JPH0237357A - Electrophotographic sensitive body - Google Patents
Electrophotographic sensitive bodyInfo
- Publication number
- JPH0237357A JPH0237357A JP63187313A JP18731388A JPH0237357A JP H0237357 A JPH0237357 A JP H0237357A JP 63187313 A JP63187313 A JP 63187313A JP 18731388 A JP18731388 A JP 18731388A JP H0237357 A JPH0237357 A JP H0237357A
- Authority
- JP
- Japan
- Prior art keywords
- phenylenediamine
- charge
- electrophotographic photoreceptor
- charge transport
- photosensitive layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000758 substrate Substances 0.000 claims abstract description 17
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 14
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 12
- 150000004988 m-phenylenediamines Chemical class 0.000 claims abstract description 7
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 58
- 108091008695 photoreceptors Proteins 0.000 claims description 55
- 239000000463 material Substances 0.000 claims description 50
- 239000010410 layer Substances 0.000 claims description 48
- 229920005989 resin Polymers 0.000 claims description 31
- 239000011347 resin Substances 0.000 claims description 31
- -1 m-phenylenediamine compound Chemical class 0.000 claims description 16
- 239000011230 binding agent Substances 0.000 claims description 14
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 10
- 125000001424 substituent group Chemical group 0.000 claims description 10
- 125000005843 halogen group Chemical group 0.000 claims description 8
- 239000002356 single layer Substances 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 3
- 230000035945 sensitivity Effects 0.000 abstract description 10
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical group NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 abstract description 6
- 238000002425 crystallisation Methods 0.000 abstract description 6
- 230000008025 crystallization Effects 0.000 abstract description 6
- 150000001875 compounds Chemical class 0.000 description 39
- 230000032258 transport Effects 0.000 description 33
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 12
- 239000000049 pigment Substances 0.000 description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 230000005684 electric field Effects 0.000 description 6
- 230000003993 interaction Effects 0.000 description 6
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 6
- 230000007423 decrease Effects 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- SLUNEGLMXGHOLY-UHFFFAOYSA-N benzene;hexane Chemical compound CCCCCC.C1=CC=CC=C1 SLUNEGLMXGHOLY-UHFFFAOYSA-N 0.000 description 4
- 238000004440 column chromatography Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- RINOYHWVBUKAQE-UHFFFAOYSA-N 1-iodo-2-methylbenzene Chemical compound CC1=CC=CC=C1I RINOYHWVBUKAQE-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- YCOXTKKNXUZSKD-UHFFFAOYSA-N as-o-xylenol Natural products CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 description 3
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 3
- JJYPMNFTHPTTDI-UHFFFAOYSA-N 3-methylaniline Chemical compound CC1=CC=CC(N)=C1 JJYPMNFTHPTTDI-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 150000004866 oxadiazoles Chemical class 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- DNXIASIHZYFFRO-UHFFFAOYSA-N pyrazoline Chemical class C1CN=NC1 DNXIASIHZYFFRO-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- QIUGUNHEXAZYIY-UHFFFAOYSA-N 1,2-dinitroacridine Chemical compound C1=CC=CC2=CC3=C([N+]([O-])=O)C([N+](=O)[O-])=CC=C3N=C21 QIUGUNHEXAZYIY-UHFFFAOYSA-N 0.000 description 1
- NMNSBFYYVHREEE-UHFFFAOYSA-N 1,2-dinitroanthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=C([N+]([O-])=O)C([N+](=O)[O-])=CC=C3C(=O)C2=C1 NMNSBFYYVHREEE-UHFFFAOYSA-N 0.000 description 1
- FKASFBLJDCHBNZ-UHFFFAOYSA-N 1,3,4-oxadiazole Chemical compound C1=NN=CO1 FKASFBLJDCHBNZ-UHFFFAOYSA-N 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- WDCYWAQPCXBPJA-UHFFFAOYSA-N 1,3-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC([N+]([O-])=O)=C1 WDCYWAQPCXBPJA-UHFFFAOYSA-N 0.000 description 1
- DTDSBSFGGRILAS-UHFFFAOYSA-N 1-n,1-n,3-n,3-n-tetrakis(4-methylphenyl)benzene-1,3-diamine Chemical compound C1=CC(C)=CC=C1N(C=1C=C(C=CC=1)N(C=1C=CC(C)=CC=1)C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 DTDSBSFGGRILAS-UHFFFAOYSA-N 0.000 description 1
- YCANAXVBJKNANM-UHFFFAOYSA-N 1-nitroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2[N+](=O)[O-] YCANAXVBJKNANM-UHFFFAOYSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- GEKJEMDSKURVLI-UHFFFAOYSA-N 3,4-dibromofuran-2,5-dione Chemical compound BrC1=C(Br)C(=O)OC1=O GEKJEMDSKURVLI-UHFFFAOYSA-N 0.000 description 1
- LWALQZXAZDVFDT-UHFFFAOYSA-N 3-n-benzo[a]anthracen-1-ylbenzene-1,3-diamine Chemical compound NC1=CC=CC(NC=2C3=C4C=C5C=CC=CC5=CC4=CC=C3C=CC=2)=C1 LWALQZXAZDVFDT-UHFFFAOYSA-N 0.000 description 1
- CLQYLLIGYDFCGY-UHFFFAOYSA-N 4-(2-anthracen-9-ylethenyl)-n,n-diethylaniline Chemical compound C1=CC(N(CC)CC)=CC=C1C=CC1=C(C=CC=C2)C2=CC2=CC=CC=C12 CLQYLLIGYDFCGY-UHFFFAOYSA-N 0.000 description 1
- QJBPBQKYCDQIQV-UHFFFAOYSA-N 4-n-benzo[a]anthracen-1-ylbenzene-1,4-diamine Chemical compound C1=CC(N)=CC=C1NC1=CC=CC2=CC=C(C=C3C(C=CC=C3)=C3)C3=C12 QJBPBQKYCDQIQV-UHFFFAOYSA-N 0.000 description 1
- XYPMAZCBFKBIFK-UHFFFAOYSA-N 9,10-dinitroanthracene Chemical compound C1=CC=C2C([N+](=O)[O-])=C(C=CC=C3)C3=C([N+]([O-])=O)C2=C1 XYPMAZCBFKBIFK-UHFFFAOYSA-N 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- 239000004709 Chlorinated polyethylene Substances 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 235000000177 Indigofera tinctoria Nutrition 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 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
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-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
- 241000143950 Vanessa Species 0.000 description 1
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 description 1
- JAWMENYCRQKKJY-UHFFFAOYSA-N [3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-ylmethyl)-1-oxa-2,8-diazaspiro[4.5]dec-2-en-8-yl]-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]methanone Chemical group N1N=NC=2CN(CCC=21)CC1=NOC2(C1)CCN(CC2)C(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F JAWMENYCRQKKJY-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000004054 acenaphthylenyl group Chemical group C1(=CC2=CC=CC3=CC=CC1=C23)* 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- HXGDTGSAIMULJN-UHFFFAOYSA-N acetnaphthylene Natural products C1=CC(C=C2)=C3C2=CC=CC3=C1 HXGDTGSAIMULJN-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 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
- CECABOMBVQNBEC-UHFFFAOYSA-K aluminium iodide Chemical compound I[Al](I)I CECABOMBVQNBEC-UHFFFAOYSA-K 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
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000004888 barrier function Effects 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
- 239000010951 brass Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 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
- 125000000609 carbazolyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000013461 design Methods 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
- 238000004821 distillation Methods 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
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical class OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 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
- 125000003707 hexyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 230000005525 hole transport Effects 0.000 description 1
- 150000007857 hydrazones Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 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
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 150000002475 indoles Chemical class 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002545 isoxazoles Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000203 mixture Substances 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
- YKZHNHRLNBPFBZ-UHFFFAOYSA-N n-[4-(4-aminophenyl)phenyl]benzo[a]anthracen-1-amine Chemical compound C1=CC(N)=CC=C1C(C=C1)=CC=C1NC1=CC=CC2=CC=C(C=C3C(C=CC=C3)=C3)C3=C12 YKZHNHRLNBPFBZ-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002916 oxazoles Chemical class 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 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
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 150000003217 pyrazoles Chemical class 0.000 description 1
- 150000003219 pyrazolines Chemical class 0.000 description 1
- WVIICGIFSIBFOG-UHFFFAOYSA-N pyrylium Chemical class C1=CC=[O+]C=C1 WVIICGIFSIBFOG-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 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
- 239000007787 solid Substances 0.000 description 1
- 238000001256 steam distillation Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 229920001909 styrene-acrylic polymer Polymers 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012360 testing 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
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 150000004867 thiadiazoles Chemical class 0.000 description 1
- 150000003557 thiazoles 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
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 150000004992 toluidines Chemical class 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 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
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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
- G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
- G03G5/0601—Acyclic or carbocyclic compounds
- G03G5/0618—Acyclic or carbocyclic compounds containing oxygen and nitrogen
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
- G03G5/02—Charge-receiving layers
- G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
- G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
- G03G5/0601—Acyclic or carbocyclic compounds
- G03G5/0612—Acyclic or carbocyclic compounds containing nitrogen
- G03G5/0614—Amines
- G03G5/06142—Amines arylamine
- G03G5/06144—Amines arylamine diamine
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Photoreceptors In Electrophotography (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、電子写真感光体における電荷輸送材料として
好適なｍ−フェニレンジアミン系化合物事＊φｉｌを用
いた電子写真感光体に関する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to an electrophotographic photoreceptor using an m-phenylenediamine compound *φil suitable as a charge transport material in an electrophotographic photoreceptor.
（従来技術）
近年、複写機などの画像形成装置における電子写真感光
体として、加工性がよく製造コスト面で有利であると共
に、機能設計の自由度が大きな有機感光体が使用されて
いる。中でも光照射により電荷を発生する電荷発生材料
と、発生した電荷を輸送する電荷輸送材料とを含有する
感光層、例えば、電荷発生材料と電荷輸送材料と結着樹
脂とを含有する単層型感光層や、上記電荷発生材料を含
有する電荷発生層と、電荷輸送材料を含有する電荷輸送
層とが積層された積層型感光層を備えた機能分離型電子
写真感光体が提案されている。(Prior Art) In recent years, organic photoreceptors have been used as electrophotographic photoreceptors in image forming apparatuses such as copying machines because they are easy to process and are advantageous in terms of manufacturing cost, and also have a large degree of freedom in functional design. Among them, a photosensitive layer containing a charge-generating material that generates charges upon light irradiation and a charge-transporting material that transports the generated charges, for example, a single-layer photosensitive layer containing a charge-generating material, a charge-transporting material, and a binder resin. A functionally separated electrophotographic photoreceptor has been proposed, which includes a stacked photosensitive layer in which a charge generation layer containing the charge generation material described above and a charge transport layer containing a charge transport material are stacked.
また、電子写真感光体を用いて複写画像を形成する場合
、カールソンプロセスが広く利用されている。このカー
ルソンプロセスは、コロナ放電により感光体を均一に帯
電させる帯電工程と、帯電した感光体に原稿像を露光し
、原稿像に対応した静電潜像を形成する露光工程と、静
電潜像をトナーを含有する現像剤で現像し、トナー像を
形成する現像工程と、トナー像を紙などの基材に転写す
る転写工程と、基材に転写されたトナー像を定着させる
定着工程と、転写工程の後、感光体上に残留するトナー
を除去するクリーニング工程とを基本工程として含んで
おり、上記カールソンプロセスにおいて高品質の画像を
形成するには、電子写真感光体が、帯電特性および感光
特性に優れるとともに露光後の残留電位が低いことが要
求される。Further, when forming a copy image using an electrophotographic photoreceptor, the Carlson process is widely used. The Carlson process consists of a charging process in which a photoreceptor is uniformly charged by corona discharge, an exposure process in which an original image is exposed to the charged photoreceptor to form an electrostatic latent image corresponding to the original image, and an electrostatic latent image a developing step of developing with a developer containing toner to form a toner image, a transfer step of transferring the toner image to a base material such as paper, and a fixing step of fixing the toner image transferred to the base material. After the transfer process, the basic process includes a cleaning process to remove toner remaining on the photoreceptor.In order to form a high-quality image in the above-mentioned Carlson process, the electrophotographic photoreceptor must have sufficient charging characteristics and photosensitive characteristics. It is required to have excellent characteristics and a low residual potential after exposure.
一方、上記機能分離型電子写真においては、電荷発生材
料および電荷輸送材料の特性が感光体の電気特性、感光
特性に大きく影響するため従来から種々の物質が研究さ
れ、上記電荷輸送材料としては、ポリビニルカルバゾー
ル、オキサジアゾール系化合物、ピラゾリン系化合物、
ヒドラゾン系化合物環条（の物質が提案されている。On the other hand, in the function-separated electrophotography, the characteristics of the charge-generating material and the charge-transporting material greatly affect the electrical and photosensitive characteristics of the photoreceptor, so various substances have been studied, and the charge-transporting materials include: polyvinylcarbazole, oxadiazole compounds, pyrazoline compounds,
Hydrazone-based compounds have been proposed.
（発明が解決しようとする問題点）
しかしながら、上記電荷輸送材料は、電荷輸送能を示す
ドリフト移動度が比較的小さい。また、ドリフト移動度
の電界強度依存性が大きいために、低電界での電荷の移
動が小さく、残留電位がぬけにくくなる。さらに、紫外
線等の照射により劣化し易い等の問題がある。(Problems to be Solved by the Invention) However, the charge transport material described above has a relatively low drift mobility indicating charge transport ability. Furthermore, since the dependence of drift mobility on electric field strength is large, charge movement is small in a low electric field, making it difficult for residual potential to escape. Furthermore, there is a problem that it is easily deteriorated by irradiation with ultraviolet rays or the like.
機能分離型感光体では、電荷輸送材料への電荷発生材料
から生成したキャリアの注入効率およびキャリアの移動
度が感光体の感度に大きく影響することが知られている
。現在、電荷輸送材料としては正札輸送性化合物および
電子輸送性化合物の二種類があるものの、電子輸送性化
合物は毒性等の不具合を持つため実用化されている電荷
輸送材料のほとんどは正孔輸送性化合物である。In a functionally separated photoreceptor, it is known that the efficiency of injection of carriers generated from a charge generation material into a charge transport material and the mobility of carriers greatly affect the sensitivity of the photoreceptor. Currently, there are two types of charge transport materials: regular transport compounds and electron transport compounds, but since electron transport compounds have problems such as toxicity, most of the charge transport materials in practical use have hole transport properties. It is a compound.
正孔注入の場合では、電荷輸送材料のイオン化ポテンシ
ャルの小さい程キャリアの注入効率が太き（なり高感度
化される。また非晶質であるを機感光体の移動度は、結
晶状態に比べて著しく小さい。また移動度は電界や温度
に依存しているため、移動度が小さいと低電場や低温で
の感度特性の低下となって現れる。従って、移動度が大
きい電荷輸送材料が望まれている。In the case of hole injection, the smaller the ionization potential of the charge transport material, the higher the carrier injection efficiency (and the higher the sensitivity. Also, the mobility of the amorphous photoreceptor is lower than that of the crystalline state). Furthermore, since mobility is dependent on electric field and temperature, low mobility results in a decrease in sensitivity characteristics in low electric fields and at low temperatures.Therefore, charge transport materials with high mobility are desired. ing.
一方、トリフェニルアミン系の電荷輸送材料はドリフト
移動度の電界依存性が小さいことが知られている。例え
ばＵＳＰ３２６５４９６号公報には、Ｎ、 Ｎ、 Ｎ′
、 Ｎ・−テトラフェニルベンジジン、Ｎ、 Ｎ、 Ｎ
＝、 Ｎ−−テトラフェニル−１，４−フェニレンジア
ミン、Ｎ、 Ｎ、 Ｎ′、 Ｎ＝−テトラフェニル
−１，３−フェニレンジアミン等が提案されているが、
これらの電荷輸送材料は分子の対称性がよいために分子
間の相互作用が大きく、樹脂との相互作用が小さくなっ
ているため樹脂中で結晶化し易くなる等の問題点があり
実用に供し得ない。On the other hand, it is known that triphenylamine-based charge transport materials have small dependence of drift mobility on electric field. For example, in USP 3265496, N, N, N'
, N-tetraphenylbenzidine, N, N, N
=, N--tetraphenyl-1,4-phenylenediamine, N, N, N', N=-tetraphenyl-1,3-phenylenediamine, etc. have been proposed.
These charge transport materials have good molecular symmetry, which causes large interactions between molecules, and small interactions with the resin, which causes problems such as easy crystallization in the resin, making them difficult to put into practical use. do not have.
この様な問題点に鑑み、移動度の電界依存性が小さく、
樹脂との相溶性のよいＮ、Ｎ、Ｎ＝、Ｎ’−テトラフェ
ニル−１，３−フェニレンジアミンのそれぞれのフェニ
ル基に対して置換し得る限り何個置換してもよいｍ−フ
ェニレンジアミン系化合物を先に提案した。In view of these problems, the electric field dependence of mobility is small,
N, N, N=, N'-tetraphenyl-1,3-phenylenediamine, which has good compatibility with the resin, may be substituted with any number of phenyl groups as long as it can be substituted. The compound was proposed earlier.
従来知られているＮ、Ｎ、Ｎ″、Ｎ′、−テトラフェニ
ル−１，３−フェニレンジアミンは、分子の対称性がよ
いために結晶化してしまい樹脂との相溶性が悪い。逆に
、Ｎ、Ｎ、Ｎ・、Ｎ・、−テトラフェニル−１，３−フ
ェニレンジアミンのそれぞれのフェニル基に置換した基
の数が増加すると、分子間の相互作用が小さくなり、樹
脂との相互作用が大きくなって樹脂中で結晶化が起きに
くい。Conventionally known N,N,N″,N′,-tetraphenyl-1,3-phenylenediamine crystallizes due to its good molecular symmetry and has poor compatibility with resins.On the contrary, As the number of groups substituted on each phenyl group of N,N,N・,N・,-tetraphenyl-1,3-phenylenediamine increases, the interaction between molecules becomes smaller and the interaction with the resin decreases. It becomes larger and is less likely to crystallize in the resin.
しかし、分子自身が大きな状態となるため分子間距離が
大きくなり、ホール状態の受は渡しが悪くなりキャリア
輸送能が低下してしまう。However, since the molecules themselves are in a large state, the intermolecular distance becomes large, making it difficult to pass the hole state, resulting in a decrease in carrier transport ability.
−船釣に電子写真感光体の特性は、目的や作成方法によ
る違いはあるものの、主に用いられる光導電性材料の影
響が大である。そこで本発明者らがさらに鋭意研究した
結果、先に提案したｍ−フェニレンジアミン系化合物を
電子写真感光体に用いた場合には、用いたｍ−フェニレ
ンジアミン系化合物のフェニル基に関する置換基の位置
によって電子写真感光体の特性に違いが生じることを見
出した。すなわち、Ｎ、 Ｎ、 Ｎ・、Ｎ″−テトラフ
ェニル−１，３−フェニレンジアミン化合物のそれぞれ
のフェニル基に、窒素原子に対してパラ位に置換基を導
入した化合物はイオン化ポテンシャルが小さく、移動度
は大きい。また、メタ位に置換基を導入した化合物は分
子の対称性が悪いため分子間の相互作用が小さく、逆に
樹脂との相互作用が大きくなっているため樹脂中で極め
て結晶化しにくい特徴をもつことを見い出した。- Although the characteristics of electrophotographic photoreceptors for boat fishing differ depending on the purpose and manufacturing method, they are largely influenced by the photoconductive material used. As a result of further intensive research by the present inventors, we found that when the previously proposed m-phenylenediamine compound is used in an electrophotographic photoreceptor, the position of the substituent with respect to the phenyl group of the m-phenylenediamine compound used is We have found that there are differences in the characteristics of electrophotographic photoreceptors depending on the characteristics of the electrophotographic photoreceptor. In other words, a compound in which a substituent is introduced into each phenyl group of the N, N, N・, N''-tetraphenyl-1,3-phenylenediamine compound at the para position relative to the nitrogen atom has a small ionization potential and is highly mobile. In addition, compounds with substituents introduced at the meta position have poor molecular symmetry, so the interaction between molecules is small, and conversely, the interaction with the resin is large, so they crystallize extremely in the resin. I discovered that it has some difficult characteristics.
従って、本発明の目的は感光層中にｍ−フェニレンジア
ミン系化合物のフェニル基に関する置換基の位置がパラ
位である化合物とメタ位である化合物の両方を含有する
ことによって、感光層が結晶化することなく高感度化さ
れたバラ置換およびメタ方墳化合物双方の特徴を反映し
た電子写真感光体を提供することにある。Therefore, the object of the present invention is to crystallize the photosensitive layer by including in the photosensitive layer both a compound in which the substituent position with respect to the phenyl group of the m-phenylenediamine compound is in the para position and a compound in which the substituent is in the meta position. It is an object of the present invention to provide an electrophotographic photoreceptor that reflects the characteristics of both rose-substituted and meta-substituted compounds that have increased sensitivity without causing any damage.
（問題点を解決するための手段および作用）本発明者ら
は、下記−船底（１）
％式％
（式中、Ｒ１、Ｒ２，Ｒ３，Ｒ４は窒素原子に対してパ
ラ位に置換した基でありアルキル基、アルコキシル基、
ハロゲン原子を示し、すべての置換基は同一でも、それ
ぞれ互いに異なっていてもよく、Ｒは水素原子、アルキ
ル基、アルコキシル基、ハロゲン原子を示す）で表され
るｍ−フェニレンジアミン系化合物
および下記−船底（Ｈ）
＼
Ｒ’ ＲＲ５
（式中、Ｒ５，Ｒ６、Ｒ７，Ｒ’は窒素原子に対してメ
タ位に置換した基でありアルキル基、アルコキシル基、
ハロゲン原子を示し、すべての置換基は同一でも、それ
ぞれ互いに異なっていてもよく、Ｒは水素原子、アルキ
ル基、アルコキシル基、ハロゲン原子を示す）で表され
るｍ−フェニレンジアミン系化合物を含有する感光層を
設けたことを特徴とする電子写真感光体を構成すること
により前記目的を達成することを見い出した。(Means and effects for solving the problem) The present inventors have developed the following - Bottom (1) % formula % (In the formula, R1, R2, R3, R4 are groups substituted at the para position with respect to the nitrogen atom. and an alkyl group, an alkoxyl group,
(represents a halogen atom, all substituents may be the same or different from each other, and R represents a hydrogen atom, an alkyl group, an alkoxyl group, or a halogen atom) and the following - Bottom (H) \ R' RR5 (In the formula, R5, R6, R7, R' are groups substituted at the meta position relative to the nitrogen atom, and are an alkyl group, an alkoxyl group,
(represents a halogen atom, all substituents may be the same or different from each other, and R represents a hydrogen atom, an alkyl group, an alkoxyl group, or a halogen atom). It has been found that the above object can be achieved by constructing an electrophotographic photoreceptor characterized by being provided with a photosensitive layer.
（発明の好適態様）
本発明の電子写真感光体で用いるｍ−フェニレンジアミ
ン系化合物は前記−船底（１）および前記−船人（ＩＩ
）で表され、式中Ｒ１，Ｒ２、Ｒ３Ｒ’、Ｒ５、Ｒ６、
Ｒ’ Ｒ’、Ｒのうちアルキル基としては、メチル、
エチル、プロピル、イソプロピル、ブチル、イソブチル
、ｔｅｒｔブチル、ペンチル、ヘキシル等の炭素数１〜
６の低級アルキル基が例示される。アルコキシ基として
は、メトキシ、エトキシ、プロポキシ、イソプロポキシ
、ブトキシ、イソブトキシ、ｔｅｒｔ−ブトキシ、ペン
チルオキシ、ヘキシルオキシ基等のアルキル部分が炭素
数１〜６の低級アルコキシ基が例示される。(Preferred Embodiment of the Invention) The m-phenylenediamine compound used in the electrophotographic photoreceptor of the present invention is
), in the formula R1, R2, R3R', R5, R6,
R' Among R' and R, the alkyl group is methyl,
1 or more carbon atoms such as ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, etc.
6 lower alkyl group is exemplified. Examples of the alkoxy group include lower alkoxy groups in which the alkyl moiety has 1 to 6 carbon atoms, such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, tert-butoxy, pentyloxy, and hexyloxy groups.
具体的には、下記−船底（１）で表されるｍ −フェニ
レンジアミン系化合物
また、
具体的には下記−船底（ＴＩ）
で表される
ｍ−フェニレンジアミン系化合物
等が例示され、
置換基Ｒの位置は特定されないが
５の位置等が示される。Specifically, m-phenylenediamine-based compounds represented by the following - bottom (1), and specifically m-phenylenediamine-based compounds represented by the following - bottom (TI), etc. Although the position of R is not specified, the position of 5, etc. is shown.
本発明で用いる前記−船底（Ｉ）で表されるパラ置換化
合物は種々の方法により合成することができるが、この
−例を下記反応により説明する。The para-substituted compound represented by the above-mentioned bottom (I) used in the present invention can be synthesized by various methods, and an example thereof will be explained by the following reaction.
等が例示され、置換基Ｒの位置は特定されないが、５の
位置等が示される。etc., and although the position of the substituent R is not specified, the position of 5 etc. is shown.
すなわち本発明は、上記式（Ａ）で表されるレソルシノ
ールと上記式（Ｂ）で表されるＰ−）ルイジンをヨウ素
と共に窒素気流下で反応させて上記式（Ｃ）で表される
Ｎ、 Ｎ・−ジ（４−トリル）−１，３−フェニレン
ジアミンを得る。さらに、Ｎ、 Ｎｏ−ジ（４−トリ
ル）−１，３−フェニレンジアミンと上記式（Ｄ）で表
されるヨードトルエンを炭酸カリウム、銅粉と共にニト
ロベンゼン中で還流させることにより上記式（Ｅ）で表
されるＮ、Ｎ、Ｎ・、Ｎ＝−テトラ（４−トリル）−１
，３−フェニレンジアミンが得られる。That is, the present invention allows resorcinol represented by the above formula (A) and P-)luidine represented by the above formula (B) to react with iodine under a nitrogen stream to produce N, represented by the above formula (C), N.-di(4-tolyl)-1,3-phenylenediamine is obtained. Furthermore, by refluxing N,No-di(4-tolyl)-1,3-phenylenediamine and iodotoluene represented by the above formula (D) together with potassium carbonate and copper powder in nitrobenzene, the above formula (E) is obtained. N, N, N・, N=-tetra(4-tolyl)-1 represented by
, 3-phenylenediamine are obtained.
本発明で用いる前記−船底〔■］で表されるメタ置換化
合物は種々の方法により合成することができるが、この
−例を下記反応により説明する。The meta-substituted compound represented by the above-mentioned bottom [■] used in the present invention can be synthesized by various methods, and an example thereof will be explained by the following reaction.
（Ｈ）
（以下余白）
（Ｊ）
すなわち本発明は、上記式（Ｆ）で表されるレソルシノ
ールと上記式（Ｇ）で表されるｍ−トルイジンをヨウ素
と共に窒素気流下で反応させて上記式（Ｈ）で表される
Ｎ、 Ｎ・−ジ（３−トリル）−１，３−フェニレンジ
アミンを得る。さらに、Ｎ、 Ｎ＝−ジ（３−トリル）
−１，３−フェニレンジアミンと上記式（ｒ）で表され
るヨードトルエンを炭酸カリウム、銅粉と共にニトロベ
ンゼン中で還流させることにより上記式（Ｊ）で表され
るＮ、 Ｎ、 Ｎ＝、Ｎ＝−テトラ（３−トリル）１．
３−フェニレンジアミンが得られる。(H) (Hereinafter in the margin) (J) That is, the present invention provides the above formula by reacting resorcinol represented by the above formula (F) and m-toluidine represented by the above formula (G) together with iodine under a nitrogen stream. N,N·-di(3-tolyl)-1,3-phenylenediamine represented by (H) is obtained. Furthermore, N, N=-di(3-tolyl)
-1,3-phenylenediamine and iodotoluene represented by the above formula (r) are refluxed in nitrobenzene with potassium carbonate and copper powder to produce N, N, N=, N represented by the above formula (J) =-tetra(3-tolyl)1.
3-phenylenediamine is obtained.
本発明の電子写真感光体は、導電性基体上に、前記−船
底ＣＩ）、（ＩＩ）で表されるｍ−フェニレンジアミン
系化合物を含有する感光層を設けることを特徴とするも
のであり、導電性基体上に少なくとも一層中に電荷発生
材料及び電荷輸送材料を含んだ機能分離型単層感光体、
導電性基体上に少なくとも電荷発生層と電荷輸送層の二
層を積層した機能分離型積層感光体等、いずれのタイプ
の電子写真感光体にも適用することができる。本発明の
前記−船底ＣＩ）、（ＩＩ）で表される化合物は、従来
公知の他の電荷輸送材料と組み合わせて使用してもよい
。その際、他の電荷輸送材料としては、従来公知の電子
吸引性化合物、電子供与性化合物を用いることができる
。上記電子吸引性化合物としては、例えば、テトラシア
ノエチレン、２．４．７−１−ジニトロ−９−フルオレ
ノン、２４．８−１−リニトロチオキサントン、３，４
，５゜７−テトラニトロ−９−フルオレノン、ジニトロ
ベンゼン、ジニトロアントラセン、ジニトロアクリジン
、ニトロアントラキノン、ジニトロアントラキノン、無
水コハク酸、無水マレイン酸、ジブロモ無水マレイン酸
等が例示される。The electrophotographic photoreceptor of the present invention is characterized in that a photosensitive layer containing an m-phenylenediamine compound represented by -bottom CI) or (II) is provided on a conductive substrate, a functionally separated single-layer photoreceptor comprising a charge-generating material and a charge-transporting material in at least one layer on a conductive substrate;
It can be applied to any type of electrophotographic photoreceptor, such as a functionally separated laminated photoreceptor in which at least two layers, a charge generation layer and a charge transport layer, are laminated on a conductive substrate. The compounds represented by the above-mentioned bottom CI) and (II) of the present invention may be used in combination with other conventionally known charge transport materials. In this case, as other charge transport materials, conventionally known electron-withdrawing compounds and electron-donating compounds can be used. Examples of the electron-withdrawing compound include tetracyanoethylene, 2.4.7-1-dinitro-9-fluorenone, 24.8-1-linitrothioxanthone, 3,4
, 5°7-tetranitro-9-fluorenone, dinitrobenzene, dinitroanthracene, dinitroacridine, nitroanthraquinone, dinitroanthraquinone, succinic anhydride, maleic anhydride, dibromomaleic anhydride and the like.
また、電子供与性化合物としては、２，５−ジ（４−メ
チルアミノフェニル）、１，３．４−オキサジアゾール
、等のオキサジアゾール系化合物、９−（４−ジエチル
アミノスチリル）アントラセン等のスチリル化合物、ポ
リビニルカルバゾール等のカルバゾール系化合物、１−
フェニル−３−（ｐ−ジメチルアミノフェニル）ピラゾ
リン等のピラゾリン化合物、ヒドラゾン化合物、トリフ
ェニルアミン系化合物、インドール系化合物、オキサゾ
ール系化合物、イソオキサゾール系化合物、チアゾール
系化合物、チアジアゾール系化合物、イミダゾール系化
合物、ピラゾール系化合物、トリアゾール系化合物等の
含窒素環式化合物、縮合多環式化合物が例示される。こ
れらの電荷輸送材料は一種または二種以上混合して用い
られる。なお、ポリビニルカルバゾール等成膜性を有す
る電荷輸送材料を用いる場合には、結合剤樹脂は必ずし
も必要ではない。Examples of electron-donating compounds include oxadiazole compounds such as 2,5-di(4-methylaminophenyl) and 1,3.4-oxadiazole, and 9-(4-diethylaminostyryl)anthracene. styryl compounds, carbazole compounds such as polyvinylcarbazole, 1-
Pyrazoline compounds such as phenyl-3-(p-dimethylaminophenyl)pyrazoline, hydrazone compounds, triphenylamine compounds, indole compounds, oxazole compounds, isoxazole compounds, thiazole compounds, thiadiazole compounds, imidazole compounds Examples include nitrogen-containing cyclic compounds such as , pyrazole compounds, and triazole compounds, and fused polycyclic compounds. These charge transport materials may be used alone or in combination of two or more. Note that when using a charge transporting material having film-forming properties such as polyvinylcarbazole, a binder resin is not necessarily required.
例えば単層型電子写真感光体とするには、電荷輸送材料
として前記−船底（１）、（Ｉｔ）で表される化合物と
、電荷発生材料と結合剤樹脂等を含有する感光層を導電
性基板上に形成すればよい。For example, in order to make a single-layer electrophotographic photoreceptor, a photosensitive layer containing a compound represented by the above-mentioned bottom (1) or (It) as a charge transporting material, a charge generating material, a binder resin, etc. is made into a conductive layer. It may be formed on a substrate.
また積層型の電子写真感光体とするには、導電性基板上
に、蒸着または塗布等の手段により上記電荷発生材料を
含有する電荷発生層を形成し、この電荷発生層上に、前
記−船底〔Ｉ・〕、（ＩＩ）で表される化合物と結合剤
樹脂とを含有する電荷輸送層を形成したり、上記とは逆
に、導電性基板上に上記と同様の電荷輸送層を形成し、
次いで蒸着または塗布等の手段により前記電荷発生材料
を含有する電荷発生層を形成すればよい。また、電荷発
生層は電荷発生材料と電荷輸送材料を結着樹脂中に分散
して塗布して形成してもよい。In order to obtain a laminated electrophotographic photoreceptor, a charge generation layer containing the charge generation material described above is formed on a conductive substrate by means such as vapor deposition or coating. A charge transport layer containing a compound represented by [I.] or (II) and a binder resin may be formed, or, contrary to the above, a charge transport layer similar to the above may be formed on a conductive substrate. ,
Next, a charge generation layer containing the charge generation material may be formed by means such as vapor deposition or coating. Further, the charge generation layer may be formed by dispersing a charge generation material and a charge transporting material in a binder resin and applying the mixture.
上記電荷発生材料としては、例えばセレン、セレン−テ
ルル、アモルファスシリコン、ピリリウム塩、アゾ系顔
料、ジスアゾ系顔料、アンサンスロン系顔料、フタロシ
アニン系顔料、インジゴ系顔料、トリフェニルメタン系
顔料、スレン系顔料、トルイジン系顔料、ピラゾリン系
顔料、ペリレン系顔料、キナクリドン系顔料等が例示さ
れ、所望の領域に吸収波長域を有するように、一種また
は二種以上混合して用いられる。Examples of the charge generating materials include selenium, selenium-tellurium, amorphous silicon, pyrylium salts, azo pigments, disazo pigments, anthanthrone pigments, phthalocyanine pigments, indigo pigments, triphenylmethane pigments, and srene pigments. , toluidine pigments, pyrazoline pigments, perylene pigments, quinacridone pigments, etc., and these pigments may be used singly or in combination of two or more so as to have an absorption wavelength range in a desired region.
また、上記感光層、電荷発生層、および電荷輸送層、に
おける結合剤樹脂としては、種々の樹脂が使用でき、例
えば、スチレン系重合体、スチレン−ブタジェン共重合
体、スチレン−アクリロニトリル共重合体、スチレン−
マレイン酸共重合体、アクリル系重合体、スチレン−ア
クリル系共重合体、ポリエチレン、エチレン−酢酸ビニ
ル共重合体、塩素化ポリエチレン、ポリ塩化ビニル、ポ
リプロピレン、塩化ビニル−酢酸ビニル共重合体、ポリ
エステル、アルキッド樹脂、ポリアミド、ポリウレタン
、ポリカーボネート、ボリアリレート、ポリスルホン、
ジアリルフタレート樹脂、ケトン樹脂、ポリビニルブチ
ラール樹脂、ポリエーテル樹脂、等の熱可塑性樹脂や、
シリコーン樹脂、エポキシ樹脂、フェノール樹脂、尿素
樹脂、メラミン樹脂、その他架橋性の熱硬化性樹脂、お
よび、エポキシアクリレート、ウレタン−アクリレート
等の光硬化型樹脂等、各種の重合体が例示できる。Various resins can be used as binder resins in the photosensitive layer, charge generation layer, and charge transport layer, such as styrene polymers, styrene-butadiene copolymers, styrene-acrylonitrile copolymers, Styrene
Maleic acid copolymer, acrylic polymer, styrene-acrylic copolymer, polyethylene, ethylene-vinyl acetate copolymer, chlorinated polyethylene, polyvinyl chloride, polypropylene, vinyl chloride-vinyl acetate copolymer, polyester, Alkyd resin, polyamide, polyurethane, polycarbonate, polyarylate, polysulfone,
Thermoplastic resins such as diallyl phthalate resin, ketone resin, polyvinyl butyral resin, polyether resin,
Examples include various polymers such as silicone resins, epoxy resins, phenol resins, urea resins, melamine resins, other crosslinkable thermosetting resins, and photocurable resins such as epoxy acrylates and urethane-acrylates.
これらの結合剤樹脂は、一種または二種以上混合して用
いられる。These binder resins may be used alone or in combination of two or more.
また、塗布手段により電荷発生層および電荷輸送層を形
成する場合溶剤が使用される。上記溶剤としては、種々
の有機溶剤が使用でき、メタノール、エタノール、イソ
プロパツール、ブタノール等のアルコール類、ｎ−へキ
サン、オクタン、シクロヘキサン等の脂肪族系炭化水素
、ベンゼン、トルエン、キシレン等の芳香族炭化水素、
ジクロロメタン、ジクロロエタン、四塩化炭素、クロロ
ベンゼン等のハロゲン化炭化水素、ジメチルエーテル、
ジエチルエーテル、テトラヒドロフラン、エチレングリ
コールジメチルエーテル、エチレングリコールジエチル
エーテル、ジエチレングリコールジメチルエーテル等の
エーテル類、アセトン、メチルエチルケトン、シクロヘ
キサノン等のケトン類、酢酸エチル、酢酸メチル、等の
エステル類、ジメチルホルムアミド、ジメチルスルホキ
シド等、種々の溶剤が例示され、一種または二種以上混
合して用いられる。Further, a solvent is used when forming the charge generation layer and the charge transport layer by coating means. Various organic solvents can be used as the solvent, including alcohols such as methanol, ethanol, isopropanol, butanol, aliphatic hydrocarbons such as n-hexane, octane, and cyclohexane, and benzene, toluene, and xylene. aromatic hydrocarbons,
Halogenated hydrocarbons such as dichloromethane, dichloroethane, carbon tetrachloride, chlorobenzene, dimethyl ether,
Ethers such as diethyl ether, tetrahydrofuran, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, ketones such as acetone, methyl ethyl ketone, cyclohexanone, esters such as ethyl acetate, methyl acetate, dimethyl formamide, dimethyl sulfoxide, etc. The following solvents are exemplified and may be used alone or in combination of two or more.
また、前記電荷発生層の感度をよくするため、例えば、
ターフェニル、ハロナフトキノン類、アセナフチレン等
従来公知の増感剤を前記電荷発生材料と共に用いてもよ
い。さらには電荷輸送材料や電荷発生材料の分散性、塗
工性等をよくするため、界面活性剤、レベリング剤等を
使用してもよい
上記導電性基板としては、導電性を有する種々の材料が
使用でき、例えば、アルミニウム、銅、錫、白金、金、
銀、バナジウム、モリブデン、クロム、カドミウム、チ
タン、ニッケル、パラジウム、インジウム、ステンレス
銅、真鍮の金属単体や、上記金属が蒸着またはラミネー
トされたプラスチック材料、ヨウ化アルミニウム、酸化
錫、酸化インジウム等で被覆されたガラス等が例示され
る。上記導電性基板はシート状やドラム状いずれであっ
てもよく、基板自体が導電性を有するか基板の表面が導
電性を有し、使用に際し、十分な機械的強度を有するも
のが好ましい。Furthermore, in order to improve the sensitivity of the charge generation layer, for example,
Conventionally known sensitizers such as terphenyl, halonaphthoquinones, and acenaphthylene may be used together with the charge generating material. Furthermore, in order to improve the dispersibility and coating properties of charge transport materials and charge generation materials, surfactants, leveling agents, etc. may be used.As the conductive substrate, various conductive materials may be used. For example, aluminum, copper, tin, platinum, gold,
Single metals such as silver, vanadium, molybdenum, chromium, cadmium, titanium, nickel, palladium, indium, stainless copper, and brass, plastic materials on which the above metals are vapor-deposited or laminated, and coated with aluminum iodide, tin oxide, indium oxide, etc. An example of this is glass. The above-mentioned conductive substrate may be in the form of a sheet or a drum, and it is preferable that the substrate itself has conductivity or the surface of the substrate has conductivity, and that it has sufficient mechanical strength during use.
上記電荷輸送材料としての前記−船底（Ｉ）および〔■
〕で表される化合物と結合剤樹脂の割合は、結合剤樹脂
１００重量部に対して、前記−船底（Ｉ）および（ＩＩ
）で表される化合物の割合を３０ニア０重量部乃至８０
：２０重量部、好ましくは５０：５０乃至７０：３０重
量部の範囲で使用することができる。例えば、前記−船
底（１）で表される化合物を８０重量部以上含むと樹脂
中で結晶化してしまい、また前記−船底（ｎ）で表され
る化合物を７０重量部以上含むと感度が下がり残留電位
が高くなるという不具合が生じてしまうのである。Said bottom (I) as said charge transporting material and [■
] The ratio of the compound represented by the above-mentioned - bottom (I) and (II) to 100 parts by weight of the binder resin is
) of the compound represented by 30 to 80 parts by weight.
:20 parts by weight, preferably 50:50 to 70:30 parts by weight. For example, if 80 parts by weight or more of the compound represented by -bottom (1) is contained, it will crystallize in the resin, and if 70 parts by weight or more of the compound represented by -bottom (n) is contained, the sensitivity will decrease. This results in a problem that the residual potential becomes high.
また、−船底（１）、（ＩＩ）で表される化合物を含有
する電荷輸送層は、２〜１００μｍ、特に、５〜３０μ
ｍ程度の層厚に形成されるのが好ましい。Further, the charge transport layer containing the compound represented by bottom (1) or (II) has a thickness of 2 to 100 μm, particularly 5 to 30 μm.
It is preferable to form the layer with a thickness of about m.
上記電荷発生材料を前記結合剤樹脂と共に用いる場合、
電荷発生材料と結合剤樹脂とは、種々の割合で使用する
ことができるが、電荷発生材料１０重量部に対して、結
合剤樹脂１〜３００重量部、特に、５〜１５０重量部用
いるのが好ましい。When the charge generating material is used with the binder resin,
The charge generating material and the binder resin can be used in various ratios, but it is preferable to use 1 to 300 parts by weight, particularly 5 to 150 parts by weight, of the binder resin per 10 parts by weight of the charge generating material. preferable.
また、上記電荷発生層は、適宜の層厚を有していてもよ
いが、０．０１〜２０μｍ、特に０． １〜１０μｍ程
度に形成されるのが好ましい。Further, the charge generation layer may have an appropriate layer thickness, but is preferably 0.01 to 20 μm, particularly 0.01 to 20 μm. It is preferably formed to have a thickness of about 1 to 10 μm.
また、単層型電子写真用感光体にあたっては、上記基板
と感光層との間に、また積層型電子写真用感光体にあた
っては、前記基板と電荷発生層との間や基板と電荷輸送
層との間および電荷発生層と電荷輸送層との間に、感光
体の特性を阻害しない範囲でバリア層が形成されていて
もよく、感光体の表面には、保護層が形成されていても
よい。Furthermore, in the case of a single-layer electrophotographic photoreceptor, there is a gap between the substrate and the photosensitive layer, and in the case of a laminated electrophotographic photoreceptor, there is a gap between the substrate and the charge generation layer, or between the substrate and the charge transport layer. A barrier layer may be formed between the photoreceptor and between the charge generation layer and the charge transport layer to the extent that it does not impede the characteristics of the photoreceptor, and a protective layer may be formed on the surface of the photoreceptor. .
上記電荷発生層および電荷輸送層を塗布手段により形成
するには、前記電荷発生材料等と結合剤樹脂等を、従来
公知の方法、例えば、ロールミル、ボールミル、アトラ
イタ、ペイントシェカあるいは超音波分散器等を用いて
調整し、従来公知の塗布手段により塗布、乾燥すればよ
い。なお前記のように電荷発生層は、前記電荷発生材料
を蒸着することにより形成してもよい。In order to form the charge generation layer and the charge transport layer by coating means, the charge generation material and the binder resin are coated using a conventionally known method such as a roll mill, ball mill, attritor, paint shaker, or ultrasonic disperser. What is necessary is just to apply|coat with a conventionally well-known coating means, and just to dry. Note that, as described above, the charge generation layer may be formed by vapor depositing the charge generation material.
以下実施例に基づき、本発明をより詳細に説明する。The present invention will be described in more detail below based on Examples.
（実験例）
（Ｎ、Ｎ、Ｎ’、Ｎ’−テトラキス（４−トリル）−１
，３−フェニレンジアミンの合成］レソルシノールｌ１
ｇ、Ｐ−）ルイジン２２゜６ｇ、ヨウ素０．５ｇ窒素気
流下で３日間還流反応させた。反応後、室温まで冷却し
、生じた固体をメタノール５００ｍ１で洗ってＮ、 Ｎ
’ −テトー７−ｔ−ス（４−）リル）−１，３−フエ
らレンジアミン得た。次に、Ｎ、Ｎ″−テトラキス（４
−トリル）、−１，３−フェニレンジアミン１４．４ｇ
、ヨードベンゼン２０．４ｇ、炭酸カリウム９．７ｇ、
銅粉末２ｇをニトロベンゼン１００ｍ２中で２４時間還
流反応させた。反応後、水蒸気蒸溜によりニトロベンゼ
ン、ヨードベンゼンをＷ去Ｌ、残香を水洗し、メタノー
ルで洗った。次に残香をベンゼン９００ｍｆｆ中に加え
、水溶物を濾別し、活性アルミナカラムクロマト展開液
（ベンゼン−ヘキサン１：１）で１ｓｔフラクシヨンを
とった。(Experiment example) (N, N, N', N'-tetrakis(4-tolyl)-1
, 3-phenylenediamine synthesis] resorcinol l1
g, P-) 22.6 g of luidine and 0.5 g of iodine were reacted under reflux for 3 days under a nitrogen stream. After the reaction, it was cooled to room temperature, and the resulting solid was washed with 500 ml of methanol and diluted with N, N.
'-tetoh7-t-su(4-)lyl)-1,3-phelalenediamine was obtained. Next, N,N''-tetrakis (4
-tolyl), -1,3-phenylenediamine 14.4g
, iodobenzene 20.4g, potassium carbonate 9.7g,
2 g of copper powder was subjected to a reflux reaction in 100 m2 of nitrobenzene for 24 hours. After the reaction, nitrobenzene and iodobenzene were removed by steam distillation, and the residual aroma was washed with water and methanol. Next, the residual aroma was added to 900 mff of benzene, the aqueous solution was filtered off, and the 1st fraction was taken with activated alumina column chromatography developer (benzene-hexane 1:1).
さらにこのフラクションを、ベンゼン−ヘキサン１：２
を展開液とし活性アルミナカラムクロマトで分離し、１
ｓｔフラクシヨンをとった。溶媒を留去しこの一部をア
セトニトリルに常温で溶解させ、生じた結晶を種として
、アセトニトリルから結晶化させることによりＮ、Ｎ、
Ｎ’、Ｎ’ −テトー７−１−ス（４−トリル）−１，
３−フェニレンジアミン（パラ置換化合物）を得た。Furthermore, this fraction was mixed with benzene-hexane 1:2
was used as a developing solution and separated by activated alumina column chromatography.
I took the st fraction. The solvent is distilled off, a part of it is dissolved in acetonitrile at room temperature, and the resulting crystals are used as seeds to crystallize from acetonitrile to obtain N, N,
N', N'-tetoh-7-1-s(4-tolyl)-1,
3-phenylenediamine (para-substituted compound) was obtained.
（Ｎ、Ｎ、Ｎ’、Ｎ″−テトラキス（３−トリル）−１
，３−フェニレンジアミンの合成〕上記合成例のＰ−１
−ルイジンの変わりにｍ−トルイジン２２．６ｇを用い
て上記実施例１と同様にして、Ｎ、Ｎ’−テトラキス（
３−トリル）＝１．３−フェニレンジアミンを得た。Ｎ
、Ｎ’テトラキス（３−１−リル）−１，３−フェニレ
ンジアミン１４．４ｇと、ヨードトルエン２１．８ｇ、
炭酸カリウム９．７ｇ、銅粉末２ｇをニトロベンゼン１
００ｍｊ２中で２４時間還流反応させた。(N, N, N', N''-tetrakis(3-tolyl)-1
, 3-phenylenediamine] P-1 of the above synthesis example
-N,N'-tetrakis(
3-tolyl)=1,3-phenylenediamine was obtained. N
, 14.4 g of N'tetrakis(3-1-lyl)-1,3-phenylenediamine, and 21.8 g of iodotoluene.
9.7g of potassium carbonate, 2g of copper powder and 11g of nitrobenzene
A reflux reaction was carried out for 24 hours in 00mj2.
反応後、水藤気蒸溜によりニトロベンゼン、ヨードベン
ゼンを留去し、残香を水洗し、メタノールで洗った。次
に残香をベンゼン９００ｍｊ２中に加え、水溶物を濾別
し、活性アルミナカラムクロマト展開液（ベンゼン−ヘ
キサン１：１）で１ｓｔフラクシヨンをとった。さらに
このフラクションを、ベンゼン−ヘキサン１：２を展開
液とし活性アルミナカラムクロマトで分離し、１ｓｔフ
ラクシヨンをとった。溶媒を留去しこの一部をアセトニ
トリルに常温で溶解させ、生じた結晶を種として、アセ
トニトリルから結晶化させることによりＮ、Ｎ、Ｎ’、
Ｎ”−テトラキス（３−トリル）−１，３−フェニレン
ジアミン（メタ置換化合物）を得た。After the reaction, nitrobenzene and iodobenzene were distilled off by hydrogen vapor distillation, and the residual aroma was washed with water and methanol. Next, the residual aroma was added to 900 mj2 of benzene, the aqueous solution was filtered off, and the 1st fraction was taken with activated alumina column chromatography developer (benzene-hexane 1:1). Further, this fraction was separated by activated alumina column chromatography using benzene-hexane 1:2 as a developing solution, and a 1st fraction was taken. The solvent is distilled off, a part of it is dissolved in acetonitrile at room temperature, and the resulting crystals are used as seeds to crystallize from acetonitrile to obtain N, N, N',
N''-tetrakis(3-tolyl)-1,3-phenylenediamine (meta-substituted compound) was obtained.
実施例１
電荷発生材料としてＮ、Ｎ’−ジ（３，５−ジメチルフ
ェニル）ペリレン−３，４，９，１０−テトラカルボキ
シジイミド８重量部、電荷輸送材料としてＮ、Ｎ、Ｎ”
Ｎ ｌ−テトラキス（４−トリル）−１，３−フェニ
レンジアミン（パラ置換化合物）８０重量部、Ｎ、Ｎ、
Ｎ’、Ｎ’ −テトラキス（３−トリル）−１，３−フ
ェニレンジアミン（メタ置換化合物）２０重量部、結合
剤樹脂としてポリカーボネートＺ樹脂１００重量部およ
び所定量のテトラヒドロフランを用い、超音波分散器に
て分散液を調整すると共に、アルマイト処理されたアル
ミニウム板上に塗布し、厚み２３μｍの感光層を有する
単層型の電子写真感光体を作成した。Example 1 8 parts by weight of N,N'-di(3,5-dimethylphenyl)perylene-3,4,9,10-tetracarboxydiimide as a charge generation material, N,N,N'' as a charge transport material
N l-tetrakis(4-tolyl)-1,3-phenylenediamine (para-substituted compound) 80 parts by weight, N, N,
Using 20 parts by weight of N',N'-tetrakis(3-tolyl)-1,3-phenylenediamine (meta-substituted compound), 100 parts by weight of polycarbonate Z resin as a binder resin, and a predetermined amount of tetrahydrofuran, an ultrasonic disperser was used. A dispersion liquid was prepared in a vacuum cleaner and coated on an alumite-treated aluminum plate to produce a single-layer electrophotographic photoreceptor having a photosensitive layer with a thickness of 23 μm.
実施例２
電荷輸送材料としてＮ、Ｎ、Ｎ’、Ｎ’ −テトラキス
（４−）リル）−１，３−フェニレンジアミン（パラ置
換化合物）７０重量部、Ｎ、Ｎ、Ｎ’。Example 2 70 parts by weight of N,N,N',N'-tetrakis(4-)lyl)-1,3-phenylenediamine (para-substituted compound) as a charge transport material, N,N,N'.
Ｎ −テトラキス（３−トリル）−１，３−フェニレン
ジアミン（メタ置換化合物）３０重量部、を用いる以外
は実施例１と同様にして電子写真感光体を作成した。An electrophotographic photoreceptor was prepared in the same manner as in Example 1 except that 30 parts by weight of N-tetrakis(3-tolyl)-1,3-phenylenediamine (meta-substituted compound) was used.
実施例３
電荷輸送材料としてＮ、Ｎ、Ｎ’、Ｎ“−テトラキス（
４−トリル）−１，３−フェニレンジアミン（パラ置換
化合物）５０重量部、Ｎ、ＮＮｏ。Example 3 N, N, N', N''-tetrakis (
50 parts by weight of 4-tolyl)-1,3-phenylenediamine (para-substituted compound), N, NNo.
Ｎｏ−テトラキス（３−トリル）−１，３−フェニレン
ジアミン（メタ置換化合物）５０重量部、を用いる以外
は実施例１と同様にして電子写真感光体を作成した。An electrophotographic photoreceptor was prepared in the same manner as in Example 1 except that 50 parts by weight of No-tetrakis(3-tolyl)-1,3-phenylenediamine (meta-substituted compound) was used.
実施例４
電荷輸送材料としてＮ、Ｎ、Ｎｏ、Ｎｏ−テトラキス（
４−トリル）−１，３−フェニレンジアミン（パラ置換
化合物）３０重量部、Ｎ、Ｎ、Ｎ’。Example 4 N, N, No, No-tetrakis (
30 parts by weight of 4-tolyl)-1,3-phenylenediamine (para-substituted compound), N, N, N'.
Ｎｏ−テトラキス（３−トリル）−１，３−フェニレン
ジアミン（メタ置換化合物）７０重量部、を用いる以外
は実施例１と同様にして電子写真感光体を作成した。An electrophotographic photoreceptor was prepared in the same manner as in Example 1 except that 70 parts by weight of No-tetrakis(3-tolyl)-1,3-phenylenediamine (meta-substituted compound) was used.
比較例１
電荷輸送材料としてＮ、Ｎ、Ｎ”、Ｎｏ−テトラキス（
４−）リル）−１，３−フェニレンジアミン（パラ置換
化合物）１００重量部、を用いる以外は実施例１と同様
にして電子写真感光体を作成した。Comparative Example 1 N, N, N'', No-tetrakis (
An electrophotographic photoreceptor was prepared in the same manner as in Example 1, except that 100 parts by weight of 4-)lyl)-1,3-phenylenediamine (para-substituted compound) was used.
比較例２
電荷輸送材料としてＮ、Ｎ、Ｎ”Ｎ ＋ −テトラキス
（３−トリル）−１，３−フェニレンジアミン（メタ置
換化合物）１００重量部、を用いる以外は実施例１と同
様にして電子写真感光体を作成した。Comparative Example 2 Electron was produced in the same manner as in Example 1 except that 100 parts by weight of N,N,N''N + -tetrakis(3-tolyl)-1,3-phenylenediamine (meta-substituted compound) was used as the charge transport material. A photographic photoreceptor was created.
〔電子写真感光体の評価］
上記各感光体の帯電特性および感光特性を静電複写試Ｍ
装置（ジエンチック社製、ジエンチックシンシア ３０
Ｍ）を用いて、前記各感光体を正に帯電させ、各感光体
の表面電位ｖｓｐ（ｖ）を測定した。また、ハロゲン光
を用いて、感光体を露光し、上記表面電位が１／２とな
るまでの時間を求め、半減露光ｆｆ１Ｅ１／２ （μＪ
／ｃｍ”）を算出すると共に、露光後、０．．１５秒経
過後の表面電位を残留電位Ｖ、ｐ（Ｖ）とした。また、
上記電子写真感光体の結晶化状態を目視で調べ、結晶化
が見られるかどうかを調べた。[Evaluation of electrophotographic photoreceptors] The charging characteristics and photosensitive characteristics of each of the above photoreceptors were evaluated using electrostatic copying test M.
Equipment (manufactured by Dientic Co., Ltd., Dientic Cynthia 30
Each photoreceptor was positively charged using M), and the surface potential vsp (v) of each photoreceptor was measured. In addition, the photoreceptor is exposed to halogen light, the time required for the surface potential to decrease to 1/2 is calculated, and the half-reduction exposure ff1E1/2 (μJ
/cm"), and the surface potential after 0.15 seconds after exposure was taken as the residual potential V, p (V).
The crystallization state of the electrophotographic photoreceptor was visually inspected to determine whether crystallization was observed.
上記実施例および比較例で得られた電子写真感光体の結
晶化状態、帯電特性および感光特性の測定結果を表１に
示す。Table 1 shows the measurement results of the crystallization state, charging characteristics, and photosensitive characteristics of the electrophotographic photoreceptors obtained in the above Examples and Comparative Examples.
（以下余白）
表１から明らかなように、本発明の電子写真感光体はい
ずれも結晶化することなく帯電特性に優れ、半減露光量
が小さく、感度がよいと共に、残留電位が小さいことが
判明した。これに対して比較例の感光体は結晶化したり
、また感度が小さく残留電位の高いものであった。(The following is a blank space) As is clear from Table 1, the electrophotographic photoreceptors of the present invention do not crystallize, have excellent charging characteristics, have a small half-life exposure, have good sensitivity, and have a small residual potential. did. In contrast, the photoreceptor of the comparative example was crystallized and had low sensitivity and high residual potential.
（発明の効果）
以上のように、本発明の電子写真感光体はパラ置換およ
びメタ置換したｍ−フェニレンジアミン系化合物双方の
特徴を反映した、感光層が結晶化することなく高感度化
された電子写真感光体を提供することができる。(Effects of the Invention) As described above, the electrophotographic photoreceptor of the present invention reflects the characteristics of both para-substituted and meta-substituted m-phenylenediamine compounds, and has a highly sensitive photosensitive layer without crystallization. An electrophotographic photoreceptor can be provided.
Claims (4)
対してパラ位に置換した基でありアルキル基、アルコキ
シル基、ハロゲン原子を示し、すべての置換基は同一で
も、それぞれ互いに異なっていてもよく、Ｒは水素原子
、アルキル基、アルコキシル基、ハロゲン原子を示す）
で表されるｍ−フェニレンジアミン系化合物、 および下記一般式〔II〕 ▲数式、化学式、表等があります▼・・・〔II〕 （式中、Ｒ＾５、Ｒ＾６、Ｒ＾７、Ｒ＾８は窒素原子に
対してメタ位に置換した基でありアルキル基、アルコキ
シル基、ハロゲン原子を示し、すべての置換基は同一で
も、それぞれ互いに異なっていてもよく、Ｒは水素原子
、アルキル基、アルコキシル基、ハロゲン原子を示す）
で表されるｍ−フェニレンジアミン系化合物を含有する
感光層を設けたことを特徴とする電子写真感光体。(1) On the conductive substrate, there are the following general formulas [I] ▲mathematical formulas, chemical formulas, tables, etc.▼...[I] (In the formula, R^1, R^2, R^3, R^4 is a group substituted at the para position to the nitrogen atom, and represents an alkyl group, an alkoxyl group, or a halogen atom, and all substituents may be the same or different from each other, and R is a hydrogen atom, an alkyl group, or an alkoxyl group. group, halogen atom)
m-phenylenediamine compound represented by, and the following general formula [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼... [II] (In the formula, R^5, R^6, R^7, R^8 is a group substituted at the meta position relative to the nitrogen atom, and represents an alkyl group, an alkoxyl group, or a halogen atom, and all substituents may be the same or different from each other, and R is a hydrogen atom, an alkyl group, alkoxyl group, halogen atom)
An electrophotographic photoreceptor comprising a photosensitive layer containing an m-phenylenediamine compound represented by:
〕で表されるｍ−フェニレンジアミン系化合物を結着樹
脂１００重量部に対して、〔 I 〕：〔II〕を３０：７
０重量部乃至８０：２０重量部の割合で含有する感光層
を設けたことを特徴とする特許請求の範囲第１項記載の
電子写真感光体。(2) On the conductive substrate, the general formulas [I] and [II]
] to 100 parts by weight of the binder resin, [I]:[II] was mixed in a ratio of 30:7.
2. The electrophotographic photoreceptor according to claim 1, further comprising a photosensitive layer containing 0 parts by weight to 80:20 parts by weight.
I 〕および〔II〕で表されるｍ−フェニレンジアミン系
化合物を電荷輸送材料として単一層中に存在させたこと
を特徴とする特許請求の範囲第１項および第２項記載の
電子写真感光体。(3) The photosensitive layer has the above general formula [
The electrophotographic photoreceptor according to claims 1 and 2, characterized in that the m-phenylenediamine compounds represented by [I] and [II] are present in a single layer as a charge transport material. .
との積層感光体から成り、該電荷輸送層が前記一般式〔
I 〕、〔II〕で表されるｍ−フェニレンジアミン系化
合物を含有することを特徴とする特許請求の範囲第１項
および第２項記載の電子写真感光体。(4) The photosensitive layer is composed of a laminated photoreceptor including at least a charge generation layer and a charge transport layer, and the charge transport layer has the general formula [
The electrophotographic photoreceptor according to claims 1 and 2, characterized in that it contains m-phenylenediamine compounds represented by [I] and [II].
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63187313A JP2657996B2 (en) | 1988-07-27 | 1988-07-27 | Electrophotographic photoreceptor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63187313A JP2657996B2 (en) | 1988-07-27 | 1988-07-27 | Electrophotographic photoreceptor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0237357A true JPH0237357A (en) | 1990-02-07 |
| JP2657996B2 JP2657996B2 (en) | 1997-09-30 |
Family
ID=16203816
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63187313A Expired - Fee Related JP2657996B2 (en) | 1988-07-27 | 1988-07-27 | Electrophotographic photoreceptor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2657996B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59175486A (en) * | 1983-03-26 | 1984-10-04 | Nippon Nohyaku Co Ltd | 4,5-dihydroxy-1,3-dithiolan-2-indenmalonic acid derivative and its use |
| EP0687668A3 (en) * | 1994-05-30 | 1996-09-25 | Mita Industrial Co Ltd | m-Phenylenediamine derivatives and electrophotosensitive material using the same |
| JP2007011315A (en) * | 2005-06-01 | 2007-01-18 | Mitsubishi Chemicals Corp | Electrophotographic photoreceptor, electrophotographic photoreceptor cartridge, and image forming apparatus |
-
1988
- 1988-07-27 JP JP63187313A patent/JP2657996B2/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59175486A (en) * | 1983-03-26 | 1984-10-04 | Nippon Nohyaku Co Ltd | 4,5-dihydroxy-1,3-dithiolan-2-indenmalonic acid derivative and its use |
| JPH0439470B2 (en) * | 1983-03-26 | 1992-06-29 | ||
| EP0687668A3 (en) * | 1994-05-30 | 1996-09-25 | Mita Industrial Co Ltd | m-Phenylenediamine derivatives and electrophotosensitive material using the same |
| JP2007011315A (en) * | 2005-06-01 | 2007-01-18 | Mitsubishi Chemicals Corp | Electrophotographic photoreceptor, electrophotographic photoreceptor cartridge, and image forming apparatus |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2657996B2 (en) | 1997-09-30 |
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