Photoreceptor for electrophotography, method for manufacturing the same, and electrophotographic device

Abstract

A photoreceptor for electrophotography, a method for manufacturing the photoreceptor, and an electrophotographic device including the photoreceptor are disclosed. The photoreceptor for electrophotography includes a conductive substrate; and a photosensitive layer that is provided on the conductive substrate and that has an outermost surface layer containing at least a resin binder and an electron transport material. The resin binder is composed of a polyarylate resin having a structural unit represented by a Chemical Structural Formula 1, and the electron transport material is composed of a compound having a structure represented by a Structural Formula (ET2-3). The photoreceptor has high sensitivity, low residual electric potential, no light fatigue and sufficient stain resistance.

Claims

1. A photoreceptor for electrophotography, comprising: a conductive substrate; a photosensitive layer that is provided on the conductive substrate and that has an outermost surface layer containing at least a resin binder and an electron transport material, the resin binder being comprised of a polyarylate resin having a structural unit represented by Chemical Structural Formula 1 below, and the electron transport material being comprised of a compound having a structure represented by Structural Formula (ET2-3) below, Chemical Structural Formula 1: ##STR00051## ##STR00052## where partial structural formulae (A.sub.1), (A.sub.2), (B.sub.1), (B.sub.2), (C), (D), (E), and (F) represent respective structural units constituting the resin binder, a.sub.1, a.sub.2, b.sub.1, b.sub.2, c, d, e, and f represents mol % of the respective structural units (A.sub.1), (A.sub.2), (B.sub.1), (B.sub.2), (C), (D), (E), and (F), where a.sub.1, a.sub.2, b.sub.1, and b.sub.2 are not zero, where a.sub.1+a.sub.2+b.sub.1+b.sub.2+c+d+e+f is 100 mol %, and where c+d+e+f range from greater than 0 up to 10 mol % and e and f are not both zero mol %; W.sub.1 and W.sub.2 are different, W.sub.1 is selected from the group consisting of a single bond, O, and CR.sub.22R.sub.23, where C is a carbon atom and R.sub.22 and R.sub.23 are different, are monovalently bonded to the carbon atom of CR.sub.22R.sub.23, and are respectively selected from the group consisting of a hydrogen atom, an alkyl group having from 1 to 12 carbon atoms, a halogenated alkyl group, and a substituted or unsubstituted aryl group having from 6 to 12 carbon atoms; and W.sub.2 is selected from the group consisting of a single bond, O, and CR.sub.22R.sub.23, where R.sub.22 and R.sub.23 are the same or different and are respectively selected from the group consisting of a hydrogen atom and an alkyl group having 1 carbon atom, wherein, in the partial structural formulas (A.sub.1) and (B.sub.1), when the group W.sub.1 is CR.sub.22R.sub.23, the groups R.sub.22 and R.sub.23 may bond together to form a cyclohexylidene group, and R.sub.1 to R.sub.20 are the same or different and are respectively selected from the group consisting of a hydrogen atom, an alkyl group having from 1 to 8 carbon atoms, a fluorine atom, a chlorine atom, or a bromine atom; R.sub.21 represents a hydrogen atom, an alkyl group having from 1 to 20 carbon atoms, an aryl group optionally containing a substituent, a cycloalkyl group optionally containing a substituent, a fluorine atom, a chlorine atom, and a bromine atom, and s and t each represent an integer of 1 or more, and Structural Formula (ET2-3): ##STR00053##

2. The photoreceptor for electrophotography according to claim 1, wherein the electron transport material further contains one or both of compounds having a structure represented by General Formulae (ET1) and (ET3) below, ##STR00054## where, in the General Formula (ET1): R.sub.24 and R.sub.25 are the same or different and respectively represent one of a hydrogen atom, an alkyl group having from 1 to 12 carbon atoms, an alkoxy group having from 1 to 12 carbon atoms, an aryl group optionally containing a substituent, a cycloalkyl group, an aralkyl group optionally containing a substituent, or a halogenated alkyl group; R.sub.26 represents a hydrogen atom, an alkyl group having from 1 to 6 carbon atoms, an alkoxy group having from 1 to 6 carbon atoms, an aryl group optionally containing a substituent, a cycloalkyl group, an aralkyl group optionally containing a substituent, or a halogenated alkyl group; and R.sub.27 to R.sub.31 are the same or different and respectively represent one of a hydrogen atom, a halogen atom, an alkyl group having from 1 to 12 carbon atoms, an alkoxy group having from 1 to 12 carbon atoms, an aryl group optionally containing a substituent, an aralkyl group optionally containing a substituent, a phenoxy group optionally containing a substituent, a halogenated alkyl group, a cyano group, or a nitro group, and two or more groups may be bonded to each other to form a ring, in which the substituent represents a halogen atom, an alkyl group having from 1 to 6 carbon atoms, an alkoxy group having from 1 to 6 carbon atoms, a hydroxyl group, a cyano group, an amino group, a nitro group, or a halogenated alkyl group, and ##STR00055## where, in the General Formula (ET3): R.sub.38 and R.sub.39 are the same or different and respectively represent one of a hydrogen atom, a halogen atom, a cyano group, a nitro group, a hydroxyl group, an alkyl group having from 1 to 12 carbon atoms, an alkoxy group having from 1 to 12 carbon atoms, an aryl group optionally containing a substituent, a heterocyclic group optionally containing a substituent, an ester group, a cycloalkyl group, an aralkyl group optionally containing a substituent, an allyl group, an amido group, an amino group, an acyl group, an alkenyl group, an alkynyl group, a carboxyl group, a carbonyl group, a carboxylic acid group, or a halogenated alkyl group in which the substituent represents a halogen atom, an alkyl group having from 1 to 6 carbon atoms, an alkoxy group having from 1 to 6 carbon atoms, a hydroxyl group, a cyano group, an amino group, a nitro group, or a halogenated alkyl group.

3. The photoreceptor for electrophotography according to claim 1, wherein the photosensitive layer is the outermost surface layer.

4. The photoreceptor for electrophotography according to claim 3, wherein the photosensitive layer is composed of a charge generation layer and a charge transport layer, and the charge transport layer is the outermost surface layer.

5. The photoreceptor for electrophotography according to claim 1, wherein a surface protective layer is provided on the photosensitive layer, and the surface protective layer is the outermost surface layer.

6. The photoreceptor for electrophotography according to claim 3, wherein the photosensitive layer is a positively charged single layer.

7. The photoreceptor for electrophotography according to claim 3, wherein the photosensitive layer is composed of a charge transport layer and a charge generation layer, and the charge generation layer is the outermost surface layer.

8. The photoreceptor for electrophotography according to claim 1, wherein the outermost surface layer contains the electron transport material in an amount of 10 parts by mass or less with respect to 100 parts by mass of the resin binder.

9. An electrophotographic device having mounted therein the photoreceptor for electrophotography according to claim 1.

10. The photoreceptor for electrophotography according to claim 1, wherein the partial structural formula (A.sub.1) is selected from the group consisting of A.sub.12, A.sub.13, A.sub.15, A.sub.16, A.sub.17, A.sub.18, and A.sub.19 below and the partial structural formula (B.sub.1) is selected from the group consisting of B.sub.12, B.sub.13, B.sub.15, B.sub.16, B.sub.17, B.sub.18, and B.sub.19 below: ##STR00056## ##STR00057## ##STR00058##

11. The photoreceptor for electrophotography according to claim 1, wherein the partial structural formula (A.sub.2) is selected from the group consisting of A.sub.20, A.sub.21, A.sub.22, A.sub.23, A.sub.24, A.sub.25, A.sub.26, A.sub.27, A.sub.28, and A.sub.29 below and the partial structural formula (B.sub.2) is selected from the group consisting of B.sub.20, B.sub.21, B.sub.22, B.sub.23, B.sub.24, B.sub.25, B.sub.26, B.sub.27, B.sub.28, and B.sub.29 below: ##STR00059## ##STR00060## ##STR00061## ##STR00062##

12. The photoreceptor for electrophotography according to claim 1, wherein the structural formula (C) is C1 below and the structural formula (D) is D1 below: ##STR00063##

13. A method for manufacturing a photoreceptor for electrophotography, comprising: forming a photosensitive layer on a conductive substrate including applying a coating liquid on the conductive substrate to form an outermost surface layer, the coating liquid containing a polyarylate resin having a structural unit represented by Chemical Structural Formula 1 below and a compound having a structure represented by General Formula (ET2-3) below, Chemical Structural Formula 1: ##STR00064## where partial structural formulae (A.sub.1), (A.sub.2), (B.sub.1), (B.sub.2), (C), (D), (E), and (F) represent respective structural units constituting the resin binder, a.sub.1, a.sub.2, b.sub.1, b.sub.2, c, d, e, and f represents mol % of the respective structural units (A.sub.1), (A.sub.2), (B.sub.1), (B.sub.2), (C), (D), (E), and (F), where a.sub.1, a.sub.2, b.sub.1, and b.sub.2 are not zero, where a.sub.1+a.sub.2+b.sub.1+b.sub.2+c+d+e+f is 100 mol %, and where c+d+e+f range from greater than 0 up to 10 mol % and e and f are not both zero mol %; W.sub.1 and W.sub.2 are different, W.sub.1 is selected from the group consisting of a single bond, O, and CR.sub.22R.sub.23, where C is a carbon atom and R.sub.22 and R.sub.23 are different, are monovalently bonded to the carbon atom of CR.sub.22R.sub.23, and are respectively selected from a monovalent group consisting of a hydrogen atom, an alkyl group having from 1 to 12 carbon atoms, a halogenated alkyl group, and a substituted or unsubstituted aryl group having from 6 to 12 carbon atoms; and W.sub.2 is selected from the group consisting of a single bond, O, and CR.sub.22R.sub.23, where R.sub.22 and R.sub.23 are the same or different and are respectively selected from the group consisting of a hydrogen atom and an alkyl group having 1 carbon atom, wherein, in the partial structural formulas (A.sub.1) and (B1), when the group W.sub.1 is CR.sub.22R.sub.23, the groups R.sub.22 and R.sub.23 may bond together to form a cyclohexylidene group, and R.sub.1 to R.sub.20 are the same or different and are respectively selected from the group consisting of a hydrogen atom, an alkyl group having from 1 to 8 carbon atoms, a fluorine atom, a chlorine atom, and a bromine atom; R.sub.21 represents a hydrogen atom, an alkyl group having from 1 to 20 carbon atoms, an aryl group optionally containing a substituent, a cycloalkyl group optionally containing a substituent, a fluorine atom, a chlorine atom, and a bromine atom, and s and t each represent an integer of 1 or more, and General Formula (ET2-3): ##STR00065##

14. The method for manufacturing a photoreceptor for electrophotography according to claim 13, wherein the partial structural formula (A.sub.1) is selected from the group consisting of A.sub.12, A.sub.13, A.sub.15, A.sub.16, A.sub.17, A.sub.18, and A.sub.19 below and the partial structural formula (B.sub.1) is selected from the group consisting of B.sub.12, B.sub.13, B.sub.15, B.sub.16, B.sub.17, B.sub.18, and B.sub.19 below: ##STR00066## ##STR00067## ##STR00068##

15. The method for manufacturing a photoreceptor for electrophotography according to claim 13, wherein the partial structural formula (A.sub.2) is selected from the group consisting of A.sub.20, A.sub.21, A.sub.22, A.sub.23, A.sub.24, A.sub.25, A.sub.26, A.sub.27, A.sub.28, and A.sub.29 below and the partial structural formula (B.sub.2) is selected from the group consisting of B.sub.20, B.sub.21, B.sub.22, B.sub.23, B.sub.24, B.sub.25, B.sub.26, B.sub.27, B.sub.28, and B.sub.29 below: ##STR00069## ##STR00070## ##STR00071## ##STR00072##

16. The method for manufacturing a photoreceptor for electrophotography according to claim 13, wherein the structural formula (C) is C1 below and the structural formula (D) is D1 below: ##STR00073##

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1A is a schematic cross-sectional view illustrating one example of a negatively charged, functionally separated multi-layer photoreceptor for electrophotography according to the present invention;

(2) FIG. 1B is a schematic cross-sectional view illustrating one example of a positively charged, single-layer photoreceptor for electrophotography according to the present invention;

(3) FIG. 1C is a schematic cross-sectional view illustrating an example of a positively charged, functionally separated multi-layer photoreceptor for electrophotography according to the present invention; and

(4) FIG. 2 is a schematic configuration diagram illustrating one configuration example of the electrophotographic device of the present invention.

DETAILED DESCRIPTION OF THE INVENTION

(5) Hereinafter, specific embodiments of the photoreceptor for electrophotography according to the present invention will be described in detail with reference to the drawings. The present invention is not limited at all by the following description.

(6) As mentioned above, photoreceptors for electrophotography are roughly classified into negatively charged multi-layer photoreceptors and positively charged multi-layer photoreceptors as functionally separated multi-layer photoreceptors and single-layer photoreceptors which are mainly positively charged type. FIG. 1A to FIG. 1C are schematic cross-sectional views illustrating photoreceptors for electrophotography according to examples of the present invention. FIG. 1A illustrates an example of a negatively charged, functionally separated multi-layer photoreceptor for electrophotography, FIG. 1B illustrates an example of a positively charged, single-layer photoreceptor for electrophotography, and FIG. 1C illustrates an example of a positively charged, functionally separated multi-layer photoreceptor for electrophotography.

(7) As illustrated, the negatively charged multi-layer photoreceptor includes a conductive substrate 1, an undercoat layer 2 and a photosensitive layer 3 comprising a charge generation layer 4 having an electric charge generating function and a charge transport layer 5 having an electric charge transport function sequentially layered. The positively charged single-layer photoreceptor includes the conductive substrate 1, the undercoat layer 2, and a single photosensitive layer 3 having both a charge generating function and a charge transporting function sequentially layered. Further, in the positively charged multi-layer photoreceptor, on the conductive substrate 1, the undercoat layer 2 and a photosensitive layer 3 comprising a charge transport layer 5 having an electric charge transporting function and a charge generation layer 4 having an electric charge generating function are sequentially layered. In any type of photoreceptor, the undercoat layer 2 may be provided as needed, and a surface protective layer 6 may be further provided on the photosensitive layer 3. In the present invention, the term photosensitive layer is a concept including both a multi-layer photosensitive layer in which a charge generation layer and a charge transport layer are layered, and a single-layer photosensitive layer.

(8) In the present invention, it is important to use a combination of a polyarylate resin and a specific electron transport material for any of the photosensitive layer, the surface protective layer, and the like constituting the outermost surface layer of the photoreceptor. Specifically, in the case of a photoreceptor having a configuration in which the outermost surface layer is a photosensitive layer, a desired effect of the present invention can be obtained by including the polyarylate resin and the specific electron transport material in the photosensitive layer. In this case, when the photosensitive layer is a negatively charged multi-layer photoreceptor composed of a charge generation layer and a charge transport layer, and the outermost surface layer is a charge transport layer, by containing a polyarylate resin and a specific electron transport material in the charge transport layer, a desired effect of the present invention can be obtained. In the case of a positively charged single-layer photoreceptor in which the photosensitive layer is positively charged single-layer type, by including a polyarylate resin and a specific electron transport material in the single-layer photosensitive layer, a desired effect of the present invention can be obtained. Further, when the photosensitive layer is a positively charged multi-layer photoreceptor composed of a charge transport layer and a charge generation layer, and the outermost surface layer is a charge generation layer, by including a polyarylate resin and a specific electron transport material in the charge generation layer, a desired effect of the present invention can be obtained. On the other hand, in the case of using a photoreceptor comprising a surface protective layer on a photosensitive layer and having a configuration in which the surface protective layer is the outermost surface layer, by including a polyarylate resin and a specific electron transport material in the surface protective layer, a desired effect of the present invention can be obtained.

(9) In any of the above-described types of photoreceptors, the addition amount of the specific electron transport material in the outermost surface layer is preferably 10 parts by mass or less with respect to 100 parts by mass of the resin binder contained in the layer, more preferably in the range of from 1 to 10 parts by mass, and particularly preferably in the range of from 3 to 5 parts by mass. When the amount of the above-described compound used exceeds 10 parts by mass, precipitation occurs, which is not preferable.

(10) The conductive substrate 1 serves as an electrode of the photoreceptor and at the same time serves as a support for each layer constituting the photoreceptor, and may be in any shape such as a cylindrical shape, a plate shape, or a film shape. As a material of the conductive substrate 1, metals such as aluminum, stainless steel, or nickel, or conductivity-treated glass or resin, or the like can be used.

(11) An undercoat layer 2 is composed of a layer containing a resin as a main component or a metal oxide film such as alumite. In order to control the injectability of electric charges from the conductive substrate 1 to the photosensitive layer or for the purpose of coating defects on the surface of the conductive substrate and improving adhesion between the photosensitive layer and the conductive substrate 1, the undercoat layer 2 is provided as needed. Examples of the resin material used for the undercoat layer 2 include insulating polymers such as casein, polyvinyl alcohol, polyamide, melamine, and cellulose, and conductive polymers such as polythiophene, polypyrrole, and polyaniline, and these resins can be used singly or in combination as appropriate. A metal oxide such as titanium dioxide or zinc oxide may be contained in these resins.

(12) Negatively Charged Multi-Layer Photoreceptor:

(13) In the negatively charged multi-layer photoreceptor, a charge generation layer 4 is formed by a method such as coating a coating liquid in which particles of an electric charge generating material are dispersed in a resin binder, and generates electric charges by receiving light. It is important that the electric charge generation efficiency is high and at the same time the charge generated is injected into the charge transport layer 5, and it is desirable that the electric field dependency is small and injection is favorable even in a low electric field.

(14) As the electric charge generating material, phthalocyanine compounds such as X-type non-metal phthalocyanine, -type non-metal phthalocyanine, -type titanyl phthalocyanine, -type titanyl phthalocyanine, Y-type titanyl phthalocyanine, -type titanyl phthalocyanine, amorphous type titanyl phthalocyanine, -type copper phthalocyanine, a variety of azo pigments, anthanthrone pigments, thiapyrylium pigments, perylene pigments, perinone pigments, squarylium pigments, quinacridone pigments or the like can be used singly or in appropriate combination, and a suitable substance can be selected according to the light wavelength region of an exposure light source used for image formation. As the resin binder, polymers, copolymers, and the like of polycarbonate resins, polyester resins, polyamide resins, polyurethane resins, vinyl chloride resins, vinyl acetate resins, phenoxy resins, polyvinyl acetal resins, polyvinyl butyral resins, polystyrene resins, polysulfone resins, diallyl phthalate resins, and methacrylic acid ester resins can be appropriately combined and used.

(15) The content of the resin binder in the charge generation layer 4 is preferably from 20 to 80% by mass, more preferably from 30 to 70% by mass, based on the solid content of the charge generation layer 4. The content of the electric charge generating material in the charge generation layer 4 is preferably from 20 to 80% by mass, more preferably from 30 to 70% by mass, based on the solid content in the charge generation layer 4.

(16) Since the charge generation layer 4 only has to have a charge generating function, its film thickness is determined by the light absorption coefficient of the electric charge generating material, and is generally 1 m or less, and preferably 0.5 m or less. The charge generation layer 4 is mainly composed of an electric charge generating material and can be used by adding an electric charge transport material or the like thereto.

(17) The charge transport layer 5 is mainly composed of an electric charge transport material and a resin binder. In the present invention, when the charge transport layer 5 is the outermost surface layer, a polyarylate resin having the structural unit represented by the chemical structural formula 1 is needed to be used as a resin binder of the charge transport layer 5.

(18) In the photoreceptor of the present invention, such a polyarylate resin may have another structural unit. When the total amount of the polyarylate resin is 100 mol %, the compounding ratio of the structural unit represented by the chemical structural formula 1 is preferably from 10 to 100 mol %, more preferably 50 to 100 mol %.

(19) In the photoreceptor of the present invention, when the total amount (a.sub.1+a.sub.2+b.sub.1+b.sub.2+c+d+e+f) of the structural unit represented by the chemical structural formula 1 is 100 mol %, (c+d+e+f) is from 0 to 10 mol % as the amount of the siloxane component. Further, in the photoreceptor of the present invention, preferably, c and d in the chemical structural formula 1 are 0 mol %, or preferably, e and f are 0 mol %.

(20) Furthermore, s and t in the chemical structural formula 1 are integers of from 1 to 400, preferably from 1 to 400, and more preferably from 8 to 250.

(21) In the photoreceptor of the present invention, in order to obtain a desired effect, in the above chemical structural formula 1, preferably, W.sub.2 is a single bond, O, or CR.sub.22R.sub.23, where R.sub.22 and R.sub.23 may be the same or different, and are a hydrogen atom, a methyl group, or an ethyl group, and preferably, W.sub.1 is CR.sub.22R.sub.23, where R.sub.22 and R.sub.23 may be the same or different, and are a hydrogen atom, a methyl group, or an ethyl group). More preferably, W.sub.1 is a methylene group, W.sub.2 is a single bond, R.sub.1 and R.sub.6 are each a methyl group, and R.sub.2 to R.sub.5 and R.sub.7 to R.sub.20 are hydrogen atoms.

(22) Further, examples of the siloxane structure of the polyarylate resin of the above chemical structural formula 1 include constituent monomers such as the following molecular formula (2) (manufactured by Chisso Corporation; Reactive Silicone SilaplaneFM4411 (weight average molecular weight 1000), FM4421 (weight average molecular weight 5000), FM4425 (weight average molecular weight 15000)) or the following molecular formula (3) (manufactured by Chisso Corporation; Reactive Silicone Silaphane FMDA 11 (weight average molecular weight 1000), FMDA 21 (weight average molecular weight 5000), FMDA 26 (weight average molecular weight 15,000)).

(23) Molecular Formula (2):

(24) TABLE-US-00001 Structural Average formula molecular Structure number Basic structure weight example Formula (2)-1 1000 manufactured by Chrisso Corporation Silaplane FM- 4411 Formula 5000 manufactured (2)-2 by Chisso Corporation Silaplane FM- 4421 Formula 10000 manufactured (2)-3 by Chisso Corporation Silaplane FM- 4425

(25) Molecular Formula (3):

(26) TABLE-US-00002 Structural Average formula molecular Structure number Basic structure* weight example Formula (3)- 1 1000 manufactured by Chisso Corporation Silaplane FM- DA11 Formula (3)- 5000 manufactured by 2 Chisso Corporation Silaplane FM- DA21 Formula (3)- 15000 manufactured by 3 Chisso Corporation Silaplane FM- DA26 *In the formula, R.sub.21 represents an n-butyl group.

(27) The polyarylate resin represented by the chemical structural formula 1 may be used singly or in combination with other resins. As such other resins, other polyarylate resins, a variety of polycarbonate resins such as bisphenol A type, bisphenol Z type, or bisphenol A type-biphenyl copolymer, bisphenol Z type-biphenyl copolymer, polyphenylene resins, polyester resins, polyvinyl acetal resins, polyvinyl butyral resins, polyvinyl alcohol resins, vinyl chloride resins, vinyl acetate resins, polyethylene resins, polypropylene resins, acrylic resins, polyurethane resins, epoxy resins, melamine resins, silicone resins, polyamide resins, polystyrene resins, polyacetal resins, polysulfone resins, a polymer of a methacrylic acid ester, a copolymer thereof, or the like can be used. Further, the same kind of resins having different molecular weights may be mixed and used.

(28) The content of the resin binder is preferably from 10 to 90% by mass, more preferably from 20 to 80% by mass, based on the solid content of the charge transport layer 5. The content of the polyarylate resin with respect to the resin binder is preferably in the range of from 1% by mass to 100% by mass, and more preferably in the range of from 5% by mass to 80% by mass.

(29) The weight average molecular weight of these polyarylate resins is preferably from 5,000 to 250,000, and more preferably from 10,000 to 150,000.

(30) In the following, specific examples of the structural formulae (A.sub.1), (A.sub.2), (B.sub.1), (B.sub.2), (C), (D), (E), and (F) which are structural units represented by the chemical structural formula 1 are described below. Specific examples of polyarylate resins having the structural formulae (A.sub.1), (A.sub.2), (B.sub.1), (B.sub.2), (C), (D), (E) and (F) are listed in Table 1 below. It is noted that the polyarylate resin according to the present invention is not limited to these illustrated structures.

(31) Specific examples of the structural formula (A.sub.1):

(32) ##STR00007## ##STR00008##

(33) Specific examples of the structural formula (A.sub.2):

(34) ##STR00009##

(35) Specific examples of the structural formula (B.sub.1):

(36) ##STR00010## ##STR00011##

(37) Specific examples of the structural formula (B.sub.2):

(38) ##STR00012## ##STR00013##

(39) A specific example of the structural formula (C):

(40) ##STR00014##

(41) A specific example of the structural formula (D):

(42) ##STR00015##

(43) A specific example of the structural formula (E):

(44) ##STR00016##

(45) A specific example of the structural formula (F):

(46) ##STR00017##
where, in the formula, R.sub.21 represents an n-butyl group.

(47) TABLE-US-00003 TABLE 1 Structure Structural monomer type No. A1 A2 B1 B2 C D E F I-1 A10 I-2 B10 I-3 A10 A20 B10 B20 C1 D1 I-4 A11 A21 B11 B21 C1 D1 I-5 A12 A22 B12 B22 C1 D1 I-6 A13 A23 B13 B23 C1 D1 I-7 A14 A24 B14 B24 C1 D1 I-8 A15 A25 B15 B25 C1 D1 I-9 A16 A26 B16 B26 C1 D1 I-10 A17 A27 B17 B27 C1 D1 I-11 A18 A28 B18 B28 C1 D1 I-12 A19 A29 B19 B29 C1 D1 I-13 A10 A20 B10 B20 E1 F1 I-14 A11 A21 B11 B21 E1 F1 I-15 A12 A22 B12 B22 E1 F1 I-16 A13 A23 B13 B23 E1 F1 I-17 A14 A24 B14 B24 E1 F1 I-18 A15 A25 B15 B25 E1 F1 I-19 A16 A26 B16 B26 E1 F1 I-20 A17 A27 B17 B27 E1 F1 I-21 A18 A28 B18 B28 E1 F1 I-22 A19 A29 B19 B29 E1 F1 I-23 A10 A20 B10 B20 C1 D1 E1 F1 I-24 A11 A21 B11 B21 C1 D1 E1 F1 I-25 A12 A22 B12 B22 C1 D1 E1 F1 I-26 A13 A23 B13 B23 C1 D1 E1 F1 I-27 A14 A24 B14 B24 C1 D1 E1 F1 I-28 A15 A25 B15 B25 C1 D1 E1 F1 I-29 A16 A26 B16 B26 C1 D1 E1 F1 I-30 A17 A27 B17 B27 C1 D1 E1 F1 I-31 A18 A28 B18 B28 C1 D1 E1 F1 I-32 A19 A29 B19 B29 C1 D1 E1 F1

(48) When the charge transport layer 5 is the outermost surface layer, it is needed for the electron transport material constituting the charge transport layer to contain a compound having the structure represented by the above general formula (ET2). Among these, when an electron transport material having an electron-withdrawing substituent such as a chloro group (Cl) is used, compared to unsubstituted material, a HOMO/LUMO gets deeper, the electron acceptability improves, the mobility becomes faster, the electron transport capability becomes higher, and, in a photoreceptor using such a material, the resistance to light fatigue improves, which is preferable. Preferably, the electron transport material constituting the charge transport layer further contains one or both of the compounds having the structure represented by the above general formula (ET1) or (ET3), and in addition, one or a combination of two or more electron transport materials (acceptor compounds) such as succinic anhydride, maleic anhydride, dibromosuccinic anhydride, phthalic anhydride, 3-nitro phthalic anhydride, 4-nitro phthalic anhydride, pyromellitic anhydride, pyromellitic acid, trimellitic acid, trimellitic anhydride, phthalimide, 4-nitrophthalimide, tetracyanoethylene, tetracyanoquinodimethane, chloranil, bromanil, o-nitrobenzoic acid, malononitrile, trinitrofluorenone, trinitrothioxanthone, dinitrobenzene, dinitroanthracene, dinitroacridine, nitroanthraquinone, dinitroanthraquinone, a thiopyran compound, a quinone compound, a benzoquinone compound, a diphenoquinone compound, a naphthoquinone compound, an azoquinone compound, an anthraquinone compound, a diiminoquinone compound, or a stilbenequinone compound can be used.

(49) Specific examples of the compound represented by general formula (ET1) used in the present invention include, but are not limited to, the following compounds.

(50) ##STR00018## ##STR00019## ##STR00020## ##STR00021## ##STR00022## ##STR00023## ##STR00024## ##STR00025## ##STR00026## ##STR00027## ##STR00028## ##STR00029## ##STR00030## ##STR00031##

(51) Specific examples of the compound represented by the general formula (ET2) used in the present invention include, but are not limited to, the following compounds.

(52) ##STR00032## ##STR00033## ##STR00034##

(53) Specific examples of the compound represented by the general formula (ET3) used in the present invention include, but are not limited to, the following compounds.

(54) ##STR00035## ##STR00036## ##STR00037##

(55) As the electric charge transport material of the charge transport layer 5, a variety of hydrazone compounds, styryl compounds, diamine compounds, butadiene compounds, indole compounds, and the like can be used singly or in combination as appropriate. Examples of such an electric charge transport material include, but are not limited to, those represented by the following (II-1) to (II-14).

(56) ##STR00038## ##STR00039## ##STR00040## ##STR00041##

(57) The content of the resin binder in the charge transport layer 5 is preferably from 20 to 90% by mass, and more preferably from 30 to 80% by mass, based on the solid content of the charge transport layer 5. The content of the hole transport material in the charge transport layer 5 is preferably from 9.8 to 71% by mass, and more preferably from 19.4 to 65.5% by mass, based on the solid content of the charge transport layer 5. The content of the electron transport material in the charge transport layer 5 is preferably from 0.2 to 9% by mass, more preferably from 0.6 to 4.5% by mass, based on the solid content of the charge transport layer 5.

(58) Further, the film thickness of the charge transport layer 5 is preferably in the range of from 3 to 50 m, and more preferably in the range of from 15 to 40 m in order to maintain the practically effective surface electric potential.

(59) Single-Layer Photoreceptor

(60) In the present invention, the photosensitive layer 3 in the case of a single-layer type is mainly composed of an electric charge generating material, a hole transport material, an electron transport material (acceptor compound), and a resin binder.

(61) As the electric charge generating material, for example, phthalocyanine type pigment, azo pigment, anthanthrone pigment, perylene pigment, perinone pigment, polycyclic quinone pigment, squarilium pigment, thiapyrylium pigment, quinacridone pigment, or the like can be used. These electric charge generating materials can be used singly or in combination of two or more. In particular, for the photoreceptor for electrophotography of the present invention, as an azo pigment, disazo pigment or trisazo pigment is preferable, as a perylene pigment, N,N-bis(3,5-dimethylphenyl)-3,4:9,10-perylene-bis (carboximide) is preferable, and as a phthalocyanine pigment, metal free phthalocyanine, copper phthalocyanine, or titanyl phthalocyanine is preferable. Further, when X-type non-metal phthalocyanine, -type non-metal phthalocyanine, -type copper phthalocyanine, -type titanyl phthalocyanine, -type titanyl phthalocyanine, Y-type titanyl phthalocyanine, amorphous titanyl phthalocyanine, or titanyl phthalocyanine having a maximum peak at Bragg angle 2 of 9.6 in the CuK:X-ray diffraction spectrum described in Japanese Unexamined Patent Application Publication No. H08-209023, U.S. Pat. Nos. 5,736,282 and 5,874,570 is used, a remarkably improved effect is exhibited in terms of sensitivity, durability, and image quality. The content of the electric charge generating material is preferably from 0.1 to 20% by mass, and more preferably from 0.5 to 10% by mass, based on the solid content of the single-layer photosensitive layer 3.

(62) As the hole transport material, for example, a hydrazone compound, a pyrazoline compound, a pyrazolone compound, an oxadiazole compound, an oxazole compound, an arylamine compound, a benzidine compound, a stilbene compound, a styryl compound, poly-N-vinylcarbazole, polysilane, or the like can be used. These hole transport materials can be used singly or in combination of two or more kinds. The hole transport material used in the present invention is preferably one which is excellent in the ability to transport holes generated upon light irradiation and is suitable for combination with an electric charge generating material. The content of the hole transport material is preferably from 3 to 80% by mass, and more preferably from 5 to 60% by mass, based on the solid content of the single-layer photosensitive layer 3.

(63) In the present invention, when the single-layer photosensitive layer 3 is the outermost surface layer, as the electron transport material of the single-layer photosensitive layer 3, a compound having the structure represented by the general formula (ET2) is needed to be contained. Preferably, the electron transport material of the single-layer photosensitive layer 3 further contains one or both of the compounds having the structure represented by the above general formula (ET1) or (ET3), and other examples thereof include succinic anhydride, maleic anhydride, dibromosuccinic anhydride, phthalic anhydride, 3-nitro phthalic anhydride, 4-nitro phthalic anhydride, pyromellitic anhydride, pyromellitic acid, trimellitic acid, trimellitic anhydride, phthalimide, 4-nitrophthalimide, tetracyanoethylene, tetracyanoquinodimethane, chloranil, bromanil, o-nitrobenzoic acid, malononitrile, trinitrofluorenone, trinitrothioxanthone, dinitrobenzene, dinitroanthracene, dinitroacridine, nitroanthraquinone, dinitroanthraquinone, a thiopyran compound, a quinone compound, a benzoquinone compound, a diphenoquinone compound, a naphthoquinone compound, an anthraquinone compound, a stilbenequinone compound, and an azoquinone compound. These electron transport materials can be used alone or in combination of two or more. The content of the electron transport material is preferably from 1 to 50% by mass, and more preferably from 5 to 40% by mass, based on the solid content of the single-layer photosensitive layer 3.

(64) In the present invention, when the single-layer photosensitive layer 3 is the outermost surface layer, a polyarylate resin having the structural unit represented by the above chemical structural formula 1 is needed to be used as the resin binder of the single-layer photosensitive layer 3. Such a polyarylate resin may have another structural unit. When the total amount of the polyarylate resin is 100 mol %, the compounding ratio of the structural unit represented by the chemical structural formula 1 is preferably from 10 to 100 mol %, and particularly preferably from 50 to 100 mol %.

(65) As the resin binder of the single-layer photosensitive layer 3, the polyarylate resin represented by the chemical structural formula 1 may be used alone, or may be used mixed with other resins. As such other resins, a variety of polycarbonate resins such as bisphenol A type, bisphenol Z type, bisphenol A type-biphenyl copolymer, or bisphenol Z type-biphenyl copolymer, polyphenylene resins, polyester resins, polyvinyl acetal resins, polyvinyl butyral resins, polyvinyl alcohol resins, vinyl chloride resins, vinyl acetate resins, polyethylene resins, polypropylene resins, acrylic resins, polyurethane resins, epoxy resins, melamine resins, silicone resins, polyamide resins, polystyrene resins, polyacetal resins, other polyarylate resins, polysulfone resins, a polymer of a methacrylic acid ester, and a copolymer thereof. Further, the same kind of resins having different molecular weights may be mixed and used.

(66) The content of the resin binder is preferably from 10 to 90% by mass, and more preferably from 20 to 80% by mass, with respect to the solid content of the single-layer photosensitive layer 3. Further, the content of the polyarylate resin with respect to the resin binder is suitably in the range of from 1% by mass to 100% by mass, and more preferably in the range of from 5% by mass to 80% by mass.

(67) The film thickness of the single-layer photosensitive layer 3 is preferably in the range of from 3 to 100 m, and more preferably in the range of from 5 to 40 m in order to maintain a practically effective surface electric potential.

(68) Positively Charged Multi-Layer Photoreceptor

(69) In the positively charged multi-layer photoreceptor, the charge transport layer 5 is mainly composed of an electric charge transport material and a resin binder. As an electric charge transport material and a resin binder used for the charge transport layer 5 in the positively charged multi-layer photoreceptor, the same materials as those described in the embodiment of the charge transport layer 5 in the negatively charged multi-layer photoreceptor can be used. The content of each material and the film thickness of the charge transport layer 5 can also be made the same as in the case of the negatively charged multi-layer photoreceptor. For the charge transport layer 5 in the positively charged multi-layer photoreceptor, a polyarylate resin having a structural unit represented by the above chemical structural formula 1 as a resin binder can be arbitrarily used.

(70) The charge generation layer 4 is mainly composed of an electric charge generating material, a hole transport material, an electron transport material, and a resin binder. As the electric charge generating material, the hole transport material, the electron transport material, and the resin binder, the same materials as those mentioned as embodiments of the single-layer photosensitive layer 3 in the single-layer photosensitive body can be used. The content of each material and the film thickness of the charge generation layer 4 can be the same as those of the single-layer photosensitive layer 3 in the single-layer photoreceptor. In the positively charged multi-layer photoreceptor, when the charge generation layer 4 is the outermost surface layer, a polyarylate resin having the structural unit represented by the chemical structural formula 1 is needed to be used as a resin binder of the charge generation layer 4 and a compound having the structure represented by the general formula (ET2) is needed to be used as the electron transport material of the charge generation layer 4, and preferably, a compound having the structure represented by the above general formula (ET1) or (ET3) is also used.

(71) In the present invention, for the purpose of improving environmental resistance and stability against harmful light, an anti-deterioration agent such as an antioxidant or a light stabilizer can be contained in either a multi-layer type or a single-layer type photosensitive layer. Examples of a compound used for such purpose include chromanol derivatives and esterification compounds such as tocopherol, polyarylalkane compounds, hydroquinone derivatives, etherified compounds, dietherated compounds, benzophenone derivatives, benzothiazole derivatives, thioether compounds, phenylenediamine derivatives, phosphonate esters, phosphite esters, phenol compounds, hindered phenol compounds, linear amine compounds, cyclic amine compounds, and hindered amine compounds.

(72) A leveling agent such as a silicone oil or a fluorine-based oil may be contained in the photosensitive layer for the purpose of improving the leveling property of the formed film and imparting lubricity. Further, for the purpose of adjusting film hardness, reducing friction coefficient, imparting lubricity, or the like, fine particles of metal oxides such as silicon oxide (silica), titanium oxide, zinc oxide, calcium oxide, aluminum oxide (alumina), or zirconium oxide, metal sulfides such as barium sulfate or calcium sulfate, or metal nitrides such as silicon nitride, or aluminum nitride, or fluorine-based resin particles such as tetrafluoroethylene resin, fluorine-based comb-type graft polymerization resin, or the like may be contained. Still further, as needed, other known additives may be contained within a range not significantly impairing the electrophotographic characteristics.

(73) Further, in the present invention, the surface protective layer 6 can be provided on the surface of the photosensitive layer, as needed, for the purpose of further improving environmental resistance and mechanical strength. The surface protective layer 6 is preferably made of a material excellent in durability against mechanical stress and environmental resistance, and desirably has a capability of transmitting the light sensed by the charge generation layer with as low loss as possible.

(74) The surface protective layer 6 is composed of a layer containing a resin binder as a main component, and fine particles of metal oxides such as silicon oxide (silica), titanium oxide, zinc oxide, calcium oxide, aluminum oxide (alumina) or zirconium oxide, metal sulfides such as barium sulfate or calcium sulfate, or metal nitrides such as silicon nitride or aluminum nitride, or particles of a fluororesin such as a tetrafluoroethylene resin, a fluorinated comb type graft polymer resin or the like may be contained in the resin binder for the purpose of improving conductivity, reducing friction coefficient, imparting lubricity, and the like.

(75) For the purpose of imparting charge transportability, an electric charge transport material or an electron accepting material used for the photosensitive layer may be contained, and for the purpose of improving the leveling property of the formed film and imparting lubricity, leveling agents such as silicone oil and fluorine-based oil may be contained.

(76) In the photoreceptor of the present invention, when the surface protective layer 6 is provided, a polyarylate resin having a structural unit represented by the chemical structural formula 1 as a resin binder and a compound having a structure represented by the general formula (ET2) as an electron transport material are contained in the surface protective layer 6 to be the outermost surface layer. By this, a desired effect of the present invention can be obtained.

(77) The content of the resin binder in the surface protective layer 6 is preferably from 50 to 90% by mass, and more preferably from 70 to 90% by mass, based on the solid content of the surface protective layer 6. The content of fine particles of a metal oxide or a metal nitride or the like is preferably from 0 to 60% by mass, and more preferably from 10 to 50% by mass, based on the solid content of the surface protective layer 6. The content of the electric charge transport material and the electron transport material in the surface protective layer 6 is preferably from 0 to 30% by mass, and more preferably from 10 to 20% by mass, based on the solid content of the surface protective layer 6. Although the thickness of the surface protective layer 6 itself depends on the composition of the surface protective layer, the thickness can be arbitrarily set as long as no adverse effect such as increase in residual electric potential occurs when repeatedly and continuously used.

(78) Method for Manufacturing a Photoreceptor

(79) In manufacturing the photoreceptor of the present invention, in forming an outermost surface layer by coating a coating liquid on a conductive substrate, it is important that the coating liquid contains a polyarylate resin having a structural unit represented by the above chemical structural formula 1 and a compound having a structure represented by the above formula (ET2), thereby obtaining a photoreceptor capable of obtaining a desired effect of the present invention. The term coating liquid for forming the outermost surface layer refers to a coating liquid for forming a charge transport layer in a case in which the outermost surface layer is a photosensitive layer, in particular, a charge transport layer, a coating liquid for forming a charge generation layer in a case in which the outermost surface layer is a charge generation layer, a coating liquid for forming a single-layer photosensitive layer in a case in which the outermost surface layer is a single-layer photosensitive layer, or a coating liquid for forming a surface protective layer in a case in which the outermost surface layer is a surface protective layer. Such a coating liquid can be applied to a variety of coating methods such as a dip coating method or a spray coating method, but is not limited thereto.

(80) Electrophotographic Device

(81) The electrophotographic device of the present invention mounts a photoreceptor according to the present invention having at least a photosensitive layer on a conductive substrate and the outermost surface layer containing the predetermined polyarylate resin and compound, and by applying the device to a variety of machine processes, a desired effect can be obtained. Specifically, a sufficient effect can be obtained in a charging process such as a contact charging method using a charging member such as a roller or a brush or a non-contact charging method using a corotron, a scorotron or the like, and also in a developing process such as contact developing and non-contact developing system using a developing system (developing agent) such as nonmagnetic one component, magnetic one component, two-component or the like.

(82) As an example, FIG. 2 illustrates a schematic configuration diagram of an electrophotographic device according to the present invention. The illustrated electrophotographic device 60 mounts the photoreceptor for electrophotography 7 of the present invention including the conductive substrate 1, the undercoat layer 2 coated on the outer circumference thereof, and a photosensitive layer 300. More specifically, the illustrated electrophotographic device 60 is composed of a roller charging member 21 arranged at the outer circumference edge portion of the photoreceptor 7, a high voltage power supply 22 for supplying an applied voltage to the roller charging member 21, an image exposure member 23, a developer 24 provided with a developing roller 241, a paper feeding member 25 provided with a paper feeding roller 251 and a paper feed guide 252, a transfer charger (direct charging type) 26, a cleaning device 27 provided with a cleaning blade 271, and a charge removing member 28, and can be a color printer.

EXAMPLES

(83) Hereinafter, specific embodiments of the present invention will be described in more detail by way of Examples, but the present invention is not limited by the following Examples as long as it goes beyond the gist thereof.

(84) Manufacturing of a Negatively Charged Multi-Layer Photoreceptor

Example 1

(85) Five parts by mass of alcohol-soluble nylon (trade name CM8000 manufactured by Toray Industries, Inc.) and 5 parts by mass of aminosilane-treated titanium oxide fine particles were dissolved and dispersed in 90 parts by mass of methanol to prepare a coating liquid 1. This coating liquid 1 was dip coated on the outer circumference of an aluminum cylinder having an outer diameter of 30 mm as the conductive substrate 1, and dried at a temperature of 100 C. for 30 minutes to form an undercoat layer 2 having a thickness of 3 m.

(86) One part by mass of Y-type titanyl phthalocyanine as an electric charge generating material and 1.5 parts by mass of polyvinyl butyral resin (trade name 5-LEC KS-1 manufactured by Sekisui Chemical Co., Ltd.) as a resin binder were dissolved and dispersed in 60 parts by mass of dichloromethane to prepare a coating liquid 2. This coating liquid 2 was dip coated on the undercoat layer 2 and dried at a temperature of 80 C. for 30 minutes to form a charge generation layer 4 having a film thickness of 0.3 m.

(87) Ninety parts by mass of a compound represented by the following formula:

(88) ##STR00042##
as an electric charge transport material, 110 parts by mass of a polyarylate resin represented by the structural formula (I-1) as a resin binder listed in Table 1, and 5 parts by mass of a compound represented by the structural formula (ET2-3) as an electron transport material were dissolved in 1,000 parts by mass of dichloromethane to prepare a coating liquid 3. The coating liquid 3 was dip coated on the charge generation layer 4 and dried at a temperature of 90 C. for 60 minutes to form a charge transport layer 5 having a film thickness of 25 m to prepare a negatively charged multi-layer photoreceptor. The prepared photoreceptor was brought into contact with a charging roller and a transfer roller mounted on a printer LJ4250 manufactured by HP Inc. and left to stand in an environment of a temperature of 60 C. and a humidity of 90% for 30 days.

Examples 2 to 32

(89) Photoreceptors were prepared in the same manner as in Example 1 except that the polyarylate resin represented by the structural formula (I-1) used in Example 1 was replaced with polyarylate resins represented by structural formulae (I-2) to (I-32), respectively. The prepared photoreceptor was left to stand for 30 days in the same manner as in Example 1.

Example 33

(90) A photoreceptor was prepared in the same manner as in Example 1 except that the Y-type titanyl phthalocyanine used in Example 1 was replaced with -type titanyl phthalocyanine. The prepared photoreceptor was left to stand for 30 days in the same manner as in Example 1.

Example 34

(91) A charge transport layer was formed in the same manner as in Example 1 except that a compound represented by the structural formula (ET2-3) and a silicone oil as electron transport materials were excluded from the charge transport layer coating liquid used in Example 1 and the charge transport layer was formed with a film thickness of 20 m. Thereafter, 80 parts by mass of a compound represented by the structural formula (II-1) as an electric charge transport material and 120 parts by mass of polyarylate resin represented by the structural formula (I-1) as a resin binder were dissolved in 900 parts by mass of dichloromethane, 0.1 parts by weight of Silicone oil (KP-340, manufactured by Shin-Etsu Polymer Co., Ltd.) was added and 12 parts by weight of a compound represented by the structural formula (ET2-3) as an electron transport material was added to prepare a coating liquid, which was further coated and formed on a layer thereon, and dried at a temperature of 90 C. for 60 minutes to form a surface protective layer having a film thickness of about 10 m to prepare a photoreceptor for electrophotography. The prepared photoreceptor was left to stand for 30 days in the same manner as in Example 1.

Comparative Example 1

(92) A photoreceptor was prepared in the same manner as in Example 1 except that the polyarylate resin represented by the structural formula (I-1) used in Example 1 was used, a compound represented by the structural formula (ET2-3) was not added as an electron transport material, and a charge transport layer was provided. The prepared photoreceptor was left to stand for 30 days in the same manner as in Example 1.

Comparative Example 2

(93) A photoreceptor was prepared in the same manner as in Example 1 except that the polyarylate resin represented by the structural formula (I-1) used in Example 1 was changed to a polycarbonate resin (PCZ-500 manufactured by Mitsubishi Gas Chemical Co., Ltd.), and the charge transport layer was provided without adding a compound represented by the structural formula (ET2-3) as the electron transport material. The prepared photoreceptor was left to stand for 30 days in the same manner as in Example 1.

Comparative Example 3

(94) A photoreceptor was prepared in the same manner as in Example 1 except that the polyarylate resin represented by the structural formula (I-1) used in Example 1 was changed to a polycarbonate resin (PCZ-500 manufactured by Mitsubishi Gas Chemical Co., Ltd.), and the charge transport layer was provided. The prepared photoreceptor was left to stand for 30 days in the same manner as in Example 1.

Comparative Example 4

(95) A photoreceptor was prepared in the same manner as in Example 1 except that 110 parts by mass of the polyarylate resin represented by the structural formula (I-1) used in Example 1 was changed to 100 parts by mass of a polyarylate resin represented by the structural formula (I-1) and 10 parts by mass of a polycarbonate resin (PCZ-500 manufactured by Mitsubishi Gas Chemical Co., Ltd.), and the charge transport layer was provided without adding a compound represented by the structural formula (ET2-3) as the electron transport material. The prepared photoreceptor was left to stand for 30 days in the same manner as in Example 1.

Comparative Example 5

(96) A photoreceptor was prepared in the same manner as in Example 1 except that 110 parts by mass of the polyarylate resin represented by the structural formula (I-1) used in Example 1 was changed to 55 parts by mass of a polyarylate resin represented by the structural formula (I-1) and 55 parts by mass of a polycarbonate resin (PCZ-500 manufactured by Mitsubishi Gas Chemical Co., Ltd.), and the charge transport layer was provided without adding a compound represented by the structural formula (ET2-3) as the electron transport material. The prepared photoreceptor was left to stand for 30 days in the same manner as in Example 1.

Comparative Example 6

(97) A photoreceptor was prepared in the same manner as in Example 1 except that 110 parts by mass of the polyarylate resin represented by the structural formula (I-1) used in Example 1 was changed to 10 parts by mass of a polyarylate resin represented by the structural formula (I-1) and 100 parts by mass of a polycarbonate resin (PCZ-500 manufactured by Mitsubishi Gas Chemical Co., Ltd.), and the charge transport layer was provided without adding a compound represented by the structural formula (ET2-3) as the electron transport material. The prepared photoreceptor was left to stand for 30 days in the same manner as in Example 1.

(98) Stain Resistance

(99) The photoreceptors prepared in Examples 1 to 34 and Comparative Examples 1 to 6 were left to stand in an environment of a temperature of 60 C. and a humidity of 90% for 30 days, and then, images of halftone images were taken out and evaluated according to the following:

(100) : No black stripes occurred in a halftone image; and

(101) x: Black streak occurred in a halftone image.

(102) Electric Characteristics

(103) The photoreceptors prepared in Examples 1 to 34 and Comparative Examples 1 to 6 were mounted on a printer LJ4250 manufactured by HP Inc. provided with a charging roller and a transfer roller and evaluated by the following method. Specifically, after the surface of the photoreceptor was charged to 650 V by corona discharge in a dark place, the surface electric potential V0 immediately after charging was measured Subsequently, the corona discharge was left to stand in a dark place for 5 seconds, then the surface potential V5 was measured, and the electric potential retention rate Vk5(%) at 5 seconds after charging was determined according to the following formula (1):
Vk5=V5/V0100(1).

(104) Next, using a halogen lamp as a light source, exposure light split into 780 nm with a filter was irradiated to the photoreceptor for 5 seconds from the time when the surface electric potential reached 600 V. The exposure needed for light attenuation until the surface electric potential became 300 V was determined as E1/2 (Jcm.sup.2), and the residual electric potential on the surface of the photoreceptor 5 seconds after exposure was determined as Vr5 (V).

(105) Next, the photoreceptor was left for 10 minutes under a fluorescent light of 1,500 (lx.Math.s), and electric potentials before and after leaving were measured as light fatigue characteristics using a photoreceptor drum electric characteristics evaluating device. Regarding the electric potential in the light fatigue characteristics, while the drum was rotated, the charged electric potential V0 was measured so that the charged electric potential V0 is about 600 V, and subsequently, a bright portion electric potential VL was measured by irradiating light of 780 nm and 2 W/cm.sup.2 for 0.25 seconds.

(106) The electric characteristics, light fatigue characteristics, and stain resistance of the photoreceptors prepared in Examples 1 to 34 and Comparative Examples 1 to 6 as the above measurement results are listed on the following Tables. In the Tables, Before and After mean before and after leaving to stand, respectively.

(107) TABLE-US-00004 TABLE 2 Light fatigue characteristics Charged electric potential Bright portion electric potential VO(V) VL(V) Change Change Stain VO(V) Vk5(%) E(Jcm.sup.2) Vr5(V) Before After amount Before After amount resistance Example 1 653 94.7 0.16 13 600 585 15 110 105 5 Example 2 655 92.7 0.15 12 590 575 15 115 105 10 Example 3 651 95.3 0.17 14 595 585 10 115 110 5 Example 4 649 93.2 0.15 10 595 580 15 125 115 10 Example 5 650 93.4 0.15 15 590 580 10 120 110 10 Example 6 653 93.2 0.12 13 585 575 10 115 105 10 Example 7 653 92.9 0.16 12 595 585 10 110 110 0 Example 8 654 94.2 0.14 16 595 585 10 115 110 5 Example 9 651 94.9 0.16 15 600 590 10 130 120 10 Example 10 652 94.3 0.17 13 600 595 5 125 120 5 Example 11 648 94.8 0.16 14 585 585 0 135 125 10 Example 12 655 95.5 0.14 10 590 595 5 130 115 15 Example 13 653 94.6 0.16 15 590 590 0 140 125 15 Example 14 654 94.3 0.14 12 585 580 5 125 115 10 Example 15 651 94.7 0.16 11 595 580 15 135 125 10 Example 16 651 93.3 0.17 16 595 590 5 115 110 5 Example 17 652 93.2 0.15 12 600 590 10 110 110 0 Example 18 654 95.4 0.14 15 600 595 5 115 110 5 Example 19 655 93.2 0.12 17 585 580 5 120 120 0 Example 20 652 94.9 0.16 12 590 590 0 120 105 15 Example 21 651 94.2 0.15 12 585 580 5 115 110 5 Example 22 653 94.9 0.16 14 595 585 10 135 125 10 Example 23 651 94.6 0.17 13 595 590 5 140 125 15 Example 24 651 93.2 0.17 10 590 585 5 135 125 10 Example 25 655 94.1 0.15 11 600 590 10 135 120 15 Example 26 654 94.2 0.16 11 585 580 5 125 115 10 Example 27 652 95.3 0.12 14 595 585 10 135 130 5 Example 28 649 92.8 0.15 15 590 580 10 125 120 5

(108) TABLE-US-00005 TABLE 3 Light fatigue characteristics Charged electric potential Bright portion electric potential VO (V) VL (V) Change Change Stain VO (V) Vk5 (%) E(Jcm.sup.2) Vr5 (V) Before After amount Before After amount resistance Example 29 650 93.8 0.14 11 595 585 10 115 105 10 Example 30 655 93.5 0.15 14 600 590 10 110 105 5 Example 31 652 95.3 0.13 14 590 585 5 110 110 0 Example 32 649 92.8 0.15 12 595 595 0 115 105 10 Example 33 652 93.4 0.13 15 595 580 15 120 110 10 Example 34 653 94.3 0.12 15 590 580 10 110 105 5 Comparative 651 93.5 0.15 15 590 645 55 125 350 225 Example 1 Comparative 651 94.6 0.17 14 590 580 10 125 115 10 x Example 2 Comparative 650 93.6 0.16 14 595 585 10 115 110 5 x Example 3 Comparative 651 94.1 0.14 35 595 635 40 150 345 195 Example 4 Comparative 655 93.9 0.17 20 600 650 50 165 335 170 Example 5 Comparative 653 94.5 0.14 33 595 645 50 140 320 180 Example 6

(109) From the results in the above Tables, it was revealed that by using a combination of a specific polyarylate resin and an electron transport material with the outermost surface layer, it is possible to realize a photoreceptor having excellent electric characteristics, no light fatigue, and sufficient stain resistance.

(110) Manufacturing of a Positively Charged Single-Layer Photoreceptor

Example 35

(111) A coating liquid prepared by stirring and dissolving 0.2 parts by mass of vinyl chloride-vinyl acetate-vinyl alcohol copolymer (trade name SOLVINE TA5R manufactured by Nissin Chemical Co., Ltd.) as an undercoat layer in 99 parts by mass of methyl ethyl ketone was applied by dip coating to the outer circumference of an aluminum cylinder with outer diameter of 24 mm as a conductive substrate 1, and dried at a temperature of 100 C. for 30 minutes to form an undercoat layer 2 having a thickness of 0.1 m.

(112) A coating liquid prepared by dissolving and dispersing 1 part by mass of metal-free phthalocyanine represented by the following formula:

(113) ##STR00043##
as an electric charge generating material, 30 parts by mass of a stilbene compound represented by the following formula:

(114) ##STR00044##
as a hole transport material, 15 parts by mass of a stilbene compound represented by the following formula:

(115) ##STR00045##
30 parts by mass of a compound represented by the following formula:

(116) ##STR00046##
as an electron transport material, 55 parts by mass of a polyarylate resin represented by the structural formula (I-1) as a resin binder, and 3 parts by mass of a compound represented by the structural formula (ET2-3) as an electron transport material in 350 parts by mass of tetrahydrofuran was coated on the undercoat layer 2 by dip coating, and dried at a temperature of 100 C. for 60 minutes to form a photosensitive layer having a film thickness of 25 m to prepare a single-layer photoreceptor. The prepared photoreceptor was left to stand for 30 days in the same manner as in Example 1.

Example 36

(117) A photoreceptor was prepared in the same manner as in Example 35 except that the metal-free phthalocyanine used in Example 35 was changed to Y-type titanyl phthalocyanine. The prepared photoreceptor was left to stand for 30 days in the same manner as in Example 1.

Example 37

(118) A photoreceptor was prepared in the same manner as in Example 35 except that the metal-free phthalocyanine used in Example 35 was changed to -type titanyl phthalocyanine.

(119) The prepared photoreceptor was left to stand for 30 days in the same manner as in Example 1.

Comparative Example 7

(120) A photoreceptor was prepared in the same manner as in Example 35 except that the polyarylate resin represented by the structural formula (I-1) used in Example 35 was used and the electron transport material was not added. The prepared photoreceptor was left to stand for 30 days in the same manner as in Example 1.

Comparative Example 8

(121) A photoreceptor was prepared in the same manner as in Example 35 except that the polyarylate resin represented by the structural formula (I-1) used in Example 35 was changed to a polycarbonate resin (PCZ-500 manufactured by Mitsubishi Gas Chemical Co., Ltd.), and no electron transport material was added. The prepared photoreceptor was left to stand for 30 days in the same manner as in Example 1.

Comparative Example 9

(122) A photoreceptor was prepared in the same manner as in Example 35 except that the polyarylate resin represented by the structural formula (I-1) used in Example 35 was changed to a polycarbonate resin (PCZ-500 manufactured by Mitsubishi Gas Chemical Co., Ltd.). The prepared photoreceptor was left to stand for 30 days in the same manner as in Example 1.

Comparative Example 10

(123) A photoreceptor was prepared in the same manner as in Example 35 except that 55 parts by mass of the polyarylate resin represented by the structural formula (I-1) used in Example 35 was changed to 50 parts by mass of a polyarylate resin represented by the structural formula (I-1) and 5 parts by mass of a polycarbonate resin (PCZ-500 manufactured by Mitsubishi Gas Chemical Co., Ltd.), and no electron transport material was added. The prepared photoreceptor was left to stand for 30 days in the same manner as in Example 1.

Comparative Example 11

(124) A photoreceptor was prepared in the same manner as in Example 35 except that 55 parts by mass of the polyarylate resin represented by the structural formula (I-1) used in Example 35 was changed to 30 parts by mass of a polyarylate resin represented by the structural formula (I-1) and 25 parts by mass of a polycarbonate resin (PCZ-500 manufactured by Mitsubishi Gas Chemical Co., Ltd.), and no electron transport material was added. The prepared photoreceptor was left to stand for 30 days in the same manner as in Example 1.

Comparative Example 12

(125) A photoreceptor was prepared in the same manner as in Example 35 except that 55 parts by mass of the polyarylate resin represented by the structural formula (I-1) used in Example 35 was changed to 5 parts by mass of a polyarylate resin represented by the structural formula (I-1) and 50 parts by mass of a polycarbonate resin (PCZ-500 manufactured by Mitsubishi Gas Chemical Co., Ltd.), and no electron transport material was added. The prepared photoreceptor was left to stand for 30 days in the same manner as in Example 1.

(126) Stain Resistance

(127) The photoreceptors prepared in Examples 35 to 37 and Comparative Examples 7 to 12 were left to stand in an environment of a temperature of 60 C. and a humidity of 90% for 30 days, and then, images of halftone images were taken out and evaluated according to the following:

(128) : No black stripes occurred in a halftone image; and

(129) x: Black streak occurred in a halftone image.

(130) Electric Characteristics

(131) The photoreceptors prepared in Examples 35 to 37 and Comparative Examples 7 to 12 were mounted on a printer HL-2040 manufactured by Brother Co., Ltd. provided with a charging roller and a transfer roller and evaluated by the following method. Specifically, after the surface of the photoreceptor was charged to +650 V by corona discharge in a dark place, the surface electric potential V0 immediately after charging was measured. Subsequently, the photoreceptor was left to stand in a dark place for 5 seconds, then the surface potential V5 was measured, and the electric potential retention rate Vk5(%) at 5 seconds after charging was determined according to the following formula (1):
Vk5=V5/V0100(1).

(132) Next, using a halogen lamp as a light source, exposure light having 1.0 W/cm.sup.2 split into 780 nm with a filter was irradiated to the photoreceptor for 5 seconds from the time when the surface electric potential reached +600 V. The exposure needed for light attenuation until the surface electric potential became +300 V was determined as E1/2 (Jcm.sup.2), and the residual electric potential on the surface of the photoreceptor 5 seconds after exposure was determined as Vr5 (V).

(133) Next, the photoreceptor was left for 10 minutes under a fluorescent light of 1,500 (lx.Math.s), and electric potentials before and after leaving were measured as light fatigue characteristics using a photoreceptor drum electric characteristics evaluating device. Regarding the electric potential in the light fatigue characteristics, while the drum was rotated, the charged electric potential V0 was measured so that the charged electric potential V0 is about +650 V, and subsequently, a bright portion electric potential VL was measured by irradiating light of 780 nm and 2 W/cm.sup.2 for 0.25 seconds.

(134) The electric characteristics, light fatigue characteristics, and stain resistance of the photoreceptors prepared in Examples 35 to 37 and Comparative Examples 7 to 12 as the above measurement results are listed on the following Tables. In the Tables, Before and After mean before and after leaving to stand, respectively.

(135) TABLE-US-00006 TABLE 4 Light fatigue characteristics Charged electric potential Bright portion electric potential VO(+V) VL (+V) Change Change Stain VO(+V) Vk5 (%) E (Jcm.sup.2) Vr5 (V) Before After amount Before After amount resistance Example 35 655 92.9 0.15 12 600 590 10 115 105 10 Example 36 650 93.8 0.13 13 585 580 5 110 105 5 Example 37 654 94.9 0.14 15 590 580 10 125 120 5 Comparative 654 94.5 0.16 16 593 643 55 125 350 225 Example 7 Comparative 652 93.2 0.14 12 595 580 15 140 130 10 x Example 8 Comparative 654 94.0 0.14 12 595 590 5 120 105 15 x Example 9 Comparative 653 95.1 0.15 32 596 635 39 155 343 188 Example 10 Comparative 652 94.9 0.17 23 601 652 51 163 332 169 Example 11 Comparative 653 93.5 0.16 27 597 645 48 148 327 17I9 Example 12

(136) From the results in the above Table, it was revealed that by using a combination of a specific polyarylate resin and an electron transport material with the outermost surface layer, it is possible to realize a photoreceptor having excellent electric characteristics, no light fatigue, and sufficient stain resistance.

(137) Manufacturing of Positively Charged Multi-Layer Photoreceptor

Example 38

(138) Fifty parts by mass of a compound represented by the following formula:

(139) ##STR00047##
as an electric charge transport material and 50 parts by mass of a polycarbonate resin (PCZ-500 manufactured by Mitsubishi Gas Chemical Company, Inc.) as a resin binder were dissolved in 800 parts by mass of dichloromethane to prepare a coating liquid. This coating liquid was dip coated on the outer circumference of an aluminum cylinder having an outer diameter of 24 mm as a conductive substrate and dried at a temperature of 120 C. for 60 minutes to form a charge transport layer having a film thickness of 15 m.

(140) A coating liquid prepared by dissolving and dispersing 1.5 parts by mass of metal-free phthalocyanine represented by the following formula:

(141) ##STR00048##
as an electric charge generating material, 10 parts by mass of a stilbene compound represented by the following formula:

(142) ##STR00049##
as a hole transport material, 25 parts by mass of a compound represented by the following formula:

(143) ##STR00050##
as an electron transport material, 60 parts by mass of a polyarylate resin represented by the structural formula (I-1) as a resin binder, and 3 parts by mass of a compound represented by the structural formula (ET2-3) as an electron transport material in 800 parts by mass of 1,2-dichloro ethane was coated on the charge transport layer by dip coating, and dried at a temperature of 100 C. for 60 minutes to form a photosensitive layer having a film thickness of 15 m to prepare a positively charged multi-layer photoreceptor. The prepared photoreceptor was left to stand for 30 days in the same manner as in Example 1.

Comparative Example 13

(144) A photoreceptor was prepared in the same manner as in Example 38 except that the polyarylate resin represented by the structural formula (I-1) used in Example 38 was used and the electron transport material was not added. The prepared photoreceptor was left to stand for 30 days in the same manner as in Example 1.

Comparative Example 14

(145) A photoreceptor was prepared in the same manner as in Example 38 except that the polyarylate resin represented by the structural formula (I-1) used in Example 38 was changed to a polycarbonate resin (PCZ-500 manufactured by Mitsubishi Gas Chemical Co., Ltd.), and no electron transport material was added. The prepared photoreceptor was left to stand for 30 days in the same manner as in Example 1.

Comparative Example 15

(146) A photoreceptor was prepared in the same manner as in Example 38 except that the polyarylate resin represented by the structural formula (I-1) used in Example 38 was changed to a polycarbonate resin (PCZ-500 manufactured by Mitsubishi Gas Chemical Co., Ltd.). The prepared photoreceptor was left to stand for 30 days in the same manner as in Example 1.

Comparative Example 16

(147) A photoreceptor was prepared in the same manner as in Example 38 except that 60 parts by mass of the polyarylate resin represented by the structural formula (I-1) used in Example 38 was changed to 50 parts by mass of a polyarylate resin represented by the structural formula (I-1) and 10 parts by mass of a polycarbonate resin (PCZ-500 manufactured by Mitsubishi Gas Chemical Co., Ltd.), and no electron transport material was added. The prepared photoreceptor was left to stand for 30 days in the same manner as in Example 1.

Comparative Example 17

(148) A photoreceptor was prepared in the same manner as in Example 38 except that 60 parts by mass of the polyarylate resin represented by the structural formula (I-1) used in Example 38 was changed to 30 parts by mass of a polyarylate resin represented by the structural formula (I-1) and 30 parts by mass of a polycarbonate resin (PCZ-500 manufactured by Mitsubishi Gas Chemical Co., Ltd.), and no electron transport material was added. The prepared photoreceptor was left to stand for 30 days in the same manner as in Example 1.

Comparative Example 18

(149) A photoreceptor was prepared in the same manner as in Example 38 except that 60 parts by mass of the polyarylate resin represented by the structural formula (I-1) used in Example 38 was changed to 10 parts by mass of a polyarylate resin represented by the structural formula (I-1) and 50 parts by mass of a polycarbonate resin (PCZ-500 manufactured by Mitsubishi Gas Chemical Co., Ltd.), and no electron transport material was added. The prepared photoreceptor was left to stand for 30 days in the same manner as in Example 1.

(150) The photoreceptors prepared in Example 38 and Comparative Examples 13 to 18 were evaluated in the same manner as in Example 35 or the like.

(151) The electric characteristics, light fatigue characteristics, and stain resistance of the photoreceptors prepared in Example 38 and Comparative Examples 13 to 18 as the above measurement results are listed on the following Tables. In the Tables, Before and After mean before and after leaving to stand, respectively.

(152) TABLE-US-00007 TABLE 5 Light fatigue characteristics Charged electric potential Bright portion electric potential VO(+V) VL (+V) Change Change Stain VO(+V) Vk5 (%) E (Jcm.sup.2) Vr5 (V) Before After amount Before After amount resistance Example 38 652 94.6 0.17 15 595 595 0 130 120 10 Comparative 657 94.3 0.18 15 592 648 56 122 328 206 Example 13 Comparative 655 93.6 0.15 14 590 585 5 115 105 10 x Example 14 Comparative 651 94.0 0.17 15 595 580 15 125 115 10 x Example 15 Comparative 653 95.4 0.15 32 598 638 40 155 348 193 Example 16 Comparative 651 92.7 0.17 25 602 653 51 169 339 170 Example 17 Comparative 655 93.5 0.18 22 596 645 49 151 328 177 Example 18

(153) From the results in the above Table, it was revealed that by using a combination of a specific polyarylate resin and an electron transport material with the outermost surface layer, it is possible to realize a photoreceptor having excellent electric characteristics, no light fatigue, and sufficient stain resistance.