JPH05100464A - Electrophotographic sensitive body, and electrophotographic device, device unit and facsimile using that - Google Patents

Abstract

PURPOSE:To suppress cracking, to improve durability and to prevent defects in picture images by incorporating a resin obtd. by hardening photosetting acryl monomers into a protective layer and incorporating a specified compd. into a photosensitive layer. CONSTITUTION:A resin obtd. by hardening photosetting acryl monomers is incorporated into a protective layer and at least one compd. selected from formulae I-III is incorporated into a photosensitive layer. A compd. of formula I is a styryl compd. having <=135 deg.C melting point. In formula I, Ar<1> and Ar<2> are aromatic ring groups, Ar<3> is a bivalent aromatic ring group or bivalent heteroring group, R<1> is an alkyl group or aromatic ring group, R<2> is a hydrocyclic atom, alkyl group or aromatic ring group, and n1 is 1 or 2. The compd. of formula II is a triaryl compd. having <=150 deg.C melting point. In formula II, Ar<4>-Ar<6> are aromatic ring groups or bivalent heterocyclic groups. The compd. of formula III is a hydrazone compd. having <=155 deg.C melting point and R<3> is an alkyl group, etc., R<4> and R<5> are aralkyl groups, etc., and n2 is 1 or 2.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic photoreceptor, and more particularly to an electrophotographic photoreceptor having a protective layer containing a specific resin and a photosensitive layer containing a specific compound. The present invention also relates to an electrophotographic apparatus, an apparatus unit and a facsimile having the above electrophotographic photosensitive member.

[0002]

2. Description of the Related Art Needless to say, an electrophotographic photosensitive member is required to have required sensitivity, electric characteristics and optical characteristics according to an electrophotographic process to be applied. In particular, in the case of a photoconductor that is repeatedly used, electrical and mechanical external forces such as corona charging, image exposure, toner development, transfer to paper and cleaning are directly applied to the surface of the photoconductor, Durability against them is required. In particular,
It is required to have durability against abrasion and scratches on the surface of the photosensitive member caused by rubbing on the surface of the photosensitive member during transfer and cleaning, and deterioration of the photosensitive member and potential characteristics due to ozone generated during corona charging. Further, there is a problem that toner is attached to the surface of the photoconductor due to repeated toner development and cleaning, and good cleaning property is also required.

In order to satisfy the above-mentioned characteristics required for a photoreceptor, attempts have been made to provide a surface protective layer containing a resin as a main component on the photosensitive layer. For example, JP-A-56-4
2863 and Japanese Patent Application Laid-Open No. 53-103741 propose to improve hardness and wear resistance by using a protective layer containing a curable resin as a main component.

However, when these curable resins are used as the surface protective layer, particularly when the lower photosensitive layer is an organic photosensitive layer containing a resin as a main component, it occurs when the curable resin is cured. The shrinkage may cause cracks in the protective layer and the photosensitive layer, resulting in defects in the obtained image.

Further, in order to obtain a better image, the protective layer of the photoconductor is required to have not only characteristics such as high hardness and excellent abrasion resistance but also appropriate resistance of the protective layer itself. It When the resistance of the protective layer is too high, by repeating the electrophotographic process such as charging-exposure, electric charge is accumulated in the protective layer, so-called increase in residual potential occurs,
The image quality becomes unstable because the potential is not stable when the photoconductor is repeatedly used. If the resistance is too low, the electrostatic latent image flows in the surface direction in the protective layer, and problems such as image bleeding and blurring occur. To solve this problem, for example, JP-A-57-30843 proposes to control the resistance of the layer by adding a metal oxide as conductive fine particles to the protective layer.

However, also in this protective layer, when a curable resin is used as the resin and an organic photosensitive layer is used as the photosensitive layer, cracks may occur in the protective layer and the photosensitive layer.

With the recent improvement in image quality and durability,
Electrophotographic photoreceptors having higher durability and capable of stably providing excellent images have been studied.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to provide an electrophotographic photosensitive member which suppresses cracking of the photosensitive member during formation of the protective layer, has high durability and does not cause image defects. ..

Another object of the present invention is to provide an electrophotographic photosensitive member which does not accumulate residual potential in repeated electrophotographic processes and can maintain high quality image quality.

A further object of the present invention is to provide an electrophotographic apparatus, an apparatus unit and a facsimile having the above electrophotographic photosensitive member.

[0011]

That is, the present invention is an electrophotographic photosensitive member having a conductive support, a photosensitive layer and a protective layer, wherein the protective layer is formed by curing a photocurable acrylic monomer. A styryl compound containing a resin having the following formula (A), (B) and (C) (A) having a structure represented by the following formula (1) and having a melting point of 135 ° C. or lower.

[0012]

[Outside 4] (In the formula, Ar ¹ and Ar ² represent an aromatic ring group, and Ar ³ represents 2
Represents a valent aromatic ring group or a divalent heterocyclic group, R ¹ represents an alkyl group or an aromatic ring group, R ² represents a hydrogen atom, an alkyl group or an aromatic ring group, and n ₁ is 1 or 2. , N ₁ = 1 and R ¹ and R ² may combine to form a ring. (B) A triarylamine compound having a structure represented by the following formula (2) and having a melting point of 150 ° C. or lower.

[0013]

[Outside 5] (In the formula, Ar ⁴ , Ar ⁵ and Ar ⁶ each represent an aromatic ring group or a heterocyclic group.) (C) A hydrazone having a structure represented by the following formula (3) and having a melting point of 155 ° C. or lower. Compound

[0014]

[Outside 6] (In the formula, R ³ represents a hydrogen atom or an alkyl group, R ⁴ and R ⁵ represent an alkyl group, an aralkyl group or an aromatic ring group,
n ₂ is 1 or 2, and A is an aromatic ring group, a heterocyclic group or-
CH = C (R ⁶ ) R ⁷ (R ⁶ and R ⁷ represent a hydrogen atom, an aromatic ring group or a heterocyclic group, but R ⁶ and R ⁷ are not hydrogen atoms at the same time). An electrophotographic photoreceptor containing at least one compound selected from the group consisting of

The present invention also provides an electrophotographic apparatus, an apparatus unit and a facsimile having the above electrophotographic photosensitive member.

The protective layer of the electrophotographic photoreceptor of the present invention contains a resin obtained by curing a photocurable acrylic monomer (hereinafter, also referred to as the acrylic monomer of the present invention).

As an attempt to use a curable acrylic resin for a protective layer for a photoconductor, for example, Japanese Patent Laid-Open Nos. 61-5253 and 1-178972 disclose examples of using a thermosetting acrylic resin. There is. However, when these thermosetting acrylic resins are coated on the organic photosensitive layer and thermally cured, the curing agent, acrylic monomer, acrylic oligomer, etc. migrate to the photosensitive layer at the time of temperature rise and charge transport material or charge Reacting with the generated material causes adverse effects such as a decrease in sensitivity and an increase in residual potential.

Therefore, as a result of various studies, the present inventors
It has been found that this adverse effect is eliminated by using a photocurable acrylic monomer.

The resin obtained from the photo-curable acrylic monomer has sufficient hardness, which is one of the important characteristics required for the protective layer.

Examples of the acrylic monomer of the present invention are shown below, but the invention is not limited thereto.

[0021]

[Outside 7]

[0022]

[Outside 8]

[0023]

[Outside 9]

[0024]

[Outside 10]

[0025]

[Outside 11]

However, R and R'in the above formulas are respectively the following formulas.

[0027]

[Outside 12]

In the present invention, two or more kinds of photocurable acrylic monomers can be used, and other resins such as polyester, polycarbonate, polyurethane, acrylic resin, epoxy resin, silicone resin,
It can also be used as a mixture with a resin such as an alkyd resin and a vinyl chloride-vinyl acetate copolymer.

When curing the acrylic monomer of the present invention, a photoinitiator is used. The addition amount of the photoinitiator is preferably 0.1 to 40% by weight, and particularly preferably 0.5 to 20% by weight, based on the total weight of the acrylic monomer. The photoinitiators used are shown below, but are not limited thereto.

[0030]

[Outside 13]

From the viewpoint of controlling the resistance of the protective layer, the protective layer of the present invention preferably contains conductive particles such as metal oxide particles dispersed therein.

Examples of such conductive metal oxides include particles of zinc oxide, titanium oxide, tin oxide, antimony oxide, indium oxide, bismuth oxide, indium-doped tin oxide, antimony-doped tin oxide and zirconium oxide. Is mentioned. These metal oxides may be used alone or in combination of two or more. When two or more kinds are mixed, they may be in the form of solid solution or fusion.
The content of the metal oxide particles in the present invention is preferably 5 to 90% by weight, more preferably 10 to 90% by weight, based on the total weight of the protective layer. When the content of the metal oxide is less than 5% by weight, the resistance value as the protective layer may be too high, and when it is more than 90% by weight, the resistance of the surface layer of the photoreceptor tends to be low, resulting in charging. It may cause deterioration of performance and pinholes.

When the conductive particles are dispersed in the protective layer, the particle diameter is preferably smaller than the wavelength of the incident light in order to prevent scattering of the incident light by the dispersed particles. Generally, the number average particle diameter is 0.3 μm. The following is preferable. Thus, the smaller the particle size of the dispersed particles, the more difficult it is for the dispersed particles to disperse. Therefore, in the present invention, a photocurable acrylic monomer having 3 or more functional groups per molecule, or a unit weight It is preferable to use a photocurable acrylic monomer having a functional group number of 0.004 mol / g or more. Thus, having a large number of functional groups in one molecule is preferable in terms of hardness because the structure of the resin tends to be more three-dimensional.

Further, in the present invention, various coupling agents and antioxidants may be added to the protective layer in order to further improve dispersibility, adhesiveness, environment resistance and the like.

The thickness of the protective layer used in the present invention is 0.1.
10 μm is preferable, and 0.5 to 7 μm is particularly preferable.
It is preferably m.

Examples of the method of applying the protective layer include a spray coating method, a beam coating method and a dip coating method.

As described above, when the protective layer using the curable resin is provided on the organic photosensitive layer, the protective layer and the photosensitive layer tend to be cracked. Although the detailed mechanism of cracking of the photoreceptor due to coating and curing of the protective layer is currently unknown, it can be easily inferred that the shrinkage of the film that occurs during curing of the protective layer is one of the causes. It is considered that this is also due to the structure of the curable monomer used for the layer resin. Specifically, it is considered that cracks tend to occur more easily as the number of functional groups per molecule of the monomer increases and as the number of functional groups per unit weight of the monomer increases. However, as described above, as the monomer for the protective layer, the higher the number of functional groups per molecule of the photocurable acrylic monomer, or the higher the number of functional groups per unit weight, the higher the hardness, the abrasion resistance and the abrasion resistance. When the conductive particles are dispersed in the protective layer, the dispersibility improves as the number of functional groups of the photocurable acrylic monomer increases. Therefore, the effect of using the photocurable acrylic monomer having a large number of functional groups as a monomer of the resin for the protective layer is great, and the resin is used to form the protective layer on the organic photosensitive layer without causing cracks. Inventing the technology was very beneficial.

As a result of various studies, the present inventors have found that cracking of a photoreceptor can be prevented by providing the protective layer of the present invention on a photosensitive layer containing a charge transport material having a specific structure and melting point. They have found the present invention and have reached the present invention.

Compound (A) used in the present invention,
(B) and (C) will be described in more detail.

In the formula (1), Ar ¹ and Ar ² represent aromatic ring groups such as phenyl, naphthyl and anthryl.
Ar ³ represents a divalent aromatic ring group or a divalent heterocyclic group obtained by removing two hydrogen atoms from an aromatic ring such as benzene, naphthalene and anthracene or a heterocycle such as thiophene and furan. R ¹ represents an alkyl group such as methyl, ethyl, propyl and butyl, or an aromatic ring group such as phenyl and naphthyl. R ² represents an alkyl group such as methyl, ethyl, propyl and butyl; an aromatic ring group such as phenyl and naphthyl, or a hydrogen atom. N ₁ represents 1 or 2.

Ar ¹ , Ar ² , Ar ³ , R ¹ and R ² may each have a substituent, and the substituent which may be substituted is an alkyl group such as methyl, ethyl, propyl and butyl. An alkoxy group such as methoxy, ethoxy and propoxy; an aryloxy group such as phenoxy and naphthoxy; a halogen atom such as fluorine, chlorine and bromine; or a disubstituted amino group such as dimethylamino, diethylamino and diphenylamino. When n ₁ = 1
R ¹ and R ² may form a ring directly or by bonding via a carbon atom, a sulfur atom, an oxygen atom or the like.

In the formula (2), Ar ⁴ , Ar ⁵ and A
r ⁶ is an aromatic ring group such as phenyl, naphthyl, anthryl, pyrenyl, fluorenyl, phenanthryl, 9,10-dihydrophenanthryl and fluorenonyl, or pyridyl, quinolyl, dibenzothenyl, dibenzofuryl,
N-methylcarbazole, N-ethylcarbazole and N-
A heterocyclic group such as tolylcarbazole is shown.

Ar ⁴ , Ar ⁵ and Ar ⁶ may each have a substituent, and the substituent which may be substituted is an alkyl group such as methyl, ethyl, propyl and butyl; benzyl, phenethyl and naphthyl. Aralkyl groups such as methyl; alkoxy groups such as methoxy, ethoxy and propoxy; aryloxy groups such as phenoxy and naphthoxy;
Halogen atoms such as fluorine, chlorine, bromine and iodine; aromatic ring groups such as phenyl and biphenyl; diarylamino groups such as diphenylamino and ditolylamino; dialkylamino groups such as dimethylamino and diethylamino; such as dibenzylamino and diphenethylamino Diaralkylamino groups; alkylaralkylamino groups such as benzylmethylamino and benzylethylamino; nitro groups and hydroxy groups.

In the formula (3), R ³ represents an alkyl group such as methyl, ethyl and propyl or a hydrogen atom. R ⁴
And R ⁵ represents an alkyl group such as methyl, ethyl and propyl, an aralkyl group such as benzyl and phenethyl, or an aromatic ring group such as phenyl, naphthyl and anthryl.
Incidentally, R ⁴ and R ⁵ may combine with each other to form a ring. n ₂ represents 1 or 2. R ³ , R ⁴ and R ⁵ may each have a substituent, and as the substituent which may be substituted, an alkyl group such as methyl and ethyl; an alkoxy group such as methoxy and ethoxy; And halogen atoms such as chlorine and bromine.

A is an aromatic ring group such as phenyl, naphthyl, anthryl and pyrenyl; a heterocyclic group such as cenyl, furyl, N-methylcarbazole and N-ethylcarbazole; or --CH═C (R ⁶ ) R ⁷ (here At R ⁶ and R ⁷
Represents a hydrogen atom, an aromatic ring group or a heterocyclic group, and R ⁶ and R
⁷ is not a hydrogen atom at the same time). Also,
These aromatic ring group and heterocyclic group may have a substituent, and as the substituent which may be substituted, an alkyl group such as methyl and ethyl; an alkoxy group such as methoxy and ethoxy;
Halogen atom such as fluorine, chlorine and bromine; Dialkylamino group such as dimethylamino and diethylamino; Diaralkylamino group such as dibenzylamino and diphenethylamino; or Diarylamino group such as diphenylamino and di (p-tolyl) amino Etc.

The styryl compound having the structural formula (1) and its melting point are shown below. Exemplified compound No.
(1) -1 to (1) -22 are styryl compounds having a melting point of 135 ° C. or less and used in the present invention. (1) -23 ~
(1) -40 has the structure represented by the formula (1), but 13
Since it does not have a melting point of 5 ° C. or lower, it is a styryl compound outside the present invention. Of course, the styryl compound used in the present invention is not limited to these.

[0047]

[Table 1]

[0048]

[Table 2]

[0049]

[Table 3]

[0050]

[Table 4]

[0051]

[Table 5]

[0052]

[Table 6]

[0053]

[Table 7]

[0054]

[Table 8]

Next, the triarylamine compound having the structural formula represented by the formula (2) and its melting point are shown. Exemplified compound No. (2) -1 to (2) -45 are triarylamine compounds having a melting point of 150 ° C. or less and used in the present invention.
o. (2) -46 to (2) -72 have the structure represented by the formula (2) but do not have a melting point of 150 ° C. or less, and thus are triarylamine compounds outside the present invention. Of course, the triarylamine compound used in the present invention is not limited to these.

[0056]

[Table 9]

[0057]

[Table 10]

[0058]

[Table 11]

[0059]

[Table 12]

[0060]

[Table 13]

[0061]

[Table 14]

[0062]

[Table 15]

[0063]

[Table 16]

[0064]

[Table 17]

[0065]

[Table 18]

[0066]

[Table 19]

[0067]

[Table 20]

[0068]

[Table 21]

[0069]

[Table 22]

[0070]

[Table 23]

Next, the hydrazone compound having the structural formula (3) and its melting point are shown. Exemplified compound No.
(3) -1 to (3) -27 are hydrazone compounds having a melting point of 155 [deg.] C. or less and used in the present invention. (3) -28
To (3) -47 have the structure represented by the formula (3), but 1
Since it does not have a melting point of 55 ° C. or lower, it is a hydrazone compound outside the present invention. Of course, the hydrazone compound used in the present invention is not limited to these.

[0072]

[Table 24]

[0073]

[Table 25]

[0074]

[Table 26]

[0075]

[Table 27]

[0076]

[Table 28]

[0077]

[Table 29]

[0078]

[Table 30]

[0079]

[Table 31]

[0080]

[Table 32]

[0081]

[Table 33]

The photosensitive layer of the electrophotographic photosensitive member of the present invention is composed of a single layer type containing a charge generating material and a charge transporting material in the same layer, or a charge transporting layer containing a charge transporting material. It may be a laminated type in which a charge generating layer containing a generating material is functionally separated.

The laminated type photosensitive layer will be described below.
As the constitution of the laminated type photosensitive layer, there are one in which a charge transport layer is laminated on the charge generation layer and one in which a charge generation layer is laminated on the charge transport layer.

The charge transport layer in the present invention is a coating liquid prepared by dissolving at least one of the compounds (A), (B) and (C), which are charge transport materials, in a resin having film-forming properties using a suitable solvent. It is formed by applying and drying.
As such a resin, in addition to the resin obtained by curing the acrylic monomer of the present invention, a conventionally used resin for a charge transport layer can be used, and examples thereof include polyester, polycarbonate, polymethacrylic acid ester and polystyrene. Etc. The thickness of the charge transport layer is preferably 5 to 40 μm, particularly 10 to
It is preferably 30 μm. In the present invention, a charge transport material other than the compounds (A), (B) and (C) can be further added.

The charge generation layer in the present invention is formed by applying and drying a dispersion liquid in which a charge generation material is dispersed in a binder resin. Examples of the binder resin include resins obtained by curing the acrylic monomer of the present invention, polyvinyl butyral, polystyrene, polyvinyl acetate, acrylic resins, cellulose acetate and ethyl cellulose. As the charge generating material, 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, and particularly preferably 0.05 to 2 μm.

Next, the single-layer type photosensitive layer will be described.
The single-layer type photosensitive layer has at least one of the compounds (A), (B) and (C) and a charge generation material dissolved in the resin,
It is formed by applying and drying the dispersed liquid.
The thickness of the single-layer type photosensitive layer is preferably 5 to 40 μm, and particularly preferably 10 to 30 μm.

The conductive support used in the present invention may be any one as long as it has conductivity. For example, metals and alloys such as aluminum, chromium, nickel, stainless steel, copper and zinc; aluminum and copper, etc. Metal foil laminated on a plastic film; aluminum, indium oxide, tin oxide, etc. deposited on a plastic film; or metal or plastic in which a conductive material is applied alone or with a suitable binder resin to form a conductive layer Examples include films and papers.

As the conductive substance used in this conductive layer, metal powder such as aluminum, copper, nickel and silver,
Metal foil and metal fiber; Conductive metal oxide such as antimony oxide, indium oxide and tin oxide; Polymer conductive material such as polypyrrole, polyaniline and polymer electrolyte; Carbon black, graphite powder and organic or inorganic electrolyte; or Examples thereof include conductive powders whose surfaces are coated with these conductive substances.

The conductive support has a drum shape,
Examples thereof include a sheet shape and a belt shape, but an arbitrary shape most suitable for the electrophotographic apparatus to be applied is preferable.

An undercoat layer may be provided between the conductive support and the photosensitive layer. The undercoat layer functions as a barrier layer or an adhesive layer for controlling charge injection at the interface with the photosensitive layer. The undercoat layer is mainly composed of a binder resin, but may contain the above-mentioned metals or alloys, or oxides, salts and surfactants thereof. As the binder resin forming the undercoat layer, polyester, polyurethane, polyacrylate, polyethylene, polystyrene, polybutadiene, polycarbonate, polyamide, polypropylene, polyimide, phenol resin, acrylic resin, silicone resin, epoxy resin, urea resin, allyl resin , Alkyd resin, polyamideimide, polysulfone, polyallyl ether, polyacetal and butyral resin. The thickness of the undercoat layer is preferably 0.05 μm to 7 μm, more preferably 0.1 μm to 2 μm.

The various layers described above can be formed by vapor deposition or coating. In particular, the coating method is preferable because it can form a wide range of films from thin films to thick films, and films of various compositions. Examples of the coating method include a dip coating method, a spray coating method, a beam coating method, a bar coating method, a blade coating method and a roller coating method.

The electrophotographic photoreceptor of the present invention can be used not only in an electrophotographic copying machine but also in a laser beam printer,
It can be widely used in electrophotographic application fields such as CRT printers, LED printers, liquid crystal printers, facsimiles, and laser plate making machines.

FIG. 1 shows a schematic constitutional example of a transfer type electrophotographic apparatus using the electrophotographic photosensitive member of the present invention.

In the figure, reference numeral 1 denotes a drum type electrophotographic photosensitive member of the present invention as an image bearing member, which is rotationally driven around an axis 1a in a direction of an arrow at a predetermined peripheral speed. In the course of its rotation, the photosensitive member 1 is uniformly charged with a predetermined positive or negative potential on its peripheral surface by the charging means 2, and then at the exposure section 3 an optical image exposure L (slit exposure Laser beam scanning exposure). As a result, electrostatic latent images corresponding to the exposed images are sequentially formed on the peripheral surface of the photoconductor.

The electrostatic latent image is then developed with toner by the developing means 4, and the toner developed image is rotated by the transfer means 5 between the photoconductor 1 and the transfer means 5 from a paper feeding portion (not shown). The transfer material P is sequentially transferred onto the surface of the transfer material P that is synchronized and fed.

The transfer material P which has received the image transfer is separated from the surface of the photoconductor and is introduced into the image fixing means 8 where it is subjected to image fixing and printed out as a copy.

After the image transfer, the surface of the photoconductor 1 is cleaned by the cleaning means 6 to remove residual toner after transfer, and is further discharged by the pre-exposure means 7 to be repeatedly used for image formation.

As the uniform charging means 2 for the photosensitive member 1, a corona charging device is generally widely used. In addition, the transfer device 5
Corona transfer means are also widely used. The electrophotographic apparatus is configured by integrally combining a plurality of components, such as the above-described photoconductor, developing unit, and cleaning unit, as an apparatus unit, and this unit is configured to be detachable from the apparatus main body. May be. For example, photoconductor 1
The cleaning means 6 and the cleaning means 6 may be integrated into one apparatus unit, and may be detachably configured by using a guide means such as a rail of the apparatus body. At this time, the above device unit may be provided with a charging unit and / or a developing unit.

When the electrophotographic apparatus is used as a copying machine or a printer, the optical image exposure L irradiates the photoconductor with reflected light or transmitted light from the original, or the original is read by a sensor and converted into a signal, In accordance with this signal, the laser beam is scanned, the LED array is driven, or the liquid crystal shutter array is driven to irradiate the photoconductor with light.

When used as a printer for a facsimile, the optical image exposure L becomes an exposure for printing received data. FIG. 2 is a block diagram showing an example of this case.

The controller 11 controls the image reading section 10 and the printer 19. The entire controller 11 is CP
It is controlled by U17. The read data from the image reading unit 10 is transmitted to the partner station via the transmission circuit 13. The data received from the partner station is sent to the printer 19 through the receiving circuit 12. The image memory 16 stores predetermined image data. The printer controller 18 controls the printer 19. 14 is a telephone.

The image information received from the line 15 (image information from a remote terminal connected via the line) is demodulated by the receiving circuit 12, then decoded by the CPU 17, and sequentially stored in the image memory 16. Is stored. When the image information of at least one page is stored in the memory 16, the image recording of that page is performed. The CPU 17 reads the image information of one page from the memory 16 and sends the decoded image information of one page to the printer controller 18. When the printer controller 18 receives the image information of one page from the CPU 17, the printer controller 18 controls the printer 19 to record the image information of the page.

The CPU 17 is receiving the next page while the printer 19 is recording.

Images are received and recorded as described above.

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

[0106]

【Example】

1. 10 parts of alcohol-soluble copolymer nylon resin (weight average molecular weight 29000) and 30 parts of methoxymethylated 6 nylon resin (weight average molecular weight 32000) were dissolved in a mixed solvent of 260 parts of methanol and 40 parts of butanol.
This prepared solution was applied onto a glass substrate by dip coating to form an undercoat layer having a thickness of 1 μm.

Next, 10 parts of the exemplified styryl compound (1) -4 as a charge transport material and 10 parts of polycarbonate (weight average molecular weight of 46000) were dissolved in a mixed solvent of 20 parts of dichloromethane and 40 parts of monochlorobenzene, This solution is dip-coated on the above-mentioned undercoat layer,
After drying at 60 ° C. for 60 minutes, a charge transport layer having a thickness of 18 μm was formed. Next, the following formula

[0108]

[Outside 14] 4 parts of a disazo pigment represented by: polyvinyl butyral (butyralization rate: 68%, weight average molecular weight: 24000)
2 parts and 34 parts of cyclohexanone were dispersed in a sand mill using φ1 mm glass beads for 12 hours, and then 60 parts of tetrahydrofuran (THF) was added to prepare a charge generation layer dispersion liquid. This dispersion is spray-coated on the charge transport layer and dried at 80 ° C. for 15 minutes to give a film thickness of 0.2.
A 0 μm charge generation layer was formed to obtain a laminated type photosensitive layer.

Next, the exemplified acrylic monomer (20)
60 parts, 30 parts of tin oxide ultrafine particles having an average particle size before dispersion of 400Å, 2-methylthioxanthone 2 as a photoinitiator
Parts, 100 parts of toluene and 200 parts of methyl cellosolve were dispersed in a sand mill for 48 hours.

Using this dispersion, a film was formed on the above photosensitive layer by the beam coating method, dried, and then cured by a high pressure mercury lamp at a light intensity of 8 mW / cm ² for 20 seconds to protect it. Layers were obtained. At this time, the film thickness of the protective layer was 4 μm. Also, the protective layer preparation liquid had good dispersibility, and the surface of the protective layer was a uniform and even surface.

Next, the state of cracking was observed with a transmission microscope while irradiating the photoreceptor with light from the back surface at an angle of 15 °.

The evaluation was judged by the state of crack generation in the entire visual field of a microscope of 10 times, and was ranked by ○, Δ and ×. ○: no cracks, △: relatively small (within 1 cm)
The number of cracks is 5 or less, and x indicates that the number of cracks is 6 or more or a large crack exceeding 1 cm is generated.

The photoconductors using the styryl compounds shown in Table 1 were evaluated in the same manner.

The results are shown in Table 1.

[0115]

[Table 34]

As shown in Table 1, the occurrence of cracks on the photoconductor became smaller as the melting point of the charge transport material decreased, and
It does not occur at temperatures below ℃.

50 parts of conductive titanium oxide powder coated with tin oxide containing 2.10% antimony oxide, 25 parts of phenol resin, 20 parts of methyl cellosolve, methanol part and silicone oil (polydimethylsiloxane polyoxyalkylene Polymer, average molecular weight 3000) 0.
002 parts were dispersed for 2 hours by a sand mill apparatus using φ1 mm glass beads to prepare a conductive layer coating material. The above coating material is applied by dipping onto an aluminum cylinder (φ30 mm × 260 mm) and dried at 140 ° C. for 30 minutes,
A conductive layer having a film thickness of 20 μm was formed.

Next, after forming an undercoat layer in the same manner as in Example 1, the above-mentioned styryl compound No. 1 was used as a charge transport material. A photosensitive layer was prepared by forming a photosensitive layer and a protective layer in the same manner as in Example 1 except that (1) -17 was used.

The electrophotographic photosensitive member produced in this manner was mounted on a copier of a positive development system in which the process of charging-exposure-developing-transfer-cleaning was repeated in a cycle of 1.5 seconds, and electrophotographic was carried out at room temperature and normal humidity. The characteristics were evaluated, and a repeated image development durability test was repeated 10,000 times.

The results are shown in Table 2. As shown in Table 2, the sensitivity and residual potential were the same as those of the photoconductor of Comparative Example 1 without the protective layer, and a stable image without unevenness or black spots could be maintained. Further, with the photoreceptor of the present invention, it was possible to obtain a stable image without causing image deterioration such as black bands (black band-shaped image defects).

3 to 7. As the charge transport material, the exemplified styryl compound No. (1) -7, (1) -9, (1) -1
3, (1) -16, and (1) -20, and the above exemplified monomers (2), (7), (13), (15), and (18) are used as acrylic monomers for the protective layer, respectively. Others were made in the same manner as in Example 2 and evaluated.

The results are shown in Table 2.

8. A conductive layer and an undercoat layer were provided on an aluminum cylinder in the same manner as in Example 2.

Next, the following formula

[0125]

[Outside 15] 4 parts of disazo pigment represented by the formula, polyvinyl benzal (benzalization rate 80%, weight average molecular weight 11,000)
After 2 parts and 30 parts of cyclohexanone were dispersed in a sand mill using φ1 mm glass beads for 20 hours, 60 parts of methyl ethyl ketone was added to prepare a dispersion liquid for the charge generation layer.

This dispersion was spray-coated on the undercoat layer and dried at 80 ° C. for 15 minutes to form a charge generation layer having a thickness of 0.20 μm.

Next, the exemplified styryl compound No. (1)
-20 parts of a charge transport material of -21 and 10 parts of polycarbonate (weight average molecular weight 25,000) were added to 20 parts of dichloromethane.
Part, and dissolved in a mixed solvent of 40 parts of monochlorobenzene,
This solution is applied onto the undercoat layer by dip coating at 60 ° C at 60 ° C.
After drying for a minute, a charge transport layer having a film thickness of 15 μm was formed.

A protective layer similar to that of Example 2 was provided on this charge transport layer to obtain an electrophotographic photosensitive member.

The electrophotographic photosensitive member thus manufactured was attached to a reversal development type laser printer in which the process of charging-laser exposure-developing-transfer-cleaning is repeated in a cycle of 1.5 seconds, and the electrophotographic characteristic of electrophotographic characteristics is maintained under normal temperature and pressure. The evaluation was performed, and the repeated image development durability test was repeated 10,000 times.

The results are shown in Table 2.

9. A photosensitive layer was formed in exactly the same manner as in Example 8. Next, 20 parts of the exemplified acrylic monomer (21), 30 parts of methanol, and 50 parts of methoxypropanol.
And 2 parts of 2-methylthioxanthone as a photoinitiator are dip-coated on the photosensitive layer, dried at 60 ° C. for 1 hour, and then protected by curing with a high-pressure mercury lamp in the same manner as in Example 1. Layers were provided. The thickness of the protective layer is 0.8 μm
Met. The obtained photoreceptor was evaluated in the same manner as in Example 8.

The results are shown in Table 2.

10-12. A photoconductor was prepared and evaluated in the same manner as in Example 2 except that the charge transport material had the composition shown below.

The results are shown in Table 2.

Example 10: Exemplified Styryl Compound No.
(1) -15 50 parts, No. (1) -29 50 parts Example 11: Exemplified styryl compound No. (1) -3
20 parts, No. (1) -30 80 parts Example 12: Exemplified styryl compound No. (1) -21
60 parts, No. (1) -31 40 parts (Comparative Example 1) Except that the protective layer of Example 2 was not formed,
A photoconductor was prepared and evaluated in the same manner as in Example 2. As a result, as shown in Table 2, the initial electrophotographic characteristics were good, but when the durability test was carried out, after 300 sheets, the charge generation layer on the surface was scraped and it was difficult to obtain a good image.

Comparative Example 2 A photoconductor was prepared in the same manner as in Example 2 except that the binder resin in the protective layer of Example 2 was changed to the polycarbonate resin. Using this photoreceptor, the same evaluation as in Example 2 was performed.

The results are shown in Table 2.

Comparative Examples 3 to 5 As the charge transport material, the above-exemplified styryl compound No. (1) -26, (1) -28
A photoconductor was prepared and evaluated in the same manner as in Example 2 except that (1) -38 was used.

The results are shown in Table 2.

[0140]

[Table 35]

13. A photoreceptor was prepared and evaluated in the same manner as in Example 1 except that the triarylamine compound shown in Table 3 was used as the charge transport material.

The results are shown in Table 3.

[0143]

[Table 36]

As shown in Table 3, the generation of cracks on the photosensitive member became smaller as the melting point of the charge transporting material became lower.
It does not occur at temperatures below ℃.

14. As the charge transport material, the above-mentioned triarylamine compound No. A photoconductor was prepared and evaluated in the same manner as in Example 2 except that (2) -18 was used.

The results are shown in Table 4. As shown in Table 4, the sensitivity and the residual potential were the same as those of the photoconductor of Comparative Example 6 having no protective layer, and a stable image without unevenness or black spots could be maintained. Further, with the photoreceptor of the present invention, it was possible to obtain a stable image without causing image deterioration such as black bands (black band-shaped image defects).

15-19. As the charge transport material, the above-mentioned triarylamine compound No. (2) -4, (2)-
17, (2) -19, (2) -30, and (2) -38.
And the above exemplified monomers (2), (7), (13), and (15) as acrylic monomers for the protective layer, respectively.
A photoconductor was prepared and evaluated in the same manner as in Example 2 except that (18) and (18) were used.

The results are shown in Table 4.

20. The thickness of the charge generation layer was set to 0.10 μm, and the above-mentioned triarylamine compound No. 1 was used as the charge transport material. A photoconductor was prepared and evaluated in the same manner as in Example 8 except that (2) -8 was used.

The results are shown in Table 4.

21. The process up to the photosensitive layer was performed in the same manner as in Example 20. (2
A photoconductor was prepared and evaluated in the same manner as in Example 9 except that the above (0) was used.

The results are shown in Table 4.

22 to 24. A photoreceptor was prepared and evaluated in the same manner as in Example 14 except that the charge transport material had the composition shown below.

The results are shown in Table 4.

Example 22: Exemplified Triarylamine Compound No. (2) -3 50 parts, No. (2) -50
50 parts Example 23: Exemplified triarylamine compound No.
(2) -18 20 parts, No. (2) -53 80 parts Example 24: Exemplified triarylamine compound No.
(2) -40 60 parts, No. (2) -57 40 parts (Comparative Example 6) A photoreceptor was prepared and evaluated in the same manner as in Example 14 except that the protective layer of Example 14 was not formed.

As a result, as shown in Table 4, the electrophotographic characteristics were good in the initial stage, but the endurance test was performed to give 300.
With the sheet, the charge generation layer on the surface was scraped off, and it became difficult to obtain a good image.

Comparative Example 7 Example 14 was repeated except that the binder resin in the protective layer of Example 14 was changed to a polycarbonate resin.
A photoconductor was prepared in the same manner as in. Using this photoconductor,
The same evaluation as in Example 14 was performed.

The results are shown in Table 4.

(Comparative Examples 8 to 10) As charge transport materials,
The triarylamine compound No. (2) -53,
Example 1 except that (2) -59 and (2) -72 were used.
A photoreceptor was prepared and evaluated in the same manner as in 4.

The results are shown in Table 4.

[0161]

[Table 37]

25. A photoreceptor was prepared and evaluated in the same manner as in Example 1 except that the hydrazone compounds shown in Table 5 were used as the charge transport material.

The results are shown in Table 5.

[0164]

[Table 38]

As shown in Table 5, the occurrence of cracks on the photosensitive member became smaller as the melting point of the charge transport material decreased, and
It does not occur at all below 5 ° C.

26. As the charge transport material, the above-mentioned hydrazone compound No. A photoconductor was prepared and evaluated in the same manner as in Example 2 except that (3) -17 was used.

The results are shown in Table 6. As shown in Table 6, the sensitivity and residual potential were the same as those of the photoreceptor of Comparative Example 11 without the protective layer, and a stable image without unevenness or black spots could be maintained. Further, with the photoreceptor of the present invention, it was possible to obtain a stable image without causing image deterioration such as black bands (black band-shaped image defects).

27-31. As the charge transport material, the above-mentioned hydrazone compound No. (3) -4, (3) -13,
(3) -15, (3) -18, and (3) -27 are used, and the above-exemplified monomers (2), (7), (13), (15), and () are used as acrylic monomers for the protective layer. A photoreceptor was prepared and evaluated in the same manner as in Example 2 except that 18) was used.

The results are shown in Table 6.

32. The thickness of the charge generation layer is 0.10 μm, and the above-mentioned hydrazone compound N is used as the charge transport material.
o. A photoconductor was prepared and evaluated in the same manner as in Example 8 except that (3) -19 was used.

The results are shown in Table 6.

33. The layers up to the photosensitive layer were formed in the same manner as in Example 32. (2
A photoconductor was prepared and evaluated in the same manner as in Example 9 except that the above (0) was used.

The results are shown in Table 6.

34-36. A photoreceptor was prepared and evaluated in the same manner as in Example 26 except that the charge transport material had the composition shown below.

The results are shown in Table 6.

Example 34: Exemplified Hydrazone Compound No.
(3) -7 50 parts, No. (3) -29 50 parts Example 35: Exemplified hydrazone compound No. (3) -4
20 parts, No. (3) -28 80 parts Example 36: Exemplified hydrazone compound No. (3) -11
60 parts, No. (3) -31 40 parts (Comparative Example 11) A photoreceptor was prepared and evaluated in the same manner as in Example 26 except that the protective layer in Example 26 was not formed. As a result, as shown in Table 6, the initial electrophotographic characteristics were good, but when the durability test was conducted, the charge generation layer on the surface was scraped after 300 sheets, and it was difficult to obtain a good image.

Comparative Example 12 Example 2 was repeated except that the binder resin in the protective layer of Example 26 was changed to a polycarbonate resin.
A photoconductor was prepared in the same manner as in 6. Using this photoreceptor, the same evaluation as in Example 26 was performed.

The results are shown in Table 6.

Comparative Examples 13 to 15 As the charge transport material, the hydrazone compound No. (3) -32, (3) -3
A photoconductor was prepared and evaluated in the same manner as in Example 26 except that 5, and (3) -40 were used.

The results are shown in Table 6.

[0181]

[Table 39]

[0182]

As described above, according to the present invention, a protective layer having a high hardness and a high durability can be formed without causing cracks in the protective layer or the photosensitive member, and further in dispersibility. It is possible to provide an electrophotographic photosensitive member which is excellent and has a small residual potential and which can obtain a high-quality image from the initial stage to the repeated use, an electrophotographic apparatus, an apparatus unit and a facsimile using the same.

[Brief description of drawings]

FIG. 1 is a diagram showing an example of the schematic configuration of an electrophotographic apparatus having an electrophotographic photosensitive member of the present invention.

FIG. 2 is a diagram showing an example of a block diagram of a facsimile having the electrophotographic photosensitive member of the present invention.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display location G03G 5/147 503 6956-2H H04N 1/29 D 9186-5C (72) Inventor Shoji Amemiya Tokyo 3-30-2 Shimomaruko, Ota-ku, Canon Inc. (72) Inventor Katsui Aoki 3-30-2 Shimomaruko, Ota-ku, Tokyo In Canon Inc. (72) Haruyuki Tsuji 3 Shimomaruko, Ota-ku, Tokyo No. 30-2 Canon Inc.

Claims (11)

[Claims] 1. An electrophotographic photoreceptor having a conductive support, a photosensitive layer and a protective layer, wherein the protective layer contains a resin formed by curing a photocurable acrylic monomer, and the photosensitive layer. (A), (B) and (C) (A) is a styryl compound having a structure represented by the following formula (1) and having a melting point of 135 ° C. or less. (In the formula, Ar ¹ and Ar ² represent an aromatic ring group, and Ar ³ represents 2
Represents a valent aromatic ring group or a divalent heterocyclic group, R ¹ represents an alkyl group or an aromatic ring group, R ² represents a hydrogen atom, an alkyl group or an aromatic ring group, and n ₁ is 1 or 2. , N ₁ = 1 and R ¹ and R ² may combine to form a ring. (B) A triarylamine compound having a structure represented by the following formula (2) and having a melting point of 150 ° C. or lower. (In the formula, Ar ⁴ , Ar ⁵ and Ar ⁶ each represent an aromatic ring group or a heterocyclic group.) (C) A hydrazone having a structure represented by the following formula (3) and having a melting point of 155 ° C. or lower. Compound [External 3] (In the formula, R ³ represents a hydrogen atom or an alkyl group, R ⁴ and R ⁵ represent an alkyl group, an aralkyl group or an aromatic ring group,
n ₂ is 1 or 2, and A is an aromatic ring group, a heterocyclic group or-
CH = C (R ⁶ ) R ⁷ (R ⁶ and R ⁷ represent a hydrogen atom, an aromatic ring group or a heterocyclic group, but R ⁶ and R ⁷ are not hydrogen atoms at the same time). An electrophotographic photoreceptor containing at least one compound selected from the group consisting of: 2. The electrophotographic photosensitive member according to claim 1, wherein the compound is (A). 3. The electrophotographic photosensitive member according to claim 1, wherein the compound is (B). 4. The electrophotographic photosensitive member according to claim 1, wherein the compound is (C). 5. The photocurable acrylic monomer is 1
The electrophotographic photosensitive member according to claim 1, which has three or more functional groups per molecule. 6. The photocurable acrylic monomer,
The electrophotographic photosensitive member according to claim 1, which has a functional group of 0.004 mol / g or more. 7. The electrophotographic photosensitive member according to claim 1, wherein the protective layer contains conductive particles. 8. The electrophotographic photosensitive member according to claim 7, wherein the conductive particles are metal oxide particles. 9. The electrophotographic photosensitive member according to claim 1, an electrostatic latent image forming means, a means for developing the formed electrostatic latent image, and a means for transferring the developed image to a transfer material. Electrophotographic device. 10. An apparatus unit integrally supporting the electrophotographic photosensitive member according to claim 1, a charging unit and a cleaning unit, wherein the apparatus unit is detachable from an apparatus body. .. 11. A facsimile comprising an electrophotographic apparatus having the electrophotographic photosensitive member according to claim 1, and means for receiving image information from a remote terminal.