JP2001117258A - Organic electronic device and image forming device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an organic electronic device containing a new electric charge transferring material which withstands deterioration such as oxidation and can tightly be held in a resin, a high durability electrophotographic photoreceptor using the electric charge transferring material and an image forming device using the photoreceptor. SOLUTION: The organic electronic device uses an electric charge transferring compound of formula I, wherein A is an electric charge transferring unit suffixl is 0 or 1, (m) is an integer of 1-4, T is a 1-10C optionally branched divalent hydrocarbon group and Q is a divalent group which may contain a hetero element.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic electronic device and an image forming apparatus containing a novel compound, and more particularly, to an electrophotographic photosensitive member and an electrophotographic apparatus using the same.

[0002]

2. Description of the Related Art In recent years, so-called organic electronic devices such as an electrophotographic photosensitive member and an organic electroluminescent element have been put to practical use and widely used. However, with the development of organic materials in regions where inorganic materials have conventionally been used due to the high performance of organic materials, the problem of the inherent mechanical strength of organic materials has also become apparent. For example, in an organic electroluminescent device, a drawback is that a low-molecular charge transporting material is melted by the generated Joule heat, and the morphology of a film is easily changed by crystallization or the like. There is a problem such as abrasion of the layer, and it is desired to increase the strength of the charge transport layer.

Hereinafter, the electrophotographic photosensitive member will be described in detail. Current organic photoreceptors, in which a charge transport layer is laminated on a charge generation layer, are commonly used as a so-called laminate type, and therefore the charge transport layer is often a surface layer,
The current mainstream low-molecule dispersion charge transport layer is getting satisfactory performance in terms of electrical properties, but because low molecules are dispersed in the binder resin and used,
The inherent mechanical performance of the binder resin is reduced, and the abrasion is essentially weak.

[0004] To improve the mechanical strength of the charge transport layer, various proposals have been made as follows. 1)
Addition of hard fine particles (for example, see JP-A-6-282093)
2) Addition of an additive such as silicone oil which reduces surface energy, 3) Modification of binder resin (for example, Idemitsu technology, 36 (2), 88 (1993), etc.),
4) Formation of an overcoat layer on the charge transporting layer (for example, JP-A-6-282092) 5) Use of a charge transporting polymer (for example, US Pat. No. 4,801,517), 6) Charge transport Curing of the layer (for example, see JP-A-6-2
No. 50423).

However, in the above methods 1) to 3), since a low molecular weight compound is basically used by dispersing it in a binder resin, no significant improvement is expected. The overcoat layer 4) can greatly reduce abrasion, but has a problem that the image is easily blurred particularly under high humidity because the conductive powder is dispersed and used. 5),
In the method 6), if a polymer having sufficient performance can be obtained, there is no need to disperse the low molecule, so that the mechanical properties can be greatly improved, and there is also an advantage that the conventional manufacturing equipment can be used as it is. is there. In particular, the method described in JP-A-6-250423 and the like is for further three-dimensionalizing the charge transporting polymer, and further effects can be expected.

On the other hand, JP-A-7-253683 discloses a hole transporting hydroxyarylamine having at least two hydroxy functional groups, a polyamide capable of forming a hydrogen bond with at least one and the hydroxy functional groups. An overcoat layer containing a film-forming binder is further added to U.S. Pat.No. 5,670,291, in which a hydroxyarylamine compound having a hydroxy functional group in a thermosetting polyamide resin and a curing catalyst are added, followed by heat curing after application. A cured film has been proposed. This is different from JP-A-6-282092,
Providing a semiconductive overcoat layer has the advantage that image blur is unlikely to occur, but the hole-transporting hydroxyarylamine compound is vulnerable to oxidation, and has the disadvantage that the image and electrical properties are likely to deteriorate, Although hydroxytriphenylmethane compounds having a hydroxy functional group can be somewhat suppressed, they have not been obtained with sufficient performance. Also, JP-A-10-177268
In Japanese Patent Application Laid-Open Publication No. H11-157, a cured film in which a hydroxyarylamine compound is crosslinked with isocyanate is proposed, but this also improves the drawback that the hole-transporting hydroxyarylamine compound is vulnerable to oxidation and easily deteriorates the image and electric characteristics. Not done.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide an organic electronic device containing a novel charge transporting material which is resistant to deterioration such as oxidation and can be firmly held in a resin. . Another object of the present invention is to provide a highly durable electrophotographic photosensitive member using the charge transport material and an image forming apparatus using the electrophotographic photosensitive member.

[0008]

Means for Solving the Problems The present inventors have conducted intensive studies in view of the above problems, and as a result, have found that a hydroxyl group-containing charge transporting compound represented by the following general formula (I) is more effective than a hole transporting hydroxyarylamine compound. Was also resistant to oxidation, and found that a cross-linking reaction with isocyanate or the like was possible. Further, this hydroxyl group-containing charge transporting compound can be dissolved in a solvent such as alcohol, which hardly dissolves the conventional charge transporting layer, and can be laminated and formed on a conventional electrophotographic photoreceptor. The present inventors have found that a film can be formed, and have completed the present invention.

[0009]

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A in the general formula (I) means a charge transporting unit. l is an integer selected from 0 or 1, m is 1
To T, and T represents a divalent hydrocarbon group having 1 to 10 carbon atoms which may be branched. Q represents a divalent group which may contain a complex element.

A in the general formula (I) represents a triarylamine compound, a benzidine compound, an arylalkane compound, an aryl-substituted ethylene compound, a stilbene compound, an anthracene compound, a hydrazone compound, a quinone compound. Fluorenone-based compounds, xanthone-based compounds, benzophenone-based compounds, cyanovinyl-based compounds, selected from materials having various electron-transporting or hole-transporting properties, such as ethylene-based compounds,
As the electron transporting material, a fluorenone derivative, an anthraquinone derivative, a thiopyran derivative, a diphenoquinone derivative, and an imide compound derivative are preferable because of their excellent electron transporting properties. As the hole transporting material, a triarylamine compound, a benzidine compound, an arylalkane compound, or a stilbene compound is preferable. In particular, those represented by the following structural formulas (II) and (III) are charged. It is excellent in transportability and stability, and is most preferable.

[0012]

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Ar in the general formulas (II) and (III)
_{1 to} Ar ₇ each independently represent a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, and X represents a divalent group. Here, specific examples of Ar _{1 to} Ar ₇ include the following structures.

[0014]

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In the above structure, R _{1 to} R ₇ are each independently hydrogen, a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 5 carbon atoms. , Halogen, a substituted or unsubstituted aryl group having 1 to 14 carbon atoms, and a plurality of aryl groups may be substituted.

Next, as the T in the general formula (I), the following structures are specifically mentioned, and T-2, T-3 and the like are particularly preferable in terms of cost and electric characteristics.

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Further, Q in the general formula (I) specifically has the following structure, and Q-2, Q-6, etc. are particularly preferable in terms of cost and electric characteristics.

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X in the general formula (III) includes those selected from the following groups (1) to (7).

[0019]

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In the above structure, R ₈ is a hydrogen atom, carbon atom 1
Represents a substituted or unsubstituted phenyl group, a substituted or unsubstituted aralkyl group, R _{9 to} R ₁₄ are a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, Substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms, substituted with 6 to 15 carbon atoms, or unsubstituted phenyl group, substituted with 6 to 15 carbon atoms, or unsubstituted aralkyl group, halogen And a represents 0 or 1.
V is selected from the following groups (8) to (17). b means an integer of 1 to 10, and c means an integer of 1 to 3.

[0021]

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In particular, the structure of X is represented by the following structural formulas (IV), (V) and (V)
The structure represented by I) is preferable because of its high mobility.

[0023]

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[0024]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
The compound of the present invention represented by the general formula (I) can be esterified with a desired alcohol after hydrolyzing an arylamine compound containing an ester group described in, for example, JP-A-9-31039. Do or
The compound can be easily synthesized by performing a transesterification reaction using an excess amount of a desired alcohol without hydrolysis.

Hydrolysis is described, for example, in Experimental Chemistry, 4th Edition, Volume 20, 51, etc.
Basic catalysts such as OH, K ₂ CO ₃ or phosphoric acid,
It can be carried out by a usual method using an acidic catalyst such as sulfuric acid. At this time, various solvents can be used, but it is preferable to use an alcohol system such as methanol, ethanol, ethylene glycol or the like, or to mix and use water. Further, when solubility is low, methylene chloride, chloroform, toluene, dimethyl sulfoxide, ether, tetrahydrofuran and the like may be added. Although the amount of the solvent is not particularly limited, it is 1 to 1 part by weight based on 1 part by weight of the arylamine compound containing an ester group.
00 parts by weight, preferably 2 to 50 parts by weight. The reaction temperature can be set from room temperature to the boiling point of the solvent, and is preferably 50 ° C. or more from the viewpoint of the reaction rate. The amount of the catalyst is not particularly limited, but it is used in an amount of 0.001 to 1 part by weight, preferably 0.01 to 0.5 part by weight, based on 1 part by weight of the arylamine compound containing an ester group. After the hydrolysis reaction, when hydrolysis is performed with a basic catalyst,
The resulting salt is neutralized with an acid such as hydrochloric acid and released. Further, after sufficiently washing with water, use after drying or, if necessary, recrystallize with a suitable solvent such as methanol, ethanol, toluene, ethyl acetate, acetone, etc., and then use after drying. Is also good.

In the transesterification reaction, a desired alcohol is added in excess, and an inorganic acid such as sulfuric acid or phosphoric acid, an acetate such as titanium alkoxide, calcium or cobalt, or a carbonate, an oxide of zinc or lead is catalyzed. And heat it to
Do. The alcohol is used in an amount of 2 to 100 equivalents, preferably 3 to 100 equivalents based on 1 equivalent of the arylamine compound containing an ester group.
Used in 50 equivalents. The catalyst is used in an amount of 1 / 10,000 to 1 part by weight, preferably 1/1000 to 1/2 part by weight, based on 1 part by weight of the arylamine compound containing an ester group. The reaction temperature can be from 100 to 300 ° C. Further, it is preferable that the reaction is performed under an atmosphere of an inert gas such as nitrogen while removing the low-boiling alcohol such as methanol generated outside the system. As an example, Tables 1 and 2 show examples of the partial structure represented by the general formula (II).

[0027]

[Table 1]

[0028]

[Table 2]

Tables 3 to 20 show examples of the partial structure represented by the general formula (III).

[0030]

[Table 3]

[0031]

[Table 4]

[0032]

[Table 5]

[0033]

[Table 6]

[0034]

[Table 7]

[0035]

[Table 8]

[0036]

[Table 9]

[0037]

[Table 10]

[0038]

[Table 11]

[0039]

[Table 12]

[0040]

[Table 13]

[0041]

[Table 14]

[0042]

[Table 15]

[0043]

[Table 16]

[0044]

[Table 17]

[0045]

[Table 18]

[0046]

[Table 19]

[0047]

[Table 20]

Next, the electrophotographic photosensitive member of the present invention will be described. The electrophotographic photoreceptor of the present invention has a single-layer type in which a single-layered photosensitive layer is provided on a conductive support, and a laminated type in which two layers of a charge generation layer and a charge transport layer are provided in an arbitrary order. Further, any type of photoreceptor in which a surface protective layer is provided on a single-layer type or a laminated type may be used. Further, the compound represented by the general formula (I) of the present invention may be contained in any of the layers of these photoreceptors, but since crosslinking can increase the strength of the resin, it is provided in the outermost surface layer. Is effective. Hereinafter, a case of a stacked type will be described in more detail.

The conductive support used in the electrophotographic photoreceptor used in the present invention includes, for example, aluminum,
Metal plates, metal drums, metal belts using metals or alloys such as copper, zinc, stainless steel, chromium, nickel, molybdenum, vanadium, indium, gold, and platinum; conductive polymers; conductive compounds such as indium oxide; and aluminum Apply metal or alloy such as palladium, gold,
Examples thereof include vapor-deposited or laminated paper, plastic films, and belts. Further, if necessary, the surface of the conductive support can be subjected to various treatments within a range that does not affect the image quality. For example, surface anodic oxide coating treatment,
Thermal hydroxylation treatment, chemical treatment, and coloring treatment, or
Diffuse reflection processing such as graining can be performed.

The charge generating material used in the photoconductive layer includes, for example, azo pigments, quinone pigments, perylene pigments, indigo pigments, thioindigo pigments, bisbenzimidazole pigments, phthalocyanine pigments, quinacridone pigments, Quinoline-based pigments, lake-based pigments, azo lake-based pigments, anthraquinone-based pigments, oxazine-based pigments, dioxazine-based pigments, triphenylmethane-based pigments, azurenium-based dyes, squarium-based dyes, pyrylium-based dyes, triallylmethane-based dyes, xanthene -Based dyes, thiazine-based dyes, various organic pigments such as cyanine-based dyes, dyes, and further amorphous silicon, amorphous selenium,
Inorganic materials such as tellurium, selenium-tellurium alloy, cadmium sulfide, antimony sulfide, zinc oxide, zinc sulfide and the like are included, and condensed aromatic pigments, perylene pigments, azo pigments, sensitivity, electrical stability, Further, it is preferable in terms of photochemical stability to irradiation light.

As the charge generating substance used in the photoconductive layer, the above-described substances can be used alone, or two or more kinds of charge generating substances can be used in combination. The charge generation layer can be formed by forming the charge generation material by vacuum evaporation, or by dispersing and applying the charge generation material to a binder resin in an organic solvent. When applied, as a binder resin in the charge generation layer, polyvinyl butyral resin, polyvinyl formal resin, polyvinyl acetal resin such as partially acetalized polyvinyl acetal resin partially modified with formal or acetoacetal, polyamide Resin, polyester resin, modified ether type polyester resin, polycarbonate resin, acrylic resin, polyvinyl chloride resin, polyvinylidene chloride resin, polystyrene resin, polyvinyl acetate resin, vinyl chloride-vinyl acetate copolymer, silicone resin, phenol resin, phenoxy Resins, melamine resins, benzoguanamine resins, urea resins, polyurethane resins, poly-N-vinylcarbazole resins, polyvinylanthracene resins, polyvinylpyrene and the like. Among these, especially polyvinyl acetal resin, vinyl chloride-vinyl acetate copolymer, phenoxy resin and modified ether type polyester resin disperse the pigment well, the pigment is not aggregated, and the dispersion coating liquid is stable for a long time, By using the coating liquid, a uniform film can be formed, and as a result, electrical characteristics can be improved and image quality defects can be reduced. However, the resin is not limited to these as long as it can form a film in a normal state.
These binder resins can be used alone or in combination of two or more. The mixing ratio of the charge generation material to the binder resin is preferably in the range of 5: 1 to 1: 2 by volume. Solvents used when preparing the coating liquid, methanol, ethanol, n-propanol, n-butanol,
Benzyl alcohol, methyl cellosolve, ethyl cellosolve, acetone, methyl ethyl ketone, cyclohexanone, chlorobenzene, methyl acetate, n-butyl acetate, dioxane, tetrahydrofuran, methylene chloride,
Commonly used organic solvents such as chloroform can be used alone or in combination of two or more.

As a method of applying the coating liquid, a commonly used method such as a blade coating method, a Meyer bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, a curtain coating method, or the like is used. be able to.
The thickness of the charge generation layer is generally from 0.01 to 5 μm, preferably from 0.1 to 2.0 μm. This thickness is 0.
When the thickness is less than 01 μm, it is difficult to form the charge generation layer uniformly, and when it exceeds 5 μm, the electrophotographic characteristics tend to be significantly reduced.

An undercoat layer may be provided between the charge generation layer and the conductive support. Examples of the binder resin used for the undercoat layer include the following. Polyamide resin, vinyl chloride resin, vinyl acetate resin, phenol resin, polyurethane resin, melamine resin, benzoguanamine resin, polyimide resin, polyethylene resin, polypropylene resin, polycarbonate resin, acrylic resin, methacrylic resin, vinylidene chloride resin, polyvinyl acetal resin, chloride Vinyl-vinyl acetate copolymer, polyvinyl alcohol resin, water-soluble polyester resin, nitrocellulose, casein, gelatin, polyglutamic acid, starch, starch thiacetate, amino starch, polyacrylic acid, polyacrylamide, zirconium chelate compound, titanyl chelate compound, Titanyl alkoxide compounds, organic titanyl compounds, alkoxysilane compounds,
Known materials such as a silane coupling agent can be used. These materials can be used alone or in combination of two or more. Further, it can be mixed with fine particles such as titanium oxide, aluminum oxide, silicon oxide, zirconium oxide, barium titanate, and silicone resin. As an application method for forming the undercoat layer 4, a normal method such as a blade coating method, a Meyer bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, and a curtain coating method is employed. Is done. The thickness of the undercoat layer is suitably from 0.01 to 10 μm, preferably from 0.05 to 2 μm.

Examples of the charge transport layer provided on the charge generation layer include pyrene-based, carbazole-based, hydrazone-based, oxazole-based, oxadiazole-based, pyrazoline-based, arylamine-based, arylmethane-based, benzidine-based, and thiazole-based. Known stilbene-based, butadiene-based charge transporting compounds, for example, polycarbonate,
Polyester, methacrylic resin, acrylic resin, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyvinyl acetate, styrene-butadiene copolymer, vinylidene chloride-acrylonitrile polymer, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate- Maleic anhydride copolymer, silicone resin, silicone-alkyd resin, phenol-formaldehyde resin, styrene-
In binder resins such as alkyd resin, poly-N-vinyl carbazole, polyvinyl butyral, polyvinyl formal, polysulfone, casein, gelatin, polyvinyl alcohol, ethyl cellulose, phenol resin, polyamide, carboxy-methyl cellulose, vinylidene chloride polymer latex, and polyurethane And, for example, poly-N-vinylcarbazole, halogenated poly-N-vinylcarbazole, polyvinylpyrene,
Charge transport polymer compounds such as polyvinyl anthracene, polyvinyl acridine, pyrene-formaldehyde resin, ethylcarbazole-formaldehyde resin, triphenylmethane polymer, and polysilane. As the charge transporting polymer compound, polycarbonates and polyesters having a triphenylamine skeleton and a benzidine skeleton are preferable in terms of mobility, stability, and transparency to light.

Further, the compound represented by the general formula (I) may be mixed in the charge transport layer. In this case, the general formula (I)
Can be used at a mixing ratio (weight ratio) of the compound represented by the formula (1) to a known charge transporting compound. When the charge transporting polymer compound is used, the compound represented by the general formula (I) can be mixed. It can be used in a mixing ratio (weight ratio) of the compound represented by the general formula (I) and the charge transporting polymer compound of 0: 100 to 10: 8, mobility,
From the viewpoint of strength, a range of 3: 100 to 10: 9 is preferable. The thickness of the charge transport layer is generally 5 to 50 μm, preferably 10 to 40 μm. If the thickness is less than 5 μm, charging becomes difficult, and if it exceeds 50 μm, the electrophotographic properties tend to be significantly reduced.

A layer containing a compound represented by the general formula (I) can be provided on a commonly used charge transport layer or a layer containing a compound represented by the general formula (I). In this case, the binder resin is used alone or as a mixture of two or more kinds, but in particular, polycarbonate, polyester, methacrylic resin, acrylic resin, polyvinyl butyral, polyvinyl formal, polyvinyl alcohol, ethyl cellulose, phenol resin, polyamide, etc. formula
Those containing a group capable of forming a hydrogen bond with the compound represented by (I) are preferred.

The layer containing the compound represented by the general formula (I) can be used after curing, if desired. As a curing method, by mixing a hydrolyzable metal compound such as a zirconium chelate compound, a titanyl chelate compound, a titanyl alkoxide compound, an organic titanyl compound, and an organic silicon compound, these metal compounds themselves cure and increase strength. In addition, by promoting the transesterification reaction, an effective crosslinking reaction occurs particularly when n is 3 or more in the general formula (I), and the strength can be further increased.
The hydrolyzable metal compound is in a weight ratio of 1: 1000 to 20: 1 with respect to all other materials forming the charge transport layer.
00, preferably from 1: 1000 to 15: 1
Use 00. Further, the curing condition is heating at 50 degrees or more for 30 minutes or more, preferably at 80 degrees or more for 40 minutes or more.
At this time, in order to avoid side reactions such as oxidation, it is also effective to carry out the reaction in an atmosphere of an inert gas such as nitrogen.

Further, an isocyanate compound, an epoxy compound and the like can also be used. As the isocyanate group-containing compound, those having three or more isocyanate groups are preferable, and specifically, 1,3,6-hexamethylene triisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-isocyanate-4-isocyanatomethyloctane, triphenylmethane triisocyanate,
Polyisocyanate monomers such as tris (isocyanatephenyl) thiophosphate are used. Also,
Among compounds containing three or more isocyanate groups,
It is more desirable to use a modified product such as a derivative or a prepolymer obtained from a polyisocyanate monomer from the viewpoints of the film forming property of the finally obtained crosslinked film, the resistance to crack generation and the ease of handling.

Examples of these are urethane-modified products obtained by modifying a polyol with an excess of an isocyanate compound, buret-modified products obtained by modifying a compound having a urea bond with an isocyanate compound, and allophanate-modified products obtained by adding an isocyanate to a urethane group. Preferably, a modified isocyanurate, a modified carbodiimide, etc. are used. Furthermore, although it is included in the above-mentioned modified polyisocyanate, a blocked isocyanate reacted with a blocking agent for temporarily masking the activity of the isocyanate group can also be preferably used. Here, the isocyanate used for the modification may have two functional groups, such as tolylene diisocyanate (TDI),
Diphenylmethane diisocyanate (MDI), 1,5
-Naphthylene diisocyanate, tolidine diisocyanate, 1,6-hexamethylene diisocyanate, xylene diisocyanate, lysine diisocyanate, tetramethyl xylene diisocyanate and the like. Specifically, Sumidur N75, Sumidur N3200, Sumidur N3290 MPA / X, Sumidur N3290 EA, Sumidur N3400, Sumidur N3300, Sumidur
N3390 EA, Sumidur HT, Death module Z4470 M
PA / X, Death Module Z4470 EA Death Module Z4470
BA, Death Module E3265, Death Module E4280, Sumidule L75, Sumidule L1375, Sumidule
L1365, Desmodur IL BA, SBU Isocyanate 081
7, Sumidur FL-2, Sumidur FL-3, Sumidur FL-4, DeathModule HL BA, DeathModule E
1160, death module E1240, death module E1361,
Death module E14, Death module E 15, Sumidule E21-1 Sumidule E21-2, Death module E2
2, death module E23, death module E25, death module E2280, death module E27, death module
E29, Sumidur T-80, Sumidur 44S, Sumidur 44V10, Sumidur 44V20, Sumidur 44V
40, Sumidule 44V70, death module VL, death module VL-R10, death module VL-R20, death module VL-50, death module H, death module W, death module I (all manufactured by Sumitomo Bayer), etc. Isocyanate. Death Module CT Stable, Death Module BL1100, Death Module BL1265 MPA / X, Sumidule BL3175, Death Module BL4265 SN, SBU Isocyanate L805, Death Module BL3370 MPA, Death Module BL3475 BA / SN (all manufactured by Sumitomo Bayer), etc. And the like are used. Furthermore, a compound having a hydroxy group and a fluorine atom can also be mixed, and since it has good lubricity and mold release properties,
This is effective for preventing paper powder or toner from adhering or sticking to the surface of the photoreceptor. Examples of the compound having a hydroxy group and a fluorine atom include glycols such as ethylene glycol, propylene glycol, and polyethylene glycols, and hydroxy group-containing compounds such as various polymers or prepolymers having a hydroxy group such as acrylic polyol and polyester polyol. In which the hydrogen atom is replaced by fluorine. Further, these hydroxy group-containing compounds may have a fluorine-substituted alkyl group.

The cross-linking polymerization reaction due to the addition of the hydroxy group and the isocyanate group depends on the reactivity of the raw material compounds used. However, in general, it is not necessary to add a catalyst or the like, and the reaction can be carried out only by heating. can do. In order to accelerate this cross-linking polymerization reaction, a catalyst such as an organic metal compound such as dibutyltin dilaurate, an inorganic metal compound, a monoamine, a diamine, a triamine, a cyclic amine, an alcoholamine, or an etheramine is usually used. You may add by the method.

Further, together with these binders, a crosslinking agent,
Additives such as plasticizers, surface modifiers, antioxidants, light degradation inhibitors, and organic or inorganic fine particles can also be used. Examples of the crosslinking agent include various polyfunctional crosslinking agents such as methoxymethylated melamine, triethylene glycol diacrylate, and pentaerythritol triacrylate. Examples of the plasticizer include biphenyl, biphenyl chloride, terphenyl, dibutyl phthalate, diethylene glycol phthalate, dioctyl phthalate, triphenylphosphoric acid, methylnaphthalene, benzophenone, chlorinated paraffin, polypropylene, polystyrene, various fluorohydrocarbons, and the like.

Examples of the antioxidant include phenol-based, sulfur-based, phosphorus-based, and amine-based antioxidants. Examples of the photo-deterioration inhibitor include benzotriazole-based compounds, benzophenone-based compounds, hindered amine-based compounds, and the like. Organic or inorganic fine particles include fluorine fine particles such as ethylene tetrafluoride, ethylene trifluoride, propylene hexafluoride, vinyl fluoride, and vinylidene fluoride; fine particles such as benzoguanamine and polystyrene beads; and ZnO-Al ₂ O ₃ , SnO ₂ -Sb ₂ O ₃ , In ₂ O ₃ -SnO ₂ , ZnO
-TiO ₂ , ZnO-TiO ₂ , MgO-Al ₂ O ₃ , FeO-TiO ₂ , TiO ₂ , SnO ₂ ,
Examples thereof include semiconductive metal oxides such as In ₂ O ₃ , ZnO, and MgO, and mixtures thereof. Fine particles have a particle size of 0.01 to
It is preferably in the range of 0.3 μm, and in the case of conductive fine particles, those having a resistance value of 10 ¹⁰ Ω or less are preferable.

The coating solvent varies depending on the type of the material.
It is preferable to select and use the optimal one. Examples of the organic solvent include, for example, methanol, ethanol, n-
Alcohols such as propanol; ketones such as acetone, methyl ethyl ketone and cyclohexanone; amides such as N, N-dimethylformamide and N, N-dimethylacetamide; ethers such as tetrahydrofuran, dioxane and methyl cellosolve; methyl acetate, ethyl acetate Esters such as dimethylsulfoxide and sulfolane and sulfones; aliphatic halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, and trichloroethane; aromatics such as benzene, toluene, xylene, monochlorobenzene, and dichlorobenzene. And the like.

The content of the compound represented by the general formula (I) can be arbitrarily set, but the mixing ratio (weight ratio) of the compound represented by the general formula (I) and the binder resin is 1: 100 to 10: 2
In particular, from the viewpoint of mobility and strength, 1:10 to 1
A range of 0: 8 is preferred. The film thickness is suitably from 1 to 25 μm, preferably from 2 to 20 μm. If this thickness is less than 1 μm, it is difficult to obtain a merit in strength.
If it exceeds μm, the electrophotographic properties tend to be significantly reduced. Further, since the compound represented by the general formula (I) has a property of easily interacting with ions, the compound of the general formula (I) alone or an ion such as Li, Na, Br, I is added,
It can also be applied as a charge transport material for wet solar cells. The image forming apparatus of the present invention is an image forming apparatus using an electrophotographic photosensitive member, wherein the photosensitive layer of the electrophotographic photosensitive member contains at least the general formula (I).

[0065]

The present invention will be described in detail with reference to the following examples.
Hereinafter, “parts” means “parts by weight” unless otherwise specified. Synthesis Example 1 The compound represented by the partial structure 3, having 10 parts of a compound having a methyl alcohol ester at the end, 100 parts of ethylene glycol, and 0.1 part of tetrabutoxytitanium was placed in a 200 ml flask and heated and refluxed for 5 hours under a nitrogen stream. After the reaction, the mixture was cooled to room temperature, 100 ml of toluene was added, and the mixture was sufficiently washed with distilled water. After concentration of the toluene layer, recrystallization from toluene-methanol gave 9.2 parts of compound (1). FIG. 1 shows the IR spectrum of the compound (1).

Synthesis Examples 2 to 20 In the same manner as in Example 1, a transesterification reaction was carried out to synthesize a corresponding hydroxyl group-containing charge transport material. Table 2 summarizes the structure
1 is shown.

[0067]

[Table 21]

Example 1 10 parts of a zirconium compound (trade name: Organix ZC540, manufactured by Matsumoto Pharmaceutical Co., Ltd.) and 1 part of a silane compound (trade name: A1110, manufactured by Nippon Unicar Co., Ltd.) and 40 parts of i-propanol were placed on an aluminum substrate. A solution consisting of 20 parts of butanol is applied by a dip coating method.
It was dried by heating at 50 ° C. for 10 minutes to form an undercoat layer having a thickness of 0.5 μm. Next, 10 parts of chlorogallium phthalocyanine, a charge generating material, were mixed with 10 parts of polyvinyl butyral resin (trade name: ESREC BM-S, manufactured by Sekisui Chemical Co., Ltd.) and 500 parts of n-butyl acetate, and the mixture was mixed with glass beads using a paint shaker. After treating and dispersing for 1 hour, the obtained coating solution was applied on the undercoat layer by a dip coating method, and dried by heating at 100 ° C. for 10 minutes to form a film having a thickness of about 0.2 μm
m of the charge generation layer was formed. Next, N, N'-diphenyl-N, N'-bis (3-methylphenyl) as a charge transport material
-[1,1'-biphenyl] -4,4'-diamine (20 parts), bisphenol (Z) polycarbonate (25 parts), and a hindered ferrule compound (0.5 part) are combined with monochlorobenzene: 100
Parts and tetrahydrofuran: dissolved in a mixture of 70 parts,
The obtained coating liquid is applied on the above-mentioned charge generation layer, and 115
Heat drying at 60 ° C. for 60 minutes to form a charge transport layer having a thickness of about 20 μm. A photosensitive layer was formed on an aluminum substrate as described above.

Next, Sb2O5-doped SnO, which is a conductive fine particle, is used.
12 parts of ₂ particles (T-1, manufactured by Mitsubishi Materials Corporation) and 8 parts of a polyamide resin (Platabond MX1602, manufactured by Elfatochem Japan) are mixed in a solution of 200 parts of n-butyl alcohol and dispersed in a sand mill for 6 hours. did. To the resulting dispersion, dip coating was performed using a solution obtained by adding 3 parts of the compound synthesized in Synthesis Example 12 and 15 parts of a block type isocyanate (Coronate 2507, manufactured by Nippon Polyurethane Industry Co., Ltd.) at 160 ° C. for 1 hour. A dry hardening treatment was applied to form a 6 μm surface layer on the charge transport layer. By the way, the liquid viscosity of the surface layer coating liquid was stable at room temperature (20 to 25 ° C.) with no significant change even at aging of 2 months because a block type is used as an isocyanate curing agent. Further, since the electrophotographic photoreceptor of the present invention uses an alcohol that does not dissolve the charge transport layer resin in the surface layer coating solvent,
As described above, a layer was formed by dip coating of all layers, and the photosensitive member was efficiently manufactured.

The electrophotographic photosensitive member obtained as described above is contact-charged with a printer (Fuji Xerox Color
28 ° C, 85% RH with a modified Laser Wind 3310)
In a high-temperature, high-humidity environment, image quality maintenance and photoreceptor wear of 30,000 sheets of A4 size and monochrome prints were evaluated. As for the image quality, good prints were obtained from the initial stage up to 30,000 sheets. The abrasion amount of the photoreceptor was 1.7 μm.

Comparative Example 1 The same procedure as in Example 1 was carried out up to the charge transport layer of the photoreceptor. Next, regarding the surface layer, conductive fine particles Sb2O5
Doped SnO ₂ particles (T-1, manufactured by Mitsubishi Materials Corporation) 12
Part, 8 parts of polyamide resin (Platabond MX1602, manufactured by Elf Atochem Japan)
The mixture was mixed with the solution dissolved in the mixture, and dispersed in a sand mill for 6 hours. To the obtained dispersion, dip coating was performed using a liquid obtained by adding 8 parts of a block type isocyanate (Coronate 2507, manufactured by Nippon Polyurethane Industry Co., Ltd.), and a drying and curing treatment was performed at 160 ° C. for 1 hour to form a 6.5 μm surface layer. Was formed on the charge transport layer. Regarding the image quality, there was a problem that a negative ghost of the previously printed character was observed in the low density solid print after the character was printed in the initial check.

Example 2 An electrophotographic photosensitive member was manufactured in the same manner as in Example 1 up to the charge transport layer. Next, SnO ₂ particles (S
-12, manufactured by Mitsubishi Materials Corporation, and 12 parts of a polyvinyl butyral resin (ESLEC BH-S, manufactured by Sekisui Chemical Co., Ltd.) were mixed in a solution of 100 parts of n-butyl alcohol and dispersed in a sand mill for 6 hours. To the obtained dispersion, dip coating was carried out using a solution obtained by adding 4 parts of the compound synthesized in Synthesis Example 12 and 7 parts of a block type isocyanate (Sumidur BL3175, manufactured by Sumitomo Bayer Urethane Co.) to 160 ° C.
A dry hardening treatment was performed for a time to form a 6.5 μm surface layer on the charge transport layer. The evaluation was performed in the same manner as in Example 1. As for the image quality, good prints were obtained from the initial stage up to 30,000 sheets. The photoreceptor abrasion was 1.8 μm.

Comparative Example 2 An electrophotographic photosensitive member was manufactured in the same manner as in Example 1 up to the charge transport layer. Next, SnO ₂ particles (S
-12, manufactured by Mitsubishi Materials Corporation, and 12 parts of a polyvinyl butyral resin (ESLEC BH-S, manufactured by Sekisui Chemical Co., Ltd.) were mixed in a solution of 100 parts of n-butyl alcohol and dispersed in a sand mill for 6 hours. The resulting dispersion was applied with dip coating using a solution obtained by adding 7 parts of a block type isocyanate (Sumidur BL3175, manufactured by Sumitomo Bayer Urethane Co.), and dried and cured at 160 ° C. for 1 hour to obtain a 6.5 μm surface layer. Was formed on the charge transport layer. The evaluation was performed in the same manner as in Example 1. Regarding the image quality, there was a problem that a negative ghost of the previously printed character was observed in the low density solid print after the character was printed in the initial check.

Example 3 An electrophotographic photosensitive member was manufactured in the same manner as in Example 1 up to the charge transport layer. Next, SnO ₂ particles (S
-1, manufactured by Mitsubishi Materials Corporation) 12 parts, 0.05μm PTFE
0.5 part of the fine particles and 7 parts of a polyvinyl butyral resin (S-lek BH-S, manufactured by Sekisui Chemical Co., Ltd.) were mixed with a solution of 100 parts of n-butyl alcohol and dispersed in a sand mill for 6 hours. To the obtained dispersion, 5 parts of the compound synthesized in Synthesis Example 9 was added to a blocked isocyanate (Sumidur BL31).
75, manufactured by Sumitomo Bayer Urethane Co., Ltd .; dip coating was performed using a liquid to which 14 parts were added, and a drying and curing treatment was performed at 160 ° C. for 1 hour to form a 7 μm surface layer on the charge transport layer.
The evaluation was performed in the same manner as in Example 1. For image quality,
Good prints were obtained from the beginning up to 30,000 sheets. The photoconductor abrasion amount was 2.1 μm. In addition, the photoreceptor has a property that toner does not easily adhere thereto, and cleaning was easy.

Example 4 A charge-generating layer was formed in the same manner as in Example 1, and 20 parts of a charge-transporting polymer having a molecular weight of about 100,000 (in terms of polystyrene) represented by the following structural formula was added to tetrahydrofuran 1
The resulting coating solution was dissolved in 00 parts, and the obtained coating solution was applied on the charge generation layer. Heat drying at 130 ° C. for 90 minutes to form a charge transport layer having a thickness of about 20 μm. Next, regarding the surface layer, Sb ₂ O ₅ -doped SnO ₂ particles (T-
1, 12 parts of Mitsubishi Materials Corporation and 8 parts of polyamide resin (Platabond MX1602, manufactured by Elf Atochem Japan) were mixed in a solution of 200 parts of n-butyl alcohol.
The mixture was dispersed in a sand mill for 6 hours. 5 parts of the compound synthesized in Synthesis Example 13 was added to the obtained dispersion, and a blocked isocyanate (Coronate 2507, manufactured by Nippon Polyurethane Industry Co., Ltd.)
Dip coating was performed using the solution to which 8 parts were added, and a drying and curing treatment was performed at 160 ° C. for 1 hour to form a 6.5 μm surface layer on the charge transport layer. The evaluation was performed in the same manner as in Example 1. As for the image quality, good prints were obtained from the initial stage up to 30,000 sheets. The abrasion amount of the photoreceptor was 2.0 μm.

[0076]

Embedded image

Example 5 A charge generation layer was formed in the same manner as in Example 1, and 20 parts of a charge transporting polymer having a molecular weight of about 100,000 (polystyrene equivalent) represented by the above structural formula was formed thereon. 5 parts of the synthesized compound and 1 part of tetramethoxysilane were dissolved in 100 parts of tetrahydrofuran, and the obtained coating solution was applied on the charge generation layer. Heat drying at 130 ° C. for 90 minutes to form a charge transport layer having a thickness of about 20 μm. The evaluation was performed in the same manner as in Example 1. As for the image quality, good prints were obtained from the initial stage up to 30,000 sheets. The wear amount of the photoreceptor was 6.9 μm.

Comparative Example 3 A charge-generating layer was formed in the same manner as in Example 1, and 20 parts of a charge-transporting polymer represented by the above structural formula and having a molecular weight of about 100,000 (in terms of polystyrene), tetramethoxysilane 1 Was dissolved in 100 parts of tetrahydrofuran, and the resulting coating solution was applied on the charge generation layer. Heat drying at 130 ° C. for 90 minutes to form a charge transport layer having a thickness of about 20 μm. The evaluation was performed in the same manner as in Example 1. As for the image quality, image quality defects occurred around 20,000 sheets. The photoconductor abrasion amount was 11.3 μm.

Example 6 An electrophotographic photosensitive member was manufactured in the same manner as in Example 1 up to the charge transport layer. Next, SnO ₂ particles (S
-12, manufactured by Mitsubishi Materials Corporation) 12 parts, primary particle size about 7 nm
Hydrophobic silica fine particles (R812: Nippon Aerosil Co., Ltd.)
0.5 parts, polyvinyl butyral resin (S-LEC BH-
S, manufactured by Sekisui Chemical Co., Ltd.) 7 parts of n-butyl alcohol 100
The mixture was mixed with the solution dissolved in the mixture, and dispersed in a sand mill for 6 hours. The compound synthesized in Synthesis Example 9 was added to the obtained dispersion liquid by 5
Parts, blocked isocyanate (Sumidur BL3175,
Dip coating was performed using a solution to which 14 parts (Sumitomo Bayer Urethane Co., Ltd.) was added, followed by drying and curing at 160 ° C. for 1 hour.
A μm surface layer was formed on the charge transport layer. The evaluation was performed in the same manner as in Example 1. As for the image quality, good prints were obtained from the initial stage up to 30,000 sheets. The abrasion amount of the photoreceptor was 2.3 μm. In addition, the photoreceptor has a property that toner does not easily adhere thereto, and cleaning was easy.

Example 7 An electrophotographic photosensitive member was manufactured in the same manner as in Example 1 up to the charge transport layer. Next, SnO ₂ particles (S
-12, manufactured by Mitsubishi Materials Corporation) 12 parts, primary particle size about 7 nm
0.5 parts of reactive silica fine particles having an epoxy functional group introduced on the surface of Aerosil (Nippon Aerosil Co., Ltd. trial product) and 7 parts of polyvinyl butyral resin (ESREC BH-S, manufactured by Sekisui Chemical Co., Ltd.) are added to 100 parts of n-butyl alcohol. It was mixed with the dissolved liquid and dispersed in a sand mill for 6 hours. To the obtained dispersion, dip coating was performed using a liquid obtained by adding 5 parts of the compound synthesized in Synthesis Example 9 and 14 parts of a block type isocyanate (Sumidur BL3175, manufactured by Sumitomo Bayer Urethane Co.) to 160 ° C. for 1 hour. And a 7 μm surface layer was formed on the charge transport layer. Evaluation was performed in Example 1.
Was carried out in the same manner as As for the image quality, good prints were obtained from the initial stage up to 30,000 sheets. Photoreceptor wear amount is 1.7
μm. In addition, the photoreceptor has a property that toner does not easily adhere thereto, and cleaning was easy.

Example 8 An electrophotographic photosensitive member was manufactured in the same manner as in Example 1 up to the charge transport layer. Next, SnO ₂ particles (S
-1, manufactured by Mitsubishi Materials Corporation) 12 parts, 0.05μm PTFE
0.5 part of the fine particles and 7 parts of a polyvinyl butyral resin (S-lek BH-S, manufactured by Sekisui Chemical Co., Ltd.) were mixed with a solution of 100 parts of n-butyl alcohol and dispersed in a sand mill for 6 hours. To the obtained dispersion, 5 parts of the compound synthesized in Synthesis Example 3 was added to a blocked isocyanate (Sumidur BL31).
75, manufactured by Sumitomo Bayer Urethane Co., Ltd.), dip coating was performed using a liquid to which 13 parts were added, and drying and curing treatment was performed at 160 ° C. for 1 hour to form a 7 μm surface layer on the charge transport layer.
The evaluation was performed in the same manner as in Example 1. For image quality,
Good prints were obtained from the beginning up to 30,000 sheets. The wear amount of the photoreceptor was 2.5 μm. In addition, the photoreceptor has a property that toner does not easily adhere thereto, and cleaning was easy.

Example 9 An electrophotographic photosensitive member was manufactured in the same manner as in Example 1 up to the charge transport layer. Next, SnO ₂ particles (S
-1, manufactured by Mitsubishi Materials Corporation) 12 parts, 0.05μm PTFE
0.5 part of the fine particles and 7 parts of a polyvinyl butyral resin (S-lek BH-S, manufactured by Sekisui Chemical Co., Ltd.) were mixed with a solution of 100 parts of n-butyl alcohol and dispersed in a sand mill for 6 hours. To the obtained dispersion, 5 parts of the compound synthesized in Synthesis Example 19 was added to a blocked isocyanate (Sumidur BL
3175, manufactured by Sumitomo Bayer Urethane Co., Ltd.), dip coating was performed using a liquid to which 16 parts were added, and a drying and curing treatment was performed at 160 ° C. for 1 hour to form a 7 μm surface layer on the charge transport layer. The evaluation was performed in the same manner as in Example 1. As for the image quality, good prints were obtained from the initial stage up to 30,000 sheets.
The abrasion amount of the photoreceptor was 1.5 μm. In addition, the photoreceptor has a property that toner does not easily adhere thereto, and cleaning was easy.

[0083]

The novel hydroxyl group-containing charge transporting material used for the organic electronic device of the present invention, particularly for the electrophotographic photoreceptor,
It is effective as a photoconductive material for an electrophotographic photoreceptor, has high mechanical strength, and can provide a stable image. In the image forming apparatus of the present invention, a long-term stable image can be obtained.

[Brief description of the drawings]

FIG. 1 is a view showing an IR spectrum of a compound (a hydroxyl group-containing charge transporting material) obtained in Synthesis 1.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Rie Ishii 1600 Takematsu, Minamiashigara-shi, Kanagawa Prefecture Inside Fuji Xerox Co., Ltd. Reference) 2H068 AA02 AA03 AA04 AA20 AA21 BA12 BA13 BA14 BA16 BB23 BB49 BB50 BB57 BB62 4H006 AA03 AB76 BJ50 BT32 BU46

Claims (5)

[Claims] 1. An organic electronic device using a charge transporting compound represented by the following general formula (I). Embedded image In the general formula (I), A means a charge transporting unit. l
Represents an integer selected from 0 or 1, m represents an integer of 1 to 4, and T represents a divalent hydrocarbon group having 1 to 10 carbon atoms which may be branched. Q represents a divalent group which may contain a complex element. 2. The organic electronic device according to claim 1, wherein A in the general formula (I) has a hole transporting property. 3. A compound represented by the following general formula (I)
The organic electronic device according to claim 1 or 2, wherein the organic electronic device is a triarylamine derivative represented by (I) or (III). Embedded image Ar _{1 to} Ar ₇ in the general formulas (II) and (III) each independently represent a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, and X represents a divalent group. 4. The electrophotographic photoreceptor according to claim 1, wherein the electrophotographic photoreceptor contains at least one compound represented by the formula (I) in a photosensitive layer. Organic electronic devices. 5. An image forming apparatus using the electrophotographic photoreceptor according to claim 4.