JP2001342182A - Isooxazolylidene compound and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electron transfer material capable of being dispersed in a light sensitive layer in high concentration and having a rapid electron mobility. SOLUTION: This isooxazolylidene compound is represented by general formula (1) (wherein, substituents R1 to R5 are each one kind of substituent selected from a hydrogen atom, a cyano group, a nitro group, a halogen atom, a hydroxy group, a substituted or nonsubstituted alkyl group, an aryl group, a heterocyclic group, an ester group, an alkoxy group, an aralkyl group, an allyl group, an amide group, an amino group, an acyl group, an alkenyl group, an alkynyl group, a carboxygroup, a carbonyl group or a carboxylic acid group, and the case in which R1 and R2, or R3 and R4 form each a ring by binding to each other is included). The isooxazolylidene compound is used as the electron transfer agent, and included in the light sensitive layer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a technical field using an electron-transporting material, and in particular, a novel isoxazolylidene compound, a method for producing the same, an electron-transfer agent containing the same, and an electrophotograph containing them. The present invention relates to a photoconductor and an organic electroluminescence device.

[0002]

2. Description of the Related Art Electrophotographic devices such as copiers and laser printers have an electrophotographic photosensitive member. An inorganic thin film made of an inorganic material such as selenium, selenium-tellurium, selenium-arsenic, and amorphous silicon has been used.

However, in recent years, there has been a demand for an electrophotographic photosensitive member having low cost and low environmental pollution. For this reason, an electrophotographic photosensitive member having an organic thin film has been mainly used in place of the inorganic thin photosensitive layer conventionally used. It is becoming. When the photosensitive layer composed of such an organic thin film is classified according to its structure, it can be roughly classified into a single-layer dispersion type photosensitive layer and a function separation type photosensitive layer.

A single-layer dispersion type photosensitive layer is composed of a single-layer film in which a charge-generating substance is dispersed in a medium of a charge-transfer substance. One layer of the single-layer film has both a charge-generating function and a charge-transfer function. I have it. On the other hand, the function-separated type photosensitive layer is composed of a multilayer film in which a charge generation layer (CGL) and a charge transfer layer (CTL) are laminated, and the charge generation layer has a function of generating charges, and the charge transfer layer has a function of generating charges. The layer has a function of transferring generated charges.

[0005] At present, both types of photosensitive layers are put into practical use, but in both types, a high-mobility charge transfer material is indispensable in order to improve the sensitivity.

On the other hand, when the organic photosensitive layers are classified by charge type, they are classified into two types: positively chargeable photosensitive layers and negatively chargeable photosensitive layers. Of the currently known charge transfer materials, most have high mobility and are practically compatible with hole mobility. A photoreceptor having a photosensitive layer is used.

However, the corona discharge phenomenon used for negatively charging the photosensitive layer involves various problems such as generation of a large amount of ozone due to the discharge, contamination of the indoor environment, and rapid deterioration of the electrophotographic photosensitive member. The inconvenience has occurred.

[0008] With respect to the inconvenience at the time of negative charging, countermeasures have been attempted for electrophotographic equipment of the prior art, and the addition of an ozone trapping filter and the adoption of a special charging method that does not generate ozone are being studied. However, new problems have arisen such as an increase in the size of the apparatus and the complexity of the electrophotographic process, and no solution has been reached.

In order to overcome this situation, recently market demands for a positively charged photoreceptor which generates less ozone, and for that purpose, high mobility electron transfer which can be used for a positively charged photosensitive layer. Material development is needed.

Therefore, intensive studies have been made in the past, and at present, trinitrofluorenone (TNF), tetracyanoethylene, tetracyanoethylene and the like can be used as electron transfer materials for such positively charged photoreceptors. Quinomethane (TCNQ), quinone, diphenoquinone, naphthoquinone, anthraquinone and derivatives thereof have been found. However, most of these electron transfer materials have poor compatibility with the binder resin and cannot be uniformly dispersed at a high concentration in the photosensitive layer. For this reason, the content is insufficient, and electrical characteristics cannot be satisfied.

Of these, diphenoquinone compounds are known to have exceptionally good resin compatibility and high electron mobility. Diphenoquinone compounds have a large molecular skeleton and a conjugated system in which five double bonds are interposed between oxygen atoms.Because the electron transfer distance within the molecule is long, electrons can easily move within the molecule and have high electron mobility. Show. On the other hand, if the molecule is strongly colored due to the long conjugated system of the molecule and the photosensitive layer is formed, light that should originally reach the charge generating substance is absorbed, and the sensitivity is reduced.

An electron transfer material which solves these problems is described in the following chemical formula (1) described in JP-A-9-34141.
0),

[0013]

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The compound (1) was studied. The above compound has a conjugate system in which three double bonds are interposed between the oxygen atom and the dicyanomethylene group in the molecular skeleton.The short conjugate system has low coloring properties and is hard to absorb light. Has a short electron transfer distance, so that electrons are less likely to move in a molecule than a diphenoquinone compound. The fact is that the electrophotographic photosensitive member using the above compound does not reach the sensitivity and residual potential of the negatively charged electrophotographic photosensitive member on the market.

As described above, for practical use as an electron transfer material, the conjugated system is made short in order to weaken the coloring property, and the molecular skeleton is enlarged in order to make electrons easily move in the molecule. Research that solves the contradictory problem of prolonging the time has been desired.

[0016]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems of the prior art, and can be dispersed at a high concentration in a photosensitive layer and has a new and useful electron mobility. An object of the present invention is to provide an electron transfer material and an electrophotographic photoreceptor having excellent sensitivity and residual potential.

[0017]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have found that a compound having a novel molecular skeleton in which a quinone ring and an isoxazolone ring are connected by a double bond. The present inventors have found that it is possible to provide a novel electron transfer agent, an electrophotographic photosensitive member containing an electron transfer material, and an organic electroluminescence element, and have completed the present invention.

The present invention has been made based on such findings, and the invention of claim 1 is an isoxazolylidene compound represented by the following general formula (1).

[0019]

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(Substituents R _{1 to} R ₅ are a hydrogen atom, a cyano group, a nitro group, a halogen atom, a hydroxy group, a substituted or unsubstituted alkyl group, an aryl group, a heterocyclic group, an ester group, an alkoxy group, An aralkyl group, an allyl group, an amide group, an amino group, an acyl group, an alkenyl group, an alkynyl group, a carboxyl group, a carbonyl group or a carboxylic acid group; and R ₁ and R ₂ , R ₃ and R ₄ also includes a case where they are bonded to each other to form a ring.)

The isoxazolone ring has a strong acidity and a high electron-accepting structure. Therefore, a novel molecular skeleton was designed in which an isoxazolone ring and a quinone ring, which is generally known to have a strong electron-accepting property, were connected by a double bond.
Since the compound has two ring structures, a 6-membered ring and a 5-membered ring, the molecular skeleton is larger than that of the compound of the above formula (10), and four double bonds are formed between oxygen atoms. Since there is an intervening conjugated system and the electron transfer distance within the molecule is long, electrons can easily move within the molecule and exhibit high electron mobility. Further, since the number of conjugated systems between oxygen atoms is as short as four as compared with the diphenoquinone compound, coloring properties are weak and light absorption is hardly caused. In addition, since the isoxazolone ring is bonded to one side of the quinone ring, the molecular structure is asymmetric, so that the resin compatibility is high and the resin can be uniformly dispersed in the resin at a high concentration. In addition, these functions can be easily changed arbitrarily depending on the combination of the substituents. This makes it possible to optimize the resin compatibility and control the electron transfer speed and the electron transfer amount.

In particular, when the substituent represented by R ₅ in the above general formula (1) is a thienyl group or a furyl group, the structure has a hetero atom, so that the electron mobility increases.

The invention according to claim 2 is an isoxazolylidene compound represented by the following general formula (2).

[0024]

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(Substituents R _{6 to} R _{8 each} represent a hydrogen atom,
Any one of an alkyl group or a phenyl group
Kind of substituent. However, this excludes the case where R ₇ is a substituent other than hydrogen and R ₆ and R ₈ are hydrogen. The substituent R ₉ is any one of a phenyl group, a thienyl group, and a furyl group. Introducing at least one alkyl group having 1 to 6 carbon atoms or phenyl group into the substituents R _{6 to} R ₈ has an effect of pushing out electrons to the molecular skeleton, increasing polarization in the molecule and increasing electron mobility. Get higher.

The introduction of an aromatic 6π-electron phenyl group, thienyl group, or furyl group into the substituent R ₉ can stabilize the molecular skeleton. Then, those substituents having good compatibility with the resin can be combined.

The invention according to claim 3 is an isoxazolylidene compound represented by the following formula (3).

[0028]

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T-Bu which is a bulky substituent on the quinone ring
The introduction of the group has the effect of extruding electrons into the molecular skeleton as well as having high resin compatibility, increasing the intramolecular polarization, and inventing a compound having extremely high electron mobility.

The invention according to claim 4 is an isoxazolylidene compound represented by the following formula (14).

[0031]

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The invention according to claim 5 is an isoxazolylidene compound represented by the following formula (15).

[0033]

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The invention according to claim 6 is an isoxazolylidene compound represented by the following formula (16).

[0035]

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The invention according to claim 7 is an isoxazolylidene compound represented by the following formula (17).

[0037]

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The invention according to claim 8 is an isoxazolylidene compound represented by the following formula (18).

[0039]

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The ninth aspect of the present invention is an isoxazolylidene compound represented by the following formula (19).

[0041]

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According to a tenth aspect of the present invention, the following formula (20) is used.
It is an isoxazolylidene compound represented by these.

[0043]

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The eleventh aspect of the present invention provides the following formula (21)
It is an isoxazolylidene compound represented by these.

[0045]

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The twelfth aspect of the present invention provides the following formula (22)
It is an isoxazolylidene compound represented by these.

[0047]

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According to a thirteenth aspect, the following formula (23)
It is an isoxazolylidene compound represented by these.

[0049]

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According to a fourteenth aspect of the present invention, there is provided the following general formula (4):

[0051]

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(Substituents R _{1 to} R ₄ represent a hydrogen atom, a cyano group, a nitro group, a halogen atom, a hydroxy group, a substituted or unsubstituted alkyl group, an aryl group, a heterocyclic group, an ester group, an alkoxy group, An aralkyl group, an allyl group, an amide group, an amino group, an acyl group, an alkenyl group, an alkynyl group, a carboxyl group, a carbonyl group or a carboxylic acid group; and R ₁ and R ₂ , R ₃ R ₄ may be bonded to each other to form a ring), and a benzoquinone compound represented by the following general formula (5):

[0053]

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(The substituent R ₅ is a hydrogen atom, a cyano group, a nitro group, a halogen atom, a hydroxy group, a substituted or unsubstituted alkyl group, an aryl group, a heterocyclic group, an ester group, an alkoxy group, an aralkyl group, An isoxazolone compound represented by the formula: allyl group, amide group, amino group, acyl group, alkenyl group, alkynyl group, carboxyl group, carbonyl group or carboxylic acid group. The reaction is carried out in an inert solvent under the following general formula (1):

[0055]

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(Substituents R _{1 to} R ₅ represent a hydrogen atom, a cyano group, a nitro group, a halogen atom, a hydroxy group, a substituted or unsubstituted alkyl group, an aryl group, a heterocyclic group, an ester group, an alkoxy group, An aralkyl group, an allyl group, an amide group, an amino group, an acyl group, an alkenyl group, an alkynyl group, a carboxyl group, a carbonyl group or a carboxylic acid group; and R ₁ and R ₂ , R ₃ and R ₄ includes a case where they are bonded to each other to form a ring.). According to the fourteenth aspect, an isoxazolylidene compound can be easily produced.

The invention according to claim 15 is characterized by the following general formula (6):

[0058]

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(Substituents R _{6 to} R _{8 each} represent a hydrogen atom,
Or any one of a phenyl group and an alkyl group. Provided that R ₇ is a substituent other than hydrogen and R ₆ ,
Except when R ₈ is hydrogen. A benzoquinone compound represented by the following general formula (7):

[0060]

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(The substituent R ₉ is a phenyl group, a thienyl group,
Any one of the substituents of the furyl group. ) With an isoxazolone compound in an inert solvent in the presence of a base catalyst to obtain the following general formula (2):

[0062]

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(Substituents R _{6 to} R _{8 each} represent a hydrogen atom,
Any one of an alkyl group or a phenyl group
Kind of substituent. However, this excludes the case where R ₇ is a substituent other than hydrogen and R ₆ and R ₈ are hydrogen. The substituent R ₉ is any one of a phenyl group, a thienyl group, and a furyl group. This is a method for producing a compound for producing an isoxazolylidene compound represented by the following formula:

Further, the invention of claim 16 provides the following chemical formula (8):

[0065]

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A benzoquinone compound represented by the following chemical formula (9):

[0067]

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The isoxazolone compound is reacted in an inert solvent in the presence of a base catalyst to give the following chemical formula (3):

[0069]

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This is a method for producing a compound for producing an isoxazolylidene compound represented by the formula:

The invention of claim 17 provides the following general formula (1):

[0072]

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(Substituents R _{1 to} R ₅ represent a hydrogen atom, a cyano group, a nitro group, a halogen atom, a hydroxy group, a substituted or unsubstituted alkyl group, an aryl group, a heterocyclic group, an ester group, an alkoxy group, An aralkyl group, an allyl group, an amide group, an amino group, an acyl group, an alkenyl group, an alkynyl group, a carboxyl group, a carbonyl group or a carboxylic acid group; and R ₁ and R ₂ , R ₃ and R Reference numeral ₄ includes an isoxazolylidene compound represented by the formula (1) in a resin.

The invention according to claim 18 is characterized by the following general formula (2):

[0075]

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(Substituents R _{6 to} R _{8 each} represent a hydrogen atom,
Any one of an alkyl group or a phenyl group
Kind of substituent. However, this excludes the case where R ₇ is a substituent other than hydrogen and R ₆ and R ₈ are hydrogen. The substituent R ₉ is any one of a phenyl group, a thienyl group, and a furyl group. ) Is an electron transfer agent containing the isoxazolylidene compound represented by the formula (1) in a resin.

The invention according to claim 19 is characterized by the following chemical formula (3):

[0078]

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An electron transfer agent containing the isoxazolylidene compound represented by the formula in a resin. Claim 17, 1
The isoxazolylidene compounds described in 8 and 19 exhibit high electron mobility.

The invention according to claim 20 is an electrophotographic photosensitive member in which a photosensitive layer is provided on a conductive substrate, wherein the photosensitive layer has the following general formula (1):

[0081]

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(Substituents R _{1 to} R ₅ are a hydrogen atom, a cyano group, a nitro group, a halogen atom, a hydroxy group, a substituted or unsubstituted alkyl group, an aryl group, a heterocyclic group, an ester group, an alkoxy group, An aralkyl group, an allyl group, an amide group, an amino group, an acyl group, an alkenyl group, an alkynyl group, a carboxyl group, a carbonyl group or a carboxylic acid group; and R ₁ and R ₂ , R ₃ and R ₄ is an electrophotographic photoreceptor containing an isoxazolylidene compound represented by the formula: As described above, by using a compound having high electron mobility and high compatibility with a resin, it is possible to provide a more sensitive electrophotographic photosensitive member.

According to a twenty-first aspect of the present invention, there is provided an electrophotographic photosensitive member having a photosensitive layer provided on a conductive substrate, wherein the photosensitive layer has the following general formula (2):

[0084]

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(Substituents R _{6 to} R _{8 each} represent a hydrogen atom,
Any one of an alkyl group or a phenyl group
Kind of substituent. However, this excludes the case where R ₇ is a substituent other than hydrogen and R ₆ and R ₈ are hydrogen. The substituent R ₉ is any one of a phenyl group, a thienyl group, and a furyl group. An electrophotographic photoreceptor containing an isoxazolylidene compound represented by the formula (1):

The invention according to claim 22 is an electrophotographic photosensitive member in which a photosensitive layer is provided on a conductive substrate, wherein the photosensitive layer has the following chemical formula (3):

[0087]

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An electrophotographic photosensitive member containing an isoxazolylidene compound represented by the formula: As described above, an electrophotographic photoreceptor with extremely high sensitivity can be provided by using a compound having high electron mobility and high compatibility with a resin.

The invention according to claim 23 is an organic electroluminescent device in which at least an organic thin film capable of emitting light is arranged between a pair of electrodes, wherein the organic thin film has the following general formula (1):

[0090]

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(Substituents R _{1 to} R ₅ represent a hydrogen atom, a cyano group, a nitro group, a halogen atom, a hydroxy group, a substituted or unsubstituted alkyl group, an aryl group, a heterocyclic group, an ester group, an alkoxy group, An aralkyl group, an allyl group, an amide group, an amino group, an acyl group, an alkenyl group, an alkynyl group, a carboxyl group, a carbonyl group or a carboxylic acid group; and R ₁ and R ₂ , R ₃ and R ₄ includes an isoxazolylidene compound represented by the formula (1).

According to a twenty-fourth aspect of the present invention, there is provided an organic electroluminescent device having at least an organic thin film capable of emitting light between a pair of electrodes, wherein the organic thin film has the following general formula (2):

[0093]

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(Substituents R _{6 to} R _{8 each} represent a hydrogen atom,
Any one of an alkyl group or a phenyl group
Kind of substituent. However, this excludes the case where R ₇ is a substituent other than hydrogen and R ₆ and R ₈ are hydrogen. The substituent R ₉ is any one of a phenyl group, a thienyl group, and a furyl group. ) Is an organic electroluminescence device containing an isoxazolylidene compound represented by the following formula:

According to a twenty-fifth aspect of the present invention, there is provided an organic electroluminescence device having at least an organic thin film capable of emitting light between a pair of electrodes, wherein the organic thin film has the following chemical formula (3):

[0096]

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An organic electroluminescent device containing an isoxazolylidene compound represented by the formula: As described above, the compounds of the present invention not only exhibit high electron mobility, but also can be designed according to the functions required as materials for electrophotographic photoreceptors and organic electroluminescence devices using electron transfer materials. It is.

[0098]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the isoxazolylidene compound, the method for producing the isoxazolylidene compound, the electron transfer agent, and the applied examples according to the present invention will be described in detail.

[Description of Compound] The isoxazolylidene compound according to the present invention has the following general formula (1):

[0100]

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(Substituents R _{1 to} R ₅ represent a hydrogen atom, a cyano group, a nitro group, a halogen atom, a hydroxy group, a substituted or unsubstituted alkyl group, an aryl group, a heterocyclic group, an ester group, an alkoxy group, An aralkyl group, an allyl group, an amide group, an amino group, an acyl group, an alkenyl group, an alkynyl group, a carboxyl group, a carbonyl group or a carboxylic acid group; and R ₁ and R ₂ , R ₃ and R ₄ has a novel molecular skeleton in which a quinone ring and an isoxazolone ring are double-bonded.

Tables 1 to 8 below show the isoxazolylidene compounds of the present invention when the substituents R _{1 to} R ₅ of the general formula (1) are specifically combined.

[0103]

[Table 1]

[0104]

[Table 2]

[0105]

[Table 3]

[0106]

[Table 4]

[0107]

[Table 5]

[0108]

[Table 6]

[0109]

[Table 7]

[0110]

[Table 8]

[Description of Production Method] The production method of the present invention comprises:
The benzoquinone compound and the isoxazolone compound are reacted in an inert solvent in the presence of a base catalyst.

The base catalyst used in the production method of the present invention includes, as organic base catalysts, primary amines such as methylamine, ethylamine, propylamine and butylamine, dimethylamine, diethylamine, methylethylamine, and the like.
Secondary amines such as dipropylamine and dibutylamine, trimethylamine, dimethylethylamine, methyldiethylamine, dimethylpropylamine, triethylamine, methylethylpropylamine, diethylpropylamine, dipropylmethylamine, ethyldipropylamine, tributylamine, etc. Secondary amine, pyridine,
2,6-dimethylpyridine, quinoline, 1,8-diazabicyclo [5.4.0] undec-7-ene (DB
U), 1,5-diazabicyclo [4.3.0] non-5
Cyclic amines such as -ene and 1,4-diazabicyclo [2.2.2] octane; metal alkoxides such as sodium methoxide, potassium methoxide and butyllithium; and metal amides such as sodium amide and potassium amide.

Examples of the inorganic base catalyst include basic gases such as ammonia, alkali metals such as sodium, potassium and lithium, metal hydroxides such as sodium hydroxide, potassium hydroxide and calcium hydroxide, sodium carbonate and potassium carbonate. Metal salts and the like. It is preferable to use a base having a base dissociation constant larger than that of pyridine, because the reaction proceeds quickly. About the kind of base catalyst, two or more kinds of base catalysts can be mixed and used.

Examples of the inert solvent include alcohols such as methanol, ethanol, 1-propanol, 2-propanol, butanol, and ethylene glycol; hexane;
Saturated aliphatic hydrocarbons such as heptane, octane, cyclohexane and cycloheptane; aromatic hydrocarbons such as benzene, toluene and xylene; chlorinated hydrocarbons such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride and chlorobenzene; diethyl ether; diisopropyl Ethers such as ether, tetrahydrofuran (THF), dioxane, methoxyethanol, etc., ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl formate, propyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, propion Esters such as methyl acid, N-methylpyrrolidone and the like. These may be used alone or as a mixture of two or more inert solvents.

The reaction temperature may proceed at room temperature depending on the base catalyst.
0 ° C. or higher is preferred.

[Explanation of Electron Transfer Agent] The electron transfer agent of the present invention contains an isoxazolylidene compound in a resin.

Examples of the resin contained in the electron transfer agent include polycarbonate resin, styrene resin, acrylic resin, styrene-acrylic resin, ethylene-vinyl acetate resin, polypropylene resin, vinyl chloride resin, chlorinated polyether, and vinyl chloride-acetic acid. Vinyl resin, polyester resin,
Nylon resin, vinyl acetate resin, furan resin, nitrile resin, alkyd resin, polyacetal resin, polymethylpentene resin, polyamide resin, polyurethane resin,
Epoxy resin, polyarylate resin, diallylate resin, polysulfone resin, polyethersulfone resin, polyallylsulfone resin, silicone resin, ketone resin,
Polyvinyl butyral resin, polyether resin, phenol resin, EVA (ethylene / vinyl acetate / copolymer)
Resins, photocurable resins such as ACS (acrylonitrile / chlorinated polyethylene / styrene) resin, ABS (acrylonitrile / butadiene / styrene) resin, and epoxy arylate. These may be used alone or a copolymer may be used, or two or more of them may be used in combination. In addition, it is preferable to use a mixture of resins having different molecular weights because hardness and abrasion resistance can be improved.

The electron transfer agent of the present invention contains the compound represented by the general formula (1) in its resin. This compound preferably has high electron mobility as represented by the general formula (2), and preferably has the chemical formulas (3) and (14) to
(The compound represented by 23 is particularly preferred in terms of electron mobility and resin compatibility.

In particular, the electron transfer agent of the present invention shows a great effect in a solid solution with a resin. At this time, when the substituent of the electron transfer agent molecule and the resin monomer have a similar structure, a solid solution is more likely to be formed as a solid solution. In order to form a solid solution, a uniform coating is formed in a solvent in which both are dissolved, and a method of drying it is uniform and has a large area. Preferred for processing into membranes. Such solvents include methanol, ethanol, 1-propanol, 2-
Alcohols such as propanol and butanol, pentane, hexane, heptane, octane, cyclohexane,
Saturated aliphatic hydrocarbons such as cycloheptane, aromatic hydrocarbons such as toluene and xylene, chlorinated hydrocarbons such as dichloromethane, dichloroethane, chloroform and chlorobenzene, ethers such as dimethyl ether, diethyl ether, tetrahydrofuran (THF) and methoxyethanol , Acetone, methyl ethyl ketone, methyl isobutyl ketone, ketones such as cyclohexanone, esters such as ethyl formate, propyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, N, N-dimethylformamide, dimethyl sulfoxide Etc. These may be used alone or as a mixture of two or more solvents.

When the resin to be used is a thermoplastic resin, the compound of the present invention can be directly added to the resin softened by heating to be used as an electron transfer agent. The heating temperature is preferably equal to or higher than the glass transition point, and more preferably equal to or higher than the melting point. When the resin has a high glass transition point or low compatibility, a small amount of a solvent may be added and kneaded to obtain an electron transfer agent.

In order to obtain optical transparency, the electron transfer agent of the present invention should contain the compound of the present invention in a minimum necessary amount with respect to the resin. It is preferably at most 50 parts by weight, more preferably at most 50 parts by weight.

Further, the electric characteristics can be improved by adding another charge transfer material to the electron transfer agent of the present invention. Charge transfer materials that can be added for such improvements include polyvinyl carbazole, halogenated polyvinyl carbazole, polyvinyl pyrene, polyvinyl indoloquinoxaline, polyvinyl benzothiophene, polyvinyl anthracene, polyvinyl acridine, polyvinyl pyrazoline, polyacetylene, polythiophene, and polypyrrole. Using conductive polymer compounds such as polyphenylene, polyphenylenevinylene, polyisothianaphthene, polyaniline, polydiacetylene, polyheptadiene, polypyridinediyl, polyquinoline, polyphenylene sulfide, polyferrosenylene, polyperinaphthylene, and polyphthalocyanine. be able to. Further, as low molecular weight compounds, trinitrofluorenone, tetracyanoethylene, tetracyanoquinodimethane, quinone, diphenoquinone, naphthoquinone, anthraquinone and derivatives thereof, anthracene, pyrene, polycyclic aromatic compounds such as phenanthrene, indole, carbazole , Imidazole, nitrogen-containing heterocyclic compounds such as fluorenone, fluorene, oxadiazole, oxazole, pyrazoline, hydrazone, triphenylmethane, triphenylamine,
Enamine, stilbene, butadiene compounds and the like can be used.

Further, a polymer solid electrolyte in which a polymer compound such as polyethylene oxide, polypropylene oxide, polyacrylonitrile, and polymethacrylic acid is doped with a metal ion such as Li ion can also be used.

Further, an organic charge transfer complex formed of an electron-donating compound represented by tetrathiafulvalene-tetracyanoquinodimethane and an electron-accepting compound can also be used. Also, desired electron transfer characteristics can be obtained by mixing and adding two or more compounds.

The electron transfer agent of the present invention includes an antioxidant, an ultraviolet absorber, and an ultraviolet absorber as long as the electron transfer characteristics are not impaired.
By adding a radical scavenger, a softening agent, a curing agent, a cross-linking agent, and the like, the electric characteristics, durability, and mechanical characteristics of the electron transfer agent can be improved.

These electron transfer agents can be used as various functional materials such as an electrophotographic photoreceptor, a conductive agent, a charge control agent, an EL device, a sensitizer of a photochemical reaction, and a highly conductive substance by a charge transfer complex. Can be applied.

[Description of Application Examples] Description of Electrophotographic Photoreceptor The electrophotographic photoreceptor of the present invention is an electrophotographic photoreceptor having a photosensitive layer provided on a conductive substrate, and charge transfer in the photosensitive layer. It contains an isoxazolylidene compound as a substance.

Reference numeral 11 in FIG. 1 and reference numeral 12 in FIG. 2 indicate an electrophotographic photosensitive member according to an embodiment of the present invention. It is of a dispersive type, and which of the electrophotographic photosensitive members 11, 1
2 is also an embodiment in which an organic thin film containing the compound of the present invention is used for a photosensitive layer.

The electrophotographic photoreceptor 11 shown in FIG. 1 has a charge generation layer 2 and a charge transfer layer 3 on a cylindrical conductive support 1.
Are formed in this order, and the charge generation layer 2 and the charge transfer layer 3 constitute the photosensitive layer 4.

The charge generation layer 2 shown in FIG. 1 has at least a charge generation substance.
It can be formed by binding a charge generating substance on the conductive support 1 serving as the base using a binder resin.

Various methods such as a known method can be used for forming the charge generation layer 2. A coating solution in which a charge generation material is dispersed or dissolved together with a binder resin in an appropriate solvent is applied to a predetermined solution. A method of applying the composition on the conductive support 1 serving as a base and drying the composition can be used. Alternatively, the charge generation layer 2 can be formed by vacuum-depositing a charge generation substance.

The charge transfer layer 3 has at least a charge transfer material to be described later. The charge transfer layer 3 is formed, for example, by bonding a charge transfer material on the charge generation layer 2 as a base using a binder resin. It can be formed by attaching.

As a method for forming the charge transfer layer 3, various methods such as a known method can be used. In a general case, a coating solution in which a charge transfer material is dispersed or dissolved in a suitable solvent together with a binder resin. Can be applied on the charge generating layer 2 serving as a predetermined base and then dried.

The electrophotographic photoreceptor of the present invention is not limited to a charging system or a layer structure. In particular, the charge-transferring material of the general formula (1) is used in a charge-transfer layer of a function-separated type photoreceptor in a positive charging system. Those containing a compound and those containing a general formula (1) as a charge transfer substance in a single-layer dispersion type photosensitive layer are preferable. In the positive charging method, a positive charge is charged on the surface of the electrophotographic photosensitive member, a negative charge generated from a charge generating substance is irradiated by exposure light irradiation for forming a latent image, and combined with the positive charge charged on the surface. A latent image is formed by eliminating surface charges. General formula (1)
Is a material for transferring negative charges generated by exposure light exposure, and has high electron mobility, so that an electrophotographic photoreceptor exhibiting good characteristics can be provided.

It is also preferable that the charge generating layer of the function-separated type photoreceptor in the negative charging system contains the compound of the general formula (1). In the negative charging method, a negative charge is charged on the surface of the electrophotographic photoreceptor, a positive charge generated from a charge generating substance is irradiated by exposure light exposure for forming a latent image, and combined with the negative charge charged on the surface. A latent image is formed by eliminating surface charges. As the charge transfer material, a material having high hole mobility is used. By including the compound of the general formula (1) in the photosensitive layer, characteristics such as a decrease in residual potential and suppression of memory can be improved by the high electron mobility of the general formula (1).

Reference numeral 12 in FIG. 2 denotes a single-layer type electrophotographic photosensitive member as an example of the present invention, and the same members as those of the electrophotographic photosensitive member 11 of the first example are denoted by the same reference numerals. Then, in the electrophotographic photoreceptor 12, the single-layered photosensitive layer 4 containing the charge generating substance and the charge transfer substance is formed on the conductive support 1.

As a method for forming the photosensitive layer 4, various methods such as a known method can be used. The charge generating substance described below is dispersed or dissolved in a suitable solvent together with a binder resin, and the charge transfer substance described later is further used. A method in which a coating solution in which a substance is dissolved is applied onto the conductive support 1 serving as a predetermined base and dried is used.

The conductive support 1 that can be used in the present invention includes simple metals such as aluminum, magnesium, brass, stainless steel, nickel, chromium, titanium, gold, silver, copper, tin, platinum, molybdenum, and indium. And a processed body of the alloy thereof, a conductive material such as the metal or carbon is deposited by a method such as evaporation, plating, and the like, and a plastic plate and a film having conductivity, further, tin oxide, indium oxide, aluminum iodide, Conductive glass coated with copper iodide,
The conductive support 1 can be configured using various conductive materials without being limited by the type or shape.

In general, a cylindrical aluminum tube alone or one whose surface is subjected to alumite treatment, or one in which a resin layer is formed on an aluminum tube or an alumite layer is often used. This resin layer has a function of improving adhesion, a function of preventing current flowing from the support, a function of covering defects on the surface of the support, and the like. Various resins such as a polyethylene resin, an acrylic resin, an epoxy resin, a polycarbonate resin, a polyurethane resin, a vinyl chloride resin, a vinyl acetate resin, a polyvinyl butyral resin, a polyamide resin, and a nylon resin can be used for the resin layer. These resin layers may be composed of a single resin,
Two or more resins may be mixed or combined with an alumite treatment. Further, a metal compound, a metal oxide, carbon, silica, a resin powder and the like can be dispersed in the layer.

Further, various pigments, an electron-accepting substance, an electron-donating substance, and the like can be contained for improving characteristics.

Examples of the charge generating substance usable in the present invention include selenium, selenium-tellurium, selenium-arsenic,
Amorphous silicon, phthalocyanine pigment, monoazo pigment, trisazo pigment, polyazo pigment, indigo pigment,
Toluidine pigments, pyrazoline pigments, perylene pigments, quinacridone pigments, pyrylium salts and the like can be used.
Among these, disazo pigments and phthalocyanine pigments are preferred because they have good compatibility with the compound of the present invention in order to obtain sensitivity.

As the phthalocyanine pigment, diol adducts of oxytitanium phthalocyanine, copper phthalocyanine, metal-free phthalocyanine, hydroxygallium phthalocyanine, and oxytitanium phthalocyanine, which exhibit light absorption in a long wavelength region, are particularly preferable. These charge generating substances may be used alone or as a mixture of two or more kinds to obtain an appropriate photosensitivity wavelength and sensitizing action.

The binder resin that can be used to form the photosensitive layer 4 includes polycarbonate resin, styrene resin, acrylic resin, styrene-acryl resin, ethylene-vinyl acetate resin, polypropylene resin, vinyl chloride resin, and chlorinated poly- mer. Ether, vinyl chloride-vinyl acetate resin, polyester resin, nylon resin, vinyl acetate resin, furan resin, nitrile resin, alkyd resin, polyacetal resin, polymethylpentene resin, polyamide resin, polyurethane resin, epoxy resin, polyarylate resin, diallylate Resin, polysulfone resin, polyether sulfone resin, polyallyl sulfone resin, silicone resin, ketone resin, polyvinyl butyral resin,
Polyether resin, phenol resin, EVA (ethylene / vinyl acetate / copolymer) resin, ACS (acrylonitrile / chlorinated polyethylene / styrene) resin, ABS
(Acrylonitrile-butadiene-styrene) resin and photo-curable resin such as epoxy arylate. These may be used alone or a copolymer may be used, or two or more of them may be used in combination.

It is preferable to use a mixture of resins having different molecular weights because hardness and abrasion resistance can be improved. The binder resin can be applied to both the charge generation layer 2 and the charge transfer layer 3 in the function separation type photoreceptor shown in FIG.

Examples of the solvent used for the coating liquid include alcohols such as methanol, ethanol, 1-propanol, 2-propanol and butanol, and saturated aliphatic hydrocarbons such as pentane, hexane, heptane, octane, cyclohexane and cycloheptane. , Aromatic hydrocarbons such as toluene, xylene, chlorinated hydrocarbons such as dichloromethane, dichloroethane, chloroform, chlorobenzene, dimethyl ether, diethyl ether, tetrahydrofuran (THF), ethers such as methoxyethanol, acetone, methyl ethyl ketone, methyl isobutyl ketone,
Examples include ketones such as cyclohexanone, esters such as ethyl formate, propyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate and methyl propionate, N, N-dimethylformamide, dimethyl sulfoxide and the like.
These may be used alone or as a mixture of two or more solvents.

The electrophotographic photosensitive member of the present invention has a photosensitive layer 4
It contains a compound represented by the general formula (1) as a charge transfer material. This compound is preferable because it has a high electron mobility and a low coloring property and can be dispersed at a high concentration in the photosensitive layer. Further, a compound represented by the general formula (2) is preferably higher in electron mobility, and is preferably a compound represented by the chemical formulas (3) and (14) to (23).
It is particularly preferable because of good compatibility with the resin.

Further, other charge transfer materials can be added to the electrophotographic photosensitive member of the present invention. In that case, the sensitivity can be increased or the residual potential can be reduced, so that the characteristics of the electrophotographic photoreceptor of the present invention can be improved.

Examples of charge transfer materials that can be added to improve such properties include polyvinyl carbazole, halogenated polyvinyl carbazole, polyvinyl pyrene, polyvinyl indoloquinoxaline, polyvinyl benzothiophene, polyvinyl anthracene, polyvinyl acridine, polyvinyl pyrazoline, and polyacetylene. , Polythiophene, polypyrrole, polyphenylene, polyphenylenevinylene, polyisothianaphthene, polyaniline, polydiacetylene, polyheptadiene, polypyridinediyl, polyquinoline, polyphenylene sulfide, polyferrosenylene, polyperinaphthylene, polyphthalocyanine, etc. Molecular compounds can be used.
Further, as low molecular weight compounds, trinitrofluorenone, tetracyanoethylene, tetracyanoquinodimethane, quinone, diphenoquinone, naphthoquinone, anthraquinone and derivatives thereof, anthracene, pyrene, polycyclic aromatic compounds such as phenanthrene, indole, carbazole , Imidazole, nitrogen-containing heterocyclic compounds such as fluorenone, fluorene, oxadiazole, oxazole,
Pyrazoline, hydrazone, triphenylmethane, triphenylamine, enamine, stilbene, butadiene compounds and the like can be used.

A polymer solid electrolyte in which a polymer compound such as polyethylene oxide, polypropylene oxide, polyacrylonitrile, and polymethacrylic acid is doped with a metal ion such as Li ion can also be used.

Further, an organic charge transfer complex formed of an electron-donating compound represented by tetrathiafulvalene-tetracyanoquinodimethane and an electron-accepting compound can also be used. However, desired photoconductor characteristics can be obtained even when two or more compounds are mixed and added.

The coating liquid for producing the photoreceptor of the present invention contains a coating solution which does not impair the characteristics of the electrophotographic photoreceptor.
Antioxidants, ultraviolet absorbers, radical scavengers, softeners,
By adding a curing agent, a crosslinking agent, etc., the characteristics, durability,
The mechanical properties can be improved.

Further, by adding a dispersion stabilizer, an anti-settling agent, an anti-segregation agent, a leveling agent, an antifoaming agent, a thickener, a matting agent, etc., the finished appearance of the photoreceptor and the life of the coating solution can be improved. Can be improved.

In addition, an epoxy resin,
An organic thin film such as a melamine resin, a polyvinyl formal resin, a polycarbonate resin, a fluorine resin, a polyurethane resin, and a silicon resin, and a thin film composed of a siloxane structure formed by a hydrolyzate of a silane coupling agent are formed into a surface protective layer. May be provided. In that case, the durability of the photoconductor is improved, which is preferable. This surface protective layer may be provided to improve functions other than the enhancement of durability.

Description of Organic Electroluminescent Element The organic electroluminescent element of the present invention is an organic electroluminescent element having a layer containing at least a luminous body between a pair of electrodes. It is characterized by containing the compound represented by (1).

The organic electroluminescence device is a device in which a single-layer or multilayer organic thin film is formed between electrodes. In the case of a single layer type, a light emitting layer is provided between an anode and a cathode. The light-emitting layer contains a light-emitting material and may further contain a hole-transfer material or an electron-transfer material for transferring holes injected from an anode or electrons transferred from a cathode to the light-emitting material. In some cases, the light-emitting material has hole mobility or electron mobility. The multilayer type includes an organic electroluminescence element in which a light emitting layer, an electron transfer layer, and a hole transfer layer are stacked between electrodes. The order of lamination of each layer is appropriately changed according to the purpose.

Examples of the luminescent material include anthracene, naphthalene, phenanthrene, pyrene, tetracene, coronene, chrysene, fluorescein, perylene, phthaloperylene, naphthaloperylene, perinone, phthaloperinone,
Naphthaloperinone, diphenylbutadiene, tetraphenylbutadiene, coumarin, oxadiazole, aldazine, bisbenzoxazoline, bisstyryl, pyrazine, cyclopentadiene, quinoline metal complex, aminoquinoline metal complex, benzoquinoline metal complex, imine, diphenylethylene, vinyl anthracene , Diaminocarbazole, triphenylamine, benzidine triphenylamine, styrylamine triphenylamine, diamine triphenylamine pyran, thiopyran, polymethine, merocyanine, imidazole chelated oxinoid compound, porphyrin metal complex, phthalocyanine complex, rare earth metal complex Quinacridone, rubrene, and fluorescent dyes for dye lasers and whitening.

As the hole transfer material, phthalocyanine derivatives, naphthalocyanine derivatives, porphyrin derivatives,
Oxazole, oxadiazole, triazole, imidazole, imidazolone, imidazolethione, pyrazoline, pyrazolone, tetrahydroimidazole, oxazole, oxadiazole, hydrazone, acylhydrazone, polyarylalkane, stilbene, butadiene, amine, diamine, triphenylamine, indole , Carbazole, triphenylmethane, enamine and the like, and derivatives thereof, and polyvinyl carbazole,
Polymer materials such as polysilane and conductive polymers can be used.

As the electron transfer material, in addition to the isoxazolylidene compound of the present invention, quinolinol complex, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetralide There are carboxylic acids, fluorenylidenemethane, anthraquinodimethane, anthrone and the like and derivatives thereof.

The conductive material used for the anode includes carbon, aluminum, brass, stainless steel, chromium, titanium, copper, tin, molybdenum, indium, vanadium,
Iron, cobalt, nickel, tungsten, silver, gold, platinum, palladium, etc. and their alloys, ITO substrate, N
Metal oxides such as tin oxide, indium oxide, aluminum iodide, and copper iodide used for the ESA substrate, and organic conductive resins such as polythiophene and polypyrrole are used.

Examples of the conductive material used for the cathode include magnesium, calcium, tin, lead, titanium, yttrium, lithium, ruthenium, manganese, aluminum and the like, and alloys thereof, but are not limited thereto. Absent. The alloy is magnesium /
Typical examples include silver, magnesium / indium, and lithium / aluminum, but are not limited thereto.

The ratio of the alloy is controlled by the temperature, atmosphere, degree of vacuum, etc. of the evaporation source, and is selected to an appropriate ratio. The anode and the cathode may be formed by two or more layers if necessary.

[0162]

EXAMPLES Hereinafter, production examples of the compound according to the present invention, examples of the electron transfer agent, and application examples of the electrophotographic photosensitive member and the organic electroluminescence device as application examples will be described in detail. First, an example of a method for producing the compound represented by the general formula (1) will be described.

<Production Example 1> 2.2 g of 2,6-di-tert-butylbenzoquinone as a benzoquinone compound and 1.6 g of 3-phenyl-5-isoxazolone as an isoxazolone compound were suspended in 25 ml of chloroform. To this, triethylamine (NE) was used as a base catalyst.
t ₃ ) 0.1 g was added and refluxed for 14 hours. After cooling, the reaction solution was washed with water, and the organic layer was concentrated under reduced pressure. The precipitate was separated by column chromatography (silica gel: developing solvent hexane / toluene = 20/1) to obtain 1.7 g of orange crystals. The yield was 47%. This reaction is shown in the following chemical reaction formula (11).

[0164]

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From the measured values shown in Table 9 below, the obtained substance was determined to be 2,6-di-tert-butyl-4- (3-phenyl-
5-oxo-4-isoxazolylidene) -2,5-cyclohexadien-1-one.

[0166]

[Table 9]

The compound represented by the chemical formula (3)
The R spectrum, MS spectrum, and ¹ H-NMR spectrum are shown in FIGS. 3, 4, and 5, respectively.

<Production Example 2> In the same experiment as in Production Example 1, triethylamine as a base catalyst was replaced with 1,8-diazabicyclo [5.4.0] undec-7-ene (DB).
An experiment was conducted in the same manner as in Example 1 except that U) was used, and the target substance was obtained in a yield of 38%.

<Production Example 3> An experiment was carried out in the same manner as in Production Example 1 except that triethylamine as a base catalyst was changed to pyridine, to obtain the target substance in a yield of 42%. .

<Production Example 4> An experiment was carried out in the same manner as in Production Example 1 except that triethylamine as a base catalyst was replaced with 2,6-dimethylpyridine, and the target substance was obtained in a yield. Obtained at 45%.

<Production Example 6> An experiment was carried out in the same manner as in Production Example 1, except that chloroform as an inert solvent was replaced with toluene and triethylamine as a base catalyst was replaced with sodium hydroxide. Was carried out to obtain a target substance in a yield of 35%.

<Comparative Production Example> An experiment was conducted in the same manner as in Production Example 1 except that triethylamine as a base catalyst was not used. Did not.

Next, examples of the electron mobility measurement of the electron transfer agent according to the present invention will be described together with comparative examples.

<Example 1> 5 g of oxytitanium phthalocyanine was dry-pulverized together with 50 ml of glass beads by a paint shaker for 100 hours. Next, 50 ml of n-propanol and 5 g of polyvinyl butyral are added, and wet milling is performed for 1 hour. Further, 100 ml of methyl ethyl ketone is added as a solvent and dispersed for 10 hours. The obtained dispersion was applied on a PET film with aluminum by using a bar coater and dried to form a charge generation layer having a thickness of 0.5 μm. Next, a coating liquid consisting of 8 parts by weight of the compound represented by the above formula (3), 10 parts by weight of polycarbonate and 100 parts by weight of tetrahydrofuran (THF) was prepared, applied with a bar coater, dried at 80 ° C. for 1 hour, and dried. 10μ
m of charge transfer layers were formed.

On the charge transfer layer, 0.00 of gold was used as a counter electrode.
The film was vapor-deposited at 4 μm (400 Å), an electric field was applied to the film, and the film was irradiated with laser pulse light to measure the electron mobility.

Comparative Example 1 In the same thin film as in Example 1, the compound represented by the chemical formula (3) was replaced with the compound represented by the chemical formula (1)
A thin film was prepared and measured in the same manner as in Example 1 except that the compound represented by (0) was used.

(Measurement result) Electric field 3.0 × 10 ⁵ V / cm
In the first embodiment, the electron mobility of 5 × 10 ^{- 8} cm
² / Vsec, which is 1 × 10 ⁻⁹ cm ² /
It was confirmed that the electron mobility was faster than Vsec.

Hereinafter, application examples of the present invention will be described together with comparative examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof.

Preparation Example of Organic Electroluminescent Element <Application Example 1> The compound represented by the above-mentioned chemical formula (3) was vacuum-deposited on a washed glass plate with an ITO electrode.
A phosphor layer having a thickness of 0.07 μm was obtained. Further on that,
An alloy in which magnesium and silver were mixed at a ratio of 10: 1 was deposited to form an electrode having a thickness of 0.2 μm, thereby obtaining an organic electroluminescent device 21 shown in FIG. Symbol 2 in FIG.
Reference numerals 3, 24, 25, and 26 denote a glass plate, an ITO electrode, a luminous body layer, and an electrode, respectively. This element has a DC voltage of 5 V
With this, light emission of about 100 cd / m ² was obtained.

Example of Preparation of Electrophotographic Photoreceptor for Copying Machine <Application Example 2> The following chemical formula (1)
2),

[0181]

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1 part by weight of the disazo pigment and 10 parts by weight of polycarbonate as a binder resin were kneaded and dispersed in a sand mill for 10 hours using 80 parts by weight of THF as a solvent. Further, as a charge transfer material, the following chemical formula (13) was used.

[0183]

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A coating liquid was prepared by dissolving 9 parts by weight of the triphenyldiamine compound shown in the following and 2 parts by weight of the compound shown in the formula (3). Then, using this coating solution, the conductive support 1
And then dried at 80 ° C. for 1 hour to form a 20 μm-thick photosensitive layer 4 having both charge generation and charge transfer, thereby producing a single-layer electrophotographic photosensitive member.

(Comparative Example 2) An electrophotographic photoreceptor similar to that of Application Example 2 was used, except that the compound represented by the formula (3) was replaced by the compound represented by the chemical formula (10).
In the same manner as in the above, a single-layer type electrophotographic photoreceptor was produced.

Preparation Example of Electrophotographic Photoreceptor for Printer <Application Example 3> 5 g of oxytitanium phthalocyanine
In a paint shaker with 50 ml of glass beads
Dry grinding for 00 hours. Next, n-propanol 50m
and 5 g of polyvinyl butyral, and wet milling for 1 hour. Furthermore, methyl ethyl ketone 10
Add 0 ml and disperse for 10 hours. The obtained dispersion was dip-coated on an aluminum drum as the conductive support 1 and dried to form a charge generation layer 2 having a thickness of 0.2 μm.

Next, a coating liquid comprising 8 parts by weight of the compound represented by the above-mentioned chemical formula (3), 10 parts by weight of polycarbonate and 100 parts by weight of tetrahydrofuran (THF) was prepared, and the charge generation layer 2 was formed on this coating liquid. The resulting drum was dip coated and dried at 80 ° C. for 1 hour to form a charge transfer layer 3 having a thickness of 20 μm, thereby producing a laminated electrophotographic photosensitive member.

(Comparative Example 3) An electrophotographic photoreceptor similar to that of Application Example 3 was prepared, except that the compound represented by the chemical formula (3) was replaced with the compound represented by the formula (10).
In the same manner as in the above, a laminated electrophotographic photoreceptor was prepared.

<Application Example 4> 1 part by weight of oxytitanium phthalocyanine as a charge generating substance and 10 parts by weight of polycarbonate as a binder resin were kneaded and dispersed in a sand mill for 10 hours using 80 parts by weight of THF as a solvent. 9) and 2 parts by weight of the compound represented by the chemical formula (3) were dissolved to prepare a coating solution. Then, using this coating solution, dip coating is performed on an aluminum drum as the conductive support 1, and dried at 80 ° C. for 1 hour to form a photosensitive layer 4 having both a charge generation and a charge transfer of 20 μm in thickness. Then, a single-layer type electrophotographic photoreceptor was manufactured.

Comparative Example 4 An electrophotographic photosensitive member similar to that of Application Example 4 was prepared in the same manner as in Example 4 except that the compound represented by the chemical formula (3) was replaced by the compound represented by the chemical formula (10). Similarly, a single-layer type electrophotographic photosensitive member was prepared.

(Measurement conditions) The corona discharger was set so that the corona discharge current was 17 μA,
4. The electrophotographic photosensitive members produced in Comparative Examples 2 to 4 were positively charged by corona discharge in a dark place, and the charged potential was measured. Then, exposure is performed with white light, and the exposure amount E / 50 at which the surface potential of each electrophotographic photosensitive member is reduced by half from 700 V to 350 V
(Lux × sec) was measured. The half-exposure amount is a value indicating the sensitivity of the electrophotographic photosensitive member.

(Measurement Results) The measurement results of the applied example 2 and the comparative example 2 are as shown in Table 10.

[0193]

[Table 10]

The results of the application example 2 and the comparative example 2 are obtained with a single-layer dispersion type photosensitive member for a positive charge copying machine. Comparing the application example and the comparative example, it is understood that the use of the electron transfer material of the chemical formula (3) can provide a photosensitive member having higher sensitivity than the electron transfer material of the chemical formula (10). In addition, by using the electron transfer material of the chemical formula (3), the chargeability is improved.

Table 11 below shows the measurement results of Application Example 3 and Comparative Example 3.

[0196]

[Table 11]

Application Example 3 and Comparative Example 3 show the results for the laminated photoreceptor for a positively charged printer. Comparing the application example and the comparative example, it is understood that the use of the electron transfer material of the chemical formula (3) can provide a photosensitive member having higher sensitivity than the electron transfer material of the chemical formula (10).

Table 12 below shows the measurement results of Application Example 4 and Comparative Example 4.

[0199]

[Table 12]

Application Example 4 and Comparative Example 4 show the results for the single-layered photoreceptor for a positively charged printer. Comparing the application example and the comparative example, it is understood that the use of the electron transfer material of the chemical formula (3) can provide a photosensitive member having higher sensitivity than the electron transfer material of the chemical formula (10).

Hereinafter, other examples of the compound represented by formula (1) will be described together with examples. <Production Example 7> 2,5-Di-t which is a benzoquinone compound
1.10 g of tert-butylbenzoquinone and 0.81 g of 3-phenyl-5-isoxazolone as an isoxazolone compound were dissolved in 25 ml of pyridine as a base catalyst, and reacted at 100 ° C. for 30 minutes. After cooling, the reaction solution was concentrated under reduced pressure. The precipitate is subjected to column chromatography (silica gel: developing solvent: hexane / ethyl acetate = 30).
/ 1) to obtain 0.70 g of brown crystals. The yield was 38%. This reaction is represented by the following chemical reaction formula (24)
Shown in

[0202]

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From the measured values shown in Table 13 below, the obtained substance was determined to be 2,5-di-tert-butyl-4- (3-phenyl-5-oxo-4-isoxazolylidene) -2,5-
It was identified as cyclohexadien-1-one.

[0204]

[Table 13]

The isoxazolylidene compound represented by the chemical formula (14) (2,5-di-tert-butyl-
FIG. 7 shows an IR spectrum, an MS spectrum, and a ¹ H-NMR spectrum of 4- (3-phenyl-5-oxo-4-isoxazolylidene) -2,5-cyclohexadien-1-one). , FIG. 8 and FIG.

<Production Example 8> 1.10 g of the same benzoquinone compound as used in Production Example 7 and 3- (4-tert-butylphenyl) -5-, which is an isoxazolone compound,
1.09 g of isoxazolone was dissolved in 12.5 ml of pyridine as a base catalyst, and reacted at 100 ° C. for 2 hours. After cooling, the reaction solution was concentrated under reduced pressure. Preparation Example 7
Separation by column chromatography under the same conditions as
0.51 g of pale yellow crystals were obtained. The yield was 24%.
This reaction is shown in the following chemical reaction formula (25).

[0207]

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From the measured values shown in Table 14 below, the obtained substance was analyzed from 2,5-di-tert-butyl-4- [3- (4-t
tert-butylphenyl) -5-oxo-4-isoxazolylidene] -2,5-cyclohexadien-1-one.

[0209]

[Table 14]

The isoxazolylidene compound represented by the chemical formula (15) (2,5-di-tert-butyl-
IR spectrum diagram, MS spectrum diagram, ¹ H-NMR of 4- [3- (4-tert-butylphenyl) -5-oxo-4-isoxazolylidene] -2,5-cyclohexadien-1-one) The spectra are shown in FIG.
0, FIG. 11, and FIG.

<Production Example 9> 0.75 g of 2,3,6-trimethylbenzoquinone, which is a benzoquinone compound, and the same isoxazolone compound 1.0 as used in Production Example 8
9 g was dissolved in 13 ml of chloroform, and 0.50 g of triethylamine (NEt ₃ ) was added thereto as a base catalyst, and the mixture was refluxed for 3 hours. After cooling, the reaction solution was concentrated under reduced pressure. The precipitate was separated by column chromatography under the same conditions as in Production Example 7 to obtain 0.21 g of yellow crystals. The yield was 12%. This reaction is represented by the following chemical reaction formula (2)
It is shown in 6).

[0212]

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From the measured values shown in Table 15 below, the obtained substance was analyzed by 2,3,6-trimethyl-4- [3- (4-tert)
-Butylphenyl) -5-oxo-4-isoxazolylidene] -2,5-cyclohexadien-1-one.

[0214]

[Table 15]

The isoxazolylidene compound represented by the chemical formula (16) (2,3,6-trimethyl-4-
IR spectrum, MS spectrum and ¹ H-NMR spectrum of [3- (4-tert-butylphenyl) -5-oxo-4-isoxazolylidene] -2,5-cyclohexadien-1-one) In FIG. 13, respectively.
FIG. 14 and FIG.

<Production Example 10> 1.10 g of the same benzoquinone compound as used in Production Example 1 and 0.61 g of 1,4-bis-3- (5-oxo-4-isoxazolyl) benzene, which is an isoxazolone compound, Was dissolved in 5 ml of pyridine as a base catalyst, and reacted at 60 to 70 ° C. for 3 hours. After cooling, the reaction solution was filtered, and the obtained crystals were washed with methanol to give tan crystals (0.65 g). Yield 40
%Met.

This reaction is shown in the following chemical reaction formula (27).

[0218]

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From the measured values shown in Table 16 below, the obtained substance was analyzed by 1,4-bis-3- (2,6-di-tert-butyl-1-oxo-2,5-cyclohexadiene-4-ylidene). -5-oxo-4-isoxazolylbenzene.

[0220]

[Table 16]

The isoxazolylidene compound represented by the chemical formula (17) (1,4-bis-3- (2,6-di-tert-butyl-1-oxo-2,5-cyclohexadiene-4) -Ylidene) -5-oxo-4-isoxazolylbenzene), its IR spectrum, MS spectrum and ¹ H-NMR spectrum are shown in FIG.
FIG. 17 and FIG.

<Production Example 11> Ethyl acetoacetate 1
After dissolving 3.01 g in a mixture of 33 ml of water and 16.5 ml of toluene, the mixture was cooled to 5 ° C. 4.3 ml of 33% by weight aqueous sodium hydroxide solution was added thereto, and 14.66 g of thenoyl chloride and 18 ml of 33% by weight sodium hydroxide were simultaneously added dropwise over 2 hours while maintaining the temperature at 10 ° C. or lower. Thereafter, the temperature was increased to 35 ° C., and the mixture was stirred for 1 hour. Then, the organic phase was separated, and 5.35 g of ammonium chloride was added to the organic phase, followed by stirring overnight. This was extracted with chloroform, and this extract was separated by column chromatography to obtain 11.7 g of ethylthenoyl acetate in the form of oil. The yield was 59%.

Next, 9.91 ethyl thenoyl acetate
g of ethanol was dissolved in 20 ml of ethanol, and a solution of 3.37 g of hydroxylamine hydrochloride and 4.97 g of sodium acetate in 12 ml of water was added thereto, followed by refluxing for 2 hours. Then, the isoxazolone compound (3
-(2-thienyl) -5-isoxazolone) was filtered. The yield was 6.05 g, and the yield was 72%.

Finally, 1.10 g of the same benzoquinone compound as used in Preparation Example 1 and 0.84 g of the isoxazolone compound obtained in the above step were dissolved in 3.3 ml of pyridine as a base catalyst to prepare The reaction was carried out under the same conditions as in Example 10. After cooling, the reaction solution was concentrated under reduced pressure. The precipitate was separated by column chromatography (silica gel: developing solvent hexane / chloroform = 1/1), and the obtained crystals were recrystallized from ethanol to obtain 1.24 g of orange crystals. The yield was 67%. This reaction is shown in the following chemical reaction formula (28).

[0225]

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From the measured values shown in Table 17 below, the obtained substance was analyzed from 2,6-di-tert-butyl-4- [3- (2-thienyl) -5-oxo-4-isoxazolylidene]-
It was identified as 2,5-cyclohexadien-1-one.

[0227]

[Table 17]

The isoxazolylidene compound represented by the chemical formula (18) (2,6-di-tert-butyl-
4- [3- (2-thienyl) -5-oxo-4-isoxazolylidene] -2,5-cyclohexadiene-1-
ON) IR spectrum, MS spectrum, ¹ H-
The NMR spectra are shown in FIGS. 19, 20, and 2, respectively.
Indicated by 1.

<Production Example 12> The reaction was carried out under the same conditions as in Production Example 11 except that chlorothenoyl chloride was used in place of thethenoyl chloride used in Production Example 11, to obtain 17.19 g of oily ethyl chlorothenoyl acetate. 74% yield
Met.

Further, it was changed to ethyl thenoyl acetate,
Using ethyl chlorothenoyl acetate obtained in the above step, a reaction was carried out under the same conditions as in Production Example 11 to obtain Production Example 11.
3- (5-chloro-2-thienyl) which is a different kind of isoxazolone compound from
8.0 g of -5-isoxazolone was obtained. 65% yield
Met.

Using 1.10 g of the same benzoquinone compound as used in Production Example 11 and 1.01 g of the isoxazolone compound obtained in the above step, an experiment was conducted under the same conditions as in Production Example 11 to obtain brown crystals. 11 g were obtained. The yield is 55
%Met. This reaction is shown in the following chemical reaction formula (29).

[0232]

Embedded image

From the measured values shown in Table 18 below, the obtained substance was analyzed by 2,6-di-tert-butyl-4- [3- (5-chloro-2-thienyl) -5-oxo-4-isoxazolyl. Ridene] -2,5-cyclohexadien-1-one.

[0234]

[Table 18]

The isoxazolylidene compound represented by the chemical formula (19) (2,6-di-tert-butyl-
IR spectrum, MS spectrum, and ¹ H- of 4- [3- (5-chloro-2-thienyl) -5-oxo-4-isoxazolylidene] -2,5-cyclohexadien-1-one) The NMR spectra are shown in FIG.
This is shown in FIGS.

<Production Example 13> The reaction was carried out under the same conditions as in Production Example 11 except that the thenoyl chloride used in Production Example 11 was changed to bromothenoyl chloride, to obtain 21.12 g of oily ethyl bromothenoyl acetate. 76% yield
Met.

Further, it was changed to ethyl thenoyl acetate,
Using the ethyl bromothenoyl acetate obtained in the above step, a reaction was carried out under the same conditions as in Production Example 11 to obtain Production Example 11.
3- (5-bromo-2-thienyl), which is a different type of isoxazolone compound from
8.19 g of -5-isoxazolone was obtained. The yield is 67
%Met.

Next, using 1.10 g of the same benzoquinone compound as used in Production Example 11 and 1.23 g of the isoxazolone compound obtained in the above step, an experiment was conducted under the same conditions as in Production Example 11, and brown crystals were obtained. 0.88 g was obtained. The yield was 39%.

This reaction is shown in the following chemical reaction formula (30).

[0240]

Embedded image

From the measured values shown in Table 19 below, the obtained substance was analyzed by 2,6-di-tert-butyl-4- [3- (5-bromo-2-thienyl) -5-oxo-4-isoxazolyl. Ridene] -2,5-cyclohexadien-1-one.

[0242]

[Table 19]

The isoxazolylidene compound represented by the chemical formula (20) (2,6-di-tert-butyl-
IR spectrum, MS spectrum, and ¹ H- of 4- [3- (5-bromo-2-thienyl) -5-oxo-4-isoxazolylidene] -2,5-cyclohexadien-1-one) NMR spectra are shown in FIG.
This is shown in FIGS. 26 and 27.

<Production Example 14> The tenoyl chloride used in Production Example 11 was changed to furanyl chloride to produce Production Example 11.
The reaction was carried out under the same conditions as described above to obtain 8.74 g of oily ethylfuranyl acetate. The yield was 48%.

Further, it was changed to ethyl thenoyl acetate,
Using the ethylfuranyl acetate obtained in the above step, a reaction was carried out under the same conditions as in Production Example 11, and a different type of isoxazolone compound from the isoxazolone compound of Production Example 11, 3- (2-furanyl) -5. 3.78 g of isoxazolone were obtained. The yield was 50%.

Next, using 1.10 g of the same benzoquinone compound as used in Production Example 11 and 0.76 g of the isoxazolone compound obtained in the above step, an experiment was conducted under the same conditions as in Production Example 11, and brown crystals were obtained. 1.0 g was obtained. The yield was 56.6%. This reaction is represented by the following chemical reaction formula (3)
Shown in 1).

[0247]

Embedded image

From the measured values shown in Table 20 below, the obtained substance was analyzed by 2,6-di-tert-butyl-4- [3- (2-furanyl) -5-oxo-4-isoxazolylidene]-
It was identified as 2,5-cyclohexadien-1-one.

[0249]

[Table 20]

The isoxazolylidene compound represented by the chemical formula (21) (2,6-di-tert-butyl-
4- [3- (2-furanyl) -5-oxo-4-isoxazolylidene] -2,5-cyclohexadiene-1-
ON) IR spectrum, MS spectrum, ¹ H-
The NMR spectra are shown in FIGS. 28, 29, and 3, respectively.
Indicated by 0.

<Production Example 15> The reaction was carried out under the same conditions as in Production Example 11 except that bromofuranyl chloride was used in place of thenoyl chloride used in Production Example 11 to obtain 19.32 g of oily ethyl bromofuranyl acetate. 74% yield
Met.

Further, it was changed to ethyl thenoyl acetate,
Using ethyl bromofuranyl acetate obtained in the above step, a reaction was carried out under the same conditions as in Production Example 11 to obtain Production Example 11.
3- (5-bromo-2-furanyl), which is a different type of isoxazolone compound from
8.97 g of -5-isoxazolone was obtained. Yield 78
%Met.

Next, using 1.10 g of the same benzoquinone compound as used in Production Example 11 and 1.15 g of the isoxazolone compound obtained in the above step, an experiment was carried out under the same conditions as in Production Example 11, and red-brown crystals were obtained. 0.56 g was obtained.
The yield was 26%. This reaction is represented by the following chemical reaction formula (3)
See 2).

[0254]

Embedded image

From the measured values shown in Table 21 below, the obtained substance was analyzed by 2,6-di-tert-butyl-4- [3- (5-bromo-2-furanyl) -5-oxo-4-isoxazolyl. Ridene] -2,5-cyclohexadien-1-one.

[0256]

[Table 21]

The isoxazolylidene compound represented by the chemical formula (22) (2,6-di-tert-butyl-
IR spectrum of 4- [3- (5-bromo-2-furanyl) -5-oxo-4-isoxazolylidene] -2,5-cyclohexadien-1-one), ¹ H-NMR
The spectrum diagrams are shown in FIGS. 31 and 32, respectively.

<Production Example 16> 1.10 g of the same benzoquinone compound as used in Production Example 1 and 0.61 g of 1,3-bis-3- (5-oxo-4-isoxazolyl) benzene which is an isoxazolone compound Was dissolved in 5 ml of pyridine as a base catalyst, and reacted under the same conditions as in Production Example 10. After cooling, the reaction solution was concentrated under reduced pressure. The precipitate was separated by column chromatography under the same conditions as in Production Example 11 to obtain 1.23 g of orange crystals. The yield was 77%. This reaction is shown in the following chemical reaction formula (33).

[0259]

Embedded image

From the measured values shown in Table 22 below, the obtained substance was analyzed from 1,3-bis-3- (2,6-di-tert-butyl-1-oxo-2,5-cyclohexadiene-4-ylidene). -5-oxo-4-isoxazolylbenzene.

[0261]

[Table 22]

The isoxazolylidene compound represented by the chemical formula (23) (1,3-bis-3- (2,6-di-tert-butyl-1-oxo-2,5-cyclohexadiene-4) -Ilidene) -5-oxo-4-isoxazolylbenzene) IR spectrum, ¹ H-NMR
The spectrum diagrams are shown in FIGS. 33 and 34, respectively.

Next, examples of the electron mobility measurement of the electron transfer agent of the present invention will be described together with comparative examples. <Examples 2 to 11> In the same thin film as in Example 1, the compound represented by the formula (3) was replaced with a compound represented by the chemical formula (14).
Thin films of Examples 2 to 11 were prepared under the same conditions as in Example 1 except that the compounds represented by formulas (1) to (23) were used, and the thin films of Examples 2 to 11 were used under the same conditions as in Example 1. The electron mobility was measured.

(Measurement Results) Electric Field of Examples 2 to 11 3.0
The measurement result at × 10 ⁵ V / cm was obtained in Example 1,
The results are shown in Table 23 below together with the measurement results of the electric field of Comparative Example 1 at an electric field of 3.0 × 10 ⁵ V / cm.

[0265]

[Table 23]

[0266] It was confirmed that the electron mobility of the above example was one order of magnitude higher than that of the comparative example. Equations (18) to (18)
Examples 6 to 10 using each compound represented by (23) as an electron transfer agent respectively correspond to formulas (3) and (14) to (1).
The electron mobility was faster than Examples 1 to 5 and 11 in which the compounds represented by 7) and (23) were used as electron transfer agents, respectively.

Formulas (3), (14)-(17), (23)
Is a compound having a phenyl group bonded as a substituent to the isoxazolone ring in the structure.
The compounds shown in 8) to (22) have a substituent (heterocyclic group) having a hetero atom such as a thienyl group or a furyl group bonded to the isoxazolone ring in the structure. From these results, It has been found that a compound in which a substituent having a hetero atom than a phenyl group is bonded to an isoxazolone ring has a higher electron mobility.

Hereinafter, application examples of the present invention will be described together with comparative examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof. Example of making an organic electroluminescent device

<Applied Embodiments 5 to 14> Applied Embodiment 1
In place of the isoxazolylidene compound represented by the formula (3) used in the above, ten kinds of isoxazolylidene compounds represented by the formulas (14) to (23) were used in the same process as in the application example 1 using the isoxazolylidene compounds represented by the formulas (14) to (23). Light-emitting layers were formed, and the organic EL devices of Application Examples 5 to 14 were obtained in the same steps as in Application Example 1 by using the light-emitting layers.

The measurement results of the luminance of the devices of Application Examples 5 to 14 at a DC voltage of 5 V together with the measurement results of the luminance of the device of Application Example 1 at a DC voltage of 5 V are shown in Table 24 below.
It describes in.

[0271]

[Table 24]

Examples of Preparation of Electrophotographic Photoreceptor for Copying Machine <Application Examples 15 to 24> In place of the compound represented by the above formula (3), compounds represented by the above formulas (14) to (23) were used, respectively. Except for the above, the single-layer electrophotographic photosensitive members of Application Examples 15 to 24 were manufactured under the same conditions as in Application Example 2.

<Application Examples 25 to 35> In the same electrophotographic photoreceptor as in Application Examples 2 and 15 to 24, 9 parts by weight of the triphenyldiamine compound represented by the formula (13) was added to 2 parts by weight. Application Examples 2 and 15 were applied under the same conditions as in Application Examples 2 and 15 to 24, except that 2 parts by weight of the isoxazolylidene compounds represented by Formulas (3) and (14) to (23) were each replaced with 9 parts by weight. 25 to 35 single-layer type electrophotographic photoreceptors were produced.

(Comparative Example 5) In the same electrophotographic photoreceptor as in the above-mentioned applied examples 25 to 35, formulas (3) and (14) were used.
Single-layer electrophotographic photoreceptor of Comparative Example 5 under the same conditions as in Examples 25 to 35 except that the isoxazolylidene compounds represented by formulas (23) to (23) were replaced with the compound represented by formula (10). Was prepared.

Examples of Preparation of Electrophotographic Photoreceptor for Printer <Application Examples 36 to 45> The compounds represented by the formulas (14) to (23) were used instead of the compound represented by the formula (3). The laminated electrophotographic photoreceptors of Application Examples 36 to 45 were produced under the same conditions as in Application Example 3 except for the above.

<Application Examples 46 to 55> The same procedures as those of Application Example 4 were carried out except that the compounds represented by the formulas (14) to (23) were used instead of the compound represented by the formula (3). Under the same conditions, the single-layer type electrophotographic photosensitive members of Application Examples 46 to 55 were produced.

<Application Examples 56 to 66> In the same electrophotographic photoreceptor as in Application Example 4, 9 parts by weight of the triphenyldiamine compound represented by the formula (13) is added to 2 parts by weight, And the single-layer electrophotographic photosensitive members of Application Examples 56 to 66 in the same manner as in Application Example 4 except that 2 parts by weight of the isoxazolylidene compounds represented by the formulas (14) to (23) were changed to 9 parts by weight. Each body was made.

(Comparative Example 6) In the same electrophotographic photosensitive member as in the above-mentioned applied examples 56 to 66, formulas (3) and (14) to (14) were used.
Application Example 5 except that the isoxazolylidene compound represented by (23) is replaced with a compound represented by formula (10)
In the same manner as in Nos. 6 to 66, a single-layer type electrophotographic photosensitive member of Comparative Example 6 was produced.

(Measurement conditions) The above-mentioned applied examples 15 to 24,
With respect to the electrophotographic photoreceptors manufactured in 36 to 45 and 46 to 55, the surface potential was from 700 V to 350 V under the same conditions as those in the case where the half-exposure amounts of the applied examples 2 to 4 were measured.
Exposure amount E / 50 (lux · sec), which is reduced to half, was measured. The half-exposure amount is a value indicating the sensitivity of the electrophotographic photosensitive member.

Further, the above-mentioned application examples 25 to 35, 56 to
Regarding Comparative Example Nos. 66 and Comparative Examples 5 and 6, the electrophotographic photosensitive member was negatively charged by corona discharge at a voltage set so that the corona discharge current was 17 μA, and the charging potential was measured.
Then, exposure is performed with white light, and the exposure amount E / 50 at which the surface potential of each electrophotographic photosensitive member is reduced by half from −700 V to −350 V
(Lux · sec) was measured.

(Measurement Results) The measurement results of the half-exposure doses of the applied examples 15 to 24 are shown in Table 25 below together with the measurement results of the half-exposure doses of the applied example 2 and comparative example 2.

[0282]

[Table 25]

Application Example 2, Application Examples 15 to 24
And Comparative Example 2 show the results for a single-layer dispersion type photoconductor for a positively charged copying machine. Comparing the measurement results of the applied examples and the measurement results of the comparative example, Expressions (3) and (14) to (2)
By using the electron transfer material of 3), the electron transfer material of the formula (10) used in the prior art is approximately 2 lux.
・ Highly sensitive photoreceptor can be obtained for at least 40 sec.
It turns out that it becomes better above.

Table 26 below shows the measurement results of Application Examples 25 to 35 and Comparative Example 5.

[0285]

[Table 26]

The above-mentioned applied examples 25 to 35 and comparative example 5 show the results in the single-layer dispersion type photoreceptor for a negative charge copying machine.
Comparing the measurement results of those applied examples and the measurement results of the comparative example, the use of the electron transfer materials of formulas (3) and (14) to (23) makes it possible to obtain a better result than the electron transfer material of formula (10). It can be seen that a photosensitive member having a high sensitivity of about 2 lux · sec or more is obtained, and the chargeability is improved by 45 V or more.

Table 27 below shows the measurement results of the half-life exposure amounts of the above-mentioned applied examples 36 to 45, together with the measurement results of the half-life exposure amounts of the above-mentioned applied example 3 and comparative example 3.

[0288]

[Table 27]

Application Examples 3, 36 to 45, and Comparative Example 3 show the results for the laminated photosensitive member for a positively charged printer.
Comparing the measurement results of the application examples and the measurement results of the comparative example, the use of the electron transfer materials of the formulas (3) and (14) to (23) makes the electron transfer material of formula (10) more zero. It is understood that a photosensitive member having a high sensitivity of 0.5 lux · sec or more can be obtained.

Table 28 below shows the measurement results of the half-life exposure amounts of Application Examples 46 to 55 together with the measurement results of Application Example 4 and Comparative Example 4.

[0291]

[Table 28]

Application Examples 4, 46 to 55, and Comparative Example 4 show the results of the single-layered photosensitive member for a positively charged printer. Comparing the application example and the comparative example, equations (3) and (1)
It can be seen that by using the electron transfer materials of 4) to (23), a photosensitive member having a sensitivity higher than that of the electron transfer material of formula (10) by 0.6 lux · sec or more can be obtained.

Table 29 shows the measurement results of Application Examples 56 to 66 and Comparative Example 6.

[0294]

[Table 29]

Application Examples 56 to 66 and Comparative Example 6 show the results in the case of a single-layer dispersion photoreceptor for a negatively charged printer. When comparing the application example and the comparative example, the expressions (3) and (14) to
By using the electron transfer material of (23), the formula (10)
It can be seen that a photosensitive member having a sensitivity of 0.5 lux · sec or more higher than that of the electron transfer material described above can be obtained.

As described above, the electrophotographic photosensitive member using the organic thin film for the photosensitive layer has been described, but the present invention is not limited thereto. For example, the present invention also includes an electrophotographic photoreceptor using the organic thin film as an undercoat layer formed between a photosensitive layer and a conductive supporting substrate.

The organic thin film used for the undercoat layer is required to have appropriate conductivity. However, since the organic thin film containing the compound represented by the general formula (1) has high electron mobility, it has high sensitivity for electrophotography. A photoreceptor can be obtained. Further, the organic thin film can be used as a protective film formed on the surface of the photosensitive layer.

In short, the present invention broadly includes an electrophotographic photosensitive member on which an organic thin film containing the compound represented by the general formula (1) is formed.

[0299]

As described above, in the isoxazolylidene compound represented by the general formula (1) of the present invention, two ring structures of a quinone ring and an isoxazolone ring are connected by a double bond. Since the structure has a large molecular skeleton and a conjugated system in which four double bonds are interposed between oxygen atoms, electrons easily move in the molecule. Therefore, the electron mobility is high, the coloring property is weak, and light absorption hardly occurs. Further, it is a compound having a novel molecular skeleton having high resin compatibility due to its asymmetric molecular structure.

Further, it was possible to provide a method for easily producing an isoxazolylidene compound using a base catalyst.
By mixing the isoxazolylidene compound with the resin, an electron transfer agent having excellent properties can be obtained.

Further, in the electrophotographic photoreceptor using the isoxazolylidene compound represented by the general formula (1) of the present invention, a highly sensitive photosensitive layer can be obtained. Further, the isoxazolylidene compound has good compatibility with the binder resin, so that it can be dispersed in a large amount and uniformly in the photosensitive layer. At this time, since the coloring property is weak, the incident light reaching the charge generating substance can be reduced. An electrophotographic photosensitive member with high sensitivity can be obtained without hindrance. This electrophotographic photoreceptor can be used particularly for a positive charging system.

Further, the isoxazolylidene compound represented by the general formula (1) of the present invention can be applied also as an electron transfer material of an organic electroluminescence device. In the present invention, the molecular structure of the electron transfer agent can be designed by selecting a substituent according to the required characteristics of the functional material.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view illustrating an example of a laminated electrophotographic photosensitive member.

FIG. 2 is a cross-sectional view illustrating an example of a single-layer electrophotographic photosensitive member.

FIG. 3 is an IR spectrum of the compound represented by the chemical formula (3).

FIG. 4 is an MS spectrum of the compound represented by the chemical formula (3).

FIG. 5 ¹ H-NMR of the compound represented by the chemical formula (3)
Spectrum diagram

FIG. 6 is a cross-sectional view illustrating an example of an organic electroluminescence element.

FIG. 7 is an IR spectrum of the compound represented by the chemical formula (14).

FIG. 8 is an MS spectrum of the compound represented by the chemical formula (14).

FIG. 9 shows ¹ H-NM of a compound represented by the chemical formula (14).
R spectrum diagram

FIG. 10 is an IR spectrum of the compound represented by the chemical formula (15).

FIG. 11 is an MS spectrum of the compound represented by the chemical formula (15).

FIG. 12 shows ¹ H—N of a compound represented by the chemical formula (15).
MR spectrum diagram

FIG. 13 is an IR spectrum of the compound represented by the chemical formula (16).

FIG. 14 is an MS spectrum of the compound represented by the chemical formula (16).

FIG. 15 shows ¹ H—N of a compound represented by the chemical formula (16).
MR spectrum diagram

FIG. 16 is an IR spectrum of the compound represented by the chemical formula (17).

FIG. 17 is an MS spectrum of the compound represented by the chemical formula (17).

FIG. 18 shows ¹ H—N of a compound represented by the chemical formula (17).
MR spectrum diagram

FIG. 19 is an IR spectrum of the compound represented by the chemical formula (18).

FIG. 20 is an MS spectrum of the compound represented by the chemical formula (18).

FIG. 21 shows ¹ H—N of a compound represented by the chemical formula (18).
MR spectrum diagram

FIG. 22 is an IR spectrum of the compound represented by the chemical formula (19).

FIG. 23 is an MS spectrum of the compound represented by the chemical formula (19).

FIG. 24 shows ¹ H—N of the compound represented by the chemical formula (19).
MR spectrum diagram

FIG. 25 is an IR spectrum of the compound represented by the chemical formula (20).

FIG. 26 is an MS spectrum of the compound represented by the chemical formula (20).

FIG. 27 shows ¹ H—N of a compound represented by the chemical formula (20).
MR spectrum diagram

FIG. 28 is an IR spectrum of the compound represented by the chemical formula (21).

FIG. 29 is an MS spectrum of the compound represented by the chemical formula (21).

FIG. 30 shows ¹ H—N of a compound represented by the chemical formula (21).
MR spectrum diagram

FIG. 31 is an IR spectrum of the compound represented by the chemical formula (22).

FIG. 32 shows ¹ H—N of a compound represented by the chemical formula (22).
MR spectrum diagram

FIG. 33 is an IR spectrum of the compound represented by the chemical formula (23).

FIG. 34 shows ¹ H—N of a compound represented by the chemical formula (23).
MR spectrum diagram

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Conductive support 2 ... Charge generation layer 3 ... Charge transfer layer 4 ... Photosensitive layer 11, 12 ... Electrophotographic photoreceptor 21 ... Organic electroluminescent element 23 ... Substrate 24 ... ITO film 25 ... Luminous body layer 26... Electrode

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Yasuyuki Kiuchi 14-29 Torihama-cho, Kanazawa-ku, Yokohama-shi, Kanagawa Prefecture Inside Permachem Asia Ltd. (72) Inventor Toyozo Sato 14 Torihamacho, Kanazawa-ku, Yokohama-shi, Kanagawa No. 29 Permachem Asia Co., Ltd. (72) Inventor Mitsuyo Takano 1014 Miyahara-cho, Kofu-shi, Yamanashi Pref.

Claims (25)

[Claims] 1. An isoxazolylidene compound represented by the following general formula (1). Embedded image (Substituents R _{1 to} R ₅ represent a hydrogen atom, a cyano group, a nitro group,
Halogen atom, hydroxy group, each substituted or unsubstituted alkyl group, aryl group, heterocyclic group, ester group, alkoxy group, aralkyl group, allyl group, amide group, amino group, acyl group, alkenyl group, alkynyl group, carboxyl R ₁ and R ₂ , and R ₃ and R ₄ may be bonded to each other to form a ring. ) 2. An isoxazolylidene compound represented by the following general formula (2). Embedded image (Substituents R _{6 to} R ₈ are any one of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, and a phenyl group, provided that R ₇ is a substituent other than hydrogen. , R ₆ , R ₈
Except when is hydrogen. The substituent R ₉ is any one of a phenyl group, a thienyl group, and a furyl group. ) 3. An isoxazolylidene compound represented by the following formula (3). Embedded image 4. An isoxazolylidene compound represented by the following formula (14). Embedded image 5. An isoxazolylidene compound represented by the following formula (15). Embedded image 6. An isoxazolylidene compound represented by the following formula (16). Embedded image 7. An isoxazolylidene compound represented by the following formula (17). Embedded image 8. An isoxazolylidene compound represented by the following formula (18). Embedded image 9. An isoxazolylidene compound represented by the following formula (19). Embedded image 10. An isoxazolylidene compound represented by the following formula (20). Embedded image 11. An isoxazolylidene compound represented by the following formula (21). Embedded image 12. An isoxazolylidene compound represented by the following formula (22). Embedded image 13. An isoxazolylidene compound represented by the following formula (23). Embedded image 14. The following general formula (4): (Substituents R _{1 to} R ₄ represent a hydrogen atom, a cyano group, a nitro group,
Halogen atom, hydroxy group, each substituted or unsubstituted alkyl group, aryl group, heterocyclic group, ester group, alkoxy group, aralkyl group, allyl group, amide group, amino group, acyl group, alkenyl group, alkynyl group, carboxyl R ₁ and R ₂ , and R ₃ and R ₄ may be bonded to each other to form a ring. And a benzoquinone compound represented by the following general formula (5): (Substituent R ₅ is a hydrogen atom, a cyano group, a nitro group, a halogen atom, a hydroxy group, a substituted or unsubstituted alkyl group, an aryl group, a heterocyclic group, an ester group, an alkoxy group, an aralkyl group, an allyl group, Amide group, amino group, acyl group, alkenyl group, alkynyl group, carboxyl group, carbonyl group or carboxylic acid group). The reaction is carried out in an active solvent, and the following general formula (1): (Substituents R _{1 to} R ₅ represent a hydrogen atom, a cyano group, a nitro group,
Halogen atom, hydroxy group, each substituted or unsubstituted alkyl group, aryl group, heterocyclic group, ester group, alkoxy group, aralkyl group, allyl group, amide group, amino group, acyl group, alkenyl group, alkynyl group, carboxyl R ₁ and R ₂ , and R ₃ and R ₄ may be bonded to each other to form a ring. A method for producing a compound for producing an isoxazolylidene compound represented by the formula: 15. The following general formula (6): (Substituents R _{6 to} R ₈ are any one of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, and a phenyl group.
However, this excludes the case where R ₇ is a substituent other than hydrogen and R ₆ and R ₈ are hydrogen. ) And a benzoquinone compound represented by
The following general formula (7): (The substituent R ₉ is any one of a phenyl group, a thienyl group and a furyl group.) Is reacted with an isoxazolone compound in an inert solvent in the presence of a base catalyst to obtain a compound represented by the following general formula (2) ), Embedded image (Substituents R _{6 to} R ₈ are any one of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, and a phenyl group, provided that R ₇ is a substituent other than hydrogen. , R ₆ , R ₈
Except when is hydrogen. The substituent R ₉ is any one of a phenyl group, a thienyl group, and a furyl group. A method for producing a compound for producing an isoxazolylidene compound represented by the formula: 16. The following chemical formula (8): And a benzoquinone compound represented by the following chemical formula (9): With an isoxazolone compound of the formula (1) in an inert solvent in the presence of a base catalyst to obtain a compound represented by the following chemical formula (3): A method for producing a compound for producing an isoxazolylidene compound represented by the formula: 17. The following general formula (1): (Substituents R _{1 to} R ₅ represent a hydrogen atom, a cyano group, a nitro group,
Halogen atom, hydroxy group, each substituted or unsubstituted alkyl group, aryl group, heterocyclic group, ester group, alkoxy group, aralkyl group, allyl group, amide group, amino group, acyl group, alkenyl group, alkynyl group, carboxyl R ₁ and R ₂ , and R ₃ and R ₄ may be bonded to each other to form a ring. An electron transfer agent comprising an isoxazolylidene compound represented by the formula (1) in a resin. 18. The following general formula (2): (Substituents R _{6 to} R ₈ are any one of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, and a phenyl group, provided that R ₇ is a substituent other than hydrogen. , R ₆ , R ₈
Except when is hydrogen. The substituent R ₉ is any one of a phenyl group, a thienyl group, and a furyl group. An electron transfer agent comprising an isoxazolylidene compound represented by the formula (1) in a resin. 19. The following chemical formula (3): An electron transfer agent comprising a resin containing an isoxazolylidene compound represented by the formula: 20. An electrophotographic photosensitive member having a photosensitive layer provided on a conductive substrate, wherein the photosensitive layer has the following general formula (1): (Substituents R _{1 to} R ₅ represent a hydrogen atom, a cyano group, a nitro group,
Halogen atom, hydroxy group, each substituted or unsubstituted alkyl group, aryl group, heterocyclic group, ester group, alkoxy group, aralkyl group, allyl group, amide group, amino group, acyl group, alkenyl group, alkynyl group, carboxyl R ₁ and R ₂ , and R ₃ and R ₄ may be bonded to each other to form a ring. An electrophotographic photoreceptor containing an isoxazolylidene compound represented by the formula: 21. An electrophotographic photosensitive member having a photosensitive layer provided on a conductive substrate, wherein the photosensitive layer has the following general formula (2): (Substituents R _{6 to} R ₈ are any one of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, and a phenyl group, provided that R ₇ is a substituent other than hydrogen. , R ₆ , R ₈
Except when is hydrogen. The substituent R ₉ is any one of a phenyl group, a thienyl group, and a furyl group. An electrophotographic photoreceptor containing an isoxazolylidene compound represented by the formula: 22. An electrophotographic photosensitive member having a photosensitive layer provided on a conductive substrate, wherein said photosensitive layer has the following chemical formula (3): An electrophotographic photosensitive member containing an isoxazolylidene compound represented by the formula: 23. An organic electroluminescent device having at least an organic thin film capable of emitting light between a pair of electrodes, wherein the organic thin film has the following general formula (1): (Substituents R _{1 to} R ₅ represent a hydrogen atom, a cyano group, a nitro group,
Halogen atom, hydroxy group, each substituted or unsubstituted alkyl group, aryl group, heterocyclic group, ester group, alkoxy group, aralkyl group, allyl group, amide group, amino group, acyl group, alkenyl group, alkynyl group, carboxyl R ₁ and R ₂ , and R ₃ and R ₄ may be bonded to each other to form a ring. An organic electroluminescent device containing the isoxazolylidene compound represented by the formula (1). 24. An organic electroluminescent device having at least an organic thin film capable of emitting light between a pair of electrodes, wherein the organic thin film has the following general formula (2): (Substituents R _{6 to} R ₈ are any one of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, and a phenyl group, provided that R ₇ is a substituent other than hydrogen. , R ₆ , R ₈
Except when is hydrogen. The substituent R ₉ is any one of a phenyl group, a thienyl group, and a furyl group. An organic electroluminescent device containing the isoxazolylidene compound represented by the formula (1). 25. An organic electroluminescent device having at least an organic thin film capable of emitting light between a pair of electrodes, wherein said organic thin film has the following chemical formula (3): The organic electroluminescent element containing the isoxazolylidene compound represented by these.