DE19752444A1 - Polycarbonate resin giving high slip, wear- and damage-resistant, very durable film on photoconductor - Google Patents

Abstract

Polycarbonate resins (I) with a main chain contain units of formula (IA) or (IB), in which A = fluorine (F) or F-substituted alkyl; R<1-7> = hydrogen (H) or F. Also claimed are electrophotographic photoconductors with a conducting substrate and a photoconducting film that contains or has a protective coating containing (I). The conducting or protective film contains a copolymer with (IA) or (IB) units and also units of formula (II), where X = a single bond, oxygen (-O-), sulphur (-S-), carbonyl (-CO-), sulphinyl (-SO-), sulphonyl (-SO2-), a (substituted) methylene (-CR<16>R<17>), silyl (-SiR<16>R<17>-), siloxy (-SiR<16>R<17>-O-), 2-5 carbon (C) alkylene, 3-8 C alkylidene, 5-10 C cycloalkylidene, arylene or aromatic heterocyclic group or a divalent group consisting of 2 or more of these groups; R<1-15> = H, halogen, 1-8 C alkyl, 1-8 C alkoxy, 5-10 C cycloalkyl, (substituted) aryl or a polysiloxane group; R<16>, R<17> = H, halogen, 1-8 C alkyl, (substituted) aryl, CF3 or a polysiloxane group. The film especially contains a polymer of bisphenol A carbonate, bisphenol carbonate or bisphenol Z carbonate; or a copolymer of n bisphenol A carbonate units with m bisphenol carbonate or m' bisphenol Z carbonate units, more especially with n, m, m' = 10-1000, n/(n+m) = 0.1-0.95 and n /(n+m') = 0-0.95.

Description

Field of invention

The invention relates to a new polycarbonate resin. The invention also relates to an electrophotographic photoconductor (hereinafter referred to simply as "photoconductor") which includes a conductive substrate and an organic photoconductive film containing the new polycarbonate resin. The invention relates to a electrophotographic photoconductor used in a printer, a copier and FAX machine which uses electrophotographic processes use.

State of the art

Recently, many organic photoconductors have been proposed, and some are already on the market because the organic photoconductors are free from environmental pollution pollution are manufactured at low cost and in various ways be designed, as there is increasing freedom in the selection of for their on suitable organic materials.

The photoconductive film of the organic photoconductor contains organic photolei tend materials dispersed in a synthetic resin. For the photoconductive film Numerous structures have been proposed, including a lami nat structure comprising a charge generation layer with an in one Resin dispersed charge generation agent and charge transport layer with a charge transport agent dispersed in a synthetic resin as well as a single layer photoconductive film which is a chargeer generating agent and a charge transport agent in a synthetic resin disper contains greed.

Bisphenol A polycarbonate is often used as the synthetic resin.

These photoconductive films are generally formed by making a Applies coating liquid containing an organic solvent, in which the organic photoconductive material and the synthetic resin are dissolved or dispersed.

Problems in the prior art and object of the invention

The bisphenol A polycarbonate used as synthetic resin has the following problems:

• (1) When as the organic solvent of the coating liquid Tetrahydrofuran (THF) is used, the bisphenol A gelatinizes coating liquid containing polycarbonate in a few days. if the gelatinized coating liquid is used, it is impossible to to obtain a uniform and excellent photoconductive film.
• (2) Solvent cracks and cracks tend to be formed due to internal stresses in the photoconductive film containing bisphenol A-polycarbonate resin. Large cracks immediately create image defects. Small Cracks result in leakage current from the charging device to the conductive one Layer of photoconductor, especially in electrophotographic devices, using a contact type charging device. The leakage current creates further image defects.
• (3) The bisphenol A polycarbonate resin-containing photoconductive film shows poor lubricating and sliding properties and repeated use the photoconductor will scratch the photoconductor. The toner sinks into the Scratches, and then it becomes a toner filming phenomenon such as unsuccessful low cleaning because of the toner and effects that have penetrated into the cracks te caused in the form of white spots in the deep black image. Since the fotolei tending film is worn out by its repeated use is the le life of the photoconductor, the photoconductive film of which is bisphenol-A- contains polycarbonate resin, shorter than that of inorganic photoconductors.

It is possible to extend the time until gelatinization occurs, in using methylene chloride as the organic solvent, although which is not a perfect way to avoid problem (1). the Japanese Unexamined Patent Publication Nos. JP-A-S59-71057 and No. JP-A-S60-172044 describes the method for avoiding the Pro blems (1) by using bisphenol-Z polycarbonate resin, however this method is not so effective in avoiding the problem (2).

Furthermore, JP-A-S61-62040 describes a mixture of bisphenol A polycarbonate resin and bisphenol-Z polycarbonate resin and JP-A-S61-105550 a copolymer with bisphenol A structure and bisphenol Z structure for prevention tion of problems (1) and (2), but provide the mixture described and the copolymer described does not provide a satisfactory solution to the problem (2).

Regarding the problem (3), JP-A-S57-21 2453 describes the addition of Silicone oil to improve lubricity and JP-A-S63-65444 the Ver use of modified polycarbonate with trifluoromethyl groups. However the lubricity is lost when the photoconductor surface passes through again fetched use wears out because the added silicone oil is close to the top surface of the photoconductor remains. So it is difficult to see the effect of the silicone oil additive to maintain for a long time. A modified polycar bonat with a content of trifluoromethyl groups improves the lubricity in To some extent, but not yet satisfactory, and neither does it avoid it the problem of gelatinization.

It has also been proposed to use a surface protective film on the fo to arrange conductive film to protect the latter and the mechanical To improve the strength and surface slip of the photoconductor. Of the However, surface protective film is subject to problems similar to those described in US Pat photoconductive film occur.

JP-A-H05-158271 describes a method for improvement the mechanical wear resistance and easier cleaning of the upper surface protection films. According to this method, the coating liquid contains a fluoroalkyl compound with epoxy and an active hydrogen containing binder is modified. These components are combined which reacted to the coating liquid after coating before cure in a subsequent drying process. However, it is not easy to control the reaction process of this method. If the Reak tion and curing conditions are not optimized, worsens the Epoxy-modified fluoroalkyl compound that did not react and on top Surface protection film remains, the electrical properties of the photoconductor.

The photoconductor is commonly used in copiers, printers and facsimiles machines using electrophotographic processes, such as (I) uniform application of electrical charges to the photoconductors surface (charging), (II) irradiation of a light image on the charged Surface (exposure), (III) visualization of the by charging and the Exposure of the electrostatic latent image formed to color powder, e.g. B. Toner (development), (IV) Transfer of the toner image onto the final image drawing medium, such as paper (copying) and (V) melting the copier th toner image on the recording medium (fixing).

In the charging process (I) is the non-contact charging method by Corona-Ent charge, such as the corotron method and scorotron method are widely used been det. Lately the contact charging with a roller or Brush designed as it has advantages such as no need of high voltage and lower ozone formation. However, the contact charging method tends to be de to cause the leakage current described above, and that for Kon The brush used with clock charging tends to scratch the photoconductor surface damage and thus shorten the life of the photoconductor.

In the development process (III), the liquid development method, which is a liquid developer consisting of an insulating Lö solvent and small toner particles dispersed therein, and the uses dry developing method using dry toner. In the case of the dry development method, one can further distinguish between the Two-component development, which consists of a toner and a carrier of the development agent used, and the one-component development, which uses a developing agent composed of toner only. Both the Two-component as well as the one-component development method are used in contact mode, with the toner layer and the photo foil ter are brought into contact with each other, and in non-contact mode, in which the toner layer and the photoconductor are not brought into contact will. The two-component development, which is a magnetic brush, magnetic toner and insulating carrier used, and the one Component development that includes a magnetic brush and an Component magnetic toners used are mainly used been. Recently, the one-component design has also been used to a greater extent winding method, which non-magnetic toner and the so-called Jump development method, the one-component magnetic toner and uses an applied AC bias to a greater extent applied. Recently there have been cleaner-free printers that do the cleaning run at the same time as developing and do not use detergents, such as a Cleaning sheet, have put on the market. In the cleaner-free print At the core, polymerized toner having a small particle diameter is used. In general, the small grain diameter toner is expected to be such as the toner for liquid development and polymerized toner, the achievement a high resolution. However, the small grain diameter toner adheres water is stronger on the photoconductor and tends to form films, since the toner with small Grain diameter increases the surface area. Also becomes the fine-grained Toner in the copying process (IV) does not completely transfer onto the recording medium transfer like paper. In addition, the fine-grain toner remains sometimes after cleaning on the photoconductor and causing image defects. There is therefore a need for a photoconductor from which the tone can be heard Can be removed more easily, since the low copying efficiency is higher Toner consumption and a larger amount of exhausted toner, which white cause pollution.

In view of the foregoing, it is a purpose of the invention to solve the above problems of the common photoconductor. It is a Another purpose of the invention is a novel polycarbonate resin and photo film ter who used the new polycarbonate resin to create the high performance is strong, wear and damage resistant and highly durable. A Another purpose of the invention is to provide a photoconductor that uses new polycarbonate resin and makes it easier to prevent image defects those that go back to film formation and similar causes and the distance Make it easier to remove the toner from the photoconductor. Another purpose of the invention is a photoconductor adaptable for the contact charging process, the Ent development process using one-component non-magnetic toner, the development process using polymerized toner, the jump development process, and the liquid ent winding process.

Another purpose of the invention is to improve the stability of the coating fluids skills for the manufacture of photoconductors and the productivity of the photoconductor ter to improve.

Solution of the task

The inventors of the present application have found that the aforementioned purposes of the invention can be achieved by using a novel polycarbonate resin having a main chain represented by one or more of those represented by a general formula (1a) or (1b) as shown in FIG indicated, contains be written building units, wherein A is a fluorine atom or a fluorine-substituted alkyl group and each radical R ¹ to R ^{7 is} a hydrogen atom or a fluorine atom, in the photoconductive film or in the surface protective film. Polycarbonate is a polymer that has -O-CO-O- in its main chain. Polycarbonates include copolymers with other polymer structures. Polycarbonates have unspecified end groups and various substituent groups such as hydroxyl and t-butyl groups. The known coating liquid for the surface protective film described in JP-A-H05-158271 is a reaction product of epoxy groups and active hydrogen and different from the polycarbonate resin of the present invention which is a reaction product of epoxy groups and carbonate groups. The known coating liquid is less effective than the polycarbonate resin of the present invention which has fluorine-containing groups in the main chain.

According to one aspect of the invention, therefore, a polycarbonate resin is provided which has a main chain which has one or more structural units described by the general formulas (1a) or (1b) of FIG. 3, wherein A is a fluorine atom or a fluorine-substituted alkyl group and each of R ¹ to R ^{7 is} a hydrogen atom or a fluorine atom. Preferably, the above-described alkyl group of the polycarbonate resin according to the invention has three to ten carbon atoms.

According to another aspect of the invention, there is provided an electrophotographic photoconductor having a conductive substrate and a photoconductive film thereon, the photoconductive film containing a polycarbonate resin comprising a main chain with one or more structural units represented by the structure shown in FIG. 3, wherein A is a fluorine atom or a fluorine-substituted alkyl group and each of R ¹ to R ^{7 is} a hydrogen atom or a fluorine atom.

According to a further aspect of the invention, there is provided an electrophotographic photoconductor which has a conductive substrate, on this one photoconductive film and on the photoconductive film a surface protective film, the surface protective film containing a polycarbonate resin comprising a main chain with one or more structural units, are described by the formula (1a) or (1b) shown in Fig. 3, wherein A is a fluorine atom or a fluorine-substituted alkyl group, and each of R ¹ to R ^{7 is} a hydrogen atom or a fluorine atom.

Advantageously, the photoconductive film or the surface protective film contains a copolymer containing one or more structural units, each of which is described by a general formula (2) in Fig. 4, wherein -X- is a single bond or -O-, -S- , -CO-, -SO-, -SO ₂ -, -CR ¹⁶ R ¹⁷ -, -SiR ¹⁶ R ¹⁷ - or SiR ¹⁶ R ¹⁷ -O-, in which each R ¹⁶ and R ^{17 is} a hydrogen atom, a halogen atom , an alkyl group with 1 to 8 carbon atoms, a substituted or unsubstituted aryl group, a trifluoromethyl group or a Polysi loxane group or X is a substituted or unsubstituted alkylene group with 2 to 5 carbon atoms, a substituted or unsubstituted alkylidene group with 3 to 8 carbon atoms, a substituted or unsubstituted cycloalkylidene group having 5 to 10 carbon atoms, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aromatic heterocyclic group or a divalent group pe denotes each of the two or more groups described above, where each of R ⁸ to R ^{15 is} a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy 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.

Advantageously, the photoconductive film or the surface protective film comprises a copolymer having a structural unit described by a formula (3) in FIG. 5 and a structural unit described by formula (4) in FIG. 6.

Advantageously, the photoconductive film or the surface protective film comprises a bisphenol A polycarbonate resin represented by a formula (5) in FIG. 7.

Further advantageously, the photoconductive film or the surface protective film comprises a bisphenol-Z polycarbonate resin represented by a formula (6) in FIG. 8.

Advantageously, the photoconductive film or the surface protective film comprises a polycarbonate resin represented by a formula (7) in FIG. 9.

Advantageously, the photoconductive film or the surface protective film comprises a polycarbonate resin represented by a formula (8) in FIG. 10.

Advantageously, the photoconductive film comprises a charge generation layer and a (laminated) charge transport arranged on it layer.

Embodiments of the invention

The polycarbonate resin having the structural unit described by the formulas (1a) or (1b) can be synthesized by the method described, for example, in Journal of Applied Polymer Science, Vol, 56 (1995), pages 1-8. That is, the polycarbonate resin is synthesized by reacting a polycarbonate compound with epoxy in the presence of a catalyst such as a quaternary ammonium salt, a tertiary amine and a metal alkoxide. The reaction is schematically described by a reaction equation (A) in FIG . By reacting the carbonate group in the polycarbonate and the epoxy group, the framework described by the general formula (1a) or (1b) can be introduced into the polycarbonate. The compounds described by structural formulas (1-1) to (1-12) in Fig. 12 can be used as a starting material for synthesizing the polycarbonate resin of the present invention. In addition to the bisphenol-A polycarbonate resin and the bisphenol-Z polycarbonate resin, the polycarbonate resins having one or more structural units represented by structural formulas (2-1) to (2-82) in Figs. 13 (a) to 13 (e ) can be used as the starting polycarbonate resin for the synthesis of the polycarbonate resin of the present invention. The starting materials for the synthesis of the polycarbonate resin of the present invention are not limited to those described above.

The Fig. 1 (a) and 1 (b) are schematic cross sections of the erfindungsge MAESSEN photoconductor of the type having a negative charge, and functional separation. Fig. 1 (c) is a schematic cross section of the photoconductor according to the invention with positive charging and functional separation. FIGS. 1 (d) and 1 (e) are schematic cross sections of the single-layer photoconductors according to the invention with positive charge. In these figures, 1 denotes a conductive substrate, 2 a base layer film, 3 a charge generation layer, 4 a charge transport layer, 5 a surface protective film, and 6 a photoconductive film. The photoconductor can be classified as one with functional separation, as shown in Figs. 1 (a), 1 (b) and 1 (c), wherein a photoconductive film 6 consists of an individual charge generation layer 3 and charge transport layer 4 , and a single layer photoconductor as shown in Figs. 1 (d) and 1 (e) which includes a photoconductive film 6 containing a charge generation agent and a charge transport agent. The Fotolei ter of Fig. 1 (a) and 1 (b) are of the type having a negative charge, wherein the charge transport layer 4 is deposited on the charge generation layer 3. The photoconductor of Fig. 1 (c) is of the positive charge type where the charge generation layer 3 is placed on the charge transport layer 4. The single-layer photoconductors of FIGS. 1 (d) and 1 (e) are mainly of the positive charge type.

The conductive substrate 1 acts as an electrode of the photoconductor and as a carrier of the other films and layers forming the photoconductor. The conductive substrate 1 may be shaped as either a cylindrical tube, plate or film and made of aluminum, stainless steel, a metal such as nickel, or glass, or a resin with a surface made electrically conductive. The base layer film 2 is a film containing a synthetic resin as a main component, or it is a film of anodized alumina and corresponding oxides. The base film 2 is arranged as necessary to prevent unnecessary charges from being injected from the conductive substrate to the photoconductive film to cover surface defects of the substrate and to improve the adhesion of the photoconductive film to the substrate. The resin binders that can be used for the base layer film 2 include polyethylene, polypropylene, polystyrene, acrylic resin, poly (vinyl chloride) resin, vinyl acetate resin, polyurethane resin, epoxy resin, polyester resin, melamine resin, silicone resin, polybutyral resin, polyamide resin, copolymers of these resins and suitable combinations of the above resins and copolymers described. Metal oxide small particles may be dispersed in these resin binders, and oxides such as SiO ₂ , TiO ₂ , In ₂ O ₃ and ZrO ₂ can be used for them. Though the thickness of the base layer film 2 depends on its composition, it can be set in any range as long as it does not cause adverse effects such as residual potential increase with repeated use.

The charge generation layer 3 is formed by vacuum deposition of the organic photoconductive material or by coating with a resin binder in which particles of the organic photoconductive material are dispersed. The charge generation layer 3 generates charges in accordance with the received light. It is important that the charge generation layer 3 has a high charge generation efficiency and a high efficiency of injection of the generated charges into the charge transport layer 4 . It is desirable that the charge generation layer 3 have a high charge injection efficiency regardless of the electric field strength and even in a weak electric field.

The thickness of the charge generation layer 3 is determined by the light absorption coefficient of the charge generation agent, usually with a thickness of 5 µm or less and preferably 1 µm or less, since it is sufficient for the charge generation layer 3 to generate electric charges. The charge generation layer 3 mainly contains a charge generation agent and, as an additional component, a charge transport agent. The charge generation agents include phthalocyanine, azo, antanthrone, perylene, perynone, squarilium, thiapyrylium, quinacridone pigments and combinations thereof. Particularly preferred are the phthalocyanine pigments such as metal-free phthalocyanine, copper phthalocyanine, titanyl phthalocyanine, metal-free X-type, τ-type, ε-copper phthalocyanine, β-titanyl phthalocyanine, Y-titanyl phthalocyanine and titanyl phthalocyanine described in JP-A-H06-289363 and shows the highest peak at 9.6 ° Bragg angle 2θ in the X-ray diffraction spectrum measured with Cu K α radiation.

The resin binders for the charge generation layer 3 include the polycarbonate resins according to the invention, the other polycarbonate resins, polyester, polyamide, polyurethane, epoxy, polybutyral, vinyl chloride copolymers, phenoxy, silicone, methacrylate resins, their copolymers and suitable combinations of these resins and copolymers.

The charge transport layer 4 is a coating film comprising a resin binder in which a charge transport agent is dispersed. The charge transport layer 4 retains the charges of the photoconductor in the dark and transports the charges injected from the charge generation layer in accordance with the received light. Charge transport agents include hydrazone, pyrazoline, pyrazolone, oxadiazole, oxazole, arylamine, benzidine, stilbene, styryl compounds, and charge transport polymers such as poly (vinyl carbazole). The compounds represented by structural formulas (3-1) to (3-11) in Fig. 14 are particularly preferred.

The binder resins for the charge transport layer 4 include the polycarbonate resins of the present invention, the other polycarbonate resins, polyester resin, polystyrene resin, methacrylate polymers, methacrylate copolymers, and suitable combinations of these resins, polymers and copolymers.

The charge transport layer 4 is preferably 3 to 50 μm thick in order to maintain the practically effective surface potential and further preferably 10 to 40 μm thick.

The single-layer photoconductive film is a coating film containing a binder resin in which a charge generation agent and a charge transport agent are dispersed. The above-mentioned materials for the charge generation layer 3 and the charge transport layer 4 are used for the one-layer photoconductive film. Preferably, the single-layer photoconductive film has a thickness of 3 to 50 µm in order to maintain the practically effective surface potential, and more preferably 10 to 40 µm in thickness.

The photoconductive film 6 may contain an electron acceptor if necessary to increase its sensitivity and reduce the residual potential and the change in properties during repeated use of the photo conductor. As the electron acceptor, compounds showing a high electron affinity can be used, such as acid anhydrides of succinic, maleic, dibromomuccinic, phthalic, 3-nitrophthalic, 4-nitrophthalic, trimellitic and pyromellitic acids, pyromellitic acid and trimellitic acid itself, phthalimide , 4-nitrophthalimide, tetracyanoethylene, tetracyanoquinodimethane, chloranil, bromanil and o-nitrobenzoic acid.

Degradation inhibitors such as an antioxidant and a light stabilizer can be contained in the photoconductive film 6 in order to improve its stability against harmful surroundings and radiation. Degradation inhibitors include chroma nol derivatives such as tocopherol, etherified compounds, esterified compounds, polyarylalkane compounds, hydroquinone derivatives, diether compounds, benzophenone derivatives, benzotriazole derivatives, thioether compounds, phenylenediamine derivatives, phosphonic acid esters, phosphite, linear phenol compounds, sterically hindered phenol compounds and hindered amine compounds.

A leveling agent such as silicone oil and fluorinated oil can be used in the photoconductive Film must be included to maintain the flatness and lubricity of the fo so formed to improve conductive film.

The surface protective film 5 can be arranged, if necessary, as shown in Figs. 1 (b), 1 (c) and 1 (e). The surface protective film 5 is made of a chemically stable material that shows excellent sliding properties and resistance to mechanical stress. The surface protection film 5 must hold back the charges generated by corona discharge in the dark and let light through to which the charge generation layer 3 is sensitive, allow the exposure light to pass through to the charge generation layer and receive the generated charges in order to neutralize and extinguish the surface charges. As described above, the materials for the surface protective film 5 must be transparent at the maximum absorption wavelength of the charge generation agent.

The polycarbonate resins, modified silicone resin, acrylic modified silicone resin, epoxy-modified silicone resin, alkyd-modified silicone resin, polyester-modified silicone resin, urethane-modified silicone resin and silicone resin of the present invention can be used as the hard coating agent alone for the surface protective film 5 . In order to further improve durability, a mixture of any of these synthetic resins and a condensation product of metal alkoxide compounds capable of forming a coating film containing _{SiO 2} , TiO ₂ , In ₂ O ₃ or ZrO _{2 is preferred.} In the surface protective film 5 , a leveling agent such as silicone oil and fluorinated oil may be contained in order to further improve the flatness and lubricity thereof.

The thickness of the surface protective film 5 can be set in any range as long as no adverse effects such as residual potential increase are caused upon repeated use.

Embodiments

Embodiments of the invention will now be explained.

First, the embodiments of synthesis (Synthesis 1 to 7) of the polycarbonate resin of the invention explained.

Synthesis 1

10 g of the bisphenol A polycarbonate resin with the structural unit (2-5) (Panlite K1300; supplier Teijin Chemicals Ltd.), 3 g of 3- (perfluoro-7-methyloctyl) 1,2-epoxypropane with the structural formula (1-7 ) (E-3830, supplier to Daikin Industries, Ltd.) and 0.05 g of tetrabutylammonium iodide (TBAI) were dissolved in 50 g of methylene chloride. After stirring, the methylene chloride was removed. The solid obtained was heated at 60 ° C. for 24 hours. The solid was then dissolved in 200 g of methylene chloride and reprecipitated by adding 500 g of methanol. The precipitate was filtered off and dried. This gave 11.2 g of the polycarbonate resin (4-1) with structural units corresponding to the structural formulas (4-1a) and (4-1b) in FIG. 15.

Synthesis 2

A polycarbonate resin was synthesized in a similar manner to the polycarbonate resin of Synthesis 1, except that the bisphenol-Z-polycarbonate resin of structural unit (2-37) (Panlite TS2050, supplier to Teijin Chemicals, Ltd.) was synthesized as the starting polycarbonate compound instead of the Panlite K1300 of the synthesis 1 was used and 9.8 g of the polycarbonate resin (4-2) having structural units corresponding to structural formulas (4-2a) and (4-2b) in Fig. 16 were obtained.

Synthesis 3

A polycarbonate resin was synthesized in a similar manner to the polycarbonate resin of Synthesis 1 except for the copolymerized polycarbonate having structural units (2-1) and (2-5) (Toughzet BPPC-3, supplier to Idemitsu Kosan Co., Ltd.) as the starting material. Polycarbonate compound was used instead of Panlite K1300 of synthesis 1 and 10.4 g of the polycarbonate resin (4-3) with structural units corresponding to the structural formulas (4-3a), (4-3b) and (4-3c) in FIG. 17 were obtained became.

Synthesis 4

A polycarbonate resin was synthesized in a similar manner to the polycarbonate resin of synthesis 3, except that 0.5 g of E3830 and 0.01 g of TBAI of synthesis 1 were used as the starting epoxy for synthesis 4 and 9.3 g of the polycarbonate resin (4 -4) with structural units corresponding to the structural formulas (4-4a), (4-4b) and (4-4c) in FIG. 18 were obtained.

Synthesis 5

A polycarbonate resin was synthesized in a similar manner to the polycarbonate resin of Synthesis 1, except that 3- (1H, 1H, 9H-hexadecafluorononyloxy) -1- 2-epoxypropane represented by the structural formula (1-12) (E5844; supplied by Daikin Industries, Ltd .) Was used as the starting epoxide instead of the E3830 of Synthe se 1 and 11.1 g of the polycarbonate resin (4-5) with structural units corresponding to the structural formulas (4-5a) and (4-5b) in FIG. 19 were obtained.

Synthesis 6

A polycarbonate resin was synthesized in a manner similar to the polycarbonate resin of Synthesis 3, except that 3- (1H, 1H, 9H-hexadecafluorononyloxy) -1- 2-epoxypropane represented by structural formula (1-12) (E5844; supplied by Daikin Industries, Ltd .) was used as the starting epoxide instead of the E3830 of Synthe se 3 and 9.8 g of the polycarbonate resin (4-6) with structural units corresponding to the structural formulas (4-6a), (4-6b) and (4-6c) in Fig. 20 were obtained.

Synthesis 7

A polycarbonate resin was synthesized in a manner similar to the polycarbonate resin of Synthesis 3, except that 3-perfluorooctyl-1,2-epoxypropane having the structural formula (1-3) (E1830; supplier to Daikin Industries, Ltd.) was used as the starting epoxide instead of the E3830 of the synthesis 3 was used and 10.0 g of the polycarbonate resin (4-7) having structural units corresponding to structural formulas (4-7a), (4-7b) and (4-7c) in Fig. 21 was obtained.

The following are embodiments of the photoconductor according to the invention explained.

Embodiment 1 (A1)

A photoconductor drum (30 mm in diameter) was prepared to evaluate the electrical properties. A base layer film of 3 μm thickness was prepared on an aluminum pipe by dip coating with a dispersion liquid and drying it at 100 ° C. for 30 minutes, the dispersion liquid having the following composition:

Alcohol Soluble Nylon (CM 8000; supplier to Toray Industrie, Inc.) 5 parts by weight Fine-grained titanium dioxide, treated with aminosilane 5 parts by weight Mixed solvent of methanol and methylene chloride in a volume ratio of 6/4 90 parts by weight

Then, a charge generation layer of 0.3 µm in thickness was formed on the base layer film by dip coating with a dispersion liquid and drying it at 100 ° C for 30 minutes, the dispersion liquid having the following composition:

Titanyl phthalocyanine (according to JP-A-H06-289363, the first embodiment of the preparation with the X-ray diffraction spectrum shown in Fig. 2) 1 weight parts Vinyl chloride copolymer (MR-110; supplier: Nippon Zeon Co., Ltd.) 1 part by weight Methylene chloride 98 parts by weight

Then, a charge transport layer 20 µm thick was formed on the charge generation layer by dip coating with a dispersion liquid and drying it at 100 ° C for 30 minutes, the dispersion liquid having the following composition:

Hydrazone Compound (3-4) (CTC191; Supplier to Anan Corporation) 9 parts by weight Butadiene Compound (3-1) (T405; Supplier to Anan Corporation) 1 part by weight Polycarbonate resin (4-1) (synthesis 1) 10 parts by weight Methylene chloride 90 parts by weight

In this way, the photoconductor of Embodiment 1 was manufactured.

Embodiments 2 to 13

In these embodiments, a photoconductor were each in a similar manner se made like the photoconductor of Embodiment 1, but each in the dispersion liquid for the charge transport layer that in the Aus Guide form 1 used 10 parts by weight of the polycarbonate resin (4-1) of Synthesis 1 have been replaced with those given for each embodiment Polycarbonate resins.

Embodiment 2 (A2):
10 parts by weight of the polycarbonate resin (4-2) of Synthesis 2.

Embodiment 3 (A3):
10 parts by weight of the polycarbonate resin (4-3) of synthesis 3.

Embodiment 4 (A4):
10 parts by weight of the polycarbonate resin (4-4) of synthesis 4.

Embodiment 5 (A5):
10 parts by weight of the polycarbonate resin (4-6) of synthesis 6.

Embodiment 6 (A6):
10 parts by weight of the polycarbonate resin (4-7) of Synthesis 7.

Embodiment 7 (A7):
7 parts by weight of the polycarbonate resin (4-1) of Synthesis 1 and 3 parts by weight of bisphenol-Z polycarbonate resin (Panlite TS2050, supplier to Teijin Chemicals, Ltd.).

Embodiment 8 (A8):
7 parts by weight of the polycarbonate resin (4-5) of synthesis 5 and 3 parts by weight of bisphenol-Z polycarbonate resin (Panlite TS2050, supplier to Teijin Chemicals, Ltd.).

Embodiment 9 (A9):
7 parts by weight of bisphenol A polycarbonate resin (Panlite K1300, supplier Teijin Chemicals, Ltd.) and 3 parts by weight of polycarbonate resin (4-2) of synthesis 2.

Embodiment 10 (A10):
7 parts by weight of the polycarbonate resin (4-3) of Synthesis 3 and 3 parts by weight of bisphenol-Z polycarbonate resin (Panlite TS2050, supplier to Teijin Chemicals, Ltd.).

Embodiment 11 (A11):
7 parts by weight of copolymerized polycarbonate resin (Toughzet BPPC-3, vendor Idemitsu Kosan Co., Ltd.) and 3 parts by weight of polycarbonate resin (4-2) of Synthesis 2.

Embodiment 12 (A12):
7 parts by weight of the polycarbonate resin (4-6) of synthesis 6 and 3 parts by weight of polycarbonate resin (4-2) of synthesis 2

Embodiment 13 (A13):
7 parts by weight of the polycarbonate resin (4-6) of synthesis 6 and 3 parts by weight of polycarbonate resin (APEC HAT KU1-9371; supplier: Bayer Japan Ltd.).

Comparative Examples 1 to 6

In the comparative examples, a photoconductor was manufactured in a manner similar to that of the photoconductor of Embodiment 1, except that 10 parts by weight of the polycarbonate resin (4-1) of Synthesis 1 used in the dispersion liquid to form the charge transport layer were replaced with that Polycarbonate resins specified for this comparative example.
Comparative example 1 (V1):
10 parts by weight of bisphenol A polycarbonate resin (Panlite K1300; supplier Teijin Chemicals, Ltd.)
Comparative example 2 (V2):
10 parts by weight bisphenol-Z polycarbonate resin (Panlite TS 2050; supplier Teijin Chemicals, Ltd.)
Comparative example 3 (V3):
10 parts by weight of the copolymerized polycarbonate resin (Toughzet BPPC-3; supplier: Idemitsu Kosan Co., Ltd.)
Comparative example 4 (V4):
7 parts by weight bisphenol A polycarbonate resin (Panlite K1300; supplier Teijin Chemicals, Ltd.) and 3 parts by weight bisphenol Z polycarbonate resin (Panlite TS 2050; supplier Teijin Chemicals, Ltd.)
Comparative example 5 (V5):
7 parts by weight of copolymerized polycarbonate resin (Toughzet BPPC-3; supplier: Idemitsu Kosan Co., Ltd.) and 3 parts by weight of bisphenol-Z polycarbonate resin (Panlite TS 2050; supplier: Teijin Chemicals, Ltd.)
Comparative example 6 (V6):
7 parts by weight of copolymerized polycarbonate resin (Toughzet BPPC-3; supplier Idemitsu Kosan Co., Ltd.) and 3 parts by weight of polycarbonate resin (APEC HAT KU1-9371; supplier Bayer Corp.)

Embodiment 14 (A14)

A photoconductor of Embodiment 14 was prepared by laminating a surface protective film on the photoconductor laminate of Comparative Example 2. The surface protective film of Embodiment 14 was formed to be 4 µm in thickness by applying a coating liquid having the following composition by dip coating and at 120 ° C for 60 minutes dried:

Polycarbonate resin (4-3) of synthesis 3 2 parts by weight THF 98 parts by weight

For testing the resistance of the coating liquids (abbreviated CTL) for the formation of the charge transport layer of the photoconductors described above the coating liquids were at a temperature of 20 ° C and allowed to stand at a relative humidity of 20% and it was taken under seeks whether gelatinization has occurred or not.

The durability of the photoconductors obtained as described above became as follows rated.

The photoconductors were printed on a laser printer (Laser Jet 4 plus; supplier Hewlett Packard Co.) and it was put on 10,000 sheets of paper Images printed at a print density of about 5%, with 1,000 sheets each a solid black and a solid white image were printed the. The evaluation points are as follows.

• 1) Assessment of the printed images by visual inspection
• 2) Visual assessment of the photoconductor surface
• 3) Evaluation of film splitting after printing 10,000 images.

Table 1 shows the results of the evaluations

Table 1

Effect of the invention

According to the invention there is provided a photoconductor with a high lubricating effect (Slidability), good abrasion resistance, good resistance to damage and high durability. The photoconductor of the present invention is very useful for electrophotographic devices such as printers, copiers and Fax machines. The photoconductor according to the invention facilitates avoidance of image defects caused by film formation and the like and the Ent removal of toner. According to the invention, the stability of the manufacture Development of the photoconductor used coating liquids improved.

Brief description of the figures

Fig. 1 (a) and 1 (b): schematic cross sections of the Fotolei ter according to the invention with negative charging and functional separation;

Fig. 1 (c) is a schematic cross-section of the photoconductor according to the invention with a positive charging and separation of functions;

Fig. 1 (d) and (e) schematic cross sections of the inventive one-layer photoconductor with positive charge;

Fig. 2 is an X-ray diffraction spectrum of the titanyl phthalocyanine used in the embodiments of the invention;

Fig. 3 shows the general formulas (1 a) and (1 b) of the structural units of the polycarbonate resin OF INVENTION to the invention.

Figs. 4 to 10 describe each of the formulas contained in the requested photoconductive film or the surface protective layer of the photoconductor according to the invention copolymers or resins, namely:

Fig. 4 shows the general formula (2) of the structural unit of the copolymer;

Fig. 5 shows the formula (3) of the structural unit of the copolymer;

Fig. 6 shows the formula (4) of the structural unit of the copolymer;

Fig. 7 shows the formula (5) of bisphenol A polycarbonate resin;

Fig. 8 shows the formula (6) of bisphenol-Z polycarbonate resin;

Fig. 9 shows the formula (7) of the polycarbonate resin;

Fig. 10 shows the formula (8) of the polycarbonate resin.

. Figure 11 shows the reaction formula for the synthesis of the inventive SEN polycarbonate resin having the structural unit describes, in Formulas 1 (a) and 1 (b) in Fig. 3;

Fig. 12 describes the structural formulas (1-1) to (1-12) of the rials as starting materials for the synthesis of the polycarbonate resin according to the invention used does compounds;

Fig. 13 (a) to 13 (e) describe the structural formulas (2-1) to (2-82) of the structural tureinheiten the output polycarbonate resins used for the synthesis of the polycarbonate resins of the invention.

Fig. 14 shows structural formulas (3-1) to (3-11) of preferred compounds for the charge transport agent;

Fig. 15 describes the structural formulas (4-1a) and (4-1b) of the structural units of the polycarbonate resin (4-1) of the present invention.

Fig. 16 shows the structural formulas (4-2a) and (4-2b) of the structural units describes the polycarbonate resin (4-2) according to the invention.

Fig. 17 describes the structural formulas (4-3a), (4-3b) and (4-3c) of the structural units of the polycarbonate resin of the present invention (4-3).

Fig. 18 describes the structural formulas (4-4a), (4-4b) and (4-4c) of the structural units of the polycarbonate resin of the present invention (4-4).

Fig. 19 describes the structure of formulas (4-5a) and (4-5b) of the structural units of the polycarbonate resin of the invention (4-5).

Fig. 20 describes the structural formulas (4-6a), (4-6b) and (4-6c) of the structural units of the polycarbonate resin of the present invention (4-6).

Fig. 21 describes the structural formulas (4-7a), (4-7b) and (4-7c) of the structural units of the polycarbonate resin of the present invention (4-7).

List of reference symbols

1

conductive substrate

2

base layer

3rd

Charge generation layer

4th

Charge transport layer

5

Surface protection film

6th

Photoconductive film

Claims (19)

1. Polycarbonate resin having a main chain containing one or more structural units represented by the following general formula (1a) or (1b):
wherein A represents a fluorine atom or a fluorine-substituted alkyl group and each of R ¹ to R ^{7 represents} a hydrogen atom or a fluorine atom. 2. Electrophotographic photoconductor having a conductive substrate and a photoconductive film arranged thereon, characterized in that the photoconductive film contains a polycarbonate resin which has a main chain which has one or more structural units represented by the fol lowing general formulas (1a) or (1b) are shown,
wherein A represents a fluorine atom or a fluorine-substituted alkyl group and each of R ¹ to R ^{7 represents} a hydrogen atom or a fluorine atom. 3. Electrophotographic photoconductor having a conductive substrate, a photoconductive film arranged thereon and a surface protective film arranged on the photoconductive film, characterized in that the surface protective film contains a polycarbonate resin having a main chain which has one or more structural units represented by the following general formulas (1a) or (1b) are given,
wherein A represents a fluorine atom or a fluorine-substituted alkyl group and each of R ¹ to R ^{7 represents} a hydrogen atom or a fluorine atom. 4. The electrophotographic photoconductor according to claim 2, characterized in that the photoconductive film contains a copolymer having one or more structural units each represented by 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 - or SiR ¹⁶ R ¹⁷ -O- and each R ¹⁶ and R ^{17 is} a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted aryl group, a trifluoromethyl group or a polysiloxane group, or where X is a substituted or unsubstituted alkylene group having 2 to 5 carbon atoms, a substituted or unsubstituted one Alkylidene group having 3 to 8 carbon atoms, a substituted or unsubstituted cycloalkylidene group having 5 to 10 carbon atoms, a substituted or unsubstituted arylene group, a substituted or unsubstituted aromatic heterocyclic group or a divalent group consisting of two or more of the groups described above and each of R ⁸ to R ^{15 are} a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms tomen, a cycloalkyl group having 5 to 10 carbon atoms, a substituted or unsubstituted aryl group or a polysiloxane group. 5. The electrophotographic photoconductor according to claim 3, characterized in that the surface protective film contains a copolymer having one or more structural units each represented by 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 - or SiR ¹⁶ R ¹⁷ -O- and each R ¹⁶ and R ^{17 is} a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted aryl group, a trifluoromethyl group or a polysiloxane group, or where X is a substituted or unsubstituted alkylene group having 2 to 5 carbon atoms, a substituted or unsubstituted one Alkylidene group having 3 to 8 carbon atoms, a substituted or unsubstituted cycloalkylidene group having 5 to 10 carbon atoms, a substituted or unsubstituted arylene group, a substituted or unsubstituted aromatic heterocyclic group or a divalent group consisting of the above-described two or more groups and each of R ⁸ to R ¹⁵ a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms omen, a cycloalkyl group having 5 to 10 carbon atoms, a substituted or unsubstituted aryl group, or a polysiloxane group. 6. The electrophotographic photoconductor according to claim 4, characterized in that the photoconductive film contains a copolymer having a structural unit represented by the following formula (3) and a structural unit represented by the following formula (4), having
7. The electrophotographic photoconductor according to claim 5, characterized in that the surface protective film contains a copolymer having a structural unit represented by the following formula (3) and a structural unit represented by the following formula (4), having
8. The electrophotographic photoconductor according to claim 4, characterized in that the photoconductive film contains a bisphenol A polycarbonate resin represented by the following formula (5), wherein n is an integer indicating the degree of polymerization,
9. Electrophotographic photoconductor according to claim 5, characterized in that the surface protective film contains a bisphenol-A polycarbonate resin corresponding to the following formula (5), wherein n is an integer indicating the degree of polymerization,
10. Electrophotographic photoconductor according to claim 4, characterized in that the photoconductive film contains a bisphenol-Z-polycarbonate resin corresponding to the following formula (6), wherein n is an integer indicating the degree of polymerization,
11. Electrophotographic photoconductor according to claim 5, characterized in that the surface protective film contains a bisphenol-Z-polycarbonate resin corresponding to the following formula (6), wherein n is an integer indicating the degree of polymerization,
12. Electrophotographic photoconductor according to claim 4, characterized in that the photoconductive film contains a polycarbonate resin corresponding to the fol lowing formula (7), wherein n and m are each an integer from 10 to 1000 and n / (n + m) = 0.1 0.95
13. Electrophotographic photoconductor according to claim 5, characterized in that the surface protective film contains a polycarbonate resin corresponding to the following formula ( 7 ), wherein n and m are each an integer from 10 to 1000 and n / (n + m) = 0, 1 ∼ 0.95
14. Electrophotographic photoconductor according to claim 4, characterized in that the photoconductive film contains a polycarbonate resin corresponding to the fol lowing formula (8), wherein n and m are each an integer from 10 to 1000 and n / (n + m) = 0 ∼ 0.95
15. The electrophotographic photoconductor according to claim 5, characterized in that the surface protective film contains a polycarbonate resin corresponding to the following formula (8), wherein n and m are each an integer from 10 to 1000 and n / (n + m) = 0 ∼ 0.95
16. Electrophotographic photoconductor according to claim 2, characterized net that the photoconductive film has a charge generation layer and a this (laminated) charge transport layer applied as a layer one or the other of these layers being a polycarbonate resin according to formula (1a) or (1b) of claim 2 contains. 17. Electrophotographic photoconductor according to claim 4, characterized in that net that the photoconductive film has a charge generation layer and a this (laminated) charge transport layer applied as a layer one or the other of these layers being a polycarbonate resin according to the formula (2) of claim 4 contains. 18. Electrophotographic photoconductor according to claim 3, characterized in that net that the photoconductive film has a charge generation layer and a this (laminated) charge transport layer applied as a layer shows. 19. Electrophotographic photoconductor according to claim 3, characterized in that net that the photoconductive film has a charge generation layer and a this (laminated) charge transport layer applied as a layer and the charge generation layer or the charge transport layer or the surface protective film is a polycarbonate resin represented by the formula (2) of claim 4 included.