its * is bonded to the naphthalene ring in formula (3-X1) or formula (3-X2). do.

[0198] Ar 3 These are phenyl, biphenylyl, terphenylyl, quaterphenylyl, naphthyl Phenanthril, fluorenil, benzofluorenil, crisenil, triphenylenil , pyrenyl, or the group represented by the above formula (A) (carbazolyl group, benzocarbazolyl This includes the yl group and the phenyl-substituted carbazolyl group. 3 This is expressed by equation (A) If it is a base, then the base represented by formula (A) is in the straight line in formula (3-X3) at that * It bonds with the single bond shown in equation (3) and the anthracene ring represented by equation (A). The groups bond directly.

[0199] Also, Ar 3 It may have substituents, Ar 3 At least one hydrogen in is Furthermore, alkyl groups with 1 to 4 carbon atoms, cycloalkyl groups with 5 to 10 carbon atoms, phenyl groups, and biphenyl groups. Lu, terpheniryl, naphthyl, phenanthryl, fluorenyl, crisenyl, triphe Nirenyl, pyrenyl, or the group represented by the above formula (A) (carbazolyl group and phenyl group) It may also be substituted with a yl-substituted carbazolyl group. 3substituents that If is a group represented by formula (A), then the group represented by formula (A) is in its * that is a group represented by formula (3- Ar in X3) 3 It combines with it.

[0200] Ar 4 These are, independently, hydrogen, phenyl, biphenylyl, terphenylyl, and naphth. ethyl, or alkyl (methyl, ethyl, t-butyl, etc.) with 1 to 4 carbon atoms and / or if k is a silyl substituted with a cycloalkyl group having 5 to 10 carbon atoms.

[0201] Alkyl atoms with 1 to 4 carbon atoms that can be substituted for silyl include methyl, ethyl, propyl, and i-propyl. Examples include silyl, butyl, sec-butyl, t-butyl, cyclobutyl, etc. Each of the three hydrogen atoms is independently substituted with these alkyl groups.

[0202] A specific example of a "silyl substituted with an alkyl group having 1 to 4 carbon atoms" is trimethylsilyl. Lyl, triethylsilyl, tripropylsilyl, tri-i-propylsilyl, tributylsilyl Lyl, trisec-butylsilyl, trit-butylsilyl, ethyldimethylsilyl, pro Pyrdimethylsilyl, i-propyldimethylsilyl, butyldimethylsilyl, sec- t-butyldimethylsilyl, t-butyldimethylsilyl, methyldiethylsilyl, propyldiethylsilyl Ilsilyl, i-propyldiethylsilyl, butyldiethylsilyl, sec-butyldiethylsilyl t-butyldiethylsilyl, methyldipropylsilyl, ethyldipropylsilyl Ryl, butyldipropylsilyl, sec-butyldipropylsilyl, t-butyldipropyl Lucilyl, methyldi-i-propylsilyl, ethyldi-i-propylsilyl, butyldi-i- Ropyrsilyl, sec-butyldi-i-propylsilyl, t-butyldi-i-propylsilyl These are some examples.

[0203] Cycloalkyl groups with 5 to 10 carbon atoms that can be substituted for silyl include cyclopentyl and cyclohexyl. , cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, norborneyl, Bicyclo[1.1.1]pentyl, Bicyclo[2.0.1]pentyl, Bicyclo[1.2 .1]hexyl, bicyclo[3.0.1]hexyl, bicyclo[2.1.2]heptyl, Bicyclo[2.2.2]octyl, adamantyl, decahydronaphthalenyl, decahydro Examples include azurenyl, where the three hydrogen atoms in the silyl are each independent of these It is substituted with a cycloalkyl group.

[0204] A specific example of a "silyl substituted with a cycloalkyl group having 5 to 10 carbon atoms" is: Examples include cyclopentylsilyl and tricyclohexylsilyl.

[0205] As for substituted silyls, di-(2 alkyl and 1 cycloalkyl) is a substituted silyl. Alkylcycloalkylsilyl and a compound substituted with one alkyl and two cycloalkyl groups There are also lucyldicycloalkylsilyls, and specific examples of substituted alkyl and cycloalkyl groups. The above-mentioned bases are examples of this.

[0206] Furthermore, the hydrogen in the chemical structure of anthracene compounds represented by general formula (3) is given by the above formula (A It may be substituted with a group represented by formula (A). If it is substituted with a group represented by formula (A), The group represented by (A) is at least one in the compound represented by formula (3) in its * Replace with hydrogen.

[0207] The group represented by formula (A) is a substituent that the anthracene compound represented by formula (3) may have. It is one of them. [ka]

[0208] In the above formula (A), Y is -O-, -S-, or >NR 29 And R 21 ~R 28 haso Each independently consists of hydrogen, an optionally substituted alkyl, and an optionally substituted cycloal. Kill, optionally substituted aryl, optionally substituted heteroaryl, substituted Optional alkoxy, optionally substituted aryloxy, optionally substituted Arylthio, trialkylsilyl, tricycloalkylsilyl, dialkylcycloal hydroxysilyl, alkyldicycloalkylsilyl, optionally substituted amino, halogen , hydroxy or cyano, R 21 ~R 28 Among them, adjacent groups are bonded to each other and form carbon They may form a hydrogenated ring, an aryl ring, or a heteroaryl ring, R 29 is hydrogen is an aryl that may be substituted.

[0209] R 21 ~R 28 In the context of "alkyl which may be substituted", the "alkyl" refers to: It can be either a linear or branched chain, for example, a linear alkyl or carbon chain with 1 to 24 carbon atoms. Examples include branched alkyl groups with 3 to 24 carbon atoms. Alkyl groups with 1 to 18 carbon atoms (3 to 18 carbon atoms) Branched alkyl groups are preferred, and alkyl groups with 1 to 12 carbon atoms (branched alkyl groups with 3 to 12 carbon atoms) are preferred. Lukil is more preferred, and alkyl groups having 1 to 6 carbon atoms (branched alkyl groups having 3 to 6 carbon atoms) More preferably, alkyl groups having 1 to 4 carbon atoms (branched alkyl groups having 3 to 4 carbon atoms) are particularly preferred. It's nice.

[0210] Specific examples of "alkyl" include methyl, ethyl, n-propyl, isopropyl, n- Butyl, isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl, neopen Tyl, t-pentyl, n-hexyl, 1-methylpentyl, 4-methyl-2-pentyl, 3,3-Dimethylbutyl, 2-Ethylbutyl, n-Heptyl, 1-Methylhexyl, n- Octyl, t-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl Tyl, n-nonyl, 2,2-dimethylheptyl, 2,6-dimethyl-4-heptyl, 3, 5,5-Trimethylhexyl, n-decyl, n-undecyl, 1-methyldecyl, n- Decyl, n-tridecyl, 1-hexylheptyl, n-tetradecyl, n-pentadecyl Examples include n-hexadecyl, n-heptadecyl, n-octadecyl, and n-eicosyl. It is possible.

[0211] R 21 ~R 28 In the case of "cycloalkyl which may be substituted", Examples include cycloalkyl groups with 3 to 24 carbon atoms, cycloalkyl groups with 3 to 20 carbon atoms, and carbon Cycloalkyl groups with 3 to 16 carbon atoms, cycloalkyl groups with 3 to 14 carbon atoms, and cycloalkyl groups with 5 to 10 carbon atoms. Cycloalkyl, cycloalkyl with 5-8 carbon atoms, cycloalkyl with 5-6 carbon atoms, cycloalkyl with 5 carbon atoms Examples include cycloalkyl groups.

[0212] Specific examples of "cycloalkyl" include cyclopropyl, cyclobutyl, and cyclopentyl , cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, And these alkyl (especially methyl) substituted derivatives having 1 to 4 carbon atoms, norborneyl, bicyl Clo[1.0.1]butyl, Bicyclo[1.1.1]pentyl, Bicyclo[2.0.1] Pentyl, bicyclo[1.2.1]hexyl, bicyclo[3.0.1]hexyl, bicyclo [2.1.2]heptyl, bicyclo[2.2.2]octyl, adamantyl, diamane Examples include til, decahydronaphthalenyl, and decahydroazurenyl.

[0213] R 21 ~R 28 In the context of "aryls that may be substituted," the "aryl" is: For example, aryls having 6 to 30 carbon atoms are used, and aryls having 6 to 16 carbon atoms are preferred. Aryl compounds having 6 to 12 carbon atoms are more preferred, and aryl compounds having 6 to 10 carbon atoms are particularly preferred.

[0214] Specific examples of "aryl" include the monocyclic phenyl and the bicyclic biphenylyl. Naphthyl is a condensed bicyclic system, and terpheniryl (m-terpheniryl, o-terpheniryl) is a tricyclic system. Rupheniryl (p-terpheniryl), a condensed tricyclic system, acenaphtyrenyl, fluore Nyl, phenalenyl, phenantrenyl, and the condensed tetracyclic systems triphenylenyl and pyrenyl Examples include naphthacenyl, and condensed pentacyclic systems such as perilenyl and pentacenyl.

[0215] R 21 ~R 28 "heteroaryls that may be substituted" Examples of such compounds include heteroaryls with 2 to 30 carbon atoms, and heteroaryls with 2 to 25 carbon atoms. Teloaryls are preferred, heteroaryls having 2 to 20 carbon atoms are more preferred, and heteroaryls having 2 to 20 carbon atoms are preferred. A heteroaryl with 15 carbon atoms is more preferred, and a heteroaryl with 2 to 10 carbon atoms is particularly preferred. Furthermore, as heteroaryls, for example, oxygen, sulfur, and carbon are used as ring constituent atoms in addition to carbon. Examples include heterocycles containing 1 to 5 heteroatoms selected from nitrogen.

[0216] Specific examples of "heteroaryls" include pyrrolyl, oxazolyl, and isoxa. Zolyl, thiazolyl, isothiazolyl, imidazolyl, oxadiazolyl, thiadiazolyl Triazolyl, tetrazolyl, pyrazolyl, pyridyl, pyrimidinyl, pyridadinyl Pyrazinyl, triazinyl, indolyl, isoindolyl, 1H-indazolyl, ben Zoimidazolyl, benzoxazolyl, benzothiazolyl, 1H-benzotriazolyl, Quinoryl, Isoquinolyl, Synnoryl, Quinazolyl, Quinoxalinyl, Phthalazinyl, Na Futilidinyl, prinyl, pteridinyl, carbazolyl, acridinyl, phenoxathi Nyl, phenoxadinyl, phenothiazinyl, phenadinyl, indolidinyl, frill, Benzofuranyl, isobenzofuranyl, dibenzofuranyl, thienyl, benzo[b]thienyl Nyl, dibenzothienyl, flazanil, oxadiazolyl, thianthrenil, naphthobene Examples include zofranil and naphthobenzothienyl.

[0217] R 21 ~R 28 As "alkoxy" in "alkoxy which may be substituted" Examples include linear alkoxys with 1 to 24 carbon atoms or branched alkoxys with 3 to 24 carbon atoms. A carbon alkoxy with 1 to 18 carbon atoms (a branched chain alkoxy with 3 to 18 carbon atoms) is preferred. More preferably, alkoxys with 1 to 12 carbon atoms (branched chain alkoxys with 3 to 12 carbon atoms) More preferably, an alkoxy having 1 to 6 carbon atoms (a branched chain alkoxy having 3 to 6 carbon atoms) Alkoxy compounds with 1 to 4 carbon atoms (branched chain alkoxy compounds with 3 to 4 carbon atoms) are particularly preferred.

[0218] Specific examples of "alkoxy" include methoxy, ethoxy, propoxy, and isopropoxy. , butoxy, isobutoxy, s-butoxy, t-butoxy, pentyloxy, hexyloxy Examples include xyloxy, heptyloxy, and octyloxy.

[0219] R 21 ~R 28 In the context of "aryloxy which may be substituted", the "aryloxy " is a group in which the hydrogen of the -OH group is replaced with an aryl group, and this aryl is as described above R 21 ~R 28 We can cite the base described as "aryl" in this context.

[0220] R 21 ~R 28 The "arylthio" in "arylthio which may be substituted" and Therefore, the -SH group is a group in which the hydrogen atom is substituted with an aryl group, and this aryl is the R mentioned above. 2 1 ~R 28 We can cite the base described as "aryl" in the context of this.

[0221] R 21 ~R 28 In this context, "trialkylsilyl" refers to the three water molecules in the silyl group. Examples include groups in which each element is independently substituted with an alkyl group, and this alkyl group is the R mentioned above. 2 1 ~R 28The group described as "alkyl" in this context can be cited. Substitution Preferred alkyl groups are alkyl groups having 1 to 4 carbon atoms, specifically methyl, ethyl, and p. Examples include propyl, i-propyl, butyl, sec-butyl, t-butyl, and cyclobutyl. It is possible.

[0222] Specific examples of "trialkylsilyl" include trimethylsilyl, triethylsilyl, and Lipropylsilyl, tri-i-propylsilyl, tributylsilyl, trisec-butylsilyl Lyl, tri-t-butylsilyl, ethyldimethylsilyl, propyldimethylsilyl, i-p Ropyrdimethylsilyl, butyldimethylsilyl, sec-butyldimethylsilyl, t- Dimethyl methylsilyl, methyl diethyl silyl, propyl diethyl silyl, i-propyl di Ethyl silyl, butyldiethyl silyl, sec-butyldiethyl silyl, t-butyldiethyl silyl Tylsilyl, methyldipropylsilyl, ethyldipropylsilyl, butyldipropylsilyl Lu, sec-butyldipropylsilyl, t-butyldipropylsilyl, methyldi-i-pro Pyrsilyl, ethyldi-i-propylsilyl, butyldi-i-propylsilyl, sec-buty Examples include di-i-propylsilyl and t-butyldi-i-propylsilyl.

[0223] R 21 ~R 28 In this context, "tricycloalkylsilyl" refers to the 3 silyl group. One example is a group in which each of the two hydrogen atoms is independently substituted with a cycloalkyl group. Kill is R as mentioned above 21 ~R 28 The group described as "cycloalkyl" in this context is cited. This is possible. Preferred cycloalkyls for substitution are cycloalkyls having 5 to 10 carbon atoms. These are cyclopentyl, specifically cyclohexyl, cycloheptyl, and cyclooctyl. , cyclononyl, cyclodecyl, bicyclo[1.1.1]pentyl, bicyclo[2.0 .1]pentyl, bicyclo[1.2.1]hexyl, bicyclo[3.0.1]hexyl, Bicyclo[2.1.2]heptyl, Bicyclo[2.2.2]octyl, adamantyl, de Examples include cahydronaphthalenyl and decahydroazlenyl.

[0224] Specific examples of "tricycloalkylsilyl" include tricyclopentylsilyl and tricyclo Examples include chlorhexylsilyl.

[0225] Dialkylcycloalkylsilyls substituted with two alkyl groups and one cycloalkyl group , alkyldicycloalkylsilyl substituted with one alkyl and two cycloalkyl groups As a specific example, a group selected from the specific alkyl and cycloalkyl groups mentioned above is placed. Cyril was replaced.

[0226] R 21 ~R 28 In the context of "aminos that may be substituted," the "substituted aminos" are defined as follows: For example, an amino group in which two hydrogen atoms are replaced by aryl or heteroaryl groups can be cited. A diaryl-substituted amino acid is an amino acid in which two hydrogen atoms are replaced by aryl atoms. A diheteroaryl-substituted amino acid is an amino acid in which two hydrogen atoms are substituted. Aminos substituted with aryl and heteroaryl are aryl heteroaryl-substituted aminos. Yes, these aryl and heteroaryl are the R mentioned above. 21 ~R 28 "Aryl" in We can refer to the group described as "heteroaryl."

[0227] Specific examples of "substituted amino acids" include diphenylamino, dinaphthylamino, and phenoamino. Nylnaphthylamino, dipyridylamino, phenylpyridylamino, naphthylpyridyl Examples include tripe.

[0228] R 21 ~R 28 Examples of "halogens" in this context include fluorine, chlorine, bromine, and iodine. It can be done.

[0229] R 21 ~R 28 Some of the elements described above may be substituted as described above. In this case, the substituents are alkyl, cycloalkyl, aryl, or heteroaryl. These include alkyl, cycloalkyl, aryl, or heteroaryl as described above. Ta R 21 ~R 28 In the context of "alkyl", "cycloalkyl", "aryl", or "he The basis for the explanation of "terror aryl" can be cited.

[0230] Y as ">NR" 29 R in " 29 Ally may be hydrogen or substituted. This is a aryl, and as mentioned above, R 21 ~R 28 The theory that "aryl" is the term used in this context. The clarified group can be cited, and its substituent is R 21 ~R 28 substituents The basis explained above can be cited.

[0231] R 21 ~R 28 Among them, adjacent groups are bonded to each other to form a hydrocarbon ring, aryl ring, or hetero ring. A loaryl ring may be formed. The case where no ring is formed is represented by the following formula (A-1). When it is a base and forms a ring, it can be represented, for example, by the following formulas (A-2) to (A-14). The following are examples of the base. Note that in the base represented by any of the formulas (A-1) to (A-14) At least one hydrogen atom is alkyl, cycloalkyl, aryl, heteroaryl, or aryl. Coxy, aryloxy, arylthio, trialkylsilyl, tricycloalkylsilyl Dialkylcycloalkylsilyl, alkyldicycloalkylsilyl, diaryl Modified amino acids, diheteroaryl-substituted amino acids, arylheteroaryl-substituted amino acids, halogens They may be substituted with hydroxyl or cyano compounds. [ka]

[0232] As for rings formed by the bonding of adjacent groups, a hydrocarbon ring is, for example, a cyclohexagonal ring. Examples include the s-ring, and as for aryl rings and heteroaryl rings, see the above-mentioned R 21 ~R 28 odor Examples include the ring structures described as "aryl" and "heteroaryl," and these rings are as described above. It is formed to condense with one or two benzene rings in formula (A-1).

[0233] The base represented by formula (A) is, for example, any of the above formulas (A-1) to (A-14). The bases represented by the above formulas (A-1) to (A-5) and (A-12) to ( A group represented by any of the above formulas (A-1) to (A-4) is preferred. A group represented by any of the above formulas (A-1), (A-3), and (A-4) is more preferred. A group represented by any of the above formulas is more preferred, and the group represented by formula (A-1) is particularly preferred. stomach.

[0234] The base represented by formula (A) is, in formula (A), where * is, formula (3-X1) or formula (3-X 2) Naphthalene ring in formula (3-X3), single bond in formula (3-X3), Ar in formula (3-X3) 3 Combined with Furthermore, substitution with at least one hydrogen in the compound represented by formula (3) is as described above. As stated above, among these combination forms, the naphth in formula (3-X1) or formula (3-X2) Talene ring, single bond in formula (3-X3) and / or Ar in formula (3-X3) 3 Combined with A form is preferred.

[0235] Furthermore, in the structure of the group represented by formula (A), the na in formula (3-X1) or formula (3-X2) Phthalene ring, single bond in formula (3-X3), Ar in formula (3-X3) 3 The position where they join, Furthermore, in the structure of the group represented by formula (A), at least one of the compounds represented by formula (3) The position where one hydrogen is substituted can be any position in the structure of formula (A), for example, formula Either of the two benzene rings in the structure of (A), or R in the structure of formula (A) 21 ~R 28 of Among these, any ring formed by the bonding of adjacent groups, or Y in the structure of formula (A) te no ">NR 29 R in " 29 They can be joined at any position in the middle.

[0236] Examples of groups represented by formula (A) include the following: Y and * in the formula are above This is the same definition as noted. [ka]

[0237] Furthermore, all of the hydrogen atoms in the chemical structure of anthracene compounds represented by general formula (3) Alternatively, part of it may be deuterium.

[0238] Specific examples of anthracene compounds include, for example, the following formulas (3-1) to (3-7) Examples include the compounds represented in 2). Note that in the structural formula below, "Me" is a methyl group, and "D" is a methyl group. 'tBu' indicates a deuterium group, and 'tBu' indicates a t-butyl group.

[0239] [ka]

[0240] [ka]

[0241] [ka]

[0242] [ka]

[0243] The anthracene compound represented by formula (3) is reactive at a desired position on the anthracene skeleton. Compounds having a group, and X, Ar 4 and have reactive groups in substructures such as the structure of formula (A). Using a compound as a starting material, Suzuki coupling, Negishi coupling, and other known couplings are performed. These can be manufactured by applying the Pulling reaction. As the reactive group of these reactive compounds Examples include halogens and boronic acids. Specific manufacturing methods include, for example, international disclosure. The synthesis method described in paragraphs

[0089] to

[0175] of the Japanese Patent Publication No. 2014 / 141725 can be used as a reference.

[0244] <Fluorene compounds> Compounds represented by general formula (4) basically function as hosts. [ka]

[0245] In the above formula (4), R 1 From R 10 These are, independently, hydrogen, aryl, and heteroaryl (the heteroaryl The reel may be bonded to the fluorene skeleton in formula (4) above via a linking group. diarylamino, diheteroarylamino, arylheteroarylamino, alkyl , cycloalkyl, alkenyl, alkoxy or aryloxy, and in these At least one hydrogen atom is aryl, heteroaryl, alkyl, or cycloalkyl. Even if it is replaced, Also, R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 5 and R 6 , R 6 and R 7 , R 7 and R 8 Ma Taha R 9 and R 10 Even if they are independently bonded together to form a fused ring or spiro ring, Furthermore, at least one hydrogen in the formed ring is an aryl, heteroaryl (the hetero The loaryl group may be bonded to the formed ring via a linking group, diarylamine No, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl They may be substituted with aryl, alkenyl, alkoxy, or aryloxy. At least one hydrogen atom is aryl, heteroaryl, alkyl, or cycloalkyl It may be replaced with, and, At least one hydrogen in the compound represented by formula (4) is a halogen, cyano, or heavy It may be substituted with hydrogen.

[0246] Details of each group in the definition of formula (4) above are as described above for the polycyclic aromatic compound of formula (1) You can quote the explanation provided there.

[0247] R 1 From R 10 Examples of alkenyls in this context include alkenyls with 2 to 30 carbon atoms. Alkenyls with 2 to 20 carbon atoms are preferred, and alkenyls with 2 to 10 carbon atoms are more preferred. Alkenyls having 2 to 6 carbon atoms are more preferred, and alkenyls having 2 to 4 carbon atoms are particularly preferred. Preferred. Preferred alkenyls are vinyl, 1-propenyl, 2-propenyl, 1-butene. nyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl 4-Pentenyl, 1-Hexenyl, 2-Hexenyl, 3-Hexenyl, 4-Hexenyl , or 5-hexenyl.

[0248] For specific examples of heteroaryls, see the following formulas: (4-Ar1), (4-Ar2), and Any one water from the compounds of formula (4-Ar3), formula (4-Ar4), or formula (4-Ar5) Examples of monovalent groups that can be represented without elementary atoms include monovalent groups. [ka] In equations (4-Ar1) to (4-Ar5), Y 1 These are, independently, O, S or NR is where R is phenyl, biphenylyl, naphthyl, anthracenyl, or hydrogen. the law of nature, In the structures of formulas (4-Ar1) to (4-Ar5) above, at least one hydrogen is Phenyl, biphenylyl, naphthyl, anthracenyl, phenantrenyl, methyl, ethyl It may be substituted with propyl or butyl.

[0249] These heteroaryls, via linking groups, are connected to the fluorene skeleton in formula (4) above. They may be bonded together. That is, the fluorene skeleton in formula (4) and the above heteroaryl. They may not only bond directly, but may also be bonded to each other via a linking group. Examples include phenylene, biphenylene, naphthylene, anthracenylene, methylene, and ethylene. Len, -OCH2CH2-, -CH2CH2O-, or -OCH2CH2O- etc. I can give it to you.

[0250] Also, R in equation (4) 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 5 and R 6 , R 6 and R 7 Ma Taha R 7 and R 8 Each of them independently bonds to form a fused ring, R 9 and R 10 They bond together to form a spiro ring It may form R 1 From R 8 The condensed ring formed by this is the ben in formula (4). It is a ring fused to a Zen ring, and is either an aliphatic or aromatic ring. Preferably, it is an aromatic ring. The structure including the benzene ring in formula (4) is a naphthalene ring or a phenanthrene ring. These are some examples. 9 and R 10 The spiro ring formed by this process is a 5-membered ring in formula (4). It is a spiro-bonded ring, and is either an aliphatic or aromatic ring. Preferably, it is an aromatic ring. Examples include the fluorene ring.

[0251] The compound represented by general formula (4) is preferably the following formula (4-1), formula (4-2), or These are compounds represented by formula (4-3), and in general formula (4), R 1 and R 2 but A compound in which benzene rings formed by bonding are fused, in general formula (4) R 3 and R 4 The A compound in which the benzene rings formed by the fusion are fused, in general formula (4) R 1 From R 8 Noi It is a compound in which no molecules are bonded together. [ka]

[0252] R in equations (4-1), (4-2), and (4-3) 1 From R 10 The definition is given by the formula ( 4) The corresponding R 1 From R 10 This is the same as, and equations (4-1) and (4-2) Okeru R 11 From R 14 The definition of R in equation (4) is also 1 From R 10 It is the same as this.

[0253] The compound represented by general formula (4) is more preferably the following formula (4-1A), formula (4- Compounds represented by formula (4-1) or formula (4-3A), respectively. -1) or in equation (4-3), R 9 and R 10 The two groups bond to form a spirofluorene ring. It is a compound that has been developed. [ka]

[0254] R in equations (4-1A), (4-2A), and (4-3A) 2 From R 7 The definition is In equations (4-1), (4-2), and (4-3), the corresponding R 2 From R 7 Same as Yes, R in equations (4-1A) and (4-2A) 11 From R 14 The definition is also given by formula (4- 1) and R in equation (4-2) 11 From R 14 It is the same as this.

[0255] Furthermore, in the compound represented by formula (4), all or part of the hydrogen is a halogen, cyanoacrylate. It may be substituted with ano or deuterium.

[0256] <Dibenzocricene compounds> Dibenzochrysene compounds as hosts include, for example, compounds represented by the following general formula (5) It is an object. [ka]

[0257] In the above formula (5), R 1 From R 16 These are, independently, hydrogen, aryl, and heteroaryl (the heteroaryl The reel may be bonded to the dibenzochrysene skeleton in formula (5) above via a linking group. i), diarylamino, diheteroarylamino, arylheteroarylamino, a These are hydroxyl, cycloalkyl, alkenyl, alkoxy, or aryloxy, and At least one hydrogen in is aryl, heteroaryl, alkyl, or cycloal It's fine if it's replaced by a kill. Also, R 1 From R 16 Among these, adjacent groups may bond to each other to form a fused ring. At least one hydrogen in the formed ring is aryl, heteroaryl (the heteroaryl The reel may be bonded to the formed ring via a linking group), diarylamino, Diheteroarylaminos, arylheteroarylaminos, alkyls, cycloalkyls, They may be substituted with alkenyl, alkoxy or aryloxy, and in these cases At least one hydrogen atom is aryl, heteroaryl, alkyl, or cycloalkyl. It's fine if it's been replaced, and, At least one hydrogen in the compound represented by formula (5) is a halogen, cyano, or heavy It may be substituted with hydrogen.

[0258] Details of each group in the definition of formula (5) above are as described above for the polycyclic aromatic compound of formula (1) You can quote the explanation provided there.

[0259] In the definition of formula (5) above, an alkenyl is, for example, an alkenyl having 2 to 30 carbon atoms. Examples include alkenyls with 2 to 20 carbon atoms, and alkenyls with 2 to 10 carbon atoms. More preferably, alkenyls having 2 to 6 carbon atoms are preferred, and even more preferably, alkenyls having 2 to 4 carbon atoms. The following are particularly preferred. Preferred alkenyls are vinyl, 1-propenyl, 2-propenyl, 1 -Butenyl, 2-Butenyl, 3-Butenyl, 1-Pentenyl, 2-Pentenyl, 3-Pentenyl Tenyl, 4-Pentenyl, 1-Hexenyl, 2-Hexenyl, 3-Hexenyl, 4-Hexenyl It is senyl, or 5-hexenyl.

[0260] For specific examples of heteroaryls, see the following formulas: (5-Ar1), (5-Ar2), and Any one water from the compounds of formula (5-Ar3), formula (5-Ar4), or formula (5-Ar5) Examples of monovalent groups that can be represented without elementary atoms include monovalent groups. [ka] In equations (5-Ar1) to (5-Ar5), Y 1 These are, independently, O, S or NR is where R is phenyl, biphenylyl, naphthyl, anthracenyl, or hydrogen. the law of nature, In the structures of formulas (5-Ar1) to (5-Ar5) above, at least one hydrogen is Phenyl, biphenylyl, naphthyl, anthracenyl, phenantrenyl, methyl, ethyl It may be substituted with propyl or butyl.

[0261] These heteroaryls, via a linking group, are related to the dibenzochrysene in formula (5) above. It may be bonded to the skeleton. That is, the dibenzochrysene skeleton in formula (5) and the above-mentioned he The teloaryl may not only bond directly, but may also bond to each other via a linking group. The linking groups include phenylene, biphenylene, naphthylene, anthracenylene, and Thilen, ethylene, -OCH2CH2-, -CH2CH2O-, or -OCH2CH Examples include 20-.

[0262] The compound represented by general formula (5) is preferably R 1 , R 4 , R 5 , R 8 , R 9 , R 1 2 , R 13 and R 16 is hydrogen. In this case, R in equation (5) 2 , R 3 , R 6 , R 7 , R 10 , R 11 , R 14 and R 15 These are, independently, hydrogen, phenyl, and biphenyl. Nilyl, naphthyl, anthracenyl, phenantrenyl, formula (5-Ar1), formula (5 It has the structure of -Ar2), formula (5-Ar3), formula (5-Ar4), or formula (5-Ar5). A monovalent group (a monovalent group having the said structure is phenylene, biphenylene, naphthylene, Anthracenylene, methylene, ethylene, -OCH2CH2-, -CH2CH2O-, Alternatively, via -OCH2CH2O-, it bonds with the dibenzochrysene skeleton in formula (5) above. (They may be combined), preferably methyl, ethyl, propyl, or butyl. .

[0263] The compound represented by general formula (5) is more preferably R 1 , R 2 , R 4 , R 5 , R 7 , R 8 , R 9 , R 10 , R 12 , R 13 , R 15 and R 16 It is hydrogen. In this case, the formula (5) R 3, R 6 , R 11 and R 14 At least one of (preferably one or two) (More preferably one) a single bond, phenylene, biphenylene, naphthylene, ant Racenylene, methylene, ethylene, -OCH2CH2-, -CH2CH2O-, or, The above formulas (5-Ar1), (5-Ar2), and (5-A) are obtained via -OCH2CH2O-. r3), a monovalent group having the structure of formula (5-Ar4) or formula (5-Ar5), Other than at least one of the above (i.e., other than the position where the monovalent group having the above structure is substituted) Hydrogen, phenyl, biphenylyl, naphthyl, anthracenyl, methyl, ethyl, prop It is phenyl or butyl, and at least one hydrogen in these is phenyl, biphenyl Nilyl, naphthyl, anthracenyl, methyl, ethyl, propyl, or butyl It may have been replaced.

[0264] Also, R in equation (5) 2 , R 3 , R 6 , R 7 , R 10 , R 11 , R 14 and R 15 and Then, a monovalent group having the structure represented by formulas (5-Ar1) to (5-Ar5) is selected. If selected, at least one hydrogen in the structure is R in formula (5). 1 From R 1 6 It may also bond with either of them to form a single bond.

[0265] The above-mentioned materials for the light-emitting layer (host material and dopant material) have reactive substituents added to them. A polymer compound obtained by polymerizing a reactive compound substituted with a monomer, or a polymer compound thereof. A molecular crosslinked polymer, or a pendant-type polymer obtained by reacting a main-chain polymer with the reactive compound. The compound, or its pendant-type polymer crosslinked form, can be used as a material for the light-emitting layer. This can be achieved. In this case, the reactive substituent is a polycyclic aromatic compound represented by formula (1). You can quote the explanation. Details of the applications of such polymer compounds and polymer crosslinks will be described later.

[0266] <An example of a polymer host material> [ka]

[0267] In equation (SPH-1), Each MU is independently a divalent aromatic compound, and each EC is independently a monovalent aromatic compound. It is a compound in which two hydrogen atoms in MU are replaced by EC or MU, and k is a constant from 2 to 50000. It is a number.

[0268] More specifically, MU is independently allirene, heteroarylene, and diarylene aryla It is mino, diarylenearylboryl, oxavorin-diyl, azavorin-diyl , ECs are, independently, hydrogen, aryl, heteroaryl, diarylamino, and di It is a heteroarylamino, arylheteroarylamino, or aryloxy, At least one hydrogen in MU and EC is further aryl, heteroaryl, They may be substituted with diarylamino, alkyl, and cycloalkyl groups. k is an integer between 2 and 50000. k is preferably an integer between 20 and 50000, and is an integer between 100 and 50000. It is preferable to do so.

[0269] In formula (SPH-1), at least one hydrogen atom in MU and EC is a carbon atom with 1 to 2 carbon atoms. Substituted with 4 alkyl groups, cycloalkyl groups with 3 to 24 carbon atoms, halogens, or deuterium. Furthermore, any -CH2- in the alkyl group may be -O- or -Si(CH 3) It may be substituted with 2-, and the EC in formula (SPH-1) in the alkyl is directly Any -CH2- groups other than those already bonded are replaced with arylene groups having 6 to 24 carbon atoms. It may be the case that any hydrogen atom in the alkyl group is substituted with fluorine.

[0270] For example, remove any two hydrogen atoms from any of the following compounds and list them in the table. Examples of divalent groups include those that are converted to iontophoresis. [ka]

[0271] More specifically, divalent groups represented by one of the following structures are included. And MU combines with other MUs or ECs in *.

[0272] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka]

[0273] Furthermore, examples of ECs include monovalent groups represented by one of the following structures. In these cases, EC is coupled with MU at *.

[0274] [ka] [ka]

[0275] The compound represented by formula (SPH-1) has the following properties in its molecule from the viewpoint of solubility and coating film-forming ability. It is preferable that 10-100% of the total number of MUs (k) have alkyl groups with 1-24 carbon atoms. Furthermore, 30-100% of the total number of MU (k) in the molecule are alkyl (carbon) with 1-18 carbon atoms. It is more preferable to have a branched alkyl group with prime numbers 3 to 18, and the total number of MUs (k) in the molecule 50-100% of MU is alkyl (C1-C12 branched-chain alkyl) It is even more preferable that it has ). On the other hand, from the viewpoint of in-plane orientation and charge transport, the molecule 10-100% of the total number of MU (k) in the molecule have alkyl groups with 7-24 carbon atoms. Preferably, 30-100% of the total number of MUs (k) in the molecule are alkyl groups with 7-24 carbon atoms. It is more preferable that it has a branched alkyl group (with 7 to 24 carbon atoms).

[0276] Details of the applications of such polymer compounds and polymer crosslinks will be described later.

[0277] <Electron injection layer and electron transport layer in organic electroluminescent devices> The electron injection layer 107 efficiently directs electrons moving from the cathode 108 into the light-emitting layer 105. Alternatively, it plays the role of injecting into the electron transport layer 106. The electron transport layer 106 is from the cathode 108 The injected electrons or electrons injected from the cathode 108 through the electron injection layer 107 are efficiently The electron transport layer 106 and electron injection layer 107 play a role in transporting electrons to the light-emitting layer 105. Each involves laminating or mixing one or more types of electron transport / injection materials, or electron transport / injection materials. It is formed from a mixture of injection material and polymer binder.

[0278] The electron injection and transport layer is responsible for the injection of electrons from the cathode and the subsequent transport of electrons. It is desirable that the layer has high electron injection efficiency and efficiently transports the injected electrons. Therefore, it is necessary to have high electron affinity, high electron mobility, and excellent stability. It is preferable that the substance is one that is less likely to generate trapping impurities during manufacturing and use. However, when considering the balance of hole and electron transport, if holes from the anode do not recombine When the primary role is to efficiently prevent electrons from flowing to the cathode side, the electron transport capacity is Even if not extremely high, the effect of improving luminescence efficiency is equivalent to that of materials with high electron transport capabilities. Therefore, the electron injection / transport layer in this embodiment can efficiently block the movement of holes. The functions of the layer may also be included.

[0279] The material used to form the electron transport layer 106 or the electron injection layer 107 (electron transport material) is: Compounds that have been conventionally used as electron transfer compounds in photoconductive materials, organic EL elements From among known compounds used in the electron injection layer and electron transport layer, any one compound may be selected and used. It is possible to be there.

[0280] Materials used in electron transport layers or electron injection layers include carbon, hydrogen, oxygen, sulfur, and kerosene. Aromatic rings or heteroaromatic compounds composed of one or more atoms selected from inium and phosphorus. Compounds consisting of rings, pyrrole derivatives and their fused ring derivatives, and compounds having electron-accepting nitrogen It is preferable to include at least one selected from among the metal complexes. Specifically, Phthalene, anthracene and other condensed ring aromatic ring derivatives, 4,4'-bis(diphenyl) Styryl aromatic ring derivatives, such as tenyl biphenyl, perinone derivatives, and coumarins. Derivatives, naphthalimide derivatives, quinone derivatives such as anthraquinone and diphenoquinone, Examples include phosphorus oxide derivatives, carbazole derivatives, and indole derivatives. Examples of metal complexes having electron-accepting nitrogen include hydroxyphenyloxazole complexes. Hydroxyazole complexes, azomethine complexes, tropolone metal complexes, flavonols, etc. Examples include metal complexes and benzoquinoline metal complexes. These materials can be used individually. However, it is acceptable to use it mixed with other materials.

[0281] Furthermore, specific examples of other electron transfer compounds include pyridine derivatives, naphthalene derivatives, and ammonium compounds. Tracene derivatives, phenanthroline derivatives, perinone derivatives, coumarin derivatives, naphthalene Imide derivatives, anthraquinone derivatives, diphenoquinone derivatives, diphenylquinone derivatives , perylene derivatives, oxadiazole derivatives (1,3-bis[(4-t-butylphenyl (e.g., 1,3,4-oxadiazolyl]phenylene), thiophene derivatives, triazoles Derivatives (such as N-naphthyl-2,5-diphenyl-1,3,4-triazole), thiadi Azole derivatives, oxine derivative metal complexes, quinolinol-based metal complexes, quinoxaline derivatives Conductors, quinoxaline derivative polymers, benzazole compounds, gallium complexes, pyrazole phenylene derivatives, perfluorinated phenylene derivatives, triazine derivatives, pyrazine derivatives, benzyl derivatives Zoquinoline derivative (2,2'-bis(benzo[h]quinoline-2-yl)-9,9'-s Pyrobifluorene, imidazopyridine derivatives, borane derivatives, benzimidazole Derivatives (such as tris(N-phenylbenzimidazole-2-yl)benzene), benzo Oxazole derivatives, benzothiazole derivatives, quinoline derivatives, terpyridine, etc. Ligopyridine derivatives, bipyridine derivatives, terpyridine derivatives (1,3-bis(4'-( 2,2':6'2"-terpyridinyl))benzene etc), naphthyridine derivatives (bis( 1-Naphthyl)-4-(1,8-Naphthyridine-2-yl)phenylphosphine oxa (e.g., aldazine derivatives, carbazole derivatives, indole derivatives, phosphorus oxide) Examples include derivatives and bis-styryl derivatives.

[0282] Furthermore, metal complexes containing electron-accepting nitrogen can also be used, for example, quinolinol-based Metal complexes and hydroxyazole complexes such as hydroxyphenyloxazole complexes, azometh Tin complexes, tropolone metal complexes, flavonol metal complexes and benzoquinoline metal complexes These are some examples.

[0283] The materials mentioned above can be used individually, but they can also be used in combination with other materials.

[0284] Among the materials mentioned above, borane derivatives, pyridine derivatives, fluorantene derivatives, BO System derivatives, anthracene derivatives, benzofluorene derivatives, phosphine oxide derivatives Pyrimidine derivatives, carbazole derivatives, triazine derivatives, benzimidazole derivatives The isomer, phenanthroline derivatives, and quinolinol-based metal complexes are preferred.

[0285] <Bolan derivatives> Borane derivatives are compounds represented by the following general formula (ETM-1), for example, and in detail... This is disclosed in Japanese Patent Publication No. 2007-27587. [ka] In the above formula (ETM-1), R 11 and R 12 These are, independently, hydrogen and alkyl. cycloalkyl, optionally substituted aryl, substituted silyl, substituted It may be a nitrogen-containing heterocycle, or at least one cyano, R 13 ~R 16 teeth, Each independently may be a substituted alkyl group or a substituted cycloalkyl group. ル, or aryl which may be substituted, and X is aryl which may be substituted. Y is an aryl with 16 or fewer carbon atoms, which may be substituted, and a substituted poly It is carbazolyl, or may be substituted, and n is independently 0 It is an integer between 3 and 3. Also, the case where it "may be substituted" or "is substituted" Examples of substitution groups include aryl, heteroaryl, alkyl, or cycloalkyl groups. It can be done.

[0286] Among the compounds represented by the above general formula (ETM-1), the following general formula (ETM-1-1) Compounds represented by the formula shown below or compounds represented by the general formula (ETM-1-2) are preferred. [ka] In formula (ETM-1-1), R 11 and R 12 These are, independently, hydrogen and alkyl. cycloalkyl, optionally substituted aryl, substituted silyl, substituted It may be a nitrogen-containing heterocycle, or at least one cyano, R 13 ~R 16 teeth, Each independently may be a substituted alkyl group or a substituted cycloalkyl group. R is an aryl that may be substituted, 21 and R 22 Each is independent And hydrogen, alkyl, cycloalkyl, optionally substituted aryl, substituted It is at least one of a silyl, a nitrogen-containing heterocycle which may be substituted, or a cyano. , X 1 n is an arylene with 20 or fewer carbon atoms, which may be substituted, and n is independent in each case. And are integers from 0 to 3, and m are each independent integers from 0 to 4. Also, Substituents that may be substituted or are substituted include aryl and helium. Examples include teloaryl, alkyl, or cycloalkyl groups. [ka] In formula (ETM-1-2), R 11 and R 12 These are, independently, hydrogen and alkyl. cycloalkyl, optionally substituted aryl, substituted silyl, substituted It may be a nitrogen-containing heterocycle, or at least one cyano, R 13 ~R16 teeth, Each independently may be a substituted alkyl group or a substituted cycloalkyl group. A aryl, or an aryl that may be substituted, X 1 The number of carbon atoms that may be substituted The numbers are all arrines less than or equal to 20, and each n is an independent integer between 0 and 3. Substituents that may be substituted or are substituted include aryl substituents. Examples include heteroaryl, alkyl, or cycloalkyl groups.

[0287] X 1 A specific example of this is a 2 expressed by any of the following equations (X-1) to (X-9). The basis of the value can be given. [ka] (In each formula, R a Each is independently an alkyl group, a cycloalkyl group, or substituted. (It is a suitable phenyl group.)

[0288] Specific examples of these borane derivatives include the following compounds. [ka]

[0289] This borane derivative can be produced using known raw materials and known synthesis methods.

[0290] <Pyridine derivatives> The pyridine derivative is, for example, a compound represented by the following formula (ETM-2), and is preferably It is a compound represented by formula (ETM-2-1) or formula (ETM-2-2). [ka]

[0291] φ is an n-valent aryl ring (preferably an n-valent benzene ring, naphthalene ring, or anthracene ring). ring, fluorene ring, benzofluorene ring, phenalene ring, phenanthrene ring or truffle It is an énylene ring, and n is an integer from 1 to 4.

[0292] In the above formula (ETM-2-1), R 11 ~R 18 These are, independently, hydrogen and A Lukyl (preferably alkyl with 1 to 24 carbon atoms), cycloalkyl (preferably with 3 carbon atoms) (~12 cycloalkyls) or aryls (preferably aryls with 6 to 30 carbon atoms) ru.

[0293] In the above formula (ETM-2-2), R 11 and R 12 Each of them independently, hydrogen , alkyl (preferably alkyl with 1 to 24 carbon atoms), cycloalkyl (preferably carbon Cycloalkyls (3 to 12 carbon atoms) or aryls (preferably aryls with 6 to 30 carbon atoms) And R 11 and R 12 They may be joined together to form a ring.

[0294] In each formula, the "pyridine substituent" is one of the following: (Py-1) to (Py-15) The pyridine substituents are either C1-C4 alkyl groups or carbon groups. It may be substituted with cycloalkyl groups of 5 to 10. Also, pyridine substituents may be phenyl Bonding to the φ, anthracene ring, or fluorene ring in each formula via a ylene group or naphthylene group. They can be combined.

[0295] [ka]

[0296] The pyridine substituent is one of the above formulas (Py-1) to (Py-15), however Among these, it is preferable that it be one of the following equations (Py-21) to (Py-44). stomach. [ka]

[0297] At least one hydrogen atom in each pyridine derivative may be substituted with deuterium, Furthermore, the two "pyridine-based" compounds in the above formulas (ETM-2-1) and (ETM-2-2) One of the substituents may be replaced with an aryl group.

[0298] R 11 ~R 18 In this context, "alkyl" can be either a straight chain or a branched chain. Examples include linear alkyl groups with 1 to 24 carbon atoms or branched alkyl groups with 3 to 24 carbon atoms. The preferred "alkyl" is an alkyl group with 1 to 18 carbon atoms (a branched-chain alkyl group with 3 to 18 carbon atoms). A more preferred "alkyl" is an alkyl group with 1 to 12 carbon atoms (3 to 12 carbon atoms). It is a branched alkyl group with 12 carbon atoms. A more preferred alkyl group is an alkyl group with 1 to 6 carbon atoms. It is a branched alkyl group (with 3 to 6 carbon atoms). Particularly preferred alkyl groups have 1 to 6 carbon atoms. It is a 4-C1 alkyl group (a branched alkyl group with 3 to 4 carbon atoms).

[0299] Specific examples of "alkyl" include methyl, ethyl, n-propyl, isopropyl, n- Butyl, isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl, neopen Tyl, t-pentyl, n-hexyl, 1-methylpentyl, 4-methyl-2-pentyl, 3,3-Dimethylbutyl, 2-Ethylbutyl, n-Heptyl, 1-Methylhexyl, n- Octyl, t-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl Tyl, n-nonyl, 2,2-dimethylheptyl, 2,6-dimethyl-4-heptyl, 3, 5,5-Trimethylhexyl, n-decyl, n-undecyl, 1-methyldecyl, n- Decyl, n-tridecyl, 1-hexylheptyl, n-tetradecyl, n-pentadecyl Examples include n-hexadecyl, n-heptadecyl, n-octadecyl, and n-eicosyl. It is possible.

[0300] For alkyl groups with 1 to 4 carbon atoms to be substituted for pyridine substituents, see the above explanation of alkyl groups. It can be quoted.

[0301] R 11 ~R 18 Examples of "cycloalkyl" in this context include cycloalkyl groups with 3 to 12 carbon atoms. Examples include cycloalkyl groups. Preferred "cycloalkyl" groups are cycloalkyl groups with 3 to 10 carbon atoms. It is a kill. A more preferred "cycloalkyl" is a cycloalkyl with 3 to 8 carbon atoms. A more preferred "cycloalkyl" is a cycloalkyl group having 3 to 6 carbon atoms. Specific examples of "cycloalkyl" include cyclopropyl, cyclobutyl, and cyclopentyl , cyclohexyl, methylcyclopentyl, cycloheptyl, methylcyclohexyl, Examples include cyclooctyl or dimethylcyclohexyl.

[0302] R 11 ~R 18 In this context, preferred aryls are those with 6 to 30 carbon atoms. It is an aryl, and more preferably an aryl with 6 to 18 carbon atoms, and even more preferably More preferably, an aryl compound having 6 to 14 carbon atoms, and particularly preferably an aryl compound having 6 to 12 carbon atoms. ru.

[0303] Specific examples of "aryls with 6 to 30 carbon atoms" include monocyclic aryls such as phenyl and fuzzy aryls. (1-,2-)naphthyl is a bicyclic aryl compound, and asenaphthyl is a tricyclic aryl compound. Chilen-(1-,3-,4-,5-)yl, Fluorene-(1-,2-,3-,4-,9 -) yl, phenalene-(1-,2-) yl, (1-,2-,3-,4-,9-) phenalene Triphenylene-(1-,2-)yl, pyrene-( 1-,2-,4-)yl, naphthacene-(1-,2-,5-)yl, condensed pentacyclic aryl Perylene-(1-,2-,3-)yl, pentasene-(1-,2-,5-,6-) Examples include Il.

[0304] Preferred "aryls with 6 to 30 carbon atoms" include phenyl, naphthyl, phenanthryl, and cyanoacrylate. Examples include lysenyl or triphenylenyl, and more preferably phenyl, 1-naphthol. Examples include phenyl, 2-naphthyl, or phenanthryl, with phenyl, 1-naphthyl being particularly preferred. Phthyl or 2-naphthyl are examples.

[0305] In the above formula (ETM-2-2), R 11 and R 12 Even if they are bonded together to form a ring Often, as a result, the five-membered ring of the fluorene skeleton contains cyclobutane, cyclopentane, and cyclo Pentene, cyclopentadiene, cyclohexane, fluorene, or indene are among the stimulants. It is acceptable for them to be joined together.

[0306] Specific examples of pyridine derivatives include the following compounds. [Chemical formula]

[0307] This pyridine derivative can be produced using known raw materials and known synthesis methods.

[0308] <Fluoranthene derivative> The fluoranthene derivative is, for example, a compound represented by the following general formula (ETM-3), Specifically, it is disclosed in International Publication No. WO2010 / 134352. [Chemical formula]

[0309] In the above formula (ETM-3), X 12 ~X 21 represents hydrogen, halogen, linear, branched or cyclic alkyl, linear, branched or cyclic alkoxy, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl. Here, when it is substituted, examples of the substituent include aryl, heteroaryl, alkyl or cycloalkyl, etc. .

[0310] Specific examples of this fluoranthene derivative include, for example, the following compounds. [Chemical formula] [[ID=4​​​​​​​​​​​​​​​

[0312] R 1 ~R 11 These are, independently, hydrogen, aryl, heteroaryl, and diarylia. Mino, diheteroarylamino, arylheteroarylamino, alkyl, cycloal It is a chloroxy, alkoxy, or aryloxy, and in these, at least one hydrogen is They may be substituted with aryl, heteroaryl, alkyl, or cycloalkyl groups.

[0313] Also, R 1 ~R 11 Among them, adjacent groups bond together to form ring a, b, or c. They may form a reel ring or a heteroaryl ring, and in the formed ring, Another hydrogen atom is aryl, heteroaryl, diarylamino, and diheteroarylamino. aryl heteroarylamino, alkyl, cycloalkyl, alkoxy or aryl They may be substituted with aryloxy, and at least one hydrogen in these is aryl, helium. They may be substituted with teloaryl, alkyl, or cycloalkyl groups.

[0314] Furthermore, at least one hydrogen in the compound or structure represented by formula (ETM-4) It may be substituted with a halogen or deuterium.

[0315] For an explanation of the substituents and ring formation in formula (ETM-4), please refer to the general formula (1) above. We can cite the explanation of polycyclic aromatic compounds represented by [the formula shown].

[0316] Specific examples of these BO derivatives include the following compounds. [ka]

[0317] This BO derivative can be produced using known raw materials and known synthesis methods.

[0318] <Anthracene derivatives> One example of anthracene derivatives is a compound represented by the following formula (ETM-5-1): ru. [ka]

[0319] Ar is independently either divalent benzene or naphthalene, and R 1 ~R 4 teeth, Each of these independently consists of hydrogen, alkyl groups with 1 to 6 carbon atoms, and cycloalkyl groups with 3 to 6 carbon atoms. These are aryl atoms with 6 to 20 carbon atoms.

[0320] Ar can be independently selected from divalent benzene or naphthalene as appropriate. The two Ar atoms may be different or the same, but the synthesis of anthracene derivatives From the standpoint of ease, it is preferable that they be the same. Ar combines with pyridine to form "Ar and It forms a "part consisting of bipyridine," and this part is, for example, the following formula (Py-1) ~ formula ( It is attached to anthracene as a group represented by one of the following (Py-12):

[0321] [ka]

[0322] Among these groups, the group represented by any of the above formulas (Py-1) to (Py-9) is Preferably, a group represented by any of the above formulas (Py-1) to (Py-6) is preferred. The two "Ar and pyridine moieties" that bind to anthracene have the same structure. They may be the same or different, but from the viewpoint of the ease of synthesis of anthracene derivatives, they are the same. It is preferable that the structure be the same. However, from the viewpoint of device characteristics, two "Ar and pyramidal" The structure of the "part consisting of din" is preferable whether it is the same or different.

[0323] R 1 ~R 4 For alkyl groups with 1 to 6 carbon atoms, both linear and branched chains are used. Good. That is, a linear alkyl group with 1 to 6 carbon atoms or a branched alkyl group with 3 to 6 carbon atoms. More preferably, an alkyl group having 1 to 4 carbon atoms (a branched alkyl group having 3 to 4 carbon atoms). Specific examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, and isopropyl. butyl, s-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, t-pentyl Tyl, n-hexyl, 1-methylpentyl, 4-methyl-2-pentyl, 3,3-dimeth Examples include methyl butyl or 2-ethylbutyl, as well as methyl, ethyl, n-propyl, and ethyl butyl. Sopropyl, n-butyl, isobutyl, s-butyl, or t-butyl are preferred, and methyl ethyl, t-butyl, or t-butyl are more preferred.

[0324] R 1 ~R 4 A specific example of a cycloalkyl group with 3 to 6 carbon atoms is cyclopropyl Cyclobutyl, cyclopentyl, cyclohexyl, methylcyclopentyl, cyclohexyl Examples include methylcyclohexyl, cyclooctyl, or dimethylcyclohexyl. It is possible.

[0325] R 1 ~R 4 Regarding aryls with 6 to 20 carbon atoms, the aryls with 6 to 16 carbon atoms are... A C6-C12 aryl is preferred, a C6-C10 aryl is particularly preferred. It is preferable.

[0326] Specific examples of "aryls with 6 to 20 carbon atoms" include monocyclic aryls such as phenyl, ( o-,m-,p-) trill, (2,3-,2,4-,2,5-,2,6-,3,4-,3 ,5-)xylyl, mesityl(2,4,6-trimethylphenyl), (o-,m-,p- )Cumenyl, a bicyclic aryl (2-,3-,4-)biphenylyl, a condensed bicyclic aryl (1-,2-)naphthyl is a aryl compound, and terpheniryl (m-terphthyl) is a tricyclic aryl compound. Enyl-2'-yl, m-terphenyl-4'-yl, m-terphenyl-5'-yl, o-terphenyl-3'-yl, o-terphenyl-4'-yl, p-terphenyl-2 '-yl, m-terphenyl-2-yl, m-terphenyl-3-yl, m-terphenyl Ru-4-yl, o-terphenyl-2-yl, o-terphenyl-3-yl, o-terf Phenyl-4-yl, p-terphenyl-2-yl, p-terphenyl-3-yl, p-terphenyl Anthracene-(1-,2-,9) is a condensed tricyclic aryl compound. -)yl, acenaphthylene-(1-,3-,4-,5-)yl, fluorene-(1-,2 -,3-,4-,9-)il, phenalene-(1-,2-)il, (1-,2-,3-, 4-,9-)phenanthryl, a condensed tetracyclic aryl triphenylene-(1-,2- )yl, pyren-(1-,2-,4-)yl, tetracene-(1-,2-,5-)yl, Examples include perylene-(1-,2-,3-)yl, a condensed pentacyclic aryl.

[0327] Preferred "aryl compounds with 6 to 20 carbon atoms" include phenyl, biphenylyl, and terphenylyl. or naphthyl, more preferably phenyl, biphenylyl, 1-naphthyl, 2- Naphthyl or m-terphenyl-5'-yl, more preferably phenyl, bian The material is phenylyl, 1-naphthyl, or 2-naphthyl, most preferably phenyl.

[0328] One example of anthracene derivatives is a compound represented by the following formula (ETM-5-2): ru. [ka]

[0329] Ar 1 These are, independently, single bonds, divalent benzene, naphthalene, anthracene, It is either fluorene or phenalene.

[0330] Ar 2 Each of these is an aryl group with 6 to 20 carbon atoms, and the above formula (ETM-5 The same explanation as in -1) for "aryls with 6 to 20 carbon atoms" can be cited. aryls with 6 to 16 carbon atoms are preferred, aryls with 6 to 12 carbon atoms are more preferred, and aryls with 6 carbon atoms are preferred. Aryl compounds of ~10 are particularly preferred. Specific examples include phenyl, biphenylyl, and naphthyl. terpheniryl, anthracenyl, acenaphtyrenyl, fluorenyl, phenalenyl, Examples include phenanthryl, triphenylenyl, pyrenyl, tetracenyl, and perirenyl. It can be done.

[0331] R 1 ~R 4 These are, independently, hydrogen, alkyl with 1 to 6 carbon atoms, and alkyl with 3 to 6 carbon atoms. It is a cycloalkyl or aryl with 6 to 20 carbon atoms, and the above formula (ETM-5-1) You can quote the explanation provided.

[0332] Specific examples of these anthracene derivatives include the following compounds: [ka]

[0333] These anthracene derivatives can be produced using known raw materials and known synthesis methods. Cut.

[0334] <Benzofluorene derivatives> Benzofluorene derivatives are compounds represented by the following formula (ETM-6), for example. [ka]

[0335] Ar 1 Each of these is an aryl group with 6 to 20 carbon atoms, and the above formula (ETM-5 The same explanation as in -1) for "aryls with 6 to 20 carbon atoms" can be cited. aryls with 6 to 16 carbon atoms are preferred, aryls with 6 to 12 carbon atoms are more preferred, and aryls with 6 carbon atoms are preferred. Aryl compounds of ~10 are particularly preferred. Specific examples include phenyl, biphenylyl, and naphthyl. terpheniryl, anthracenyl, acenaphtyrenyl, fluorenyl, phenalenyl, Examples include phenanthryl, triphenylenyl, pyrenyl, tetracenyl, and perirenyl. It can be done.

[0336] Ar 2 These are, independently, hydrogen and alkyl (preferably alkyl having 1 to 24 carbon atoms). ), cycloalkyl (preferably cycloalkyl with 3 to 12 carbon atoms) or aryl (preferably The aryl atoms have 6 to 30 carbon atoms, and two Ar 2 They are joined together to form a ring. That's good too.

[0337] Ar 2 The "alkyl" in this context can be either a linear or branched chain, for example, Examples include linear alkyl groups with 1 to 24 carbon atoms or branched alkyl groups with 3 to 24 carbon atoms. The term "alkyl" refers to alkyl groups with 1 to 18 carbon atoms (branched-chain alkyl groups with 3 to 18 carbon atoms). A more preferred "alkyl" is an alkyl group with 1 to 12 carbon atoms (a fraction of which has 3 to 12 carbon atoms). It is a branched alkyl. A more preferred "alkyl" is an alkyl (carbon) having 1 to 6 carbon atoms. It is a branched alkyl group with 3 to 6 carbon atoms. Particularly preferred alkyl groups are those with 1 to 4 carbon atoms. It is a branched alkyl group (with 3-4 carbon atoms). A specific example of "alkyl" is methyl. ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl Tyl, n-pentyl, isopentyl, neopentyl, t-pentyl, n-hexyl, 1- Methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl Examples include 1-methylhexyl, n-heptyl, and 1-methylhexyl.

[0338] Ar 2 In this context, "cycloalkyl" refers to, for example, cycloalkyl groups with 3 to 12 carbon atoms. Examples include: A preferred "cycloalkyl" is a cycloalkyl with 3 to 10 carbon atoms. A more preferred "cycloalkyl" is a cycloalkyl with 3 to 8 carbon atoms. Preferred "cycloalkyl" is a cycloalkyl with 3 to 6 carbon atoms. Examples of "roalkyl" include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl Methylcyclopentyl, cycloheptyl, methylcyclohexyl, cyclooctyl Examples include dimethylcyclohexyl.

[0339] Ar 2 In this context, preferred aryls are those with 6 to 30 carbon atoms. A more preferred aryl is an aryl with 6 to 18 carbon atoms, and even more preferably a carbon aryl. The aryl group has 6 to 14 prime numbers, and is particularly preferably an aryl group with 6 to 12 carbon atoms.

[0340] Specific examples of "aryl compounds with 6 to 30 carbon atoms" include phenyl, naphthyl, and acenaphthyl Nyl, fluorenyl, phenalenyl, phenanthryl, triphenylenyl, pyrenyl, na Examples include phthalocenyl, perirenyl, and pentacenyl.

[0341] Two Ar 2 These may be bonded together to form a ring, resulting in a five-membered ring of the fluorene skeleton. It contains cyclobutane, cyclopentane, cyclopentene, cyclopentadiene, and cyclohexane. Xane, fluorene, or indene may be spirolinked to it.

[0342] Specific examples of these benzofluorene derivatives include the following compounds: [ka]

[0343] This benzofluorene derivative can be produced using known raw materials and known synthesis methods. Cut.

[0344] <Phosphine oxide derivatives> Phosphine oxide derivatives are compounds represented by the following formula (ETM-7-1), for example. Yes, it exists. Further details are also described in International Publication No. 2013 / 079217. [ka] R 5 These are substituted or unsubstituted alkyl groups with 1 to 20 carbon atoms, and cycloa groups with 3 to 16 carbon atoms. Lukyl is an aryl or heteroaryl with 6 to 20 carbon atoms. R 6 This includes CN, substituted or unsubstituted alkyl groups with 1 to 20 carbon atoms, and silicic compounds with 3 to 16 carbon atoms. Chloalkyl, heteroalkyl with 1-20 carbon atoms, aryl with 6-20 carbon atoms, 5 carbon atoms ~20 heteroaryls, alkoxys with 1-20 carbon atoms, or aryls with 6-20 carbon atoms. It is an oxy, R 7 and R 8 Each of these is independently a substituted or unsubstituted ally with 6 to 20 carbon atoms. It is a heteroaryl with 5 to 20 carbon atoms. R 9 It is oxygen or sulfur, j is 0 or 1, k is 0 or 1, r is an integer from 0 to 4, and q is an integer from 1 to 3 It is an integer. In this case, the substituents that are substituted are aryl, heteroaryl, and alkyl. Other examples include cycloalkyl groups.

[0345] Phosphine oxide derivatives are compounds represented by the following formula (ETM-7-2), for example. That's good too. [ka]

[0346] R 1 ~R 3 They may be the same or different, and include hydrogen, alkyl groups, cycloalkyl groups, Aralkyl group, alkenyl group, cycloalkenyl group, alkynyl group, alkoxy group, alkyl group Kilthio group, cycloalkylthio group, aryl ether group, arylthioether group, A Lille group, heterocyclic group, halogen, cyano group, aldehyde group, carbonyl group, carboxyl Among the condensed rings formed between the amino group, nitro group, silyl group, and adjacent substituents They were selected.

[0347] Ar 1 These may be the same or different, and are either an arylene group or a heteroarylene group. Ar 2 These may be the same or different, and are either an aryl group or a heteroaryl group. However, Ar 1 and Ar 2 At least one of them has a substituent, or adjacent A fused ring is formed between the substituent and the compound. n is an integer from 0 to 3, and when n is 0, it is unsaturated. There are no structural parts, and when n is 3, R 1 It does not exist.

[0348] Among these substituents, alkyl groups include, for example, methyl, ethyl, propyl, and b This group exhibits saturated aliphatic hydrocarbon groups such as til groups, and these can be unsubstituted or substituted. There are no particular restrictions on the substituents when substituted; for example, alkyl groups, aryl groups. Examples include heterocyclic groups, and this point is also common to the following description. Furthermore, alkyl groups are also included. The number of carbon atoms in the base is not particularly limited, but due to availability and cost considerations, it is usually in the range of 1 to 20. It is enclosed.

[0349] Furthermore, cycloalkyl groups include, for example, cyclopropyl, cyclohexyl, norbornyl. It exhibits saturated alicyclic hydrocarbon groups such as ru and adamantyl, which are either unsubstituted or substituted. That's fine. The number of carbon atoms in the alkyl group is not particularly limited, but is usually in the range of 3 to 20. be.

[0350] Furthermore, aralkyl groups are aliphatic carbonized groups such as benzyl groups and phenylethyl groups. It shows an aromatic hydrocarbon group via an element, and both aliphatic hydrocarbons and aromatic hydrocarbons are unsubstituted. However, substitution is acceptable. The number of carbon atoms in the aliphatic portion is not particularly limited, but is usually 1. The range is ~20.

[0351] Furthermore, alkenyl groups are double bonds such as vinyl groups, allyl groups, and butadienyl groups. This represents an unsaturated aliphatic hydrocarbon group containing a compound, which may be unsubstituted or substituted. The number of carbon atoms in the alkenyl group is not particularly limited, but is usually in the range of 2 to 20.

[0352] Furthermore, cycloalkenyl groups include, for example, cyclopentenyl and cyclopentadienyl groups. It shows an unsaturated alicyclic hydrocarbon group containing a double bond, such as a cyclohexene group, and this is ostagmoid. It doesn't matter whether it's a substitution or a replacement.

[0353] Furthermore, an alkynyl group is an unsaturated aliphatic group containing a triple bond, such as an acetylenyl group. This represents a hydrocarbon group, which may be unsubstituted or substituted. The carbon of the alkynyl group. The number is not particularly limited, but it is usually in the range of 2 to 20.

[0354] Furthermore, alkoxy groups are, for example, aliphatic carbon groups that undergo ether bonding. It represents a hydrogen group, and the aliphatic hydrocarbon group may be unsubstituted or substituted. The number of carbon atoms in the group is not particularly limited, but it is usually in the range of 1 to 20.

[0355] Furthermore, an alkylthio group is defined as a group in which the oxygen atom in the ether bond of an alkoxy group is replaced by a sulfur atom. It is the basis.

[0356] Furthermore, a cycloalkylthio group is a group in which the oxygen atom of the ether bond of a cycloalkoxy group is sulfur It is a group substituted with a yellow atom.

[0357] Furthermore, aryl ether groups are aromatic compounds that are linked to ether bonds, such as phenoxy groups. It represents a fragrant hydrocarbon group, and the aromatic hydrocarbon group may be unsubstituted or substituted. The number of carbon atoms in the reel ether group is not particularly limited, but is usually in the range of 6 to 40.

[0358] Furthermore, an arylthioether group is defined as the oxygen atom of the ether bond of an aryl ether group. It is a group substituted with a sulfur atom.

[0359] Furthermore, aryl groups include, for example, phenyl, naphthyl, biphenyl, and phenant groups. This refers to aromatic hydrocarbon groups such as lyl groups, terphenyl groups, and pyrenyl groups. Aryl groups are absent. Substitution or substituted is acceptable. The number of carbon atoms in the aryl group is not particularly limited, but usually The range is 6 to 40.

[0360] Furthermore, heterocyclic groups include, for example, furanyl groups, thiophenyl groups, oxazolyl groups, and pyridyl groups. It shows cyclic structural groups having atoms other than carbon, such as a quinolinyl group and a carbazolyl group. This can be unsubstituted or substituted. The number of carbon atoms in the heterocyclic group is not particularly limited. The range is usually between 20 and 30.

[0361] Halogens refer to fluorine, chlorine, bromine, and iodine.

[0362] Aldehyde groups, carbonyl groups, and amino groups include aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic compounds. Groups substituted with cyclic hydrocarbons, heterocyclic rings, etc., can also be included.

[0363] Furthermore, aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, and heterocyclic hydrocarbons can be substituted even if they are unsubstituted. It's okay if it's included.

[0364] A silyl group refers to a silicon compound group such as a trimethylsilyl group, and this is an unassigned group. It can be either a substitution or a substitution. The number of carbon atoms in the silyl group is not particularly limited, but usually it is 3. The range is ~20. Also, the silicon number is usually between 1 and 6.

[0365] The fused ring formed between adjacent substituents is, for example, Ar 1 and R 2 Ar 1 and R 3 , A r 2 and R 2 Ar 2 and R 3 , R 2 and R 3 Ar 1 and Ar 2 Conjugation or It is a non-conjugated fused ring. Here, when n is 1, there are two R 1 Contraction of conjugate or non-conjugate terms between two entities. They may form fused rings. These fused rings contain nitrogen, oxygen, and sulfur atoms in their intraring structure. Alternatively, it may be fused with another ring.

[0366] Specific examples of these phosphine oxide derivatives include the following compounds: . [ka]

[0367] This phosphine oxide derivative is manufactured using known raw materials and known synthesis methods. It is possible.

[0368] <Pyrimidine derivatives> The pyrimidine derivative is, for example, a compound represented by the following formula (ETM-8), and is preferably This compound is represented by the following formula (ETM-8-1). For details, see International Publication No. 2011 / 021689. It is also stated in the official gazette. [ka]

[0369] Each Ar is an aryl that may be substituted, or may be substituted. It is a good heteroaryl. n is an integer from 1 to 4, preferably an integer from 1 to 3. More preferably, 2 or 3.

[0370] Examples of "aryls that may be substituted" include those with 6 to 30 carbon atoms. Examples include aryls, preferably aryls having 6 to 24 carbon atoms, more preferably aryls having 6 carbon atoms. ~20 aryl atoms, more preferably aryl atoms with 6 to 12 carbon atoms.

[0371] Specific examples of "aryl" include monocyclic aryls such as phenyl and bicyclic aryls. (2-,3-,4-)biphenylyl is a condensed bicyclic aryl (1-,2-)naphthyl The tricyclic aryl terpheniryl (m-terphenyl-2'-yl, m-terf) phenyl-4'-yl, m-terphenyl-5'-yl, o-terphenyl-3'-yl, o-terphenyl-4'-yl, p-terphenyl-2'-yl, m-terphenyl-2 -yl, m-terphenyl-3-yl, m-terphenyl-4-yl, o-terphenyl -2-yl, o-terphenyl-3-yl, o-terphenyl-4-yl, p-terphenyl (Nyl-2-yl, p-terphenyl-3-yl, p-terphenyl-4-yl), condensed tri The cyclic aryl is acenaphthylene-(1-,3-,4-,5-)yl, fluorene- (1-,2-,3-,4-,9-) yl, phenalene-(1-,2-) yl, (1-,2 -,3-,4-,9-)phenanthryl, tetracyclic aryl quaterpheniryl (5 '-phenyl-m-terphenyl-2-yl, 5'-phenyl-m-terphenyl-3- Il, 5'-phenyl-m-terphenyl-4-yl, m-quaterphenylyl), condensation The tetracyclic aryls are triphenylene-(1-,2-)yl and pyrene-(1-,2-,4 -)yl, naphthasen-(1-,2-,5-)yl, and perylene, a condensed pentacyclic aryl system. Examples include -(1-,2-,3-)il and pentase-(1-,2-,5-,6-)il. It is possible.

[0372] Examples of "heteroaryls that may be substituted" include carbon Examples include heteroaryl compounds with 2 to 30 prime numbers, with heteroaryl compounds having 2 to 25 carbon atoms being preferred. Heteroaryls having 2 to 20 carbon atoms are more preferred, and heteroaryls having 2 to 15 carbon atoms are preferred. More preferably, heteroaryls having 2 to 10 carbon atoms are particularly preferred. For example, the ring constituent atoms may be selected from oxygen, sulfur, and nitrogen in addition to carbon. Examples include heterocycles containing one to five ion atoms.

[0373] Specific heteroaryl compounds include, for example, furyl, thienyl, pyrrolyl, and oxazoli. Lu, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, oxy Sadiazolyl, flazanil, thiadiazolyl, triazolyl, tetrazolyl, pyridyl, Pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, benzofuranyl, isobenzo Furanyl, benzo[b]thienyl, indolyl, isoindolyl, 1H-indazolyl, Benzimidazolyl, benzoxazolyl, benzothiazolyl, 1H-benzotriazolyl Lu, quinolyl, isoquinolyl, cinnolyl, quinazolyl, quinoxalinyl, phthalazinyl Naphthilidinyl, Purinyl, Pteridinyl, Carbazolyl, Acridinyl, Phenoxa Zinyl, phenothiazinyl, phenazinyl, phenoxathiinyl, thianthrenyl, yn Examples include dridinil.

[0374] Furthermore, the above aryl and heteroaryl may be substituted, for example, the above It may be substituted with an aryl or heteroaryl.

[0375] Specific examples of these pyrimidine derivatives include the following compounds. [ka]

[0376] This pyrimidine derivative can be produced using known raw materials and known synthesis methods.

[0377] <Carbazole derivatives> Carbazole derivatives include, for example, compounds represented by the following formula (ETM-9), or compounds that are... It is a polymer formed by multiple single bonds or other linkages. Further details are described in U.S. Public Gazette No. 2014 / 0197386. It is being done. [ka]

[0378] Each Ar is an aryl that may be substituted, or may be substituted. It is a good heteroaryl. n is an integer between 0 and 4, preferably an integer between 0 and 3. More preferably, it is 0 or 1.

[0379] Examples of "aryls that may be substituted" include those with 6 to 30 carbon atoms. Examples include aryls, preferably aryls having 6 to 24 carbon atoms, more preferably aryls having 6 carbon atoms. ~20 aryl atoms, more preferably aryl atoms with 6 to 12 carbon atoms.

[0380] Specific examples of "aryl" include monocyclic aryls such as phenyl and bicyclic aryls. (2-,3-,4-)biphenylyl is a condensed bicyclic aryl (1-,2-)naphthyl The tricyclic aryl terpheniryl (m-terphenyl-2'-yl, m-terf) phenyl-4'-yl, m-terphenyl-5'-yl, o-terphenyl-3'-yl, o-terphenyl-4'-yl, p-terphenyl-2'-yl, m-terphenyl-2 -yl, m-terphenyl-3-yl, m-terphenyl-4-yl, o-terphenyl -2-yl, o-terphenyl-3-yl, o-terphenyl-4-yl, p-terphenyl (Nyl-2-yl, p-terphenyl-3-yl, p-terphenyl-4-yl), condensed tri The cyclic aryl is acenaphthylene-(1-,3-,4-,5-)yl, fluorene- (1-,2-,3-,4-,9-) yl, phenalene-(1-,2-) yl, (1-,2 -,3-,4-,9-)phenanthryl, tetracyclic aryl quaterpheniryl (5 '-phenyl-m-terphenyl-2-yl, 5'-phenyl-m-terphenyl-3- Il, 5'-phenyl-m-terphenyl-4-yl, m-quaterphenylyl), condensation The tetracyclic aryls are triphenylene-(1-,2-)yl and pyrene-(1-,2-,4 -)yl, naphthasen-(1-,2-,5-)yl, and perylene, a condensed pentacyclic aryl system. Examples include -(1-,2-,3-)il and pentase-(1-,2-,5-,6-)il. It is possible.

[0381] Examples of "heteroaryls that may be substituted" include carbon Examples include heteroaryl compounds with 2 to 30 prime numbers, with heteroaryl compounds having 2 to 25 carbon atoms being preferred. Heteroaryls having 2 to 20 carbon atoms are more preferred, and heteroaryls having 2 to 15 carbon atoms are preferred. More preferably, heteroaryls having 2 to 10 carbon atoms are particularly preferred. For example, the ring constituent atoms may be selected from oxygen, sulfur, and nitrogen in addition to carbon. Examples include heterocycles containing one to five ion atoms.

[0382] Specific heteroaryl compounds include, for example, furyl, thienyl, pyrrolyl, and oxazoli. Lu, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, oxy Sadiazolyl, flazanil, thiadiazolyl, triazolyl, tetrazolyl, pyridyl, Pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, benzofuranyl, isobenzo Furanyl, benzo[b]thienyl, indolyl, isoindolyl, 1H-indazolyl, Benzimidazolyl, benzoxazolyl, benzothiazolyl, 1H-benzotriazolyl Lu, quinolyl, isoquinolyl, cinnolyl, quinazolyl, quinoxalinyl, phthalazinyl Naphthilidinyl, Purinyl, Pteridinyl, Carbazolyl, Acridinyl, Phenoxa Zinyl, phenothiazinyl, phenazinyl, phenoxathiinyl, thianthrenyl, yn Examples include dridinil.

[0383] Furthermore, the above aryl and heteroaryl may be substituted, for example, the above It may be substituted with an aryl or heteroaryl.

[0384] Carbazole derivatives are compounds represented by the above formula (ETM-9) with multiple bonds such as single bonds. It may also be a combined polymer. In this case, in addition to single bonds, there may be an aryl ring (preferably a polyvalent one). Benzene ring, naphthalene ring, anthracene ring, fluorene ring, benzofluorene ring, phen They may be linked by a narene ring, a phenanthrene ring, or a triphenylene ring.

[0385] Specific examples of these carbazole derivatives include the following compounds. [ka]

[0386] This carbazole derivative can be produced using known raw materials and known synthesis methods. .

[0387] <Triadine derivatives> Triazine derivatives are, for example, compounds represented by the following formula (ETM-10), and are preferred. The compound is represented by the following formula (ETM-10-1). For details, see U.S. Public Notice 2011 / 015. It is described in Gazette No. 6013. [ka]

[0388] Each Ar is an aryl that may be substituted, or may be substituted. It is a good heteroaryl. n is an integer from 1 to 3, preferably 2 or 3.

[0389] Examples of "aryls that may be substituted" include those with 6 to 30 carbon atoms. Examples include aryls, preferably aryls having 6 to 24 carbon atoms, more preferably aryls having 6 carbon atoms. ~20 aryl atoms, more preferably aryl atoms with 6 to 12 carbon atoms.

[0390] Specific examples of "aryl" include monocyclic aryls such as phenyl and bicyclic aryls. (2-,3-,4-)biphenylyl is a condensed bicyclic aryl (1-,2-)naphthyl The tricyclic aryl terpheniryl (m-terphenyl-2'-yl, m-terf) phenyl-4'-yl, m-terphenyl-5'-yl, o-terphenyl-3'-yl, o-terphenyl-4'-yl, p-terphenyl-2'-yl, m-terphenyl-2 -yl, m-terphenyl-3-yl, m-terphenyl-4-yl, o-terphenyl -2-yl, o-terphenyl-3-yl, o-terphenyl-4-yl, p-terphenyl (Nyl-2-yl, p-terphenyl-3-yl, p-terphenyl-4-yl), condensed tri The cyclic aryl is acenaphthylene-(1-,3-,4-,5-)yl, fluorene- (1-,2-,3-,4-,9-) yl, phenalene-(1-,2-) yl, (1-,2 -,3-,4-,9-)phenanthryl, tetracyclic aryl quaterpheniryl (5 '-phenyl-m-terphenyl-2-yl, 5'-phenyl-m-terphenyl-3- Il, 5'-phenyl-m-terphenyl-4-yl, m-quaterphenylyl), condensation The tetracyclic aryls are triphenylene-(1-,2-)yl and pyrene-(1-,2-,4 -)yl, naphthasen-(1-,2-,5-)yl, and perylene, a condensed pentacyclic aryl system. Examples include -(1-,2-,3-)il and pentase-(1-,2-,5-,6-)il. It is possible.

[0391] Examples of "heteroaryls that may be substituted" include carbon Examples include heteroaryl compounds with 2 to 30 prime numbers, with heteroaryl compounds having 2 to 25 carbon atoms being preferred. Heteroaryls having 2 to 20 carbon atoms are more preferred, and heteroaryls having 2 to 15 carbon atoms are preferred. More preferably, heteroaryls having 2 to 10 carbon atoms are particularly preferred. For example, the ring constituent atoms may be selected from oxygen, sulfur, and nitrogen in addition to carbon. Examples include heterocycles containing one to five ion atoms.

[0392] Specific heteroaryl compounds include, for example, furyl, thienyl, pyrrolyl, and oxazoli. Lu, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, oxy Sadiazolyl, flazanil, thiadiazolyl, triazolyl, tetrazolyl, pyridyl, Pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, benzofuranyl, isobenzo Furanyl, benzo[b]thienyl, indolyl, isoindolyl, 1H-indazolyl, Benzimidazolyl, benzoxazolyl, benzothiazolyl, 1H-benzotriazolyl Lu, quinolyl, isoquinolyl, cinnolyl, quinazolyl, quinoxalinyl, phthalazinyl Naphthilidinyl, Purinyl, Pteridinyl, Carbazolyl, Acridinyl, Phenoxa Zinyl, phenothiazinyl, phenazinyl, phenoxathiinyl, thianthrenyl, yn Examples include dridinil.

[0393] Furthermore, the above aryl and heteroaryl may be substituted, for example, the above It may be substituted with an aryl or heteroaryl.

[0394] Specific examples of these triazine derivatives include the following compounds. [ka]

[0395] This triazine derivative can be produced using known raw materials and known synthesis methods.

[0396] <Benzimidazole derivatives> Benzimidazole derivatives are compounds represented by the following formula (ETM-11), for example. . [ka]

[0397] φ is an n-valent aryl ring (preferably an n-valent benzene ring, naphthalene ring, or anthracene ring). ring, fluorene ring, benzofluorene ring, phenalene ring, phenanthrene ring or truffle It is an phenylene ring, where n is an integer from 1 to 4, and the "benzoimidazole substituent" is above The "peri" in notation (ETM-2), formula (ETM-2-1), and formula (ETM-2-2) A substituent in which the pyridyl group in the "zin-based substituent" is replaced by a benzimidazole group. In benzimidazole derivatives, at least one hydrogen atom may be substituted with deuterium. stomach. [ka]

[0398] R in the above benzimidazole group 11It consists of hydrogen, alkyl groups with 1 to 24 carbon atoms, and carbon atoms. The above formula (ETM- 2-1) and R in equation (ETM-2-2) 11 You can quote the explanation.

[0399] φ is further preferably an anthracene ring or a fluorene ring, in this case The structure can be described by referring to the explanation in the above formula (ETM-2-1) or formula (ETM-2-2). And in each equation, R 11 ~R 18 This is the above formula (ETM-2-1) or formula (ETM-2-2) The explanation can be cited. Also, the above formula (ETM-2-1) or formula (ETM- In 2-2), it is described as a form in which two pyridine substituents are bonded, but these are bent When replacing with zoimidazole substituents, replace both pyridine substituents with benzimidazole substituents. It may be replaced with a zole substituent (i.e., n=2), or any one of the pyridine substituents Replace one substitution group with a benzimidazole substituent and the other pyridine substituent with R 11 ~R 1 8 It may also be replaced with (i.e., n=1). Furthermore, for example, in the above equation (ETM-2-1) Okeru R 11 ~R 18 Replace at least one of the benzimidazole substituents to form "P "Lysine substituent" 11 ~R 18 You can replace it with this.

[0400] A specific example of this benzimidazole derivative is, for example, 1-phenyl-2-(4-( 10-phenylanthracene-9-yl)phenyl)-1H-benzo[d]imidazole , 2-(4-(10-(naphthalene-2-yl)anthracene-9-yl)phenyl)- 1-Phenyl-1H-benzo[d]imidazole, 2-(3-(10-(naphthalene-2 -yl)anthracene-9-yl)phenyl)-1-phenyl-1H-benzo[d]imi Dazole, 5-(10-(naphthalene-2-yl)anthracene-9-yl)-1,2- Diphenyl-1H-benzo[d]imidazole, 1-(4-(10-(naphthalene-2- Il)anthracene-9-yl)phenyl)-2-phenyl-1H-benzo[d]imida Zol, 2-(4-(9,10-di(naphthalene-2-yl)anthracene-2-yl) Phenyl)-1-phenyl-1H-benzo[d]imidazole, 1-(4-(9,10- Di(naphthalene-2-yl)anthracene-2-yl)phenyl)-2-phenyl-1H -Benzo[d]imidazole, 5-(9,10-di(naphthalene-2-yl)anthrace Examples include 1,2-diphenyl-1H-benzo[d]imidazole. ru. [ka]

[0401] This benzimidazole derivative can be produced using known raw materials and known synthesis methods. can.

[0402] <Phenanthroline derivatives> Phenanthroline derivatives include, for example, those of the following formula (ETM-12) or formula (ETM-12- It is the compound represented by 1). Details are described in International Publication No. 2006 / 021982. [ka]

[0403] φ is an n-valent aryl ring (preferably an n-valent benzene ring, naphthalene ring, or anthracene ring). ring, fluorene ring, benzofluorene ring, phenalene ring, phenanthrene ring or truffle It is an énylene ring, and n is an integer from 1 to 4.

[0404] R in each formula 11 ~R 18 These are, independently, hydrogen, alkyl (preferably with 1 carbon atom) 24 alkyl groups, cycloalkyl groups (preferably cycloalkyl groups with 3 to 12 carbon atoms), and is an aryl (preferably an aryl with 6 to 30 carbon atoms). Also, the above formula (ETM-1 In 2-1), R 11 ~R 18 One of these bonds with φ, which is an aryl ring.

[0405] Even if at least one hydrogen atom in each phenanthroline derivative is substituted with deuterium good.

[0406] R 11 ~R 18 The alkyl, cycloalkyl and aryl in the above formula ( R in ETM-2) 11 ~R 18 The explanation can be quoted. Also, φ is as described above. In addition to the examples above, the following structural formulas can be given as an example. Note that R in the following structural formulas represents each These are independently hydrogen, methyl, ethyl, isopropyl, cyclohexyl, phenyl, 1-na These are phthyl, 2-naphthyl, biphenylyl, or terpheniryl. [ka]

[0407] A specific example of this phenanthroline derivative is, for example, 4,7-diphenyl-1,10 -Phenanthroline, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthrone Phosphorus, 9,10-di(1,10-phenanthroline-2-yl)anthracene, 2,6- Di(1,10-phenanthroline-5-yl)pyridine, 1,3,5-tri(1,10- Phenanthroline-5-yl)benzene, 9,9'-difluoro-bi(1,10-phen (Centroline-5-yl), basocproine, 1,3-bis(2-phenyl-1,10-f) Examples include phenanthroline-9-yl)benzene and compounds represented by the following structural formula. [ka]

[0408] This phenanthroline derivative can be produced using known raw materials and known synthesis methods. Cut.

[0409] <Quinolinol-based metal complexes> Quinolinol-based metal complexes are compounds represented by the following general formula (ETM-13), for example. ru. [ka] In the formula, R 1 ~R 6 These are, independently, hydrogen, fluorine, alkyl, cycloalkyl, It is aralkyl, alkenyl, cyano, alkoxy or aryl, and M is Li, Al, It is Ga, Be, or Zn, and n is an integer between 1 and 3.

[0410] Specific examples of quinolinol-based metal complexes include 8-quinolinol lithium and tris(8- Aluminum (4-methyl-8-quinolinolate), Tris(4-methyl-8-quinolinolate)aluminium Tris(5-methyl-8-quinolinolate)aluminum, Tris(3,4-dimethicone) (Lu-8-Quinolinolate) Aluminum, Tris(4,5-Dimethyl-8-Quinolinolate) Aluminum, Tris(4,6-dimethyl-8-quinolinolate)aluminum, S(2-methyl-8-quinolinolate)(phenolate)aluminum, bis(2-methyl) (Lu-8-Quinolinolate)(2-methylphenolate)aluminum, bis(2-methyl -8-Quinolinolate)(3-methylphenolate)aluminum, bis(2-methyl- 8-Quinolinolate)(4-Methylphenolate)Aluminum, Bis(2-Methyl-8 -Quinolinolate)(2-phenylphenolate)aluminum, bis(2-methyl-8 -Quinolinolate)(3-phenylphenolate)aluminum, bis(2-methyl-8 -Quinolinolate)(4-phenylphenolate)aluminum, bis(2-methyl-8 -Quinolinolate)(2,3-dimethylphenolate)aluminum, bis(2-methyl -8-Quinolinolate)(2,6-dimethylphenolate)aluminum, bis(2-Me (3,4-dimethylphenolate)aluminum, bis(2 -Methyl-8-quinolinolate)(3,5-dimethylphenolate)aluminum, bis (2-methyl-8-quinolinolate)(3,5-di-t-butylphenolate)aluminium Um, bis(2-methyl-8-quinolinolate)(2,6-diphenylphenolate) Luminium, bis(2-methyl-8-quinolinolate)(2,4,6-triphenylphenyl (Nolat) Aluminum, bis(2-methyl-8-quinolinolate)(2,4,6-tri Methylphenolate)aluminum, bis(2-methyl-8-quinolinolate)(2,4 ,5,6-tetramethylphenolate)aluminum, bis(2-methyl-8-quinolino (1-naphtholate)aluminum, bis(2-methyl-8-quinolinolate) (2-naphtholate)aluminum, bis(2,4-dimethyl-8-quinolinolate)( 2-Phenylphenolate)aluminum, bis(2,4-dimethyl-8-quinolinolate) (3-phenylphenolate)aluminum, bis(2,4-dimethyl-8-quinol) (4-phenylphenolate)aluminum, bis(2,4-dimethyl-8- (3,5-Dimethylphenolate) Aluminum, Bis(2,4-Dimethyl (3,5-di-t-butylphenolate)aluminum, butylphenolate S(2-methyl-8-quinolinolate)aluminum-μ-oxo-bis(2-methyl- 8-Quinolinolate)aluminum, bis(2,4-dimethyl-8-quinolinolate)a Luminium-μ-oxo-bis(2,4-dimethyl-8-quinolinolate)aluminum , bis(2-methyl-4-ethyl-8-quinolinolate)aluminum-μ-oxo-bi S(2-methyl-4-ethyl-8-quinolinolate)aluminum, bis(2-methyl- 4-Methoxy-8-Quinolinolate)aluminum-μ-oxo-bis(2-methyl-4 -Methoxy-8-Quinolinolate)aluminum, bis(2-methyl-5-cyano-8- (Quinolinolate) Aluminum-μ-oxo-bis(2-methyl-5-cyano-8-quino Linolate) Aluminum, bis(2-methyl-5-trifluoromethyl-8-quinoline (RAH) Aluminum-μ-oxo-bis(2-methyl-5-trifluoromethyl-8- (Quinoline) Aluminum, Bis(10-hydroxybenzo[h]quinoline) Beryl Examples include Um.

[0411] This quinolinol-based metal complex can be produced using known raw materials and known synthesis methods. Cut.

[0412] <Thiazole derivatives and benzothiazole derivatives> Thiazole derivatives are compounds represented by the following formula (ETM-14-1), for example. [ka] Benzothiazole derivatives are compounds represented by the following formula (ETM-14-2), for example. ru. [ka]

[0413] In each formula, φ represents an n-valent aryl ring (preferably an n-valent benzene ring, naphthalene ring, or ant). Helical ring, fluorene ring, benzofluorene ring, phenalene ring, phenanthrene ring or It is a triphenylene ring, and n is an integer from 1 to 4, and it is a "thiazole substituent" or "ben The "zothiazole substituents" are the above formulas (ETM-2), (ETM-2-1), and (E In TM-2-2), the pyridyl group among the "pyridine substituents" is the thiazole group or A substituent that replaces the benzothiazole group, and is used in thiazole derivatives and benzothiazole At least one hydrogen atom in the ion derivative may be substituted with deuterium. [ka]

[0414] φ is further preferably an anthracene ring or a fluorene ring, in this case The structure can be described by referring to the explanation in the above formula (ETM-2-1) or formula (ETM-2-2). And in each equation, R 11 ~R 18 This is the above formula (ETM-2-1) or formula (ETM-2-2) The explanation can be cited. Also, the above formula (ETM-2-1) or formula (ETM- In 2-2), it is described as a form in which two pyridine substituents are bonded, but these are When replacing with a zole substituent (or benzothiazole substituent), both pyri Even if you replace the din substituent with a thiazole substituent (or benzothiazole substituent) Okay (i.e., n=2), and replace any one of the pyridine substituents with a thiazole substituent ( (or a benzothiazole substituent) is replaced with the other pyridine substituent R 11 ~R 18 It may also be replaced with (i.e., n=1). Furthermore, for example, in the above equation (ETM-2-1) Keru R 11 ~R 18 At least one of them is a thiazole substituent (or benzothiazole substituent) Replace with a substituent to make a "pyridine substituent" R 11 ~R 18 You can replace it with this.

[0415] These thiazole derivatives or benzothiazole derivatives are synthesized using known raw materials and known synthesis methods. It can be manufactured using the law.

[0416] The electron transport layer or electron injection layer further comprises the material forming the electron transport layer or electron injection layer. It may contain a substance that can reduce the material. This reducing substance is a substance that has a certain degree of reducing properties. Therefore, various substances are used, for example, alkali metals, alkaline earth metals, rare earth metals Groups, alkali metal oxides, alkali metal halides, alkaline earth metal oxides, Alkaline earth metal halides, rare earth metal oxides, rare earth metal halides, A Organic complexes of lucid metals, organic complexes of alkaline earth metals, and organic complexes of rare earth metals At least one selected from the group can be suitably used.

[0417] Preferred reducing substances include Na (work function 2.36 eV) and K (work function 2.28 eV). , alkali metals such as Rb (2.16 eV) or Cs (1.95 eV), and Ca ( (2.9eV), Sr (2.0-2.5eV), or Ba (2.52eV), etc. Examples include earth metals, with materials having a work function of 2.9 eV or less being particularly preferred. Of these, the more preferred reducing substances are alkali metals such as K, Rb, or Cs, and even more preferred These alkali metals are either Rb or Cs, with Cs being the most preferred. In particular, it has high reducing ability and is used as an additive in relatively small amounts to materials that form electron transport layers or electron injection layers. This will improve the luminescence brightness and extend the lifespan of organic EL elements. As reducing substances with a voltage of 2.9 eV or less, combinations of two or more of these alkali metals are also preferred. In particular, combinations containing Cs, for example, Cs and Na, Cs and K, Cs and Rb, Alternatively, a combination of Cs, Na, and K is preferred. Including Cs enhances the reducing ability. It can be efficiently exerted by adding it to the material forming the electron transport layer or electron injection layer. This will improve the luminescence brightness and extend the lifespan of organic EL elements.

[0418] The electron injection layer material and electron transport layer material described above are provided with substituted reactive substituents. A polymer compound obtained by polymerizing a reactive compound using a monomer, or a polymeric frame thereof. A bridge structure, or a pendant-type polymer compound obtained by reacting a main-chain polymer with the reactive compound. It can be used as an electronic layer material, either as a material or as a pendant-type polymer crosslinked material thereof. In this case, the reactive substituent is explained using a polycyclic aromatic compound represented by formula (1). It can be quoted. Details of the applications of such polymer compounds and polymer crosslinks will be described later.

[0419] <Cathode in an organic electroluminescent device> The cathode 108 transmits electrons to the light-emitting layer 105 via the electron injection layer 107 and the electron transport layer 106. It plays the role of injecting offspring.

[0420] Any material that can efficiently inject electrons into the organic layer can be used as the material for forming cathode 108. While not particularly limited, materials similar to those used to form the anode 102 can be used. However, tin, indium, calcium, aluminum, silver, copper, nickel, chromium, gold Platinum, iron, zinc, lithium, sodium, potassium, cesium, and magnesium, etc. The metal or alloys thereof (magnesium-silver alloy, magnesium-indium alloy, f Lithium oxide (such as aluminum-lithium alloys like aluminum) is preferred. To increase electron injection efficiency and improve device characteristics, lithium, sodium, potassium Alloys containing cesium, calcium, magnesium, or these low work function metals are effective. Yes, they exist. However, these low work function metals are generally unstable in the atmosphere. To improve this point, for example, trace amounts of lithium, cesium, and magnesium can be added to the organic layer. A method is known to use doping to create highly stable electrodes. Other dopants Examples include lithium fluoride, cesium fluoride, lithium oxide, and cesium oxide. Inorganic salts can also be used, however, they are not limited to these.

[0421] Furthermore, platinum, gold, silver, copper, iron, tin, aluminum, and indigo are used for electrode protection. Metals such as um, or alloys using these metals, as well as silica, titania, and silicon nitride. Inorganic materials such as ions, polyvinyl alcohol, vinyl chloride, hydrocarbon polymer compounds, etc. Layering is a preferred example. Methods for fabricating these electrodes include resistance heating and electronic heating. Beam deposition, sputtering, ion plating, and coating, etc., to remove electrical conductivity. If you can do that, there are no particular restrictions.

[0422] <Binding agents that may be used in each layer> Materials used in the above hole injection layer, hole transport layer, light emission layer, electron transport layer, and electron injection layer The material can form each layer on its own, but polyvinyl chloride and polycarbonate are used as polymer binders. Polycarbonate, polystyrene, poly(N-vinylcarbazole), polymethyl methacrylate Polybutyl methacrylate, polyester, polysulfone, polyphenylene oxide Polybutadiene, hydrocarbon resins, ketone resins, phenoxy resins, polyamides, ethyl Solvent-soluble resins such as cellulose, vinyl acetate resin, ABS resin, and polyurethane resin, Phenolic resin, xylene resin, petroleum resin, urea resin, melamine resin, unsaturated polyester Dispersed in curable resins such as epoxy resins, alkyd resins, epoxy resins, and silicone resins. It can also be used in combination.

[0423] <Method for fabricating organic electroluminescent devices> Each layer constituting the organic EL element is created by depositing the material to be made up of each layer using methods such as evaporation, resistance heating evaporation, and electron deposition. Beam deposition, sputtering, molecular stacking, printing, spin coating, or casting, It can be formed by creating a thin film using methods such as coating. There are no particular limitations on the film thickness of each layer formed; it can be set appropriately according to the properties of the material. It is possible, but it is usually in the range of 2nm to 5000nm. Film thickness is usually measured using a quartz crystal oscillator. It can be measured with measuring devices, etc. When thin films are formed using the vapor deposition method, the vapor deposition conditions depend on the type of material. The type of film varies depending on the desired crystal structure and association structure of the film. Vapor deposition conditions are generally as follows: Heating temperature +50 to +400℃, vacuum degree 10 -6 ~10 -3 Pa, deposition rate 0.01~ Set the wavelength as appropriate within the range of 50 nm / second, substrate temperature -150 to +300°C, and film thickness 2 nm to 5 μm. It is preferable to do so.

[0424] When applying a DC voltage to the organic EL element obtained in this way, the anode is set to + and the cathode is set to +. It should be applied with the negative polarity, and when a voltage of about 2 to 40V is applied, it will become transparent or semi-transparent. Light emission can be observed from the electrode side (anode or cathode, or both). Also, this organic EL element The child also emits light when pulsed current or alternating current is applied. The waveform of the applied alternating current is It's optional.

[0425] Next, as an example of a method for fabricating an organic EL element, anode / hole injection layer / hole transport layer / Organic material consisting of a light-emitting layer / electron transport layer / electron injection layer / cathode made of a stock material and a dopant material This section explains the method for fabricating EL elements.

[0426] <Vapor deposition method> After fabricating an anode by forming a thin film of anode material on a suitable substrate using a vapor deposition method, A thin film of a hole injection layer and a hole transport layer is formed on the anode. A host material and a dove are placed on top of this. A thin film is formed by co-depositing a pantothenic material to create a light-emitting layer, and an electron transport layer is placed on top of this light-emitting layer. An injection layer is formed, and then a thin film made of cathode material is formed by vapor deposition or the like to create the cathode. By doing so, the desired organic EL element can be obtained. Therefore, reverse the manufacturing order: cathode, electron injection layer, electron transport layer, light emission layer, hole transport layer, It is also possible to fabricate the pore-injected layer followed by the anode.

[0427] <Wet film formation method> The wet film deposition method involves forming each organic EL element's organic layer using low-molecular-weight compounds in liquid form. The process is carried out by preparing a composition for use and using it. Dissolve this low molecular weight compound. If a suitable organic solvent is not available, the reaction is carried out by substituting a reactive substituent into the low molecular weight compound. High polymers formed by polymerizing with other monomers or main-chain polymers that have solubility as soluble compounds. A composition for forming an organic layer may be prepared from molecular compounds or the like.

[0428] Wet film deposition generally involves a coating step of applying an organic layer-forming composition to a substrate and a coating step of applying the composition to the substrate. A coating film is formed by a drying process that removes the solvent from the organic layer-forming composition. When the polymer compound has a crosslinkable substituent (also called a crosslinkable polymer compound), This drying process further cross-links the polymers, forming a cross-linked polymer. The method using a spin coater is called the spin coating method, and the method using a slit coater is called the slit coating method. The printing method using a printing plate is called gravure, offset, reverse offset, or flexographic. Printing methods: The method using an inkjet printer is called the inkjet method, and the method of spraying in a mist is called the atomizing method. This is called the spray method. Drying processes include methods such as air drying, heating, and vacuum drying. Drying process This may be done only once, or it may be done multiple times using different methods or conditions. Also, for example... For example, different methods may be used in combination, such as firing under reduced pressure.

[0429] Wet film deposition is a film deposition method that uses a solution, and is used, for example, in some printing methods (inkjet method). These include methods such as spin coating or casting, and coating. Wet film deposition methods include vacuum vapor Unlike conventional methods, this method does not require expensive vacuum deposition equipment and allows for film formation under atmospheric pressure. In addition, the wet film deposition method allows for large-area deposition and continuous production, leading to a reduction in manufacturing costs. .

[0430] On the other hand, compared to vacuum deposition, wet deposition methods can sometimes make layering difficult. When fabricating a multilayer film using the formula deposition method, it is necessary to prevent the lower layer from dissolving due to the composition of the upper layer. Furthermore, compositions with controlled solubility, crosslinking of the lower layer and orthogonal solvent, mutual Solvents that do not dissolve in each other are used. However, even with these techniques, not all It can be difficult to use wet film deposition methods for coating films.

[0431] Therefore, generally, only a few layers are deposited using the wet deposition method, and the rest are deposited using the vacuum deposition method with organic E The method of fabricating an L element is adopted.

[0432] For example, the procedure for fabricating an organic EL element by partially applying a wet film deposition method is shown below. (Step 1) Film deposition by vacuum deposition of the anode (Step 2) Wet deposition of a hole injection layer-forming composition containing hole injection layer material. (Step 3) Wet deposition of a hole transport layer forming composition containing a hole transport layer material. (Step 4) Formation of a light-emitting layer composition containing a host material and a dopant material by wet deposition method film (Step 5) Deposition of electron transport layer by vacuum deposition (Step 6) Deposition of electron injection layer by vacuum deposition (Step 7) Film deposition by vacuum deposition of cathode This procedure involves the anode / hole injection layer / hole transport layer / host material and dopant material. An organic EL element can be obtained consisting of a light-emitting layer, an electron transport layer, an electron injection layer, and a cathode. Of course, there are ways to prevent the dissolution of the lower light-emitting layer, or, conversely to the procedure described above, on the cathode side... By using methods such as film formation, layers containing electron transport layer material and electron injection layer material are formed. The compositions can be prepared and then deposited into films using a wet deposition method.

[0433] <Other film formation methods> Laser heating lithography (LITI) can be used to form organic layer-forming compositions. LITI is a method of depositing a compound attached to a substrate using a laser heating and vapor deposition. An organic layer-forming composition can be used in the material to be fabricated.

[0434] <Optional steps> Appropriate processing steps, cleaning steps, and drying steps may be added before and after each film formation step. The processing steps include, for example, exposure treatment, plasma surface treatment, ultrasonic treatment, ozone treatment, Examples include washing and heating treatments using appropriate solvents. Furthermore, a bank is prepared. The series of steps involved can also be cited.

[0435] Photolithography technology can be used to create the image bank. Positive-type and negative-type resist materials are used as available bank materials. It is possible to use inkjet printing, gravure offset printing, and reverse offset printing. Printing methods that allow for patterns, such as printing and screen printing, can also be used. It is also possible to use a durable resist material.

[0436] Materials used in the bank include polysaccharides and their derivatives, and hydroxyl compounds. Homopolymers and copolymers of ethylene monomers, biopolymers, polyacryloylated polymers Polyethylene, polyester, polystyrene, polyimide, polyamideimide, polyetherimide Polysulfide, polysulfone, polyphenylene, polyphenyl ether, polyure Tan, epoxy (meth)acrylate, melamine (meth)acrylate, polyolefin , cyclic polyolefin, acrylonitrile-butadiene-styrene copolymer (AB S) Silicone resin, polyvinyl chloride, chlorinated polyethylene, chlorinated polypropylene, Polyacetate, polynorbornene, synthetic rubber, polyfluorovinylidene, polytetraphth Fluorinated polymers such as polyethylene, polyhexafluoropropylene, and fluoroolefins Examples include copolymer polymers of n-hydrocarbon olefins and fluorocarbon polymers. However, it is not limited to that.

[0437] <Compositions for forming organic layers used in wet film deposition methods> The composition for forming the organic layer is a low-molecular-weight compound capable of forming each organic layer of an organic EL device, or It is obtained by dissolving the polymer compound, which is a polymerized version of the low molecular weight compound, in an organic solvent. The composition for forming the light-emitting layer includes at least one polycyclic aromatic compound as the first component, which is a dopant material. A fragrance compound (or a polymer thereof) and at least one host material as a second component. The composition contains at least one organic solvent as a third component. The first component is from the composition. The first component functions as a dopant component in the resulting luminescent layer, while the second component functions as a host component in the luminescent layer. The third component functions as a solvent that dissolves the first and second components in the composition, and is applied. Sometimes, the controlled evaporation rate of the third component itself provides a smooth and uniform surface shape.

[0438] <organic solvents> The composition for forming the organic layer contains at least one organic solvent. The evaporation rate of the organic solvent during film formation. By controlling these factors, film formation, the presence or absence of defects in the coating, surface roughness, and smoothness can be controlled and improved. It is possible to do so. Also, when forming a film using the inkjet method, the inkjet head This allows for control of meniscus stability in pinholes, thereby controlling and improving discharge performance. By controlling the drying rate of the film and the orientation of the derivative molecules, the organic layer-forming composition can be improved. To improve the electrical properties, luminescence characteristics, efficiency, and lifespan of organic EL elements having the resulting organic layer. It is possible.

[0439] (1) Physical properties of organic solvents The boiling point of at least one organic solvent is between 130°C and 300°C, and between 140°C and 270°C. More preferably, 150°C to 250°C is even more preferable. If the boiling point is higher than 130°C, This is preferable from the viewpoint of inkjet ejection performance. Also, if the boiling point is lower than 300°C, the coating film It is preferable in terms of defects, surface roughness, residual solvent and smoothness. The organic solvent is good From the viewpoint of the jet's discharge properties, film formation properties, smoothness, and low residual solvent, two or more organic solvents are used. A configuration including a medium is more preferable. On the other hand, in some cases, considering transportability, an organic layered form may be preferable. The composition may be in a solid state obtained by removing the solvent from the active composition.

[0440] Furthermore, organic solvents are classified as good solvents (GS) and poor solvents (PS) for at least one solute. It contains the boiling point (BP) of a good solvent (GS). GS ) is the boiling point (BP) of a poor solvent (PS) PS ) Low, the composition is particularly preferable. By adding a high-boiling point poor solvent, the low-boiling point good solvent volatilizes first during film formation, and the content of the composition The concentration of the substance and the concentration of the poor solvent increase, promoting rapid film formation. As a result, there are fewer defects. A coating film with low surface roughness and high smoothness can be obtained.

[0441] Difference in solubility (S GS -S PS ) is preferably 1% or more, and preferably 3% or more. More preferably, and even more preferably, the difference in boiling points (BP) PS -BP G S ) is preferably 10℃ or higher, more preferably 30℃ or higher, and 50 It is even more preferable that the temperature be above ℃.

[0442] The organic solvent is removed from the coating film after film formation by drying processes such as vacuum, reduced pressure, and heating. When heating is performed, from the viewpoint of improving coating film formation properties, at least one glass transition temperature of the solute should be considered. It is preferable to carry out the process at a temperature (Tg) of 30°C or lower. Furthermore, from the viewpoint of reducing residual solvent, It is preferable to heat the material to a glass transition temperature (Tg) of at least one of the materials at -30°C or higher. Even if the thermal temperature is lower than the boiling point of the organic solvent, the thin film ensures that the organic solvent is sufficiently removed. Furthermore, drying may be performed multiple times at different temperatures, or multiple drying methods may be used in combination.

[0443] (2) Specific examples of organic solvents Organic solvents used in compositions for forming organic layers include alkylbenzene solvents and phenyl Lu ether solvents, alkyl ether solvents, cyclic ketone solvents, aliphatic ketone solvents, Examples include monocyclic ketone solvents, solvents having a diester skeleton, and fluorine-containing solvents. Specific examples include pentanol, hexanol, heptanol, octanol, and nonanol. Lu, Decanol, Undecanol, Dodecanol, Tetradecanol, Hexane-2-O Heptane-2-ol, octan-2-ol, decane-2-ol, dodecane- 2-ol, cyclohexanol, α-terpineol, β-terpineol, γ-terpineol Pineol, δ-terpineol, terpineol (mixture), ethylene glycol mono Methyl ether acetate, propylene glycol monomethyl ether acetate, die Diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, diethylene glycol Ethylene glycol ethyl methyl ether, diethylene glycol isopropyl methyl ether Dipropylene glycol monomethyl ether, diethylene glycol diethyl ether Diethylene glycol monomethyl ether, diethylene glycol butyl methyl ether Tel, tripropylene glycol dimethyl ether, triethylene glycol dimethyl ether Ethylene glycol monobutyl ether, diethylene glycol monophenyl ether Ether, triethylene glycol monomethyl ether, diethylene glycol dibutyl ether Polyethylene glycol butyl methyl ether, polyethylene glycol dimethyl methyl ether Lu ether, tetraethylene glycol dimethyl ether, p-xylene, m-xylene o-xylene, 2,6-lutidine, 2-fluoro-m-xylene, 3-fluoro-o- Xylene, 2-chlorobenzotrifluoride, cumene, toluene, 2-chloro-6-fluoro Toluene, 2-fluoroanisole, anisole, 2,3-dimethylpyrazine, bromobe Nzen, 4-fluoroanisole, 3-fluoroanisole, 3-trifluoromethyl Nisol, mesitylene, 1,2,4-trimethylbenzene, t-butylbenzene, 2- Chillanisole, phenetol, benzodioxole, 4-methylanisole, s-buty Benzene, 3-methylanisole, 4-fluoro-3-methylanisole, cymene, 1 ,2,3-trimethylbenzene, 1,2-dichlorobenzene, 2-fluorobenzonitrile Lu, 4-fluoroveratrol, 2,6-dimethylanisole, n-butylbenzene, 3 -Fluorobenzonitrile, decalin (decahydronaphthalene), neopentylbenzene , 2,5-dimethylanisole, 2,4-dimethylanisole, benzonitrile, 3,5 -Dimethylanisole, diphenyl ether, 1-fluoro-3,5-dimethoxybenzene Methyl benzoate, isopentylbenzene, 3,4-dimethylanisole, o-torni Tolyl, n-amylbenzene, veratrol, 1,2,3,4-tetrahydronaphthalene Ethyl benzoate, n-hexylbenzene, propyl benzoate, cyclohexylbenzene 1-Methylnaphthalene, butyl benzoate, 2-methylbiphenyl, 3-phenoxyl E, 2,2'-vitryl, dodecylbenzene, dipentylbenzene, tetramethylbenzyl Zene, trimethoxybenzene, trimethoxytoluene, 2,3-dihydrobenzofuran, 1-Methyl-4-(propoxymethyl)benzene, 1-Methyl-4-(butyloxymethyl)benzene Benzene, 1-methyl-4-(pentyloxymethyl)benzene, 1-methyl-4-(hexyloxymethyl) Xymethyl)benzene, 1-methyl-4-(heptyloxymethyl)benzenebenzylbutyl Lu ether, benzylpentyl ether, benzylhexyl ether, benzylheptyl Examples include ether and benzyl octyl ether, but it is not limited to these. Furthermore, the solvent may be used alone or in mixtures.

[0444] <Optional ingredients> The organic layer-forming composition may contain optional components as long as they do not impair its properties. Optional components include binders and surfactants.

[0445] (1) Binder The organic layer-forming composition may contain a binder. The binder is used during film formation. A film is formed, and the resulting film is bonded to the substrate. Furthermore, in the organic layer forming composition... It plays a role in dissolving, dispersing, and binding other components.

[0446] Examples of binders used in organic layer-forming compositions include acrylic resins and polyethylene. Teylene terephthalate, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol Polymers, acrylonitrile-ethylene-styrene copolymer (AES) resins, ionomers , chlorinated polyether, diallyl phthalate resin, unsaturated polyester resin, polyethylene Polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyvinyl acetate Nyl, Teflon, Acrylonitrile-butadiene-styrene copolymer (ABS) resin, A Crylonitrile-styrene copolymer (AS) resin, phenolic resin, epoxy resin, melamine Min resin, urea resin, alkyd resin, polyurethane, and the above resins and polymers Copolymers are one example, but the term is not limited to them.

[0447] The binder used in the organic layer-forming composition may be a single type or a mixture of multiple types. It may be used in this way.

[0448] (2) Surfactants For example, the composition for forming an organic layer has film surface uniformity and solvent-hydrophilic properties on the film surface. And it may contain a surfactant to control the liquid repellency. The surfactant is a hydrophilic group structure They are classified into ionic and nonionic based on their structure, and further, alkyl groups are classified based on the structure of their hydrophobic groups. They are classified into silicon-based and fluorine-based types. Also, due to their molecular structure, they have relatively small molecular weights. This includes monomolecular systems with simple structures and polymeric systems with large molecular weights and side chains or branching. It is classified into the following categories based on its composition: single system, mixture of two or more surfactants and a base material. It is classified as a compound. The surfactants that can be used in the organic layer-forming composition are all Various types of surfactants can be used.

[0449] Examples of surfactants include Polyflow No. 45, Polyflow KL-245, Poly Flow No. 75, Polyflow No. 90, Polyflow No. 95 (product names, Kyoeisha Chemical) Industrial Co., Ltd., Disperbyk 161, Disperbyk 1 62, Disper Bake 163, Disper Bake 164, Disper Bake 166, De Disper Bake 170, Disper Bake 180, Disper Bake 181, Disper Bake 182, BYK300, BYK306, BYK310, BYK320, BYK33 0, BYK342, BYK344, BYK346 (product name, BYK Chemie Japan Co., Ltd.) ), KP-341, KP-358, KP-368, KF-96-50CS, KF-5 0-100CS (product name, manufactured by Shin-Etsu Chemical Co., Ltd.), Surflon SC-101, Surflo KH-40 (product name, manufactured by Seimi Chemical Co., Ltd.), Futergent 222F, Futergent Ent 251, FTX-218 (product name, manufactured by Neos Co., Ltd.), EFTOP EF-351 , EFTOP EF-352, EFTOP EF-601, EFTOP EF-801, EFTOP EF-802 (product name, manufactured by Mitsubishi Materials Corporation), MegaFac F-47 0, Megafuck F-471, Megafuck F-475, Megafuck R-08, Megaf F-477, Megafuck F-479, Megafuck F-553, Megafuck F -554 (product name, manufactured by DIC Corporation), fluoroalkylbenzenesulfonate, fluor Alalkylcarboxylates, fluoroalkyl polyoxyethylene ethers, fluoroalkyl Killammonium iodide, fluoroalkyl betaine, fluoroalkyl sulfonate , diglycerin tetrakis(fluoroalkyl polyoxyethylene ether), fluoro Alkyltrimethylammonium salts, fluoroalkylaminosulfonates, polyoxy Ethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, poly Oxyethylene alkyl ether, polyoxyethylene laurate, polyoxyethylene Oleate, polyoxyethylene stearate, polyoxyethylene laurylamine, so Sorbitan laurate, sorbitan palmitate, sorbitan stearate, sorbitan o Laurate, sorbitan fatty acid ester, polyoxyethylene sorbitan laurate, poly Oxyethylene sorbitan palmitate, polyoxyethylene sorbitan stearate, Polyoxyethylene sorbitan oleate, polyoxyethylene naphthyl ether, aldehyde Examples include carboxymethylbenzenesulfonate and alkyldiphenyl ether disulfonate. It is possible.

[0450] Furthermore, a single surfactant may be used, or two or more may be used in combination.

[0451] <Composition and physical properties of organic layer-forming compositions> The content of each component in the organic layer-forming composition is important for the good quality of each component in the organic layer-forming composition. The solubility, storage stability, and film-forming properties, as well as the coating film obtained from the organic layer-forming composition. The composition provides excellent film quality, good ejection properties when using an inkjet method, and Observations of good electrical characteristics, luminescence characteristics, efficiency, and lifespan of organic EL elements having fabricated organic layers. The factors are taken into consideration when making the decision. For example, in the case of a composition for forming an emissive layer, the first component is the emissive layer type. The second component is in the form of a light-emitting layer, at a concentration of 0.0001% to 2.0% by weight relative to the total weight of the composition. The third component is in the form of a light-emitting layer, at a concentration of 0.0999% to 8.0% by weight relative to the total weight of the composition. The amount is preferably 90.0% to 99.9% by weight of the total weight of the adult composition.

[0452] More preferably, the first component is 0.005% by weight of the total weight of the composition for forming the light-emitting layer. ~1.0% by weight, with the second component making up 0.095% by weight of the total weight of the composition for forming the light-emitting layer~ 4.0% by weight, the third component is 95.0% to 99% by weight of the total weight of the composition for forming the light-emitting layer. It is 0.9% by weight. More preferably, the first component is equal to the total weight of the composition for forming the light-emitting layer. , 0.05% by weight to 0.5% by weight, the second component is 0 0.25% by weight to 2.5% by weight, the third component is 97% of the total weight of the composition for forming the light-emitting layer. The weight range is from 0% to 99.7%.

[0453] The organic layer-forming composition is prepared by stirring, mixing, heating, cooling, and dissolving the above-mentioned components in a known manner. It can be manufactured by appropriately selecting and performing dispersion, etc. Furthermore, after preparation, filtration, degassing ( Degassing (also known as degassing), ion exchange treatment, and inert gas replacement / sealing treatment are performed as appropriate. That's fine.

[0454] Regarding the viscosity of the organic layer-forming composition, a higher viscosity is preferable for better film formation and inkjet properties. Good discharge performance can be obtained using the T method. On the other hand, a lower viscosity makes it easier to form a thin film. Therefore, the viscosity of the organic layer-forming composition is such that the viscosity at 25°C is 0.3 to 3 m The pressure is preferably Pa·s, and more preferably 1 to 3 mPa·s. In this case, viscosity is a value measured using a cone-plate type rotational viscometer. ru.

[0455] For organic layer-forming compositions, a lower surface tension results in better film formation and a defect-free coating. This can be obtained. On the other hand, a higher value can be obtained to obtain better inkjet ejection performance. The viscosity of the organic layer-forming composition is such that its surface tension at 25°C is 20 to 40 mN / m. It is preferable that the surface tension is 20 to 30 mN / m, and more preferably 20 to 30 mN / m. This value was measured using the drop test method.

[0456] <Cross-linkable polymer compounds: Compounds represented by the general formula (XLP-1)> Next, we will explain the case where the polymer compound described above has a crosslinkable substituent. A crosslinkable polymer compound is, for example, a compound represented by the following general formula (XLP-1). [ka] In equation (XLP-1), MUx, ECx, and k are defined the same as MU, EC, and k in equation (SPH-1) above. However, the compound represented by formula (XLP-1) has at least one crosslinkable substituent ( Contents of monovalent or divalent aromatic compounds having XLS, preferably having a crosslinkable substituent. The amount is 0.1 to 80% by weight of the molecule.

[0457] The content of monovalent or divalent aromatic compounds having crosslinkable substituents is 0.5 to 50% by weight. This is preferable, and 1 to 20% by weight is more preferable.

[0458] The crosslinkable substituent (XLS) is a group that can further crosslink the polymer compounds mentioned above. While not particularly limited, substituents with the following structures are preferred. * in each structural formula indicates the bond position. show. [ka]

[0459] L is independent of each other, a single bond, -O-, -S-, >C=O, -OC(=O)-, Alkylenes with 1 to 12 carbon atoms, oxyalkylenes with 1 to 12 carbon atoms, and C1-12 It is a polyoxyalkylene. Among the substituents above, formula (XLS-1), formula (XLS- 2) Formula (XLS-3), Formula (XLS-9), Formula (XLS-10), or Formula (XLS-1 7) The group represented by formula (XLS-1), formula (XLS-3), or formula (XLS- The group represented by 17) is more preferred.

[0460] Examples of divalent aromatic compounds having crosslinkable substituents include the following compounds having the following substructures Items can be listed. [ka] [ka] [ka] [ka]

[0461] <Method for producing polymer compounds and crosslinked polymer compounds> Regarding the method for producing polymer compounds and crosslinkable polymer compounds, the above formula (SPH-1 We will explain using the compounds represented by (XLP-1) and (XLP-1) as examples. These compounds can be synthesized by appropriately combining known manufacturing methods.

[0462] The solvents used in the reaction include aromatic solvents, saturated / unsaturated hydrocarbon solvents, and alcohols. Examples of solvents include ether-based solvents, such as dimethoxyethane and 2-(2-methoxy). Examples include ethoxy)ethane and 2-(2-ethoxyethoxy)ethane.

[0463] Furthermore, the reaction may be carried out in a two-phase system. If the reaction is carried out in a two-phase system, the fourth phase may be used as needed. A phase-transfer catalyst such as a ammonium salt may be added.

[0464] When producing compounds of formula (SPH-1) and (XLP-1), they can be manufactured in a single step. It is also possible to manufacture it in a multi-stage process. Alternatively, all the raw materials may be placed in a reaction vessel before the reaction process begins. The process may be carried out by a batch polymerization method in which the reaction is initiated, or by dropwise polymerization in which the raw materials are added dropwise to the reaction vessel. It may be carried out by the method, or by precipitation polymerization, in which the product precipitates as the reaction progresses. Often, these can be combined and synthesized as appropriate. For example, in formula (SPH-1) When synthesizing a compound in one step, monomer units (MUs) and end cap units are used. The target product is obtained by carrying out the reaction with nit (EC) added to the reaction vessel. Also, the general formula When synthesizing the compound represented by (SPH-1) in multiple steps, the monomer unit (MU) is targeted. After polymerization to the target molecular weight, end cap units (EC) are added and the reaction is carried out. The target product is obtained. By adding different types of monomer units (MU) in multiple steps and carrying out the reaction, the target product can be obtained. It is possible to create polymers with a concentration gradient in the structure of the nomeric units. After preparing the precursor polymer, the target polymer can be obtained by further reaction.

[0465] Furthermore, by selecting polymerizable groups in monomer units (MU), it is possible to control the primary structure of the polymer. This is possible. For example, as shown in synthesis schemes 1-3, having a random primary structure Polymer (synthesis scheme 1), polymer having a regular primary structure (synthesis scheme 2) It is possible to synthesize (3) and other materials, and use them in appropriate combinations depending on the target material. This can be done. Furthermore, if monomer units having three or more polymerizable groups are used, hyper - Branched polymers and dendrimers can be synthesized.

[0466] [ka]

[0467] Examples of monomer units that can be used in this invention include those described in Japanese Patent Publication No. 2010-189630, and the Japanese Patent Publication No. International Publication No. 2012 / 086671, International Publication No. 2013 / 191088, International Publication No. 2002 / 045184, International Publication Publication No. 2011 / 049241, International Publication No. 2013 / 146806, International Publication No. 2005 / 049546, International Publication No. 2 Japanese Patent Publication No. 015 / 145871, Japanese Patent Publication No. 2010-215886, Japanese Patent Publication No. 2008-106241, Japanese Patent Publication No. 2010-215886, International Publication No. 2016 / 031639, Japanese Patent Publication No. 2011-174062, International Publication No. 2016 / 031639, International It can be synthesized in accordance with the method described in Publication No. 2016 / 031639 and International Publication No. 2002 / 045184. ru.

[0468] Furthermore, for specific polymer synthesis procedures, please refer to Japanese Patent Publication No. 2012-036388 and International Publication No. 201 Japanese Patent Publication No. 5 / 008851, Japanese Patent Publication No. 2012-36381, Japanese Patent Publication No. 2012-144722, International Publication No. 2015 / 194448 International Publication No. 2013 / 146806, International Publication No. 2015 / 145871, International Publication No. 2016 / 031639, Country International Publication No. 2016 / 125560, International Publication No. 2016 / 031639, International Publication No. 2016 / 031639, International Publication Publication No. 2016 / 125560, International Publication No. 2015 / 145871, International Publication No. 2011 / 049241, JP 2012-14 It can be synthesized in accordance with the method described in Publication No. 4722.

[0469] <Application examples of organic electroluminescent devices> Furthermore, the present invention relates to a display device equipped with an organic EL element or a lighting device equipped with an organic EL element. It can also be applied to other areas. A display device or lighting device equipped with an organic EL element, and the organic EL element according to this embodiment It can be manufactured by known methods, such as connecting it to a known drive device, and is DC drive, It can be driven using known driving methods such as LS drive and AC drive as appropriate.

[0470] As a display device, for example, a panel display such as a color flat panel display Ray, flexible display such as flexible color organic electroluminescent (EL) displays Examples include play (for example, Japanese Patent Publication No. 10-335066, Japanese Patent Publication No. 2003-321546, etc.) (See Publication No. 2004-281086, etc.). Also, as a display method for the display, for example, Examples include the trix and / or segmentation method. Mention displays can coexist within the same panel.

[0471] In a matrix, pixels for display are arranged in two dimensions, such as a grid or mosaic. A collection of pixels displays characters and images. The shape and size of the pixels are determined by their purpose. Example For example, images and text displayed on personal computers, monitors, and televisions typically have sides of 300 μm or less. The pixels in the square shape below are used, and in the case of large displays such as display panels, This will involve using pixels with sides on the order of millimeters. In the case of monochrome display, pixels of the same color will be arranged. You can simply arrange them, but in the case of color display, the red, green, and blue pixels are displayed side by side. In total, there are typically delta type and stripe type. And the driving of this matrix Either a linear sequential drive method or an active matrix method can be used. While it has the advantage of a simpler structure, when considering the operating characteristics, the active matrix In some cases, Rix may be superior, so it's necessary to choose the appropriate one depending on the application. .

[0472] In the segmentation method (type), patterns are formed to display predetermined information. This causes a designated area to emit light. For example, in digital clocks and thermometers. Time and temperature displays, operating status displays for audio equipment and induction cookers, and automotive panel displays. Examples include the following.

[0473] Examples of lighting devices include indoor lighting and backlights for liquid crystal displays. Examples include (for example, Japanese Patent Publication No. 2003-257621, Japanese Patent Publication No. 2003-277741, Japanese Patent Publication No. 2004-1 (See Publication No. 19211, etc.) Backlights are primarily used to improve the visibility of non-self-illuminating display devices. Used for purposes such as liquid crystal displays, clocks, audio equipment, automotive panels, display boards, and It is used for signs and other applications. In particular, liquid crystal display devices, especially PCs where miniaturization is a challenge. For backlight applications, conventional methods consist of fluorescent lamps and light guide plates, making them thinner. Given the difficulties involved, the backlight using the light-emitting element according to this embodiment is thin and lightweight. Quantity is the defining characteristic.

[0474] 3-2. Other Organic Devices The polycyclic aromatic compound according to the present invention, in addition to the above-mentioned organic field light-emitting device, is also an organic field effect device. It can be used to fabricate transistors or organic thin-film solar cells.

[0475] Organic field-effect transistors control current using an electric field generated by a voltage input. A transistor is a device that has a source electrode, a drain electrode, and a gate electrode. When a voltage is applied to the gate electrode, an electric field is generated, and electricity flows between the source electrode and the drain electrode. A transistor that can control the current by arbitrarily blocking the flow of particles (or holes). It is a field-effect transistor. A field-effect transistor is a simple transistor (bipolar transistor) In comparison, it is easier to miniaturize and is often used as a component in integrated circuits and other devices.

[0476] The structure of an organic field-effect transistor is typically formed using the polycyclic aromatic compound according to the present invention. Source electrodes and drain electrodes are provided in contact with the organic semiconductor active layer that is formed, Furthermore, a gate electrode is provided with an insulating layer (dielectric layer) in contact with the organic semiconductor active layer. That would be fine. Examples of such element structures include the following: (1) Substrate / Gate electrode / Insulator layer / Source electrode / Drain electrode / Organic semiconductor active layer (2) Substrate / Gate electrode / Insulator layer / Organic semiconductor active layer / Source electrode / Drain electrode (3) Substrate / Organic semiconductor active layer / Source electrode / Drain electrode / Insulator layer / Gate electrode (4) Substrate / Source electrode / Drain electrode / Organic semiconductor active layer / Insulator layer / Gate electrode The organic field-effect transistor configured in this way is an active matrix driven system. Pixel driving switches for liquid crystal displays and organic electroluminescent displays It can be applied as a component, etc.

[0477] Organic thin-film solar cells consist of an anode made of ITO, a hole transport layer, and a light source on a transparent substrate such as glass. It has a structure in which an electron conversion layer, an electron transport layer, and a cathode are stacked. The photoelectric conversion layer has a p-type semiconductor on the anode side. It has a body layer and an n-type semiconductor layer on the cathode side. The polycyclic aromatic compound according to the present invention is Depending on the physical properties, the materials used for the hole transport layer, p-type semiconductor layer, n-type semiconductor layer, and electron transport layer are selected. It can be used. The polycyclic aromatic compound according to the present invention can be used in organic thin-film solar cells. It can function as a hole transport material or electron transport material. Organic thin-film solar cells can function as hole transport materials in addition to the above. A scalable block layer, electron blocking layer, electron injection layer, hole injection layer, smoothing layer, etc. are appropriately provided. It is acceptable. For organic thin-film solar cells, known materials used in organic thin-film solar cells are appropriately selected. They can be selected and used in combination. [Examples]

[0478] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. It is not possible. First, the synthesis of polycyclic aromatic compounds will be explained below.

[0479] Synthesis Example (1): Synthesis of Compounds (1-25) [ka]

[0480] Under a nitrogen atmosphere, 4-(1-adamantyl)aniline (15.0g) was dissolved in acetonitrile ( Dissolve in 300 ml, add bromine (21.1 g) dropwise under ice cooling, and stir for 0.5 hours. After the reaction, water and ethyl acetate were added to the reaction solution and stirred, then toluene was added, and the organic layer was prepared. The mixture was separated and washed with water. The organic layer was then concentrated to obtain the crude product. The crude product was then placed on silica gel. After purification using a YOTH column (eluent: toluene), the intermediate is washed with heptane. IA) was obtained (21.0g). [ka]

[0481] Under a nitrogen atmosphere, dissolve intermediate (IA) (21.0 g) in acetonitrile (200 ml). Dissolve it, and then add t-butyl nitrite dissolved in acetonitrile (50 ml) at 60°C. 8.4g) was added dropwise, and the mixture was stirred at the same temperature for 30 minutes. After the reaction, dilute hydrochloric acid and ethyl acetate were added to the reaction solution. After adding and stirring, the organic layer was separated and washed with water. The organic layer was then concentrated to obtain the crude product. The crude product was extracted using a silica gel short column (eluent: toluene / heptane = 1 / 3 (volume). By purifying the mixture using the ratio, an intermediate (IB) was obtained (16.0 g). [ka]

[0482] Under a nitrogen atmosphere, intermediate (IB) (12.0 g), N-(3-tert-butylphenyl )-3,5-Ditert-butylaniline (21.0g), palladium catalyst as dichloro Bis[(di-t-butyl(4-dimethylaminophenyl)phosphino)palladium(Pd -132, 0.21g), sodium t-butoxide (NaOtBu, 7.1g) 120 ml of xylene was placed in a flask and heated at 100°C for 1.5 hours. After the reaction, After adding water and ethyl acetate to the reaction mixture and stirring, the organic layer was separated and washed with water. The crude product was concentrated to obtain the crude product. The crude product was collected using a silica gel short column (eluent: toluene / By purifying with heptane (2 / 8 by volume), an intermediate (IC) was obtained (26.0g). ). [ka]

[0483] Intermediate (IC) (24.0g) and tert-butylbenzene (120ml) In a flask, under a nitrogen atmosphere, at 0°C, add 1.56M tert-butyllithium. 33.5 ml of tan solution was added. After the dropwise addition was complete, the temperature was raised to 60°C and stirred for 1 hour. Components with a lower boiling point than tert-butylbenzene were removed by distillation under reduced pressure. The mixture was cooled to -50°C and then 3 Boron bromide (13.1g) was added, and the mixture was heated to room temperature and stirred for 0.5 hours. Then, again Cool to 0°C and add N,N-diisopropylethylamine (6.8g), and wait until the exothermic reaction subsides. After stirring at room temperature until the mixture was cooled, the temperature was raised to 100°C and heated and stirred for 1 hour. The sodium acetate aqueous solution was cooled and then cooled in an ice bath, followed by ethyl acetate, and then separated into liquid and liquid. After concentrating the cell layer, a silica gel short column (eluent: toluene / heptane = 2 / 8 (volume) The product was purified in a specific ratio. The resulting crude product was dissolved in toluene and reprecipitation with methanol. By doing so, compound (1-25) was obtained (6.0g). [ka]

[0484] The structure of the compound obtained by NMR measurement was confirmed. 1 H-NMR(CDCl3): δ=1.21(s,18H), 1.36(s,36H) , 1.48-1.66(m,12H), 1.89(s,3H), 6.18(s,2H), 6.78(s,2H), 7.22(d,4H), 7.25-7.28(m,2H), 7. 59 (t, 2H), 8.86 (d, 2H).

[0485] Synthesis Example (2): Synthesis of Compounds (1-16) [ka]

[0486] Under a nitrogen atmosphere, intermediate (IB) (10.0 g), N-(4-tert-butylphenyl )-4-tert-butylaniline (14.0g), palladium catalyst Pd-132( 0.18g), sodium t-butoxide (NaOtBu, 5.9g), and xylene (80 ml) was placed in a flask and heated at 100°C for 1.5 hours. After the reaction, water and After adding ethyl acetate and stirring, the organic layer was separated and washed with water. The organic layer was then concentrated and crude The product was obtained. The crude product was purified using a silica gel short column (eluent: toluene). And so, an intermediate (ID) was obtained (13.1g). [ka]

[0487] Intermediate (ID) (13.0g) and tert-butylbenzene (100ml) In a flask, under a nitrogen atmosphere, at 0°C, add 1.56M tert-butyllithium. 18.3 ml of tan solution was added. After the dropwise addition was complete, the temperature was raised to 70°C and stirred for 1 hour. Components with a lower boiling point than tert-butylbenzene were removed by distillation under reduced pressure. The mixture was cooled to -50°C and then 3 Boron bromide (7.0g) was added, and the mixture was heated to room temperature and stirred for 0.5 hours. After that, it was stirred again. Cool to ℃ and add N,N-diisopropylethylamine (3.6g), then the exothermic reaction will subside. After stirring at room temperature, the temperature was raised to 80°C and heated and stirred for 1 hour. The reaction mixture was then cooled to room temperature. Then, a sodium acetate aqueous solution cooled in an ice bath was added, followed by ethyl acetate, and the mixture was separated. After concentrating the solution, a small amount of ethyl acetate was added and heated to dissolve it, then heptane was added and cooled, and the precipitated compound was formed. The crystals were filtered off and washed with cooled heptane. The crystals were then placed in a silica gel short cell. The product was purified with rum (eluent: toluene). Heptane was added to the resulting crude product, and it was heated, stirred, and then cooled. The resulting crystals were filtered off. Then, they were dissolved in toluene and concentrated, and heptane was added. By repeating the filtration process after crystal precipitation, compounds (1-16) were obtained (5. 3g). [ka]

[0488] The structure of the compound obtained by NMR measurement was confirmed. 1 H-NMR(CDCl3): δ=1.46(s,18H), 1.47(s,18H) , 1.51-1.54(m,9H), 1.62-1.65(m,3H), 1.87-1. 89(m,3H), 6.05(s,2H), 6.79(d,2H), 7.30(d,4H ), 7.50(dd,2H), 7.69(d,4H), 8.98(d,2H).

[0489] Synthesis Example (3): Synthesis of Compound (1-321) [ka]

[0490] Under a nitrogen atmosphere, dissolve the intermediate (IE) (40.0 g) in chloroform (100 ml). Then, add iron (powder) (0.53g), add bromine (45g) dropwise at room temperature, and then at the same temperature It was stirred for 4 hours. After adding water, sodium carbonate was added gradually until the foaming subsided. After that, an appropriate amount of sodium bisulfite was added. After washing the organic layer with water, the organic layer was concentrated and crudely prepared. The product was obtained. The crude product was purified using a silica gel short column (eluent: heptane), The organic layer was concentrated to obtain the crude product. Heptane was added to the crude product, and after cooling, it was filtered to obtain the crude product. An intermediate (IF) was obtained (44.0 g). [ka]

[0491] Under a nitrogen atmosphere, intermediate (IG) (10.0g), intermediate (IF) (11.8g), As a palladium catalyst, Pd-132 (0.26g) and sodium-t-butoxide (Na Place OtBu (5.3g) and xylene (70ml) in a flask and infuse at 100°C for 1 hour. The mixture was heated. After the reaction, water and ethyl acetate were added to the reaction solution and stirred. The organic layer was then separated and washed with water. Then, the organic layer was concentrated to obtain the crude product, to which heptane was added and cooled. The crystals were filtered. The crude product was filtered through a silica gel short column (eluent: toluene / hepta The crude product obtained by purifying the organic layer with a ratio of 1 / 1 (by volume) and concentrating the organic layer was then mixed with heptane. The intermediate (IH) was obtained by filtering the crystals obtained after cooling (10.0 g). [ka]

[0492] Under a nitrogen atmosphere, intermediate (IH) (10.0g), N-(4-tertbutylphenyl) )-4-tert-butylaniline (12.8g), bis(dibenzylideneacetone)para Dium(0)(Pd(dba)2, 0.24g), dicyclohexyl(2',6'-dimethyl Toxy-[1,1'-biphenyl]-2-yl)phosphine (SPhos), sodium -t-butoxide (NaOtBu, 5.0g) and xylene (80ml) in a flask. It was added and heated at 100°C for 1 hour. After the reaction, water and ethyl acetate were added to the reaction solution and stirred, The organic layer was separated and washed with water. The organic layer was concentrated, and heptane was added to the resulting crude product and cooled. The resulting crystals were filtered. The crude product was filtered through a silica gel short column (eluent: True). The crude product is obtained by purifying it with (n), concentrating the organic layer, adding heptane, and then cooling. The resulting crystals were filtered to obtain intermediate (II) (10.2 g). [ka]

[0493] Intermediate (II) (10.0g) and tert-butylbenzene (70ml) In a flask, under a nitrogen atmosphere, at 0°C, 1.56 M tert-butyllithium was dissolved in penta Add 13.5 ml of solution. After the dropwise addition is complete, raise the temperature to 70°C and stir for 1 hour, Components with lower boiling points than tert-butylbenzene were removed by vacuum distillation. The mixture was cooled to -50°C and then converted to triodiobenzene. Boron (5.2g) was added, and the mixture was heated to room temperature and stirred for 0.5 hours. After that, it was heated again to 0°C. Cool to the desired temperature, add N,N-diisopropylethylamine (2.7g), and wait until the heat dissipates. After stirring at room temperature, the temperature was raised to 80°C and heated and stirred for 1 hour. The reaction mixture was then cooled to room temperature. Then, an aqueous solution of sodium acetate cooled in an ice bath is added, followed by ethyl acetate, and after stirring for 1 hour, precipitation occurs. The resulting yellow precipitate was filtered, and the filtrate was washed with methanol, distilled water, and methanol in that order. After washing the yellow precipitate twice with hot heptane, further elution was performed using a silica gel short column ( The solution was purified with toluene / heptane (3 / 7 by volume). Then, it was dissolved in toluene. The compound is obtained by repeating the process of concentrating it, adding heptane, allowing crystals to precipitate, and then filtering it. (1-321) was obtained (5.5g). [ka]

[0494] 1 H-NMR(CDCl3): δ=1.33(s,18H), 1.46(s,18H ), 1.72-1.80(m,6H), 1.84-1.85(m,6H), 2.07-2 .09(m,3H), 5.69(s,2H), 6.67(d,2H), 6.86-6.9 2(m,5H), 7.03-7.07(m,4H), 7.14(dt,4H), 7.43 -7.46 (m, 6H), 8.94 (d, 2H).

[0495] Synthesis Example (4): Synthesis of Compound (1-328) [ka]

[0496] Under a nitrogen atmosphere, 4-(1-adamantyl)aniline (25.0g), intermediate (IF) (32.0g), Pd-132 (0.78g) as palladium catalyst, sodium-t- Butoxide (NaOtBu, 15.9g) and xylene (100ml) are placed in a flask. Then, it was heated at 130°C for 2 hours. After the reaction, water and ethyl acetate were added to the reaction solution and stirred, and then... The organic layer was separated and washed with water. Then, methanol was added to the crude product obtained by concentrating the organic layer. The resulting crystals were filtered after cooling. The crude product was dissolved in silica gel short column (dissolved). The excipient (toluene) was purified, and the organic layer was concentrated to obtain the crude product. Heptane was added to the crude product and cooled. The resulting crystals were filtered to obtain an intermediate (IJ) (41.0 g). [ka]

[0497] Under a nitrogen atmosphere, intermediate (IJ) (7.6g), intermediate (IK) (8.0g), para Pd-132 (0.12g) and sodium-t-butoxide (NaOt) are used as the zinc catalyst. Place Bu (2.5g) and xylene (40ml) in a flask and heat at 120°C for 1 hour. The reaction was carried out. After the reaction, water and toluene were added to the reaction mixture and stirred, then the organic layer was separated and washed with water. The crude product obtained by concentrating the bed was mixed with heptane, cooled, and the resulting crystals were filtered. The crystals were purified using a silica gel short column (eluent: toluene), and the organic layer was concentrated. Heptane was added to the crude product obtained, and after cooling, the resulting crystal was filtered to obtain an intermediate. (IL) was obtained (13.6g). [ka]

[0498] The intermediate (IL) (13.5g) and tert-butylbenzene (100ml) are included. In a flask, under a nitrogen atmosphere, at 0°C, add 1.56M tert-butyllithium. 18.9 ml of tan solution was added. After the dropwise addition was complete, the temperature was raised to 70°C and stirred for 1 hour. Components with a lower boiling point than tert-butylbenzene were removed by distillation under reduced pressure. The mixture was cooled to -50°C and then 3 Boron bromide (7.2g) was added, and the mixture was heated to room temperature and stirred for 0.5 hours. After that, it was stirred again. Cool to ℃ and add N,N-diisopropylethylamine (3.7g) until the exothermic reaction subsides. After stirring at room temperature, the temperature was raised to 90°C and heated and stirred for 1 hour. The reaction mixture was then cooled to room temperature. Then, add the sodium acetate aqueous solution cooled in an ice bath, followed by ethyl acetate, and stir for 1 hour, After adding heptane, the resulting yellow precipitate was filtered, and the filtrate was mixed with methanol, distilled water, The washing was performed in methanol, followed by washing with hot toluene, and then with silica gel. It was purified using a short-column eluent (eluent: toluene). Then, it was dissolved in toluene and concentrated. By repeating the process of adding heptane, allowing crystals to precipitate, and then filtering, the compound (1-32) can be obtained. 8) was obtained (5.7g). [ka]

[0499] 1 H-NMR(CDCl3): δ=1.47(s,9H), 1.48(s,9H), 1.78-1.87(m,12H), 2.07-2.09(m,12H), 2.14-2 .18(m,6H), 2.17(s,3H), 5.95(d,1H), 6.68(d,2 H), 7.27(t,2H), 7.28(d,2H), 7.45(dd,1H), 7.4 9(dd,1H), 7.64(dd,2H), 7.67(dd,2H), 8.98(d, 1H), 9.01(d,1H).

[0500] Synthesis Example (5): Synthesis of Compound (1-327) [ka]

[0501] Under a nitrogen atmosphere, intermediate (IJ) (5.9g), intermediate (IM) (6.0g), para Pd-132 (0.10g) and sodium-t-butoxide (NaOt) are used as the dinium catalyst. Place Bu (1.9g) and xylene (30ml) in a flask and heat at 120°C for 1 hour. The reaction was carried out. After the reaction, water and toluene were added to the reaction mixture and stirred, then the organic layer was separated and washed with water. The crude product obtained by concentrating the bed was mixed with heptane, cooled, and the resulting crystals were filtered. The crystals were purified using a silica gel short column (eluent: toluene), and the eluent was concentrated. Heptane was added to the crude product obtained, and after cooling, the resulting crystal was filtered to obtain an intermediate. (IN) was obtained (7.0g). [ka]

[0502] Intermediate (IM) (7.0g) and tert-butylbenzene (60ml) In a flask, under a nitrogen atmosphere at 0°C, 1.56 M tert-butyllithium pentane The solution (11.1 ml) was added. After the dropwise addition was complete, the temperature was raised to 70°C and stirred for 1 hour, then t Components with lower boiling points than ert-butylbenzene were removed by reduced-pressure distillation. The mixture was cooled to -50°C and tribromation was performed. Boron (4.2g) was added, and the mixture was heated to room temperature and stirred for 0.5 hours. After that, it was heated again to 0°C. Cool it down and add N,N-diisopropylethylamine (2.2g), and continue until the heat subsides. After stirring at room temperature, the temperature was raised to 80°C and heated and stirred for 1 hour. The reaction mixture was cooled to room temperature. After cooling the sodium acetate aqueous solution in an ice bath, add ethyl acetate and stir for 1 hour, then After adding heptane, the resulting yellow precipitate was filtered, and the filtrate was mixed with methanol, distilled water, and Washed with tanol in that order. Further purification was performed using a silica gel short column (eluent: toluene). Then, it was dissolved in toluene and concentrated, heptane was added, and after crystals precipitated, it was filtered. By repeating the process, compound (1-327) was obtained (3.0 g). [ka]

[0503] 1 H-NMR(CDCl3): δ=1.45(s,9H), 1.49(s,9H), 1.79-1.86(m,12H), 2.05-2.10(m,12H), 2.15-2 .17(m,6H), 6.11(d,1H), 6.13(d,1H), 6.74(d,2 H), 7.24(t,2H), 7.28(d,2H), 7.30(d,2H), 7.47 (dd,1H), 7.52(dd,1H), 7.64(dd,2H), 7.67(dd, 2H), 9.00(d,1H), 9.02(d,1H).

[0504] Synthesis Example (6): Synthesis of Compound (1-332) [ka]

[0505] Under a nitrogen atmosphere, intermediate (IJ) (6.6g), intermediate (IO) (5.0g), para Pd-132 (0.11g) and sodium-t-butoxide (NaOt) are used as the dinium catalyst. Place Bu (2.2g) and xylene (35ml) in a flask and heat at 120°C for 1 hour. After the reaction, water and ethyl acetate were added to the reaction mixture and stirred. The organic layer was then separated and washed with water. The crude product obtained by concentrating the layer was mixed with ethyl acetate and cooled, after which the resulting crystals were filtered. The crystals were purified using a silica gel short column (eluent: toluene), and the eluent was concentrated. Heptane was added to the crude product obtained by shrinking, and after cooling, the resulting crystals were filtered to obtain the medium Intermediate material (IP) was obtained (9.6g). [ka]

[0506] This product contains intermediate (IP) (9.5g) and tert-butylbenzene (100ml). In a flask, under a nitrogen atmosphere, at 0°C, 1.56 M tert-butyllithium was dissolved in penta 18.9 ml of solution was added. After the dropwise addition was complete, the temperature was raised to 70°C and stirred for 1 hour, Components with lower boiling points than tert-butylbenzene were removed by vacuum distillation. The mixture was cooled to -50°C and then converted to triodiobenzene. Boron (7.2g) was added, and the mixture was heated to room temperature and stirred for 0.5 hours. After that, it was heated again to 0°C. Cool to the desired temperature, add N,N-diisopropylethylamine (3.7g), and continue until the heat dissipates. After stirring at room temperature, the temperature was raised to 80°C and heated and stirred for 1 hour. The reaction mixture was then cooled to room temperature. Then, add an aqueous sodium acetate solution cooled in an ice bath, followed by ethyl acetate, and stir for 1 hour, then organic The layers were separated. After removing the organic solvent by distillation, silica gel short column (eluent: toluene / hepta It was purified using a ratio of 2 / 8 (by volume). Then, it was dissolved in toluene and concentrated, and heptane was extracted. Furthermore, by repeating the process of filtering after crystal precipitation, compound (1-332) was obtained. (3.8g). [ka]

[0507] The structure of the compound obtained by NMR measurement was confirmed. 1 H-NMR(CDCl3): δ=1.81-1.87(m,12H), 2.05-2 .07(m,12H), 2.16-2.17(m,6H), 6.09(d,1H), 6. 16(d,1H), 6.75(dd,2H), 7.23-7.31(m,6H), 7.3 9(d,2H), 7.43(dt,1H), 7.50(dd,1H), 7.59(dt, 1H), 7.65(dd,2H), 7.69(t,2H), 8.88(d,1H), 8. 93(d,1H).

[0508] Synthesis Example (7): Synthesis of Compound (1-334) [ka]

[0509] Under a nitrogen atmosphere, 4-(1-adamantyl)aniline (12.7g), 3,5-di-t- Butylbromobenzene (15.0g), Pd-132 (0.39g) as a palladium catalyst. ), sodium-t-butoxide (NaOtBu, 8.0g) and xylene (100m l) was placed in a flask and heated at 130°C for 2 hours. After the reaction, water and ethyl acetate were added to the reaction solution. After mixing, the organic layer was separated and washed with water. The organic layer was then concentrated to obtain the crude product. Solmix (A-11) was added to the material, cooled, and the resulting crystals were filtered. The substance was purified using a silica gel short column (eluent: toluene), and the organic layer was concentrated to obtain the result. Heptane was added to the crude product and cooled, and the resulting crystal was filtered to obtain the intermediate (IQ (16.0g) was obtained. [ka]

[0510] Under a nitrogen atmosphere, intermediate (IQ) (8.0g), intermediate (IK) (8.9g), para Pd-132 (0.14g) and sodium-t-butoxide (NaOt) are used as the dinium catalyst. Place Bu (2.8g) and xylene (40ml) in a flask and heat at 120°C for 1 hour. The reaction was carried out. After the reaction, water and toluene were added to the reaction mixture and stirred, then the organic layer was separated and washed with water. The crude product obtained by concentrating the bed was mixed with heptane, cooled, and the resulting crystals were filtered. The crystals were purified using a silica gel short column (eluent: toluene), and the organic layer was concentrated. Heptane was added to the crude product obtained, and after cooling, the resulting crystal was filtered to obtain an intermediate. (IR) was obtained (13.0g). [ka]

[0511] Intermediate (IR) (13.0g) and tert-butylbenzene (100ml) In a flask, under a nitrogen atmosphere, at 0°C, add 1.56M tert-butyllithium. 20.9 ml of tan solution was added. After the dropwise addition was complete, the temperature was raised to 70°C and stirred for 1 hour. Components with a lower boiling point than tert-butylbenzene were removed by distillation under reduced pressure. The mixture was cooled to -50°C and then 3 Boron bromide (7.9g) was added, and the mixture was heated to room temperature and stirred for 0.5 hours. After that, it was stirred again. Cool to ℃ and add N,N-diisopropylethylamine (4.1g), then the exothermic reaction will subside. After stirring at room temperature, the temperature was raised to 90°C and heated and stirred for 1 hour. The reaction mixture was then cooled to room temperature. Then, add the sodium acetate aqueous solution cooled in an ice bath, followed by ethyl acetate, and stir for 1 hour, then... The organic layer was separated using a liquid. After removing the organic solvent by distillation, a silica gel short column was used (eluent: True It was purified using ( ). Then it was dissolved in toluene and concentrated, and ethyl acetate was added to precipitate crystals. The compound (1-334) was obtained by repeating the filtration process (7.2g). [ka]

[0512] The structure of the compound obtained by NMR measurement was confirmed. 1 H-NMR(CDCl3): δ=1.37(s,18H), 1.47(s,9H), 1.49(s,9H), 1.79-1.85(m,6H), 2.10-2.11(m,6 H), 2.15-2.16(m,6H), 5.96(s,1H), 5.97(s,1H) , 6.68(d,1H), 6.70(d,1H), 7.20(d,2H), 7.26-7 .28(m,2H), 7.47(dd,1H), 7.50(dd,2H), 7.60(t ,2H), 7.67(tt,2H), 9.00(d,1H), 9.01(d,1H).

[0513] Synthesis Example (8): Synthesis of Compound (1-339) [ka]

[0514] Under a nitrogen atmosphere, 2,3-dichloroaniline (10.0 g), 4-cyclohexylbromo Benzene (36.9g), Pd-132 (0.44g) as a palladium catalyst, sodium Moo-t-butoxide (NaOtBu, 14.8g) and xylene (120ml) are used in a flannel solution. It was placed in a container and heated at 120°C for 1 hour. After the reaction, water and ethyl acetate were added to the reaction mixture and stirred. Afterward, the organic layer was separated and washed with water. The crude product obtained by concentrating the organic layer was saturated with silica gel. The solution was purified using a tetrafluoroethylene column (eluent: toluene / heptane = 2 / 8 (volume ratio)), and the eluent was concentrated. After adding Solmix (A-11) to the crude product obtained and cooling, the resulting crystals were filtered. An intermediate (IS) was obtained by passing the mixture through a process (25.5g). [ka]

[0515] Under a nitrogen atmosphere, N-(4-tertbutylphenyl)-4-tertbutylaniline ( 4.5g), intermediate (IS) (36.9g), palladium catalyst Pd-132 (0 0.11g), sodium t-butoxide (NaOtBu, 2.3g) and xylene ( 35 ml was placed in a flask and heated at 120°C for 1 hour. After the reaction, water and acetate were added to the reaction solution. After adding Chill and stirring, the organic layer was separated and washed with water. The crude product obtained by concentrating the organic layer. The product was purified using a silica gel short column (eluent: toluene), and the eluent was concentrated to obtain the product. After adding heptane to the crude product and cooling, the resulting crystals are filtered to obtain the intermediate (IT). I obtained (10.5g). [ka]

[0516] The intermediate (IT) (10.5g) and tert-butylbenzene (100ml) are included. In a flask, under a nitrogen atmosphere, at 0°C, add 1.56M tert-butyllithium. 19.1 ml of tan solution was added. After the dropwise addition was complete, the temperature was raised to 70°C and stirred for 1 hour. Components with a lower boiling point than tert-butylbenzene were removed by distillation under reduced pressure. The mixture was cooled to -50°C and then 3 Boron bromide (7.2g) was added, and the mixture was heated to room temperature and stirred for 0.5 hours. After that, it was stirred again. Cool to ℃ and add N,N-diisopropylethylamine (3.7g) until the exothermic reaction subsides. After stirring at room temperature, the temperature was raised to 80°C and heated and stirred for 1 hour. The reaction mixture was then cooled to room temperature. Then, add the sodium acetate aqueous solution cooled in an ice bath, followed by ethyl acetate, and stir for 1 hour, then... Butane was added, and the resulting yellow precipitate was filtered. The obtained precipitate was then filtered through a silica gel short column. It was purified with toluene (eluent). Then, it was dissolved in toluene and concentrated, and ethyl acetate was added. Furthermore, by adding heptane and repeating the process of filtering after crystals have precipitated, the compound ( (1-339) was obtained (5.3g). [ka]

[0517] The structure of the compound obtained by NMR measurement was confirmed. 1 H-NMR(CDCl3): δ=1.25-1.64(m,28H), 1.79-1 .81(m,2H), 1.89-1.93(m,4H), 2.03-2.07(m,4H ), 2.61-2.70(m,2H), 6.12(t,2H), 6.71(d,1H), 6.74(d,1H), 7.22-7.30(m,6H), 7.48-7.53(m,3 H), 7.67(d,2H), 8.83(d,1H), 8.99(d,1H).

[0518] By appropriately changing the raw material compounds, the present invention can be reproduced in a manner similar to the synthesis example described above. Polycyclic aromatic compounds can be synthesized.

[0519] Next, in order to further explain the present invention, an organic EL element using the compound of the present invention Examples are shown, but the present invention is not limited to these.

[0520] <Evaluation of vapor-deposited organic EL elements> Organic EL elements according to Example 1, Examples 2-3 and Examples 4-28 were fabricated, and 1000 cd / m 2 The characteristics of light emission, such as voltage (V), emission wavelength (nm), and external quantum efficiency (%), are measured. Set, then 10 mA / cm 2 When driven with a constant current at this current density, the initial brightness is 90% or more. The time it took to maintain the degree was measured.

[0521] The quantum efficiency of a light-emitting element includes internal quantum efficiency and external quantum efficiency, but internal quantum efficiency is... External energy injected as electrons (or holes) into the light-emitting layer of a light-emitting element is purely converted into photons. This indicates the conversion rate. On the other hand, the external quantum efficiency indicates how far these photons go beyond the light-emitting element. Based on the amount emitted, the photons generated in the light-emitting layer are calculated, and some of them become light-emitting elements. Because it is absorbed or continuously reflected inside and not emitted outside the light-emitting element Therefore, the external quantum efficiency will be lower than the internal quantum efficiency.

[0522] The method for measuring external quantum efficiency is as follows: Advantest voltage / current generator R6 Using 144, the brightness of the element is 1000 cd / m². 2 Applying a voltage that results in this will cause the element to emit light. Using a TOPCON SR-3AR spectroradiometer, the measurement was taken perpendicular to the light-emitting surface. The spectral radiance in the visible light region was measured. The measurement was performed assuming that the light-emitting surface was a perfectly diffusive surface. The spectral radiance values ​​for each wavelength component are divided by the wavelength energy and multiplied by π to obtain the values ​​for each wavelength. This is the number of photons emitted. Next, the number of photons is integrated across the entire wavelength range observed, and the number of photons emitted from the device is calculated. This was defined as the total number of photons produced. The value obtained by dividing the applied current by the elementary charge is the carrier injected into the element. The A-number is calculated by dividing the total number of photons emitted from the element by the number of carriers injected into the element. This is the external quantum efficiency.

[0523] <Example 1> The material composition of each layer and the EL characteristic data of the organic EL element according to Example 1 are shown in the table below. This is shown in 1A and Table 1B. [Table 1A] [Table 1B]

[0524] In Table 1A, "HI" is N 4 ,N 4’ -diphenyl-N 4 ,N 4’ -bis(9-f (phenyl-9H-carbazole-3-yl)-[1,1'-biphenyl]-4,4'-dia The compound is "HAT-CN," which is 1,4,5,8,9,12-hexaazatriphenylene. It is hexacarbonnitrile, and "HT-1" is N-([1,1'-biphenyl]-4-i Lu-9,9-dimethyl-N-[4-(9-phenyl-9H-carbazole-3-yl) It is (phenyl)-9H-fluoren-2-amine[1,1'-biphenyl]-4-amine "HT-2" is N,N-bis(4-(dibenzo[b,d]furan-4-yl)phenyl )-[1,1':4',1”-terphenyl]-4-amine, and "BH-1" is 2- (10-phenylanthracene-9-yl)naphtho[2,3-b]benzofuran, "ET-1" is 4,6,8,10-tetraphenyl[1,4]benzoxavorinino[2, [3,4-kl]phenoxabolinine, and "ET-2" is 3,3'-((2-phenyl Anthracene-9,10-diyl)bis(4,1-phenylene)bis(4-methylpyrylene) It is din. Its chemical structure, along with "Liq," is shown below.

[0525] [ka]

[0526] ITO, deposited to a thickness of 180 nm by sputtering, was polished to 150 nm. A 26mm x 28mm x 0.7mm glass substrate (manufactured by OptoScience Co., Ltd.) is transparently supported. This was used as the substrate. This transparent support substrate was placed in the substrate holder of a commercially available deposition apparatus (manufactured by Showa Vacuum Co., Ltd.). Fixed, HI, HAT-CN, HT-1, HT-2, BH-1, compound (1-25), E Molybdenum deposition boats containing T-1 and ET-2 respectively, Liq, LiF and Aluminum nitride deposition boats, each containing aluminum, were attached.

[0527] The following layers were sequentially formed on the ITO film of the transparent support substrate. The vacuum chamber was 5 × 10 -4 Pa Reduce the pressure to the desired level, first heat the HI to deposit it so that the film thickness reaches 40 nm, then HAT-C N was heated and deposited to a film thickness of 5 nm, and then HT-1 was heated to a film thickness of 45 nm. The film is deposited in this manner, and then HT-2 is heated and deposited to a film thickness of 10 nm, creating 4 layers. A hole layer consisting of the following was formed. Next, BH-1 and compound (1-25) were heated simultaneously to create a film thickness. A light-emitting layer was formed by depositing it to a wavelength of 25 nm. The weights of BH-1 and compound (1-25) were measured. The deposition rate was adjusted so that the ratio was approximately 98:2. Furthermore, ET-1 was heated to increase the film thickness. The film is deposited to a thickness of 5 nm, and then ET-2 and Liq are heated simultaneously to a film thickness of 25 nm. The electron layer consisting of two layers was formed by depositing the material in this manner. The weight ratio of ET-2 to Liq was approximately The deposition rate was adjusted to achieve a 50 / 50 ratio. The deposition rate for each layer was 0.01 to 1 nm / second. Yes. After that, the LiF was heated at a rate of 0.01 to 0.1 nm / second until the film thickness reached 1 nm. The material is deposited at the deposition rate, and then the aluminum is heated and deposited to a film thickness of 100 nm. A cathode was formed, and an organic EL element was obtained.

[0528] A DC voltage is applied with the ITO electrode as the anode and the LiF / aluminum electrode as the cathode, and 100°C. 0 cd / m 2 When the characteristics during emission were measured, blue light emission at a wavelength of 458 nm was obtained, driving The voltage was 3.68V, and the external quantum efficiency was 7.96%. Furthermore, the initial brightness was over 90%. The brightness was maintained for 329 hours.

[0529] <Examples 2 and 3> Material composition of each layer and EL characteristic data for the organic EL elements in Examples 2 and 3 These are shown in Tables 2A and 2B below. [Table 2A] [Table 2B]

[0530] <Example 2> ITO, deposited to a thickness of 180 nm by sputtering, was polished to 150 nm. A 26mm x 28mm x 0.7mm glass substrate (manufactured by OptoScience Co., Ltd.) is transparently supported. This was used as the substrate. This transparent support substrate was placed in the substrate holder of a commercially available deposition apparatus (manufactured by Showa Vacuum Co., Ltd.). Fixed, HI, HAT-CN, HT-1, HT-2, BH-1, compound (1-16), E Molybdenum deposition boats containing T-1 and ET-2 respectively, Liq, LiF and Aluminum nitride deposition boats, each containing aluminum, were attached.

[0531] The following layers were sequentially formed on the ITO film of the transparent support substrate. The vacuum chamber was 5 × 10 -4 Pa Reduce the pressure to the desired level, first heat the HI to deposit it so that the film thickness reaches 40 nm, then HAT-C N was heated and deposited to a film thickness of 5 nm, and then HT-1 was heated to a film thickness of 45 nm. The film is deposited in this manner, and then HT-2 is heated and deposited to a film thickness of 10 nm, creating 4 layers. A hole layer consisting of the following was formed. Next, BH-1 and compound (1-16) were heated simultaneously to create a film thickness. A light-emitting layer was formed by depositing a material to a wavelength of 25 nm. The weights of BH-1 and compounds (1-16) were measured. The deposition rate was adjusted so that the ratio was approximately 98:2. Furthermore, ET-1 was heated to increase the film thickness. The film is deposited to a thickness of 5 nm, and then ET-2 and Liq are heated simultaneously to a film thickness of 25 nm. The electron layer consisting of two layers was formed by depositing the material in this manner. The weight ratio of ET-2 to Liq was approximately The deposition rate was adjusted to achieve a 50 / 50 ratio. The deposition rate for each layer was 0.01 to 1 nm / second. Yes. After that, the LiF was heated at a rate of 0.01 to 0.1 nm / second until the film thickness reached 1 nm. The material is deposited at the deposition rate, and then the aluminum is heated and deposited to a film thickness of 100 nm. A cathode was formed, and an organic EL element was obtained.

[0532] A DC voltage is applied with the ITO electrode as the anode and the LiF / aluminum electrode as the cathode, and 100°C. 0 cd / m 2 When the characteristics during emission were measured, blue light emission at a wavelength of 464 nm was obtained, and the drive The voltage was 3.49V, and the external quantum efficiency was 8.57%. Furthermore, the initial brightness was over 90%. The brightness was maintained for 111 hours.

[0533] <Example 3> Organic EL elements were fabricated using the method described in Example 2 (Table 2A), and their EL characteristics were measured (Table 2A). B).

[0534] <Examples 4-28> Material composition of each layer and EL characteristic data of the organic EL elements in Examples 4 to 28 This is shown in Tables 3A and 3B below. [Table 3A] [Table 3B]

[0535] <Example 4> ITO, deposited to a thickness of 180 nm by sputtering, was polished to 150 nm. A 26mm x 28mm x 0.7mm glass substrate (manufactured by OptoScience Co., Ltd.) is transparently supported. This was used as the substrate. This transparent support substrate was placed in the substrate holder of a commercially available deposition apparatus (manufactured by Showa Vacuum Co., Ltd.). Fixed, HI, HAT-CN, HT-1, HT-2, BH-1, compound (1-16), E Molybdenum deposition boats containing T-1 and ET-2 respectively, Liq, LiF and Aluminum nitride deposition boats, each containing aluminum, were attached.

[0536] The following layers were sequentially formed on the ITO film of the transparent support substrate. The vacuum chamber was 5 × 10 -4 Pa Reduce the pressure to the desired level, first heat the HI to deposit it so that the film thickness reaches 40 nm, then HAT-C N was heated and deposited to a film thickness of 5 nm, and then HT-1 was heated to a film thickness of 45 nm. The film is deposited in this manner, and then HT-2 is heated and deposited to a film thickness of 10 nm, creating 4 layers. A hole layer consisting of the following was formed. Next, BH-1 and compound (1-16) were heated simultaneously to create a film thickness. A light-emitting layer was formed by depositing a material to a wavelength of 25 nm. The weights of BH-1 and compounds (1-16) were measured. The deposition rate was adjusted so that the ratio was approximately 98:2. Furthermore, ET-1 was heated to increase the film thickness. The film is deposited to a thickness of 5 nm, and then ET-2 and Liq are heated simultaneously to a film thickness of 25 nm. The electron layer consisting of two layers was formed by depositing the material in this manner. The weight ratio of ET-2 to Liq was approximately The deposition rate was adjusted to achieve a 50 / 50 ratio. The deposition rate for each layer was 0.01 to 1 nm / second. Yes. After that, the LiF was heated at a rate of 0.01 to 0.1 nm / second until the film thickness reached 1 nm. The material is deposited at the deposition rate, and then the aluminum is heated and deposited to a film thickness of 100 nm. A cathode was formed, and an organic EL element was obtained.

[0537] A DC voltage is applied with the ITO electrode as the anode and the LiF / aluminum electrode as the cathode, and 100°C. 0 cd / m 2 When the characteristics during emission were measured, blue light emission at a wavelength of 464 nm was obtained, and the drive The voltage was 3.49V, and the external quantum efficiency was 8.57%. Furthermore, the initial brightness was over 90%. The brightness was maintained for 111 hours.

[0538] <Examples 5-28> Organic EL elements were fabricated using the method described in Example 4 (Table 3A), and their EL characteristics were measured (Table 3A). B).

[0539] <Evaluation of coated organic EL elements> Next, we will describe an organic EL element obtained by coating and forming an organic layer.

[0540] <Synthesis of polymer host compound: SPH-101> SPH-101 was synthesized according to the method described in International Publication No. 2015 / 008851. Next to M1 This yields a copolymer in which M2 or M3 is bonded, and the ratio of each unit is 50:26 based on the initial charge ratio. It is estimated that the molar ratio is 24. [ka]

[0541] <Synthesis of the polymer hole transport compound: XLP-101> XLP-101 was synthesized according to the method described in Japanese Patent Publication No. 2018-61028. Next to M7 is A copolymer with M2 or M3 bonded is obtained, and the ratio of each unit is 40:10:5 It is presumed to be 0 (molar ratio). [ka]

[0542] <Examples 29-37> A coating solution for the materials forming each layer is prepared to fabricate a coated organic EL element.

[0543] <Fabrication of Organic EL Devices in Examples 29-31> Table 4 shows the material composition of each layer in an organic EL device. [Table 4]

[0544] The structure of "ET1" in Table 4 is shown below. [ka]

[0545] <Preparation of the composition for forming the light-emitting layer (1)> A composition (1) for forming an emissive layer is prepared by stirring the following components until a homogeneous solution is formed. The prepared light-emitting layer-forming composition is spin-coated onto a glass substrate and then heated and dried under reduced pressure. This results in a coated film free of defects and exhibiting excellent smoothness. Compound (A) 0.04% by weight SPH-101 1.96% by weight Xylene 69.00% by weight Decalin 29.00% by weight

[0546] Compound (A) is a polycyclic aromatic compound represented by general formula (1), its polymer, and the aforementioned A polycyclic aromatic compound or its polymer is a monomer (i.e., the monomer is a reactive substituent). A polymer compound that has been polymerized as having (a) or a polymer compound that has been further crosslinked This is a polymer crosslinked material. The polymer compound used to obtain the polymer crosslinked material has crosslinkable substituents. ru.

[0547] <PEDOT:PSS Solution> A commercially available PEDOT:PSS solution (Clevios(TM) P VP AI4083, an aqueous dispersion of PEDOT:PSS, manufactured by Heraeus Holdings) is used.

Chemical formula

[0548] <Preparation of OTPD Solution> OTPD (LT-N159, manufactured by Luminescence Technology Corp) and IK-2 (a photo cationic polymerization initiator, manufactured by San-Apro) are dissolved in toluene to prepare an OTPD solution with an OTPD concentration of 0.7 wt% and an IK-2 concentration of 0.007 wt%.

Chemical formula

[0549] <Preparation of XLP-101 Solution> XLP-101 is dissolved in xylene at a concentration of 0.6 wt% to prepare a 0.7 wt% XLP-101 solution.

[0550] <Preparation of PCz Solution> PCz (polyvinylcarbazole) is dissolved in dichlorobenzene to prepare a 0.7 wt% PCz solution.

Chemical formula

[0551] <Example 29> On a glass substrate on which ITO is deposited to a thickness of 150 nm, the PEDOT:PSS solution is spin-coated and baked on a hot plate at 200 °C for 1 hour to form a PEDOT:PSS film with a film thickness of 40 nm (hole injection layer). Then, the OTPD solution is spin-coated. After drying on an 80°C hot plate for 10 minutes, expose it to light with an exposure intensity of 100 mJ / cm². 2 By exposing it to light and baking it on a 100°C hot plate for 1 hour, a film thickness 3 that is insoluble in solution is created. A 0 nm OTPD film is formed (hole transport layer). Next, the light-emitting layer formation composition (1) is added. By applying a pin coat and baking it on a hot plate at 120°C for 1 hour, a film thickness of 20 nm is achieved. A light-emitting layer is formed.

[0552] The fabricated multilayer film is fixed to a substrate holder in a commercially available deposition apparatus (manufactured by Showa Vacuum Co., Ltd.), and ET A molybdenum deposition boat containing 1, a molybdenum deposition boat containing LiF, A Install a tungsten deposition boat filled with aluminum. The vacuum chamber is 5 x 10 -4 Pa After reducing the pressure, ET1 is heated and deposited to a thickness of 30 nm to form an electron transport layer. The deposition rate for forming the electron transport layer is set to 1 nm / second. After that, the LiF is heated. Deposition is carried out at a deposition rate of 0.01 to 0.1 nm / second to achieve a film thickness of 1 nm. Then, aluminum... Minium is heated and deposited to a thickness of 100 nm to form the cathode. This is how an organic EL element is obtained.

[0553] <Example 30> An organic EL element is obtained using the same method as in Example 29. The hole transport layer is XLP-101. The solution is spin-coated and baked on a hot plate at 200°C for 1 hour, resulting in a film thickness of 30 A film with a thickness of nm is deposited.

[0554] <Example 31> An organic EL element is obtained in the same manner as in Example 29. The hole transport layer is prepared by using a PCz solution. By pin coating and baking on a hot plate at 120°C for 1 hour, a film with a thickness of 30 nm is created. A thin film is formed.

[0555] <Fabrication of Organic EL Devices in Examples 32-34> Table 5 shows the material composition of each layer in an organic EL device. [Table 5]

[0556] <Preparation of compositions (2) to (4) for forming the light-emitting layer> A composition (2) for forming an emissive layer is prepared by stirring the following components until a homogeneous solution is formed. . Compound (A) 0.02% by weight mCBP 1.98% by weight Toluene 98.00% by weight

[0557] A composition (3) for forming an emissive layer is prepared by stirring the following components until a uniform solution is formed. . Compound (A) 0.02% by weight SPH-101 1.98% by weight Xylene 98.00% by weight

[0558] A composition (4) for forming an emissive layer is prepared by stirring the following components until a homogeneous solution is formed. . Compound (A) 0.02% by weight DOBNA 1.98% by weight Toluene 98.00% by weight

[0559] In Table 5, "DOBNA" is 3,11-di-o-tril-5,9-dioxa-13b - It is boranaphtho[3,2,1-de]anthracene. Its chemical structure is shown below. [ka]

[0560] <Example 32> On a glass substrate on which ITO has been deposited to a thickness of 45 nm, ND-3202 (Nissan Chemical Industries) After spin-coating the solution, it is heated in an air atmosphere at 50°C for 3 minutes, and then further heated for 2 minutes. By heating at 30°C for 15 minutes, an ND-3202 film with a thickness of 50 nm is deposited (holes note). (Inlay layer). Next, the XLP-101 solution is spin-coated and then heated under a nitrogen gas atmosphere. By heating on a plate at 200°C for 30 minutes, XLP-101 with a film thickness of 20 nm is produced. A film is formed (hole transport layer). Next, the light-emitting layer forming composition (2) is spin-coated, and nitrogen By heating at 130°C for 10 minutes in a gas atmosphere, a 20nm light-emitting layer is formed. To form a membrane.

[0561] The fabricated multilayer film is fixed to a substrate holder in a commercially available deposition apparatus (manufactured by Showa Vacuum Co., Ltd.), and the TS A molybdenum deposition boat containing PO1, a molybdenum deposition boat containing LiF, Install a tungsten deposition boat filled with aluminum. The vacuum chamber is 5 x 10 -4 P After reducing the pressure to a, TSPO1 is heated and deposited to a thickness of 30 nm to form the electron transport layer. Form the electron transport layer. The deposition rate for forming the electron transport layer is set to 1 nm / second. Then, the LiF is formed. Heat and deposit at a deposition rate of 0.01 to 0.1 nm / second until the film thickness reaches 1 nm. Next... Then, aluminum is heated and deposited to a thickness of 100 nm to form the cathode. Organic EL elements are obtained in this manner.

[0562] <Examples 33 and 34> Using the light-emitting layer forming composition (3) or (4), an organic EL is produced in the same manner as in Example 32. Obtain the element.

[0563] <Examples 35-37: Fabrication of Organic EL Devices> Table 6 shows the material composition of each layer in an organic EL device. [Table 6]

[0564] <Preparation of compositions (5) to (7) for forming the light-emitting layer> A composition for forming a light-emitting layer is prepared by stirring the following components until a uniform solution is formed. Compound (A) 0.02% by weight 2PXZ-TAZ 0.18% by weight mCBP 1.80% by weight Toluene 98.00% by weight

[0565] A composition for forming a light-emitting layer is prepared by stirring the following components until a uniform solution is formed. Compound (A) 0.02% by weight 2PXZ-TAZ 0.18% by weight SPH-101 1.80% by weight Xylene 98.00% by weight

[0566] A composition for forming a light-emitting layer is prepared by stirring the following components until a uniform solution is formed. Compound (A) 0.02% by weight 2PXZ-TAZ 0.18% by weight DOBNA 1.80% by weight Toluene 98.00% by weight

[0567] In Table 6, "2PXZ-TAZ" is 10,10'-((4-phenyl-4H-1,2 ,4-triazole-3,5-diyl)bis(4,1-phenyl)bis(10H-f It is enoxazine. Its chemical structure is shown below. [ka]

[0568] <Example 35> On a glass substrate on which ITO has been deposited to a thickness of 45 nm, ND-3202 (Nissan Chemical Industries) After spin-coating the solution, it is heated in an air atmosphere at 50°C for 3 minutes, and then further heated for 2 minutes. By heating at 30°C for 15 minutes, an ND-3202 film with a thickness of 50 nm is deposited (holes note). (Inlay layer). Next, the XLP-101 solution is spin-coated and then heated under a nitrogen gas atmosphere. By heating on a plate at 200°C for 30 minutes, XLP-101 with a film thickness of 20 nm is produced. A film is formed (hole transport layer). Next, the light-emitting layer forming composition (5) is spin-coated, and nitrogen By heating at 130°C for 10 minutes in a gas atmosphere, a 20nm light-emitting layer is formed. To form a membrane.

[0569] The fabricated multilayer film is fixed to a substrate holder in a commercially available deposition apparatus (manufactured by Showa Vacuum Co., Ltd.), and the TS A molybdenum deposition boat containing PO1, a molybdenum deposition boat containing LiF, Install a tungsten deposition boat filled with aluminum. The vacuum chamber is 5 x 10 -4 P After reducing the pressure to a, TSPO1 is heated and deposited to a thickness of 30 nm to form the electron transport layer. Form the electron transport layer. The deposition rate for forming the electron transport layer is set to 1 nm / second. Then, the LiF is formed. Heat and deposit at a deposition rate of 0.01 to 0.1 nm / second until the film thickness reaches 1 nm. Next... Then, aluminum is heated and deposited to a thickness of 100 nm to form the cathode. Organic EL elements are obtained in this manner.

[0570] <Examples 36 and 37> Using the light-emitting layer forming composition (6) or (7), an organic EL is produced in the same manner as in Example 35. Obtain the element. [Industrial applicability]

[0571] The present invention provides novel cycloalkyl-substituted polycyclic aromatic compounds, for example, This will increase the range of materials available for organic devices, such as materials for electroluminescent (EL) elements. By using cycloalkyl-substituted polycyclic aromatic compounds as materials for organic EL elements, for example, Organic EL elements with excellent luminous efficiency and element lifespan, a display device equipped therewith, and a device equipped therewith We can provide lighting equipment and other related items. [Explanation of symbols]

[0572] 100 Organic Electroluminescent Devices 101 circuit board 102 Anode 103 Hole injection layer 104 Hole transport layer 105 Light-emitting layer 106 Electron transport layer 107 Electron injection layer 108 Cathode

Claims

1. A polycyclic aromatic compound represented by the following general formula (1), or a compound represented by the following general formula (1) A polymer of polycyclic aromatic compounds having multiple structures. 【Chemistry 1】 (In the above formula (1), Rings A, B, and C are each independently an aryl ring or a heteroaryl ring. Furthermore, at least one hydrogen in these rings may be substituted. Y １ These are B, P, P=O, P=S, Al, Ga, As, Si-R, or Ge-R. The R in the Si-R and Ge-R is aryl or alkyl. X １ and X ２ These are, independently, >O, >N-R, and >C(-R). ２ , > S or >Se, and the R in the above >N-R is an aryl that may be substituted, even if it is substituted A heteroaryl, optionally substituted alkyl, or optionally substituted cycloaryl It is Lukil, and the above >C(-R) ２ R is hydrogen, or may be substituted with aryl or a It is Rukiru, and also the R of >N-R and / or the >C(-R) ２ R is a linking group Alternatively, the rings A, B and / or C may be bonded by single bonds. At least one hydrogen in the compound or structure represented by formula (1) is deuterium, cyano Alternatively, it may be substituted with a halogen, and, At least one hydrogen in the compound or structure represented by formula (1) is cycloalkyl (It has been replaced with...)

2. Rings A, B, and C are each independently an aryl ring or a heteroaryl ring. Furthermore, at least one hydrogen in these rings is either substituted or unsubstituted aryl, substituted or is an unsubstituted heteroaryl, a substituted or unsubstituted diarylamino, a substituted or unsubstituted Diheteroarylaminos, substituted or unsubstituted arylheteroarylaminos, substituted or This is an unsubstituted diarylboryl (the two aryls are linked by a single bond or a linking group). (may be), substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy or substituted Alternatively, they may be substituted with an unsubstituted aryloxy, and these rings may be Y １ , X １ oh Call X ２ A 5- or 6-membered ring that shares a bond with the condensed 2-ring structure in the center of the above formula, which is composed of It has, Y １ These are B, P, P=O, P=S, Al, Ga, As, Si-R, or Ge-R. The R in the Si-R and Ge-R is aryl or alkyl. X １ and X ２ These are, independently, >O, >N-R, and >C(-R). ２ , > S or >Se, and the R in >N-R may be substituted with an alkyl group. A heteroaryl, alkyl, or cycloalkyl which may be substituted with the above > C(-R) ２ R is hydrogen, or an aryl or alkyl which may be substituted with an alkyl group. Furthermore, the R of >N-R and / or the >C(-R) ２ The R is -O-, -S-, -C (-R) ２ - Or bonded to the A, B and / or C rings by a single bond Also, the aforementioned -C(-R) ２ The R in - is hydrogen or alkyl, At least one hydrogen in the compound or structure represented by formula (1) is deuterium, cyano Alternatively, it may be substituted with a halogen. In the case of a polymer, it is a dimer or trimer having two or three structures represented by general formula (1). And, At least one hydrogen in the compound or structure represented by formula (1) is cycloalkyl It is replaced by A polycyclic aromatic compound or a polymer thereof as described in claim 1.

3. A polycyclic aromatic compound as described in claim 1, represented by the following general formula (2). 【Chemistry 2】 (In the above formula (2), R １ ~R １１ These are, independently, hydrogen, aryl, heteroaryl, and diarylia. Mino, diheteroarylamino, arylheteroarylamino, diarylboryl (2 The aryl groups may be linked by single bonds or via linking groups), alkyl, alkoxy It is either aryloxy or aryloxy, and at least one hydrogen in these is aryl, heterooxy. It may be substituted with a loaryl or alkyl group, and R １ ~R １１ Among the adjacent The groups bond together to form an aryl ring or heteroaryl ring with the a, b, or c ring. It may be formed, and at least one hydrogen in the formed ring is aryl, heteroaryl. Diarylamino, Diheteroarylamino, Arylheteroarylamino, Di Arylboryl (the two aryls may be linked by a single bond or a linking group), They may be substituted with alkyl, alkoxy or aryloxy, and in small amounts At the very least, one hydrogen atom may be substituted with an aryl, heteroaryl, or alkyl group. 、 Y １ These are B, P, P=O, P=S, Al, Ga, As, Si-R, or Ge-R. The R in Si-R and Ge-R is an aryl or a aryl with 6 to 12 carbon atoms or aryl with 1 to 6 carbon atoms. It is Lukil, X １ and X ２ These are, independently, >O, >N-R, and >C(-R). ２ , > S or >Se, and the R in >N-R is an aryl with 6 to 12 carbon atoms, and a hetero with 2 to 15 carbon atoms. The aryl, C1-C6 alkyl, or C3-C4 cycloalkyl, >C(-R) ２ R is hydrogen, an aryl group with 6 to 12 carbon atoms, or an alkyl group with 1 to 6 carbon atoms. Yes, and also the R of >N-R and / or the >C(-R) ２ The R in -O- and -S- , -C (-R) ２ - Or bonded to the a, b and / or c rings by a single bond The above-mentioned -C(-R) ２ The R in - is an alkyl group having 1 to 6 carbon atoms. In the compound represented by formula (2), at least one hydrogen is deuterium, cyano or halo It may be substituted with Gen, and, In the compound represented by formula (2), at least one hydrogen atom is substituted with a cycloalkyl group. (It is.)

4. R １ ~R １１ These are, independently, hydrogen, aryl atoms with 6 to 30 carbon atoms, and aryl atoms with 2 to 3 carbon atoms. 0 heteroaryl and diarylamino (where aryl is an aryl with 6 to 12 carbon atoms) diarylboryl (where aryl is an aryl with 6 to 12 carbon atoms, and two aryls) (The atoms may be bonded via single bonds or linking groups) or alkyl groups having 1 to 24 carbon atoms. And also, R １ ~R １１ Adjacent groups among them bond together to form an a-ring, b-ring, or c-ring. Both form an aryl ring with 9 to 16 carbon atoms or a heteroaryl ring with 6 to 15 carbon atoms. It is also possible that at least one hydrogen in the formed ring is an aryl group having 6 to 10 carbon atoms. It may be substituted with an alkyl group having 1 to 12 carbon atoms. Y １ The elements are B, P, P=O, P=S, or Si-R, where R in Si-R represents the number of carbon atoms (6). It is an aryl group of up to 10 or an alkyl group having 1 to 4 carbon atoms. X １ and X ２ These are, independently, >O, >N-R, and >C(-R). ２ Or with >S Yes, the R in >N-R is an aryl with 6 to 10 carbon atoms, an alkyl with 1 to 4 carbon atoms, or a carbon atom. It is a cycloalkyl group with prime numbers 5 to 10, and the above >C(-R) ２ R is hydrogen, carbon atoms 6-10 It is an aryl or alkyl group having 1 to 4 carbon atoms. In the compound represented by formula (2), at least one hydrogen is deuterium, cyano or halo It may be substituted with Gen, and, In the compound represented by formula (2), at least one hydrogen atom is substituted with a cycloalkyl group. It is The polycyclic aromatic compound as described in claim 3.

5. R １ ~R １１ These are, independently, hydrogen, aryl atoms with 6 to 16 carbon atoms, and aryl atoms with 2 to 2 carbon atoms. 0 heteroaryl and diarylamino (where aryl is an aryl with 6 to 10 carbon atoms) or alkyl groups having 1 to 12 carbon atoms, Y １ B, P, P=O or P=S, X １ and X ２ These are, independently, >O, >N-R, or >C(-R) ２ And, In the above >N-R, R is an aryl group with 6 to 10 carbon atoms, an alkyl group with 1 to 4 carbon atoms, or a group with 5 carbon atoms. ~10 cycloalkyl, and the above >C(-R) ２ R stands for hydrogen, and ants have 6 to 10 carbon atoms. It is either a C1 or C1-C4 alkyl group, and, In the compound represented by formula (2), at least one hydrogen atom is substituted with a cycloalkyl group. It is The polycyclic aromatic compound as described in claim 3.

6. R １ ~R １１ These are, independently, hydrogen, aryl and diarylar atoms with 6 to 16 carbon atoms. Mino (however, aryls must be aryls with 6 to 10 carbon atoms) or alkyls with 1 to 12 carbon atoms can be, Y １ is B, X １ and X ２ Both are either >N-R or X １ is > N-R and X ２ Ha>O The R in >N-R is an aryl atom having 6 to 10 carbon atoms, an alkyl atom having 1 to 4 carbon atoms, or It is a cycloalkyl group having 5 to 10 carbon atoms, and, In the compound represented by formula (2), at least one hydrogen atom is substituted with a cycloalkyl group. It is The polycyclic aromatic compound as described in claim 3.

7. Diarylamino groups substituted with cycloalkyl groups, carba groups substituted with cycloalkyl groups Substituted with a benzocarbazolyl group substituted with a zolyl group or a cycloalkyl group, please A polycyclic aromatic compound or a polymer thereof, as described in any of the requests 1 to 6.

8. R ２ is a diarylamino group substituted with a cycloalkyl group or a cycloalkyl group A polycyclic aromatic compound according to any one of claims 3 to 6, wherein the carbazolyl group is modified.

9. The cycloalkyl is a cycloalkyl having 3 to 20 carbon atoms, as per any of claims 1 to 8. Polycyclic aromatic compounds as described above.

10. The halogen is fluorine, or a polycyclic aromatic compound as described in any one of claims 1 to 9. or its polymer.

11. A polycyclic aromatic compound as described in claim 1, represented by any of the following structural formulas. 【Transformation 3】 【Chemistry 4】 (In each of the above structural formulas, "Me" represents a methyl group and "tBu" represents a t-butyl group.)

12. Reactive substitution of a polycyclic aromatic compound or its polymer according to any one of claims 1 to 11 A reactive compound with a substituted group.

13. A polymer compound obtained by polymerizing the reactive compound described in claim 12 as a monomer, Alternatively, a polymer crosslinked material obtained by further crosslinking the polymer compound.

14. Pendant-type polymer obtained by substituting the reactive compound described in claim 12 into the main chain polymer. A composite, or a pendant-type polymer frame obtained by further crosslinking the said pendant-type polymer compound. Bridge structure.

15. A polycyclic aromatic compound or a polymer thereof as described in any one of claims 1 to 11, Materials for organic devices.

16. A material for an organic device containing the reactive compound described in claim 12.

17. A material for organic devices containing the polymer compound or polymer crosslinker described in claim 13. Fee.

18. The pendant-type polymer compound or pendant-type polymer crosslinked material described in claim 14 Materials for organic devices.

19. The aforementioned organic device material is an organic electroluminescent device material, an organic field-effect transistor material The organic material or material for organic thin-film solar cells as described in any one of claims 15 to 18 Materials for vises.

20. The organic electroluminescent material is a material for the light-emitting layer, as described in claim 19. Materials for use.

21. A polycyclic aromatic compound or a polymer thereof as described in any one of claims 1 to 11, and an organic solvent An ink composition containing the following.

22. An ink composition comprising the reactive compound described in claim 12 and an organic solvent.

23. An ink mixture comprising a main-chain polymer, the reactive compound described in claim 12, and an organic solvent. Finished product.

24. An ink comprising the polymer compound or polymer crosslinker described in claim 13 and an organic solvent. composition.

25. A pendant-type polymer compound or pendant-type polymer crosslinked material as described in claim 14, An ink composition containing an organic solvent.

26. A pair of electrodes consisting of an anode and a cathode, and disposed between the pair of electrodes, according to claims 1 to 11 A polycyclic aromatic compound or a polymer thereof as described in any of the above, or the reactivity described in claim 12. A compound, a polymer compound or polymer crosslinked material as described in claim 13, or claim 14 Organic compounds containing the pendant-type polymer compound or pendant-type polymer crosslinked material described below An organic electroluminescent element having a layer.

27. A pair of electrodes consisting of an anode and a cathode, and disposed between the pair of electrodes, according to claims 1 to 11 A polycyclic aromatic compound or a polymer thereof as described in any of the above, or the reactivity described in claim 12. A compound, a polymer compound or polymer crosslinked material as described in claim 13, or claim 14 Light-emitting materials containing the pendant-type polymer compound or pendant-type polymer crosslinker described above. An organic electroluminescent element having a layer.

28. The light-emitting layer comprises a host, the polycyclic aromatic compound as a dopant, its polymer, and an antagonist. Responsive compounds, polymer compounds, polymer crosslinks, pendant-type polymer compounds or pendants The organic electroluminescent element according to claim 27, comprising a crosslinked polymer.

29. The host is an anthracene compound, a fluorene compound, or a dibenzochrycene compound. The organic electroluminescent element according to claim 28, which is a compound.

30. The cathode and / or electron injection layer are disposed between the cathode and the light-emitting layer. At least one of the electron transport layer and the electron injection layer is a borane derivative, a pyridine derivative, Fluorantene derivatives, BO derivatives, anthracene derivatives, benzofluorene derivatives, Phosphine oxide derivatives, pyrimidine derivatives, carbazole derivatives, triazine derivatives The body, benzimidazole derivatives, phenanthroline derivatives, and quinolinol-based metal complexes. The following is a description of any one of claims 26 to 29, which includes at least one selected from the group consisting of the following: Organic electroluminescent element to be mounted.

31. The electron transport layer and / or electron injection layer further comprises alkali metals, alkaline earth metals Groups, rare earth metals, alkali metal oxides, alkali metal halides, alkaline earth metals Oxides of the genus, halides of alkaline earth metals, oxides of rare earth metals, halides of rare earth metals Alkali metal oxidides, alkali metal organic complexes, alkaline earth metal organic complexes, and rare earth metal organic complexes The organic electrochemical compound according to claim 30, comprising at least one selected from the group consisting of organic complexes. World-emitting diode.

32. At least one of the following: hole injection layer, hole transport layer, light emission layer, electron transport layer, and electron injection layer Each layer is a polymer compound formed by polymerizing low-molecular-weight compounds that can form each layer as monomers. Alternatively, a polymer crosslinked polymer obtained by further crosslinking the polymer compound, or forming each layer The resulting low molecular weight compound is reacted with a main chain polymer to form a pendant-type polymer compound, or A claim comprising a pendant-type polymer crosslinked material obtained by further crosslinking the pendant-type polymer compound. An organic electroluminescent element as described in any of items 26 to 31.

33. Display device or lighting equipped with an organic electroluminescent element as described in any one of claims 26 to 32 Device.

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