JP3039894B2 - Image holding member - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an image holding member which can be widely used in electrophotographic applications such as an electrophotographic copying machine, a laser beam printer, a CRT printer, and an electrophotographic plate making system.

[0002]

2. Description of the Related Art Inorganic photoconductive materials such as selenium, cadmium sulfide and zinc oxide have been conventionally used as photoconductive materials for electrophotographic photosensitive members. On the other hand, organic photoconductive materials such as polyvinyl carbazole, oxadiazole and phthalocyanine have advantages such as non-pollution and high productivity as compared with inorganic photoconductive materials, but have low sensitivity and are difficult to be put to practical use. Therefore, several sensitization methods have been proposed, but as an effective method, it is known to use a function-separated type photoconductor in which a charge generation layer and a charge transport layer are laminated.

On the other hand, an electrophotographic photosensitive member is required to have predetermined sensitivity, electrical characteristics, and optical characteristics according to an applied electrophotographic process. Particularly, in the case of a photoreceptor which can be used repeatedly, electric and mechanical external forces such as corona charging, toner development, transfer to paper, and cleaning treatment are directly applied to the surface layer of the photoreceptor. Durability is required.

[0004] More specifically, deterioration due to ozone generated during corona charging causes a decrease in sensitivity, a decrease in potential, and an increase in residual potential. In addition, the surface may be worn or scratched by rubbing. Durability against these is required. Since the surface of the photoreceptor is coated with a resin, the performance of the resin is particularly important, and a resin having excellent durability has been demanded. Recently, a polycarbonate resin having bisphenol A as a skeleton (hereinafter referred to as bisphenol A type polycarbonate) has been studied as a binder for the surface layer as a resin satisfying these requirements. Bisphenol A type polycarbonate resin is not satisfactory, and has the following problems. (1) The solubility of the resin is poor. Dichloromethane or 1,2-
It shows good solubility only in some halogenated aliphatic hydrocarbons such as dichloroethane. Since these halogenated aliphatic hydrocarbons have a low boiling point, when a photoreceptor is manufactured using a coating solution prepared with these solvents, the coated surface tends to be whitened. Also, it takes time and effort to control the process such as the solid content of the coating liquid. (2) It is partially soluble in solvents other than halogenated aliphatic hydrocarbons in tetrahydrofuran, dioxane, cyclohexanone, or a mixed solvent thereof, but the solution gels within a few days, Poor stability,
It is not suitable for the production of photoreceptors. (3) Even if the above-mentioned drawbacks (1) and (2) are improved, there is a drawback that solvent cracks occur in a polycarbonate resin having a main chain skeleton containing only bisphenol A or a bisphenol A derivative. (4) In addition, in the case of the conventional polycarbonate resin, the coating formed of the resin does not have much lubricity, so that the photoreceptor is scratched, resulting in image defects, poor cleaning due to early deterioration of the cleaning blade, In addition, cleaning failure due to the reversal of the cleaning blade and damage to the photoconductor result in a significant reduction in the life of the photoconductor.

Conventionally, the solution stability described in (1) and (2) has been solved by using a polycarbonate Z resin having a bulky cyclohexylene group as a structural unit of a polymer. However, as pointed out in (3), not only the above-mentioned polycarbonate Z resin but also polycarbonate A resin has a relatively large volume shrinkage when a film is formed from a solution by a casting method, and may leave stress inside the film. . For this reason, it has a disadvantage that it is relatively vulnerable to stress corrosion. In order to solve this, for example, JP-A-61-62040 discloses a method of reducing stress corrosion cracking by mixing a polycarbonate A resin and a polycarbonate Z resin. Japanese Patent Application Laid-Open No. 61-62039 discloses a method of reducing stress corrosion cracking by copolymerizing bisphenol A and bisphenol Z, but none of these methods is sufficient for solvent cracking.

In addition, as shown in (4), the ordinary polycarbonate resin has relatively low lubricity with respect to the cleaning blade used in the electrophotographic process, and the cleaning blade reverses due to the progress of the durability. As a result, it has been pointed out that a defect such as cleaning failure occurs and a scratch is generated due to a strong force applied to the photosensitive drum. To improve this, a silicone oil is added, or JP-A-61-132 is used.
As disclosed in Japanese Patent No. 954, a method of copolymerizing a polydimethylsiloxane block with a polycarbonate resin is known. However, in the method of adding silicone oil, electrical properties in electrophotography, specifically, sensitivity and residual potential are degraded, and the silicone oil in the surface layer is lost due to the progress of durability, and permanent lubricity is obtained. There was a drawback that it was not possible. In addition, if a product obtained by copolymerizing the above-mentioned polydimethylsiloxane block is used, the lubricity becomes good, but the conventional polydimethylsiloxane copolymer becomes cloudy or gels when used as a solution. There is a difficulty, and even when used as a surface layer of an electrophotographic photosensitive member, it is not satisfactory in durability.

[0007]

SUMMARY OF THE INVENTION The present invention solves the problems of an image holding member such as an electrophotographic photosensitive member using a conventional polycarbonate resin as a surface layer, and improves lubricity and abrasion resistance. Accordingly, an object of the present invention is to provide an image holding member which has excellent mechanical properties and durability and is easily manufactured.

[0008]

That is, the present invention relates to an image holding member having a photosensitive layer on a conductive support, wherein the surface layer of the photosensitive layer has the following general formula [1]:

[0009]

Embedded image (Wherein, R ₁ to R ₁₆ are a hydrogen atom, a halogen atom, a methyl group, an ethyl group or a phenyl group, and R ₁₇ is a group having 1 to 1 carbon atoms.
3 alkylene group, to no R ₁₈ R ₂₁ is an alkyl group or an aryl group, A is shows an alkylidene group, an arylene group, an aryl-substituted alkylidene group, arylene alkylidene group, n is an integer of 1 to 200, X and Y
Represents a copolymerization ratio (molar ratio), and Z represents a weight% of the Z structural unit in the copolymer). An image holding member comprising titanium phthalocyanine.

The general formula [1] contained in the above copolymer
The copolymer component of the X structural unit represented by is introduced to impart suitable flexibility to the polycarbonate resin, does not hinder free rotation of the phenol group, and introduces a non-bulky group to impart flexibility. It is introduced for the purpose of improving the solvent crackability. Specific examples of the compound providing such a structural unit include the following.

[0011]

Embedded image Further, the copolymerization component of the Y structural unit contained in the copolymer is introduced in order to give appropriate mechanical strength to the above-mentioned copolymer. No.

[0012]

Embedded image

[0013]

Embedded image

[0014]

Embedded image

[0015]

Embedded image Further, the Z structural unit represented by the above-mentioned structural formula [1] is introduced for the purpose of improving the lubricity of the copolymer. Examples of the compound which gives the Z structural unit include the following.

[0016]

Embedded image The copolymer of the present invention has particularly excellent solvent crack resistance and surface lubricity. This is because, in addition to the introduction of the X structural unit, a polyorganosiloxane segment having chemical resistance is introduced into the surface layer. It is presumed that by doing so, the rate at which chemicals causing solvent cracks enter the copolymer is reduced, and the rate at which abnormalities occur in the coating is reduced. The above-mentioned structural unit contained in such a copolymer must be determined in consideration of scratch resistance, hardness, production stability and the like required according to the electrophotographic process. The ratios of the structural unit of X, the structural unit of Y, and the structural unit of Z used at this time are: solvent crack resistance, durability, and environmental stability with respect to electrical characteristics;
It must be strictly controlled taking into account the production stability that depends on the solution stability. In such a copolymer, the composition ratio (X + Y) / (X + Y + Z) is 70 to 9
It is necessary that the content be in the range of 9.5% by weight in order to obtain proper surface lubricity and solvent crack resistance.

The above-mentioned ratios of X and Y are determined particularly in consideration of electrophotographic sensitivity, solvent cracking property and solution stability, and X / Y ranges from 1/9 to 9/1. Is preferable, and the range of 2/8 to 7/3 is particularly preferable. That is, if X / Y is less than 2/8, the introduction of the polyorganosiloxane structural unit does not improve the solvent crack resistance and further lowers the sensitivity. When X / Y is more than 7/3, the solvent crack resistance is improved and the sensitivity is improved, but image defects such as black spots are significantly reduced. As the cause, various factors are considered and it is not accurate to limit to a specific factor, but as described above, the copolymer composition of the copolymer is an important factor in the solvent crack resistance and the electrophotographic image as described above. Thus, a photoreceptor having excellent mechanical and electrical properties has been provided.

The solubility of the polycarbonate resin having the component represented by the general formula [1] is preferably 1 g or more, more preferably 5 g or more, per 100 cc of the aromatic hydrocarbon solvent and the halogenated aromatic hydrocarbon solvent. preferable.
Because the solubility is less than 1g / 100cc,
For example, when a charge transport layer solution is prepared, the viscosity of the solution is too low, so that an appropriate film thickness as the charge transport layer cannot be obtained.

Further, the molecular weight of such a copolymer is preferably 10% in consideration of durability, ie, abrasion resistance, scratch resistance, and viscosity at the time of production, ie, productivity, in consideration of the viscosity average molecular weight (Mv). It is preferably in the range of 20,000 to 150,000, especially 20,000 to 100,0.
It is preferably in the range of 00.

The copolymer used in the present invention is synthesized by interfacial polycondensation of the above-mentioned polyhydric phenols in the presence of phosgene. The composition is made with sufficient consideration of the ratio.

When the image holding member of the present invention is an electrophotographic photosensitive member, the photosensitive layer contains a charge generating material even if the photosensitive layer is a so-called single layer type in which the charge generating material and the charge transporting material are contained in the same layer. A function-separated type in which a charge generation layer and a charge-transporting layer containing a charge-transporting material are laminated may be used. A photoreceptor is preferred.

The above-mentioned copolymer used in the present invention can be used as a binder resin for a photosensitive layer and a binder resin for a charge generation layer and a charge transport layer.

In the production of the image holding member of the present invention, as the conductive support, metals such as aluminum and stainless steel, and cylindrical cylinders or films of paper and plastic are used. On these supports, an undercoat layer having a barrier function and an adhesive function can be provided.

The undercoat layer improves the adhesion and coating properties of the photosensitive layer, protects the support, protects the support, covers defects on the support, improves the charge injection property from the support, and protects the photosensitive layer against electrical breakdown. Formed for etc. Known materials for the undercoat layer include polyvinyl alcohol, poly-N-vinylimidazole, polyethylene oxide, ethyl cellulose, ethylene-acrylic acid copolymer, casein, polyamide, copolymerized nylon, glue, gelatin and the like. These are dissolved in a suitable solvent and applied on a support. The thickness at this time is preferably about 0.1 to 2 μm.

The charge generating layer is prepared by mixing a charge generating material with a binder resin and a solvent in an amount of 0.3 to 4 times the amount of a homogenizer, an ultrasonic dispersion, a ball mill, a vibration ball mill, a sand mill,
It is well dispersed by a method such as an attritor and a roll mill, coated, and dried to form. Its film thickness is 0.
It is desirable to be in the range of 1-2 μm.

As the charge transport material, pyrene, N
-Ethylcarbazole, N-isopropylcarbazole, N-methyl-N-phenylhydrazino-3-methylidene-9-ethylcarbazole, N, N-diphenylhydrazino-3-methylidene-9-ethylcarbazole,
N, N-diphenylhydrazino-3-methylidene-10
-Ethylphenothiazine, N, N-diphenylhydrazino-3-methylidene-10-ethylphenoxazine, p
-Diethylaminobenzaldehyde-N, N-diphenylhydrazone, p-diethylaminobenzaldehyde-
N-α-naphthyl-N-phenylhydrazone, p-pyrrolinodibenzaldehyde N, N-diphenylhydrazone, 1,3,3-trimethylindolenine-ω-aldehyde-N, N-diphenylhydrazone, p-diethylbenzaldehyde-3 -Methylbenzthiazolinone-2-
Hydrazones such as hydrazone, 2,5-bis (p-diethylaminophenyl) -1,3,4-oxadiazole, 1-phenyl-3- (p-diethylaminostyryl) -5- (p-diethylaminophenyl) pyrazoline , 1- [quinolyl (2)]-3- (p-diethylaminostyryl) -5- (p-diethylaminophenyl) pyrazolin, 1- [pyridyl (2)]-3- (p-diethylaminostyryl) -5- ( p-diethylaminophenyl) pyrazolin, 1- [6-methoxy-pyridyl (2)]-3- (p-diethylaminostyryl) -5-
(P-diethylaminophenyl) pyrazolin, 1- [pyridyl (3)]-3- (p-diethylaminostyryl)
-5- (p-diethylaminophenyl) pyrazoline, 1
-[Pyridyl (2)]-3- (p-diethylaminostyryl) -5- (p-diethylaminophenyl) pyrazolin, 1- [pyridyl (2)]-3- (p-diethylaminostyryl) -4-methyl-5 -(P-diethylaminophenyl) pyrazolin, 1- [pyridyl (2)]-3-
(Α-methyl-p-diethylaminostyryl) -5-
(P-diethylaminophenyl) pyrazolin, 1-phenyl-3- (p-diethylaminostyryl) -4-methyl-5- (p-diethylaminophenyl) pyrazolin,
Pyrazolines such as 1-phenyl-3- (α-benzyl-p-diethylaminostyryl) -5- (p-diethylaminophenyl) pyrazoline and spiropyrazoline;
(P-diethylaminostyryl) -6-diethylaminobenzoxazole, 2- (p-diethylaminophenyl) -4- (p-dimethylaminophenyl) -5- (2
Oxazole compounds such as -chlorophenyl) oxazole, thiazole compounds such as 2- (p-diethylaminostyryl) -6-diethylaminobenzothiazole,
Triarylmethane compounds such as bis (4-diethylamino-2-methylphenyl) phenylmethane;
Bis (4-N, N-diethylamino-2-methylphenyl) heptane, 1,1,2,2-tetrakis-4-N,
And polyarylalkanes such as (N-dimethylamino-2-methylphenyl) ethane.

The charge transport layer is applied and formed by dissolving the charge transport material and the binder resin in a solvent. The mixing ratio of the charge transport material and the binder resin is 2: 1.
The solvent is preferably about 1: 2. As the solvent, in addition to aromatic solvents such as toluene, xylene, and monochlorobenzene, cyclic ethers such as dioxane, tetrahydrofuran, and tetrahydropyran can be used. As a method for applying this solution, for example, a dip coating method, a spray coating method, a curtain coating method, a spin coating method and the like are known. Dip coating is the best method for mass-producing electrophotographic photoreceptors efficiently and is made possible by using the polycarbonate resin of the present invention. 10 ℃ -2 after application
00 ° C., preferably at 20 ° C. to 150 ° C. for 5 minutes to 5 hours,
Ventilation drying or still drying is preferably performed for 10 minutes to 2 hours to obtain a charge transport layer of 5 to 30 μm.

Further, in addition to the above-described charge generation layer and charge transport layer, the copolymer of the present invention may further comprise an outermost surface layer of a photoreceptor,
It can be used as a so-called surface protective layer.

When the copolymer of the present invention is used as a surface protective layer, the resin alone can be used as the outermost surface layer. However, tin oxide, ITO, It is preferable to add a conductive powder such as titanium oxide and carbon black or a charge transport material to form a film. These conductive powders or charge transport materials are added in consideration of electrophotographic properties, durability, and surface lubricity.
It is preferably added at 0% by weight. If the addition amount is too small, the residual potential and sensitivity decrease, and if the addition amount is too large, lubricity as a surface layer and coating strength decrease.

The thickness of the surface protective layer is 1 μm
It is preferably in the range of 2 to 20 μm, and in consideration of durability, electrical characteristics, and image quality, 2 to 1 μm.
Most preferably, it is in the range of 5 μm.

Such a surface protective layer can be suitably manufactured by a spray coating method, an electrostatic coating method, or the like.

[0032]

Next, the present invention will be described with reference to examples.

Example 1 Conductive titanium oxide powder 50 coated with tin oxide containing 10% antimony oxide
Parts, phenolic resin 25 parts, methyl cellosolve 20 parts,
5 parts of methanol and 0.002 part of silicone oil (polydimethylsiloxane polyoxyalkylene copolymer, average molecular weight 3000) were dispersed in a sand mill using φ1 mm glass beads for 2 hours to obtain a paint for a conductive layer. The paint was applied on an aluminum sheet by a wire bar and dried at 140 ° C. for 30 minutes to form a conductive layer having a thickness of 20 μm.

Next, 5 parts of N-methoxymethylated nylon was dissolved in 95 parts of methanol to prepare a coating for an intermediate layer. This paint was applied on the conductive layer by a wire bar and dried at 100 ° C. for 20 minutes to form a 0.6 μm intermediate layer.

Then, the following structural formula

[0036]

Embedded image 3 parts of oxytitanium phthalocyanine, polyvinyl benzal (benzalization ratio 80%, weight average molecular weight 1
1,000 parts) and 35 parts of cyclohexanone at φ1
The mixture was dispersed in a sand mill using mm glass beads for 12 hours, and then 60 parts of methyl ethyl ketone was added to obtain a dispersion for a charge generation layer. This dispersion was applied on the above-mentioned intermediate layer with a wire bar and dried at 80 ° C. for 20 minutes to obtain a charge generation layer having a thickness of 0.2 μm.

Next, the structural formula

[0038]

Embedded image 10 parts of a compound of the following structural formula

[0039]

Embedded image Copolymer (viscosity-average molecular weight 2.05 × 10 ⁴⁾ 20 parts of dichloromethane and 10 parts of was dissolved in a mixed solvent of monochlorobenzene 40 parts, was coated by a wire bar and the solution to the above charge generation layer After drying at 120 ° C. for 60 minutes, a charge transport layer having a thickness of 23 μm was formed.

Next, abrasion resistance, surface lubricity, and electrophotographic characteristics were measured using this photoreceptor. For abrasion resistance, see Ablation Tester N manufactured by Yasuda Seiki Co., Ltd.
o. A 101 Taber type was used, and commercially available copy paper was used as an abrasive. Regarding the surface lubricity, a cleaning blade made of urethane rubber for a copying machine was used, and the cleaning blade was brought into contact with the surface of the photoreceptor at a contact angle of 30 °, and the sliding resistance was H.
EIDON-14 type surface tester (Shinto Chemical Co., Ltd.)
It measured using. The electrophotographic characteristics are 100
It was obtained by measuring photodischarge characteristics using conductive glass of cm ² . In addition, finger oil adheres to this surface layer,
After leaving at room temperature and humidity for 24 hours, 5 days, and 1 week,
The presence or absence of solvent cracks was observed under a microscope. Table 1 shows the results.

Example 2 A copolymer having the following composition:

[0042]

Embedded image A photoreceptor was prepared in the same manner as in Example 1 except that a charge transport layer was formed using (viscosity average molecular weight 2.56 × 10 ⁴ ), and various measurements were made.

Table 1 shows the obtained results.

Example 3 A copolymer having the following composition:

[0045]

Embedded image A photoreceptor was prepared in the same manner as in Example 1 except that a charge transport layer was formed using (viscosity average molecular weight 9.21 × 10 ⁴ ), and various measurements were made.

Table 1 shows the obtained results.

Example 4 A copolymer having the following composition:

[0048]

Embedded image A photoreceptor was prepared in the same manner as in Example 1 except that a charge transport layer was formed using (viscosity average molecular weight 3.15 × 10 ⁴ ), and various measurements were performed.

Table 1 shows the obtained results.

Example 5 A copolymer having the following composition:

[0051]

Embedded image A photoconductor was prepared in the same manner as in Example 1 except that the charge transport layer was formed using (viscosity average molecular weight 2.04 × 10 ⁴ ), and various measurements were made.

Table 1 shows the obtained results.

(Example 6) A copolymer having the following composition:

[0054]

Embedded image A photoconductor was prepared in the same manner as in Example 1 except that the charge transport layer was formed using (viscosity average molecular weight 2.02 × 10 ⁴ ), and various measurements were made.

Table 1 shows the obtained results.

Comparative Example 1 A photoreceptor was prepared in the same manner as in Example 1, except that a charge transport layer was formed using polycarbonate Z (viscosity average molecular weight: 1.92 × 10 ⁴ ). A measurement was made.

Table 1 shows the obtained results.

Comparative Example 2 A copolymer having the following structural formula

[0059]

Embedded image A photoreceptor was prepared in the same manner as in Example 1 except that a charge transport layer was formed using (viscosity average molecular weight 2.53 × 10 ⁴ ), and various measurements were made.

Table 1 shows the obtained results.

Example 7 A photoconductor was prepared in exactly the same manner as in Example 1, except that a charge transport layer was formed using polycarbonate Z (viscosity average molecular weight: 1.92 × 10 ⁴ ). On this photoreceptor, a copolymer of the following structural formula

[0062]

Embedded image (Viscosity average molecular weight 3.23 × 10 ⁴ ) 7 parts, a compound of the following structural formula

[0063]

Embedded image A coating prepared by dissolving 3 parts in 100 parts of dichlorobenzene was spray-coated and dried at 120 ° C. for 1 hour to obtain a photoconductor having a surface protective layer having a thickness of 3 μm. Various measurements were performed on this photoreceptor in the same manner as in Example 1.

Table 1 shows the obtained results.

Example 8 A photoconductor was prepared in exactly the same manner as in Example 1, except that a charge transport layer was formed using polycarbonate Z (viscosity average molecular weight: 1.92 × 10 ⁴ ). On this photoreceptor, a paint prepared by dispersing 6 parts of the copolymer of Example 7 and 4 parts of ultrafine tin oxide in 100 parts of dichlorobenzene was spray-coated, dried at 120 ° C. for 1 hour, and dried. A photoreceptor having a 2 μm surface protective layer was obtained. Various measurements were performed on this photoreceptor in the same manner as in Example 1.

Table 1 shows the results.

Example 9 Conductive titanium oxide powder 50 coated with tin oxide containing 10% antimony oxide
Parts, phenolic resin 25 parts, methyl cellosolve 20 parts,
5 parts of methanol and 0.002 part of silicone oil (polydimethylsiloxane polyoxyalkylene copolymer, average molecular weight 3000) were dispersed in a sand mill using φ1 mm glass beads for 2 hours to obtain a paint for a conductive layer. This paint was dip-coated on an aluminum cylinder and dried at 140 ° C. for 30 minutes to form a conductive layer having a thickness of 20 μm.

Next, 5 parts of N-methoxymethylated nylon was dissolved in 95 parts of methanol to prepare a coating for an intermediate layer. This paint is dip-coated on the conductive layer,
After drying at 0 ° C. for 20 minutes, a 0.6 μm intermediate layer was formed.

Next, the following structural formula

[0070]

Embedded image 3 parts of oxytitanium phthalocyanine, polyvinyl benzal (benzalization ratio 80%, weight average molecular weight 11
000) 2 parts and cyclohexanone 35 parts are φ1 mm
The mixture was dispersed in a sand mill using glass beads for 12 hours, and then 60 parts of methyl ethyl ketone was added to obtain a dispersion for a charge generation layer. This dispersion was dip-coated on the intermediate layer and dried at 80 ° C. for 20 minutes to form a film having a thickness of 0.2 μm.
m of the charge generation layer was obtained.

Next, the structural formula

[0072]

Embedded image 10 parts of the compound of Example 1 and 10 parts of the copolymer of Example 1 were dissolved in a mixed solvent of 20 parts of dichloromethane and 40 parts of monochlorobenzene. After drying, a charge transport layer having a thickness of 23 μm was formed.

Next, the electrophotographic characteristics of this photoreceptor were evaluated using a commercially available laser printer.
The photoreceptor has good surface lubricity with no fine cracks, no scratches even after 10,000 sheets of durability, no inconvenience such as poor cleaning due to reversal of the cleaning blade, etc. And a good image without scratches was obtained.
In addition, no crack image was observed on the image even after 5 days had passed since finger grease was adhered, and good crack resistance was exhibited.

Example 10 Conductive titanium oxide powder 50 coated with tin oxide containing 10% antimony oxide
Parts, phenolic resin 25 parts, methyl cellosolve 20 parts,
5 parts of methanol and 0.002 parts of silicone oil (polydimethylsiloxane polyoxyalkylene copolymer, average molecular weight 3000) were dispersed in a sand mill using φ1 mm glass beads for 2 hours to obtain a coating for a conductive layer.
This paint was dipped on an 80φ aluminum cylinder and dried at 140 ° C. for 30 minutes to give a film thickness of 20 μm.
Was formed.

Next, 5 parts of N-methoxymethylated nylon was dissolved in 95 parts of methanol to prepare a coating for an intermediate layer. This paint is dipped on the conductive layer,
After drying at 0 ° C. for 20 minutes, a 0.6 μm intermediate layer was formed.

Next, the following structural formula

[0077]

Embedded image 3 parts of oxytitanium phthalocyanine, polyvinyl benzal (benzalization ratio 80%, weight average molecular weight 11
000) and 35 parts of cyclohexanone were dispersed in a sand mill using φ1 mm glass beads for 12 hours, and then 60 parts of methyl ethyl ketone was added to obtain a dispersion for a charge generation layer. This dispersion was dipped on the intermediate layer and dried at 80 ° C. for 20 minutes to form a film having a thickness of 0.2 μm.
Was obtained.

Next, the structural formula

[0079]

Embedded image 10 parts of the compound of Example 1 and 10 parts of the copolymer of Example 1 were dissolved in a mixed solvent of 20 parts of dichloromethane and 40 parts of monochlorobenzene, and this solution was dip-coated on the above-mentioned charge generating layer, and then heated at 120 ° C. for 60 minutes. After drying, a charge transport layer having a thickness of 23 μm was formed.

Next, the electrophotographic characteristics of this photoreceptor were evaluated using a commercially available color copier (PIXCELDIO, manufactured by Canon Inc.). As a result, there were no black spots, fine cracks, etc. Almost no scratches were generated, and even after 10,000 sheets of durability, there was almost no occurrence of deep scratches, and a good image was obtained. No deterioration in image quality due to growth of the scratches due to progress of durability was observed. Was. During this time, no inconvenience such as reversal of the cleaning blade occurred, and therefore, the life of the photosensitive drum was not shortened, and no cleaning failure occurred. In addition, no crack image was observed on the image even after 5 days had passed since finger grease was adhered, and good crack resistance was exhibited.

(Comparative Example 3) A photosensitive member was prepared using a polycarbonate Z resin (viscosity average molecular weight 2.20 × 10 ⁴ ) in the same manner as in Example 5, and the electrophotographic characteristics were evaluated using a commercially available laser printer. After 1000 sheets, relatively deep scratches were observed. In addition, 10,000
After the endurance of the sheet, it was confirmed that relatively deep scratches occurred on the surface layer and defects were generated on the image. In addition, the cleaning blade tends to be turned over during the endurance examination, and thus inconveniences such as poor cleaning tend to occur. At the stage where the resin was adhered and 24 hours had passed, a crack image was clearly observed on the image at the adhered portion, resulting in an image defect.

[0082]

[Table 1]

[0083]

As described above, the image holding member of the present invention has excellent durability, abrasion resistance, friction resistance, and electrical properties, and further has a gelling property of a polycarbonate resin as a binder resin, and a high resistance. Since the solvent cracking property is also improved, the production is easy, and it is industrially extremely advantageous.

──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Shinya Mayama 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. (56) References JP-A-5-72753 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) G03G 5/05 101 G03G 5/06 371 G03G 5/147 502

Claims (1)

(57) [Claims] 1. An image holding member having a photosensitive layer on a conductive support, wherein the surface layer of the photosensitive layer has the following general formula [1]: (Wherein, R ₁ to R ₁₆ are a hydrogen atom, a halogen atom, a methyl group, an ethyl group or a phenyl group, and R ₁₇ is a group having 1 to 1 carbon atoms.
3 alkylene group, to no R ₁₈ R ₂₁ is an alkyl group or an aryl group, A is shows an alkylidene group, an arylene group, an aryl-substituted alkylidene group, arylene alkylidene group, n is an integer of 1 to 200, X and Y
Represents a copolymerization ratio (molar ratio), and Z represents weight% in the copolymer), and the photosensitive layer contains oxytitanium phthalocyanine as a charge generation material. An image holding member.