CN108693721B - Electrophotographic photoreceptor, process cartridge, and image forming apparatus - Google Patents
Electrophotographic photoreceptor, process cartridge, and image forming apparatus Download PDFInfo
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- CN108693721B CN108693721B CN201810318259.9A CN201810318259A CN108693721B CN 108693721 B CN108693721 B CN 108693721B CN 201810318259 A CN201810318259 A CN 201810318259A CN 108693721 B CN108693721 B CN 108693721B
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- chemical formula
- photosensitive layer
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- resin
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- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 description 1
- QLNFINLXAKOTJB-UHFFFAOYSA-N [As].[Se] Chemical compound [As].[Se] QLNFINLXAKOTJB-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- PGEHNUUBUQTUJB-UHFFFAOYSA-N anthanthrone Chemical compound C1=CC=C2C(=O)C3=CC=C4C=CC=C5C(=O)C6=CC=C1C2=C6C3=C54 PGEHNUUBUQTUJB-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 150000001502 aryl halides Chemical class 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- VJGNLOIQCWLBJR-UHFFFAOYSA-M benzyl(tributyl)azanium;chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CC1=CC=CC=C1 VJGNLOIQCWLBJR-UHFFFAOYSA-M 0.000 description 1
- 125000002619 bicyclic group Chemical group 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- FNIATMYXUPOJRW-UHFFFAOYSA-N cyclohexylidene Chemical group [C]1CCCCC1 FNIATMYXUPOJRW-UHFFFAOYSA-N 0.000 description 1
- PWAPCRSSMCLZHG-UHFFFAOYSA-N cyclopentylidene Chemical group [C]1CCCC1 PWAPCRSSMCLZHG-UHFFFAOYSA-N 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 229940097275 indigo Drugs 0.000 description 1
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 150000002475 indoles Chemical class 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002545 isoxazoles Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- CUONGYYJJVDODC-UHFFFAOYSA-N malononitrile Chemical class N#CCC#N CUONGYYJJVDODC-UHFFFAOYSA-N 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- PRMHOXAMWFXGCO-UHFFFAOYSA-M molport-000-691-708 Chemical compound N1=C(C2=CC=CC=C2C2=NC=3C4=CC=CC=C4C(=N4)N=3)N2[Ga](Cl)N2C4=C(C=CC=C3)C3=C2N=C2C3=CC=CC=C3C1=N2 PRMHOXAMWFXGCO-UHFFFAOYSA-M 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- BYPNIFFYJHKCFO-UHFFFAOYSA-N n,n-dimethyl-4-(2-phenyl-1,3-dihydropyrazol-5-yl)aniline Chemical compound C1=CC(N(C)C)=CC=C1C1=CCN(C=2C=CC=CC=2)N1 BYPNIFFYJHKCFO-UHFFFAOYSA-N 0.000 description 1
- UDJWHGNSQWLKGR-UHFFFAOYSA-N n-methyl-4-[5-[4-(methylamino)phenyl]-1,3,4-oxadiazol-2-yl]aniline Chemical compound C1=CC(NC)=CC=C1C1=NN=C(C=2C=CC(NC)=CC=2)O1 UDJWHGNSQWLKGR-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 150000004866 oxadiazoles Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920000548 poly(silane) polymer Polymers 0.000 description 1
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- DNXIASIHZYFFRO-UHFFFAOYSA-N pyrazoline Chemical compound C1CN=NC1 DNXIASIHZYFFRO-UHFFFAOYSA-N 0.000 description 1
- 150000003219 pyrazolines Chemical class 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- PWEBUXCTKOWPCW-UHFFFAOYSA-N squaric acid Chemical compound OC1=C(O)C(=O)C1=O PWEBUXCTKOWPCW-UHFFFAOYSA-N 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- NLDYACGHTUPAQU-UHFFFAOYSA-N tetracyanoethylene Chemical group N#CC(C#N)=C(C#N)C#N NLDYACGHTUPAQU-UHFFFAOYSA-N 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 150000003557 thiazoles Chemical class 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 150000004882 thiopyrans Chemical class 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 150000004992 toluidines Chemical class 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Images
Classifications
-
- 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
- G03G5/05—Organic bonding materials; Methods for coating a substrate with a photoconductive layer; Inert supplements for use in photoconductive layers
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G21/00—Arrangements not provided for by groups G03G13/00 - G03G19/00, e.g. cleaning, elimination of residual charge
- G03G21/16—Mechanical means for facilitating the maintenance of the apparatus, e.g. modular arrangements
- G03G21/18—Mechanical means for facilitating the maintenance of the apparatus, e.g. modular arrangements using a processing cartridge, whereby the process cartridge comprises at least two image processing means in a single unit
Abstract
The invention provides an electrophotographic photoreceptor, a process cartridge and an image forming apparatus. An electrophotographic photoreceptor includes a conductive substrate and a photosensitive layer. The photosensitive layer is a single layer and includes a charge generator, a hole transport agent, an electron transport agent, and a polyarylate resin. The polyarylate resin has a main chain and a terminal group bonded to a terminal of the main chain. The main chain contains a repeating unit represented by the following general formula (1). In the general formula (1), X and Y are each independently a divalent group represented by the following chemical formula (1A), (1B), (1C), (1D) or (1E). The terminal group is represented by the following general formula (2). The hole-transporting agent includes compounds represented by the following general formulae (HTM1) to (HTM 7). The depth of scratch resistance of the photosensitive layer is 0.50 μm or less. The Vickers hardness of the photosensitive layer is 18.0HV or more.
Description
Technical Field
The invention relates to an electrophotographic photoreceptor, a process cartridge and an image forming apparatus.
Background
Electrophotographic photoreceptors are used as image carriers in electrophotographic image forming apparatuses (e.g., printing apparatuses and multifunction machines). The electrophotographic photoreceptor includes a photosensitive layer. The electrophotographic photoreceptor is, for example, a single-layer type electrophotographic photoreceptor or a laminated type electrophotographic photoreceptor. The single-layer type electrophotographic photoreceptor comprises: a photosensitive layer having a charge generation function and a charge transport function. The laminated electrophotographic photoreceptor includes a photosensitive layer comprising: a charge generation layer having a charge generation function, and a charge transport layer having a charge transport function.
A photosensitive layer of an electrophotographic photoreceptor contains a polyarylate resin obtained based on a dicarboxylic acid component and a divalent phenol component having a specific structure.
Disclosure of Invention
However, the above electrophotographic photoreceptor is insufficient in fog resistance.
In view of the above-described problems, an object of the present invention is to provide an electrophotographic photoreceptor having a photosensitive layer excellent in fog resistance. Another object of the present invention is to provide a process cartridge and an image forming apparatus that suppress the occurrence of image defects.
The electrophotographic photoreceptor of the present invention includes a conductive substrate and a photosensitive layer. The photosensitive layer is a single layer and includes a charge generator, a hole transporting agent, an electron transporting agent, and a binder resin. The binder resin comprises a polyarylate resin. The polyarylate resin has a main chain and a terminal group bonded to a terminal of the main chain. The main chain includes a repeating unit represented by the following general formula (1). The terminal group is represented by the following general formula (2). The hole transporting agent includes a compound represented by the following general formula (HTM1), general formula (HTM2), general formula (HTM3), general formula (HTM4), general formula (HTM5), general formula (HTM6), or general formula (HTM 7). The depth of scratch resistance of the photosensitive layer is less than 0.50 mu m. The Vickers hardness of the photosensitive layer is 18.0HV or more.
[ CHEM 1 ]
In the general formula (1), Q1、Q2、Q3、Q4、Q7、Q8、Q9And Q10Each independently represents a methyl group or a hydrogen atom. Q5、Q6、Q11And Q12Each independently represents a C1-C4 alkyl group or a hydrogen atom. Q5And Q6May be combined with each other to represent C5-C7 cycloalkylene (cycloakylidine). Q11And Q12May be combined with each other and represent C5-C7 cycloalkylene. r, s, t and u are each independently a number of 0 or more. r + s + t + u is 100. r + t is s + u. r/(r + t) is 0.00 to 0.90. s/(s + u) is 0.00 to 0.90. X and Y are each independently represented by the following chemical formulae (1A), (1B), (B)1C) A divalent group represented by (1D) or (1E).
[ CHEM 2 ]
[ CHEM 3 ]
-O-Rf (2)
In the general formula (2), RfRepresents a chain aliphatic group having a fluorine group.
[ CHEM 4 ]
In the general formula (HTM1), R1、R2、R3And R4Each independently represents a C1-C6 alkyl group. a1, a2, a3 and a4 are independent of each other and each represents an integer of 0 to 5. a1 represents an integer of 2 to 5, and R's are several1May be the same or different. a2 represents an integer of 2 to 5, and R's are several2May be the same or different. a3 represents an integer of 2 to 5, and R's are several3May be the same or different. a4 represents an integer of 2 to 5, and R's are several4May be the same or different.
[ CHEM 5 ]
In the general formula (HTM2), R5、R6、R7And R8Each independently represents a C1-C6 alkyl group or a hydrogen atom.
[ CHEM 6 ]
In the general formula (HTM3), R9、R10、R11And R12Each independently represents a C1-C6 alkyl group. b1, b2, b3 and b4 are independent of each other and each represents an integer of 0 to 5. b1 represents an integer of 2 to 5 inclusive, a plurality of R9May be the same or different. b2 represents an integer of 2 to 5 inclusive, a plurality of R10May be the same or different. b3 represents an integer of 2 to 5 inclusive, a plurality of R11May be the same or different. b4 represents an integer of 2 to 5 inclusive, a plurality of R12May be the same or different.
[ CHEM 7 ]
In the general formula (HTM4), R13、R14、R15And R16Each independently represents a C1-C6 alkyl group. c1, c2, c3 and c4 are each independently an integer of 0 to 5. c1 represents an integer of 2 to 5, a plurality of R13May be the same or different. c2 represents an integer of 2 to 5, a plurality of R14May be the same or different. c3 represents an integer of 2 to 5, a plurality of R15May be the same or different. c4 represents an integer of 2 to 5, a plurality of R16May be the same or different.
[ CHEM 8 ]
In the general formula (HTM5), R17、R18、R19、R20And R21Each independently represents a C1-C6 alkyl group or a hydrogen atom.
[ CHEM 9 ]
In the general formula (HTM6), R22、R23And R24Each independently represents a C1-C6 alkyl group. d1, d2 and d3 are each independently an integer of 0 to 5. d1 represents an integer of 2 to 5 inclusive, and R's are several22May be the same or different. d2 represents an integer of 2 to 5 inclusive, and R's are several23May be the same or different. d3 represents an integer of 2 to 5 inclusive, and R's are several24May be the same or different. R25Represents a C1-C6 alkyl group or a hydrogen atom.
[ CHEM 10 ]
In the general formula (HTM7), R26、R27And R28Each independently represents a C1-C6 alkyl group. e1, e2, and e3 are each independently an integer of 0 to 5. e1 represents an integer of 2 to 5 inclusive, a plurality of R26May be the same or different. e2 represents an integer of 2 to 5 inclusive, a plurality of R27May be the same or different. e3 represents an integer of 2 to 5 inclusive, a plurality of R28May be the same or different. R29、R30And R31Each independently represents a C6-C14 aryl group or a hydrogen atom.
The process cartridge of the present invention includes the electrophotographic photoreceptor.
An image forming apparatus of the present invention includes: an image carrier, a charging section, an exposure section, a developing section, and a transfer section. The image bearing member is the electrophotographic photoreceptor. The charging unit charges a surface of the image carrier. The charging polarity of the charging portion is positive. The exposure section exposes the charged surface of the image carrier to form an electrostatic latent image on the surface of the image carrier. The developing section develops the electrostatic latent image into a toner image. The transfer section transfers the toner image from the image bearing member to a transfer target while the surface of the image bearing member is in contact with the transfer target.
The electrophotographic photoreceptor of the present invention is excellent in fog resistance. Further, the process cartridge and the image forming apparatus of the present invention can suppress the occurrence of an image failure.
Drawings
Fig. 1 is a partial cross-sectional view of an example of the structure of an electrophotographic photoreceptor according to a first embodiment of the present invention.
Fig. 2 is a partial cross-sectional view of an example of the structure of the electrophotographic photoreceptor according to the first embodiment of the present invention.
Fig. 3 is a partial cross-sectional view of an example of the structure of the electrophotographic photoreceptor according to the first embodiment of the present invention.
Fig. 4 shows an example of an image forming apparatus according to a second embodiment of the present invention.
Fig. 5 shows an example of the structure of the scoring device.
Fig. 6 is a cross-sectional view taken along line IV-IV of fig. 5.
Fig. 7 is a side view of the fixing table, the scribing needle, and the electrophotographic photoreceptor shown in fig. 5.
Fig. 8 shows scratches formed on the surface of the photosensitive layer.
Detailed Description
The present invention is not limited to the following embodiments, and can be carried out with appropriate modifications within the intended scope of the present invention. Note that, although the description thereof may be omitted as appropriate, the gist of the present invention is not limited thereto. In the present specification, the compound and its derivatives may be collectively referred to by adding "class" to the compound name. When a compound name is followed by "class" to indicate a polymer name, the repeating unit indicating the polymer is derived from the compound or a derivative thereof.
Hereinafter, C1-C6 alkyl group, C1-C4 alkyl group, C5-C7 cycloalkylene group, C6-C14 aryl group and chain aliphatic group respectively represent the following meanings.
The C1-C6 alkyl group is linear or branched and unsubstituted. C1-C6 alkyl such as: methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl and hexyl.
The C1-C4 alkyl group is linear or branched and unsubstituted. C1-C4 alkyl such as: methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, and tert-butyl.
C5-C7 cycloalkylene (cycloakylidine) is unsubstituted. C5-C7 cycloalkylene for example: cyclopentylidene (cyclophenylidene), cyclohexylidene (cyclophenylidene) and cycloheptylidene (cyclophenylidene).
The C6-C14 aryl group is unsubstituted. C6-C14 aryl, for example: a C6-C14 unsubstituted aromatic monocyclic hydrocarbon group, a C6-C14 unsubstituted aromatic condensed bicyclic hydrocarbon group, and a C6-C14 unsubstituted aromatic condensed tricyclic hydrocarbon group. More specifically, C6-C14 aryl groups such as: phenyl, naphthyl, anthryl and phenanthryl.
The linear aliphatic group means a linear or branched organic group among organic groups having no aromatic property.
In the following description, the "main chain of the polyarylate resin" refers to the longest chain among chains composed of repeating units in the polyarylate resin. "having a fluorine group" means that a part or all of hydrogen atoms of an organic group is substituted by a fluorine group.
< first embodiment: electrophotographic photoreceptor
The structure of an electrophotographic photoreceptor (hereinafter, may be referred to as a photoreceptor) according to a first embodiment of the present invention will be described. Fig. 1, 2, and 3 are partial cross-sectional views showing a structure of the photoreceptor 1 according to the first embodiment. As shown in fig. 1, the photoreceptor 1 includes a conductive substrate 2 and a photosensitive layer 3. The photosensitive layer 3 is a single layer. As shown in fig. 1, the photosensitive layer 3 may be directly provided on the conductive substrate 2. As shown in fig. 2, the photoreceptor 1 may include, for example: a conductive substrate 2, an intermediate layer 4 (e.g., an undercoat layer), and a photosensitive layer 3. In the example shown in fig. 2, the photosensitive layer 3 is indirectly provided on the conductive substrate 2 via the intermediate layer 4. As shown in fig. 3, the photoreceptor 1 may have a protective layer 5 as the outermost layer.
Hereinafter, the elements (the conductive substrate 2, the photosensitive layer 3, and the intermediate layer 4) of the photoreceptor 1 will be described, and a method for manufacturing the photoreceptor 1 will also be described.
[1. conductive substrate ]
The conductive substrate 2 is not particularly limited as long as it can be used as a conductive substrate of the photoreceptor 1. As the conductive substrate 2, a conductive substrate at least a surface portion of which is made of a conductive material can be used. The conductive substrate 2 is, for example: a conductive substrate made of a material having conductivity (conductive material), and a conductive substrate coated with the conductive material. Conductive materials such as: aluminum, iron, copper, tin, platinum, silver, vanadium, molybdenum, chromium, cadmium, titanium, nickel, palladium, and indium. These conductive materials may be used alone or in combination of two or more. Combinations of two or more such as alloys (more specifically, aluminum alloys, stainless steel, brass, etc.). Among these conductive materials, aluminum and aluminum alloys are preferable in terms of the good ability to transfer charges from the photosensitive layer 3 to the conductive substrate 2.
The shape of the conductive substrate 2 can be appropriately selected according to the structure of the image forming apparatus to be used. The shape of the conductive substrate 2 is, for example: sheet-like and drum-like. The thickness of the conductive substrate 2 may be appropriately selected according to the shape of the conductive substrate 2.
[2. photosensitive layer ]
The photosensitive layer 3 contains: a charge generating agent, a hole transporting agent, an electron transporting agent, and a binder resin. The photosensitive layer 3 may further contain an additive. The thickness of the photosensitive layer 3 is not particularly limited as long as it can sufficiently function as a photosensitive layer. Specifically, the thickness of the photosensitive layer 3 may be 5 μm to 100 μm, and preferably 10 μm to 50 μm.
The vickers hardness of the photosensitive layer 3 is measured by a method based on Japanese Industrial Standards (JIS) Z2244. Vickers hardness was measured using a hardness meter (for example, Matsuzawa co., Ltd manufactures "micro vickers DMH-1 type"). The vickers hardness can be measured under conditions such as a temperature of 23 ℃, a load (test force) of the diamond indenter of 10gf, a time required to reach the test force of 5 seconds, an approach speed of the diamond indenter of 2 mm/second, and a holding time of the test force of 1 second.
The vickers hardness of the photosensitive layer 3 is 18.0HV or more, and from the viewpoint of further improving the fog resistance, it is preferably 18.5HV or more, and more preferably 19.0HV or more. The upper limit of the vickers hardness of the photosensitive layer 3 is not particularly limited as long as the photosensitive layer of the photoreceptor 1 can function, and is preferably 27.0HV in view of the production cost.
The vickers hardness can be controlled by adjusting the type of polyarylate resin (1) described later and the type and content of a hole transporting agent described later, for example.
The scratch resistance depth (hereinafter, sometimes referred to as scratch depth) of the photosensitive layer 3 is the depth of a scratch formed when the photosensitive layer 3 is scratched under specific conditions shown below. The scratch depth was measured by the following first, second, third and fourth steps using a scoring device as defined in JIS K5600-5-5. The scoring device includes a fixing table and a scoring needle. The top end of the scratching needle is hemispherical sapphire with the diameter of 1 mm.
In the first step, the photoreceptor 1 is fixed to the top surface of the fixed stage so that the longitudinal direction thereof is parallel to the longitudinal direction of the fixed stage. In the second step, the scratching pin is vertically abutted against the surface of the photosensitive layer 3. In the third step, the stationary stage and the photoreceptor 1 fixed to the top surface of the stationary stage were moved by 30mm at a speed of 30 mm/min in the longitudinal direction of the stationary stage while applying a load of 10g to the photosensitive layer 3 from the scratch. By the third step, scratches are formed on the surface of the photosensitive layer 3. In the fourth step, the maximum depth of the scratch, i.e., the scratch depth, is measured.
The outline of the measuring method of the scratch depth is described above. The method of measuring the scratch depth will be described in detail in examples.
The depth of scratches of the photosensitive layer 3 is 0.50 μm or less, and is preferably 0.49 μm or less, and more preferably 0.48 μm or less, from the viewpoint of further improving the fogging resistance. The lower limit of the scratch depth of the photosensitive layer 3 is not particularly limited as long as the function of the photosensitive layer of the photoreceptor 1 can be exhibited, and may be, for example, 0.00 μm, but is preferably 0.09 μm in view of production cost.
The scratch depth can be controlled by adjusting the type of polyarylate resin (1) described later, and the type and content of a hole transporting agent described later, for example.
Hereinafter, the charge generating agent, the hole transporting agent, the electron transporting agent, the binder resin, and optional additives will be described.
(Charge generating agent)
The charge generating agent is not particularly limited as long as it is a charge generating agent for a photoreceptor. Charge generators such as: phthalocyanine pigments, perylene pigments, disazo pigments, trisazo pigments, dithione-pyrrolopyrrole (dithioketo-pyrrozole) pigments, metal-free naphthalocyanine pigments, metal naphthalocyanine pigments, squaric acid pigments, indigo pigments, azulene pigments, cyanine pigments, powders of inorganic photoconductive materials (e.g., selenium-tellurium, selenium-arsenic, cadmium sulfide, and amorphous silicon), pyran pigments, anthanthrone pigments, triphenylmethane pigments, threne pigments, toluidine pigments, pyrazoline pigments, and quinacridone pigments. One kind of charge generating agent may be used alone, or two or more kinds may be used in combination. Examples of the phthalocyanine pigments include metal-free phthalocyanine and metal phthalocyanine. Metal phthalocyanines such as: oxytitanium phthalocyanine, hydroxygallium phthalocyanine and chlorogallium phthalocyanine. The phthalocyanine pigment may be crystalline or amorphous. The crystal shape (for example, α -type, β -type, X-type, Y-type, V-type, and II-type) of the phthalocyanine pigment is not particularly limited, and phthalocyanine pigments having various crystal shapes can be used.
The metal-free phthalocyanine crystal is, for example, an X-type metal-free phthalocyanine crystal (hereinafter, sometimes referred to as an X-type metal-free phthalocyanine). Examples of the crystal of oxytitanium phthalocyanine include α -type, β -type and Y-type crystals of oxytitanium phthalocyanine (hereinafter, sometimes referred to as α -type, β -type and Y-type oxytitanium phthalocyanines, respectively). Crystals of hydroxygallium phthalocyanine such as V-type crystals of hydroxygallium phthalocyanine.
When the photoreceptor 1 is used in a digital optical image forming apparatus, it is preferable to use a charge generating agent having sensitivity in a wavelength region of 700nm or more. The charge generating agent having sensitivity in a wavelength region of 700nm or more, for example, a phthalocyanine-based pigment, is preferably an X-type metal-free phthalocyanine in terms of efficiently generating charges. The digital optical image forming apparatus is, for example, a laser printer and a facsimile using a light source such as a semiconductor laser.
When the photoreceptor 1 is used in an image forming apparatus using a short-wavelength laser light source, for example, an anthraquinone pigment or a perylene pigment is preferably used as the charge generating agent. The wavelength of the short-wavelength laser light is, for example, 350nm or more and 550nm or less.
The charge generating agent is, for example, phthalocyanine pigments represented by the following chemical formulae (CGM-1) to (CGM-4) (hereinafter, sometimes referred to as charge generating agents (CGM-1) to (CGM-4), respectively).
[ CHEM 11 ]
[ CHEM 12 ]
[ CHEM 13 ]
[ CHEM 14 ]
From the viewpoint of efficiently generating electric charges, the content of the charge generating agent is preferably 0.1 part by mass or more and 50 parts by mass or less, more preferably 0.5 part by mass or more and 30 parts by mass or less, and particularly preferably 0.5 part by mass or more and 4.5 parts by mass or less, with respect to 100 parts by mass of the binder resin.
(hole transport agent)
The hole transporting agent includes a compound represented by the following general formula (HTM1), general formula (HTM2), general formula (HTM3), general formula (HTM4), general formula (HTM5), general formula (HTM6), or general formula (HTM 7). Hereinafter, these hole transport agents are sometimes referred to as hole transport agents (HTM1) to (HTM7), respectively. The photosensitive layer 3 may contain one kind of these hole transport agents alone, or may contain two or more kinds thereof.
[ CHEM 15 ]
In the general formula (HTM1), R1、R2、R3And R4Each independently represents a C1-C6 alkyl group. a1, a2, a3 and a4 are independent of each other and each represents an integer of 0 to 5. a1 represents an integer of 2 to 5, and R's are several1May be the same or different. a2 represents an integer of 2 to 5, and R's are several2May be the same or different. a3 represents an integer of 2 to 5 inclusive, and a plurality of R3May be the same or different. a4 represents an integer of 2 to 5, and R's are several4May be the same or different.
[ CHEM 16 ]
In the general formula (HTM2), R5、R6、R7And R8Each independently represents a C1-C6 alkyl group or a hydrogen atom.
[ CHEM 17 ]
In the general formula (HTM3), R9、R10、R11And R12Each independently represents a C1-C6 alkyl group. b1, b2, b3 and b4 each independently represent a whole number of 0 to 5And (4) counting. b1 represents an integer of 2 to 5 inclusive, a plurality of R9May be the same or different. b2 represents an integer of 2 to 5 inclusive, a plurality of R10May be the same or different. b3 represents an integer of 2 to 5 inclusive, a plurality of R11May be the same or different. b4 represents an integer of 2 to 5 inclusive, a plurality of R12May be the same or different.
[ CHEM 18 ]
In the general formula (HTM4), R13、R14、R15And R16Each independently represents a C1-C6 alkyl group. c1, c2, c3 and c4 are each independently an integer of 0 to 5. c1 represents an integer of 2 to 5, a plurality of R13May be the same or different. c2 represents an integer of 2 to 5, a plurality of R14May be the same or different. c3 represents an integer of 2 to 5, a plurality of R15May be the same or different. c4 represents an integer of 2 to 5, a plurality of R16May be the same or different.
[ CHEM 19 ]
In the general formula (HTM5), R17、R18、R19、R20And R21Each independently represents a C1-C6 alkyl group or a hydrogen atom.
[ CHEM 20 ]
In the general formula (HTM6), R22、R23And R24Each independently represents a C1-C6 alkyl group. d1, d2 and d3 are independent of each otherAnd represents an integer of 0 to 5 inclusive. d1 represents an integer of 2 to 5 inclusive, and R's are several22May be the same or different. d2 represents an integer of 2 to 5 inclusive, and R's are several23May be the same or different. d3 represents an integer of 2 to 5 inclusive, and R's are several24May be the same or different. R25Represents a C1-C6 alkyl group or a hydrogen atom.
[ CHEM 21 ]
In the general formula (HTM7), R26、R27And R28Each independently represents a C1-C6 alkyl group. e1, e2, and e3 are each independently an integer of 0 to 5. e1 represents an integer of 2 to 5 inclusive, a plurality of R26May be the same or different. e2 represents an integer of 2 to 5 inclusive, a plurality of R27May be the same or different. e3 represents an integer of 2 to 5 inclusive, a plurality of R28May be the same or different. R29、R30And R31Each independently represents a C6-C14 aryl group or a hydrogen atom.
In the general formula (HTM1), a1 and a3 preferably represent 1 in order to further improve the fogging resistance. In the same respect, R1And R3Each independently preferably represents a C1-C4 alkyl group, more preferably a methyl group. In the same respect, a2 and a4 preferably represent 0. The hole-transporting agent (HTM1) represented by the general formula (HTM1) is, for example: a hole-transporting agent represented by the following chemical formula (HTM1-1) (hereinafter, sometimes referred to as a hole-transporting agent (HTM 1-1)).
[ CHEM 22 ]
In the general formula (HTM2), R is represented by5And R6Independently of one another, preferablyRepresents a C1-C6 alkyl group, more preferably a C1-C4 alkyl group, and still more preferably a methyl group. In the same respect, R7And R8Preferably represents a hydrogen atom. The hole-transporting agent (HTM2) represented by the general formula (HTM2) is, for example: a hole-transporting agent represented by the following chemical formula (HTM2-1) (hereinafter, sometimes referred to as a hole-transporting agent (HTM 2-1)).
[ CHEM 23 ]
In the general formula (HTM3), b1 and b3 preferably represent 1 in order to further improve the fogging resistance. In the same respect, R9And R11Each independently preferably represents a C1-C4 alkyl group, more preferably a methyl group. In the same respect, b2 and b4 preferably represent 0. The hole-transporting agent (HTM3) represented by the general formula (HTM3) is, for example: a hole-transporting agent represented by the following chemical formula (HTM3-1) (hereinafter, sometimes referred to as a hole-transporting agent (HTM 3-1)).
[ CHEM 24 ]
In the general formula (HTM4), c1 and c2 preferably represent 1 in order to further improve the fogging resistance. In the same respect, R13And R14Each independently preferably represents a C1-C4 alkyl group, more preferably a methyl group. In the same respect, c3 and c4 preferably represent 0. The hole-transporting agent (HTM4) represented by the general formula (HTM4) is, for example: a hole-transporting agent represented by the following chemical formula (HTM4-1) (hereinafter, sometimes referred to as a hole-transporting agent (HTM 4-1)).
[ CHEM 25 ]
To further improve the ash resistanceIn view of fogging, R in the formula (HTM5)17、R18、R19、R20And R21Each independently preferably represents a C1-C6 alkyl group, more preferably a C1-C4 alkyl group, and still more preferably a methyl group. The hole-transporting agent (HTM5) represented by the general formula (HTM5) is, for example: a hole-transporting agent represented by the following chemical formula (HTM5-1) (hereinafter, sometimes referred to as a hole-transporting agent (HTM 5-1)).
[ CHEM 26 ]
In the general formula (HTM6), d1, d2 and d3 preferably represent 0 in order to further improve the fogging resistance. In the same respect, R25Preferably represents a hydrogen atom. The hole-transporting agent (HTM6) represented by the general formula (HTM6) is, for example: a hole-transporting agent represented by the following chemical formula (HTM6-1) (hereinafter, sometimes referred to as a hole-transporting agent (HTM 6-1)).
[ CHEM 27 ]
In the general formula (HTM7), e1, e2 and e3 are each independently, preferably 0 or 1, from the viewpoint of further improving the fogging resistance. When e1, e2 and e3 represent 0, R is a group represented by formula (I) in order to further improve the fogging resistance29、R30And R31Each independently preferably represents a C6-C14 aryl group, more preferably a phenyl group. When e1, e2 and e3 represent 1, R is a group represented by formula (I)29、R30And R31Preferably represents a hydrogen atom. In addition, when e1, e2 and e3 represent 1, R is more excellent in the fogging resistance26、R27And R28Preferably represents a C1-C4 alkyl group, more preferably a methyl group. The hole-transporting agent (HTM7) represented by the general formula (HTM7) is, for example: a hole-transporting agent represented by the following chemical formula (HTM7-1) (hereinafter referred to as "hole-transporting agent")These may be referred to as a hole transport agent (HTM7-1)) or a hole transport agent represented by the chemical formula (HTM7-2) (hereinafter, may be referred to as a hole transport agent (HTM 7-2)).
[ CHEM 28 ]
[ CHEM 29 ]
Among these hole transport agents, the hole transport agent (HTM1), the hole transport agent (HTM2), the hole transport agent (HTM5), and the hole transport agent (HTM6) are preferable, and the hole transport agent (HTM1-1), the hole transport agent (HTM2-1), the hole transport agent (HTM5-1), and the hole transport agent (HTM6-1) are more preferable, from the viewpoint of further improving the fogging resistance.
From the viewpoint of efficiently transporting holes, the content of the hole transporting agent is preferably 10 parts by mass or more and 200 parts by mass or less, and more preferably 10 parts by mass or more and 100 parts by mass or less, with respect to 100 parts by mass of the binder resin.
The photosensitive layer 3 may contain other hole transport agents in addition to the hole transport agents (HTM1) to (HTM 7). Examples of the other hole-transporting agent include compounds having a structure different from that of the hole-transporting agents (HTM1) to (HTM7) among the following compounds: diamine derivatives (more specifically, N '-tetraphenylphenylenediamine derivatives, N' -tetraphenylnaphthalenediamine derivatives, N '-tetraphenylphenylenediamine (N, N' -tetraphenylphenylenediamine) derivatives, and the like); oxadiazole compounds (more specifically, 2, 5-bis (4-methylaminophenyl) -1, 3, 4-oxadiazole and the like); a styrene compound (more specifically, 9- (4-diethylaminostyryl) anthracene, etc.); carbazole-based compounds (more specifically, polyvinylcarbazole and the like); an organic polysilane compound; pyrazolines (more specifically, 1-phenyl-3- (p-dimethylaminophenyl) pyrazoline, etc.); a hydrazone compound; indole compounds; an oxazole compound; isoxazoles compounds; thiazole compounds; a thiadiazole compound; imidazole compounds; a pyrazole compound; a triazole compound. The total content of the hole-transporting agents (HTM1) to (HTM7) is preferably 80 mass% or more, more preferably 90 mass% or more, and particularly preferably 100 mass% with respect to the total mass of the hole-transporting agents.
(Electron transport agent)
Electron transport agents such as: quinone compounds, imide compounds, hydrazone compounds, malononitrile compounds, thiopyran compounds, trinitrothioxanthone compounds, 3, 4, 5, 7-tetranitro-9-fluorenone compounds, dinitroanthracene compounds, dinitroacridine compounds, tetracyanoethylene, 2, 4, 8-trinitrothioxanthone, dinitrobenzene, dinitroacridine, succinic anhydride, maleic anhydride and dibromomaleic anhydride. Quinone compounds are exemplified by: diphenoquinone compounds, azoquinone compounds, anthraquinone compounds, naphthoquinone compounds, nitroanthraquinone compounds and dinitroanthraquinone compounds. These electron transport agents may be used alone or in combination of two or more.
Among these electron transport agents, a compound represented by the following general formula (ETM1) is preferable, and a compound represented by the following chemical formula (ETM1-1) is more preferable (hereinafter, sometimes referred to as an electron transport agent (ETM1-1)) from the viewpoint of efficiently transporting electrons.
[ CHEM 30 ]
In the general formula (ETM1), R41And R44Each independently represents a C1-C6 alkyl group or a hydrogen atom. R42And R43Each independently represents a C1-C6 alkyl group. f1 and f2 are each independently an integer of 0 to 4. f1 represents an integer of 2 to 4, and R's are several42May be the same or different. When f2 represents an integer of 2 to 4, a plurality of R43May be the same or different.
[ CHEM 31 ]
From the viewpoint of efficiently transporting electrons, the content of the electron transporting agent is preferably 5 parts by mass or more and 100 parts by mass or less, and more preferably 10 parts by mass or more and 80 parts by mass or less, with respect to 100 parts by mass of the binder resin.
(Binder resin)
The binder resin includes a polyarylate resin (hereinafter, may be referred to as polyarylate resin (1)), and the polyarylate resin (1) has a main chain including a repeating unit represented by the following general formula (1) and a specific terminal group bonded to a terminal of the main chain. The specific terminal group is represented by the following general formula (2). The photosensitive layer 3 may contain one or two or more types of polyarylate resins (1).
[ CHEM 32 ]
In the general formula (1), Q1、Q2、Q3、Q4、Q7、Q8、Q９And Q10Each independently represents a methyl group or a hydrogen atom. Q5、Q6、Q11And Q12Each independently represents a C1-C4 alkyl group or a hydrogen atom. Q5And Q6May be combined with each other and represent C5-C7 cycloalkylene. Q11And Q12May be combined with each other and represent C5-C7 cycloalkylene. r, s, t and u are each independently a number of 0 or more. r + s + t + u is 100. r + t is s + u. r/(r + t) is 0.00 to 0.90. s/(s + u) is 0.00 to 0.90. X and Y are each independently a divalent group represented by the following chemical formula (1A), (1B), (1C), (1D) or (1E).
[ CHEM 33 ]
[ CHEM 34 ]
Mono O-Rf (2)
In the general formula (2), RfRepresents a chain aliphatic group having a fluorine group.
The main chain of the polyarylate resin (1) preferably has no halogen atom. When the main chain of the polyarylate resin (1) does not have a halogen atom, the compatibility of the hole transporting agent with the polyarylate resin (1) is improved, and crystallization of the photosensitive layer 3 is likely to be suppressed. This can further improve the fogging resistance.
In the general formula (1), Q is added to improve the fogging resistance1、Q3、Q7And Q9Preferably represents a methyl group. In the same respect, Q2、Q4、Q8And Q10Preferably represents a hydrogen atom. In the same respect, Q5And Q6Preferably in combination with each other, represent C5-C7 cycloalkylene, more preferably in combination with each other, represent cyclohexylene. In the same respect, Q11And Q12Preferably in combination with each other, represent C5-C7 cycloalkylene, more preferably in combination with each other, represent cyclohexylene.
In the general formula (1), r/(r + t) is preferably 0.10 to 0.70, more preferably 0.30 to 0.70, from the viewpoint of further improving the fogging resistance. From the same viewpoint, s/(s + u) is preferably 0.10 to 0.70, more preferably 0.30 to 0.70.
In the general formula (1), X and Y are preferably different from each other in view of further improving the fogging resistance. In this case, from the viewpoint of further improving the fogging resistance, at least one of X and Y is preferably a divalent group represented by chemical formula (1B) or (1C), and more preferably a divalent group represented by chemical formula (1C).
The main chain of the polyarylate resin (1) is, for example, a repeating unit represented by the following general formula (1-5) (hereinafter, may be referred to as a repeating unit (1-5)), a repeating unit represented by the following general formula (1-6) (hereinafter, may be referred to as a repeating unit (1-6), a repeating unit represented by the following general formula (1-7) (hereinafter, may be referred to as a repeating unit (1-7)), and a repeating unit represented by the following general formula (1-8) (hereinafter, may be referred to as a repeating unit (1-8)).
[ CHEM 35 ]
Q in the general formula (1-5)1、Q2、Q3、Q4、Q5And Q6Are respectively connected with Q in the general formula (1)1、Q2、Q3、Q4、Q5And Q6Have the same meaning. X in the general formulae (1 to 6) has the same meaning as that of X in the general formula (1). Q in the general formula (1-7)7、Q8、Q9、Q10、Q11And Q12Are respectively connected with Q in the general formula (1)7、Q8、Q9、Q10、Q11And Q12Have the same meaning. Y in the general formulae (1 to 8) has the same meaning as that of Y in the general formula (1).
The main chain of the polyarylate resin (1) may contain a repeating unit other than the repeating units (1-5) to (1-8). The ratio (mole fraction) of the total amount of the repeating units (1-5) to (1-8) to the total amount of the repeating units in the main chain of the polyarylate resin (1) is preferably 0.80 or more, more preferably 0.90 or more, and further preferably 1.00.
The arrangement of the repeating units (1-5) to (1-8) in the main chain of the polyarylate resin (1) is not particularly limited as long as the repeating unit derived from the aromatic diol and the repeating unit derived from the aromatic dicarboxylic acid are adjacent to each other. For example, the repeating units (1-5) are bonded to each other adjacent to the repeating units (1-6) or the repeating units (1-8). Similarly, the repeating units (1-7) are bonded to each other adjacent to the repeating units (1-6) or the repeating units (1-8).
In the general formula (1), r represents the number of the repeating units (1 to 5), the number of the repeating units (1 to 6) and the repeating unit relative to the number of the repeating units (1 to 5) contained in the main chain of the polyarylate resin (1)The total percentage of the number of elements (1-7) and the number of repeating units (1-8). s represents the percentage of the number of the repeating units (1 to 6) relative to the total of the number of the repeating units (1 to 5), the number of the repeating units (1 to 6), the number of the repeating units (1 to 7) and the number of the repeating units (1 to 8) contained in the main chain of the polyarylate resin (1). t represents the percentage of the total of the number of the repeating units (1 to 7) relative to the number of the repeating units (1 to 5), the number of the repeating units (1 to 6), the number of the repeating units (1 to 7) and the number of the repeating units (1 to 8) contained in the main chain of the polyarylate resin (1). u represents the percentage of the number of the repeating units (1 to 8) relative to the total of the number of the repeating units (1 to 5), the number of the repeating units (1 to 6), the number of the repeating units (1 to 7) and the number of the repeating units (1 to 8) contained in the main chain of the polyarylate resin (1). R, s, t and u are arithmetic average values obtained from the whole main chain (several main chains) of the polyarylate resin (1) contained in the photosensitive layer 3, respectively, and are not values obtained from 1 main chain. Further, r, s, t and u can be measured by proton nuclear magnetic resonance spectrometer, for example, of polyarylate resin (1)1H-NMR spectrum.
The main chain of the polyarylate resin (1) is, for example, a main chain represented by the following chemical formulae (R-1) to (R-6) (hereinafter, sometimes referred to as main chains (R-1) to (R-6)).
[ CHEM 36 ]
[ CHEM 37 ]
From the viewpoint of further improving the fogging resistance, the main chain of the polyarylate resin (1) is preferably the main chains (R-2), (R-4) and (R-5), and more preferably the main chains (R-2) and (R-4).
The end group of the polyarylate resin (1) contains a chain aliphatic group having a fluorine group as R in the general formula (2)f. The polyarylate resin (1) has one or two or more of such terminal groups. Utensil for cleaning buttockThe chain aliphatic group having a fluorine group may have a hetero atom having a valence of 2 or more in its structure. Hetero atoms having a valence of 2 or more such as oxygen atom, nitrogen atom, sulfur atom, silicon atom, phosphorus atom and boron atom. The terminal group of the chain aliphatic group having a heteroatom having a valence of 2 or more is, for example, a terminal group represented by the following chemical formula (MA).
[ CHEM 38 ]
From the viewpoint of further improving the fogging resistance, RfThe chain aliphatic group having a fluorine group is preferably a C1-C6 alkyl group having at least 1 fluorine group, more preferably a C1-C6 perfluoroalkyl group, still more preferably a C1-C6 linear perfluoroalkyl group, and particularly preferably a heptafluoro-n-propyl group. RfWhen the chain aliphatic group having a fluoro group represented by (a) is a heptafluoro-n-propyl group, the terminal group is represented by the following chemical formula (M1). Hereinafter, the terminal group represented by the formula (M1) may be referred to as a terminal group (M1).
[ CHEM 39 ]
-O-CF2-CF2-CF3 (M1)
The method for producing the binder resin is not particularly limited as long as the polyarylate resin (1) can be produced. The method for producing the binder resin includes, for example: a method of polycondensing an aromatic diol constituting a repeating unit, an aromatic dicarboxylic acid constituting a repeating unit, and a terminal terminator constituting a terminal group. The polycondensation method is not particularly limited, and a known synthesis method (more specifically, solution polymerization, melt polymerization, interfacial polymerization, and the like) can be employed.
The aromatic dicarboxylic acid used for the production of the polyarylate resin (1) has 2 carboxyl groups and is represented by the following general formula (1-9) or general formula (1-10). X in the general formulae (1 to 9) and Y in the general formulae (1 to 10) have the same meanings as those of X and Y in the general formula (1), respectively.
[ CHEM 40 ]
The aromatic dicarboxylic acid is, for example, an aromatic dicarboxylic acid having 2 carboxyl groups bonded to an aromatic ring (more specifically, 4, 4 '-diphenyletherdicarboxylic acid, 4, 4' -biphenyldicarboxylic acid, etc.). Further, as the aromatic dicarboxylic acid, a derivative such as a diacid chloride, a dimethyl ester, or a diethyl ester can be used. The aromatic dicarboxylic acid used for the polycondensation may contain an aromatic dicarboxylic acid other than the aromatic dicarboxylic acids represented by the general formulae (1 to 9) and (1 to 10).
The aromatic diol has 2 phenolic hydroxyl groups and is represented by the following general formula (1-11) or general formula (1-12). Q in the general formula (1-11)1、Q2、Q3、Q4、Q5And Q6Are respectively connected with Q in the general formula (1)1、Q2、Q3、Q4、Q5And Q6Have the same meaning. Q in the general formula (1-12)7、Q8、Q9、Q10、Q11And Q12Are respectively connected with Q in the general formula (1)7、Q8、Q9、Q10、Q11And Q12Have the same meaning.
[ CHEM 41 ]
When the polyarylate resin (1) is synthesized, a derivative such as diacetate can be used as the aromatic diol. The aromatic diol used for the polycondensation may contain other aromatic diols in addition to the aromatic diols represented by the general formulae (1 to 11) and (1 to 12).
As the terminal terminator constituting the terminal group, for example, an alcohol represented by the following general formula (2-1) can be used. R in the general formula (2-1)fAnd R in the general formula (2)fHave the same meaning.
[ CHEM 42 ]
HO-Rf (2-1)
In the case of synthesizing the polyarylate resin (1) by polycondensation, the amount of the terminal terminator to be reacted is preferably 0.001 mol or more and 0.1 mol or less with respect to 1 mol of the aromatic dicarboxylic acid in order to further improve the fogging resistance.
The binder resin may be the polyarylate resin (1) alone, or the polyarylate resin (1) may be used in combination with a resin (other resin) other than the polyarylate resin (1). Other resins such as: thermoplastic resins (polyarylate resin other than polyarylate resin (1), polycarbonate resin, styrene-butadiene copolymer, styrene-acrylonitrile copolymer, styrene-maleic acid copolymer, styrene-acrylic acid copolymer, polyethylene resin, ethylene-vinyl acetate copolymer, chlorinated polyethylene resin, polyvinyl chloride resin, polypropylene resin, ionomer, vinyl chloride-vinyl acetate copolymer, polyester resin, alkyd resin, polyamide resin, polyurethane resin, polysulfone resin, diallyl phthalate resin, ketone resin, polyvinyl butyral resin, polyether resin, polyester resin, etc.), thermosetting resins (silicone resin, epoxy resin, phenol resin, urea resin, melamine resin, crosslinked thermosetting resin other than these, etc.), and photocurable resins (epoxy-acrylic resin, etc.) Polyurethane-acrylic copolymers, etc.). These may be used alone or in combination of two or more. The content of the polyarylate resin (1) is preferably 80% by mass or more, more preferably 90% by mass or more, and further preferably 100% by mass, relative to the total amount of the binder resin.
The viscosity average molecular weight of the binder resin is preferably 10,000 or more, more preferably 20,000 or more, further preferably 30,000 or more, and particularly preferably 40,000 or more. When the viscosity average molecular weight of the binder resin is 10,000 or more, the abrasion resistance of the binder resin is improved, and the photosensitive layer 3 tends to be less likely to be abraded. On the other hand, the viscosity average molecular weight of the binder resin is preferably 80,000 or less, more preferably 70,000 or less. If the viscosity average molecular weight of the binder resin is 80,000 or less, the binder resin is easily dissolved in a solvent for forming the photosensitive layer, and the photosensitive layer 3 may be easily formed.
(additives)
Additives as optional components are, for example: deterioration inhibitors (more specifically, antioxidants, radical scavengers, quenchers, ultraviolet absorbers, etc.), softeners, surface modifiers, extenders, thickeners, dispersion stabilizers, waxes, donors, surfactants, and leveling agents. When an additive is added, one of these additives may be used alone, or two or more of these additives may be used in combination.
Antioxidants such as: hindered phenol compounds, hindered amine compounds, thioether compounds, and phosphite compounds. Among these antioxidants, hindered phenol compounds and hindered amine compounds are preferable.
(combination of materials)
From the viewpoint of further improving the fogging resistance, the binder resin and the hole transporting agent are preferably combination examples 1 to 22 shown in table 1 below. From the same viewpoint, it is more preferable that the binder resin and the hole transport agent are combination examples 1 to 22 shown in table 1 below, and the electron transport agent is an electron transport agent (ETM 1-1). From the same viewpoint, it is more preferable that the binder resin and the hole transporting agent are combination examples 1 to 22 shown in table 1 below, and the charge generating agent is X-type metal-free phthalocyanine. From the same viewpoint, it is more preferable that the binder resin and the hole transport agent are combination examples 1 to 22 shown in table 1, the electron transport agent is an electron transport agent (ETM1-1), and the charge generation agent is X-type metal-free phthalocyanine. In addition, the polyarylate resins (R-1-M1) to (R-6-M1) will be described in examples.
[ TABLE 1 ]
| Example of the combination | Adhesive resin | Hole transport agent |
| Combination example 1 | Polyarylate resin (R-1-M1) | Hole transport agent (HTM1-1) |
| Combination example 2 | Polyarylate resin (R-2-M1) | Hole transport agent (HTM1-1) |
| Combination example 3 | Polyarylate resin (R-3-M1) | Hole transport agent (HTM1-1) |
| Combination example 4 | Polyarylate resin (R-4-M1) | Hole transport agent (HTM1-1) |
| Combination example 5 | Polyarylate resin (R-5-M1) | Hole transport agent (HTM1-1) |
| Combination example 6 | Polyarylate resin (R-6-M1) | Hole transport agent (HTM1-1) |
| Combination example 7 | Polyarylate resin (R-1-M1) | Hole transport agent (HTM2-1) |
| Example of combination 8 | Polyarylate resin (R-2-M1) | Hole transport agent (HTM2-1) |
| Combination example 9 | Polyarylate resin (R-3-M1) | Hole transport agent (HTM2-1) |
| Combination example 10 | Polyarylate resin (R-4-M1) | Hole transport agent (HTM2-1) |
| Combination example 11 | Polyarylate resin (R-5-M1) | Hole transport agent (HTM2-1) |
| Combination example 12 | Polyarylate resin (R-6-M1) | Hole transport agent (HTM2-1) |
| Combination example 13 | Polyarylate resin (R-1-M1) | Hole transport agent (HTM6-1) |
| Combination example 14 | Polyarylate resin (R-2-M1) | Hole transport agent (HTM6-1) |
| Combination example 15 | Polyarylate resin (R-3-M1) | Hole transport agent (HTM6-1) |
| Combination example 16 | Polyarylate resin (R-4-M1) | Hole transport agent (HTM6-1) |
| Combination example 17 | Polyarylate resin (R-5-M1) | Hole transport agent (HTM6-1) |
| Example of Assembly 18 | Polyarylate resin (R-6-M1) | Hole transport agent (HTM6-1) |
| Combination example 19 | Polyarylate resin (R-4-M1) | Hole transport agent (HTM3-1) |
| Example of Assembly 20 | Polyarylate resin (R-4-M1) | Hole transport agent (HTM4-1) |
| Combination example 21 | Polyarylate resin (R-4-M1) | Hole transport agent (HTM5-1) |
| Example of Assembly 22 | Polyarylate resin (R-4-M1) | Hole transport agent (HTM7-1) |
[3. intermediate layer ]
As described above, the photoreceptor 1 of the present embodiment may have the intermediate layer 4 (e.g., undercoat layer). The intermediate layer 4 contains, for example: inorganic particles, and a resin for the intermediate layer (resin for the intermediate layer). The presence of the intermediate layer 4 allows smooth current flow to be generated when the photoreceptor 1 is exposed to light, and suppresses an increase in resistance, while maintaining an insulating state to such an extent that leakage current can be suppressed.
Inorganic particles such as: particles of metal (more specifically, aluminum, iron, copper, etc.), particles of metal oxide (more specifically, titanium dioxide, aluminum oxide, zirconium oxide, tin oxide, zinc oxide, etc.), and particles of non-metal oxide (more specifically, silicon dioxide, etc.). These inorganic particles may be used alone or in combination of two or more. Also, the inorganic particles may be surface-treated.
The resin for the intermediate layer is not particularly limited as long as it can be used as a resin for forming the intermediate layer.
[4 ] method for producing photoreceptor
A method for manufacturing the photoreceptor 1 will be described. The method of manufacturing the photoreceptor 1 includes, for example, a photosensitive layer forming step. In the photosensitive layer forming step, a coating liquid for forming the photosensitive layer 3 (hereinafter, sometimes referred to as a photosensitive layer coating liquid) is prepared. Next, a coating liquid for photosensitive layer is applied onto the conductive substrate 2. Then, the photosensitive layer 3 is formed by drying by an appropriate method to remove at least a part of the solvent contained in the coating liquid for the photosensitive layer applied. The coating liquid for photosensitive layer includes, for example: a charge generating agent, a hole transporting agent, an electron transporting agent, a polyarylate resin (1) as a binder resin, and a solvent. Such a coating liquid for photosensitive layers is prepared by dissolving or dispersing a charge generator, a hole transporting agent, an electron transporting agent, and a polyarylate resin (1) as a binder resin in a solvent. Various additives may be added to the coating liquid for photosensitive layer as necessary.
The photosensitive layer forming step will be described in detail below. The solvent contained in the coating liquid for photosensitive layer is not particularly limited as long as it can dissolve or disperse the respective components contained in the coating liquid for photosensitive layer. Solvents such as: alcohols (more specifically, methanol, ethanol, isopropanol, butanol, etc.), aliphatic hydrocarbons (more specifically, n-hexane, octane, cyclohexane, etc.), aromatic hydrocarbons (more specifically, benzene, toluene, xylene, etc.), halogenated hydrocarbons (more specifically, dichloromethane, dichloroethane, carbon tetrachloride, chlorobenzene, etc.), ethers (more specifically, dimethyl ether, diethyl ether, tetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, etc.), ketones (more specifically, acetone, methyl ethyl ketone, cyclohexanone, etc.), esters (more specifically, ethyl acetate, methyl acetate, etc.), dimethyl formaldehyde, dimethyl formamide, and dimethyl sulfoxide. These solvents may be used alone, or two or more of them may be used in combination. Among these solvents, halogen-free solvents are preferably used.
The coating liquid for photosensitive layer is prepared by mixing the respective components and dispersing in a solvent. The mixing or dispersing can be carried out, for example, using a bead mill, roll mill, ball mill, attritor, paint shaker or ultrasonic disperser.
In order to improve the dispersibility of each component, for example, a surfactant may be contained in the coating liquid for photosensitive layer.
The method for applying the coating liquid for photosensitive layer is not particularly limited as long as it can uniformly coat the coating liquid for photosensitive layer. The coating method includes, for example: dip coating, spray coating, spin coating, and bar coating.
The method for removing at least a part of the solvent contained in the coating liquid for the photosensitive layer is not particularly limited as long as it is a method capable of evaporating at least a part of the solvent in the coating liquid for the photosensitive layer. Examples of the removal method include: heating, reducing pressure, and heating and reducing pressure. For example, a specific method is heat treatment (hot air drying) using a high-temperature dryer or a reduced-pressure dryer. The heat treatment conditions are, for example, a temperature of 40 ℃ to 150 ℃ and a time of 3 minutes to 120 minutes.
The method for manufacturing the photoreceptor 1 may further include a step of forming the intermediate layer 4, if necessary. In the step of forming the intermediate layer 4, a known method can be appropriately selected.
The photoreceptor of the present embodiment described above is excellent in fog resistance, and therefore can be preferably used in various image forming apparatuses.
< second embodiment: image Forming apparatus
The following describes an image forming apparatus according to a second embodiment. An image forming apparatus according to a second embodiment includes: an image carrier, a charging section, an exposure section, a developing section, and a transfer section. The image bearing member is the photoreceptor according to the first embodiment. The charging unit charges a surface of the image carrier. The charging polarity of the charging portion is positive. The exposure section exposes the charged surface of the image carrier to form an electrostatic latent image on the surface of the image carrier. The developing section develops the electrostatic latent image into a toner image. The transfer section transfers the toner image from the image bearing member to a transfer target while the surface of the image bearing member is in contact with the transfer target.
The image forming apparatus according to the second embodiment can suppress the occurrence of image defects. The reason is presumed as follows. An image forming apparatus according to a second embodiment includes the photoreceptor according to the first embodiment as an image carrier. The photoreceptor according to the first embodiment is excellent in fog resistance. Therefore, the image forming apparatus according to the second embodiment can suppress image defects (more specifically, blurring and the like).
An embodiment of an image forming apparatus according to a second embodiment will be described below with reference to fig. 4, taking a tandem color image forming apparatus as an example.
The image forming apparatus 100 shown in fig. 4 is a direct transfer type image forming apparatus. In general, in an image forming apparatus employing a direct transfer method, an image carrier is in contact with a recording medium as a transfer target, and a fine component is likely to adhere to the surface of the image carrier, which is likely to cause an image failure. However, in an example of the second embodiment, the image forming apparatus 100 includes the photoreceptor according to the first embodiment as the image carrier 30. The photoreceptor according to the first embodiment is excellent in fog resistance. Therefore, when the photoreceptor according to the first embodiment is provided as the image carrier 30, the occurrence of image defects can be suppressed even if the image forming apparatus 100 employs the direct transfer method.
The image forming apparatus 100 includes: image forming units 40a, 40b, 40c, and 40d, transfer belt 50, and fixing unit 52. Hereinafter, the image forming units 40a, 40b, 40c, and 40d are all described as the image forming unit 40 in the case where distinction is not necessary.
The image forming unit 40 includes: an image carrier 30, a charging section 42, an exposure section 44, a developing section 46, and a transfer section 48. The image carrier 30 is disposed at the center of the image forming unit 40. The image carrier 30 is provided to be rotatable in an arrow direction (counterclockwise direction). Around the image carrier 30, a charging section 42, an exposure section 44, a developing section 46, and a transfer section 48 are provided in this order from the upstream side in the rotational direction of the image carrier 30 with reference to the charging section 42. The image forming unit 40 may further include one or both of a cleaning unit (not shown) and a discharging unit (not shown).
The image forming units 40a to 40d sequentially superimpose toner images of a plurality of colors (for example, four colors of black, cyan, magenta, and yellow) on the recording medium P (transferred body) on the transfer belt 50.
The charging section 42 is a charging roller. The charging roller is brought into contact with the surface of the image carrier 30 to charge the surface of the image carrier 30. In general, in an image forming apparatus including a charging roller, an image failure is likely to occur. However, the image forming apparatus 100 includes the photoreceptor of the first embodiment as the image carrier 30. The photoreceptor of the first embodiment is excellent in fog resistance. Therefore, even if the image forming apparatus 100 includes the charging roller as the charging section 42, occurrence of an image failure can be suppressed. In this way, the image forming apparatus 100 as an example of the second embodiment employs a contact charging method. The charging portion of another contact charging system is, for example, a charging brush. The charging unit may be of a non-contact type. The non-contact type charging portion includes, for example, a grid electrode-less type charging portion (Corotron) and a grid electrode-type charging portion (Scorotron).
The voltage applied by the charging section 42 is not particularly limited. The voltage applied by the charging section 42 is, for example: the dc voltage, the ac voltage, and the superimposed voltage (voltage in which the ac voltage is superimposed on the dc voltage) are preferably dc voltages. The dc voltage has the following advantages compared to the ac voltage and the superimposed voltage. When only the dc voltage is applied to the charging section 42, the voltage applied to the image carrier 30 is constant, and therefore, the surface of the image carrier 30 is easily charged uniformly to a constant potential. Further, when only a direct current voltage is applied to the charging section 42, the amount of abrasion of the photosensitive layer tends to decrease. As a result, a preferable image can be formed.
The exposure section 44 exposes the surface of the charged image carrier 30. Thereby, an electrostatic latent image is formed on the surface of the image carrier 30. An electrostatic latent image is formed based on image data input to the image forming apparatus 100.
The developing section 46 supplies toner to the surface of the image carrier 30, and develops the electrostatic latent image into a toner image. The developing unit 46 may employ a contact developing method of developing the electrostatic latent image into a toner image while contacting the surface of the image carrier 30. In general, in an image forming apparatus employing a contact development method, image defects are likely to occur due to fogging. However, since the image forming apparatus 100 includes the photoreceptor according to the first embodiment as the image carrier 30 and the photoreceptor according to the first embodiment is excellent in fog resistance, the image forming apparatus 100 including such a photoreceptor can suppress image defects due to fog even when the contact development method is employed.
The developing unit 46 can clean the surface of the image carrier 30. That is, the image forming apparatus 100 may adopt a so-called cleanerless system. In this case, the developing unit 46 can remove the residual component on the surface of the image carrier 30. In general, an image forming apparatus including a cleaning unit (e.g., a cleaning blade) can scrape off residual components on the surface of an image bearing member by the cleaning unit. However, in the case of the image forming apparatus of the cleanerless system, the residual components on the surface of the image carrier are not scraped off. Therefore, in the image forming apparatus adopting the cleanerless system, the residual component is generally likely to remain on the surface of the image bearing member. However, the image forming apparatus 100 includes the photoreceptor of the first embodiment having excellent fog resistance as the image carrier 30. Therefore, even if the cleanerless system is adopted in the image forming apparatus 100 including such a photoreceptor, residual components, particularly fine components (e.g., paper dust) of the recording medium P, are less likely to remain on the surface of the photoreceptor. As a result, the image forming apparatus 100 can suppress the occurrence of image defects (e.g., fogging).
In order to efficiently clean the surface of the image carrier 30 while the developing unit 46 performs development, the following conditions (a) and (b) are preferably satisfied.
Condition (a): the contact development method is adopted, and a difference in rotational speed (rotational speed) is provided between the image carrier 30 and the developing portion 46.
Condition (b): the surface potential of the image carrier 30 and the potential of the developing bias satisfy the following equations (b-1) and (b-2).
0(V) < potential of developing bias (V) < surface potential of unexposed region (V) … … (b-1) of image carrier 30
Potential of developing bias (V) > surface potential of exposed region of image bearing body 30 (V) > 0(V) … … (b-2)
As shown in the condition (a), when the contact development method is adopted and a difference in rotation speed is provided between the image carrier 30 and the developing portion 46, the surface of the image carrier 30 is brought into contact with the developing portion 46, and the residual component on the surface of the image carrier 30 is removed by friction with the developing portion 46. The rotation speed of the developing portion 46 is preferably higher than the rotation speed of the image carrier 30.
In the condition (b), it is assumed that the development method is a reversal development method. In order to improve the electrical characteristics of the image bearing member 30 having a positive charging polarity, it is preferable that the charging polarity of the toner, the surface potential of the unexposed area of the image bearing member 30, the surface potential of the exposed area of the image bearing member 30, and the potential of the developing bias are all positive. The surface potential of the unexposed area and the surface potential of the exposed area of the image carrier 30 are measured after the transfer section 48 transfers the toner image from the image carrier 30 to the recording medium P, and before the charging section 42 charges the surface of the image carrier 30.
When the formula (b-1) of the condition (b) is satisfied, the electrostatic repulsive force acting between the toner remaining on the image bearing member 30 (hereinafter, sometimes referred to as residual toner) and the unexposed area of the image bearing member 30 is larger than the electrostatic repulsive force acting between the residual toner and the developing unit 46. Therefore, the residual toner in the unexposed area of the image bearing member 30 moves from the surface of the image bearing member 30 to the developing unit 46 and is collected.
When the formula (b-2) of the condition (b) is satisfied, the electrostatic repulsive force acting between the residual toner and the exposure area of the image carrier 30 is smaller than the electrostatic repulsive force acting between the residual toner and the developing portion 46. Therefore, the residual toner in the exposed area of the image carrier 30 is held on the surface of the image carrier 30. The toner held in the exposure region of the image carrier 30 is directly used for image formation.
The transfer belt 50 conveys the recording medium P between the image carrier 30 and the transfer portion 48. The transfer belt 50 is an endless belt. The transfer belt 50 is provided to be rotatable in an arrow direction (clockwise direction).
The transfer section 48 transfers the toner image developed by the developing section 46 from the surface of the image carrier 30 to the recording medium P. When the toner image is transferred from the image carrier 30 to the recording medium P, the image carrier 30 comes into contact with the recording medium P. The transfer section 48 is, for example, a transfer roller.
The fixing section 52 heats and/or pressurizes the unfixed toner image transferred to the recording medium P by the transfer section 48. The fixing unit 52 is, for example, a heating roller and/or a pressure roller. The toner image is heated and/or pressurized, whereby the toner image is fixed to the recording medium P. As a result, an image is formed on the recording medium P.
The above description has been made of an example of the image forming apparatus according to the second embodiment, but the image forming apparatus according to the second embodiment is not limited to the image forming apparatus 100. For example, although the image forming apparatus 100 is a tandem type image forming apparatus, the present invention is not limited to the image forming apparatus according to the second embodiment, and a rotation type or the like may be adopted. The image forming apparatus according to the second embodiment may be a monochrome image forming apparatus. In this case, the image forming apparatus may include only 1 image forming unit, for example. The image forming apparatus according to the second embodiment may employ an intermediate transfer system. In the case where the image forming apparatus according to the second embodiment employs the intermediate transfer system, the intermediate transfer belt corresponds to the transfer target.
< third embodiment: treatment Cartridge >
A process cartridge according to a third embodiment includes the photosensitive member according to the first embodiment as an image carrier. Next, an example of a process cartridge according to a third embodiment will be described with reference to fig. 4.
The process cartridge according to the third embodiment corresponds to, for example, each of the image forming units 40a to 40d (fig. 4). These process cartridges contain portions that are unitized. The unitized portion includes an image carrier 30. The unit may include at least 1 selected from the group consisting of the charging unit 42, the exposure unit 44, the developing unit 46, and the transfer unit 48, in addition to the image carrier 30. The process cartridge may further include one or both of a cleaning unit (not shown) and a discharging unit (not shown). The process cartridge is designed to be detachable from the image forming apparatus 100, for example. In this case, the process cartridge is easy to handle, and when the sensitivity characteristics and the like of the image carrier 30 are deteriorated, the process cartridge including the image carrier 30 can be easily and quickly replaced.
The process cartridge according to the third embodiment described above includes the photoreceptor according to the first embodiment as an image carrier, and thus can suppress the occurrence of an image failure.
[ examples ] A method for producing a compound
The present invention will be described in more detail below with reference to examples. The present invention is not limited to the following embodiments.
< materials used in examples and comparative examples >
The following charge generating agent, hole transporting agent, electron transporting agent, and binder resin were prepared as materials for producing a single-layer type photoreceptor.
[ Charge generating agent ]
The charge generating agent (CGM-1) explained in the first embodiment was prepared. The charge generating agent (CGM-1) is a metal-free phthalocyanine represented by the formula (CGM-1), and the crystal structure thereof is X-type. That is, the charge generating agent (CGM-1) used is X-type metal-free phthalocyanine.
[ hole-transporting agent ]
The hole-transporting agents (HTM1-1), (HTM2-1), (HTM3-1), (HTM4-1), (HTM5-1), (HTM6-1) and (HTM7-1) described in the first embodiment were prepared. Further, hole-transporting agents (HTM8-1) and (HTM9-1) were prepared. The hole-transporting agents (HTM8-1) and (HTM9-1) are represented by the following chemical formulas (HTM8-1) and (HTM9-1), respectively.
[ CHEM 43 ]
[ Electron transporting agent ]
The electron transporting agent (ETM1-1) described in the first embodiment was prepared.
[ Binder resin ]
[ polyarylate resin ]
Polyarylate resins (R-1-M1) to (R-6-M1), (R-1-M10), (R-2-M10) and (R-2-M11) were synthesized as binder resins by the following methods, respectively.
(method for synthesizing polyarylate resin (R-2-M1))
First, a method for synthesizing a polyarylate resin (R-2-M1) having a main chain (R-2) represented by the following chemical formula (R-2) and a terminal group (M1) represented by the following chemical formula (M1) will be described.
[ CHEM 44 ]
--O-CF2-CF2-CF3 (M1)
A three-necked flask having a capacity of 1L and equipped with a thermometer, a three-way valve and a titration funnel was used as a reaction vessel. To a reaction vessel were added 12.2g (41.3 mmol) of 1, 1-bis (4-hydroxy-3-methylphenyl) cyclohexane, 0.2g (4.2 mmol) of heptafluoro-n-propyl alcohol as a terminal stopper, 3.9g (98 mmol) of sodium hydroxide, and 0.12g (0.38 mmol) of benzyltributylammonium chloride. Then, the inside of the reaction vessel was replaced with argon. Thereafter, a further 600mL of water was added to the reaction vessel. The internal temperature of the reaction vessel was maintained at 20 ℃, and the contents of the reaction vessel were stirred for 1 hour. Subsequently, the contents of the reaction vessel were cooled to lower the internal temperature of the reaction vessel to 10 ℃. Thereby preparing an alkaline aqueous solution.
On the other hand, 4.5g (16.2 mmol) of 4, 4 '-biphenylacetyl chloride (4, 4' -Biphenyldicarboxylic dichloride) and 4.1g (16.2 mmol) of 2, 6-naphthalenedicarboxylic acid dichloride (2, 6-Naphthalene dicarboxylic dichloride) were prepared as arylacid halides (arylhalide) and dissolved in 300g of chloroform to prepare a chloroform solution.
Next, while the temperature of the alkaline aqueous solution was kept at 10 ℃, the chloroform solution was added to the alkaline aqueous solution while stirring the contents of the reaction vessel, and the polymerization reaction was started. For the polymerization reaction, the contents of the reaction vessel were stirred to maintain the internal temperature of the reaction vessel at 13. + -. 3 ℃ and reacted for 3 hours. Then, the upper layer (aqueous layer) was removed with a decanter to obtain an organic layer.
Subsequently, 500mL of ion-exchanged water was added to a three-necked flask having a capacity of 2L, and the obtained organic layer was added thereto. Further, 300g of chloroform and 6mL of acetic acid were added. The contents of the three-necked flask were stirred at room temperature (25 ℃ C.) for 30 minutes. Then, the upper layer (aqueous layer) of the contents of the three-necked flask was removed by a decanter to obtain an organic layer. The obtained organic layer was repeatedly washed 8 times with 500mL of ion-exchanged water using a separatory funnel to obtain a washed organic layer.
Next, the organic layer after washing was filtered to obtain a filtrate. To a 3L Erlenmeyer flask was added 1.5L of methanol. The obtained filtrate was slowly added dropwise to the above Erlenmeyer flask to obtain a precipitate. The precipitate was filtered off by filtration. The resulting precipitate was dried under vacuum at a temperature of 70 ℃ for 12 hours. As a result, a polyarylate resin (R-2-M1) having a viscosity average molecular weight of 56,300 was obtained.
From the obtained polyarylate resin (R-2-M1)1H-NMR spectrum and13the polyarylate resin (R-2-M1) was confirmed to have a main chain (R-2) and a terminal group (M1) bonded to the end of the main chain (R-2) by C-NMR spectroscopy. In addition to this, the present invention is,1H-NMR spectrum and13C-NMR spectrum ofMeasured by a nuclear magnetic resonance spectrometer ("JNM-AL 300" manufactured by Nippon electronics Co., Ltd.). When measuring, the CDCl is added3As solvent Tetramethylsilane (TMS) was used as internal standard. In addition, measure1Resonance frequency at H-NMR spectrum of 300MHz, measurement13The resonance frequency in the C-NMR spectrum was 75 MHz.
(methods for synthesizing polyarylate resins (R-1-M1), (R-3-M1) to (R-6-M1), (R-1-M10), (R-2-M10) and (R-2-M11))
Polyarylate resins (R-1-M1), (R-3-M1) to (R-6-M1), (R-1-M10), (R-2-M10) and (R-2-M11) were produced by the same method as that for polyarylate resin (R-2-M1), except that the following modifications were made.
(location of change)
The aromatic acid halide used for the synthesis of the polyarylate resin (R-2-M1) was changed to the aromatic acid halide described in Table 2. The end terminator used for the synthesis of the polyarylate resin (R-2-M1) was changed to the end terminator described in Table 2. The total amount of aromatic acid halide in the synthesis of polyarylate resin (R-1-M1), (R-3-M1) to (R-6-M1), (R-1-M10), (R-2-M10) and (R-2-M11) was the same as the total amount of aromatic acid halide in the synthesis of polyarylate resin (R-2-M1). The amount of the end terminator substance in the synthesis of polyarylate resin (R-1-M1), (R-3-M1) to (R-6-M1), (R-1-M10), (R-2-M10) and (R-2-M11) was the same as the amount of the end terminator substance in the synthesis of polyarylate resin (R-2-M1). The viscosity average molecular weights of the polyarylate resins (R-1-M1), (R-3-M1) to (R-6-M1), (R-1-M10), (R-2-M10) and (R-2-M11) were 56,200, 55,100, 54,800, 54,200, 56,700, 54,800, 51,300 and 57,000, respectively.
From the obtained polyarylate resin (R-1-M1)1H-NMR spectrum and13the C-NMR spectrum showed that the polyarylate resin (R-1-M1) had a main chain (R-1) and a terminal group (M1) bonded to the end of the main chain (R-1). From the obtained polyarylate resin (R-3-M1)1H-NMR spectrum and13C-NMR spectrum confirmed thatThe polyarylate resin (R-3-M1) has a main chain (R-3) and a terminal group (M1) bonded to the end of the main chain (R-3). From the obtained polyarylate resin (R-4-M1)1H-NMR spectrum and13the polyarylate resin (R-4-M1) was confirmed to have a main chain (R-4) and a terminal group (M1) bonded to the end of the main chain (R-4) by C-NMR spectroscopy. From the obtained polyarylate resin (R-5-M1)1H-NMR spectrum and13the polyarylate resin (R-5-M1) was confirmed to have a main chain (R-5) and a terminal group (M1) bonded to the end of the main chain (R-5) by C-NMR spectroscopy. From the obtained polyarylate resin (R-6-M1)1H-NMR spectrum and13the C-NMR spectrum showed that the polyarylate resin (R-6-M1) had a main chain (R-6) and a terminal group (M1) bonded to the end of the main chain (R-6). And the number of the first and second electrodes,1H-NMR spectrum and13the measurement of the C-NMR spectrum was carried out by the same method as that for the measurement of the polyarylate resin (R-2-M1).
Further, from the obtained polyarylate resin (R-1-M10)1H-NMR spectrum and13the polyarylate resin (R-1-M10) was confirmed by C-NMR spectroscopy to have a main chain (R-1) and a terminal group (M10) (terminal group represented by the following chemical formula (M10)) bonded to the end of the main chain (R-1). From the obtained polyarylate resin (R-2-M10)1H-NMR spectrum and13the C-NMR spectrum showed that the polyarylate resin (R-2-M10) had a main chain (R-2) and a terminal group (M10) bonded to the end of the main chain (R-2). From the obtained polyarylate resin (R-2-M11)1H-NMR spectrum and13the polyarylate resin (R-2-M11) was confirmed by C-NMR spectroscopy to have a main chain (R-2) and a terminal group (M11) (a terminal group represented by the following chemical formula (M11)) bonded to the end of the main chain (R-2). And the number of the first and second electrodes,1H-NMR spectrum and13the measurement of the C-NMR spectrum was carried out by the same method as that for the measurement of the polyarylate resin (R-2-M1).
[ CHEM 45 ]
[ polycarbonate resin ]
Polycarbonate resins (R-10-M1) and (R-11-M1) were prepared as the other binder resins. The polycarbonate resin (R-10-M1) is a polycarbonate resin comprising a main chain having a repeating unit represented by the following chemical formula (R-10) and a terminal group (M1). The polycarbonate resin (R-11-M1) is a polycarbonate resin comprising a main chain having a repeating unit represented by the following chemical formula (R-11) and a terminal group (M1).
[ CHEM 46 ]
< production of photoreceptor >
[ photoreceptor (A-1) ]
The method for producing the photoreceptor (a-1) according to example 1 will be described below. 2 parts by mass of a charge generating agent (CGM-1), 65 parts by mass of a hole transporting agent (HTM1-1), 35 parts by mass of an electron transporting agent (ETM1-1), 100 parts by mass of a polyarylate resin (R-1-M1) as a binder resin, and 300 parts by mass of tetrahydrofuran as a solvent were charged into a container. The material in the container was mixed with the solvent for 2 minutes using a rod-shaped ultrasonic transducer to disperse the material in the solvent. The material in the container was mixed with the solvent for 50 hours by using a ball mill to disperse the material in the solvent. Thus, a coating liquid for photosensitive layer was obtained. This coating liquid for photosensitive layer was applied onto an aluminum drum support as a conductive substrate by a dip coating method. The coating liquid for the photosensitive layer thus coated was dried with hot air at 100 ℃ for 40 minutes. Thus, a photosensitive layer (film thickness: 25 μm) was formed on the conductive substrate. As a result, a photoreceptor (A-1) which was a single-layer type photoreceptor was obtained.
[ photoreceptors (A-2) to (A-22) and photoreceptors (B-1) to (B-9) ]
Photoreceptors (A-2) to (A-22) and photoreceptors (B-1) to (B-9) were obtained in the same manner as the photoreceptor (A-1) except that the binder resin and the hole-transporting agent shown in Table 3 were used. In Table 3, R-1-M1 to R-6-M1, R-1-M10, R-2-M10 and R-2-M11 in the column "binder resin" represent polyarylate resins (R-1-M1) to (R-6-M1), (R-1-M10), (R-2-M10) and (R-2-M11), respectively. R-10-M1 and R-11-M1 in the column of "adhesive resin" represent polycarbonate resins (R-10-M1) and (R-11-M1), respectively.
< measurement method and evaluation method >
[ measurement of scratch depth ]
The obtained photoreceptors (A-1) to (A-22) and photoreceptors (B-1) to (B-9) were measured for the scratch depth of the photosensitive layer, respectively. The scratch depth was measured by the following method using a scratching apparatus 200 (see fig. 5) prescribed in JIS K5600-5-5 (japanese industrial standard K5600: general paint test method, fifth: mechanical properties of the coating, fifth: scratch hardness (load pin method)).
The scoring apparatus 200 defined in JIS K5600-5-5 will be described below with reference to FIG. 5. Fig. 5 shows an example of the structure of the scoring device 200. The scoring device 200 includes: a fixed bed 201, a fixed tool 202, a scarification needle 203, a support arm 204, 2 shaft support parts 205, a base 206, 2 rail parts 207, a weight pan 208 and a constant speed motor (not shown). The weight 209 is carried on the weight tray 208.
In fig. 5, the X-axis direction and the Y-axis direction are horizontal directions, and the Z-axis direction is a vertical direction. The X-axis direction indicates the longitudinal direction of the fixed base 201. The Y-axis direction indicates a direction orthogonal to the X-axis direction in a plane parallel to the top surface 201a (mounting surface) of the fixed stage 201. The X-axis direction, Y-axis direction, and Z-axis direction in fig. 6 to 8 to be described later are also the same as those in fig. 5.
The mount 201 corresponds to a test plate mount in JIS K5600-5-5. The fixed base 201 includes: a top surface 201a, one end 201b, and the other end 201 c. The top surface 201a of the stationary stage 201 is a horizontal surface. One end 201b is opposed to the 2 shaft supporting portions 205.
The scoring needle 203 has a tip 203b (see fig. 6). The tip 203b is formed in a hemispherical shape having a diameter of 1 mm. The material of the top 203b is sapphire.
The support arm 204 supports the scribe needle 203. The support arm 204 rotates about the support shaft 204a in a direction in which the scratching needle 203 approaches the photoreceptor 1 and in a direction away from the photoreceptor 1.
The support arm 204 is supported by the 2 shaft support portions 205, and the support arm 204 is rotatable.
The submount 206 has a top surface 206 a. The 2 shaft support portions 205 are provided on one end side of the top surface 206 a.
The 2 rail portions 207 are provided on the other end side of the top surface 206 a. The 2 rail portions 207 are disposed to be parallel to and opposed to each other. The 2 rail portions 207 are provided parallel to the longitudinal direction (X-axis direction) of the fixed base 201. The fixed base 201 is installed between the 2 rail portions 207. The fixed base 201 is horizontally movable along the rail portion 207 in the longitudinal direction (X-axis direction) of the fixed base 201.
The fixed stage 201 is moved in the X-axis direction along the rail portion 207 by a constant speed motor.
The following describes a method for measuring the scratch depth. The method for measuring the scratch depth comprises a first step, a second step, a third step and a fourth step. The scratching device 200 was a surface texture measuring machine ("HEIDON TYPE 14" manufactured by new eastern science corporation). The scratch depth was measured in an environment at a temperature of 23 ℃ and a humidity of 50% RH. The photoreceptor 1 has a drum shape (cylindrical shape).
(first step)
In the first step, the photoreceptor 1 is fixed to the top surface 201a of the fixed stage 201 so that the longitudinal direction thereof is parallel to the longitudinal direction of the fixed stage 201. At this time, the photoreceptor 1 is mounted as the central axis L of the photoreceptor 12The (rotation axis) direction is parallel to the longitudinal direction of the fixed base 201.
(second step)
In the second step, the scratching pin 203 is brought into vertical contact with the surface 3a of the photosensitive layer 3. Referring to fig. 6 and 7 in addition to fig. 5, a method of bringing the scratching pin 203 into vertical contact with the surface 3a of the photosensitive layer 3 of the drum-shaped photoreceptor 1 will be described.
Fig. 6 is a sectional view taken along line IV-IV of fig. 5, and is a sectional view when the scratching needle 203 abuts on the photoreceptor 1. Fig. 7 is a side view of the fixing table 201, the scribing needle 203, and the photoreceptor 1 shown in fig. 5.
With the central axis A of the scoring needle 2031The scratching needle 203 is brought close to the photoreceptor 1 so that the extended line of (A) is perpendicular to the top surface 201a of the fixed base 201. Next, the tip 203b of the scratching pin 203 is brought into contact with a point (contact point P) farthest from the top surface 201a of the fixed base 201 in the vertical direction (Z-axis direction) in the surface 3a of the photosensitive layer 3 of the photoreceptor 12). Thereby, the scribing needle 203 has its center axis A1Perpendicular to tangent line A2In the embodiment (1), the tip 203b of the scribing needle 203 abuts on the photoreceptor 1. At this time, the contact P connected to the top surface 201a1Point of contact P with tip 203b2Line segment of (a) and the central axis L of the photoreceptor 12Are orthogonal. In addition, tangent line A2Is perpendicular to the central axis L2Contact point P of the outer circumference circle formed by the cross section of the photoreceptor 12Tangent to (d).
(third step)
Next, the third step will be described with reference to fig. 5 and 6. In the third step, the scratching pin 203 applies a load W of 10g to the photosensitive layer 3 in a state where the scratching pin 203 is vertically abutted against the surface 3a of the photosensitive layer 3. Specifically, a 10g weight 209 is placed on the weight tray 208. The fixing table 201 is moved in this state. Specifically, the constant velocity motor is driven to move the fixed stage 201 horizontally in the X-axis direction along the rail portion 207. That is, the one end 201b of the stationary stage 201 is moved from the first position N1Move to a second position N2. And, the second position N2Is located at a first position N1On the downstream side of the flow path. The downstream side is a side of the fixing table 201 in a direction in which the fixing table 201 is separated from the 2 shaft support portions 205 in the longitudinal direction of the fixing table 201. As the fixed stage 201 moves in the longitudinal direction, the photoreceptor 1 also moves horizontally in the longitudinal direction of the fixed stage 201. The moving speed of the fixed stage 201 and the photoreceptor 1 was 30 mm/min. The moving distance between the fixed stage 201 and the photoreceptor 1 was 30 mm. The moving distance between the fixed stage 201 and the photoreceptor 1 corresponds to the first position N1And a second position N2A distance D between1-2. After the fixing base 201 and the photoreceptor 1 move, the scratching pin 203 forms scratches on the surface 3a of the photosensitive layer 3 of the photoreceptor 1Trace S.
Next, the scratches S will be described with reference to fig. 8 in addition to fig. 5 to 7. Fig. 8 shows the scratches S formed on the surface 3a of the photosensitive layer 3. The scratches S are formed to be in contact with the top surface 201a and the tangent line A of the fixing stage 201, respectively2And is vertical. Further, the scratches S are formed through the line L shown in fig. 73. Line L3Is composed of multiple contact points P2The resulting wire. Line L3Respectively connected with the top surface 201a of the fixed table 201 and the central axis L of the photoreceptor 12Parallel. Line L3Perpendicular to the central axis A of the scribing needle 2031。
(fourth step)
In the fourth step, the maximum value of the depth Ds of the scratch S, i.e., the scratch depth, is measured. Specifically, the photoreceptor 1 is detached from the fixed stage 201. The scratch S formed on the photosensitive layer 3 of the photoreceptor 1 was observed at a magnification of 5 times with a three-dimensional interference microscope (sold by Bruker "WYKO NT-1100"), and the depth Ds of the scratch S was measured. The depth Ds of the scratch S is from the tangent line A2Distance to the valley of the scratch S. The maximum value among the depths Ds of the scratches S is taken as the scratch depth. The measured scratch depths are shown in table 3.
[ measurement of Vickers hardness ]
The Vickers hardness of the photosensitive layer was measured for each of the photoreceptors (A-1) to (A-22) and the photoreceptors (B-1) to (B-9). The vickers hardness of the photosensitive layer is measured by a method in accordance with Japanese Industrial Standards (JIS) Z2244. Vickers hardness is measured using a hardness meter (for example, Matsuzawa co., Ltd manufactures "micro vickers DMH-1 type"). The vickers hardness was measured under the conditions that the temperature was 23 ℃, the load (test force) of the diamond indenter was 10gf, the time required to reach the test force was 5 seconds, the approach speed of the diamond indenter was 2 mm/second, and the retention time of the test force was 1 second. The measured vickers hardness is shown in table 3.
[ evaluation of fog resistance ]
The fogging resistance of the formed images was evaluated for each of the obtained photoreceptors (A-1) to (A-22) and photoreceptors (B-1) to (B-9). An image forming apparatus (a changer of "monochrome printer FS-1300D" manufactured by Kyowa office information systems Co., Ltd.) was used as the evaluation equipment. The image forming apparatus employs a direct transfer method, a contact development method, and a cleanerless method. In this image forming apparatus, the developing section cleans toner remaining on the photoreceptor. Further, the charging section of the image forming apparatus is a charging roller. As the paper, paper "Beijing porcelain office information system brand paper VM-A4" (size: A4) sold by Beijing porcelain office information system corporation was used. Evaluation of evaluation equipment a one-component developer (test production sample) was used.
With the evaluation apparatus, the rotation speed of the photoreceptor was set to 168 mm/sec, and the image I was continuously printed on 12,000 sheets of paper under a charged potential + 600V. Image I is an image with 1% print coverage. Next, a blank image was printed on 1 sheet of paper. The printing was carried out at a temperature of 32.5 ℃ and a humidity of 80% RH. With respect to the obtained white paper image, the image density at 3 points in the white paper image was measured with a reflection densitometer ("RD 914" manufactured by X-rite). The sum of the image densities at 3 of the white paper image is divided by the number of measurement positions. Thereby, an arithmetic average of the image density of the white paper image is obtained. The fog density is determined as a value obtained by subtracting the image density of the reference sheet from the arithmetic average of the image densities of the white sheet images. The measured fog density was judged according to the following criteria. The photoreceptor judged as A or B was evaluated to have good fog resistance. The photoreceptor determined as C was evaluated to have poor fog resistance. The fog density (FD value) and the results of the determination are shown in table 3.
(criterion for fog resistance)
And (3) judging A: the fog density is less than 0.010.
And B, judgment: the density of the fog is more than 0.010 and less than 0.020.
And C, judgment: the density of the fog is more than 0.020.
[ TABLE 3 ]
As shown in table 3, the photoreceptors (a-1) to (a-22) contain one of polyarylate resins (R-1-M1) to (R-6-M1), and the polyarylate resins (R-1-M1) to (R-6-M1) have: a main chain comprising a repeating unit represented by general formula (1), and a terminal group represented by general formula (2). The photoreceptors (a-1) to (a-22) contain one of the hole transport agents (HTM1-1) to (HTM7-1), and the hole transport agents (HTM1-1) to (HTM7-1) are contained in the general formula (HTM1), the general formula (HTM2), the general formula (HTM3), the general formula (HTM4), the general formula (HTM5), the general formula (HTM6), or the general formula (HTM 7). In the photoreceptors (A-1) to (A-22), the depth of the scratch on the photosensitive layer is 0.16 μm or more and 0.50 μm or less. In the photoreceptors (A-1) to (A-22), the Vickers hardness of the photosensitive layer is 19.0HV or more and 24.5HV or less. The results of determination of fog resistance in the photoreceptors (A-1) to (A-22) were A (good).
As shown in Table 3, the photoreceptors (B-1) and (B-2) did not contain a polyarylate resin. The photoreceptors (B-3), (B-4), and (B-9) each contain one of polyarylate resins (R-1-M10), (R-2-M10), and (R-2-M11), and the polyarylate resins (R-1-M10), (R-2-M10), and (R-2-M11) have a terminal group not included in the general formula (2). The photoreceptors (B-5) to (B-8) each contain one of the hole transport agents (HTM8-1) and (HTM9-1), and the hole transport agents (HTM8-1) and (HTM9-1) are not contained in the general formula (HTM1), the general formula (HTM2), the general formula (HTM3), the general formula (HTM4), the general formula (HTM5), the general formula (HTM6), and the general formula (HTM 7). In the photoreceptors (B-1) to (B-9), the depth of the scratch of the photosensitive layer exceeded 0.50. mu.m. In the photoreceptors (B-1) and (B-2), the Vickers hardness of the photosensitive layer is less than 18.0 HV. The results of the determination of fog resistance in the photoreceptors (B-1) to (B-9) were C (poor).
As is clear from Table 3, the photoreceptors (A-1) to (A-22) are superior in fog resistance to the photoreceptors (B-1) to (B-9).
Claims (3)
1. An electrophotographic photoreceptor comprising a conductive substrate and a photosensitive layer,
the photosensitive layer is a single layer and comprises a charge generator, a hole transport agent, an electron transport agent and a binding resin,
the binding resin comprises a polyarylate resin,
the polyarylate resin having a main chain and a terminal group represented by the following chemical formula (M1) bonded to a terminal of the main chain,
the hole-transporting agent and the binder resin in the photosensitive layer are in the following combination:
a combination of the hole transport agent comprising a compound represented by the following chemical formula (HTM1-1), chemical formula (HTM2-1), or chemical formula (HTM6-1) and the binder resin comprising the polyarylate resin having the main chain represented by the following chemical formula (R-1), chemical formula (R-2), chemical formula (R-3), chemical formula (R-5), or chemical formula (R-6), or a combination of the hole transport agent comprising a compound represented by the following chemical formula (HTM1-1), chemical formula (HTM2-1), chemical formula (HTM3-1), chemical formula (HTM4-1), chemical formula (HTM5-1), chemical formula (HTM6-1), or chemical formula (HTM7-1) and the binder resin comprising the polyarylate resin having the main chain represented by the following chemical formula (R-4),
the depth of scratch resistance of the photosensitive layer is less than 0.50 mu m,
the Vickers hardness of the photosensitive layer is 18.0HV or more,
2. a kind of processing box is disclosed, which comprises a box body,
the electrophotographic photoreceptor according to claim 1.
3. An image forming apparatus includes:
an image bearing body;
a charging unit for charging a surface of the image carrier;
an exposure section that exposes the surface of the charged image carrier to form an electrostatic latent image on the surface of the image carrier;
a developing section that develops the electrostatic latent image into a toner image; and
a transfer section for transferring the toner image from the image bearing member to a transfer object,
the image forming apparatus is characterized in that,
the image bearing member is the electrophotographic photoreceptor according to claim 1,
the charging polarity of the charging portion is positive,
the transfer section transfers the toner image from the image bearing member to the transfer target while the surface of the image bearing member is in contact with the transfer target.
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| JP2017078839A JP6677211B2 (en) | 2017-04-12 | 2017-04-12 | Electrophotographic photosensitive member, process cartridge, and image forming apparatus |
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| JP7415330B2 (en) * | 2019-04-23 | 2024-01-17 | 京セラドキュメントソリューションズ株式会社 | Electrophotographic photoreceptors, process cartridges, and image forming devices |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01118142A (en) * | 1987-10-30 | 1989-05-10 | Mita Ind Co Ltd | Electrophotographic sensitive body |
| CN1808288A (en) * | 2005-01-18 | 2006-07-26 | 京瓷美达株式会社 | Single layer type electrophotographic photoconductor and image forming device |
| CN104597730A (en) * | 2013-10-30 | 2015-05-06 | 京瓷办公信息系统株式会社 | Multi-layer electrophotographic photosensitive member |
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| JP3155843B2 (en) * | 1992-03-03 | 2001-04-16 | 出光興産株式会社 | Polycarbonate polymer, method for producing the same, and electrophotographic photoreceptor using the same |
| JPH0959364A (en) * | 1995-08-23 | 1997-03-04 | Unitika Ltd | Polyarylate and electron photographic photosensitive body using the same |
| JPH0962017A (en) * | 1995-08-29 | 1997-03-07 | Canon Inc | Electrophotographic photoreceptor, process cartridge and electrophotographic device |
| CN107428922B (en) * | 2015-03-23 | 2021-06-01 | 三菱化学株式会社 | Electrophotographic photoreceptor and image forming apparatus |
| CN108885415B (en) * | 2016-03-29 | 2021-11-09 | 三菱化学株式会社 | Electrophotographic photoreceptor, electrophotographic photoreceptor cartridge, image forming apparatus, and dispersant for fluorine-based resin |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01118142A (en) * | 1987-10-30 | 1989-05-10 | Mita Ind Co Ltd | Electrophotographic sensitive body |
| CN1808288A (en) * | 2005-01-18 | 2006-07-26 | 京瓷美达株式会社 | Single layer type electrophotographic photoconductor and image forming device |
| CN104597730A (en) * | 2013-10-30 | 2015-05-06 | 京瓷办公信息系统株式会社 | Multi-layer electrophotographic photosensitive member |
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