JPH11149821A - Electric charge transporting material and photoconductive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a compound comprising a polymerizable group capable of turning into liquid crystal phase and forming a thin film with fixed molecular arrangement in the liquid crystal phase by these of a disk-like compound comprising a substituent, capable of forming a chemical bond through a reaction by light or thermal energy or its reaction product as an electric charge transporting material. SOLUTION: A compound having a disk-like core part to be used for this electric charge transporting material preferably has formula I, An-k -D-(L-P)k . In the formula I, D represents a group existing in the center of the molecule and bonded with radiately arranged functional substituent groups A and functional substituent group (P-L) to the number of (n), A is for separately independent substituent groups which do not contribute to the formation of a reaction composition, (n) for an integer from 3 to 8: (k) for an integer from 1 to (n), and L for a group for bonding the reactive substituent group P and the disk-like mother core D and generally preferably a bonding group easier to moderate the volumetric strain caused by polymerization rather than a chemical bond or the oxy group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photoconductive material useful as a recording material and a display material, and a charge transport material usable for an electroluminescent device, a secondary battery, a fuel cell and the like.

[0002]

2. Description of the Related Art In recent years, in an electrophotographic photosensitive member, for example, poly-N-vinylcarbazole has been widely used as an organic photoconductive material from the viewpoints of environmental safety and cost superiority. .

[0003] However, the organic photoconductive materials currently used have a drawback that they have low charge mobility and are not sufficiently applicable to applications such as laser printing, which require high speed. There is a demand for the development of an organic photoconductive material having a large value.

In addition, recently, in the field of electroluminescent devices (EL devices) using a charge transporting material, an electroluminescent device (organic EL device) using an organic material has been considered from the viewpoint of full color, high luminance, and the like.
Research on devices has been actively conducted. However, mainly because the charge transfer speed of the organic charge transport material is not sufficient, the luminous efficiency of the organic EL device is not yet sufficient, and development of an organic charge transport material having a high charge transfer speed is desired.

[0005]

The charge transport material is used for a photoconductive material, an electroluminescent device and the like. At the same time, there are concerns about environmental and energy issues such as global warming caused by carbon dioxide, and secondary batteries such as lithium ion secondary batteries or fuel cells that can be a new power generation engine are one of the promising solutions. It is expected and is being actively studied. These batteries often use a liquid as an electrolyte. In such a case, however, there are problems such as leakage of the electrolyte, loss such as evaporation, and flammability when an organic solvent is used. Therefore, researches on solid ionic conductors using metal oxides and the like for fuel cells are being conducted.However, the ion conduction cannot be performed efficiently unless the temperature is high, and the development of solid electrolytes that can be used at low temperatures has been developed. Is desired.

[0006] The discotic compound refers to a compound having a core of a discotic liquid crystal compound, and a triphenylene derivative has attracted particular attention. JP-A-7-
306317, JP-A-8-27284 and JP-A-8-27284
No. 231470 describes that a thin film is formed by polymerizing a discotic compound having a reactive group in a liquid crystal phase. Accordingly, an object of the present invention is to provide a compound having a polymerizable group which can take a liquid crystal phase and can produce a thin film having a fixed molecular arrangement in the liquid crystal phase. And these compounds or polymers,
Another object is to provide a charge transporting material or a photoconductive material using a thin film.

[0007]

As a result of intensive studies, the present inventor has found that the object of the present invention can be achieved as follows. (1) A charge transport material comprising a discotic compound having a substituent capable of forming a chemical bond by reacting with light or heat energy, or a reaction product thereof. (2) The charge transport material according to (1), wherein the discotic compound is represented by the following general formula (I).

[0008]

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In the formula, P represents a reactive substituent, D is at the center of the molecule, and a total of n substituents A and substituents (P-
L) represents an n-functional group radially arranged. (Nk) A each independently represents a substituent that does not contribute to the formation of the reaction composition, L each independently represents a group or a chemical bond connecting P and D, and n represents 3 to 8 Represents an integer, and k represents an integer from 1 to n. k Ps are each independently an isocyanate group, a thiocyanate group, an amino group, an alkylamino group, an arylamino group, a mercapto group, a formyl group, an acyl group, a hydroxyl group, a carboxyl group, a sulfo group, a phosphoryl group, a halocarbonyl group. , A halosulfonyl group, a halophosphoryl group, an acryloyl group, a methacryloyl group, a crotonyl group, a vinyloxy group, an epoxy group, an acetylene group, a propargyl group, an allenyl group, and a diacetylene group. (3) The charge transport material according to (1), wherein in the general formula (I), the reactive substituents P are each independently represented by any of the following polymerizable substituents M _{1 to} M _4. .

[0010]

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R ₁₁ , R ₁₂ , R ₃ of the substituents M ₁ , M ₂ , M _3
13 represents _{R 21, R 22, R 23} , R 31, R 32, R 33 each independently represent a hydrogen atom or an alkyl group. In the substituent M ₄ , R ₄₁ represents a hydrogen atom, an alkyl group, or an aryl group.
In the substituent M _1, m represents 0 or 1. (4) A charge generation layer that absorbs light to generate charges by charge separation and a charge transport composed of the compound represented by the general formula (I) of (1) to (3) or a reaction product or polymer thereof. A photoconductive material comprising a layer. (5) The charge transport material according to (1), comprising a compound represented by the following general formulas (II) to (V) or a polymer thereof.

[0012]

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In the general formulas (II) to (V), M _{1 to} M ₄ have the same meaning as in the general formula (I). In the general formula (II), six R ₁ bonded to the triphenylene ring represent the same or different alkyl group or aryl group which may be substituted,
Of which at least one having a substituent group M _1. In the general formula (III), 6 one R ₂ that bind to a triphenylene ring represents an alkyl group or an aryl group which may be substituted may be the same or different, of which at least one having a substituent group M _2. In the general formula (IV), 6 one R ₃ which binds to a triphenylene ring represents an alkyl group or an aryl group which may be substituted may be the same or different, of which at least one having a substituent M _3. In the general formula (V), 6 one R ₄ that binds to the triphenylene ring represents an alkyl group or an aryl group which may be substituted it may be the same or different, of which at least one having a substituent M _4. (6) A charge generation layer which absorbs light to generate charges by performing charge separation and a charge transport layer comprising a compound represented by the general formulas (II) to (V) of (5) or a polymer thereof. A photoconductive material characterized by the following.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The compound having a disc-shaped core used in the present invention will be described first. The morphological characteristics of the disk-shaped portion forming the mother nucleus portion (core portion) of the disk-shaped molecule can be expressed as follows, for example, for a hydrogen-substituted product as its original compound. First, the size of the molecule is determined as follows. 1) Construct a nearly planar, preferably planar, molecular structure for the molecule. In this case, as the bond distance and bond angle, it is preferable to use standard values according to the orbital mixture. For example, the Chemical Society of Japan, the Chemical Handbook Revised 4th Edition, Basic Edition,
See Vol. II, Chapter 15 (Maruzen, 1993). 2) Using the structure obtained in 1) as an initial value, optimize the structure by a molecular orbital method or a molecular force field method. Examples of the method include Gaussian92, MOPAC93, CHARMm / QUANTA, and MM3, and preferably Gaussian92. 3) The center of gravity of the structure obtained by the structure optimization is moved to the origin, and the coordinate axis is set to the principal axis of inertia (the principal axis of the inertial tensor ellipsoid). 4) Each atom is given a sphere defined by a van der Waals radius, which describes the shape of the molecule. 5) Measure the length in the direction of each coordinate axis on the van der Waals surface, and let them be a, b, and c. When a disk-like form is defined using a, b, and c obtained by the above procedure, a ≧ b> c and a ≧ b ≧ a /
2, preferably a ≧ b> c and a ≧ b ≧ 0.7a. Further, it is preferable that b / 2> c.

Hereinafter, the compounds represented by formulas (I) to (V) of the present invention will be described in detail. Here, when the compounds represented by the general formulas (I) to (V) have an alkyl group, an alkenyl group, a cycloalkyl group, an alkylene group and the like, these may be linear or branched unless otherwise specified. May be substituted. In addition, general formulas (I) to
When the compound represented by (V) has an aryl group, a heterocyclic group, an arylene group (a divalent group) or the like, these may be condensed or substituted unless otherwise specified.

Discotic compounds are described, for example, in The Chemical Society of Japan,
Quarterly Chemistry Review No.22 "Chemistry of Liquid Crystal" Chapter 5, Chapter 10 2
Section (1994, Gakkai Shuppan Center), a research report by C. Destrade et al., Mol. Cryst. Liq. Cryst. 71, 117 (1981)
Chem., 96, 70 (1984), JMLehn et al., J. Chem. Soc. Chem.
Commun., 1794 (1985), J. Zhang, JSMoore et al., J. Am. Chem. Soc., 116, 2655 (1994)
And derivatives of the mother nucleus compound described in (1). For example, as the core compound D, a benzene derivative, a triphenylene derivative, a truxene derivative, a phthalocyanine derivative, a porphyrin derivative, an anthracene derivative, an azacrown derivative, a cyclohexane derivative, a β-diketone metal complex derivative, a hexaethynylbenzene derivative, a dibenzopyrene derivative, Coronene derivatives and derivatives of phenylacetylene macrocycle. Further, there may be mentioned cyclic compounds and their heteroatom-substituted isoelectronic structures described in “Chemical Review No. 15 New Aromatic Chemistry” (edited by The Chemical Society of Japan) (published by The University of Tokyo Press, 1977). Further, as in the case of the above-described metal complex, an assembly of a plurality of molecules may be formed by hydrogen bonding, coordination bond, or the like to form a disk-shaped molecule. Preferred examples of the mother nucleus compound D include triphenylene and truxene, and triphenylene is more preferred. Examples of the substituent capable of forming a chemical bond by reacting by applying light or heat energy to the compound of claim 1 include, for example, SR Sandler and
Written by SRSandler, W. Karo, Organic Functional Group Preparations
ic Functional Group Preparations) Volumes 1 and 2
Volume (Academic Press, New York, London
1968). Among them, preferred are a multiple bond, oxirane, and aziridine. More preferred are the research reports of RAMHikmet et al. [Macromolecules, 25, 4194 (1992)] and [Po
lymer, Volume 34, Issue 8, 1736 (1993)], DJBroer
[Macromolecules, 26, 1244 (1993)
Years)], a double bond, ie, an acryl group, a vinyl ether group and an epoxy group.

The compound of the first aspect of the present invention is more preferably represented by the general formula (I) of the second aspect.
In the general formula (I), D represents an n-functional group which is located at the center of the molecule and radially arranges a total of n substituents A and substituents (PL). D is preferably the mother nucleus of the discotic compound described above.

In the general formula (I), A independently represents a substituent which does not contribute to the formation of the reaction composition, and is preferably an alkyl group substituted or unsubstituted by a halogen atom, a nitro group, a cyano group, an alkoxy group or the like. , An aryl group, an aralkyl group, an alkylthio group, an arylthio group, an arylamino group, an alkylamino group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, and a benzoyloxy group.

In the general formula (I), n represents an integer of 3 to 8, and k represents an integer of 1 to n.

In the general formula (I), L represents a group linking the reactive substituent P and the discotic mother nucleus D, and is generally a linking group which is easier to reduce volumetric strain caused by polymerization than a chemical bond or an oxy group. Is preferred. Specifically, preferably, the alkylene group has 1 to 18 carbon atoms (hereinafter referred to as C number), and 1 to 1 carbon atoms.
An alkyleneoxy group of 18; an alkylenethio group of 1 to 18 carbon atoms; an alkyleneamino group of 1 to 18 carbon atoms;
20 oligoethyleneoxy groups, alkyleneoxycarbonyl groups having 1 to 18 carbon atoms, phenylene groups having 6 to 26 carbon atoms, phenyleneoxy groups having 6 to 26 carbon atoms, 6 to 26 carbon atoms
Phenylenethio group, a C6-C26 phenyleneamino group, a C7-26 phenyleneoxycarbonyl group, and the like. Preferred examples of the linking group L will be specifically described below.

[0021]

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The linking group L is more preferably an alkylene group, an alkyleneoxy group, an alkylenethio group, an alkyleneoxycarbonyl group, a phenylene group, a phenyleneoxy group, or a phenyleneoxycarbonyl group. In the general formula (I), k reactive substituents P are each independently an isocyanate, thiocyanate group, amino group, alkylamino group, arylamino group, mercapto group, formyl group, acyl group, hydroxyl group, carboxyl group , Sulfo group, phosphoryl group, halocarbonyl group, halosulfonyl group, halophosphoryl group, acryloyl group, methacryloyl group, crotonyl group, vinyloxy group, epoxy group,
Represents an acetylene group, a propargyl group, an allenyl group, or a diacetylene group.

It is preferable that the reactive substituents P in the general formula (I) are each independently represented by any of the polymerizable substituents M _{1 to} M ₄ .

[0024]

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R in the polymerizable substituents M ₁ , M ₂ and M _{3
11, R 12, R 13,} R 21, R 22, R 23, R 31, R 32, R 33
Each independently represents a hydrogen atom or an alkyl group (preferably having 1 to 12 carbon atoms (hereinafter referred to as C number), such as methyl, ethyl, n-propyl, i-propyl, t-butyl, butyl, pentyl, hexyl, octyl, 2-chloroethyl, 3-methoxyethyl, methoxyethoxyethyl), preferably a hydrogen atom or an unsubstituted linear alkyl group having 1 to 4 carbon atoms. R ₁₁ , R ₁₂ , R ₁₃ , R ₂₁ ,
Preferably, R ₂₂ , R ₂₃ , R ₃₁ , R ₃₂ and R ₃₃ are all hydrogen atoms.

In M _1, m represents 0 or 1, and is more preferably 1.

In M _4, R ₄₁ is an optionally substituted alkyl group (preferably having 1 to 12 carbon atoms, for example, methyl, ethyl, propyl, i-propyl, t-butyl, butyl, pentyl, hexyl, octyl, cyclohexyl) , 2-ethylhexyl, 2-chloroethyl, 3-methoxyethyl, 2
-Hydroxyethyl, methoxyethoxyethyl, benzyl, allyl) or an optionally substituted aryl group (for example, phenyl having 1 to 18 carbon atoms, 1-naphthyl, 2-naphthyl, 4-propylphenyl, 4-ethoxyphenyl,
-Pentyloxyphenyl, 3-hydroxyphenyl,
4-biphenyl, 3-acetyloxyphenyl, 2-chlorophenyl), and preferably an unsubstituted linear alkyl group having 1 to 6 carbon atoms or a phenyl group. General formula (I)
Preferably, the discotic nucleus D is a triphenylene ring, and the compounds of the general formulas (II) to (II)
2,3,6,7,10,11-hexaalkoxytriphenylene or hexaaryloxytriphenylene represented by (V) is more preferable for achieving the object of the present invention.

Now, the compounds of the present invention represented by formulas (II) to (V) will be described in detail. M ₁ in the general formula (II), M _2, the general formula (IV) of M _3, M ₁ ~M ₄ synonymous of M ₄ each of the general formula (V) (I) of general formula (III) It is.

In the general formula (II), six R _{1 's} may be the same or different and each represents an alkyl group or an aryl group which may be substituted, at least one of which is a substituent M ₁
Having. Here, R ₁ is preferably an alkyl group, and it is preferable that all six R ₁ have M ₁ as a substituent and are all the same.

In the general formula (III), six R _{2 's} may be the same or different and each represents an alkyl group or an aryl group which may be substituted, at least one of which is a substituent M ₂
Having. Here, R ₂ is preferably an alkyl group, and it is preferable that all six R ₂ have M ₂ as a substituent and are all the same.

In the general formula (IV), six R _{3 's} may be the same or different and each represents an alkyl group or an aryl group which may be substituted, at least one of which is a substituent M ₃
Having. Here, R ₃ is preferably an alkyl group, and it is preferable that all six R ₃ have M ₃ as a substituent and are all the same.

In the general formula (V), six R _{4 's} may be the same or different and each represents an alkyl group or an aryl group which may be substituted, at least one of which is a substituent M ₄
Having. Here, R ₄ is preferably an alkyl group, and it is preferable that all six R ₄ have M ₄ as a substituent and are all the same.

The residue obtained by substituting the terminal substituents M _{1 to} M ₄ at R _{1 to} R _{4 in the} general formulas (II) to (V) is preferably C
It is a substituted or unsubstituted alkylene group having 1 to 12 carbon atoms or a substituted or unsubstituted phenylene group having 6 to 18 carbon atoms. In addition,
In the present invention,-(CH ₂ ) ₂ OCH _2- , -CH ₂ Ph-, -PhCH _2- and the like are also regarded as a substituted alkylene group, a substituted phenylene group and the like. Preferred examples of the residue are specifically described below.

[0034]

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The general formula R ₁ of (II), R ₂ of formula (III), terminal substituent M ₁ in R ₄ of the general formula (V), M _2,
The residue obtained by substituting each of M ₄ is preferably a C 1 to 1
8 unsubstituted linear alkylene groups, more preferably ethylene, propylene, butylene and hexylene.

The residue obtained by substituting the terminal substituent M ₃ with R _{3 in the} formula (IV) is preferably an unsubstituted linear alkylene group having 1 to 8 carbon atoms or a substituted alkylene group, more preferably Is ethylene, propylene, butylene,-(CH ₂ ) ₂ OCH
₂ -,-(CH ₂ ) ₃ OCH _2- and-(CH ₂ ) ₄ OCH _2- . The compounds of the present invention include compounds represented by the general formula (I) among the general formulas (II) to (V):
I), (III), and (V) are more preferable, and the general formulas (III),
(V) is more preferred, and formula (III) is particularly preferred.

Specific examples of the compounds represented by formula (I) or formulas (II) to (V) of the present invention are shown below, but the present invention is not limited thereto.

[0038]

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[0039]

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[0040]

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[0041]

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[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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[0050]

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[0051]

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[0052]

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Many of the compounds represented by formulas (I) to (V) of the present invention have a liquid crystal phase, particularly a columnar liquid crystal phase or a discotic nematic liquid crystal phase. The compounds represented by the general formulas (I) to (V) of the present invention may be used alone, or may be used in a mixture at any ratio.
It may be used by mixing with various compounds other than the present invention. For example, it may be a low molecule such as a surfactant, a synthetic polymer such as polycarbonate, a compound derived from a natural polymer such as a cellulose derivative, a liquid crystal property, or a non-liquid crystal property, and may be used as an ultraviolet curable resin or a thermosetting resin. Those that can form new bonds between or within molecules such as monomers,
Any material that cannot easily form a new bond, such as xylene, may be used. As a mixed composition, Japanese Patent Application No. Hei 6-97
443 and the discotic compounds described in Japanese Patent Application No. 7-41276, and further, the compounds described in Japanese Patent Application Nos. 7-110511, 7-221186, and 7-222785. May be included. The material of the present invention can be used after being molded into various shapes using a mold, for example, or in the form of a film. When the material of the present invention is used in the form of a film, it can be formed as a thin film on a support by a coating method such as evaporation, spin coating, dip coating, or extrusion coating. The film thickness is 0.
It is preferably 1 μm or more and 30 μm or less, more preferably 20 μm or less.

In coating, the compound is preferably in the form of a solution, and the solvent used has a boiling point of 30 ° C. to 200 ° C. under atmospheric pressure, preferably 30 ° C. to 15 ° C.
The temperature is 0 ° C, more preferably 30 ° C to 130 ° C. Examples include 2-butanone, 2,4-dimethyl-3-pentanone, ethyl acetate, 1-butanol, fluorobenzene, 1,2-dimethoxyethane, acetone, methylene chloride and the like. When used in the form of a film, they can be stacked. In the case of lamination, it may be composed of only the layer containing the material of the present invention. However, at least one layer of the material of the present invention is provided on the support, Alternatively, between the material layers, layers exhibiting different functions (for example, a charge generation layer, a light absorption layer,
A layer or a support made of another material such as an electrode layer) and a protective film may be present.

Examples of the support material include glass, Zeonex (Nippon Zeon), ARTON (Nippon Synthetic Rubber), Fujitac (Fujifilm), polyester, polycarbonate, polyacrylate, polysulfone, and polyethersulfone. The support is not necessarily transparent, and a conductive compound such as indium-tin-oxide (ITO) may be deposited on the support as required even if a metal such as aluminum, gold, or platinum is deposited on the support. May be painted.

Examples of the material for the protective film include polymethyl methacrylate, acrylic acid / methacrylic acid copolymer, styrene / maleimide anhydride-free polymer, polyvinyl alcohol, N-methylolacrylamide, styrene
Vinyl toluene copolymer, chlorosulfonated polyethylene, nitrocellulose, polyvinyl chloride, chlorinated polyolefin, polyester, polyimide, vinyl acetate / vinyl chloride copolymer, ethylene / vinyl acetate copolymer, polyethylene, polypropylene, polycarbonate, etc. Organic substances such as polymer substances and silane coupling agents can be mentioned. In addition, a Langmuir-Blodgett method (LB) such as ω-tricosanoic acid, dioctadecyldimethylammonium chloride and methyl stearate is used.
) Can also be used.

When the compound used in the present invention has a substituent capable of forming a new bond by polymerization or the like, a bond can be formed by heat or light. That is, in the present invention, the liquid crystal thin film is formed on a suitable support by a general coating method, in which at least one interface is in contact with the gas phase, and after drying, the disc is formed at a temperature within the liquid crystal phase formation temperature range. A desired thin film can be obtained by subjecting to heat treatment for a certain period of time while forming a tick nematic phase or discotic phase, followed by thermal polymerization or photocrosslinking polymerization, followed by cooling, followed by cooling. Radical polymerization and cationic polymerization using a photopolymerization initiator by ultraviolet rays generally have a very high polymerization rate, and are preferable in terms of productivity in the production process.

As the photopolymerization initiator in the present invention, α
-Carbonyl compounds, acyloin ethers, aromatic acyloin compounds substituted with α-hydrocarbons, polynuclear quinone compounds, combinations of triarylimidazole dimers / p-aminophenyl ketone, acridine and phenazine compounds, oxadiazole compounds and the like. Can be In the present invention, the amount of the photoinitiator system in the range of 0.01% to 20% of the coating composition excluding the solvent is sufficient, and more preferably 0.5% to 5% to obtain good results.

Further, in the present invention, if necessary, various organic amine compounds can be used in combination, whereby the effect can be increased. Examples of these organic amine compounds include triethanolamine, diethanolaniline, ethyl p-dimethylaminobenzoate, and Michler's ketone. The addition amount of the organic amine compound is preferably 50 to 200% of the total photopolymerization initiator. Further, the photopolymerization initiator used in the present invention may optionally contain N
Addition of a hydrogen-donating compound such as -phenylglycine, 2-mercaptobenzothiazole, or alkyl N, N-dialkylaminobenzoate can further enhance the photopolymerization initiation ability. In addition, it is often effective to add a small amount of a surfactant in order to suppress polymerization inhibition caused by oxygen.

For the polymerization of the epoxy group, allyldiazonium salts (hexafluorophosphate, tetrafluoroborate), diallyliodonium salts, group VIa allylonium salts (PF-6,
Allylsulfonium salts having anions such as AsF6 and SbF6) are preferably used. Light rays for polymerization include electron beam, ultraviolet ray, visible ray, infrared ray (heat ray).
Can be used as needed, but generally, ultraviolet rays are used. The light rays include low-pressure mercury lamps (germicidal lamps, fluorescent chemical lamps, brat lights), high-pressure discharge lamps (high-pressure mercury lamps, metal halide lamps), and short arc discharge lamps (ultra-high-pressure mercury lamps, xenon lamps, mercury xenon lamps). No. In the case of the compound of the present invention, short-wave ultraviolet rays such as 254 nm may not be used effectively. Therefore, the photopolymerization initiator is preferably a compound having an absorption band in the near ultraviolet range described below, and a light source such as a high-pressure mercury lamp or a metal halide lamp capable of strongly emitting near ultraviolet light is preferably used.

[0061]

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When a bond is formed by heat, a substance for accelerating the reaction can be added. For example, a base such as a hydroxide (eg, sodium hydroxide,
Potassium hydroxide and ammonium hydroxide),
Alkoxides (eg, sodium methoxide, sodium ethoxide, potassium-t-butoxide), metal hydrides (eg, sodium hydride, calcium hydride), amines (eg, pyridine, triethylamine, piperidine, 1,8-diazabicyclo [5,4,0] -7-undecene (DBU), tetramethylbutanediamine (TMBDA), 1,4-diaza [2,2,2] bicyclooctane (DABCO)), Carbonates (for example, sodium carbonate, potassium carbonate, sodium hydrogencarbonate) and acetates (for example, sodium acetate, potassium acetate).

Further, for example, metal compounds (for example, di-n-butyltin dilaurate, tin octoate, zinc acetylacetonate) can be mentioned. Acids, such as mineral acids (eg, sulfuric acid, hydrochloric acid), carboxylic acids (eg, chloroacetic acid, trifluoroacetic acid, salicylic acid and derivatives thereof), sulfonic acids (eg, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid). In addition,
The polymerization is preferably carried out under an inert gas (eg, argon, helium, nitrogen) from the viewpoint of the polymerization rate.

A film prepared by using the compounds represented by the general formulas (I) to (V) of the present invention or a polymer thereof may be coated with a metal such as gold, platinum, silver, magnesium or aluminum depending on the purpose. An electrode layer may be made. In that case, a vapor deposition method is generally used, but it may be produced by a chemical method or an electric method.

When a photoconductive material is prepared using the compounds represented by the general formulas (I) to (V) of the present invention, only a thin film obtained by applying and polymerizing the compound of the present invention may be used. However, in that case, since many films made of the compound of the present invention have absorption only to ultraviolet light, in order to generate photocharge, for example, excimer laser, YA
In many cases, only an ultraviolet laser such as a G third harmonic or an N ₂ laser can be used. On the other hand, if a charge generation layer capable of generating a charge by absorbing visible light or infrared light is laminated on the upper layer or the lower layer of the film composed of the compound of the present invention, the film composed of the compound of the present invention is used as a charge transport layer. Used to detect visible light (eg, the second harmonic of YAG) or infrared light (eg, YA).
It is possible to produce a photocharge generation / transport material using a G laser or a semiconductor laser, that is, a photoconductive material. Note that a film made of the compound of the present invention is more preferably used as a hole transporting agent. Here, as a method for preparing the charge generation layer, generally, a method in which a dye is dissolved in an appropriate solvent and applied by a method such as spin coating, dip coating, or extrusion coating, a method by vapor deposition, or a method in which a dye or pigment is appropriately coated A method in which a polymer (polyester, polyethylene, polymethacrylate, polyacrylate, etc.) and a solid dispersed using a paint shaker, a sand grinder mill or the like are applied in the same manner.

Generally, phthalocyanine-based, perylene-based, polycyclic quinone-based, and azo-based dyes are used as dyes and pigments that absorb visible light, and phthalocyanine-based and azurenium-based dyes are used as dyes and pigments that absorb infrared light. Can be Examples of these charge generating materials include compounds known in the field of electrophotography (for example, compounds described in Electrophotography Society, Basics and Applications of Electrophotographic Technology, pp. 440-442 (Corona, 1988)). ) May be provided.

[0067]

EXAMPLES Example 1 (Compounds D-111, D-113,
Synthesis of D-115)

[0068]

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9,3 g (27.8 mmol) of 2,3,6,7,10,11-hexahydroxytriphenylene 1 synthesized by the method described in JP-A-7-306317, chloride 2
C50g (0.332mol), potassium carbonate 70.0g
(0.5 mol), 7.5 g (50 mmol) of sodium iodide
Was dissolved in 200 ml of dimethylacetamide and stirred at 120 ° C. for 6 hours. After cooling, water and ethyl acetate were added to carry out liquid separation, and the organic phase was washed twice with water. After drying over magnesium sulfate and concentrating, silica gel-ethyl acetate: hexane =
Purification by a 1: 1 → 2: 1 column gave 25.1 g (yield 89.7%) of hexaacetyloxy form 3C crystals.

17.2 g (17 mmol) of 3C was dissolved in 100 ml of ethanol, and sodium hydroxide 12.2 g was added thereto.
g (0.306 mol) in 30 ml of water was added and refluxed for 2 hours. After cooling, hydrochloric acid was added to adjust the pH to 10, then sodium chloride was added, and the mixture was extracted three times with ethyl acetate. After drying over magnesium sulfate and concentrating, 11.5 g of 4C crystals of hexahydroxy compound
(89.4%).

3.78 g (5 mmol) of 4C, triethyl
Amine 10.2 g (10.1 mmol), nitrobenzene
0.3 g was dissolved in 50 ml of dimethylacetamide and cooled on ice.
It was stirred under. Here, 6.27 g of methacrylic acid chloride
(60 mmol) was slowly added dropwise and further at 60 ° C. for 1 hour.
While stirring. Water and ethyl acetate are added to carry out liquid separation, and the organic phase is separated.
After washing twice with water, the mixture was concentrated in an open system. Silage
Eluate-ethyl acetate: hexane = 1: 2 → 1: 1 column
And crystallized from methanol to give the desired D-115
3.95 g (yield 67.8%) of white crystals were obtained. NMR spectrum (CDCl_Three, δ, ppm) 1.97 (18H, S, -CH_Three),
2.0-2.2 (24H, m, -CH_TwoCH _TwoCH_TwoCH_Two-), 4.31 (24H, -OCH_Two-),
5.56 (6H, S, = CH_Two), 6.13 (6H, S, = CH_Two) 、 7.82 (6H, S, arom
atic) Phase transition temperature measurement by DSC and polarizing microscope Discotic liquid crystal phase → 71 ℃ → isotropic phase

The following procedure was repeated in exactly the same manner except that 2a and 2b were used instead of chloride 2C.
11, D-113 can be synthesized.

D-111, NMR spectrum (CDCl ₃ ,
δ, ppm) 1.97 (18H, S, -CH 3), 4.56 (12H, t, -CH 2 O -), 4.67
_{(12H, t, -CH 2 O} -), 5.60 (6H, S, = CH 2), 6.18 (6H, S, = CH 2)
, 8.02 (6H, S, aromatic) Phase transition temperature measurement by DSC and polarizing microscope Crystal phase → 84 ℃ → Discotic liquid crystal phase → 107 ℃ →
Isotropic phase

D-113, NMR spectrum (CDCl ₃ ,
δ, ppm) 1.97 (18H, S, -CH 3), 2.34 (12H, m, -CH 2 CH 2 CH 2 -)
, 4.37 (12H, t, -CH 2 O -), 4.50 (12H, t, -CH 2 O -), 5.60 (6
H, S, = CH ₂ ), 6.16 (6H, S, = CH ₂ ), 7.90 (6H, S, aromatic) Phase transition temperature measurement by DSC and polarizing microscope Crystal phase → 70 ° C. → Discotic liquid crystal phase → 82 ° C. → isotropic phase

Example 2 (Synthesis of Compounds D-112 and D-114)

[0076]

Embedded image

By reacting with 4b and 4c in Example 1 in the same manner except that an equimolar amount of acrylic acid chloride was used instead of methacrylic acid chloride, the desired D-112 and D-114 could be obtained. .

D-112, NMR spectrum (CDCl ₃ ,
δ, ppm) 2.32 (12H, m, -CH ₂ CH ₂ CH _2- ), 4.35 (12H, m, -CH ₂ O
-), 4.50 (12H, m , -CH 2 O -), 5.85 (6H, d, -CH = CH 2), 6.18 (6
H, t oft, -CH = CH ₂ ), 6.47 (6H, d, -CH = CH ₂ ), 7.88 (6H, S, ar
omatic) Phase transition temperature measurement by DSC and polarization microscope Crystal phase → 76 ℃ → Discotic liquid crystal phase → 83 ℃ → Isotropic phase

D-114, NMR spectrum (CDCl ₃ ,
δ, ppm) 1.95-2.15 (24H, m, -CH ₂ CH ₂ CH ₂ CH _2- ), 4.30 (24
H, m, -OCH _2- ), 5.82 (6H, d, -CH = CH ₂ ), 6.15 (6H, d of d, -C
H = CH ₂ ), 6.44 (6H, d, -CH = CH ₂ ), 7.86 (6H, S, aromatic) Phase transition temperature measurement by DSC and polarizing microscope Discotic liquid crystal phase → 56 ° C. → isotropic phase

Example 3 (Synthesis of Compound D-92)

[0081]

Embedded image

53.4 g of calcium hydroxide (0.64 mol
l) was dissolved in 600 ml of water and stirred, and 69.5 g of bromine was maintained at 20 ° C. in a dry ice-methanol bath.
(0.435 mol) was added dropwise over 30 minutes. Further 25
0 ml of ether was added, and while keeping the temperature at -8 ° C, 36.8 g (0.375 mol) of alcohol was added dropwise.
The mixture was stirred at 8 ° C for 30 minutes. Thereafter, the mixture was stirred at 30 ° C. for 1 hour, cooled again to 10 ° C. in an ice water bath, added with 15 g (14.4 mmol) of sodium sulfite, and stirred for 20 minutes.
Hydrochloric acid (72 g) and ethyl acetate were added, and the mixture was separated.
Wash with 6.3 g, 6.9 g of concentrated sulfuric acid in 130 ml aqueous solution,
Washed twice with 10% aqueous sodium carbonate solution. Sodium sulfate was added, dried, and purified by distillation (5 mmHg, 92 ° C) to obtain 38.6 g of a bromide 6 liquid (yield: 58.3%).

0.068 g (0.68 mmol) of copper (I) chloride
l), hydroxylamine hydrochloride 0.23 g (3.3 mmol)
Is dissolved in 33% ethylamine, 13.5 ml of an aqueous solution,
The mixture was stirred under ice-water cooling, and 4.7 g of ethynylbenzene (45 g) was added.
(mmol) / methanol (11 ml) was added dropwise. After the temperature was raised to 30 ° C., a solution of 7.97 g (45 mmol) of bromide in 7 ml of methanol was added dropwise, and the mixture was stirred at 40 ° C. for 1 hour.
Water and methylene chloride were added for liquid separation, and the organic phase was washed twice with water. After drying over magnesium sulfate, the mixture was concentrated, purified by a silica gel-ethyl acetate: hexane = 1: 5 → 1: 2 column, and 7.30 g of diacetylene alcohol 8 liquid was obtained.
(81.8% yield).

6.94 g of diacetylenic alcohol 8
(35 mmol), 3.04 g (38.5 mmol) of pyridine,
Stir the DMF 0.1 g solution, and thionyl chloride 6.25 g
(52.5 mmol) was added and heated at 60 ° C. for 1 hour.
Water and ether were added to carry out liquid separation, and the organic phase was washed with water. The extract was dried over magnesium sulfate and concentrated to obtain 7.40 g (yield 97.4%) of diacetylene chloride 9 as a liquid.

Diacetylene chloride 9 3.80 (1
7.6 mmol), 2.66 g of ethyl hydroxybenzoate
(16 mmol), 3.4 g (24 mmol) of potassium carbonate and 2.4 g (16 mmol) of sodium iodide were dissolved in 50 ml of dimethylacetamide and stirred at 70 ° C. for 2 hours. After cooling, water and ethyl acetate were added to carry out liquid separation, and the organic phase was extracted with water.
Washed twice. After drying over magnesium sulfate, the mixture was concentrated, and purified by a silica gel-ethyl acetate: hexane = 1: 10 column, and 3.60 g of a liquid of ester 10 (yield: 65.0%).
I got

3.46 g (10 mmol) of the ester 10 was dissolved in 20 ml of ethanol, and potassium hydroxide was added to the solution.
4 g (25 mmol) / 10 ml of water was added, and the mixture was stirred at 60 ° C. for 1 hour. After cooling, hydrochloric acid was added to make the mixture acidic, ethyl acetate was added to carry out liquid separation, and the organic phase was washed twice with water. The extract was dried and concentrated with magnesium sulfate to obtain 3.18 g (yield: 100%) of carboxylic acid 11 as a solid.

1.15 g of methanesulfonyl chloride
(10 mmol) was dissolved in 10 ml of tetrahydrofuran, stirred, and 3.18 g of carboxylic acid 11 was added in an ice-methanol bath.
(10 mmol), 1.42 g of diisopropylethylamine
(11 mmol) in 10 ml of tetrahydrofuran was added,
The mixture was stirred at 5 ° C for 20 minutes. Furthermore, a tetrahydrofuran solution of 0.12 g (1 mmol) of 4-dimethylaminopyridine, 1.29 g (10 mmol) of diisopropylethylamine and 10.32 g (1 mmol) of hexahydroxytriphenylene was added dropwise, and the mixture was returned to room temperature and stirred for 5 hours. Water and methylene chloride were added for liquid separation, and the organic phase was washed twice with water. After drying over magnesium sulfate, the mixture was concentrated and purified with a silica gel-ethyl acetate: hexane = 1: 3 → methylene chloride: hexane = 1: 1 column.

Recrystallization from methanol gave the desired D-92
1.68 g of crystals (yield 78.9%) were obtained. NMR spectrum (CDCl ₃ , δ, ppm) 1.7-1.9 (12H, m, -CH ₂
CH ₂ CH _2- ), 1.9-2.1 (12H, m, -CH ₂ CH ₂ CH _2- ), 2.50 (12H, t,-
CH ₂ C≡C-), 3.96 (12H, t, -OCH _2- ), 6.65 (12H, d, aromati
c), 7.2-7.4 (18H, m, aromatic), 7.48 (12H, m, aromati)
c) 、 7.88 (12H, d, aromatic) 、 8.34 (6H, S, aromatic) Phase transition temperature measurement by DSC and polarizing microscope Liquid crystal phase → 135 ℃ → Discotic liquid crystal phase → 147 ℃
→ isotropic phase

Example 4 (Preparation of Thin Film-1) 100 μL of a 20% by weight solution of compound D-112 of the present invention in ethyl acetate was placed on a 2 cm × 2 cm ITO-coated glass (masked with a tape to form a partial electrode). → 100
It was applied by spin coating at 0 rpm to form a thin film of D-112. When heated on a Mettler FP-82 hot stage and the phase change behavior was observed with a polarizing microscope, it became a dark field at 83 ° C. via a crystal phase and a discotic liquid crystal phase, and transitioned to an isotropic phase. When this thin film was allowed to stand at 70 ° C., the phase changed to a discotic liquid crystal state in a supercooled state.

Here, an ultraviolet irradiation device (ULTRA-VIOLET PRO)
DUCTS UVSL-588 (16W)) and light source from film to 1
At a distance of 4 cm, 254 nm light was irradiated 20 times in an argon atmosphere. In this state, no change was observed in the morphology of the discotic liquid crystal phase within the visual field of the microscope. Further, even when the temperature is raised to 120 ° C., no transition to an isotropic phase occurs, and even when cooled to 25 ° C., no transition to a crystalline phase occurs. It shows what was done. Note that this film has sufficient strength to form an element. The film thickness is 8.5μ
m. This thin film sample is named D-112-70.

Example 5 (Formation of Thin Film-2) A polymerization initiator Irgacure 907 (IRG-907, Ciba-Geigy) was added to a solution of D-112 in a 20% by weight methylene chloride solution.
The same experiment as in Example 4 was carried out except that 0.03 wt% of 112 was added and photopolymerization was performed in air, and a thin film having sufficient rigidity to maintain a discotic liquid crystal phase in the range of 25 to 120 ° C. was prepared. We were able to. The thickness was 5.0 μm.

Example 6 (Preparation of Thin Film-3) A thin film D-112-60 was prepared in the same manner as in Example 4 except that the photopolymerization temperature during supercooling was changed to 60 ° C.
Also in this case, a thin film having sufficient strength to maintain the discotic liquid crystal phase in the range of 25 to 120 ° C. could be formed.
The film thickness was 4.4 μm.

Example 7 (Preparation of thin film-4) Except that in Example 4, D-114 was used instead of D-112, heating was performed to 60 ° C, and then the polymerization temperature in supercooling was set to 30 ° C. Thus, a thin film D-114-30 was produced. This thin film also maintains a discotic liquid crystal phase in the range of 25 to 120 ° C., and has sufficient rigidity. The film thickness is 5.
It was 0 μm.

Example 8 (Preparation of Sample for Measuring Hole Drift Mobility) 70 mg of trisazo pigment 21 and 70 mg of polyester Byron 200 (manufactured by Toyobo Co., Ltd.) were mixed with tetrahydrofuran 8
The mixture was put in a mayonnaise bottle together with 1 ml of glass beads and 1 mmφ of glass beads, and solid-dispersed with a paint shaker.

[0095]

Embedded image

The thin films D-112-70, D-112-60, D-112 on ITO glass produced in Examples 4 and 6
50 μl of a solid dispersion of the above trisazo pigment 21 in tetrahydrofuran was spin-coated on 114-30 at 500 rpm to form a charge generation layer. After drying, gold was vacuum-deposited as an electrode at about 1000 ° C., and the samples for hole drift mobility measurement D-112-70-G and D-11 were used.
2-60-G and D-114-30-G were produced.

Example 9 (Measurement of hole drift mobility) The hole drift mobility was measured by the Time of Flight method. The measurement by the Time of Flight method has been described in many documents and books, but is described in detail, for example, in the Journal of the Institute of Electrographic Photography, Vol. 22, No. 1, p. 69 (1983).

[0098] Connect ITO glass to the negative electrode and gold to the positive electrode.
Voltage of 200V (about 2-4 × 10 ^FiveV / cm electric field)
Plus the second harmonic of a Q-switched Nd: YAG laser
(532 nm) with a light source (160 mW / cm^Two) At 25 ° C
Irradiated from the ITO side. 2000Ω resistor and Oscillator
Connected to the scope, and
Hole drift mobility μ = L^Two/ vxt_Tcm^Two/ vs (L: film thickness,
V: voltage, t_T: Charge transfer time). Compare results
Table 1 together with examples are shown.

[0099]

[Table 1]

Known polyvinyl carbazoles 22 and TPs dispersed in polymers, which are mainly used in electrophotography at present.
Compared with a value of D23 or the like of 10 ⁻⁵ to 10 ⁻⁶ cm ² / vs, the thin film composed of the compounds D-112 and D-114 of the present invention has a very large hole of 1 × 10 ⁻³ or more. It can be seen that it gives a drift movement speed. Especially in D-122,
The photopolymerized thin films D-112-70-G and D-112-6 of the present invention can be used even at a measurement temperature of 25 ° C. which is a crystalline phase.
0-G suggests that the discotic liquid crystal phase in the supercooled state is solidified while being maintained. Note that when a voltage is applied in reverse, the movement of electrons is observed even though it is slower than holes, and the layer can function as an electron transporting material.

On the other hand, D. Adam et al., Ber. Bunsenges. Phy
s. Chem., 97 1366 (1993), Phys. Rev. Lett., 70 457 (1993).
Hexapentyloxytriphenylene 24 described in (1) shows a hole drift migration speed of 10 ⁻³ cm ² / vs in a discotic liquid crystal phase at 77 ° C. in a liquid crystal cell, which is equivalent to that of the present invention. , It cannot be hardened as it is in a liquid crystal phase. Further, at 26 ° C., the phase shifts to a crystal phase having a deep trap, and shows only a hole drift moving speed of 10 ⁻⁵ cm ² / vs or less, which is much lower than that of the present invention. It is also impossible to form a strong thin film using only 24.

[0102]

As is apparent from the above description, by polymerizing a film coated with the compounds represented by the general formulas (I) to (V) of the present invention at a temperature at which a liquid crystal phase can be obtained,
A liquid crystal phase structure can be maintained over a wide temperature range, and a strong thin film having high charge transportability can be formed. The thin film of the present invention having high charge transporting property and robustness can be applied not only to electrophotography but also to various fields such as electroluminescent devices, secondary batteries, and fuel cells.

Claims (6)

[Claims] 1. A charge transport material comprising a discotic compound having a substituent capable of forming a chemical bond by reacting with light or heat energy, or a reaction product thereof. 2. The charge transport material according to claim 1, wherein the discotic compound is represented by the following general formula (I). Embedded image In the formula, P represents a reactive substituent, D represents an n-functional group located at the center of the molecule and radially distributing a total of n substituents A and substituents (PL). (Nk) A each independently represents a substituent that does not contribute to the formation of the reaction composition, L each independently represents a group or a chemical bond connecting P and D, and n represents 3 to 8 Represents an integer, and k represents an integer from 1 to n. k Ps are each independently an isocyanate group, a thiocyanate group, an amino group, an alkylamino group, an arylamino group, a mercapto group, a formyl group, an acyl group, a hydroxyl group, a carboxyl group, a sulfo group, a phosphoryl group, a halocarbonyl group. , A halosulfonyl group, a halophosphoryl group, an acryloyl group, a methacryloyl group, a crotonyl group, a vinyloxy group, an epoxy group, an acetylene group, a propargyl group, an allenyl group, and a diacetylene group. 3. A compound of the formula (I) wherein a reactive substituent P
Is independently represented by any _one of the following polymerizable substituents M _{1 to} M ₄ . Embedded image R ₁₁ , R ₁₂ , R ₁₃ , R ₂₁ , R _{21 of} the substituents M ₁ , M ₂ , M _3
22 , R ₂₃ , R ₃₁ , R ₃₂ and R ₃₃ each independently represent a hydrogen atom or an alkyl group. In the substituent M ₄ , R ₄₁ represents a hydrogen atom, an alkyl group, or an aryl group. In the substituent M ₁ , m represents 0 or 1. 4. A charge generation layer which absorbs light to generate charges by charge separation and charge transport comprising a compound represented by the general formula (I) of claim 1 or a reaction product or polymer thereof. A photoconductive material comprising a layer. 5. The charge transport material according to claim 1, comprising a compound represented by the following general formulas (II) to (V) or a polymer thereof. Embedded image In the general formulas (II) to (V), M _{1 to} M ₄ have the same meaning as in the general formula (I). In the general formula (II), 6 one of R ₁ that bind to the triphenylene ring represents an alkyl group or an aryl group which may be substituted may be the same or different, of which at least one having a substituent group M _1. In the general formula (III),
Represents a six R ₂ represents an alkyl group or an aryl group which may be substituted may be the same or different that binds to a triphenylene ring, of which at least one having a substituent group M _2. 6 bonded to a triphenylene ring in the general formula (IV)
One R ₃ represents an alkyl group or an aryl group which may be the same or different, and at least one of them has a substituent M ₃ . In the general formula (V), 6 one R ₄ that binds to the triphenylene ring represents an alkyl group or an aryl group which may be substituted it may be the same or different, of which at least one having a substituent M _4. 6. A charge generation layer which absorbs light to generate charges by charge separation and a charge transport layer comprising a compound represented by formulas (II) to (V) of claim 5 or a polymer thereof. A photoconductive material, comprising: