JPH0912630A - Polymer, electrophotographic photoreceptor and electro-luminescent element containing this polymer and process cartridge and electrophotographic apparatus having this photoreceptor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polymer having very excellent hole transport capacity, film-forming properties and mechanical strengths and being useful for the preparation of electrophotographic photoreceptors, electroluminescent elements, process cartridges, electrophotographic apparatuses, etc., by forming it so as to have a specified molecular structure. SOLUTION: This polymer comprises structural units represented by the formula [wherein R1 , R2 and R3 , which may be the same or different from each other, are each hydrogen, a (substituted) alkyl or a halogen; X is a (substituted) alkylene; Ar is a (substituted) phenylene; Ar2 and Ar3 , which may be the same or different from each other are each a (substituted) aromatic hydrocarbon ring group or a (substituted) aromatic heterocyclic ring group].

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polymer having a novel structure, and more particularly to a polymer having an excellent hole transporting property. The present invention also relates to an electrophotographic photosensitive member and an electroluminescent element containing the polymer, a process cartridge having the electrophotographic photosensitive member, and an electrophotographic apparatus.

[0002]

2. Description of the Related Art In producing various electronic devices, a material capable of efficiently transporting only charge carriers of either electrons or holes is required.

Hole transport materials that transport only holes with high efficiency are currently widely used as materials for electrophotographic photoreceptors, and are expected to be applied to organic electroluminescence (EL) materials.

For example, an electrophotographic photosensitive member (OPC photosensitive member) using an organic hole transport material is superior in productivity and the like to an inorganic photosensitive member, and is often used in a copying machine or a printer. There is.

In many cases, these OPC photoconductors have a structure in which a charge generation layer (CGL) and a charge transport layer (CTL) are sequentially laminated. Generally, CTL is a solution of a low molecular weight charge (hole) transport material (CTM), such as a triarylamine derivative, a hydrazone derivative, and a dialkylaminobenzene derivative, dissolved in a transparent high molecular weight polymer such as a polycarbonate resin. It is formed by applying and drying. Therefore, if the CTM concentration in the polymer matrix is high, image defects due to the precipitation of CTM crystals are likely to occur, and conversely, if it is low, a sufficient hole transporting ability cannot be obtained. Furthermore, since the CTL mechanical strength is lowered, image defects due to scratches and cracks on the OPC photoreceptor are likely to occur. Further, as a high molecular weight charge (hole) transporting material, there are JP-A-2-272005 and JP-A-3-272005.
Although a polystyrene polymer having a hydrazone group is described in Japanese Patent No. 180852, these materials were not sufficient in terms of film-forming property, hole transport rate and residual potential.

On the other hand, the electroluminescence (EL) phenomenon of organic materials was observed in 1963 by Pope et al. In anthracene single crystals. Since then, research on carrier injection and light emission has been carried out, but a single crystal in which the thickness of the sample cannot be made so thin requires a driving voltage of several hundreds of V or more, and has not been put into practical use.

In 1987, Tang et al. Devised an organic EL device in which a hole transport layer and a light emitting layer having a thickness of about 100 nm were laminated by vacuum vapor deposition, and a driving voltage of 10 V or less was applied to 2000.
A high brightness of cd / m ² could be obtained. Organic EL
The features of the device include low drive voltage, easy multicoloring, and low cost and large area. However, the hole-transporting materials that have been conventionally used, for example, vapor-deposited films of triarylamine and dialkylamine derivatives have not been sufficient in terms of film-forming property and hole-transporting ability.

[0008]

An object of the present invention is to provide a polymer having extremely excellent hole transporting property, film forming property and mechanical strength.

Another object of the present invention is to provide an electrophotographic photosensitive member having excellent sensitivity, potential stability and mechanical strength.

Another object of the present invention is to provide an electroluminescent device capable of obtaining high brightness at a low voltage and having excellent film-forming property and durability.

Another object of the present invention is to provide a process cartridge and an electrophotographic apparatus having the above electrophotographic photosensitive member.

[0012]

That is, the present invention provides the following formula (1):

[0013]

[Outside 2] (In the formula, R ₁ , R ₂ and R ₃ are the same or different and each represents a hydrogen atom, a substituted or unsubstituted alkyl group and a halogen atom, X represents a substituted or unsubstituted alkylene group, and Ar ₁ represents a substituted or unsubstituted Represents an unsubstituted phenylene group, and Ar ₂ and Ar ₃ are the same or different and represent a substituted or unsubstituted aromatic hydrocarbon ring group and a substituted or unsubstituted aromatic heterocyclic group). It is a polymer having a structural unit represented by.

The present invention also relates to an electrophotographic photoreceptor having a photosensitive layer containing the above polymer, an electroluminescent device having a light emitting layer or a hole transport layer containing the above polymer, and a process having the electrophotographic photoreceptor. A cartridge and an electrophotographic device.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION Examples of the alkyl group represented by R _{1 to} R ₃ include methyl group, ethyl group and propyl group, and examples of the halogen atom include fluorine atom, chlorine atom and bromine atom. Examples of the substituent that the alkyl group may have include a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom.

Examples of the alkylene group for X include a methylene group, an ethylene group and a propylene group, and examples of the substituent that X may have include a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom. .

Further, the substituent which Ar ₁ may have includes a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom, an alkyl group such as a methyl group, an ethyl group and a propyl group, a methoxy group, an ethoxy group and a propoxy group. And alkoxy groups such as groups.

Examples of the aromatic hydrogenated carbon ring group of Ar ₂ and Ar ₃ include phenyl group, biphenyl group, terphenyl group, naphthyl, anthracenyl group and pyrenyl group, and the aromatic heterocyclic group is pyridyl group. Group and thiophenyl group and the like, and as the substituent which Ar ₂ and Ar ₃ may have, a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom; an alkyl group such as a methyl group, an ethyl group and a propyl group; Examples thereof include alkoxy groups such as methoxy group, ethoxy group and propoxy group; aryloxy groups such as phenoxy group and naphthoxy group; and aralkyl groups such as benzyl group and phenethyl group.

In the present invention, among these, R ₁ and R ₂ represent a hydrogen atom, R ₃ represents a hydrogen atom or a methyl group, and X represents a straight chain unsubstituted alkylene group having 1 to 10 carbon atoms. It is preferable that Ar ₂ and Ar ₃ each represent a substituted or unsubstituted phenyl group.

Specific examples of the structural unit represented by the formula (1) of the present invention are shown below, but the present invention is not limited thereto. The structural unit is represented by showing R _{1 to} R ₃ , X and Ar _{1 to} Ar ₃ , which are variable moieties in the formula (1).

[0021]

[Table 1]

[0022]

[Table 2]

[0023]

[Table 3]

[0024]

[Table 4]

[0025]

[Table 5]

[0026]

[Table 6]

[0027]

[Table 7]

[0028]

[Table 8]

[0029]

[Table 9]

The polymer of the present invention has the following formula (2)

[0031]

[Outside 3] (In the formula, R _{1 to} R ₃ , X and Ar _{1 to} Ar ₃ have the same meanings as those in the formula (1)), and can be obtained by polymerizing the monomer. Specifically, the above monomer is dissolved in a solvent such as toluene, benzene, chloroform, tetrachloromethane, tetrahydrofuran and dioxane, and benzoyl peroxide or a polymerization initiator such as azobisisobutyronitrile is added and reacted. Can be obtained.

The above-mentioned monomer can be obtained by condensing a triarylamine compound having a corresponding hydroxyl group and acrylic acid chloride.

Such a polymer of the present invention has extremely excellent hole transporting property, film forming property and mechanical strength.

In the present invention, hole transportability (μd)
Is preferably 1 × 10 ⁻⁶ cm ² / V · sec or more, and particularly preferably 1 × 10 ⁻⁵ cm ² / V · sec or more. The hole transport property in the present invention is measured as follows.

First, a layer of oxytitanium phthalocyanine having a thickness of 0.1 μm is formed on an aluminum substrate by a vacuum deposition method. Next, on this layer, a suitable method (for example, 3 g of the polymer and 10 ml of toluene in the examples described later) is applied.
15μ thickness by applying the solution dissolved in
Form a layer of m objects to be measured. Then, an electric field of 3 × 10 ⁵ V / cm is applied to this sample, and the target hole transport property is measured by the xerographic time of flight method.

The molecular weight of the polymer of the present invention is G.I. P. Styrene equivalent weight average molecular weight by C of 5,0
It is preferably from 0 to 1,000,000, and particularly preferably from 10,000 to 200,000. If the molecular weight is less than 5,000, it may be difficult to obtain sufficient film-forming property, and if it exceeds 1,000,000, it may be difficult to obtain sufficient solubility.

The polymer of the present invention may have two or more kinds of constitutional units represented by the formula (1), or may have a constitutional unit represented by the formula (1) and other acrylic constitutional units. May be. At that time, the ratio of the structural unit represented by the formula (1) is preferably 10 mol% or more based on all the structural units,
It is particularly preferably 50 mol% or more.

The polymer of the present invention can be used as a mixture with other resins. Such resins include polymethylmethacrylate, polystyrene, polyarylate,
Examples include polycarbonate, polyvinyl butyral and polyester. At that time, the proportion of the polymer of the present invention is 10% by weight based on the total weight of the resin including the polymer of the present invention.
It is preferably not less than 30% by weight, more preferably not less than 30% by weight.

Next, the electrophotographic photosensitive member of the present invention will be described.

The electrophotographic photoreceptor of the present invention has a photosensitive layer containing the polymer of the present invention on a conductive support. As such a photosensitive layer, a laminated type photosensitive layer having a charge transport layer containing the polymer of the present invention and a charge generating layer containing a charge generating substance, and a single layer containing the polymer of the present invention in the same layer containing the charge generating substance. A layer type photosensitive layer and the like can be mentioned.

The charge transport layer may contain not only the polymer of the present invention but also the above-mentioned resin, a low molecular weight charge transport material and a high molecular weight charge transport material. Polycyclic aromatic compounds such as pyrene and anthracene as charge transport materials; carbazole, indole, imidazole,
Heterocyclic compounds such as oxazole, thiazole, oxadiazole, pyrazole, pyrazoline, thiadiazole and triazole; p-diethylaminobenzaldehyde-N, N-diphenylhydrazone and N, N-diphenylhydrazino-3-methylidene-9-ethylcarbazole Human razone compound; a-phenyl-4'-
N, N-diphenylaminostilbene and 5- [4-
A styryl compound such as (di-p-tolylamino) benzylidene] -5H-dibenzo [a, d] cycloheptene;
Benzidine compounds; triarylmethane compounds; triphenylamine compounds; or polymers having a group derived from these compounds in the main chain or side chain (poly-N-vinylcarbazole, polyvinylanthracene, etc.). . In addition to these organic charge transport materials, inorganic materials such as selenium, selenium-tellurium, amorphous silicon and cadmium sulfide can also be used.
These charge transport materials may be used alone or in combination of two or more. The thickness of the charge transport layer is preferably 5 to 40 μm, and particularly 10 to 3
It is preferably 0 μm.

The charge generating layer is formed by applying and drying a dispersion liquid in which a charge generating substance is dispersed in a binder resin. Examples of the binder resin include polyvinyl butyral, polystyrene, polyvinyl acetate, acrylic resin, cellulose acetate and ethyl cellulose, and the polymer of the present invention. As the charge generating substance, azo pigments such as Sudan red and Diane blue; quinone pigments such as pyrene quinone and anthanthrone; quinocyanine pigments;
Perylene pigments; indigo pigments such as indigo and thioindigo; azurenium salt pigments; phthalocyanine pigments such as copper phthalocyanine and titanyl phthalocyanine. The thickness of the charge generation layer is preferably 5 μm or less, particularly preferably 0.05 to 2 μm.

The single-layer type photosensitive layer contains the polymer of the present invention and the above-mentioned charge generating substance, and may further contain other resins and charge transporting substances. As the charge transport substance, not only the above-mentioned substances but also electron transport substances such as 2,4,7-trinitrofluorenone, 2,4,5,7-tetranitrofluorenone, chloranil and tetracyanoquinodimethane, and these The thing which polymerized the electron carrying substance is also mentioned. The thickness of the photosensitive layer is 5 to 40 μm.
It is particularly preferable that the thickness be 10 to 30 μm.

Examples of the material of the conductive support used in the present invention include aluminum, aluminum alloys, copper,
Zinc, stainless steel, vanadium, molybdenum, chromium,
Examples include titanium, nickel, indium, gold, platinum, and the like. In addition, a support of plastics (for example, polyethylene, polypropylene, polyvinyl chloride, polyethylene terephthalate, acrylic resin, etc.) and conductive particles (for example, carbon black, silver particles, etc.) formed by coating these metals or alloys by a vacuum deposition method. It is possible to use a support prepared by coating the above with a suitable binder resin on the above plastic, metal or alloy, or a support obtained by impregnating plastic or paper with conductive particles. The shape may be a drum shape, a sheet shape, a belt shape, or the like, but a shape most suitable for the electrophotographic apparatus to be applied is preferable.

In the present invention, an undercoat layer having a barrier function and an adhesive function may be provided between the conductive support and the photosensitive layer. The thickness of the undercoat layer is preferably 5 μm or less, and particularly preferably 0.1 to 3 μm. Examples of the material of the undercoat layer include casein, polyvinyl alcohol, nitrocellulose, polyamide (nylon 6, nylon 66, nylon 610, copolymerized nylon, alkoxymethylated nylon, etc.), polyurethane, aluminum oxide and the like.

Further, in the present invention, for the purpose of protecting the photosensitive layer from external mechanical and chemical adverse effects, a resin layer as a protective layer, or a resin layer containing conductive particles and a charge transport substance is used. Can also be provided on the photosensitive layer.

The electrophotographic photoreceptor of the present invention can be used not only in electrophotographic copying machines but also in laser beam printers, C
RT printer, LED printer, LCD printer,
It can be widely used in electrophotographic applications such as laser plate making and facsimile.

FIG. 3 shows a schematic structure of an electrophotographic apparatus having a process cartridge having the electrophotographic photosensitive member of the present invention.

In the figure, reference numeral 1 denotes a drum-shaped electrophotographic photosensitive member of the present invention, which is rotationally driven around a shaft 2 in a direction of an arrow at a predetermined peripheral speed. The photoreceptor 1 rotates during the rotation process.
The peripheral surface of the primary charging means 3 is uniformly charged with a positive or negative predetermined potential, and then image exposure light 4 from an image exposure means (not shown) such as slit exposure or laser beam scanning exposure is received. Thus, an electrostatic latent image is sequentially formed on the peripheral surface of the photoconductor 1.

The formed electrostatic latent image is then developed by the developing means 5.
The toner-developed image is developed by the toner, and the developed toner-developed image is transferred to the transfer material 7 which is fed between the photosensitive member 1 and the transfer unit 6 in synchronization with the rotation of the photosensitive member 1 from a sheet feeding unit (not shown). The images are sequentially transferred by the transfer means 6.

The transfer material 7 which has received the image transfer is separated from the surface of the photoconductor and introduced into the image fixing means 8 to undergo the image fixing, so that it is printed out to the outside of the apparatus as a copy.

The surface of the photoconductor 1 after the image transfer is cleaned by the cleaning means 9 by removing the transfer residual toner, and further pre-exposure light 10 from pre-exposure means (not shown).
Is used for image formation repeatedly after the charge removal processing. When the primary charging unit 3 is a contact charging unit using a charging roller or the like, pre-exposure is not necessarily required.

In the present invention, among the constituent elements such as the electrophotographic photosensitive member 1, the primary charging means 3, the developing means 5 and the cleaning means 9, a plurality of components are integrally combined as a process cartridge, The process cartridge may be detachably attached to the main body of an electrophotographic apparatus such as a copying machine or a laser beam printer. For example, a process in which at least one of the primary charging unit 3, the developing unit 5, and the cleaning unit 9 is integrally supported together with the photoreceptor 1 to form a cartridge, and can be attached to and detached from the apparatus main body by using a guide unit such as the rail 12 of the apparatus main body. The cartridge 11 can be used.

Further, when the electrophotographic apparatus is a copying machine or a printer, the image exposure light 4 is reflected light or transmitted light from the original, or the original is read by a sensor and converted into a signal,
Laser beam scanning and LE performed according to this signal
The light is emitted by driving the D array and driving the liquid crystal shutter array.

On the other hand, when used as a facsimile printer, the image exposure light 4 becomes exposure light for printing received data. FIG. 4 is a block diagram showing an example of this case.

The controller 14 controls the image reading unit 13 and the printer 22. The entire controller 14 is controlled by the CPU 20. The read data from the image reading unit 13 is transmitted to the partner station through the transmission circuit 16. The data received from the partner station is sent to the printer 22 through the receiving circuit 15. Predetermined image data is stored in the image memory. The printer controller 21 controls the printer 22. 17 is a telephone.

The image received from the line 18 (image information from a remote terminal connected via the line) is demodulated by the receiving circuit 15, and then the image information is decoded by the CPU 20 and sequentially stored in the image memory 19. Is stored. When the image of at least one page is stored in the image memory 19, the image of that page is recorded. CPU 20
Reads one page of image information from the image memory 19 and sends the decoded one page of image information to the printer controller 21. Upon receiving the image information of one page from the CPU 20, the printer controller 21 controls the printer 22 to record the image information of the page. The CPU 20 is receiving the next page during recording by the printer 22.

Thus, the reception and recording of the image are performed.

The electroluminescent device of the present invention has at least a light emitting layer, an anode and a cathode. The light emitting layer is a layer in which holes and electrons are recombined with each other to emit light.

In the present invention, in order to improve the efficiency of the above recombination, it is preferable to provide a hole transport layer and an electron transport layer in addition to the light emitting layer.

That is, the layers other than the electrodes in the electroluminescent device of the present invention are composed of only a light emitting layer, a light emitting layer and a hole transport layer, a light emitting layer and an electron transport layer, a hole transport layer, a light emitting layer and an electron transport layer. Is mentioned.

The light emitting layer has an injection function and a transportation function in addition to the above light emitting function. Here, the injection function means a function of injecting holes from the anode or the hole transport layer and a function of injecting electrons from the cathode or the electron transport layer when an electric field is applied. Further, the transport function is a function of transporting the injected holes and electrons by the force of the electric field. Materials used include, in addition to the polymer of the present invention, metal complexes such as aluminum-quinolinol complex, zinc-thiazole complex and beryllium-quinolinol complex, stilbenes, oxadiazoles, aromatic condensed ketones and imidazoles. And so on.

The hole transport layer is required to have a function of transporting holes to the light emitting layer under a smaller electric field, and the polymer of the present invention is preferably used.

The electron transport layer is required to have a function of transporting electrons to the light emitting layer under a smaller electric field, and triazoles and quinones are preferably used.

The method for forming each of the above layers is not particularly limited,
Examples thereof include a coating method such as dipping, spin coating and blade coating, and a vapor deposition method.
From the viewpoint of productivity, the coating method is preferable.

As the material for the anode, it is preferable to use a metal or an electrically conductive compound having a relatively large work function, and transparent electrode materials such as ITO, SnO ₂ and ZnO, and metal electrode materials such as gold and aluminum are used. Used. As the material for the cathode, it is preferable to use a metal having a relatively small work function or an electrically conductive compound, and a metal such as aluminum, magnesium, calcium, lithium, copper and silver, and a metal electrode such as an alloy or mixture of these metals. Material is used. It is preferable that at least one of these electrodes is transparent or translucent in order to increase the transmittance of light emission. The electrode is a known method,
For example, it is formed by a vapor deposition method or a sputtering method. The electroluminescent device of the present invention is preferably manufactured on a substrate, and as the substrate material, those conventionally used for electroluminescent devices, such as glass and transparent plastic, can be used.

Hereinafter, the present invention will be described in more detail with reference to examples.

[0068]

【Example】

Example 1 To a solution of 10.0 g of N, N-di-p-toluyl-4-aminophenethyl alcohol dissolved in 100 ml of tetrahydrofuran was added 5 ml of pyridine, and then 5.0 g of acrylic acid chloride was added dropwise at 10 ° C. . After the dropping, the temperature was returned to room temperature and stirring was continued for 3 hours. This liquid was added to 200 ml of water and extracted twice with 100 ml of ethyl acetate. The extract was washed with 100 ml of water three times, concentrated, and then subjected to silica gel column chromatography to develop N, N-di-p-toluyl-4-aminophenethyl as a colorless viscous liquid by developing with ethyl acetate / hexane. 9.5 g of acrylate was obtained. The yield was 80.6%.

The obtained N, N-di-p-toluyl-4-
Aminophenethyl acrylate 5.0 g toluene 15
To a solution dissolved in ml, 50 mg of azobisisobutyronitrile was added at 70 ° C. under a nitrogen stream and reacted for 3 hours. Furthermore, after reacting at 80 ° C. for 2 hours,
The reaction solution was added dropwise to 300 ml of methanol to precipitate a polymer. The precipitate was collected by filtration, dried and then dissolved in 30 ml of tetrahydrofuran.
By repeating the reprecipitation purification, which is added dropwise to ml, three times,
No. 4.2 g of a purified polymer product having 12 constituent units
I got The yield was 84.0%. In addition, G. P. C
The styrene-equivalent weight average molecular weight was 5.0 × 10 ⁴ .

The infrared absorption spectrum of the obtained polymer was measured by P
ERKIN-ELMER1600 seriesFTIR
It measured using. The results are shown in FIG. Based on the starting materials and molecular weight, the resulting polymer was identified as No. It was confirmed to be a polymer having 12 structural units.

The hole transport property of the polymer obtained by the above method was evaluated to be 3.0 × 10 ^-4 cm ² /
It was a very good V · sec.

Furthermore, when the layer formed during the evaluation of the hole transportability was visually observed, no crack was found.

Example 2 The same as Example 1 except that 4.0 g of N, N-di-p-toluyl-aminophenethyl acrylate obtained in Example 1 and 1.0 g of methyl methacrylate were dissolved in 20 ml of toluene. Then, a polymer was synthesized. The yield of the polymer was 3.8 g, the yield was 76.0%, and the weight average molecular weight was 3.2 × 10 ⁴ .

Based on the starting materials and the molecular weight, the polymer obtained was identified as No. It was confirmed that the polymer had 12 structural units and other acrylic structural units.

When the hole transport property was evaluated in the same manner as in Example 1, it was 1.0 × 10 ⁻⁴ cm ² / V · sec, which was extremely excellent, and no crack was observed. It was

Example 3 As Example 1 except that N, N-di-3,4-xylyl-4-aminobenzyl alcohol was used in place of N, N-di-p-toluyl-4-aminophenethyl alcohol. Similarly, No. 3. A purified product of a polymer having 7 structural units.
4 g were obtained. G. FIG. P. The styrene-equivalent weight average molecular weight by C was 6.4 × 10 ⁵ . The hole transport property was 2.1 × 10 ⁻⁴ cm ² / V · sec, and no crack was observed.

Example 4 The same as Example 1 except that N, N-di-p-toluyl-4-aminoheptyl alcohol was used in place of N, N-di-p-toluyl-4-aminophenethyl alcohol. No. Polymer purified product having 37 structural units 4.5
g was obtained. G. FIG. P. The styrene-equivalent weight average molecular weight by C was 4.5 × 10 ⁴ . The hole transport property was 1.1 × 10 ⁻⁴ cm ² / V · sec, and no crack was observed.

Comparative Example 1 Instead of the polymer of the present invention, the following formula

[0079]

[Outside 4] Other than using a polymer having a structural unit represented by
When a layer was formed and evaluated in the same manner as in Example 1, the hole transportability was 5.0 × 10 ⁻⁶ cm ² / V · sec, and many cracks were generated.

Comparative Example 2 The following formula was used instead of the polymer of the present invention.

[0081]

[Outside 5] Other than using a polymer having a structural unit represented by
When a layer was formed and evaluated in the same manner as in Example 1, the hole transportability was 3.0 × 10 ⁻⁶ cm ² / V · sec, and many cracks were generated.

Comparative Example 3 The following formula was used instead of the layer containing the polymer of the present invention.

[0083]

[Outside 6] A sample was prepared in the same manner as in Example 1 except that a hole-transporting layer was formed using a solution in which 5.0 g of the triarylamine compound represented by 5 and 5.0 g of polymethylmethacrylate were dissolved in 40.0 g of toluene. evaluated.

The hole transportability was 5.0 × 10 ^-7 cm ² , and although no cracks were generated, precipitation of a large number of crystals was confirmed.

Example 5 A solution prepared by dissolving 5 g of methoxymethylated nylon (number average molecular weight of 32,000) and 10 g of alcohol-soluble copolymerized nylon (number average molecular weight of 29,000) in 95 g of methanol was applied on an aluminum substrate with a wire bar. Then, an undercoat layer having a film thickness of 1 μm was formed by drying.

Next, the following formula

[0087]

[Outside 7] 5 g of the disazo pigment represented by 95 g of cyclohexanone
Polyvinyl butyral (butyralization degree 63% or more,
2g of number average degree of polymerization 2,000) was added to the solution,
It was dispersed for 20 hours using a sand mill. This dispersion was applied onto the undercoat layer with a wire bar and dried to form a charge generation layer having a thickness of 0.2 μm.

Then, a solution prepared by dissolving 3 g of the polymer obtained in Example 1 in 8 g of monochlorobenzene was applied on the charge generation layer with a wire bar and dried to form a charge transport layer having a thickness of 19 μm. did.

The obtained electrophotographic photosensitive member was subjected to -5 by using an electrostatic copying paper test device (SP-428, manufactured by Kawaguchi Electric Co., Ltd.).
The charging characteristics were evaluated by negatively charging with a corona discharge of kV, holding in the dark for 1 second, and then exposing with halogen light having an illuminance of 10 lux. As the charging characteristics, the surface potential V ₀ immediately after charging and the exposure amount necessary to attenuate the surface potentials V ₁ and V ₁ after standing in the dark for 1 second to 1/5, that is, the sensitivity (E _1/5 ) It was measured. Table 1 shows the results.

Further, the produced electrophotographic photosensitive member was attached to a cylinder of an electrophotographic copying machine NP-3825 (manufactured by Canon Inc.).

The initial dark portion potential V _D and the light portion potential _VL are set to −700 V and −200 V, respectively, and repeatedly used 5,000 times, and the dark portion potential and the bright portion potential after the initial and repeated use are measured. Thus, the durability was evaluated. Table 1 shows the results.

[0092]

[Table 10]

Examples 6 to 11 Polymers obtained in Examples 3 and 2 in place of the polymer obtained in Example 1, No. A polymer having 17 structural units,
No. No. 24 polymer, the polymer obtained in Example 4 and No. An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 5 except that the polymer having 59 structural units was used. Examples 6 to 11 were made in the above order. Table 2 shows the results.

[0094]

[Table 11]

Comparative Examples 4 to 6 Electrophotographic photosensitive members were prepared in the same manner as in Example 5 except that the polymers obtained in Comparative Examples 1 and 2 were used in place of the polymers obtained in Example 1. evaluated. These were designated as Comparative Examples 4 and 5, respectively. Table 3 shows the results.

Further, an electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 5 except that the charge transport layer was formed using the material of Comparative Example 3. However, the amount of triarylamine compound and polymethylmethacrylate used is 3
The solvent was 20 g of molychlorbenzene. This was designated as Comparative Example 6. Table 3 shows the results.

[0097]

[Table 12]

Example 12 A glass substrate with a transparent electrode in which an ITO film having a thickness of 0.1 μm was formed on a glass substrate was ultrasonically cleaned in acetone and then boiled in ethanol. Further, it was boiled in toluene and dried with hot air. This substrate was set on a spin coater, and No. Polymer having 39 structural units
A solution of 1 g dissolved in 10 g of chloroform was applied and dried to form a hole transport layer having a thickness of 0.05 μm. An aluminum complex of 8-oxyquinoline was vapor-deposited thereon under vacuum to a thickness of 0.03 μm. Further, magnesium and silver were co-evaporated at a weight ratio of 10: 1 to a thickness of 0.1 μm.

When the obtained electroluminescent device was driven by direct current in the atmosphere, the luminance was 2500 cd / m at a driving voltage of 15V.
A green emission of ² was observed. Furthermore, the brightness is 100 cd / m
^When it was driven so as to be maintained at ² , there was no decrease in brightness even after 150 hours.

Example 13 No. An electroluminescent device was prepared and evaluated in the same manner as in Example 12 except that the polymer having 44 structural units was used.

As a result, a driving voltage of 15 V was 2300 cd.
A green emission of / m ² was observed. Furthermore, the brightness is 100 cd
When it was driven so as to be maintained at / m ² , the brightness did not decrease even after 150 hours.

[0102]

As described above, according to the present invention, a polymer having extremely excellent hole transporting property, film forming property and mechanical strength, and an electrophotographic photosensitive member having excellent sensitivity, potential stability and mechanical strength. The object is to provide a body, a process cartridge and an electrophotographic apparatus having the electrophotographic photosensitive member, and an electric field generating element which can obtain high brightness at a low voltage and has excellent film-forming property and durability.

[Brief description of the drawings]

1 is a diagram showing an infrared absorption spectrum of the polymer of the present invention obtained in Example 1. FIG.

FIG. 2 is a diagram showing an infrared absorption spectrum of the polymer of the present invention obtained in Example 2.

FIG. 3 is a diagram showing a schematic configuration of an electrophotographic apparatus having a process cartridge having the electrophotographic photosensitive member of the present invention.

FIG. 4 is a diagram showing an example of a block diagram of a facsimile having the electrophotographic photosensitive member of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Electrophotographic photoreceptor of this invention 2 axis 3 Primary charging means 4 Image exposure light 5 Developing means 6 Transfer means 7 Transfer material 8 Image fixing means 9 Cleaning means 10 Pre-exposure light 11 Process cartridge 12 Rail 13 Image reading section 14 Controller 15 Receiving circuit 16 transmitting circuit 17 telephone 18 line 19 image memory 20 CPU 21 printer controller 22 printer

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Norihiro Kikuchi 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc.

Claims (10)

[Claims] 1. The following formula (1) [1] (In the formula, R ₁ , R ₂ and R ₃ are the same or different and each represents a hydrogen atom, a substituted or unsubstituted alkyl group and a halogen atom, X represents a substituted or unsubstituted alkylene group, and Ar ₁ represents a substituted or unsubstituted Represents an unsubstituted phenylene group, and Ar ₂ and Ar ₃ are the same or different and represent a substituted or unsubstituted aromatic hydrocarbon ring group and a substituted or unsubstituted aromatic heterocyclic group). A polymer having a structural unit represented by. 2. R ₁ and R ₂ in the formula (1) each represent a hydrogen atom, R ₃ represents a hydrogen atom or a methyl group, and X represents a straight-chain unsubstituted alkylene group having 1 to 10 carbon atoms. Indicates
The polymer according to claim 1, wherein Ar ₂ and Ar ₃ represent a substituted or unsubstituted phenyl group. 3. The hole transport property of the polymer is 1 × 10 ^−6.
The polymer according to claim 1, which has a cm ² / V · sec or more. 4. The hole transporting property is 1 × 10 ⁻⁵ cm ² /
The polymer according to claim 3, which has V · sec or more. 5. An electrophotographic photoreceptor having a photosensitive layer on a conductive support, wherein the photosensitive layer contains the polymer according to any one of claims 1 to 4. . 6. The photosensitive layer has a charge generation layer and a charge transport layer, and the charge transport layer contains the polymer.
The electrophotographic photosensitive member according to the above. 7. An electrophotographic photoreceptor having a photosensitive layer containing the polymer according to claim 1 on a conductive support, and selected from the group consisting of charging means, developing means and cleaning means. A process cartridge, which integrally supports at least one means described above and is detachable from the main body of the electrophotographic apparatus. 8. An electron having an electrophotographic photosensitive member having a photosensitive layer containing the polymer according to claim 1 on a conductive support, a charging unit, an exposing unit, a developing unit and a transferring unit. Photographic equipment. 9. An electroluminescent device having an electrode and a light emitting layer or an electrode, a light emitting layer and a hole transport layer, wherein the light emitting layer or the hole transport layer contains the polymer according to any one of claims 1 to 4. An electroluminescent device characterized by: 10. The electroluminescent device according to claim 9, wherein the hole transport layer contains the polymer according to any one of claims 1 to 4.