EP0690351B1 - Matérial électrophotosensible - Google Patents

Matérial électrophotosensible Download PDF

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EP0690351B1
EP0690351B1 EP95303624A EP95303624A EP0690351B1 EP 0690351 B1 EP0690351 B1 EP 0690351B1 EP 95303624 A EP95303624 A EP 95303624A EP 95303624 A EP95303624 A EP 95303624A EP 0690351 B1 EP0690351 B1 EP 0690351B1
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group
formula
indicate
layer
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EP0690351A2 (fr
EP0690351A3 (fr
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Toshiyuki Fukami
Hideo Nakamori
Hiroshi Shiomi
Hirofumi Kawaguchi
Hisakazu Uegaito
Nariaki Muto
Mikio Kakui
Keisuke Sumida
Sakae Saito
Maki Uchida
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Kyocera Mita Industrial Co Ltd
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Mita Industrial Co Ltd
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
    • G03G5/0664—Dyes
    • G03G5/0675—Azo dyes
    • G03G5/0679—Disazo dyes
    • G03G5/0681—Disazo dyes containing hetero rings in the part of the molecule between the azo-groups
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
    • G03G5/0601—Acyclic or carbocyclic compounds
    • G03G5/0605—Carbocyclic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
    • G03G5/0601—Acyclic or carbocyclic compounds
    • G03G5/0605—Carbocyclic compounds
    • G03G5/0607—Carbocyclic compounds containing at least one non-six-membered ring
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
    • G03G5/0601—Acyclic or carbocyclic compounds
    • G03G5/0609—Acyclic or carbocyclic compounds containing oxygen
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
    • G03G5/0601—Acyclic or carbocyclic compounds
    • G03G5/0612—Acyclic or carbocyclic compounds containing nitrogen
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
    • G03G5/0601—Acyclic or carbocyclic compounds
    • G03G5/0618—Acyclic or carbocyclic compounds containing oxygen and nitrogen
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
    • G03G5/0601—Acyclic or carbocyclic compounds
    • G03G5/062—Acyclic or carbocyclic compounds containing non-metal elements other than hydrogen, halogen, oxygen or nitrogen
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
    • G03G5/0664—Dyes
    • G03G5/0675—Azo dyes
    • G03G5/0679—Disazo dyes

Definitions

  • the present invention relates to an electrophotosensitive material which is used for image forming apparatuses such as copying apparatus and the like.
  • an organic photosensitive material having a sensitivity within the wavelength range of a light source of the apparatus has exclusively been used.
  • the organic photosensitive material there have been known a single-layer type photosensitive material comprising a single-layer type photosensitive layer wherein an electric charge generating material and an electric charge transferring material are dispersed in a membrane of a suitable binding resin, a multi-layer type photosensitive material comprising an electric charge transferring layer containing the above electric charge transferring material and an electric charge generating layer containing an electric charge generating material, which are mutually laminated and the like.
  • the single-layer type organic photosensitive layer had a problem that an interaction between diphenoquinone and a hole transferring material inhibits electrons from transferring.
  • the scope of application of the photosensitive material can be widen if one photosensitive material can be used for both positively charged and negatively charged types. Further, if the organic photosensitive material can be used for the single-layer dispersion type, it becomes easy to produce the photosensitive material, thereby preventing generation of a coating defect. Therefore, there are many advantages in improving optical properties.
  • an organic photosensitive layer provided on a conductive substrate comprises a binding resin, at least one bisazo pigment selected from those represented by the formulas (I) to (V) [in the formula (I), Z is a methyl group or a methoxy group] as an electric charge generating material and a trinitrofluorenoneimine derivative represented by the above formula (1) as an electron transferring material.
  • an organic photosensitive layer provided on a conductive substrate comprises a binding resin, an electric charge generating material, a trinitrofluorenoneimine derivative represented by the above formula (1) as an electron transferring material and at least one benzidine derivative selected from those represented by the following formulas (2) to (5) and a phenylenediamine derivative represented by the formula (6) as a hole transferring material.
  • R 6 and R 7 are the same or different and indicate a hydrogen atom or an alkyl group
  • R 8 , R 9 , R 10 and R 11 are the same or different and indicate an alkyl group, an alkoxy group or a halogen atom
  • a, b, c and d are the same or different and indicate an integer from 0 to 5; provided that at least one of a, b, c and d indicate an integer of 2 or more, and c and d indicate an integer other than 0 when a and b indicate 0, simultaneously]
  • R 12 and R 13 are the same or different and indicate a hydrogen atom or an alkyl group
  • R 14 and R 15 are the same or different and indicate an alkyl group, an alkoxy group, a substituted or unsubstituted aryl group, or a halogen atom
  • R 16 and R 17 are the same or different and indicate an alkyl group, an alkoxy group or a halogen atom
  • e
  • the trinitrofluorenoneimine derivative represented by the formula (1) as the electron transferring material can be superior in solubility in solvent and good compatibility with binding resin, and can also be superior in matching with the respective bisazo pigments represented by the formulas (I) to (V) as the electric charge generating material and, therefore, the electrons are smoothly injected. Particularly, it can be superior in electron transferring properties in the low magnetic field. Further, since any bulky substituent is introduced into the molecule of the trifluorenoneimine derivative, it is inhibited to form an electric charge transfer complex which can cause deterioration in sensitivity due to steric hindrance between the trifluorenoneimine derivative and hole transferring material, when it is used in combination with the hole transferring material.
  • the electrophotosensitive material of the present invention can have a high sensitivity within the visible region because the bisazo pigment selected from those represented by the formulas (I) to (V) responds to the wavelength of the visible region, and it can be suitably used for analog-optical image forming apparatuses.
  • the benzidine derivative represented by any one of the formulas (2) to (5) and phenylenediamine derivative represented by the formula (6), which are used in combination with the above trinitrofluorenoneimine derivative can be superior in hole transferring properties and compatibility with binding resin. Further, since the benzidine derivative represented by any one of the formulas (2) to (5) has a high melting point, the glass transition temperature of the organic photosensitive layer can be improved. In addition, when the phenylenedimaine derivative represented by the formula (6) is added, the surface of the organic photosensitive layer is modified, thereby decreasing the friction coefficient and increasing the loss elastic modulus of the whole layer and, therefore, a wear resistance of the organic photosensitive layer can be improved.
  • the electrophotosensitive material of the present invention can have a high sensitivity and be superior in durability and stability, thereby realizing high speed of image forming apparatuses such as copying apparatus, etc.
  • the organic photosensitive layer of the electrophotosensitive material of the present invention contains trinitrofluorenoneimine of the formula (1) as the electron transferring material, at least one bisazo pigment selected from those represented by the formulas (I) to (V) as the electric charge generating material and at least one benzidine derivative selected from those represented by the formulas (2) to (5) and a phenylenediamine derivative represented by the formula (6) as the hole transferring material.
  • the organic photosensitive layer of the electrophotosensitive material of the present invention contains an electron attractive compound having a redox potential of -0.8 to -1.4 V, in addition to the above respective components.
  • the electrophotosensitive material containing the electron attractive compound has a higher sensitivity and is also superior in stability, as described hereinafter.
  • Fig. 1 is a graph illustrating a relation between the tractive voltage (V) and current (A) for determining the redox potential of the electron attractive compound.
  • examples of the alkyl group corresponding to the groups R 1 to R 5 include alkyl groups having 1 to 6 carbon atoms, such as methyl group, ethyl group, n-propyl group, isopropyl group, t-butyl group, pentyl group, hexyl group and the like.
  • alkoxy group examples include alkoxy groups having 1 to 6 carbon atoms, such as methoxy group, ethoxy group, propoxy group, t-butoxy group, pentyloxy group, hexyloxy group and the like.
  • aryl group examples include phenyl group, o-terphenyl group, naphthyl group, anthryl group, phenanthryl group and the like.
  • the aryl group may contain a substituent such as alkyl group, alkoxy group, halogen atom, etc. on any position.
  • aralkyl group examples include benzyl, ⁇ -phenethyl group, ⁇ -phenethyl group, 3-phenylpropyl group, benzhydryl group, trityl group and the like.
  • the aralkyl group may contain a substituent such as alkyl group, alkoxy group, halogen atom, etc. on any position.
  • halogen atom examples include chlorine, bromine, fluorine, and iodine.
  • this derivative can be synthesized by condensing 2,4,7-trinitrofluorenone with aniline or its derivative in a solvent.
  • the solvent include acetic acid, propionic acid, butyric acid, chloroform, tetrahydrofuran, dimethylformamide, dimethyl sulfoxide and the like.
  • the reaction may be conducted in the presence of a suitable catalyst such as zinc chloride, if necessary.
  • the reaction may be normally conducted at a temperature of 30 to 170 °C for about 20 minutes to 4 hours. [wherein R 1 to R 5 are as defined above]
  • Preferred examples of the trinitrofluorenoneimine derivative include the compounds represented by the following formulas (7) to (9).
  • R 39 , R 40 , R 41 , R 42 and R 43 are the same or different and indicate a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom
  • R 44 and R 45 are the same or different and indicate an alkyl group, an alkoxy group or a halogen atom; and ⁇ and ⁇ indicate an integer, the sum of which is 0 to 4
  • R 46 and R 47 are the same or different and indicate an alkyl group, an alkoxy group or a halogen atom; and ⁇ and ⁇ indicate an integer, the sum of which is 0 to 4]
  • Embodied compounds of the trinitrofluorenoneimine derivative are not specifically limited, but examples of the trinitrofluorenoneimine derivative represented by the formula (7) include the compounds represented by the following formulas (7a) to (7d).
  • examples of the trinitrofluorenoneimine derivative represented by the formula (8) include the compounds represented by the following formulas (8a) to (8d).
  • examples of the trinitrofluorenoneimine derivative represented by the formula (9) include the compounds represented by the following formulas (9a) to (9d).
  • examples of the alkyl group, alkoxy group, aryl group and halogen atom which correspond to any one of the groups R 12 to R 33 include the same groups as those described above.
  • examples of the alkyl group, alkoxy group, aryl group and halogen atom which correspond to any one of the groups R 34 to R 38 include the same groups as those described above.
  • N-substituted amino group corresponding to the groups R 34 to R 38 examples include methylamino group, dimethylamino group, ethylamino group, diethylamino group and the like.
  • Examples of the electron attractive group corresponding to the group R 38 include nitro group, carbonyl group, carboxyl group, nitrile group and the like.
  • the benzidine derivative represented by the formula (2) has a high melting point in comparison with a conventional benzidine derivative (Japanese Patent Publication No. 5-21099) represented by the following formula (A): because at least one of four outer phenyl groups is substituted with two or more of alkyl group, alkoxy group or halogen atom and, therefore, the glass transition temperature of the photosensitive layer can be improved. Further, the benzidine derivative wherein the phenyl group other than that containing two or more substituents among outer four phenyl groups is substituted with an alkyl group having three or more carbon atoms is superior in compatibility with binding resin so that the hole transferring properties are improved in comparison with a conventional one.
  • Non-limited examples of the benzidine derivative represented by the formula (2) include the compounds represented by the following formulas (2a) to (2e).
  • the benzidine derivative represented by the formula (3) has a high melting point in comparison with a conventional benzidine derivative represented by the above formula (A) because at least two of four outer phenyl groups are further substituted with aryl groups such as phenyl group, etc. and, therefore, the glass transition temperature of the photosensitive layer can be improved. Further, the above benzidine derivative has large spreading of the ⁇ -electron conjugate system in comparison with a conventional one and, therefore, the hole transferring properties are also improved.
  • Non-limited examples of the benzidine derivative represented by the formula (3) include the compounds represented by the following formulas (3a) to (3g).
  • the benzidine derivative represented by the formula (4) has a high melting point in comparison with a conventional benzidine derivative represented by the above formula (A) because biphenyl as its center skeleton is substituted with four alkyl groups and, therefore, the glass transition temperature of the organic photosensitive layer can be improved. Further, since the benzidine derivative wherein at least one of four outer phenyl groups is substituted with aryl groups such as phenyl group, etc. has a higher melting point, the glass transition temperature of the organic photosensitive material can be further improved.
  • Non-limited examples of the benzidine derivative represented by the formula (4) include the compounds represented by the following formulas (4a) to (4d).
  • the benzidine derivative represented by the formula (5) has a high melting point in comparison with a conventional benzidine derivative represented by the above formula (A) because biphenyl as its center skeleton is substituted with four alkyl groups and, therefore, the glass transition temperature of the organic photosensitive layer can be improved. Further, it is superior in compatibility with binding resin because the substitution position of four alkyl groups is unsymmetrical and, therefore, the hole transferring properties are also improved.
  • Examples of he benzidine derivative represented by the formula (5) include the compounds represented by the following formulas (5a) to (5d).
  • the surface of the organic photosensitive layer is modified, thereby decreasing a friction coefficient and increasing a loss elastic modulus of the whole layer and, therefore, a wear resistance of the organic photosensitive layer can be improved.
  • the phenylenediamine derivative wherein four outer phenyl groups are substituted with two or more substituents or that wherein at least one of four phenyl groups and phenyl group as the center skeleton is substituted with aryl groups such as phenyl group, etc. has a high melting point and, therefore, the glass transition temperature of the organic photosensitive layer can be improved.
  • the phenylenediamine derivative wherein any one of the respective phenyl groups is substituted with an aryl group has large spreading of the ⁇ -electron conjugate system and, therefore, the hole transferring properties are also improved.
  • the phenylenediamine derivative wherein the substitution position of the substituent on four outer phenyl groups is not 3-position but 2-position of the phenyl group or that wherein at least one of four phenyl groups is substituted with an alkyl group having three or more carbon atoms is superior in compatibility with binding resin and, therefore, the hole transferring properties are improved.
  • Non-limited examples of the benzidine derivative represented by the formula (6) include the compounds represented by the following formulas (6a) to (6n).
  • the organic photosensitive layer is classified into two types, that is, a single-layer type photosensitive layer containing the electron transferring material and hole transferring material in the same layer, together with the electric charge generating material, and a multi-layer type photosensitive material comprising the electric charge transferring layer and electric charge generating layer. Further, it is possible to use positively charged and negatively charged type photosensitive materials as the photosensitive material of the present invention. Particularly, it is preferred to use the positively charged type photosensitive material.
  • the positively charged type photosensitive material electrons emitted from the electron generating material in the exposure process are smoothly injected into the trinitrofluorenone derivative (electron transferring material) represented by the formula (1) and then transferred to the surface of the photosensitive layer by means of the giving and receiving of electrons between electron transferring materials to cancel the positive electric charge (+) which has previously been charged on the surface of the photosensitive layer.
  • holes (+) are injected into the hole transferring material represented by any one of the formulas (2) to (6) and transferred to the surface of the conductive substrate without being trapped on the way, and then holes are canceled by the negative electric charge (-) which has previously been charged on the surface of the conductive substrate. It is considered that the sensitivity of the positively charged type photosensitive material is improved in this manner.
  • the electric charge generating material there can be used selenium, selenium-tellurium, amorphous silicon, pyrilium salt, azo pigments, bisazo pigments (pigments of the formulas (2) to (5) are excluded), anthanthrone pigments, phthalocyanine pigments, naphthalocyanine pigments, indigo pigments, triphenylmethane pigments, threne pigments, toluidine pigments, pyrazoline pigments, quinacridone pigments, dithioketopyrrolopyrrole pigments and the like, in place of the bisazo pigments represented by the formulas (I) to (V).
  • These electric charge generating materials can be used alone or in combination thereof to present an absorption wavelength within a desired range.
  • the electric charge generating material suitable for the organic photosensitive material having a sensitivity within the wavelength range of 700 nm or more which is particularly used for digital-optical image forming apparatuses using a light source such -as semi-conductor, etc.
  • phthalocyanine pigments such as X-type metal-free phthalocyanine, oxotitanyl phthalocyanine and the like. Since these phthalocyanine pigments are superior in matching with the above trinitrofluorenoneimine derivative represented by the formula (1), the electrophotosensitive material using both pigments in combination has a high sensitivity within the above wavelength range, and it can be suitably used for digital-optical image forming apparatuses.
  • the electron attractive compound having a redox potential of -0.8 to -1.4 V may be further added to the organic photosensitive layer.
  • the energy level of LUMO which means the level of which energy is the lowest in molecular orbitals that is not occupied by electrons in the molecule, and electrons to be excited are normally moved to this level
  • LUMO the level of which energy is the lowest in molecular orbitals that is not occupied by electrons in the molecule, and electrons to be excited are normally moved to this level
  • it serves to extract electrons (-) generated in the electric charge generating material so that the electric charge-generating efficiency in the electric charge generating material is improved and, at the same time, the residual potential at the time of image forming is reduced, thereby realizing higher sensitivity.
  • the electron attractive compound also serves as the electron transferring material, the sensitivity of the organic photosensitive material can be further enhanced by adding a large amount of the electron attractive compound which is particularly superior in compatibility with binding resin.
  • Non-limited examples of the electron attractive compound include quinones (e.g. benzoquinone derivatives, naphthoquinone derivatives, anthraquinone derivatives, diphenoquinone derivatives, etc.), malononitrile compounds, thiopyran compounds, fluorenone compounds (e.g. 3,4,5,7-tetranitro-9-fluorenone, etc.), tetracyanoethylene, 2,4,8-trinitrothioxanthone, dinitrobenzene, dinitroanthracene, dinitroacridine, nitroanthraquinone, dinitroanthraquinone, succinic anhydride, maleic anhydride, dibromomaleic anhydride, etc.
  • quinones e.g. benzoquinone derivatives, naphthoquinone derivatives, anthraquinone derivatives, diphenoquinone derivatives, etc.
  • malononitrile compounds e.g. 3,4,5,7
  • examples of the preferred compound include quinones such as diphenoquinone derivative represented by the formula (10): [wherein R 48 , R 49 , R 50 and R 51 are the same or different and indicate a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aralkyl group, a cycloalkyl group, an amino group, a N-substituted amino group or a halogen atom], p-benzoquinone derivative represented by the formula (11): [wherein R 52 , R 53 , R 54 and R 55 are the same or different and indicate a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aralkyl group, a cycloalkyl group, an amino group, a N-substituted amino group or a halogen atom].
  • quinones such as diphenoquinone derivative represented by the formula (10): [wherein R 48 , R 49 , R 50 and
  • the diphenoquinoine derivative is particularly preferred because a quinone oxygen atom having excellent electron attractive properties is bonded to the molecular chain terminal and a conjugate double bond exists along with the whole long molecular chain, thereby facilitating electron transfer in the molecule as well as giving and receiving of electrons between molecules.
  • examples of the cycloalkyl group corresponding to any one of the groups R 48 to R 55 include cycloalkyl groups having 3 to 7 carbon atoms, such a s cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group and the like.
  • Examples of the alkyl group, alkoxy group, aryl group, aralkyl group, amino group, N-substituted amino group and halogen atom include the same groups as those described above.
  • Embodied compounds of the quinones as the electron attractive compound are not specifically limited, but examples of the diphenoquinone derivative represented by the formula (10) include the compounds represented by the following formulas (10a) to (10b).
  • the redox potential of the diphenoquinone derivative represented by the formula (10a) is -0.94 V and that of the diphenoquinone derivative represented by the formula (10b) is -0.86 V.
  • examples of the p-benzoquinone derivative represented by the formula (11) include the compound represented by the following formula (11a).
  • the redox potential of the p-benzoquinone derivative represented by the formula (11a) is -1.30 V.
  • the redox potential of the electron attractive compound is limited within a range of -0.8 to -1.4 V.
  • the electron attractive compound having the redox potential of less than -0.8 V makes a separated free carrier (particularly, electron) to fall into the level where detrapping can not be effected to cause carrier trapping. Therefore, the photosensitivity is deteriorated and the residual potential becomes high.
  • the electron attractive compound having the redox potential of more than -1.4 V the energy level of LUMO becomes higher than that of the electric charge generating material so that the above-described electron-extracting effect is not obtained, which fails to improve the electric charge-generating efficiency.
  • the redox potential will be measured by means of a three-electrode system cyclic voltametry using the following materials.
  • the above materials are mixed to prepare a measuring solution.
  • thermoplastic resins such as styrene polymer, styrene-butadiene copolymer, styreneacrylonitrile copolymer, styrene-maleic acid copolymer, acrylic polymer, styrene-acrylic acid copolymer, polyethylene, ethylene-vinyl acetate copolymer, chlorinated polyethylene, polyvinyl chloride, polypropylene, ionomer, vinyl chloride-vinyl acetate copolymer, polyester, alkyd resin, polyamide, polyurethane, polycarbonate, polyarylate, polysulfon, diaryl phthalate resin, ketone resin, polyvinyl butyral resin, polyether resin, polyester resin, etc.; crosslinking thermosetting resins such as silicone resin, epoxy resin, phenol resin, ureadiene copolymer, styreneacrylonitrile copolymer, styrene-maleic acid copolymer
  • additives known to the public such as deterioration inhibitors (e.g. antioxidants, radical scavengers, singlet quenchers, ultraviolet absorbers, etc.), softeners, plasticizers, surface modifiers, bulking agents, thickening agents, dispersion stabilizers, wax, acceptors, donors, etc. can be formulated in the photosensitive layer without injury to the electrophotographic characteristics.
  • the amount of these additives to be added may be the same as that used in a conventional technique.
  • a steric hindered phenolic antioxidant is formulated in the amount of about 0.1 to 50 parts by weight, based on 100 parts by weight of the binding resin.
  • sensitizers such as terphenyl, halonaphthoquinones, acenaphthylene, etc. may be used in combination with the electric charge generating material.
  • electric charge generating materials which have hitherto been known can be formulated in the photosensitive layer, together with the bisazo pigment represented by any one of the formulas (I) to (V).
  • the electric charge generating material include selenium, selenium-tellurium, amorphous silicon, pyrilium salt, azo pigments, bisazo pigments other than those described above, anthanthrone pigments, phthalocyanine pigments, naphthalocyanine pigments, indigo pigments, triphenylmethane pigments, threne pigments, toluidine pigments, pyrazoline pigments, quinacridone pigments, dithioketopyrrolopyrrole pigments and the like.
  • These electric charge generating materials can be used alone or in combination thereof to present an absorption wavelength within a desired range.
  • electron transferring materials which have hitherto been known can be formulated in the photosensitive layer, together with the trinitrofluorenoneimine derivative represented by the formula (1).
  • the electron transferring material include benzoquinone compounds, diphenoquinone compounds, malononitrile compounds, thiopyran compounds, tetracyanoethylene, 2,4,8-trinitrothioxanthone, fluorenone compounds (e.g.
  • hole transferring materials which have hitherto been known may be formulated in the photosensitive layer, together with the hole transferring materials represented by the formulas (2) to (6).
  • the hole transferring material include nitrogen-containing cyclic compounds and condensed polycyclic compounds, e.g.
  • oxadiazole compounds such as 2,5-di(4-methylaminophenyl), 1,3,4-oxadiazole, etc.; styryl compounds such as 9-(4-diethylaminostyryl)anthracene, etc.; carbazole compounds such as polyvinyl carbazole, etc.; organosilicon compounds; pyrazoline compounds such as 1-phenyl-3-(p-dimethylaminophenl)pyrazoline, etc.; hydrazone compounds; triphenylamine compounds; indol compounds; oxazole compounds; isooxazole compounds, thiazole compounds; thiadiazole compounds; imidazole compounds; pyrazole compounds; triazole compounds and the like.
  • These hole transferring materials are used alone or in combination thereof. Further, the binding resin is not necessarily required when using the hole transferring material having film forming properties, such as polyvinyl carbazole, etc.
  • various materials having a conductivity can be used, and examples thereof include metals such as aluminum, copper, tin, platinum, silver, vanadium, molybdenum, chromium, cadmium, titanium, nickel, palladium, indium, stainless steel, brass, etc.; plastic materials vapor-deposited or laminated with the above metal; glass materials coated with aluminum iodide, tin oxide, indium oxide, etc.
  • the conductive substrate may be made in the form of a sheet or a drum.
  • the substrate itself may have a conductivity or only the surface of the substrate may have a conductivity. It is preferred that the conductive substrate has a sufficient mechanical strength when used.
  • the photosensitive layer in the present invention is produced by applying a coating solution, which is prepared by dissolving or dispersed a resin composition containing the above-described respective components in a solvent, on the conductive substrate, followed by drying.
  • the effect due to the use of the electric charge generating material, electron transferring material and hole transferring material in the present invention can be obtained in the single-layer type photosensitive material, particularly.
  • the single-layer type photosensitive material of the present invention can be applied to positively charged and negatively charged type photosensitive materials, and it is particularly preferred to use for the positively charged type photosensitive material.
  • the electric charge generating material may be formulated in the photosensitive layer in the amount of 0.5 to 20 parts by weight, particularly 0.5 to 10 parts by weight, based on 100 parts by weight of the binding resin.
  • the hole transferring material may be formulated in the photosensitive layer in the amount of 5 to 200 parts by weight, particularly 30 to 150 parts by weight, based on 100 parts by weight of the binding resin.
  • the electron transferring material may be formulated in the photosensitive layer in the amount of 5 to 100 parts by weight, particularly 10 to 80 parts by weight, based on 100 parts by weight of the binding resin.
  • the amount of the electron attractive compound is preferably 0.01 to 100 parts by weight, particularly 0.1 to 30 parts by weight, based on 100 parts by weight of the binding resin.
  • the thickness of the photosensitive layer to be formed is preferably 5 to 50 ⁇ m, particularly 10 to 40 ⁇ m.
  • the electric charge generating material may be deposited alone on the conductive substrate to form an electric charge generating layer (vapor deposition type electric charge generating layer), or an electric charge generating layer (resin dispersion type electric charge generating layer) containing the electric charge generating material, binding resin and, if necessary, hole transferring material may be formed using a means such as coating, followed by forming an electric charge transferring layer containing the electron transferring material and binding resin on this electric charge generating layer.
  • the electric charge generating layer may be formed after forming the electric charge transferring layer on the conductive substrate.
  • the electric charge generating material and the binding resin which constitute the resin dispersion type electric charge generating layer may be used in various proportions. It is preferred that the electric charge generating material may be used in the amount of 5 to 1000 parts by weight, particularly 30 to 500 parts by weight, based on 100 parts by weight of the binding resin. Further, when the electron attractive compound is added to the resin dispersion type electric charge generating layer, the amount is preferably 0.1 to 100 parts by weight, particularly 1 to 30 parts by weight, based on 100 parts by weight of the binding resin.
  • the electron transferring material and binding resin which constitute the electric charge transferring layer can be used in various proportions within such a range as not to prevent the transfer of electrons and to prevent the crystallization. It is preferred that the electron transferring material may be used in the amount of 10 to 500 parts by weight, particularly 25 to 200 parts by weight, based on 100 parts by weight of the binding resin to easily transfer electrons generated by light irradiation in the electric charge generating layer. Further, when the electron attractive compound is added to the electric charge transferring layer, the amount of the electron attractive compound is preferably 0.01 to 100 parts by weight, particularly 0.1 to 30 parts by weight, based on 100 parts by weight of the binding resin.
  • the thickness of the electric charge generating layer is preferably about 0.01 to 5 ⁇ m, particularly about 0.1 to 3 ⁇ m, and that of the electric charge transferring layer is preferably about 2 to 100 ⁇ m, particularly about 5 to 50 ⁇ m.
  • a conventional multi-layer type photosensitive material having the electric charge transferring layer containing the hole transferring material has a problem that photofatigue has arisen by exposure or discharge at the time of repeated using, thereby causing deterioration of charging properties and sensitivity.
  • the trinitrofluorenoneimine derivative (1) to be used as the electric charge transferring material is formulated in the electric charge transferring layer, together with the hole transferring material, a multi-layer type photosensitive material having an excellent light resistance can be obtained.
  • the reason is not apparent, but is considered as follows. That is, when the electric charge transferring layer is formed, the bisazo pigment molecule is eluted from the electric charge generating layer to the vicinity of the interface between both layers, and electrons trapped by the bisazo pigment are extracted by the trinitrofluorenoneimine derivative (1) to transfer to the electric charge generating layer, thereby inhibiting deterioration of charging properties. Further, the trinitrofluorenoneimine derivative (1) also serves as the quencher and is effective for inhibiting photo-deterioration of the electric charge transferring material.
  • the hole transferring material may be added in the amount of 30 to 200 parts by weight, preferably 50 to 150 parts by weight, based on 100 parts by weight of the binding resin.
  • the trinitrofluorenoneimine derivative (1) may be added in the amount of 0.1 to 30 parts by weight, preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the binding resin.
  • Others are the same as those described in the above-described multi-layer type photosensitive material.
  • a barrier layer may be formed, in such a range as not to injure the characteristics of the photosensitive material, between the conductive substrate and photosensitive layer in the single-layer type photosensitive material, or between the conductive substrate and electric charge generating layer or between the conductive substrate layer and electric charge transferring layer in the multi-layer type photosensitive material. Further, a protective layer may be formed on the surface of the photosensitive layer.
  • the electric charge generating material, electric charge transferring material and binding resin may be dispersed and mixed with a suitable solvent by a known method, for example, using a roll mill, a ball mill, an attritor mill, a paint shaker, a supersonic dispenser, etc. to prepare a dispersion, which is applied by a known means and then allowed to dry.
  • the solvent for preparing the dispersion there can be used various organic solvents, and examples thereof include alcohols such as methanol, ethanol, isopropyl alcohol, butanol, etc.; aliphatic hydrocarbons such as n-hexane, octane, cyclohexane, etc.; aromatic hydrocarbons such as benzene, toluene, xylene, etc.; halogenated hydrocarbons such as dichloromethane, dichloroethane, carbon tetrachloride, chlorobenzene, etc.; ethers such as dimethyl ether, diethyl ether, tetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, etc.; ketones such as acetone, methyl ethyl ketone, cyclohexanone, etc.; esters such as ethyl acetate, methyl acetate, etc.; dimethylformaldeh
  • surfactants In order to improve a dispersibility of the electric charge transferring material and electric charge generating material as well as a smoothness of the surface of the photosensitive layer, there may be used surfactants, leveling agents, etc.
  • CGM in Tables the electric charge generating material
  • HTM hole transferring material
  • this coating solution was applied on an aluminum tube as the conductive substrate by a dip coating method, followed by hot-air drying at 100 °C for 60 minutes to give a single-layer type photosensitive material for analog light source which has a single-layer type photosensitive layer of 15 to 20 ⁇ m in film thickness.
  • Embodied compounds of the electric charge generating material, hole transferring material, electron transferring material, etc. used in the above Examples and Comparative Examples area shown in the tables, using the above-described compound No. (same with the following Examples and Comparative Examples).
  • a photosensitive material of the respective Examples was fit with an imaging unit of a facsimile for paper (Model LDC-650, manufactured by Mita Kogyo Co., Ltd.) and, after standing at an environmental temperature of 50 °C for 10 days in such a state that a cleaning blade keeps in contact with the surface of the photosensitive material under linear pressure of 1.5 g/mm, the surface state of the photosensitive layer was measured using an universal surface shape tester (Model SE-3H, manufactured by Kosaka Kenkyusho) and a maximum depth of dent was recorded, respectively.
  • the description of "less than 0.3 ⁇ m" in the item of the dent in Table 2 means that no dent was observed because the surface roughness of a normal photosensitive material having no dent is about 0.5 ⁇ m.
  • the photosensitive materials of Examples 37 to 64 are superior in sensitivity characteristics to those of Examples 1, 6, 11 and 12 using conventional benzidine (A) because of their low potential after exposure V L (V), and are superior in durability and heat resistance because the extrapolated glass transition initiation temperature (Tig) is high and no dent is observed.
  • V L V
  • extrapolated glass transition initiation temperature Tig °C
  • maximum depth of dent ⁇ m
  • the photosensitive materials of Examples 65 to 100 are superior in sensitivity characteristics to those of the above respective Examples using conventional benzidine (A) because of their low potential after exposure V L (V), and are superior in durability and heat resistance because the extrapolated glass transition initiation temperature (Tig) is high and no dent is observed.
  • V L V
  • extrapolated glass transition initiation temperature Tig °C
  • maximum depth of dent ⁇ m
  • the photosensitive materials of Examples 101 to 124 are superior in sensitivity characteristics to those of the above respective Examples using conventional benzidine (A) because of their low potential after exposure V L (V), and are superior in durability and heat resistance because the extrapolated glass transition initiation temperature (Tig) is high and no dent is observed.
  • V L V
  • extrapolated glass transition initiation temperature Tig °C
  • maximum depth of dent ⁇ m
  • the photosensitive materials of Examples 125 to 148 are superior in sensitivity characteristics to those of the above respective Examples using conventional benzidine (A) because of their low potential after exposure V L (V), and are superior in durability and heat resistance because the extrapolated glass transition initiation temperature (Tig) is high and no dent is observed.
  • a photosensitive material of the respective Examples was fit with a facsimile for paper (Model LDC-650, manufactured by Mita Kogyo Co., Ltd.) and, after rotating 150,000 times without passing a paper through it, a change in film thickness of the organic photosensitive layer was determined, respectively.
  • the photosensitive materials of Examples 149 to 186 are superior in sensitivity characteristics to those of the above respective Examples using conventional benzidine (A) because of their low potential after exposure V L (V), and are superior in durability, particularly hardness, because of their small amount of wear.
  • V L V
  • extrapolated glass transition initiation temperature Tig °C
  • maximum depth of dent ⁇ m
  • the photosensitive materials of Examples 187 to 214 are superior in sensitivity characteristics to those of Examples 13, 18, 23 and 24 using conventional benzidine (A) because of their low potential after exposure V L (V), and are superior in durability and heat resistance because the extrapolated glass transition initiation temperature (Tig) is high and no dent is observed.
  • V L V
  • extrapolated glass transition initiation temperature Tig °C
  • maximum depth of dent ⁇ m
  • the photosensitive materials of Examples 215 to 250 are superior in sensitivity characteristics to those of the above respective Examples using conventional benzidine (A) because of their low potential after exposure V L (V), and are superior in durability and heat resistance because the extrapolated glass transition initiation temperature (Tig) is high and no dent is observed.
  • V L V
  • extrapolated glass transition initiation temperature Tig °C
  • maximum depth of dent ⁇ m
  • the photosensitive materials of Examples 251 to 274 are superior in sensitivity characteristics to those of the above respective Examples using conventional benzidine (A) because of their low potential after exposure V L (V), and are superior in durability and heat resistance because the extrapolated glass transition initiation temperature (Tig) is high and no dent is observed.
  • V L V
  • extrapolated glass transition initiation temperature Tig °C
  • maximum depth of dent ⁇ m
  • the photosensitive materials of Examples 275 to 298 are superior in sensitivity characteristics to those of the above respective Examples using conventional benzidine (A) because of their low potential after exposure V L (V), and are superior in durability and heat resistance because the extrapolated glass transition initiation temperature (Tig) is high and no dent is observed.
  • the photosensitive materials of Examples 299 to 336 are superior in sensitivity characteristics to those of the above respective Examples using conventional benzidine (A) because of their low potential after exposure V L (V), and are superior in durability, particularly hardness, because of their small amount of wear.
  • V L V
  • extrapolated glass transition initiation temperature Tig °C
  • maximum depth of dent ⁇ m
  • the photosensitive materials of Examples 337 to 364 are superior in sensitivity characteristics to those of Examples 25, 30, 35 and 36 using conventional benzidine (A) because of their low potential after exposure V L (V), and are superior in durability and heat resistance because the extrapolated glass transition initiation temperature (Tig) is high and no dent is observed.
  • V L V
  • extrapolated glass transition initiation temperature Tig °C
  • maximum depth of dent ⁇ m
  • the photosensitive materials of Examples 365 to 400 are superior in sensitivity characteristics to those of the above respective Examples using conventional benzidine (A) because of their low potential after exposure V L (V), and are superior in durability and heat resistance because the extrapolated glass transition initiation temperature (Tig) is high and no dent is observed.
  • the photosensitive materials of Examples 401 to 424 are superior in sensitivity characteristics to those of the above respective Examples using conventional benzidine (A) because of their low potential after exposure V L (V), and are superior in durability and heat resistance because the extrapolated glass transition initiation temperature (Tig) is high and no dent is observed.
  • the photosensitive materials of Examples 425 to 448 are superior in sensitivity characteristics to those of the above respective Examples using conventional benzidine (A) because of their low potential after exposure V L (V), and are superior in durability and heat resistance because the extrapolated glass transition initiation temperature (Tig) is high and no dent is observed.
  • the photosensitive materials of Examples 449 to 486 are superior in sensitivity characteristics to those of the above respective Examples using conventional benzidine (A) because of their low potential after exposure V L (V), and are superior in durability, particularly hardness, because of their small amount of wear.
  • a bisazo pigment represented by any one of the formulas (I) to (V) as the electric charge generating material and 100 parts by weight of polyvinyl butyral as the binding resin were mixed and dispersed with 1500 parts by weight of tetrahydrofuran using a ball mill to prepare a coating solution for electric charge generating layer. Then, this coating solution was applied on an aluminum tube as the conductive substrate by a dip coating method, followed by hot-air drying at 100 °C for 30 minutes to form an electric charge generating layer of 0.5 ⁇ m in film thickness.
  • this coating solution was applied on the above electric charge generating layer by a dip coating method, followed by hot-air drying at 110 °C for 30 minutes to form an electric charge transferring layer of 20 ⁇ m in film thickness, thereby affording a multi-layer negative-charging type photosensitive material.
  • the kind and amount (based on 100 parts by weight of binding resin) of the electron transferring material used in the respective Examples and Comparative Examples and kind of the electric charge generating material and hole transferring material used are shown in Table 27, respectively.
  • the compounds represented by the formulas (7e) and (7f) are as follows.
  • EX. 488 7e 3 I (Z CH 3 ) 6b
  • EX. 489 7e 5 I (Z CH 3 ) 6b
  • EX. 491 7e 3 I (Z OCH 3 ) 6b EX.
  • a photosensitive material obtained in the respective Examples and Comparative Examples was fit with an electrophotographic copying apparatus modified with a negative- changing specification (Model DC-2556, manufactured by Mita Kogyo Co., Ltd.) and, after printing 10,000 copies, a difference ( ⁇ V 0 ) between a charged potential before printing and that after printing was determined and, further, a difference ( ⁇ V r ) between a residual potential before printing and that after printing was determined.
  • a negative- changing specification Model DC-2556, manufactured by Mita Kogyo Co., Ltd.
  • this coating solution was applied on an aluminum tube as the conductive substrate by a dip coating method, followed by hot-air drying at 100 °C for 60 minutes to give a single-layer type photosensitive material for digital light source which has a single-layer type photosensitive layer of 15 to 20 ⁇ m in film thickness.
  • Embodied compounds of the electric charge generating material, hole transferring material and electron transferring material used in the above Examples and Comparative Examples are shown in Table 29, using the above-described compound No. of the respective embodiments. Further, two kinds of phthalocyanine pigments (i.e. X-type metal-free phthalocyanine and oxotitanyl phthalocyanine) were used, and the kind of the phthalocyanine pigment to be used in the respective Examples and Comparative Examples is shown in Table 29, using the following symbols.
  • X X-type metal-free phthalocyanine Ti: Oxotitanyl phthalocyanine
  • a photosensitive material of the respective Examples and Comparative Examples was fit with an imaging unit of a facsimile for paper (Model LDC-650, manufactured by Mita Kogyo Co., Ltd.) and, after standing at an environmental temperature of 50 °C for 10 days in such a state that a cleaning blade keeps in contact with the surface of the photosensitive material under linear pressure of 1.5 g/mm, the surface state of the photosensitive layer was measured using an universal surface shape tester (Model SE-3H, manufactured by Kosaka Kenkyusho) and a maximum depth of dent was recorded, respectively.
  • the description of "less than 0.3 ⁇ m" in the item of the dent in Table 29 means that no dent was observed because the surface roughness of a normal photosensitive material having no dent is about 0.5 ⁇ m.
  • the photosensitive materials of Examples 500 to 525 are superior in sensitivity characteristics because of their low potential after exposure V L (V), and are superior in durability and heat resistance to those of Comparative Examples 1 to 4 using conventional benzidine (A) because the extrapolated glass transition initiation temperature Tig (°C) is high and no dent is observed.
  • the photosensitive materials of Examples 526 to 557 are superior in sensitivity characteristics because of their low potential after exposure V L (V), and are superior in durability and heat resistance to those of Comparative Examples 14 to 17 using conventional benzidine (A) because the extrapolated glass transition initiation temperature Tig (°C) is high and no dent is observed.
  • the photosensitive materials of Examples 558 to 579 are superior in sensitivity characteristics because of their low potential after exposure V L (V), and are superior in durability and heat resistance to those of Comparative Examples 14 to 17 using conventional benzidine (A) because the extrapolated glass transition initiation temperature Tig (°C) is high and no dent is observed.
  • the photosensitive materials of Examples 580 to 601 are superior in sensitivity characteristics because of their low potential after exposure V L (V), and are superior in durability and heat resistance to those of Comparative Examples 14 to 17 using conventional benzidine (A) because the extrapolated glass transition initiation temperature Tig (°C) is high and no dent is observed.
  • a photosensitive material of the respective Examples was fit with a facsimile for paper (Model LDC-650, manufactured by Mita Kogyo Co., Ltd.) and, after rotating 150,000 times without passing a paper through it, a change in film thickness of the organic photosensitive layer was determined, respectively.
  • the photosensitive materials of Examples 602 to 639 are superior in sensitivity characteristics because of their low potential after exposure V L (V), and are superior in durability, particularly wear resistance, to Comparative Examples 14 to 17 using conventional benzidine (A) because of their small amount of wear.
  • the photosensitive materials of Examples 640 to 665 are superior in sensitivity characteristics because of their low potential after exposure V L (V), and are superior in durability and heat resistance to those of Comparative Examples 18 to 21 using conventional benzidine (A) because the extrapolated glass transition initiation temperature Tig (°C) is high and no dent is observed.
  • the photosensitive materials of Examples 666 to 697 are superior in sensitivity characteristics because of their low potential after exposure V L (V), and are superior in durability and heat resistance to those of Comparative Examples 18 to 21 using conventional benzidine (A) because the extrapolated glass transition initiation temperature Tig (°C) is high and no dent is observed.
  • the photosensitive materials of Examples 698 to 719 are superior in sensitivity characteristics because of their low potential after exposure V L (V), and are superior in durability and heat resistance to those of Comparative Examples 18 to 21 using conventional benzidine (A) because the extrapolated glass transition initiation temperature Tig (°C) is high and no dent is observed.
  • the photosensitive materials of Examples 720 to 741 are superior in sensitivity characteristics because of their low potential after exposure V L (V), and are superior in durability and heat resistance to those of Comparative Examples 18 to 21 using conventional benzidine (A) because the extrapolated glass transition initiation temperature Tig (°C) is high and no dent is observed.
  • the photosensitive materials of Examples 742 to 779 are superior in sensitivity characteristics because of their low potential after exposure V L (V), and are superior in durability, particularly wear resistance, to those of Comparative Examples 18 to 21 using conventional benzidine (A) because of their small amount of wear.
  • the photosensitive materials of Examples 780 to 805 are superior in sensitivity characteristics because of their low potential after exposure V L (V), and are superior in durability and heat resistance to those of Comparative Examples 22 to 25 using conventional benzidine (A) because the extrapolated glass transition initiation temperature Tig (°C) is high and no dent is observed.
  • the photosensitive materials of Examples 806 to 837 are superior in sensitivity characteristics because of their low potential after exposure V L (V), and are superior in durability and heat resistance to those of Comparative Examples 22 to 25 using conventional benzidine (A) because the extrapolated glass transition initiation temperature Tig (°C) is high and no dent is observed.
  • the photosensitive materials of Examples 838 to 859 of the present invention are superior in sensitivity characteristics because of their low potential after exposure V L (V), and are superior in durability and heat resistance to those of Comparative Examples 22 to 25 using conventional benzidine (A) because the extrapolated glass transition initiation temperature Tig (°C) is high and no dent is observed.
  • the photosensitive materials of Examples 860 to 881 are superior in sensitivity characteristics because of their low potential after exposure V L (V), and are superior in durability and heat resistance to those of Comparative Examples 22 to 25 using conventional benzidine (A) because the extrapolated glass transition initiation temperature Tig (°C) is high and no dent is observed.
  • the photosensitive materials of Examples 882 to 919 are superior in sensitivity characteristics because of their low potential after exposure V L (V), and are superior in durability, particularly wear resistance, to those of Comparative Examples 22 to 25 using conventional benzidine (A) because of their small amount of wear.
  • this coating solution was applied on an aluminum tube as the conductive substrate by a dip coating method, followed by hot-air drying at 100 °C for 60 minutes to give a single-layer type photosensitive material for digital light source which has a single-layer type photosensitive layer of 15 to 20 ⁇ m in film thickness.
  • the photosensitive materials of Examples 920 to 937 are superior in sensitivity characteristics to those of Comparative Examples 26 to 28 using an electron attractive compound of the formula (B) having a redox potential of less than -0.8 V and those of Examples 500, 501, etc. containing no electron attractive compound because of their low potential after exposure V L (V), and are superior in durability and heat resistance to those of Comparative Examples 29 and 30 using conventional benzidine (A) because the extrapolated glass transition initiation temperature Tig (°C) is high and no dent is observed.
  • the photosensitive materials of Examples 938 to 957 are superior in sensitivity characteristics to those of Comparative Examples 31 to 33 using an electron attractive compound of the formula (B) having a redox potential of less than -0.8 V and those of Examples 526, 527, etc. containing no electron attractive compound because of their low potential after exposure V L (V), and are superior in durability and heat resistance to those of Comparative Examples 29 and 30 using conventional benzidine (A) because the extrapolated glass transition initiation temperature Tig (°C) is high and no dent is observed.
  • the photosensitive materials of Examples 958 to 974 are superior in sensitivity characteristics to those of Comparative Examples 34 to 36 using an electron attractive compound of the formula (B) having a redox potential of less than -0.8 V and those of Examples 558, 559, etc. containing no electron attractive compound because of their low potential after exposure V L (V), and are superior in durability and heat resistance to those of Comparative Examples 29 and 30 using conventional benzidine (A) because the extrapolated glass transition initiation temperature Tig (°C) is high and no dent is observed.
  • the photosensitive materials of Examples 975 to 991 are superior in sensitivity characteristics to those of Comparative Examples 37 to 39 using an electron attractive compound of the formula (B) having a redox potential of less than -0.8 V and those of Examples 580, 581, etc. containing no electron attractive compound because of their low potential after exposure V L (V), and are superior in durability and heat resistance to those of Comparative Examples 29 and 30 using conventional benzidine (A) because the extrapolated glass transition initiation temperature Tig (°C) is high and no dent is observed.
  • the photosensitive materials of Examples 992 to 1018 are superior in sensitivity characteristics to those of Comparative Examples 40 to 42 using an electron attractive compound of the formula (B) having a redox potential of less than -0.8 V and those of Examples 603, 607, etc. containing no electron attractive compound because of their low potential after exposure V L (V), and are superior in durability, particularly wear resistance, to those of Comparative Examples 29 and 30 using conventional benzidine (A) because of their small amount of wear.
  • the photosensitive materials of Examples 1019 to 1036 are superior in sensitivity characteristics to those of Comparative Examples 43 to 45 using an electron attractive compound of the formula (B) having a redox potential of less than -0.8 V and those of Examples 640, 641, etc. containing no electron attractive compound because of their low potential after exposure V L (V), and are superior in durability and heat resistance to those of Comparative Examples 46 and 47 using conventional benzidine (A) because the extrapolated glass transition initiation temperature Tig (°C) is high and no dent is observed.
  • an electron attractive compound of the formula (B) having a redox potential of less than -0.8 V and those of Examples 640, 641, etc. containing no electron attractive compound because of their low potential after exposure V L (V) and are superior in durability and heat resistance to those of Comparative Examples 46 and 47 using conventional benzidine (A) because the extrapolated glass transition initiation temperature Tig (°C) is high and no dent is observed.
  • the photosensitive materials of Examples 1037 to 1056 are superior in sensitivity characteristics to those of Comparative Examples 48 to 50 using an electron attractive compound of the formula (B) having a redox potential of less than -0.8 V and those of Examples 666, 667, etc. containing no electron attractive compound because of their low potential after exposure V L (V), and are superior in durability and heat resistance to those of Comparative Examples 46 and 47 using conventional benzidine (A) because the extrapolated glass transition initiation temperature Tig (°C) is high and no dent is observed.
  • an electron attractive compound of the formula (B) having a redox potential of less than -0.8 V and those of Examples 666, 667, etc. containing no electron attractive compound because of their low potential after exposure V L (V) and are superior in durability and heat resistance to those of Comparative Examples 46 and 47 using conventional benzidine (A) because the extrapolated glass transition initiation temperature Tig (°C) is high and no dent is observed.
  • the photosensitive materials of Examples 558 to 574 are superior in sensitivity characteristics to those of Comparative Examples 51 to 53 using an electron attractive compound of the formula (B) having a redox potential of less than -0.8 V and those of Examples 698, 699, etc. containing no electron attractive compound because of their low potential after exposure V L (V), and are superior in durability and heat resistance to those of Comparative Examples 46 and 47 using conventional benzidine (A) because the extrapolated glass transition initiation temperature Tig (°C) is high and no dent is observed.
  • the photosensitive materials of Examples 1074 to 1090 are superior in sensitivity characteristics to those of Comparative Examples 54 to 56 using an electron attractive compound of the formula (B) having a redox potential of less than -0.8 V and those of Examples 720, 721, etc. containing no electron attractive compound because of their low potential after exposure V L (V), and are superior in durability and heat resistance to those of Comparative Examples 46 and 47 using conventional benzidine (A) because the extrapolated glass transition initiation temperature Tig (°C) is high and no dent is observed.
  • an electron attractive compound of the formula (B) having a redox potential of less than -0.8 V and those of Examples 720, 721, etc. containing no electron attractive compound because of their low potential after exposure V L (V) and are superior in durability and heat resistance to those of Comparative Examples 46 and 47 using conventional benzidine (A) because the extrapolated glass transition initiation temperature Tig (°C) is high and no dent is observed.
  • the photosensitive materials of Examples 1091 to 1117 are superior in sensitivity characteristics to those of Comparative Examples 57 to 59 using an electron attractive compound of the formula (B) having a redox potential of less than -0.8 V and those of Examples 743, 747, etc. containing no electron attractive compound because of their low potential after exposure V L (V), and are superior in durability, particularly wear resistance, to those of Comparative Examples 46 and 47 using conventional benzidine (A) because of their small amount of wear.
  • the photosensitive materials of Examples 1118 to 1135 are superior in sensitivity characteristics to those of Comparative Examples 60 to 62 using an electron attractive compound of the formula (B) having a redox potential of less than -0.8 V and those of Examples 780, 781, etc. containing no electron attractive compound because of their low potential after exposure V L (V), and are superior in durability and heat resistance to those of Comparative Examples 63 and 64 using conventional benzidine (A) because the extrapolated glass transition initiation temperature Tig (°C) is high and no dent is observed.
  • the photosensitive materials of Examples 1136 to 1155 are superior in sensitivity characteristics to those of Comparative Examples 65 to 67 using an electron attractive compound of the formula (B) having a redox potential of less than -0.8 V and those of Examples 806, 807, etc. containing no electron attractive compound because of their low potential after exposure V L (V), and are superior in durability and heat resistance to those of Comparative Examples 63 and 64 using conventional benzidine (A) because the extrapolated glass transition initiation temperature Tig (°C) is high and no dent is observed.
  • the photosensitive materials of Examples 1156 to 1172 are superior in sensitivity characteristics to those of Comparative Examples 68 to 70 using an electron attractive compound of the formula (B) having a redox potential of less than -0.8 V and those of Examples 838 and 839 containing no electron attractive compound because of their low potential after exposure V L (V), and are superior in durability and heat resistance to those of Comparative Examples 63 and 64 using conventional benzidine (A) because the extrapolated glass transition initiation temperature Tig (°C) is high and no dent is observed.
  • the photosensitive materials of Examples 1173 to 1189 are superior in sensitivity characteristics to those of Comparative Examples 71 to 73 using an electron attractive compound of the formula (B) having a redox potential of less than -0.8 V and those of Examples 860, 861, etc. containing no electron attractive compound because of their low potential after exposure V L (V), and are superior in durability and heat resistance to those of Comparative Examples 63 and 64 using conventional benzidine (A) because the extrapolated glass transition initiation temperature Tig (°C) is high and no dent is observed.
  • the photosensitive materials of Examples 1190 to 1216 are superior in sensitivity characteristics to those of Comparative Examples 74 to 76 using an electron attractive compound of the formula (B) having a redox potential of less than -0.8 V and those of Examples 883, 887, etc. containing no electron attractive compound because of their low potential after exposure V L (V), and are superior in durability, particularly wear resistance, to Comparative Examples 63 and 64 using conventional benzidine (A) because of their small amount of wear.

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Claims (8)

  1. Un matériau électrophotosensible comprenant une couche organique photosensible sur un substrat conducteur, la couche organique photosensible comprenant une résine de liaison, au moins un pigment disazo choisi parmi ceux représentés par les formules (I) à (V) :
    Figure 02170001
    Figure 02170002
    Figure 02180001
    Figure 02180002
    Figure 02180003
    [dans la formule (I), Z est un groupe méthyle ou un groupe méthoxy]
    en tant que matériau générateur de charges électriques et un dérivé de trinitrofluorénone imine représenté par la
    formule (1) :
    Figure 02190001
    [dans laquelle R1, R2, R3, R4 et R5 sont identiques ou différents et indiquent un atome d'hydrogène, un groupe alkyle, un groupe alkoxy, un groupe aryle substitué ou non substitué, un groupe aralkyle substitué ou non substitué ou un atome d'halogène]
    en tant que matériau de transfert d'électrons.
  2. Un matériau électrophotosensible selon la revendication 1,
    dans lequel le dérivé de trinitrofluorénone imine est représenté par la formule (7) :
    Figure 02190002
    [dans laquelle R39, R40, R41, R42 et R43 sont identiques ou différents et indiquent un atome d'hydrogène, un groupe alkyle, un groupe alkoxy ou un atome d'halogène]
    et comprenant en outre au moins un composé choisi parmi ceux représentés par les formules (2) à (6) suivantes en tant que matériau de transfert de trous :
    Figure 02200001
    [dans laquelle R6 et R7 sont identiques ou différents et indiquent un atome d'hydrogène ou un groupe alkyle ; R8, R9, R10 et R11 sont identiques ou différents et indiquent un groupe alkyle, un groupe alkoxy ou un atome d'halogène ; et a, b, c et d sont identiques ou différents et indiquent un nombre entier de 0 à 5 ; à condition qu'au moins un parmi a, b, c et d indique un nombre entier égal à 2 ou plus et que c et d indiquent un nombre entier autre que 0 quand a et b indiquent 0 simultanément].
    Figure 02200002
    [dans laquelle R12 et R13 sont identiques ou différents et indiquent un atome d'hydrogène ou un groupe alkyle ; R14 et R15 sont identiques ou différents et indiquent un groupe alkyle, un groupe alkoxy, un groupe aryle substitué ou non substitué ou un atome d'halogène ; R16 et R17 sont identiques ou différents et indiquent un groupe alkyle, un groupe alkoxy ou un atome d'halogène ; et e, f, g et h sont identiques ou différents et indiquent un nombre entier de 0 à 5]
    Figure 02210001
    [dans laquelle R18, R19, R20 et R21 sont identiques ou différents et indiquent un groupe alkyle ; et R22, R23, R24 et R25 sont identiques ou différents et indiquent un atome d'hydrogène, un groupe alkyle, un groupe alkoxy, un groupe aryle substitué ou non substitué ou un atome d'halogène]
    Figure 02210002
    [dans laquelle R26, R27, R28 et R29 sont identiques ou différents et indiquent un groupe alkyle ; et R30, R31, R32 et R33 sont identiques ou différents et indiquent un atome d'hydrogène, un groupe alkyle, un groupe alkoxy, un groupe aryle substitué ou non substitué ou un atome d'halogène]
    Figure 02210003
    [dans laquelle R34, R35, R36 et R37 sont identiques ou différents et indiquent un groupe alkyle, un groupe alkoxy, un groupe aryle substitué ou non substitué, un atome d'halogène, un groupe amino ou un groupe amino N-substitué; R38 est un groupe alkyle, un groupe alkoxy, un atome d'halogène, un groupe amino, un groupe amino N-substitué, un groupe allyle, un groupe aryle substitué ou non substitué ou un groupe attracteur d'électrons ; q, r, s et t sont identiques ou différents et indiquent un nombre entier de 0 à 5 ; et u est un nombre entier de 0 à 2].
  3. Un matériau électrophotosensible selon la revendication 1,
    dans lequel le dérivé de trinitrofluorénone imine est représenté par la formule (8) :
    Figure 02220001
    [dans laquelle R44 et R45 sont identiques ou différents et indiquent un groupe alkyle, un groupe alkoxy ou un atome d'halogène ; et α et β indiquent un nombre entier, leur somme étant de 0 à 4]
    et comprenant en outre au moins un composé choisi parmi ceux représentés par les formules (2) à (6) de la revendication 2 en tant que matériau de transfert de trous.
  4. Un matériau électrophotosensible selon la revendication 1,
    dans lequel le dérivé trinitrofluorénone imine est représenté par la formule (9) :
    Figure 02230001
    [dans laquelle R46 et R47 sont identiques ou différents et indiquent un groupe alkyle, un groupe alkoxy ou un atome d'halogène ; et γ et δ indiquent un nombre entier, leur somme étant de 0 à 4]
    et comprenant en outre au moins un composé choisi parmi ceux représentés par les formules (2) à (6) de la revendication 2 en tant que matériau de transfert de trous.
  5. Un matériau électrophotosensible comprenant une couche organique photosensible sur un substrat conducteur, la couche organique photosensible comprenant une résine de liaison, un matériau générateur de charges électriques et un dérivé de trinitrofluorénone imine représenté par la formule (1) de la revendication 1 en tant que matériau de transfert d'électrons et au moins un composé choisi parmi ceux représentés par les formules (2) à (6) de la revendication 2 en tant que matériau de transfert de trous.
  6. Un matériau électrophotosensible selon la revendication 5,
    dans lequel le matériau générateur de charges électriques est un pigment phthalocyanine.
  7. Un matériau électrophotosensible selon la revendication 5,
    dans lequel le dérivé de trinitrofluorénone imine est représenté par la formule (7) de la revendication 2, la formule (8) de la revendication 3 ou la formule (9) de la revendication 4.
  8. Un matériau électrophotosensible selon la revendication 5 ou la revendication 7,
    dans lequel la couche organique photosensible contient en outre un composé attracteur d'électrons ayant un potentiel d'oxydoréduction de -0,8 à -1,4 V.
EP95303624A 1994-05-31 1995-05-26 Matérial électrophotosensible Expired - Lifetime EP0690351B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP119185/94 1994-05-31
JP6119185A JPH07325413A (ja) 1994-05-31 1994-05-31 電子写真感光体

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EP0690351A2 EP0690351A2 (fr) 1996-01-03
EP0690351A3 EP0690351A3 (fr) 1996-01-17
EP0690351B1 true EP0690351B1 (fr) 1998-08-26

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Publication number Priority date Publication date Assignee Title
JP2000330302A (ja) * 1999-05-21 2000-11-30 Kyocera Mita Corp 正帯電単層型電子写真感光体
KR100416718B1 (ko) * 2000-12-19 2004-01-31 광주과학기술원 작용기로서 카르바졸을 측쇄로 갖는 스티렌 유도체의 합성방법
CN100458572C (zh) * 2006-08-23 2009-02-04 邯郸光导重工高技术有限公司 一种正充电性有机光导鼓的制备方法

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Publication number Priority date Publication date Assignee Title
JPS5642236A (en) * 1979-09-14 1981-04-20 Hitachi Ltd Composite type electrophotographic plate
US4631242A (en) * 1984-09-13 1986-12-23 Mitsubishi Paper Mills, Ltd. Bisazo electrophotographic sensitive materials with --CF3 group
JPH01198763A (ja) * 1988-02-03 1989-08-10 Mitsubishi Kasei Corp 電子写真用感光体
JP2718048B2 (ja) 1988-02-15 1998-02-25 株式会社ブリヂストン 電子写真感光体用電荷輸送剤及び電子写真感光体
JP2782108B2 (ja) * 1990-06-13 1998-07-30 キヤノン株式会社 電子写真感光体、該電子写真感光体を備えた電子写真装置並びにファクシミリ
JPH0521099A (ja) 1991-07-08 1993-01-29 Idec Izumi Corp インターフエース用コネクタ端子台装置
JPH07233134A (ja) * 1994-02-24 1995-09-05 Mita Ind Co Ltd トリニトロフルオレノンイミン誘導体および電子写真感光体

Also Published As

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EP0690351A2 (fr) 1996-01-03
KR950033704A (ko) 1995-12-26
EP0690351A3 (fr) 1996-01-17
DE69504251T2 (de) 1999-01-07
CN1116732A (zh) 1996-02-14
JPH07325413A (ja) 1995-12-12
DE69504251D1 (de) 1998-10-01

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