JPS59214858A - Electrophotographic sensitive body - Google Patents

Abstract

PURPOSE:To enhance mechanical durability of a photoconductor layer by incorporating a specified coupling agent in at least one of layers contg. an org. photoconductor formed on a substrate. CONSTITUTION:A Ti type coupling agent is added to at least one of layers contg. an org. photoconductor formed on a substrate, preferably, in an amt. of >=5wt% of the total solid weight of the layer contg. it. A single photoconductive layer may be formed on the substrate, but sensitivity is improved to laminate an electrostatic charge generating layer and a charge transfer layer. Said coupling agent has the formula : (RO)m-Ti-Xm, where Ro is alkoxy; m is 1-4; X is a fatty acid group; and n is 1-5. Mechanical durability can be enhanced without lowering sensitivity of the org. photoconductor by thus adding the Ti type coupling agent to at least one of the photoconductor layers contg. the photoconductor formed on the substrate of the photosensitive body.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to an electrophotographic photoreceptor, and particularly to a layer containing an organic photoconductive substance in a laminated electrophotographic photoreceptor using an organic charge generating substance. This layer contains a titanium-based camping agent to improve the mechanical durability of this layer.

Background Art The basic structure of electrophotographic photoreceptors used in electrophotographic copying machines is a photoconductor layer consisting of a resin layer containing a photoconductor and binding the photoconductor on a conductive support. be. The photoconductor contains, for example, S as an inorganic charge generating substance.
e, S, 5e-Te, 5e-As,, As-3,, 5e
-Cd, CdS, and 5e-Te-Cd, but these inorganic materials have the problem of being toxic and being expensive because the photoconductor layer must be mainly formed by vapor deposition. be. Therefore, organic photoconductors that do not have these problems are also used.

A photoconductor has the property of generating and moving charges when exposed to light, and there are also photoreceptors that generate and move these charges using a single substance. However, when an organic photoconductive material is used as a charge generating material, forming a single layer containing it on a support is insufficient in terms of photosensitivity. A photoreceptor is used which has a photoconductor layer which is separated into a charge generation layer having a generation function and a charge transport layer having a charge transport function, and these are laminated.

Examples of using organic charge generating substances as charge generating substances include perylene pigments in JP-A-47-30330, indigo pigments in JP-A-47-30331, and indigo pigments in JP-A-47-30332. , quinacridone pigments in JP-A-4'1-18543, bishenzimidazonyl pigments in JP-A-47-18544, polycyclic quinone pigments in JP-A-47-18544, and JP-A-44-1.2671 and JP-B-Sho.46.
Examples of using lid 1:2 cyanine pigments are found in JP-A-30035, JP-A No. 41-17535, JP-A-41-11136, JP-A-50-99142, JP-A-57-148745, etc. .

However, photoreceptors using the above-mentioned organic charge generating materials have insufficient mechanical durability.

In other words, in an electrophotographic copying machine, a photoreceptor is charged by corona discharge and exposed to light according to the brightness of the original image, and the areas hit by the light are discharged and toner is deposited there, and this toner comes into contact with the paper and The image is transferred to the paper by being attracted from the back side of the paper by electrostatic attraction.
- The toner remaining on the photoreceptor is neutralized and scraped off with a brush. Since this series of operations is repeated, the photoconductor layer on the surface of the photoreceptor may be worn out, peeled off, damaged, etc. while being rubbed with a brush or paper, for example. When such a photoreceptor is used for copying, undesirable influences such as background smudges and image quality deterioration occur on the copied images. Therefore, efforts have been made to improve the durability of the photoreceptor, and the following methods have been known.

(1) Method of providing a protective layer on the photoconductor layer For example, Japanese Patent Publication No. 3
Japanese Patent Publication No. B-15446 discloses a structure in which a photoconductive insulating layer is coated with a highly polymerized resin film, and Japanese Patent Publication No. 19748/1974 discloses a structure in which a photoconductive layer is coated with an insulating layer made of, for example, a fluororesin. A layered version is shown. This method can improve the abrasion resistance against rubbing by paper or brushes as described above, but in any case of this structure, the photoconductive insulating layer or photoconductive layer is coated with a resin film or a photoconductive layer. Since the light is exposed through the insulating layer, a decrease in sensitivity is unavoidable, and as a result, the charge generated by corona discharge in the photoconductive insulating layer or photoconductive layer is less likely to be dissipated by exposure, and the remaining This will increase the potential. When this happens, it is necessary to reduce the copying processing speed, and if this speed is not reduced, it will adversely affect the electrophotographic characteristics, such as background stains on the copied paper and deterioration of image quality. Become. in this case,
If the protective layer is made thinner, the decrease in sensitivity can be reduced, but the abrasion resistance cannot be improved. Moreover, since the layer structure becomes complicated, it has the disadvantage that it increases the cost and tends to cause manufacturing problems.

In addition to providing a protective layer on this photoconductor layer,
Japanese Patent Publication Nos. 42-23910, 43-24748, 46-3713, 57-35457, 57-39414, 57-39416
No. 50-103342, JP-A No. 54-1
6.31 Publications 54-1632, 54-57
Publication No. 31, Publication No. 51115746, Publication No. 57-14
It is described in Publication No. 8744.

(2) Method of providing an adhesive layer and/or intermediate layer An adhesive layer between the photoconductor layer and the support that improves their adhesion, or an intermediate layer between the protective layer, the photoconductor layer, and the support layer. In this method, an intermediate layer is provided to improve adhesion. This method improves the adhesive strength of each layer in the layered structure and prevents peeling and damage of the entire layer.

An example of such a thing is
No. 48-26141, No. 48-2614
No. 2, JP-A-5.0-99326, JP-A No. 51-
No. 36140, No. 51-36140, No. 56
Examples include those described in JP-72448. However, in this method as well, when the photoconductive layer is exposed to light, the charge does not move smoothly, resulting in the same decrease in sensitivity and increase in residual potential as in (1) above. , resulting in similar problems.

(3) Method for increasing the resin ratio of the photoconductive layer” - (2)
) Based on the same idea, a method is also known in which the ratio of the resin component in the photoconductor layer is increased to improve the adhesion to the support.

However, this method also suffers from the same reduction in sensitivity as described above since the ratio of the photoconductor is relatively reduced.

(4) Method of using titanium-based coupling agent JP-A No. 5
'? Publication No. 158652 discloses a method of surface-treating a photoconductive material with a titanium-based coupling agent, and forming a photoconductive layer with a paint made by dispersing the treated material in a resin solution. No. 165843 discloses a structure in which an organic titanate of dialkyl pyrophosphate is contained in a photoconductive layer consisting of a binder resin and a photoconductive pigment.

However, all of these methods are aimed at improving the moisture resistance of photoreceptors that use CdS, an inorganic charge-generating material, as a photoconductor; If a large amount of a titanium-based coupling agent is used, the sensitivity decreases, so only a small amount of this titanium-based coupling agent can be used.As a result, although the moisture resistance is improved, the durability of the photoconductive layer may be affected.
can hardly be improved, nor is it expected to.

As mentioned above, although conventional photoconductor layers using organic charge-generating substances have good sensitivity, they have a major problem with their mechanical durability. Therefore, even if a protective layer or an adhesive layer is provided on the photoconductor layer, there is still room for improvement in order to minimize the decrease in sensitivity and maintain its mechanical strength. There is a problem in that even if a titanium-based coupling agent is contained in a photoconductor layer, its mechanical durability cannot be increased without decreasing its sensitivity.Mechanical strength can be improved with minimal or no decrease in sensitivity. It has been desired to develop a photoreceptor having a photoconductor layer.

As a result of various studies, the present inventor has discovered that if a titanium-based coupling agent is contained in at least one layer of each layer formed on the support of a photoreceptor, it will be formed on the support without adversely affecting the sensitivity. The researchers discovered that it is possible to improve the mechanical strength of the protective layer, thereby reducing the decrease in sensitivity, for example, by reducing the thickness of the protective layer. The inventors have found that the mechanical strength of the photoconductor layer can be increased without deteriorating the electrophotographic characteristics such as a decrease in sensitivity even when the photoconductor layer is used, and the present invention has been developed based on this finding.

OBJECTS OF THE INVENTION A first object of the present invention is to provide an electrophotographic photoreceptor in which the mechanical durability of the photoconductor layer is improved without adversely affecting electrophotographic properties such as sensitivity.

A second object of the present invention is to improve the mechanical durability of photoconductor layers using organic photoconductive materials without adversely affecting the electrophotographic properties such as sensitivity of the photoconductor layers. The present invention provides a flexible electrophotographic photoreceptor.

A third object of the present invention is to improve the mechanical durability of the photoconductor layer without adversely affecting the electrophotographic properties such as the sensitivity of a laminated electrophotographic photoreceptor using an organic charge-generating substance as a charge-generating substance. An object of the present invention is to provide an electrophotographic photoreceptor with improved properties.

A fourth object of the present invention is to provide an electrophotographic photoreceptor that has minimal toxicity and can be manufactured at relatively low cost.

Structure of the Invention In order to achieve the object of the present invention, the present invention provides an electrophotographic photoreceptor comprising at least one layer on a support, this one layer containing an organic photoconductive substance. It is characterized in that at least IN of the layer provided on the support contains a titanium-based coupling agent. In particular, the above object can be effectively achieved by controlling the content of the titanium-based coupling agent to 5% by weight or more based on the total solid content of the scrap containing the titanium coupling agent.

The titanium-based coupling agent used in the present invention has the general formula (
RO)m -Ti-Xn, RO is an alkoxy group, m is 1 to 4, X is a fatty acid group, an alkoxy group, a phenol group, a phenoxy group, a phosphite group, a phosphate group, etc., and nbal to 5, and when n is 2 or more, X may be the same or different.

Examples of the ulnar compounds of Tsushichi include the following:

(1) (10) (12) (13) (14) (15) (16) (17) (18) (19) (20) (21) (22) (23) (24) Layer structure in the present invention Although a single photoconductor layer may be provided on the support, it is also possible to provide a photoconductor layer on the support in this order, or in reverse depending on the application. It is practical to use a dark type because the sensitivity improves as described above. The thickness of the charge generation layer is 0.
．． The thickness of the charge transport layer is preferably 5 to 100μ, preferably 0.2 to 5μ. Further, the ratio of the thickness of the charge generation layer and the charge transport layer is 1:2 to i:z
oo is preferred. Furthermore, an adhesive layer may be provided between the photoconductor layer and the support in order to increase the adhesion of the photoconductor layer to the support, and a protective ff1 layer may be provided to protect the surface of the photoconductor layer. . Only one of these may be provided, or both may be provided. An intermediate layer for improving adhesion may be provided between each of the protective layer, charge generation layer, charge transport layer, adhesive layer, and support. In these layer structures, the titanium-based coupling agent is contained in a single layer or a plurality of layers. The content is preferably 5% by weight or more based on the total solid content of each layer, and when it is 5% by weight or more,
Since the mechanical strength of the layer containing a titanium-based coupling agent increases significantly, a similar layer structure that does not contain this titanium-based coupling agent is also used as the entire layer with a layer containing this titanium-based coupling agent. It has increased mechanical strength compared to other materials, and when used as a photoreceptor, it can improve durability against paper abrasion and brush abrasion as described above. Moreover, even when a titanium-based coupling agent is contained in this way, the sensitivity of the charge generation layer and the charge transport layer is not reduced. In particular, in order to achieve the best sensitivity, a charge generation layer is provided on the support, and a charge transport layer is further provided on this charge generation layer. By containing 5% by weight or more, the durability as a photoreceptor can be effectively improved without reducing sensitivity. In this case as well, a titanium-based coupling agent may be used only in one of the layers, and the durability is increased compared to a similar layered structure that does not contain this agent, and the sensitivity is not decreased. If a protective layer is provided as the top layer and a titanium-based coupling agent is used in this protective layer, the above durability will be lower than that of a similar layer structure with a protective layer that does not contain this titanium-based coupling agent. However, the sensitivity does not decrease. As a result, even if the thickness of the protective layer is reduced, the above durability can be maintained, and the attenuation of transmitted light in the protective layer can be reduced, and the charge-generating ability of the charge-generating substance can be exhibited in response to transmitted light. Decrease in sensitivity can be reduced. Even when a titanium-based coupling agent is contained in the adhesive layer or intermediate layer, the durability of the entire layer is improved, but the sensitivity is not reduced, compared to a similar layer structure that does not contain this agent.

The charge-generating substance used in the present invention includes known organic charge-generating substances, such as those disclosed in Japanese Patent Application Laid-open No. 47-3033.
Perylene pigments described in JP-A No. 0, JP-A-56-5552, etc., quinacridone pigments described in JP-A-47-30331, etc., JP-A-47-185, etc.
Bisbenzimidazole pigments described in JP-A-43, etc., JP-A-47-18544, JP-A-55-9
Aromatic polycondensed ring compounds described in JP-A No. 8754, JP-A-55-126254, JP-A-55-163543; Kaisho 56-321465
Azo pigments described in Japanese Patent Publications No. 50-74
No. 34, JP-A-47-37543, JP-A-Sho. 5
Disazo pigments described in JP-A No. 5-11715, JP-A-56-1944, JP-A-56-9752, JP-A-56-2352, JP-A-56-80050, etc. Publication No. 44'-12671, Japanese Patent Publication No. 30035, Japanese Patent Publication No. 41-17535
No. 49-11136, JP-A-49-11136, JP-A-49-11136
Examples include phthalocyanine pigments described in JP-A No. 99142, JP-A-5'1-148745, and the like.

The charge transport substance used in the present invention includes known charge transport substances, such as carbazole, N-ethylcarbazole, N-isopropylcarbazole, N-phenylcarbazole, tetraphenylpyrene, 1-methylpyrene, anthracenetetraphene, 2 -Phenylnaphthalene, azapyrene, fluorene, fluorenone, 1-
Ethylpyrene, acetylpyrene, 2,3-benzochrysene, 3,4-benzopyrene, 1. 4-bromopyrene, and hole transport substances such as phenyl-indole, polyvinylcarbazole, polyvinylpyrene, polyvinyltetracene or 2,4,7-dolinitrofluorenone, 2,4
, 5.7-tetranitrofluorenone, dinitroanthracene, dinitroacridine, tetracyanopyrene, dinitroanthraquinone and the like.

Examples of the resin for the photoconductor binder used in the present invention include insulating resins known for use in electrophotographic photoreceptors.
For example, polystyrene, styrene-butadiene copolymer,
Hydrocarbon polymers such as polyisobutylene; vinyl 414J such as polyvinyl chloride, chlorinated polyethylene, chlorinated polyvinyl chloride, polyvinyl acetate, polyvinyl acecool, polyvinyl butyral, polyvinyl ether, etc.]1i maleic acid, crotonic acid, acrylic acid, Acrylic resins such as homopolymers of methacrylic acid, acrylic acid, or esters of methacrylic acid, copolymers of these with each other, copolymers of these with other vinyl monomers, or modified products of these polymers; Silicone resin; alkyd resin consisting of a condensation product of phthalic acid resin, maleic acid resin, or other polybasic acid and polyol; polyamide resin; polyurethane; phenolic resin; urea resin; amino resin such as melamine resin; epoxy resin binders such as cellulose resins such as cellulose ether and cellulose ester; polycarbonate; and natural resins such as modified or unmodified rosin and balsam.

In the present invention, it is also possible to use a sensitizer in combination; examples of these sensitizers include xanthene dyes such as rose bengal, eosin S1 fluorescein, and phloxine; bromphenol flu, bromcresol purple, and chlorophenol 9 ．． Phenolsulfophthalein dyes such as Alphazurin 2G, Bontasil Brilliant Blue FCF, Acid Violet 6B, etc.; Triphenylmethane dyes such as Auramine; Diphenylmethane dyes such as Acridine Yellow, Acridine Orange, etc. Acridine dyes; rhodamine dyes such as sulforodamine B and acid eosin G; benzoic acid, phthalic acid,
Examples include organic carboxylic acids and their anhydrides such as maleic acid, fumaric acid, maleic anhydride, and phthalic anhydride.

To produce the photoreceptor of the present invention, a resin as a binder is dissolved in a solvent, a titanium-based coupling agent is added thereto, and the mixture is dispersed and homogenized using, for example, glass beads. In this way, iJ! The amped dispersion is applied onto a conductive support such as an aluminum plate using a coating device such as a roll coater, and dried using this F&J suitable means. In this way, a photoconductor layer is formed, but in order to make it a multilayer structure, another layer may be formed on top of the layer formed above in the same manner as above.

In this way, a photoreceptor containing a titanium-based coupling agent in the photoconductor layer is formed. When this photoreceptor is used as a photoreceptor in an electrophotographic copying machine, it undergoes a series of charging, exposure, adhesion of toner, transfer of toner to paper, neutralization of residual toner, and removal of the neutralized toner with a brush as described above. However, the following effects are observed due to the inclusion of this titanium-based coupling agent.

(1) The mechanical strength of the charge generation layer can be improved without reducing the efficiency of charge generation from the charge generation substance during light irradiation. Therefore, even if the charge generation layer is repeatedly rubbed with paper or a brush, phenomena such as abrasion, peeling, and chipping of the charge generation layer can be reduced.

(2) It does not impede the movement of charges generated from the charge-generating substance in the charge-generating layer.

(3) At the interface between the charge generation layer and scraps adjacent to the charge generation layer, such as a charge transport layer, an adhesive layer, or a support, the adhesion between these layers can be improved without interfering with the movement of charges.

(4) A titanium-based coupling agent is added to the charge transport layer, the intermediate layer,
Even if it is included in a protective layer or the like, the transport of charges is not hindered, and the mechanical strength of each layer is improved, as well as the adhesion between adjacent layers.

DETAILED DESCRIPTION OF THE INVENTION According to the present invention, at least one of the photoconductor layer containing an organic photoconductive material and other layers provided on the support of a photoreceptor includes a titanium-based cup. Since the ring agent is included, the mechanical durability can be improved without reducing the sensitivity of the organic photoconductive material compared to a material having the same layer structure but not containing a titanium-based camping agent.

This makes it possible, for example, to reduce the thickness of the protective layer and thereby suppress a decrease in sensitivity. However, since the sensitivity can be prevented from decreasing, only the mechanical durability can be selectively improved. This adds another excellent property of mechanical durability to the highly sensitive photoconductor layer, which is a stack of a charge generation layer and a charge transport layer, further increasing its utility as an electrophotographic photoreceptor. .

EXAMPLES The present invention will be described in detail below in Examples, but the present invention is not limited thereto.

Example 1 A dispersion liquid for a charge generation layer was prepared as follows. After melting 2 parts by weight of a phenolic resin with the following structural formula in 40 parts by weight of ethylene glycol monoethyl ether, β-type copper phthalocyanine (Chromophthal Blue 4GN manufactured by Ciba Geigy) was obtained.
3 parts by weight and 0.4 parts by weight of isopropyl tris(dioctylbairobosphene-1~) titanate (exemplified compound 3 above) were added and dispersed and homogenized using glass beads.

Here, m:n=2:8, average molecular weight about 2000. This dispersion was applied to the surface of an aluminum photoreceptor drum using a drum coater so that the dry film thickness was 0.5 μm.
Dry.

Next, a solution for the charge transport layer was prepared as follows. 1 part by weight of a charge transport material having the following structural formula and 1 part by weight of polycarbonate are dissolved in 10 parts by weight of dichloroethane.

This solution was applied onto the charge generating layer formed on the photoreceptor drum using a drum coater to a dry film thickness of 10 μm, and dried to obtain the photoreceptor drum of this example.

Comparative Example 1 This was carried out in the same manner as in Example 1, except that the dispersion for the charge generation layer in Example 1 was prepared without adding isopropyl tris(dioctylpyrophosphate) chicnate. A photosensitive drum of a comparative example was obtained.

Example 2 Epoxy resin (She II Epon 100
2) After dissolving 2 parts by weight in 40 parts by weight of ethylene glycol monomethyl ether, N,N'-bis(p-chlorophenyl)-perylene-3,4,9,10-tetracarboxylic acid diimide (Indofast brilliant scarlet; Allied Chemical Co., Ltd.) and 0.4 parts by weight of bis(dioctylpyrophosphate) oxyacetate titanate (exemplified compound 7 above) were added and dispersed in glass beads to homogenize, resulting in a charge generation layer dispersion. It was created.

This was applied to the surface of an aluminum photoreceptor drum using a drum coater so that the dry film thickness was 0.5μ.
Dry. Next, poly-N-vinylcarbazole (B
manufactured by ASF Chemical Co., Ltd., poly-N-vinylcarbazole)
Dissolve 1 part by weight in 5 parts by weight of a solvent of toluene:cyclohexanone=9:1. This solution was coated on the charge generation layer formed on the photoreceptor drum using a drum coater so that the dry film thickness was 10 μm, and dried to produce the photoreceptor drum of this example.

Comparative Example 2 Same as Example 2 except that the charge generation layer dispersion in Example 2 was prepared without adding bis(dioctylpylobosphate)oxyacetate titanate. A photosensitive drum of this comparative example was produced in the same manner.

Example 3 After melting 2 parts by weight of a phenolic resin having the following structural formula in 40 parts by weight of ethylene glycol monoethyl ether, 1
．． After adding 3 parts by weight of 4-dibromoanthrone (Monolite-2Y; manufactured by Imperial Chemical Co., Ltd.) and 0.4 parts by weight of bis(dioctylpyrobosphate) ethylene titanate (exemplified compound 8 above), and mixing these. The mixture was dispersed and homogenized using glass beads to prepare a dispersion liquid for charge generation.

Average molecular weight: 5000 This dispersion was coated on the surface of an aluminum photoreceptor drum using a drum coater so that the dry film thickness was 0.5 μm, and dried.

Next, 1 part by weight of a charge generating substance having the following structural formula and 1 part by weight of topholycarbonate are dissolved in 10 parts by weight of dichloroethane.

This solution was applied onto the charge generation layer formed on the photoreceptor tram using a drum coater so that the dry film thickness was 10 μm, and was dried to produce the photoreceptor drum of this example.

Comparative Example 3 Example 3 except that the dispersion for the charge generation layer was prepared without adding bis(dioctylpyrobosphate)conytylene ditanate when preparing the dispersion for charge generation in Example 3. A photoreceptor drum of this comparative example was produced in the same manner as ζ.

The photoreceptor drums of Examples 1 to 3 and Comparative Examples 1 to 3 were negatively charged by corona charging at an applied voltage of -6.0 KV, irradiated with white tungsten light, and after irradiation with this light,
Exposure 1tE1/2' where the surface potential is attenuated by 1/2
(lux-sec), 1154: Attenuated exposure 1tE
115 (lux-sec), and the exposure amount El/10 (lux-sec) attenuated to 1/10 was measured, and the results were as shown in the table below.

Next, each of the photoreceptor drums described above was installed in a copying machine, the exposure intensity was adjusted, and copies were made repeatedly.
Even when 0 copies were made, there was no image disturbance due to damage, peeling, or decreased sensitivity of the photoconductor layer. Example 4 Isopropyl tris (dioctyl pyrophosphate) where either damage to the photoconductor layer or decreased peeling sensitivity was observed when
The photoreceptor drum of this example was subjected to fJ in the same manner as in Example 1 except that 8.0% by weight of titanate was added to the charge transport layer in terms of solid content instead of adding titanate to the charge generation layer of Example 1.

Example 5 The same procedure as Example 2 was carried out except that 8.0% by weight of bis(dioctylpyrophosphate-1)oxyacetate titanate was added to the charge transport layer in terms of solid content instead of adding it to the charge generation layer of Example 2. A photosensitive drum of this example was obtained.

Example 6 Same as Example 3 except that 8.0% by weight of bis(dioctyl pyrophosphate) ethylene titanate was added to the charge transport layer in solid content ratio instead of adding it to the charge generation layer of Example 3. ζ This example A photoreceptor drum was obtained.

The sensitivities of each of the photoreceptor drums in Examples 4, 5 and 6 are approximately the same as those of the corresponding photoreceptor drums in Comparative Examples 1 and 2.3. No disturbance in image quality due to damage to the photoconductor layer, peeling, decrease in sensitivity, etc. occurred in any of the body drums after repeated copying of 35,000 sheets.

Example physopropyl tris (dioctyl pyrophosphate)
The photoreceptor drum of this example was prepared in the same manner as in Example 1 except that titanate was added to both the charge generation layer and the charge transport layer at a solid content ratio of 6.0% by weight.
Ta.

Example 2 This was carried out in the same manner as in Example 2, except that bis(dioctyl pyrophosphate) oxyacetate titanate was added to both the charge generation layer and the charge transport layer at a solid content of 6.0% by weight. A photosensitive drum of Example was obtained.

Example 9 Same as Example 3, except that Hiss(diocdilepaish!phosphate-1.)ethylene titanate was added to the charge generation layer and the charge transport layer so that the solid content ratio was 6.0 i% in both layers. A photosensitive drum of this example was obtained in the same manner.

The sensitivities of the photoreceptor drums of Examples 7 to 9 are the same as those of the corresponding shield comparative examples 1 to 3 in this order, and the photoreceptor drums of Examples 7 to 9 have a sensitivity of 40.000.
Repeated copying of the photoconductor layer did not result in image disturbance due to damage, peeling, or decreased sensitivity of the photoconductor layer.

Example 10 In Example 1, isopropyl tris(cyoctylpyrophosophate) titanate was added only to the charge generation layer in an amount of 3.0% by weight based on the total solid content of the charge generation layer. Other configurations were the same as in Example 1 to obtain a photosensitive drum of this example.

The photoreceptor drum of this example exhibited electrophotographic characteristics equivalent to those of the photoreceptor drum of Comparative Example 1, and the conductor layer showed wear and peeling even after 25,000 copies were made. There was no deterioration in image quality due to a decrease in sensitivity or the like.

Example 11 In Example 2, his(dioctyl pyrophosphate) oxyacetate titanate was added only to the charge transport layer,
It was added in an amount of 3.0% by weight based on the total solid content of this charge transport layer. Other configurations were the same as in Example 2 to obtain a photosensitive drum of this example.

The photoreceptor drum of this example exhibited electrophotographic characteristics equivalent to those of the photoreceptor drum of Example 10, and even after repeated copying and 25,000 copies, the conductor layer did not wear out. MIJ li! There was no disturbance in image quality due to a decrease in sensitivity or the like.

Example 12 In Example 3, bis(dioctyl pyrophosphate) ethylene titanate was added to the charge generation layer and the charge transport layer in an amount of 2.0% by weight based on the total solid content of each layer. . The other configurations were the same as in Example 3 to obtain the photosensitive drum of this example.

The photoconductor drum of this example exhibited electrophotographic characteristics equivalent to those of the photoconductor drum of Comparative Example 3, and even after repeated copying and 25,000 copies, the photoconductor layer wore out. There was no disturbance in image quality due to peeling, deterioration of sensitivity, etc.

May 20, 1980 Patent applicant Konishi Roku Photo Industry Co., Ltd. Agent Yoshimi Kuwahara Procedural amendment June 24, 1982 Commissioner of the Patent Office Kazuo Wakasugi 1, Indication of case 1989 Patent application No. 89657 No. 2, Name of the invention Electrophotographic photoreceptor 3, Relationship with the person making the amendment Patent applicant address 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo (127) Name Konishiroku Photo Industry Co., Ltd. Representative Nobuhiko Kawamoto Address: 1-5, Konkura-cho, Hino-shi, Tokyo ? ili Date of official order Voluntary action 6. Subject of amendment: ``Claims column of the specification'' ``Detailed explanation of the invention column of the specification'' 7. Contents of amendment 1: From line 4 to page 1 of the specification "2. Scope of Claims" on line 13 is corrected as shown in the attached sheet.

2. On page 4, line 12 of the specification, "V setting method", Correct it to "How to set it up."

3. On page 10, lines 7 to 10 of the specification, the phrase ``a layer provided...on a support'' is replaced with ``a layer containing an organic photoconductive substance provided on a support.'' In the electrophotographic photoreceptor having the above-mentioned structure, at least one of the above-mentioned layers and/or a layer other than the above-mentioned layer provided on the above-mentioned layer side on the above-mentioned support.''

4. On page 10 of the specification, line 16 to line ff120, “
Titanium-based coupling agents include bosphate groups, etc.," instead of "Typical titanium-based coupling agents are represented by the general formula (RO)m -Ti-Xn. and addition compounds containing the compound.

Here, RO is an alkoxy group, m is 1 to 4, X is a fatty acid group, 'r alkoxy group, phenol group, phenoxy group,
These are phosphite groups, phosphate groups, sulfide groups, sulfate groups, etc.''

5. In the second line of page 11 of the specification, [ may also be different. " may be different. The alkoxy group represented by RO may be substituted, and examples of this substituent (or atom) include a halogen atom, an oxo group, an alkoxy group, an alkenyl group, and an alkenyl group. Examples include oxy groups, aryl groups, heterocyclic groups, etc., and when m is 2 or more, 2 or more R may be connected.''

6. On page 11 of the specification, (2) There is a certain (2) I am corrected.

7. On pages 11 and 12 of the specification, (4) There is a certain (4) I am corrected.

8. On page 14 of the specification, (16) There is a certain (16) I am corrected.

9. On page 17, line 14 of the specification, The text “used as a photoreceptor” Correct it to "as a photoreceptor."

10, page 18, lines 14 to 16 of the specification, it says, "The attenuation can be reduced, and the attenuation can be reduced." This is corrected as follows: the charge generation ability can be fully demonstrated, or the distance of charge movement is not too long, and the probability that the charge is trapped during that time does not increase too much, so that the reduction in sensitivity can be reduced.

11. On page 26, line 17 of the specification, It says "developmental layer", Correct it to "generation layer."

12. On page 26, line 18 of the specification, It says, “Let it become μ.” I corrected myself by saying, "So that it becomes μ."

2. Claims (1) An electrophotographic photoreceptor containing an organic light-conducting substance on a support, wherein ↓IJΩ5%≧1. Electrophotographic photosensitive material, characterized in that at least one layer of the markings provided on the elbows of the supporting member and the supporting member contains a titanium-based coupling agent. body.

(2) The electronic device according to claim 1, characterized in that the content of the titanium-based coupling agent is 5% by weight or more based on the total solid content of the layer containing the titanium-based coupling agent. Photographic photoreceptor.

Procedural amendment / November 1989 IG Director-General of the Japan Patent Office Kazuo Wakasugi l Indication of matter f'1 1989 Special Patent Application No. 89657 4) 2 Title of invention Electrophotographic photoreceptor 3 Case of person making supplement Relationship with Patent Applicant Address 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Name (1271 Konishiroku Photo Industry Co., Ltd. Representative Director Nobuhiko Kawamoto 4, Agent 191 Address Sakura-cho, Detsuno-shi, Tokyo) 1 address 5, date of amendment order (= 1 spontaneous 6, subject of amendment "column for detailed explanation of the invention in the specification") 7, contents of amendment ρ page 17 line to page 8 line 8 " ``The present invention is formed.'' and the following sentence is inserted in its place.

"In order to create a layer containing the titanium-based coupling agent of the present invention, if the components of the layer are only those that are soluble in a solvent such as a binder resin, these are dissolved in a solvent.
, if necessary) Add the titanium-based coupling agent to the filtrate and stir evenly. In order to avoid uneven distribution of the coupling agent, it is also preferable to dilute the titanium-based coupling agent with a solvent before adding it. In addition, when a layer component contains a substance that is hardly soluble in a solvent, such as a pigment-based photoconductive substance, first dissolve the soluble component such as a binder resin in the solvent, and then add the pigment-based photoconductive substance. 3. After adding Saki IB dissolved substances such as substances, dispersion is performed using a glass bead, ball mill, sand grinder, colloid mill, etc. In this case, the titanium-based coupling agent may be added either before or after dispersion, but the titanium-based coupling agent may be added uniformly to the subsequent lifting platform (with stirring).

The solution containing the titanium coupling agent prepared in this way is coated on the support or a layer already provided on the support, and if necessary, another layer is coated on the layer containing the titanium coupling agent. An electrophotographic photoreceptor of the present invention is produced. ”

Claims (1)

[Claims] (]) Having at least one layer on the support -1-, and this II'
An electrophotographic photoreceptor comprising a layer in which H contains an organic photoconductive substance, wherein at least IJW of the layer provided on the support contains a titanium-based coupling agent. . (2) The electronic device according to claim 1, characterized in that the content of the titanium-based coupling agent is 5% by weight or more based on the total solid content of the layer containing the titanium-based coupling agent. Photographic photoreceptor.