JPH10158380A - New polycarbonate resin and electrophotographic photoreceptor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject by introducing a specific fluorine-contg. group into its main chain so as to give highly durable electrophotographic photoreceptors excellent in lubricity, shaving resistance and scratch resistance, causing no image defects due to filming, etc., and good in toner separation. SOLUTION: This polycarbonate resin is characterized by containing, in the main chain (A) a constituent unit of formula I [A is F or an F-substituted alkyl (pref. of 3-10C); R<1> to R<5> are each H or F] or (B) a constituent unit of formula II (R<6> and R<7> are each same as R<1> ). This resin is obtained by reaction of a polycarbonate compound such as bisphenol A- or Z-type polycarbonate with the corresponding epoxide (e.g. 3-perfluorobutyl-1,2-epoxypropane, 2,2,3,3,3- tetrafluoropropyl glycidyl ether) in the presence of a base catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel polycarbonate resin and an electrophotographic photoreceptor using the same.
Such an electrophotographic photoreceptor mainly comprises a conductive substrate and a photosensitive layer containing an organic material, and is used for an electrophotographic printer, a copying machine, a facsimile, and the like.

[0002]

2. Description of the Related Art In recent years, electrophotographic photoreceptors using organic photoconductive materials have been designed to have various characteristics of photoreceptors due to low pollution, low cost, and increased freedom of material selection. Many have been proposed and put into practical use from the viewpoint of being able to do so.

The photosensitive layer of an organic electrophotographic photoreceptor mainly comprises a layer in which an organic photoconductive material is dispersed in a resin, and a layer in which a charge generating material is dispersed in a resin (charge generating layer) and a charge transporting material in a resin. Many structures have been proposed, including a structure in which dispersed layers (charge transport layers) are stacked, a single-layer structure in which a charge generation material and a charge transport material are dispersed in a resin, and the like. As these resins, bisphenol A type polycarbonate is widely used.

[0004] These photosensitive layers are generally formed by coating a coating liquid in which an organic photoconductive material and a resin are dissolved or dispersed in an organic solvent.

However, the use of bisphenol A type polycarbonate as a resin has the following disadvantages. (1) When preparing the above-mentioned coating liquid, when preparing using tetrahydrofuran (THF) etc. as an organic bath agent,
The solution gels in a few days, and it becomes impossible to form a uniform and good photosensitive layer when coated with the coating solution. (2) The formed photosensitive layer is liable to cause a solvent crack or a crack due to internal stress. Large cracks appear as image defects as they are, and small cracks tend to cause current leakage from the charging member to the conductive layer of the photoreceptor, particularly in an electrophotographic apparatus using a contact charging type charging device, and current leakage occurs. And appear as image defects. (3) The formed photosensitive layer has poor lubricity, and is liable to be scratched by repeated use of the photoreceptor, causing a filming phenomenon in which toner is entrapped and fixed in the scratch to cause a cleaning failure, and a black solid image is formed. White spot defects are produced. Further, the film is scraped by repeated use, and the life of the photoconductor is shorter than that of the inorganic photoconductor.

[0006] To solve the above-mentioned disadvantage (1), it is possible to extend the time until gelation by using methylene chloride or the like as an organic solvent, but it is not a sufficient solution. . Further, for example, Japanese Patent Application Laid-Open No. 59-710
No. 57 and JP-A-60-172444 disclose a method for solving the disadvantage (1) by using a bisphenol Z-type polycarbonate resin.
However, bisphenol Z type polycarbonate resin,
The disadvantage of (2) is not so effective. To solve this disadvantage, for example, Japanese Patent Application Laid-Open No. 61-62040 discloses a method of mixing a bisphenol A type polycarbonate resin and a bisphenol Z type polycarbonate resin. Is disclosed, JP-A-61-105550 discloses,
It is disclosed to use a copolymer of a bisphenol A type structure and a bisphenol Z type structure. However, at present, none of the methods is a sufficient solution to the disadvantage (2). Regarding the disadvantage of (3), for example, Japanese Patent Application Laid-Open No. 57-212453 discloses a method of adding silicone oil for the purpose of improving lubricity, and Japanese Patent Application Laid-Open No. 63-65444 discloses a method.
A method using a modified polycarbonate having a trifluoromethyl group is disclosed. However, the method of adding silicone oil has a disadvantage that since the silicone oil exists only in the vicinity of the surface of the photoreceptor, if the film is scraped by repeated use, lubricity is lost and the effect cannot be continued. Further, the method of using a modified polycarbonate having a trifluoromethyl group,
Although the lubricity is improved, the effect is still not enough.
The problem of gelation has not been solved.

Further, it has been proposed to form a surface protective layer on the photosensitive layer for the purpose of protecting the photosensitive layer, improving mechanical strength, and improving surface lubricity. However, these surface protective layers also have the same disadvantages as the above-mentioned disadvantages of the photosensitive layer.

In Japanese Patent Application Laid-Open No. 5-158271, an epoxy-modified fluoroalkyl compound and an active hydrogen-containing binder are contained in a coating solution for such a surface protective layer in order to improve mechanical abrasion and cleaning properties. A method of reacting and curing at the time of drying after coating is described. However, in this method, if the reaction curing conditions are not optimized, the unreacted epoxy-modified fluoroalkyl compound remains in the photoreceptor, causing deterioration of the photoreceptor electrical characteristics, making it difficult to control the production of the photoreceptor. There is a disadvantage that.

At present, these photoconductors for electrophotography are generally provided with (I) the application of a uniform charge to the surface (charging),
(II) Light image irradiation (exposure) there, (III) Visualization of electrostatic latent image formed by charging and exposure by adhesion of colored powder (toner) (development), (IV) Finalization of toner image on paper etc. A copying machine using an electrophotographic process of transferring (transferring) to a recording medium, and (V) fusing (fixing) a transferred toner image to the recording medium;
Used for printers, faxes, etc.

Here, in the charging step (I), charging by corona discharge, such as corotron or scorotron, which is one of the non-contact methods, has been conventionally used in many cases. Because of the merit that the generation amount is small, contact charging using a roller or a brush has been put to practical use. However, contact charging easily causes the above-described current leakage, and charging by a brush easily damages the surface of the photoconductor, shortening the life of the photoconductor.

In the developing step (III), a liquid developing method using a developing solution in which small-sized toner particles are dispersed in an insulating liquid, a developing method using a dry toner, and the like are used.
Development methods using dry toner include a two-component development method using a developer consisting of a toner and a carrier and a one-component development method using a developer consisting of only a toner. A non-contact method is used. Among these, a two-component contact development method using a magnetic brush and a magnetic toner and an insulating carrier, and a one-component contact development method using a one-component magnetic toner are mainly used.
In recent years, a one-component contact developing method using a non-magnetic toner and a developing method called a jumping developing method using a one-component magnetic toner and applying an AC bias are becoming mainstream. Recently, a cleaner-less printer that performs cleaning at the same time as development and does not have a cleaner system such as a cleaning blade has been commercialized. For this, a polymerized toner having a small particle diameter and a spherical diameter is used. Generally, small particle size toners such as liquid developing toners and polymerized toners are expected to have high resolution, but because of their large surface area, the adhesion to the photoreceptor increases, and filming is likely to occur. In the transfer step IV), not only does the toner not completely transfer to a recording medium such as paper, but also in a subsequent cleaning step, the toner remains on the photoreceptor and may appear as an image defect. Further, if the transfer efficiency is low, it causes an increase in the amount of toner consumption and waste toner, which is also becoming an environmental issue, and a photoreceptor with good toner separation is desired.

[0012]

SUMMARY OF THE INVENTION An object of the present invention is to provide an electrophotographic photosensitive member having a photosensitive layer on a conductive substrate.
Removes the above defects, excellent lubricity, hard to scrape, hard to scratch, prevent image defects due to filming,
Provided is a novel polycarbonate resin capable of providing a highly durable electrophotographic photosensitive member with good toner separation and an electrophotographic photosensitive member using the same.
An object of the present invention is to provide an electrophotographic photoconductor adapted to a developing process using a nonmagnetic one-component toner or a polymerized toner, a jumping developing process, and a liquid developing process.

Another object of the present invention is to improve the stability of a coating solution for an electrophotographic photosensitive member and to improve the productivity of an electrophotographic photosensitive member.

[0014]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, a novel polycarbonate resin represented by the following general formula (1a) or (1b): (Wherein, A represents a fluorine atom or a fluorine-substituted alkyl group, and R ^{1 to} R ⁷ represent a hydrogen atom or a fluorine atom, and may be the same or different). Here, polycarbonate is a polymer having -O-CO-O- in the main chain, and also includes a copolymer with a polymer having another structure,
The end group of the polymer is not specified, and may have various groups such as a hydroxyl group and a t-butyl group) for the photosensitive layer or the surface protective layer of the electrophotographic photoreceptor. They have found that this can be achieved and have completed the present invention. The coating solution for the surface protective layer described in JP-A-5-158271 is a reaction product of an epoxy group and active hydrogen, and the polycarbonate resin which is a reaction product of an epoxy group and a carbonate group of the present invention. Are different. Further, the effect is lower than in the present invention having a fluorine-containing group in the main chain.

In order to solve the above problems, the novel polycarbonate resin of the present invention comprises: (1) a compound represented by the following general formula (1a) or (1b) (Wherein, A represents a fluorine atom or a fluorine-substituted alkyl group, and R ^{1 to} R ⁷ each independently represent a hydrogen atom or a fluorine atom.) It is characterized by the following. Here, the fluorine-substituted alkyl group preferably has 3 to 10 carbon atoms.
It is.

The electrophotographic photoreceptor of the present invention is an electrophotographic photoreceptor having a photosensitive layer on a conductive substrate.
The photosensitive layer contains the polycarbonate resin.

Further, the electrophotographic photoreceptor of the present invention comprises an electrophotographic photoreceptor having a photosensitive layer and a surface protective layer on a conductive substrate, wherein the surface protective layer contains the polycarbonate resin. It is a feature.

In the photosensitive layer or the surface protective layer, the following general formula (2): (Wherein X is a single bond, -O-, -S-, -CO-,-
^{_{SO -, - SO 2 -,}} - CR 16 R 17 -, - SiR
^{16 R 17 -, - SiR 16} R 17 -O- (R 16, R
¹⁷ is a hydrogen atom, a halogen atom, a carbon atom of 1
To 8 alkyl groups, substituted or unsubstituted aryl groups,
A trifluoromethyl group or a polysiloxane group), a substituted or unsubstituted alkylene group having 2 to 5 carbon atoms, a substituted or unsubstituted alkylidene group having 3 to 8 carbon atoms, a substituted or unsubstituted alkylene group having 5 to 10 carbon atoms. Represents a cycloalkylidene group, a substituted or unsubstituted arylene group, a substituted or unsubstituted aromatic heterocyclic group, or a divalent group in which a plurality of these groups are bonded, and R ^{8 to} R ¹⁵ are each individually A hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms,
Represents an alkoxyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, a substituted or unsubstituted aryl group, or a polysiloxane group. 1)
Or a copolymer having two or more species,
In particular, in the photosensitive layer or the surface protective layer, at least the following formula (3): And a structural unit represented by the following formula (4), A copolymer having a structural unit represented by the following formula (5): Bisphenol A type polycarbonate resin represented by
The following equation (6), Bisphenol Z-type polycarbonate resin represented by
The following equation (7), And / or the following formula (8): Can be contained.

The present invention can be suitably applied to a structure in which the photosensitive layer has a charge transport layer laminated on a charge generation layer.

[0020]

DETAILED DESCRIPTION OF THE INVENTION The polycarbonate resin having the structural unit of the above formula (1a) or (1b) can be prepared by a known method, for example, Journal of Applied Polymer Science, Vo.
It can be synthesized using the method described in l.56, 1-8 (1995). That is, it can be synthesized by reacting a polycarbonate compound with an epoxide in the presence of a catalyst such as a quaternary ammonium salt, a tertiary amine, or a metal alkoxide. This reaction is schematically represented by the following reaction formula, The skeleton represented by the general formula (1a) or (1b) can be introduced into the polycarbonate by the reaction between the carbonate group and the epoxy group in the polycarbonate. As the epoxide as a raw material for synthesizing the polycarbonate resin of the present invention, for example, compounds represented by the following structural formulas (1-1) to (1-12) can be used. The polycarbonate resin used as a raw material for synthesizing the polycarbonate resin of the present invention includes, for example, bisphenol A type, bisphenol Z type polycarbonate, and the following structural formulas (2-1) to (2-82)
A polycarbonate resin having one or more structural units represented by the following formula (1) can be used. However, the present invention is not limited to the illustrated ones.

[0021]

[0022]

[0023]

[0024]

[0025]

[0026]

Hereinafter, embodiments of the present invention will be described with reference to the drawings. FIG. 1 is a conceptual cross-sectional view showing one embodiment of the photoreceptor of the present invention.
Denotes an undercoat layer, 3 denotes a charge generation layer, 4 denotes a charge transport layer, 5 denotes a surface protective layer, and 6 denotes a photosensitive layer. The photosensitive layer 6 has a function separation type separated into a charge generation layer 3 and a charge transport layer 4,
It is roughly classified into a single-layer type containing a charge generating substance and a charge transporting substance. The photosensitive layer 6 in FIGS. 1A and 1B is of a negative charge type in which a charge generation layer 3 and a charge transport layer 4 are laminated in this order, and the photosensitive layer 6 in FIG. Transport layer 4,
The charge generation layer 3 is a positively-charged type laminated in this order, and the photosensitive layer 6 in FIGS. 1D and 1E is a single-layer type, mainly a positively-charged type.

The conductive substrate 1 functions as an electrode of the photoreceptor and serves as a support for the other layers, and may be cylindrical, plate-like, or film-like. Alternatively, a conductive material may be applied to a metal such as nickel, glass, resin, or the like.

The undercoat layer 2 is made of a layer mainly composed of a resin, an oxide film such as alumite, etc., and prevents the injection of unnecessary electric charges from the conductive substrate to the photosensitive layer; It is provided as needed for the purpose of improving adhesiveness and the like. As a resin binder, polyethylene, polypropylene, polystyrene, acrylic resin, vinyl chloride resin, vinyl acetate resin, polyurethane resin, epoxy resin, polyester resin, melamine resin, silicone resin, polybutyral resin, polyamide resin, and copolymers thereof, as appropriate. It is possible to use them in combination. Further, metal oxide fine particles and the like may be contained in the resin binder. As the metal oxide fine particles, SiO ₂ , Ti
O ₂ , In ₂ O ₃ , ZrO _2, or the like can be used.

The thickness of the undercoat layer 2 depends on the composition of the undercoat layer 2, but can be arbitrarily set within a range where adverse effects such as an increase in residual potential do not occur when repeatedly used continuously. . The charge generation layer 3 is formed by vacuum-depositing an organic photoconductive substance or applying a material in which particles of the organic photoconductive substance are dispersed in a resin binder, and generates charges by receiving light. In addition, it is important that the charge generation efficiency is high, and at the same time, the injected property of the generated charge into the charge transport layer 4 is important.

Since the charge generation layer 3 only needs to have a charge generation function, its thickness is determined by the light absorption coefficient of the charge generation substance and is generally 5 μm or less, preferably 1 μm or less. The charge generation layer 3 may be mainly composed of a charge generation substance and may be used by adding a charge transport substance or the like thereto. As the charge generation material, phthalocyanine pigments, azo pigments, anthrone pigments, perylene pigments, perinone pigments, squarylium pigments, thiapyrylium pigments, quinacridone pigments, and the like can be used, or these pigments can be used in combination. In particular, as the phthalocyanine-based pigment, metal-free phthalocyanine, copper phthalocyanine, and titanyl phthalocyanine are preferable. Further, X-type metal-free phthalocyanine, τ-type metal-free phthalocyanine, ε
Type copper phthalocyanine, β-type titanyl phthalocyanine, Y
Preference is given to titanyl phthalocyanine of the type, a CuKα described in Japanese Patent Application No. Hei 6-289363: a titanyl phthalocyanine having a maximum peak at a Bragg angle 2θ of 9.6 ° in an X-ray diffraction spectrum.

The resin binder used for the charge generation layer 3 includes the polycarbonate resin of the present invention and other polycarbonate resins, polyester resins, polyamide resins, polyurethane resins, epoxy resins, polybutyral resins, vinyl chloride copolymers, and phenoxy resins. , A silicone resin, a methacrylate resin and a copolymer thereof can be used in an appropriate combination.

The charge transporting layer 4 is a coating film made of a material in which a charge transporting substance is dispersed in a resin binder. The charge transporting layer 4 holds the charge of the photoreceptor as an insulator layer in a dark place. It has the function of transporting injected charges.

As the charge transporting substance, charge transporting polymers such as hydrazone compounds, pyrazoline compounds, pyrazolone compounds, oxadiazole compounds, oxazole compounds, arylamine compounds, benzidine compounds, stilbene compounds, styryl compounds and polyvinylcarbazole are used. It is possible to Particularly, a compound having a structure represented by the following structural formulas (3-1) to (3-11) is preferable.

[0035]

As the resin binder used for the charge transport layer 4, the polycarbonate resin of the present invention and other polycarbonate resins, polyester resins, polystyrene resins, methacrylic acid ester polymers and copolymers, etc. may be used in appropriate combination. Is possible.

The thickness of the charge transport layer 4 is preferably in the range of 3 to 50 μm, more preferably 10 to 40 μm, in order to maintain a practically effective surface potential.

In the case of the single-layer type photosensitive layer, it is a coating film composed of a material in which a charge generating substance and a charge transporting substance are dispersed in a resin binder. It can be used as well. The film thickness should be 3-5 to maintain a practically effective surface potential.
The range is preferably 0 μm, more preferably 10 to 40 μm
It is.

The photosensitive layer 6 may optionally contain an electron acceptor for the purpose of improving the sensitivity, reducing the residual potential, or reducing the characteristic fluctuation upon repeated use. As the electron acceptor, succinic anhydride, maleic anhydride, dibromo succinic anhydride, phthalic anhydride, 3-nitrophthalic anhydride, 4-nitrophthalic anhydride, pyromellitic anhydride, pyromellitic acid, trimellitic acid, Trimellitic anhydride, phthalimide, 4-nitrophthalimide,
Examples thereof include compounds having a high electron affinity such as tetracyanoethylene, tetracyanosinodimethane, chloranil, bromanyl, and o-nitrobenzoic acid.

The photosensitive layer 6 may contain a deterioration inhibitor such as an antioxidant or a light stabilizer for the purpose of improving environmental resistance and stability against harmful light. Compounds used for such purposes include chromanol derivatives such as tocopherol and etherified compounds, esterified compounds, polyarylalkane compounds,
Hydroquinone derivatives, etherified compounds, dietherified compounds, benzophenone derivatives, benzotriazole derivatives, thioether compounds, phenylenediamine derivatives, phosphonate esters, phosphite esters, phenol compounds, hindered phenol compounds, linear amine compounds, cyclic amine compounds And hindered amine compounds.

Further, in the photosensitive layer 6, for the purpose of improving the leveling property of the formed film and imparting further lubricity,
A leveling agent such as silicone oil or fluorine-based oil may be contained.

The surface protective layer 5 can be provided as needed, and is provided in the form shown in FIGS. 1 (b), (c) and (e). The surface protective layer 5 has excellent lubricity, excellent durability against mechanical stress, and is made of a chemically stable substance, and has a function of receiving and holding a charge of corona discharge in a dark place. In addition, the charge generation layer 3 has a performance of transmitting light that is sensitive to the light, and transmits light at the time of exposure, reaches the charge generation layer 3, and receives the injected charge to neutralize and eliminate the surface charge. is necessary. As described above, it is desirable that the material used is as transparent as possible in the wavelength region where the light absorption of the charge generating substance is maximum.

As the material of the surface protective layer 5, in addition to the polycarbonate resin of the present invention, a modified silicone resin
An acrylic-modified silicone resin, an epoxy-modified silicone resin, an alkyd-modified silicone resin, a polyester-modified silicone resin, a urethane-modified silicone resin, and the like, and a silicone resin as a hard coat agent can be applied. These resins can be used alone, but for the purpose of further improving durability, SiO ₂ , TiO ₂ , In ₂ O
₃ , a mixed material with a condensate of a metal alkoxy compound capable of forming a film containing ZrO ₂ as a main component is preferable. Further, for the purpose of improving the leveling property of the surface protective layer 5 and imparting further lubricity, a leveling agent such as silicone oil or fluorine-based oil may be contained.

The thickness of the surface protective layer 5 can be arbitrarily set within a range that does not cause an adverse effect such as an increase in residual potential when used repeatedly and continuously.

[0045]

DESCRIPTION OF THE PREFERRED EMBODIMENTS An embodiment of the present invention will be described below.
First, Synthesis Examples (Synthesis Examples 1 to 7) of the polycarbonate resin of the present invention will be described. Synthesis Example 1 Bisphenol A type polycarbonate compound having a constitutional unit of the above (2-5) (trade name: Panlite K13)
00, manufactured by Teijin Chemicals Ltd.) and 10 g of the above-mentioned (1-7) 3- (perfluoro-7-methyloctyl) 1,2-epoxypropane (trade name: E-3830, manufactured by Daikin Kasei Co., Ltd.) 3 g and 0.05 g of tetrabutylammonium iodide (TBAI) were dissolved in 50 g of methylene chloride and stirred. Thereafter, methylene chloride was removed and the resulting solid was heated at 60 ° for 24 hours. This was dissolved in 200 g of methylene chloride, reprecipitated by adding 500 g of methanol, filtered, and dried. Thus, the following structural formulas (4-1a) and (4-1b), Thus, 11.2 g of a polycarbonate resin (4-1) composed of the structural units was obtained.

Synthesis Example 2 As a raw material polycarbonate compound, bisphenol Z type polycarbonate compound having the structural unit of the above (2-37) (trade name: Panlite TS2050, Teijin Chemicals Ltd.) instead of (Panlite K1300) in Synthesis Example 1 The synthesis was performed in the same manner as in Synthesis Example 1 except that
9.8 g of a polycarbonate resin (4-2) comprising the structural units of the following structural formulas (4-2a) and (4-2b) was obtained.

Synthesis Example 3 As a raw material polycarbonate compound, a copolymer polycarbonate (commercial product) having the structural unit of (2-1) and the structural unit of (2-5) instead of (Panlite K1300) in Synthesis Example 1 Name: Toughzet BPPC-3, manufactured by Idemitsu Kosan Co., Ltd.), and synthesized in the same manner as in Synthesis Example 1, except that the following structural formulas (4-3a), (4-3b) and (4-3c) 10.4 g of a polycarbonate resin (4-3) composed of constituent units was obtained.

Synthesis Example 4 Synthesis was carried out in the same manner as in Synthesis Example 3 except that 0.5 g of (E3830) and 0.01 g of TBAI were used as the raw material epoxide, and the following structural formula (4-4a): (4-4
9.3 g of a polycarbonate resin (4-4) composed of the constituent units (b) and (4-4c) was obtained.

Synthesis Example 5 As a starting material epoxide, 3- (1H, 1H, 9H-hexadecafluoroonyloxy) -1,2-epoxypropane of the above (1-12) was used instead of (E3830) in Synthesis Example 1. (Product name: E5844, Daikin Kasei Co., Ltd.)
The synthesis was performed in the same manner as in Synthesis Example 1 except that the above-mentioned process was used to obtain 11.1 g of a polycarbonate resin (4-5) comprising the structural units of the following structural formulas (4-5a) and (4-5b).

Synthesis Example 6 As the starting epoxide, 3- (1H, 1H, 9H-hexadecafluoroonyloxy) -1,2-epoxypropane of the above (1-12) was used instead of (E3830) in Synthesis Example 3. (Product name: E5844, Daikin Kasei Co., Ltd.)
), Except that the following resin was used. Synthesis was performed in the same manner as in Synthesis Example 3 to obtain a polycarbonate resin (4-6) composed of structural units represented by the following structural formulas (4-6a), (4-6b), and (4-6c). 9.8 g were obtained.

Synthesis Example 7 As a raw material epoxide, 3-perfluorooctyl- (1-3) was used in place of (E3830) in Synthesis Example 3.
Synthesized in the same manner as in Synthesis Example 3 except that 1,2-epoxypropane (trade name: E1830, manufactured by Daikin Kasei Co., Ltd.) was used, and the following structural formulas (4-7a), (4-7b), and ( 10.0 g of a polycarbonate resin (4-7) comprising the structural unit of 4-7c) was obtained.

Next, examples of the electrophotographic photosensitive member of the present invention will be described. Hereinafter, “parts” means “parts by weight”. Example 1 A drum photoreceptor (30 mmφ) was prepared for evaluating electrical characteristics. An undercoat layer dispersion having the following composition was dip-coated on an aluminum tube and dried at 100 ° C. for 30 minutes to form a film having a thickness of 3
An undercoat layer of μm was formed. Alcohol-soluble nylon (CM8000: Toray Industries, Inc.) 5 parts Titanium oxide fine particles treated with aminosilane 5 parts Methanol / methylene chloride mixed solvent (6/4 (v / v)) 90 parts Next, a charge generation layer having the following composition Dip coating the dispersion,
After drying at 00 ° C. for 30 minutes, a charge generation layer having a thickness of 0.3 μm was formed. Titanyl phthalocyanine (Japanese Patent Application No. Hei 6-289363) Production Example 1 1 part Vinyl chloride copolymer resin (MR-110: Nippon Zeon Co., Ltd.) 1 part Methylene chloride 98 parts The above titanyl used in this example X of phthalocyanine
FIG. 2 shows the line diffraction spectrum. Next, a charge transport layer solution having the following composition was applied by dip coating and dried at 100 ° C. for 30 minutes to form a charge transport layer having a thickness of 20 μm. 9 parts of hydrazone compound (the above (3-4) CTC191: anan flavoring company) 1 part of butadiene compound (the above (3-1) T405: anan flavoring company) Polycarbonate resin (Synthesis example 1 (4-1)) 10 parts Methylene chloride 90 parts An electrophotographic photoreceptor was prepared as described above.

Example 2 The polycarbonate resin used in Example 1 (Synthesis Example 1)
(4-1)) Example 1 except that 10 parts of a polycarbonate resin (Synthesis Example 2 (4-2)) was used instead of 10 parts.
A photoreceptor was prepared in the same manner as described above.

Example 3 The polycarbonate resin used in Example 1 (Synthesis Example 1)
(4-1)) Example 1 was repeated except that 10 parts of a polycarbonate resin (Synthesis Example 3 (4-3)) was used instead of 10 parts.
A photoreceptor was prepared in the same manner as described above.

Example 4 The polycarbonate resin used in Example 1 (Synthesis Example 1)
(4-1)) Example 1 was repeated except that 10 parts of a polycarbonate resin (Synthesis Example 4 (4-4)) was used instead of 10 parts.
A photoreceptor was prepared in the same manner as described above.

Example 5 The polycarbonate resin used in Example 1 (Synthesis Example 1)
(4-1)) Example 1 was repeated except that 10 parts of a polycarbonate resin (Synthesis Example 6 (4-6)) was used instead of 10 parts.
A photoreceptor was prepared in the same manner as described above.

Example 6 The polycarbonate resin used in Example 1 (Synthesis Example 1)
(4-1)) Example 1 except that 10 parts of a polycarbonate resin (Synthesis Example 7 (4-7)) was used instead of 10 parts.
A photoreceptor was prepared in the same manner as described above.

Example 7 The polycarbonate resin used in Example 1 (Synthesis Example 1)
(4-1)) Instead of 10 parts, 7 parts of a polycarbonate resin (Synthesis Example 1 (4-1)) and a bisphenol Z-type polycarbonate resin (trade name: Panlite TS205)
A photoconductor was prepared in the same manner as in Example 1 except that 3 parts (0, manufactured by Teijin Chemicals Ltd.) were used.

Example 8 The polycarbonate resin used in Example 1 (Synthesis Example 1)
(4-1)) Instead of 10 parts, 7 parts of a polycarbonate resin (Synthesis Example 5 (4-5)) and a bisphenol Z-type polycarbonate resin (trade name: Panlite TS205)
A photoconductor was prepared in the same manner as in Example 1 except that 3 parts (0, manufactured by Teijin Chemicals Ltd.) were used.

Example 9 The polycarbonate resin used in Example 1 (Synthesis Example 1)
(4-1)) Instead of 10 parts, bisphenol A type polycarbonate resin (trade name: Panlite K130)
0, manufactured by Teijin Chemicals Limited, and 3 parts of a polycarbonate resin (Synthesis Example 2 (4-2)), and a photoconductor was prepared in the same manner as in Example 1.

Example 10 Polycarbonate resin used in Example 1 (Synthesis Example 1)
(4-1)) Instead of 10 parts, 7 parts of a polycarbonate resin (Synthesis Example 3 (4-3)) and a bisphenol Z-type polycarbonate resin (trade name: Panlite TS205)
A photoconductor was prepared in the same manner as in Example 1 except that 3 parts (0, manufactured by Teijin Chemicals Ltd.) were used.

Example 11 The polycarbonate resin used in Example 1 (Synthesis Example 1)
(4-1)) Instead of 10 parts, 7 parts of a copolymerized polycarbonate resin (trade name: TUFZET BPPC-3, manufactured by Idemitsu Kosan Co., Ltd.) and a polycarbonate resin (Synthesis Example 2)
(4-2)) A photoconductor was prepared in the same manner as in Example 1, except for using 3 parts.

Example 12 The polycarbonate resin used in Example 1 (Synthesis Example 1)
(4-1)) Example 1 was repeated except that instead of 10 parts, 7 parts of a polycarbonate resin (Synthesis Example 6 (4-6)) and 3 parts of a polycarbonate resin (Synthesis Example 2 (4-2)) were used. Similarly, a photoreceptor was prepared.

Example 13 The polycarbonate resin used in Example 1 (Synthesis Example 1)
(4-1)) Instead of 10 parts, 7 parts of a polycarbonate resin (Synthesis Example 6 (4-6)) and 3 parts of a polycarbonate resin (trade name: APEC HT KU1-9371, manufactured by Bayer K.K.) were used. A photoconductor was prepared in the same manner as in Example 1 except for the above.

Comparative Example 1 The polycarbonate resin used in Example 1 (Synthesis Example 1)
(4-1)) Instead of 10 parts, bisphenol A type polycarbonate resin (trade name: Panlite K130)
Example 1 except that 10 parts (0, manufactured by Teijin Chemicals Ltd.) were used.
A photoreceptor was prepared in the same manner as described above.

Comparative Example 2 The polycarbonate resin used in Example 1 (Synthesis Example 1)
(4-1)) Instead of 10 parts, bisphenol Z-type polycarbonate resin (trade name: Panlite TS205)
Example 1 except that 10 parts (0, manufactured by Teijin Chemicals Ltd.) were used.
A photoreceptor was prepared in the same manner as described above.

Comparative Example 3 The polycarbonate resin used in Example 1 (Synthesis Example 1)
(4-1)) A photoreceptor was prepared in the same manner as in Example 1 except that 10 parts of a copolymerized polycarbonate resin (trade name: TUFZET BPPC-3, manufactured by Idemitsu Kosan Co., Ltd.) was used instead of 10 parts. did.

Comparative Example 4 The polycarbonate resin used in Example 1 (Synthesis Example 1)
(4-1)) Instead of 10 parts, bisphenol A type polycarbonate resin (trade name: Panlite K130)
0, Teijin Chemicals Limited) and 7 parts of bisphenol Z-type polycarbonate resin (trade name: Panlite TS205)
A photoconductor was prepared in the same manner as in Example 1 except that 3 parts (0, manufactured by Teijin Chemicals Ltd.) were used.

Comparative Example 5 The polycarbonate resin used in Example 1 (Synthesis Example 1)
(4-1)) Instead of 10 parts, 7 parts of a copolymerized polycarbonate resin (trade name: TUFZET BPPC-3, manufactured by Idemitsu Kosan Co., Ltd.) and bisphenol Z-type polycarbonate resin (trade name: Panlite TS2050, Teijin) A photoreceptor was prepared in the same manner as in Example 1, except that 3 parts of the product was used.

Comparative Example 6 The polycarbonate resin used in Example 1 (Synthesis Example 1)
(4-1)) Instead of 10 parts, 7 parts of a copolymerized polycarbonate resin (trade name: TUFZET BPPC-3, manufactured by Idemitsu Kosan Co., Ltd.) and 7 parts of a polycarbonate resin (trade name: A)
(PEC HT KU1-9371, manufactured by Bayer K.K.)
A photoconductor was prepared in the same manner as in Example 1, except that three parts were used.

Example 14 A surface protective layer solution having the following composition was dip-coated on a photoreceptor produced in the same manner as in Comparative Example 2, and dried at 120 ° C. for 60 minutes to form a surface protective layer having a thickness of 4 μm. did. Polycarbonate resin (Synthesis Example 3 (4-3)) 2 parts THF 98 parts A photoconductor was prepared as described above.

The charge transport layer solution (CTL solution) used for the preparation of the photoreceptor was allowed to stand for one month in a dark place at a temperature of 20 ° C. and a humidity of 50% for one month to determine whether the charge transport layer solution gelled. confirmed.

Next, the durability of the obtained photosensitive member was evaluated as follows. That is, the photoreceptor was mounted on a laser printer (Laser Jet4 plus) manufactured by Hewlett-Packard Company, and 10,000 images of a printing rate of about 5% were printed, and a full black image and a full white image were printed every 1,000 sheets. The evaluation items are as follows. Visual Evaluation of Image Visual Evaluation of Photoreceptor Surface Evaluation of Abrasive Film Amount After 10,000 Sheets of Images Appeared The results of these evaluations are shown in Table 1 below.

[0074]

[Table 1]

[0075]

As described above, according to the present invention, a highly durable electrophotographic material having excellent lubricity, being hard to scrape, not being easily damaged, preventing image defects due to filming, etc., and having good toner separation. A photoreceptor is obtained, which is useful for a printer, a copying machine, a facsimile and the like using an electrophotographic system. Further, it is possible to improve the stability of the coating solution for the electrophotographic photosensitive member.

[Brief description of the drawings]

1 (a) to 1 (e) are schematic cross-sectional views of an electrophotographic photoconductor of the present invention, and FIGS. 1 (a) and 1 (b) show a configuration of a negative charging function separated type photoconductor; (C) shows the configuration of a positively charged function-separated type photoconductor, and (d) and (e) show the configuration of a positively charged single-layer type photoconductor.

FIG. 2 is an X-ray diffraction spectrum of titanyl phthalocyanine used in Examples of the present invention.

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 conductive substrate 2 undercoat layer 3 charge generation layer 4 charge transport layer 5 surface protective layer 6 photosensitive layer

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[Procedure amendment]

[Submission date] November 13, 1997

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0035

[Correction method] Change

[Correction contents]

[0035]

Claims (16)

[Claims] 1. In the main chain, the following general formula (1a) or (1b): (Wherein, A represents a fluorine atom or a fluorine-substituted alkyl group, and R ^{1 to} R ⁷ each independently represent a hydrogen atom or a fluorine atom.) A polycarbonate resin, characterized in that: 2. An electrophotographic photosensitive member having a photosensitive layer on a conductive substrate, comprising the polycarbonate resin according to claim 1 in the photosensitive layer. 3. An electrophotographic photoreceptor having a photosensitive layer and a surface protective layer on a conductive substrate, wherein the surface protective layer contains the polycarbonate resin according to claim 1. Photoconductor. 4. In the photosensitive layer, the following general formula (2): (Wherein X is a single bond, -O-, -S-, -CO-,-
^{_{SO -, - SO 2 -,}} - CR 16 R 17 -, - SiR
^{16 R 17 -, - SiR 16} R 17 -O- (R 16, R
¹⁷ is a hydrogen atom, a halogen atom, a carbon atom of 1
To 8 alkyl groups, substituted or unsubstituted aryl groups,
A trifluoromethyl group or a polysiloxane group), a substituted or unsubstituted alkylene group having 2 to 5 carbon atoms, a substituted or unsubstituted alkylidene group having 3 to 8 carbon atoms, a substituted or unsubstituted alkylene group having 5 to 10 carbon atoms. Represents a cycloalkylidene group, a substituted or unsubstituted arylene group, a substituted or unsubstituted aromatic heterocyclic group, or a divalent group in which a plurality of these groups are bonded, and R ^{8 to} R ¹⁵ are each individually A hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms,
Represents an alkoxyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, a substituted or unsubstituted aryl group, or a polysiloxane group. 1)
3. The electrophotographic photoreceptor according to claim 2, comprising a copolymer having one or more species. 5. In the surface protective layer, the following general formula (2): (Wherein X is a single bond, -O-, -S-, -CO-,-
^{_{SO -, - SO 2 -,}} - CR 16 R 17 -, - SiR
^{16 R 17 -, - SiR 16} R 17 -O- (R 16, R
¹⁷ is a hydrogen atom, a halogen atom, a carbon atom of 1
To 8 alkyl groups, substituted or unsubstituted aryl groups,
A trifluoromethyl group or a polysiloxane group), a substituted or unsubstituted alkylene group having 2 to 5 carbon atoms, a substituted or unsubstituted alkylidene group having 3 to 8 carbon atoms, a substituted or unsubstituted alkylene group having 5 to 10 carbon atoms. Represents a cycloalkylidene group, a substituted or unsubstituted arylene group, a substituted or unsubstituted aromatic heterocyclic group, or a divalent group in which a plurality of these groups are bonded, and R ^{8 to} R ¹⁵ are each individually A hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms,
Represents an alkoxyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, a substituted or unsubstituted aryl group, or a polysiloxane group. 1)
The electrophotographic photoreceptor according to claim 3, comprising a copolymer having one or more species. 6. In the photosensitive layer, at least the following formula (3): And a structural unit represented by the following formula (4), The electrophotographic photoreceptor according to claim 4, comprising a copolymer having a structural unit represented by the following formula: 7. The surface protective layer according to claim 1, wherein at least the following formula (3): And a structural unit represented by the following formula (4), The electrophotographic photoreceptor according to claim 5, comprising a copolymer having a structural unit represented by the following formula: 8. The photosensitive layer further comprises the following formula (5): The electrophotographic photoconductor according to claim 4 or 6, further comprising a bisphenol A-type polycarbonate resin represented by the following formula: 9. The method according to claim 1, wherein the surface protective layer further comprises the following formula (5): The electrophotographic photoconductor according to claim 5, comprising a bisphenol A-type polycarbonate resin represented by the formula: 10. The photosensitive layer further comprises the following formula (6): The electrophotographic photoconductor according to claim 4, 6 or 8, comprising a bisphenol Z-type polycarbonate resin represented by the following formula: 11. The surface protective layer further comprises the following formula (6):
10. The electrophotographic photoconductor according to claim 5, which comprises a bisphenol Z-type polycarbonate resin represented by the following formula: 12. The photosensitive layer further comprises the following formula (7): The polycarbonate resin represented by the formula 4,
11. The photoconductor for electrophotography according to 6, 8, or 10. 13. The surface protective layer further comprises the following formula (7): A polycarbonate resin represented by the formula 5,
12. The photoconductor for electrophotography according to 7, 9, or 11. 14. The photosensitive layer further comprises the following formula (8): The polycarbonate resin represented by the formula 4,
13. The photoconductor for electrophotography according to 6, 8, 10 or 12. 15. The surface protective layer further comprises the following formula (8): A polycarbonate resin represented by the formula 5,
14. The photoconductor for electrophotography according to 7, 9, 11, or 13. 16. The electrophotographic photoconductor according to claim 2, wherein the photosensitive layer has a structure in which a charge transport layer is laminated on a charge generation layer.