JP3171755B2 - Electrophotographic photoreceptor - Google Patents
Electrophotographic photoreceptorInfo
- Publication number
- JP3171755B2 JP3171755B2 JP17439594A JP17439594A JP3171755B2 JP 3171755 B2 JP3171755 B2 JP 3171755B2 JP 17439594 A JP17439594 A JP 17439594A JP 17439594 A JP17439594 A JP 17439594A JP 3171755 B2 JP3171755 B2 JP 3171755B2
- Authority
- JP
- Japan
- Prior art keywords
- examples
- phenylenediamine derivative
- phenylenediamine
- charge
- general formula
- 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.)
- Expired - Fee Related
Links
- 108091008695 photoreceptors Proteins 0.000 title claims description 44
- 150000004986 phenylenediamines Chemical class 0.000 claims description 127
- 239000003795 chemical substances by application Substances 0.000 claims description 58
- 239000010410 layer Substances 0.000 claims description 51
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 48
- 125000000217 alkyl group Chemical group 0.000 claims description 38
- 239000002356 single layer Substances 0.000 claims description 22
- 239000000758 substrate Substances 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 11
- 125000001424 substituent group Chemical group 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 3
- 125000006267 biphenyl group Chemical group 0.000 claims description 2
- 239000003610 charcoal Substances 0.000 claims 1
- 230000035945 sensitivity Effects 0.000 description 35
- 229920005989 resin Polymers 0.000 description 34
- 239000011347 resin Substances 0.000 description 34
- 150000001875 compounds Chemical class 0.000 description 33
- 239000011230 binding agent Substances 0.000 description 28
- 230000000052 comparative effect Effects 0.000 description 25
- 239000000049 pigment Substances 0.000 description 19
- 125000003118 aryl group Chemical group 0.000 description 16
- 238000000576 coating method Methods 0.000 description 15
- 239000011248 coating agent Substances 0.000 description 14
- -1 hydrazone compounds Chemical class 0.000 description 14
- 150000004988 m-phenylenediamines Chemical class 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 7
- 150000004989 p-phenylenediamines Chemical class 0.000 description 7
- 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 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 238000012844 infrared spectroscopy analysis Methods 0.000 description 6
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000006467 substitution reaction Methods 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000003618 dip coating Methods 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 description 4
- 239000004417 polycarbonate Substances 0.000 description 4
- 229920000515 polycarbonate Polymers 0.000 description 4
- 125000003107 substituted aryl group Chemical group 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-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
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-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
- 238000004458 analytical method Methods 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 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 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- UDHAWRUAECEBHC-UHFFFAOYSA-N 1-iodo-4-methylbenzene Chemical compound CC1=CC=C(I)C=C1 UDHAWRUAECEBHC-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
- 206010034972 Photosensitivity reaction Diseases 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 150000001716 carbazoles Chemical class 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 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
- 230000003287 optical effect Effects 0.000 description 2
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 2
- 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 2
- 230000036211 photosensitivity Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 2
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- DNXIASIHZYFFRO-UHFFFAOYSA-N pyrazoline Chemical compound C1CN=NC1 DNXIASIHZYFFRO-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-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
- 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
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 1
- DUQFCMVIJVWQMX-UHFFFAOYSA-N 1-ethyl-4-(4-iodophenyl)benzene Chemical group C1=CC(CC)=CC=C1C1=CC=C(I)C=C1 DUQFCMVIJVWQMX-UHFFFAOYSA-N 0.000 description 1
- VLCPISYURGTGLP-UHFFFAOYSA-N 1-iodo-3-methylbenzene Chemical compound CC1=CC=CC(I)=C1 VLCPISYURGTGLP-UHFFFAOYSA-N 0.000 description 1
- QUTZMKSKWOZVNY-UHFFFAOYSA-N 1-n,1-n,2-n,2-n-tetrakis(3-methylphenyl)benzene-1,2-diamine Chemical compound CC1=CC=CC(N(C=2C=C(C)C=CC=2)C=2C(=CC=CC=2)N(C=2C=C(C)C=CC=2)C=2C=C(C)C=CC=2)=C1 QUTZMKSKWOZVNY-UHFFFAOYSA-N 0.000 description 1
- KAHJCJLXCFPNGK-UHFFFAOYSA-N 1-n,1-n,2-n,2-n-tetrakis(4-methylphenyl)benzene-1,2-diamine Chemical compound C1=CC(C)=CC=C1N(C=1C(=CC=CC=1)N(C=1C=CC(C)=CC=1)C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 KAHJCJLXCFPNGK-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
- FVNMKGQIOLSWHJ-UHFFFAOYSA-N 2,4,5,7-tetranitroxanthen-9-one Chemical compound C1=C([N+]([O-])=O)C=C2C(=O)C3=CC([N+](=O)[O-])=CC([N+]([O-])=O)=C3OC2=C1[N+]([O-])=O FVNMKGQIOLSWHJ-UHFFFAOYSA-N 0.000 description 1
- VHQGURIJMFPBKS-UHFFFAOYSA-N 2,4,7-trinitrofluoren-9-one Chemical compound [O-][N+](=O)C1=CC([N+]([O-])=O)=C2C3=CC=C([N+](=O)[O-])C=C3C(=O)C2=C1 VHQGURIJMFPBKS-UHFFFAOYSA-N 0.000 description 1
- WCQLACGUXBFKGM-UHFFFAOYSA-N 2-(2,4,7-trinitro-1-oxo-2h-fluoren-9-ylidene)propanedinitrile Chemical compound [O-][N+](=O)C1=CC=C2C(C(=CC(C3=O)[N+](=O)[O-])[N+]([O-])=O)=C3C(=C(C#N)C#N)C2=C1 WCQLACGUXBFKGM-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
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-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
- QJQMLCUZRRVCPJ-UHFFFAOYSA-N 4-(3,5-ditert-butyl-4-oxocyclohexa-2,5-dien-1-ylidene)-2,6-dimethylcyclohexa-2,5-dien-1-one Chemical compound C1=C(C)C(=O)C(C)=CC1=C1C=C(C(C)(C)C)C(=O)C(C(C)(C)C)=C1 QJQMLCUZRRVCPJ-UHFFFAOYSA-N 0.000 description 1
- DDTHMESPCBONDT-UHFFFAOYSA-N 4-(4-oxocyclohexa-2,5-dien-1-ylidene)cyclohexa-2,5-dien-1-one Chemical compound C1=CC(=O)C=CC1=C1C=CC(=O)C=C1 DDTHMESPCBONDT-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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- IVAVGWRLVNSEPZ-UHFFFAOYSA-N C(C)C1=CC=C(C=C1)C1=CC=C(C=C1)NC1=C(C=CC=C1)N Chemical compound C(C)C1=CC=C(C=C1)C1=CC=C(C=C1)NC1=C(C=CC=C1)N IVAVGWRLVNSEPZ-UHFFFAOYSA-N 0.000 description 1
- LZXFIGHMLNXKOX-UHFFFAOYSA-N CNC(C=C1)=CC=C1C(C=C1)=NN1C(C=C1)=CC=C1NC Chemical class CNC(C=C1)=CC=C1C(C=C1)=NN1C(C=C1)=CC=C1NC LZXFIGHMLNXKOX-UHFFFAOYSA-N 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
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 235000000177 Indigofera tinctoria Nutrition 0.000 description 1
- 239000004640 Melamine resin Substances 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
- 229930192627 Naphthoquinone Natural products 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
- 239000004698 Polyethylene 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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-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
- 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
- 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
- 239000000654 additive Substances 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
- 150000001412 amines Chemical class 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
- 238000010533 azeotropic distillation Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical class C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process 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
- 238000007664 blowing Methods 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
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 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
- 239000011521 glass Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 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
- 239000000314 lubricant Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 150000002791 naphthoquinones Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-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
- 150000004866 oxadiazoles Chemical class 0.000 description 1
- 150000002916 oxazoles Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer 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
- 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
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer 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
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003217 pyrazoles Chemical class 0.000 description 1
- 150000003219 pyrazolines Chemical class 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon 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
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000001256 steam distillation Methods 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical class C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 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
- 238000003786 synthesis reaction Methods 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
- UGNWTBMOAKPKBL-UHFFFAOYSA-N tetrachloro-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(Cl)=C(Cl)C1=O UGNWTBMOAKPKBL-UHFFFAOYSA-N 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
- PCCVSPMFGIFTHU-UHFFFAOYSA-N tetracyanoquinodimethane Chemical compound N#CC(C#N)=C1C=CC(=C(C#N)C#N)C=C1 PCCVSPMFGIFTHU-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
- IBBLKSWSCDAPIF-UHFFFAOYSA-N thiopyran Chemical compound S1C=CC=C=C1 IBBLKSWSCDAPIF-UHFFFAOYSA-N 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
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical class C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 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
- 239000006097 ultraviolet radiation absorber Substances 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
- 238000007740 vapor deposition Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Landscapes
- Electroluminescent Light Sources (AREA)
- Luminescent Compositions (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Photovoltaic Devices (AREA)
- Photoreceptors In Electrophotography (AREA)
Description
【０００１】[0001]
【産業上の利用分野】この発明は、新規なフェニレンジ
アミン誘導体を用いた、静電式複写機やレーザービーム
プリンタ等の画像形成装置に使用される電子写真感光体
に関するものである。BACKGROUND OF THE INVENTION This invention is a new phenylenediamine induced body used, it relates to an electrophotographic photoreceptor used in an image forming apparatus such as electrostatic copying machines and laser beam printers.
【０００２】[0002]
【従来の技術】電子写真感光体に使用される電荷輸送剤
としては、カルバゾール系化合物、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、ス
チルベン系化合物、フェニレンジアミン系化合物、ベン
ジジン系化合物等の種々の有機化合物が知られている。2. Description of the Related Art Charge transporting agents used in electrophotographic photoreceptors include carbazole compounds, oxadiazole compounds, pyrazoline compounds, hydrazone compounds, stilbene compounds, phenylenediamine compounds, benzidine compounds, and the like. Are known.
【０００３】これら電荷輸送剤は、通常、適当な結着樹
脂からなる膜中に分散された状態で使用される。すなわ
ち上記電荷輸送剤を、光照射により電荷を発生する電荷
発生剤とともに結着樹脂中に分散した単層型の感光層を
備えた単層型感光体や、上記電荷輸送剤を含有する電荷
輸送層と、電荷発生剤を含有する電荷発生層とを備えた
積層型感光体等の、いわゆる有機感光体（ＯＰＣ）が多
く使用されている。[0003] These charge transporting agents are usually used in a state of being dispersed in a film made of a suitable binder resin. Sand
The Chi the electric charge transferring material, or a single layer type photosensitive member having a photosensitive layer of single layer type dispersed in the binder resin together with the charge generating agent that generates charges by light irradiation, the charge transport containing the charge transporting material A so-called organic photoconductor (OPC) such as a laminated photoconductor including a layer and a charge generating layer containing a charge generating agent is often used.
【０００４】かかる有機感光体は、無機半導体材料を用
いた無機感光体に比べて製造が容易であるとともに、上
記電荷発生剤、電荷輸送剤、結着樹脂等の選択肢が多様
であり、機能設計の自由度が大きいという利点がある。
上記各電荷輸送剤のうちフェニレンジアミン系化合物と
しては、下記一般式(2) で表されるｍ−フェニレンジア
ミン誘導体や、一般式(3) で表されるｐ−フェニレンジ
アミン誘導体が一般的に用いられている。Such an organic photoreceptor is easier to manufacture than an inorganic photoreceptor using an inorganic semiconductor material, and has a variety of options such as the above-described charge generator, charge transport agent, binder resin, etc. There is an advantage that the degree of freedom is large.
As the phenylenediamine-based compound among the above charge transporting agents, m-phenylenediamine derivatives represented by the following general formula (2) and p-phenylenediamine derivatives represented by the general formula (3) are generally used. Have been.
【０００５】[0005]
【化３】 Embedded image
【０００６】（両式中Ｒ5 ，Ｒ6 ，Ｒ7 およびＲ8 は同
一または異なって水素原子、アルキル基、アルコキシ
基、ハロゲン原子、もしくは置換基を有するまたは有さ
ないアリール基を示す。〕(In both formulas, R 5 , R 6 , R 7 and R 8 are the same or different and represent a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, or an aryl group having or not having a substituent.)
【０００７】[0007]
【発明が解決しようとする課題】上記のうち、一般式
(3) で表されるｐ−フェニレンジアミン誘導体は、中心
骨格を構成する２つの窒素原子の、ベンゼン環への置換
位置がｐ位であり、分子構造の対称性が高いために分子
間の相互作用が強く、したがって結着樹脂との相溶性が
悪い。加えて、それ自体の電荷輸送能力も十分でない。Among the above, the general formula
In the p-phenylenediamine derivative represented by (3), the two nitrogen atoms constituting the central skeleton are substituted at the p-position on the benzene ring, and the mutual symmetry of the molecular structure is high. The action is strong, and therefore, the compatibility with the binder resin is poor. In addition, the charge transport capability of itself is not sufficient.
【０００８】一方、一般式(2) で表されるように、２つ
の窒素原子の、ベンゼン環への置換位置がｍ位であるｍ
−フェニレンジアミン誘導体は、上記ｐ−フェニレンジ
アミン誘導体に比べると分子構造の対称性は低い。しか
し、たとえば式(2) 中の置換基Ｒ5 〜Ｒ8 が、いずれも
フェニル基の４位に置換したｍ−フェニレンジアミン誘
導体は、未だ分子構造の対称性が十分に低くなっておら
ず、結着樹脂との相溶性が十分に改善されていないた
め、材料自体は電荷輸送能力にすぐれることが予測され
ているが、たとえばこれを電荷輸送剤として使用した電
子写真感光体は、上記のようなすぐれた電荷輸送能力が
十分に発揮されず、光感度が十分でないという問題があ
る。On the other hand, as represented by the general formula (2), the m-position at which the substitution position of two nitrogen atoms on the benzene ring is m-position.
-The phenylenediamine derivative has a lower molecular structure symmetry than the p-phenylenediamine derivative. However, for example, the m-phenylenediamine derivative in which all of the substituents R 5 to R 8 in the formula (2) are substituted at the 4-position of the phenyl group has not yet had a sufficiently low symmetry in the molecular structure, Since the compatibility with the binder resin has not been sufficiently improved, the material itself is expected to have excellent charge transporting ability.For example, the electrophotographic photoreceptor using this as a charge transporting agent has the above-mentioned properties. There is a problem that such excellent charge transporting ability is not sufficiently exhibited, and that the photosensitivity is not sufficient.
【０００９】また上記置換基Ｒ5〜Ｒ8が、いずれもフェ
ニル基の３位に置換したｍ−フェニレンジアミン誘導体
は、分子構造の対称性が低く、結着樹脂との相溶性にす
ぐれるものの、それ自体の電荷輸送能力が十分でないた
め、これを電荷輸送剤として使用した電子写真感光体
は、やはり光感度が十分でないという問題がある。 The m-phenylenediamine derivative in which the above substituents R 5 to R 8 are all substituted at the 3-position of the phenyl group has low symmetry of the molecular structure and excellent compatibility with the binder resin. However, since the charge transporting ability of the electrophotographic photosensitive member itself is not sufficient, there is a problem that the photosensitivity of the electrophotographic photosensitive member using the charge transporting agent is not sufficient .
【００１０】この発明の目的は、電荷輸送能力にすぐれ
るとともに結着樹脂との相溶性にもすぐれた、新規なフ
ェニレンジアミン誘導体を電荷輸送剤として含有し、高
感度の電子写真感光体を提供することにある。[0010] The purpose is of this invention, excellent in charge transport capability
Another object of the present invention is to provide a high- sensitivity electrophotographic photoreceptor which contains a novel phenylenediamine derivative as a charge transporting agent and has excellent compatibility with a binder resin .
【００１１】[0011]
【課題を解決するための手段および作用】上記課題を解
決するため、発明者らは、フェニレンジアミン誘導体の
分子構造の対称性を低くして、結着樹脂との相溶性を向
上し、かつ電荷輸送能力も向上することを検討し、その
方針に沿って分子設計を行った。その結果、(1) フェニ
レンジアミン誘導体の中心骨格を構成する２つの窒素原
子の、ベンゼン環への置換位置をｍ位からｏ位に変更す
ると、電荷輸送能力が向上すること、(2) またこのｏ置
換のフェニレンジアミン誘導体は、両窒素原子に置換し
たフェニル基の立体障害により、ｍ−フェニレンジアミ
ン誘導体では平面であった分子構造にわずかなねじれが
生じて対称性が低下し、結着樹脂との相溶性が向上する
こと、を見出し、この発明を完成するに至った。In order to solve the above-mentioned problems, the present inventors have reduced the symmetry of the molecular structure of the phenylenediamine derivative, improved the compatibility with the binder resin, and improved the chargeability. We considered improving the transport capacity and designed the molecule in accordance with that policy. As a result, (1) when the substitution position of the two nitrogen atoms constituting the central skeleton of the phenylenediamine derivative to the benzene ring is changed from the m-position to the o-position, the charge transport ability is improved, and (2) The o-substituted phenylenediamine derivative has a slight twist in the planar molecular structure of the m-phenylenediamine derivative due to the steric hindrance of the phenyl group substituted on both nitrogen atoms, the symmetry is reduced, and the Have been found to improve the compatibility of the present invention, and have completed the present invention.
【００１２】すなわちこの発明の電子写真感光体は、導
電性基体上に、一般式(1)：That is, the electrophotographic photosensitive member of the present invention is
On an electrically conductive substrate, the general formula (1):
【００１３】[0013]
【化４】 Embedded image
【００１４】〔式中Ｒ1，Ｒ2，Ｒ3およびＲ4は同一また
は異なって炭素数１〜６のアルキル基、炭素数１〜６の
アルコキシ基、もしくは置換基として炭素数１〜６のア
ルキル基を有するまたは有さないフェニル基、またはビ
フェニル基を示す。ｍ，ｎ，ｐおよびｑは同一または異
なって０〜３の整数を示す。〕で表されるフェニレンジ
アミン誘導体を含む感光層を設けたことを特徴とする。[0014] [wherein R 1, R 2, R 3 and R 4 are the same or different alkyl group of 1 to 6 carbon atoms, <br/> alkoxy group having 1 to 6 carbon atoms, and also properly substituent C 1-6
A phenyl group with or without an alkyl group , or
Indicates a phenyl group . m, n, p and q are the same or different and represent an integer of 0-3. Phenylenediamine represented by]
A photosensitive layer containing an amine derivative is provided .
【００１５】以下にこの発明を説明する。上記一般式
(1)中の基Ｒ1，Ｒ2，Ｒ3，Ｒ4に相当するアルキル基と
しては、たとえばメチル基、エチル基、プロピル基、イ
ソプロピル基、ブチル基、イソブチル基、tert−ブチル
基、ペンチル基、ヘキシル基等の、炭素数１〜６の低級
アルキル基があげられる。The present invention will be described below. The above general formula
Examples of the alkyl group corresponding to the groups R 1 , R 2 , R 3 and R 4 in (1) include, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl And lower alkyl groups having 1 to 6 carbon atoms such as a hexyl group and a hexyl group.
【００１６】またアルコキシ基としては、たとえばメト
キシ基、エトキシ基、イソプロポキシ基、ブトキシ基、
tert−ブトキシ基、ヘキシルオキシ基等の、炭素数１〜
６のアルコキシ基があげられる。 The alkoxy group includes, for example, methoxy, ethoxy, isopropoxy, butoxy,
tert- butoxy group, a hexyl group, 1 carbon atoms
And 6 alkoxy groups .
【００１７】フェニル基、またはビフェニル基に置換し
てもよい置換基としては、上記炭素数１〜６のアルキル
基があげられる。一般式(1)中の符号ｍ，ｎ，ｐおよび
ｑで規定される上記各基の置換数は、いずれも０〜３の
範囲で任意に選択できるが、ｍ，ｎ，ｐおよびｑがいず
れも０であるフェニレンジアミン誘導体は、前記分子構
造の非対称性にも拘らず、結着樹脂との相溶性が低いの
で、ｍ，ｎ，ｐおよびｑは同時に０でないのが好まし
い。また製造の容易さ等を考慮すると、ｍ，ｎ，ｐおよ
びｑは上記範囲内でも少ない方が好ましく、３より２、
２より１であるのが好ましい。[0017] As a phenyl group or a biphenyl group substituted with the substituent be in, the alkyl groups of 1 to 6 carbon atoms and the like. The number of substitutions of each of the above groups defined by the symbols m, n, p and q in the general formula (1) can be arbitrarily selected in the range of 0 to 3, but any of m, n, p and q can be selected. Since the phenylenediamine derivative, which is also 0, has low compatibility with the binder resin irrespective of the asymmetry of the molecular structure, m, n, p and q are preferably not simultaneously 0. In consideration of the ease of production, etc., it is preferable that m, n, p and q are smaller even within the above range, and it is more preferable that m, n, p and q be 2,
It is preferably 1 rather than 2.
【００１８】フェニレンジアミン誘導体の具体例として
は、たとえば基Ｒ1 ，Ｒ4 が互いに同じアルキル基で、
かつ基Ｒ2 ，Ｒ3 が上記Ｒ1 ，Ｒ4 と同じまたは違う、
互いに同じアルキル基で、ｍ，ｎ，ｐ，ｑが１または２
である化合物があげられる。上記のうちｍ，ｎ，ｐ，ｑ
がいずれも１であるフェニレンジアミン誘導体として
は、基Ｒ1 〜Ｒ4 がいずれもフェニル基の３位または４
位に置換した化合物があげられる。このうち前者の、基
Ｒ1 〜Ｒ4 がいずれもフェニル基の３位に置換したフェ
ニレンジアミン誘導体は、とくに結着樹脂との相溶性が
よく、後者の、基Ｒ1 〜Ｒ4 がいずれもフェニル基の４
位に置換したフェニレンジアミン誘導体は、とくに電荷
輸送能力にすぐれるとともに、結着樹脂との相溶性も実
用化に供し得るレベルである。As a specific example of the phenylenediamine derivative, for example, the groups R 1 and R 4 are the same alkyl group,
And groups R 2 and R 3 are the same as or different from R 1 and R 4 described above;
M, n, p, q are 1 or 2
The compound which is is mentioned. M, n, p, q
Is a phenylenediamine derivative wherein all of the groups R 1 to R 4 are 3 or 4 of the phenyl group.
And the like. Of these, the former, a phenylenediamine derivative in which all of the groups R 1 to R 4 are substituted at the 3-position of the phenyl group, has particularly good compatibility with the binder resin, and all of the latter, the groups R 1 to R 4, Phenyl group 4
The substituted phenylenediamine derivative is particularly excellent in charge transporting ability, and has a compatibility with a binder resin at a level that can be put to practical use.
【００１９】上記のうち基Ｒ1 〜Ｒ4 がいずれもフェニ
ル基の３位に置換したフェニレンジアミン誘導体の具体
的化合物としては、これに限定されないが、たとえば式
(4)：Specific examples of the phenylenediamine derivative in which all of the groups R 1 to R 4 are substituted at the 3-position of the phenyl group include, but are not limited to,
(Four):
【００２０】[0020]
【化５】 Embedded image
【００２１】で表される化合物があげられる。また、上
記のうち基Ｒ1 〜Ｒ4 がいずれもフェニル基の４位に置
換したフェニレンジアミン誘導体の具体的化合物として
は、これに限定されないが、たとえば式(5)(6)：The compound represented by the following formula: Specific examples of the phenylenediamine derivative in which all of the groups R 1 to R 4 are substituted at the 4-position of the phenyl group include, but are not limited to, for example, compounds of the formulas (5) and (6):
【００２２】[0022]
【化６】 Embedded image
【００２３】で表される化合物があげられる。また、
ｍ，ｎ，ｐ，ｑがいずれも２であるフェニレンジアミン
誘導体としては、とくに電荷輸送能力を考慮すると、各
フェニル基に置換する２つの基のうちの１つが、フェニ
ル基の４位に置換した化合物が好適に採用される。この
フェニレンジアミン誘導体は、先の、ｍ，ｎ，ｐ，ｑが
いずれも１であるフェニレンジアミン誘導体のうち、基
Ｒ1 〜Ｒ4 がいずれもフェニル基の４位に置換したもの
よりも、さらに電荷輸送能力にすぐれている。The compound represented by the following formula: Also,
As the phenylenediamine derivative in which m, n, p, and q are all 2, particularly considering the charge transporting ability, one of the two groups substituted for each phenyl group is substituted at the 4-position of the phenyl group. Compounds are suitably employed. This phenylenediamine derivative is more evident than the phenylenediamine derivative in which m, n, p, and q are all 1, wherein all of the groups R 1 to R 4 are substituted at the 4-position of the phenyl group. Excellent charge transport capability.
【００２４】上記フェニレンジアミン誘導体の具体的化
合物としては、これに限定されないが、たとえば式(7)
(8)：Specific examples of the phenylenediamine derivative include, but are not limited to, compounds of the formula (7)
(8):
【００２５】[0025]
【化７】 Embedded image
【００２６】で表される化合物があげられる。またフェ
ニレンジアミン誘導体の他の具体例としては、たとえば
基Ｒ1 ，Ｒ4が互いに同じアルキル基で、かつ基Ｒ2 ，
Ｒ3 が互いに同じアリール基で、ｍ，ｎ，ｐ，ｑが１で
ある化合物や、あるいは基Ｒ1 ，Ｒ4 が互いに同じアリ
ール基で、かつ基Ｒ2 ，Ｒ3 が上記Ｒ1 ，Ｒ4 と同じま
たは違う互いに同じアリール基で、ｍ，ｎ，ｐ，ｑが１
である化合物があげられる。The compound represented by the following formula: As another specific example of the phenylenediamine derivative, for example, the groups R 1 and R 4 are the same alkyl group and the groups R 2 and R 2
A compound in which R 3 is the same aryl group and m, n, p and q are 1 or a group in which the groups R 1 and R 4 are the same aryl group and the groups R 2 and R 3 are the above R 1 and R The same or different aryl groups as in 4, wherein m, n, p, and q are 1
The compound which is is mentioned.
【００２７】これらのフェニレンジアミン誘導体はいず
れも、アリール基によってπ電子共役系が大きく拡がる
ため、とくに電荷輸送能力にすぐれている。基Ｒ1 〜Ｒ
4 に相当するアリール基は、立体障害等を考慮すると、
いずれもフェニル基の４位に置換するのが好ましい。ま
たとくに基Ｒ1 〜Ｒ4 がいずれも同じアリール基である
場合には、結着樹脂との相溶性を確保するために、各ア
リール基に置換基を置換させるのが好ましい。置換基の
置換位置はとくに限定されないが、たとえばアリール基
がフェニル基である場合、当該フェニル基の４位に置換
基を置換させたものは、さらに電荷輸送能力にすぐれて
いる。All of these phenylenediamine derivatives are particularly excellent in charge transport ability because the π-electron conjugate system is greatly expanded by the aryl group. Groups R 1 to R
Aryl group corresponding to 4 , considering steric hindrance and the like,
In any case, substitution at the 4-position of the phenyl group is preferred. In particular, when the groups R 1 to R 4 are all the same aryl group, it is preferable to substitute a substituent for each aryl group in order to ensure compatibility with the binder resin. The substitution position of the substituent is not particularly limited. For example, when the aryl group is a phenyl group, the phenyl group obtained by substituting the substituent at the 4-position has further excellent charge transport ability.
【００２８】上記のうち前者の、基Ｒ1 ，Ｒ4 がアルキ
ル基で、かつ基Ｒ2 ，Ｒ3 がアリール基で、ｍ，ｎ，
ｐ，ｑが１であるフェニレンジアミン誘導体の具体的化
合物としては、これに限定されないが、たとえば式(9)
(10) ：Of the above, groups R 1 and R 4 are alkyl groups, groups R 2 and R 3 are aryl groups, and m, n,
Specific examples of the phenylenediamine derivative in which p and q are 1 include, but are not limited to, compounds of the formula (9)
(Ten) :
【００２９】[0029]
【化８】 Embedded image
【００３０】で表される化合物があげられる。また後者
の、基Ｒ1 〜Ｒ4 がアリール基で、ｍ，ｎ，ｐ，ｑが１
であるフェニレンジアミン誘導体の具体的化合物として
は、これに限定されないが、たとえば式(11)：The compound represented by the following formula: The latter groups R 1 to R 4 are aryl groups and m, n, p and q are 1
Specific examples of the phenylenediamine derivative represented by the following formula (11) include, but are not limited to, formula (11):
【００３１】[0031]
【化９】 Embedded image
【００３２】で表される化合物があげられる。上記フェ
ニレンジアミン誘導体は、種々の方法で合成することが
できる。たとえば前記式(5)のフェニレンジアミン誘導
体は、下記反応工程式にしたがって合成することができ
る。すなわち、式(12)で表されるｏ−フェニレンジアミ
ンと、式(13)で表されるｐ−ヨードトルエンとを、モル
比で１：４の割合で、銅粉、酸化銅あるいはハロゲン化
銅などと共に混合し、塩基性物質の存在下で反応させる
と、式(5)のフェニレンジアミン誘導体が合成される。The compound represented by the following formula: The phenylenediamine derivative can be synthesized by various methods. For example, the phenylenediamine derivative of the formula (5) can be synthesized according to the following reaction step formula. That is, o-phenylenediamine represented by the formula (12) and p-iodotoluene represented by the formula (13) are mixed at a molar ratio of 1: 4 with copper powder, copper oxide or copper halide. And reacting in the presence of a basic substance, a phenylenediamine derivative of formula (5) is synthesized.
【００３３】[0033]
【化１０】 Embedded image
【００３４】この発明の電子写真感光体は、前記一般式
(1)で表されるフェニレンジアミン誘導体の１種または
２種以上を含む感光層を、導電性基体上に設けたもので
ある。感光層には、いわゆる単層型感光層と積層型感光
層とがあるが、この発明はこのいずれにも適用可能であ
る。The electrophotographic photosensitive member of this invention, the general formula
A photosensitive layer containing one or more of the phenylenediamine derivatives represented by (1) is provided on a conductive substrate. The photosensitive layer includes a so-called single-layer photosensitive layer and a laminated photosensitive layer, and the present invention can be applied to any of them.
【００３５】単層型の感光層は、電荷輸送剤である、一
般式(1) で表されるフェニレンジアミン誘導体を、電荷
発生剤、結着樹脂等とともに適当な溶媒に溶解または分
散した塗布液を、塗布等の手段によって導電性基体上に
塗布し、乾燥させることで形成される。また積層型の感
光層は、まず導電性基体上に、蒸着または塗布等の手段
によって、電荷発生剤を含有する電荷発生層を形成し、
ついでこの電荷発生層上に、電荷輸送剤である一般式
(1) で表されるフェニレンジアミン誘導体と結着樹脂と
を含む塗布液を、塗布等の手段によって塗布し、乾燥さ
せて電荷輸送層を形成することで形成される。また上記
とは逆に、導電性基体上に電荷輸送層を形成し、その上
に電荷発生層を形成してもよい。The single-layer type photosensitive layer is formed by dissolving or dispersing a phenylenediamine derivative represented by the general formula (1), which is a charge transporting agent, in a suitable solvent together with a charge generating agent, a binder resin and the like. Is applied on a conductive substrate by a means such as application and dried. In addition, the laminated type photosensitive layer first forms a charge generation layer containing a charge generation agent on a conductive substrate by means such as vapor deposition or coating,
Then, on this charge generation layer, a general formula of a charge transport agent
It is formed by applying a coating solution containing the phenylenediamine derivative represented by (1) and a binder resin by means such as coating and drying to form a charge transport layer. Conversely, a charge transport layer may be formed on a conductive substrate, and a charge generation layer may be formed thereon.
【００３６】電荷発生剤としては、これに限定されるも
のではないが、たとえばセレン、セレン−テルル、セレ
ン−ヒ素、硫化カドミウム、α−シリコン等の無機光導
電材料の粉末、アゾ系顔料、ペリレン系顔料、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、キナクリドン系顔料、
ジチオケトピロロピロール系顔料等があげられる。これ
ら電荷発生剤は、電子写真感光体の感度領域等に合わせ
て、それぞれ単独で使用される他、２種以上を併用する
こともできる。Examples of the charge generator include, but are not limited to, powders of inorganic photoconductive materials such as selenium, selenium-tellurium, selenium-arsenic, cadmium sulfide, α-silicon, azo pigments, perylene Pigments, anthanthrone pigments, phthalocyanine pigments, indigo pigments, triphenylmethane pigments, sulene pigments, toluidine pigments, pyrazoline pigments, quinacridone pigments,
And dithioketopyrrolopyrrole pigments. These charge generating agents may be used alone or in combination of two or more in accordance with the sensitivity range of the electrophotographic photoreceptor.
【００３７】たとえば７００ｎｍ以上の波長領域に感度
を有する有機感光体に好適な電荷発生剤としては、Ｘ型
無金属フタロシアニン、オキソチタニルフタロシアニン
等のフタロシアニン系顔料があげられる。これらフタロ
シアニン系顔料を電荷発生剤として使用するとともに、
前記一般式(1) で表されるこの発明のフェニレンジアミ
ン誘導体を電荷輸送剤として使用した電子写真感光体
は、上記波長領域において高感度であり、たとえばレー
ザービームプリンタ、ファクシミリ等のデジタル光学系
の画像形成装置等に好適に使用することができる。For example, phthalocyanine pigments such as X-type non-metallic phthalocyanine and oxotitanyl phthalocyanine can be used as a charge generating agent suitable for an organic photoreceptor having a sensitivity in a wavelength region of 700 nm or more. While using these phthalocyanine pigments as a charge generating agent,
An electrophotographic photoreceptor using the phenylenediamine derivative of the present invention represented by the general formula (1) as a charge transporting agent has high sensitivity in the above wavelength range, and is, for example, a laser beam printer, a digital optical system such as a facsimile. It can be suitably used for an image forming apparatus and the like.
【００３８】一方、可視領域において高感度な有機感光
体に好適な電荷発生材料としては、アゾ系顔料やペリレ
ン系顔料等があげられる。これらの顔料を電荷発生剤と
して使用するとともに、前記一般式(1) で表されるこの
発明のフェニレンジアミン誘導体を電荷輸送剤として使
用した電子写真感光体は、可視領域において高感度であ
り、たとえば静電式複写機等のアナログ光学系の画像形
成装置等に好適に使用することができる。On the other hand, examples of the charge generating material suitable for an organic photoreceptor having high sensitivity in the visible region include azo pigments and perylene pigments. An electrophotographic photoreceptor using these pigments as a charge generating agent and using the phenylenediamine derivative of the present invention represented by the general formula (1) as a charge transporting agent has high sensitivity in the visible region. It can be suitably used for an analog optical system image forming apparatus such as an electrostatic copying machine.
【００３９】電荷輸送剤である一般式(1) で表されるフ
ェニレンジアミン誘導体は、単独で使用できる他、従来
公知の他の電荷輸送剤と組み合わせて使用することもで
きる。他の電荷輸送剤としては、種々の電子輸送剤およ
び正孔輸送剤があげられる。電荷輸送剤のうち電子輸送
剤としては、たとえばジフェノキノン系化合物、ベンゾ
キノン系化合物、ナフトキノン系化合物、マロノニトリ
ル、チオピラン系化合物、テトラシアノエチレン、テト
ラシアノキノジメタン、クロルアニル、ブロモアニル、
２，４，７−トリニトロ−９−フルオレノン、２，４，
５，７−テトラニトロ−９−フルオレノン、２，４，７
−トリニトロ−９−ジシアノメチレンフルオレノン、
２，４，５，７−テトラニトロキサントン、２，４，８
−トリニトロチオキサントン、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の電子吸引性
材料や、これら電子吸引性材料を高分子化したもの等が
あげられる。The phenylenediamine derivative represented by the general formula (1), which is a charge transporting agent, can be used alone or in combination with other conventionally known charge transporting agents. Other charge transporting agents include various electron transporting and hole transporting agents. Among the charge transporting agents, examples of the electron transporting agent include diphenoquinone-based compounds, benzoquinone-based compounds, naphthoquinone-based compounds, malononitriles, thiopyran-based compounds, tetracyanoethylene, tetracyanoquinodimethane, chloranil, bromoanil,
2,4,7-trinitro-9-fluorenone, 2,4
5,7-tetranitro-9-fluorenone, 2,4,7
-Trinitro-9-dicyanomethylene fluorenone,
2,4,5,7-tetranitroxanthone, 2,4,8
-Electron-withdrawing materials such as trinitrothioxanthone, dinitrobenzene, dinitroanthracene, dinitroacridine, nitroanthraquinone, dinitroanthraquinone, succinic anhydride, maleic anhydride, and dibromomaleic anhydride, and these electron-withdrawing materials were polymerized. And the like.
【００４０】また正孔輸送剤としては、たとえば一般式
(1) で表されるフェニレンジアミン誘導体以外のジアミ
ン系化合物、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
等のスチリル系化合物、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系化合
物、ヒドラゾン系化合物、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で代表される含窒素環
式化合物、縮合多環式化合物などの電子供与性材料等が
あげられる。As the hole transporting agent, for example, those represented by the general formula
Diamine compounds other than the phenylenediamine derivative represented by (1), 2,5-di (4-methylaminophenyl)
Diazole compounds such as -1,3,4-oxadiazole, styryl compounds such as 9- (4-diethylaminostyryl) anthracene, carbazole compounds such as polyvinylcarbazole, 1-phenyl-3- (p-dimethylamino Pyrazoline compounds such as phenyl) pyrazoline, hydrazone compounds, triphenylamine compounds, indole compounds, oxazole compounds, isoxazole compounds, thiazole compounds, thiadiazole compounds, imidazole compounds, pyrazole compounds, triazole compounds Examples include electron-donating materials such as nitrogen-containing cyclic compounds represented by compounds and condensed polycyclic compounds.
【００４１】これら電荷輸送剤についても、それぞれ単
独で使用できる他、２種以上を併用することもできる。
なおポリビニルカルバゾール等の成膜性を有する電荷輸
送剤を用いる場合には、結着樹脂は必ずしも必要ではな
い。結着樹脂としては、たとえばスチレン系重合体、ス
チレン−ブタジエン共重合体、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、ポリア
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、さらにエポキシ−アクリレート、
ウレタン−アクリレート等の光硬化性樹脂等があげられ
る。これら結着樹脂は単独で使用できるほか、２種以上
を併用することもできる。These charge transporting agents can be used alone or in combination of two or more.
When a charge transporting agent having a film-forming property such as polyvinyl carbazole is used, a binder resin is not necessarily required. Examples of the binder resin include a styrene polymer, a styrene-butadiene copolymer, a styrene-acrylonitrile copolymer, a styrene-maleic acid copolymer, an acrylic polymer, a styrene-acrylic copolymer, polyethylene, and ethylene. -Vinyl acetate copolymer, chlorinated polyethylene, polyvinyl chloride, polypropylene, vinyl chloride-
Vinyl acetate copolymer, polyester, alkyd resin,
Thermoplastic resins such as polyamide, polyurethane, polycarbonate, polyarylate, polysulfone, diallyl phthalate resin, ketone resin, polyvinyl butyral resin, polyether resin, silicone resin, epoxy resin, phenol resin, urea resin, melamine resin and other cross-linkable Thermosetting resin, further epoxy-acrylate,
Photocurable resins such as urethane-acrylates and the like can be mentioned. These binder resins can be used alone or in combination of two or more.
【００４２】感光層には、上記各成分の他に、たとえば
増感剤、フルオレン系化合物、紫外線吸収剤、可塑剤、
界面滑性剤、レベリング剤等の種々の添加剤を添加する
こともできる。また感光体の感度を向上させるために、
たとえばターフェニル、ハロナフトキノン類、アセナフ
チレン等の増感剤を、電荷発生剤と併用してもよい。積
層感光体において、電荷発生層を構成する電荷発生剤と
結着樹脂とは、種々の割合で使用することができるが、
結着樹脂１００重量部に対して、電荷発生剤５〜１００
０重量部、特に３０〜５００重量部の割合で用いるのが
好ましい。In the photosensitive layer, in addition to the above components, for example, a sensitizer, a fluorene compound, an ultraviolet absorber, a plasticizer,
Various additives such as an interfacial lubricant and a leveling agent can also be added. Also, to improve the sensitivity of the photoconductor,
For example, sensitizers such as terphenyl, halonaphthoquinones, and acenaphthylene may be used in combination with the charge generator. In the laminated photoreceptor, the charge generating agent and the binder resin constituting the charge generating layer can be used in various ratios,
Charge generating agent 5-100 based on 100 parts by weight of binder resin
It is preferable to use 0 parts by weight, particularly 30 to 500 parts by weight.
【００４３】電荷輸送層を構成する電荷輸送剤と結着樹
脂とは、電荷の輸送を阻害しない範囲および結晶化しな
い範囲で、種々の割合で使用することができるが、光照
射により電荷発生層で生じた電荷が容易に輸送できるよ
うに、結着樹脂１００重量部に対して、一般式(1) で表
されるフェニレンジアミン誘導体を含む電荷輸送剤を総
量で１０〜５００重量部、特に２５〜２００重量部の割
合で用いるのが好ましい。上記電荷輸送剤の含有割合
は、電荷輸送剤として、一般式(1) で表されるフェニレ
ンジアミン誘導体を単独で使用する場合は、当該フェニ
レンジアミン誘導体の含有割合である。The charge transporting agent and the binder resin constituting the charge transporting layer can be used in various ratios within a range that does not hinder charge transport and a range that does not crystallize. In order to easily transport the charge generated in the above, the charge transport agent containing the phenylenediamine derivative represented by the general formula (1) is added in a total amount of 10 to 500 parts by weight, particularly 25 parts by weight, based on 100 parts by weight of the binder resin. Preferably, it is used in a proportion of up to 200 parts by weight. When the phenylenediamine derivative represented by the general formula (1) is used alone as the charge transport agent, the content ratio of the charge transport agent is the content ratio of the phenylenediamine derivative.
【００４４】また、積層型の感光層の厚さは、電荷発生
層が０．０１〜５μｍ程度、特に０．１〜３μｍ程度に
形成されるのが好ましく、電荷輸送層が２〜１００μ
ｍ、特に５〜５０μｍ程度に形成されるのが好ましい。
単層型の感光体においては、結着樹脂１００重量部に対
して電荷発生剤は０．１〜５０重量部、特に０．５〜３
０重量部、一般式(1) で表されるフェニレンジアミン誘
導体を含む電荷輸送剤は総量で２０〜５００重量部、特
に３０〜２００重量部であるのが適当である。上記電荷
輸送剤の含有割合は、電荷輸送剤として、一般式(1) で
表されるフェニレンジアミン誘導体を単独で使用する場
合は、当該フェニレンジアミン誘導体の含有割合であ
る。The thickness of the layered photosensitive layer is preferably such that the charge generation layer is formed to a thickness of about 0.01 to 5 μm, particularly about 0.1 to 3 μm, and the thickness of the charge transport layer is 2 to 100 μm.
m, particularly preferably about 5 to 50 μm.
In the case of a single-layer type photoreceptor, the charge generator is used in an amount of 0.1 to 50 parts by weight, particularly 0.5 to 3 parts by weight, based on 100 parts by weight of the binder resin.
The total amount of the charge transporting agent containing the phenylenediamine derivative represented by the general formula (1) is preferably 0 to 500 parts by weight, more preferably 30 to 200 parts by weight. When the phenylenediamine derivative represented by the general formula (1) is used alone as the charge transport agent, the content ratio of the charge transport agent is the content ratio of the phenylenediamine derivative.
【００４５】また、単層型の感光層の厚さは５〜１００
μｍ、特に１０〜５０μｍ程度に形成されるのが好まし
い。単層型感光体にあっては、導電性基体と感光層との
間に、また、積層型感光体にあっては、導電性基体と電
荷発生層との間や、導電性基体と電荷輸送層との間、ま
たは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。The thickness of the single-layer type photosensitive layer is 5 to 100.
It is preferably formed to a thickness of about μm, especially about 10 to 50 μm. In the case of a single layer type photoreceptor, between the conductive substrate and the photosensitive layer, and in the case of the laminated type photoreceptor, between the conductive substrate and the charge generation layer, or between the conductive substrate and the charge transport. A barrier layer may be formed between the charge transport layer and the charge generation layer or between the charge transport layer and the charge transport layer as long as the properties of the photoreceptor are not impaired. You may.
【００４６】上記各層が形成される導電性基体として
は、導電性を有する種々の材料を使用することができ、
たとえばアルミニウム、銅、スズ、白金、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、ステンレス鋼、真鍮等の
金属や、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、酸化スズ、酸化イン
ジウム等で被覆されたガラス等が例示される。Various conductive materials can be used as the conductive substrate on which the above layers are formed.
For example, metals such as aluminum, copper, tin, platinum, silver, vanadium, molybdenum, chromium, cadmium, titanium, nickel, palladium, indium, stainless steel, brass, etc .; plastic materials on which the above metals are deposited or laminated; aluminum iodide , Tin oxide, glass coated with indium oxide, and the like.
【００４７】導電性基体の形状は使用する画像形成装置
の構造に合わせて、シート状、ドラム状等のいずれであ
ってもよい。基体自体が導電性を有するか、あるいは基
体の表面が導電性を有していればよい。また、導電性基
体は、使用に際して、充分な機械的強度を有するものが
好ましい。感光体を構成する各層を、塗布の方法により
形成する場合には、前記例示の電荷発生剤、電荷輸送
剤、結着樹脂等を、適当な溶剤とともに、公知の方法、
たとえば、ロールミル、ボールミル、アトライタ、ペイ
ントシェーカーあるいは超音波分散器等を用いて分散混
合して塗布液を調整し、これを公知の手段により塗布、
乾燥すればよい。The shape of the conductive substrate may be any of a sheet shape, a drum shape and the like according to the structure of the image forming apparatus to be used. It is sufficient that the substrate itself has conductivity, or that the surface of the substrate has conductivity. In addition, the conductive substrate preferably has sufficient mechanical strength when used. When each layer constituting the photoreceptor is formed by a coating method, the above-described charge generating agent, charge transporting agent, binder resin and the like, together with a suitable solvent, a known method,
For example, a roll mill, a ball mill, an attritor, a paint shaker or an ultrasonic disperser or the like to disperse and mix to prepare a coating solution, and apply this by a known means.
It may be dried.
【００４８】塗布液をつくるための溶剤としては、種々
の有機溶剤が使用可能で、たとえばメタノール、エタノ
ール、イソプロパノール、ブタノール等のアルコール
類、ｎ−ヘキサン、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、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
アルデヒド、ジメチルホルムアミド、ジメチルスルホキ
シド等があげられる。これらの溶剤は１種又は２種以上
を混合して用いることができる。As the solvent for preparing the coating solution, various organic solvents can be used, for example, alcohols such as methanol, ethanol, isopropanol and butanol, aliphatic hydrocarbons such as n-hexane, octane and cyclohexane, and the like. Benzene, toluene, aromatic hydrocarbons such as xylene, dichloromethane, dichloroethane, carbon tetrachloride, halogenated hydrocarbons such as chlorobenzene, dimethyl ether, diethyl ether, tetrahydrofuran,
Ethers such as ethylene glycol dimethyl ether and diethylene glycol dimethyl ether; ketones such as acetone, methyl ethyl ketone and cyclohexanone; esters such as ethyl acetate and methyl acetate; dimethyl formaldehyde, dimethyl formamide, dimethyl sulfoxide and the like. These solvents can be used alone or in combination of two or more.
【００４９】さらに、電荷輸送剤や電荷発生剤の分散
性、感光層表面の平滑性をよくするため、塗布液には界
面活性剤、レベリング剤等を添加してもよい。Further, in order to improve the dispersibility of the charge transporting agent and the charge generating agent and the smoothness of the surface of the photosensitive layer, a surfactant, a leveling agent and the like may be added to the coating solution.
【００５０】[0050]
【実施例】以下にこの発明を、実施例、比較例に基づい
て説明する。 《フェニレンジアミン誘導体の合成》 実施例１ 前記式(12)で表されるｏ−フェニレンジアミン５．４ｇ
と、式(13)で表されるｐ−ヨードトルエン４２．６ｇと
を、２７．６ｇの炭酸カリウム、および２ｇの銅粉とと
もに、３００mlのニトロベンゼン中に加え、強く攪拌し
つつ、この反応系に窒素ガスを吹き込みながら２４時
間、還流させた。反応中に生成する水分は、ニトロベン
ゼンと共沸させて反応系外へ取り出した。The present invention will be described below with reference to examples and comparative examples. << Synthesis of phenylenediamine derivative >> Example 1 5.4 g of o-phenylenediamine represented by the above formula (12)
And 42.6 g of p-iodotoluene represented by the formula (13) are added to 300 ml of nitrobenzene together with 27.6 g of potassium carbonate and 2 g of copper powder. The mixture was refluxed for 24 hours while blowing nitrogen gas. Water generated during the reaction was taken out of the reaction system by azeotropic distillation with nitrobenzene.
【００５１】つぎに反応液を冷却後、無機物をろ別し、
さらに水蒸気蒸留によってニトロベンゼンを留去した残
渣をシクロヘキサンに溶解し、シリカゲルカラムクロマ
トグラフィーによって分離精製し、シクロヘキサンを留
去して白色沈澱を得た。そしてこの白色沈澱を、ｎ−ヘ
キサンを用いて再結晶させて、目的物である、前記式
(5) で表されるＮ，Ｎ，Ｎ′，Ｎ′−テトラキス（４−
メチルフェニル）−ｏ−フェニレンジアミンを得た。収
量は１２．２ｇ、収率は５２．１％であった。Next, after cooling the reaction solution, the inorganic substance was filtered off.
The residue from which nitrobenzene was distilled off by steam distillation was dissolved in cyclohexane, separated and purified by silica gel column chromatography, and cyclohexane was distilled off to obtain a white precipitate. The white precipitate was recrystallized using n-hexane to obtain the target compound represented by the above formula
N, N, N ', N'-tetrakis (4-
Methylphenyl) -o-phenylenediamine was obtained. The yield was 12.2 g, and the yield was 52.1%.
【００５２】上記化合物の赤外分光分析の結果を図１に
示す。またその他の分析結果を以下に示す。 元素分析結果 計算値（％） Ｃ：８７．１５ Ｈ：６．８８ Ｎ：
５．９８ 実測値（％） Ｃ：８７．２１ Ｈ：７．００ Ｎ：
５．８０ 融点 １８６．４℃（ＤＳＣ） 実施例２ 前記式(12)で表されるｏ−フェニレンジアミン５．４ｇ
と、式(14)：FIG. 1 shows the results of infrared spectroscopic analysis of the above compound. The other analysis results are shown below. Elemental analysis result Calculated value (%) C: 87.15 H: 6.88 N:
5.98 actual value (%) C: 87.21 H: 7.00 N:
5.80 Melting point 186.4 ° C. (DSC) Example 2 5.4 g of o-phenylenediamine represented by the above formula (12)
And equation (14):
【００５３】[0053]
【化１１】 Embedded image
【００５４】で表されるｍ−ヨードトルエン４２．６ｇ
とを出発原料として使用したこと以外は、実施例１と同
様にして、前記式(4) で表されるＮ，Ｎ，Ｎ′，Ｎ′−
テトラキス（３−メチルフェニル）−ｏ−フェニレンジ
アミンを得た。収量は１２．６ｇ、収率は５５．１％で
あった。上記化合物の赤外分光分析の結果を図２に示
す。またその他の分析結果を以下に示す。42.6 g of m-iodotoluene represented by the formula
And N, N, N ', N'- represented by the formula (4) in the same manner as in Example 1 except that
Tetrakis (3-methylphenyl) -o-phenylenediamine was obtained. The yield was 12.6 g, and the yield was 55.1%. FIG. 2 shows the results of infrared spectroscopic analysis of the above compound. The other analysis results are shown below.
【００５５】元素分析結果 計算値（％） Ｃ：８７．１５ Ｈ：６．８８ Ｎ：
５．９８ 実測値（％） Ｃ：８７．１１ Ｈ：６．９１ Ｎ：
５．９８ 融点 １３８．１℃（ＤＳＣ） 実施例３ 前記式(12)で表されるｏ−フェニレンジアミン５．４ｇ
と、式(15)：Elemental analysis result Calculated value (%) C: 87.15 H: 6.88 N:
5.98 actual value (%) C: 87.11 H: 6.91 N:
5.98 Melting point 138.1 ° C (DSC) Example 3 5.4 g of o-phenylenediamine represented by the above formula (12)
And equation (15):
【００５６】[0056]
【化１２】 Embedded image
【００５７】で表される４−エチル−４′−ヨードビフ
ェニル６０．２ｇとを出発原料として使用したこと以外
は、実施例１と同様にして、前記式(11)で表されるＮ，
Ｎ，Ｎ′，Ｎ′−テトラキス（４′−エチルビフェニル
−４−イル）−ｏ−フェニレンジアミンを得た。収量は
２０．４ｇ、収率は５０．３％であった。上記化合物の
赤外分光分析の結果を図３に示す。またその他の分析結
果を以下に示す。In the same manner as in Example 1 except that 60.2 g of 4-ethyl-4'-iodobiphenyl represented by the following formula was used, N, represented by the formula (11) was used.
N, N ', N'-tetrakis (4'-ethylbiphenyl-4-yl) -o-phenylenediamine was obtained. The yield was 20.4 g, and the yield was 50.3%. FIG. 3 shows the results of infrared spectroscopic analysis of the above compound. The other analysis results are shown below.
【００５８】元素分析結果 計算値（％） Ｃ：８９．８０ Ｈ：６．８２ Ｎ：
３．３８ 実測値（％） Ｃ：８９．８２ Ｈ：６．８１ Ｎ：
３．３６ 融点 ２５４．１℃（ＤＳＣ） 実施例４〜１１、比較例１，２（デジタル光源用単層型
感光体） 電荷発生剤としてのＸ型メタルフリーフタロシアニン５
重量部、電荷輸送剤のうち正孔輸送剤としてのフェニレ
ンジアミン誘導体５０重量部、電子輸送剤としての式(1
6)：Elemental analysis result Calculated value (%) C: 89.80 H: 6.82 N:
3.38 actual value (%) C: 89.82 H: 6.81 N:
3.36 melting point 254.1 ° C. (DSC) Examples 4 to 11, Comparative Examples 1 and 2 (single-layer photoreceptor for digital light source) X-type metal-free phthalocyanine 5 as a charge generating agent
Parts by weight, 50 parts by weight of a phenylenediamine derivative as a hole transporting agent among the charge transporting agents, and formula (1) as an electron transporting agent.
6):
【００５９】[0059]
【化１３】 Embedded image
【００６０】で表される３，５−ジメチル−３′，５′
−ジ−tert−ブチルジフェノキノン３０重量部、ならび
に結着樹脂としてのポリカーボネート１００重量部を、
溶媒である８００重量部のテトラヒドロフランととも
に、ボールミルにて５０時間混合分散させて、単層型感
光層用の塗布液を作成した。そしてこの塗布液を、導電
性基材としてのアルミニウム素管上に、ディップコート
法にて塗布し、１００℃で６０分間、熱風乾燥して、膜
厚１５〜２０μｍの単層型感光層を有するデジタル光源
用の単層型感光体を製造した。3,5-dimethyl-3 ', 5'
30 parts by weight of di-tert-butyl diphenoquinone, and 100 parts by weight of polycarbonate as a binder resin,
The mixture was mixed and dispersed in a ball mill for 50 hours together with 800 parts by weight of tetrahydrofuran as a solvent to prepare a coating solution for a single-layer type photosensitive layer. The coating solution is applied on an aluminum tube as a conductive substrate by a dip coating method, and dried with hot air at 100 ° C. for 60 minutes to have a single-layer photosensitive layer having a thickness of 15 to 20 μm. A single-layer type photoreceptor for a digital light source was manufactured.
【００６１】実施例で使用したフェニレンジアミン誘導
体の具体的化合物は、表１中に、前記した各具体例の化
合物番号を用いて示した。また比較例１，２で使用した
符号(17)(18)のフェニレンジアミン誘導体は、下記の化
合物である。The specific compounds of the phenylenediamine derivatives used in the examples are shown in Table 1 using the compound numbers of the specific examples described above. The phenylenediamine derivatives denoted by reference numerals (17) and (18) used in Comparative Examples 1 and 2 are the following compounds.
【００６２】[0062]
【化１４】 Embedded image
【００６３】上記各実施例、比較例の電子写真感光体に
ついて、以下に記す初期電気特性試験（Ｉ）を行い、そ
の特性を評価した。初期電気特性試験（Ｉ） ジェンテック（ＧＥＮＴＥＣ）社製のドラム感度試験機
を用いて、各実施例、比較例の電子写真感光体の表面に
印加電圧を加えて、その表面を＋７００Ｖに帯電させ
た。そして、露光光源であるハロゲンランプの白色光か
らバンドパスフィルターを用いて取り出した、波長７８
０nm（半値幅２０nm）、光強度１６μＷ／ｃｍ2 の単色
光を感光体の表面に照射（照射時間８０ｍｓｅｃ．）し
て、上記表面電位が１／２つまり＋３５０Ｖになるのに
要した時間を測定し、半減露光量Ｅ 1/2 （μＪ／ｃ
ｍ2 ）を算出した。また露光開始から３３０ｍｓｅｃ．
経過した時点での表面電位を、露光後電位ＶL （Ｖ）と
して測定した。The electrophotographic photoreceptors of each of the above Examples and Comparative Examples were used.
Then, the following initial electrical property test (I) was performed, and
Were evaluated.Initial electrical property test (I) Drum sensitivity tester manufactured by GENTEC
On the surface of the electrophotographic photoreceptor of each example and comparative example using
Apply an applied voltage to charge the surface to + 700V
Was. And the white light of the halogen lamp
Using a band-pass filter at a wavelength of 78
0 nm (half-width 20 nm), light intensity 16 μW / cmTwoSingle color
The surface of the photoreceptor is irradiated with light (irradiation time: 80 msec.)
The surface potential becomes 1/2, that is, + 350V
The required time was measured, and the half-exposure 1/2(ΜJ / c
mTwo) Was calculated. 330 msec. From the start of exposure.
The surface potential at the elapse of time is referred to as the post-exposure potential V.L(V) and
And measured.
【００６４】結果を表１に示す。Table 1 shows the results.
【００６５】[0065]
【表１】 [Table 1]
【００６６】上記表１の結果より、一般式(2) のｍ−フ
ェニレンジアミン誘導体に属するフェニレンジアミン誘
導体(17)を用いた比較例１の感光体、および一般式(3)
のｐ−フェニレンジアミン誘導体に属するフェニレンジ
アミン誘導体(18)を用いた比較例２の感光体は、いずれ
も、半減露光量Ｅ1/2 （μＪ／ｃｍ2 ）が大きく、かつ
露光後電位ＶL （Ｖ）が高いことから感度特性が悪いこ
とがわかった。From the results shown in Table 1, the photoreceptor of Comparative Example 1 using the phenylenediamine derivative (17) belonging to the m-phenylenediamine derivative of the general formula (2) and the general formula (3)
Each of the photoconductors of Comparative Example 2 using the phenylenediamine derivative (18) belonging to the p-phenylenediamine derivative of ( 1 ) has a large half-reduction exposure amount E 1/2 (μJ / cm 2 ) and a potential V L after exposure. Since (V) was high, it was found that the sensitivity characteristics were poor.
【００６７】これに対し、一般式(1) で表されるフェニ
レンジアミン誘導体に属するフェニレンジアミン誘導体
(4) 〜(11)を用いた実施例４〜１１の感光体はいずれ
も、半減露光量Ｅ1/2 （μＪ／ｃｍ2 ）が小さく、かつ
露光後電位ＶL （Ｖ）が低いことから、感度特性にすぐ
れたものであることがわかった。また各実施例のうち、
一般式(1) 中の基Ｒ1 〜Ｒ4 がアルキル基で、ｍ，ｎ，
ｐ，ｑがいずれも１であるものに相当するフエニレンジ
アミン誘導体(4)(5)(6)を用いた実施例４，５，６を比
較すると、上記アルキル基が各フェニル基の４位に置換
したフェニレンジアミン誘導体(5)(6)を用いた実施例
５，６の感光体はいずれも、アルキル基が各フェニル基
の３位に置換したフェニレンジアミン誘導体(4) を用い
た実施例４より感度特性にすぐれていることがわかっ
た。On the other hand, a phenylenediamine derivative belonging to the phenylenediamine derivative represented by the general formula (1)
The photoreceptors of Examples 4 to 11 using (4) to (11) all have a small half-reduction exposure amount E 1/2 (μJ / cm 2 ) and a low post-exposure potential V L (V). From this, it was found that the sensitivity characteristics were excellent. In each embodiment,
The groups R 1 to R 4 in the general formula (1) are alkyl groups, and m, n,
Comparing Examples 4, 5, and 6 using the phenylenediamine derivatives (4), (5), and (6), each of which has p and q being 1, the alkyl group is the 4-position of each phenyl group. The photoreceptors of Examples 5 and 6 using the phenylenediamine derivatives (5) and (6) substituted with the phenylenediamine derivatives (4) in which the alkyl group was substituted at the 3-position of each phenyl group were used. 4, it was found that the sensitivity characteristics were better.
【００６８】また上記実施例５，６と、一般式(1) 中の
基Ｒ1 〜Ｒ4 がアルキル基で、ｍ，ｎ，ｐ，ｑがいずれ
も２で、かつ各フェニル基に置換する２つのアルキル基
のうちの１つがフェニル基の４位に置換したものに相当
するフェニレンジアミン誘導体(7)(8)を用いた実施例
７，８を比較すると、前者（実施例５，６）より後者
（実施例７，８）の方が感度特性にすぐれていることが
わかった。In Examples 5 and 6, the groups R 1 to R 4 in the general formula (1) are alkyl groups, m, n, p and q are all 2, and each phenyl group is substituted. Comparing Examples 7 and 8 using phenylenediamine derivatives (7) and (8) corresponding to one in which one of the two alkyl groups is substituted at the 4-position of the phenyl group, the former (Examples 5 and 6) It was found that the latter (Examples 7 and 8) had better sensitivity characteristics.
【００６９】さらに上記実施例５〜８と、一般式(1) 中
の基Ｒ1 ，Ｒ4 がフェニル基の４位に置換したアルキル
基で、かつ基Ｒ2 ，Ｒ3 がフェニル基の４位に置換した
アリール基で、ｍ，ｎ，ｐ，ｑが１であるものに相当す
るフェニレンジアミン誘導体(9)(10) を用いた実施例
９，１０と、一般式(1) 中の基Ｒ1 〜Ｒ4 がいずれもフ
ェニル基の４位に置換したアリール基で、ｍ，ｎ，ｐ，
ｑが１であるものに相当するフェニレンジアミン誘導体
(11)を用いた実施例１１を比較すると、前者（実施例５
〜８）より後者（実施例９〜１１）の方が、さらに感度
特性にすぐれていることがわかった。 実施例１２，１３（デジタル光源用積層型感光体） 電荷発生剤としてのＸ型メタルフリーフタロシアニン２
重量部と、結着樹脂としてのポリビニルブチラール１重
量部とを、溶媒である１２０重量部のジクロロメタンと
ともに、ボールミルにて混合分散させて、電荷発生層用
の塗布液を作成した。そしてこの塗布液を、導電性基材
としてのアルミニウム素管上に、ディップコート法にて
塗布し、１００℃で６０分間、熱風乾燥して、膜厚０．
５μｍの電荷発生層を形成した。Further, in Examples 5 to 8, the groups R 1 and R 4 in the general formula (1) are alkyl groups substituted at the 4-position of the phenyl group, and the groups R 2 and R 3 are the same as Examples 9 and 10 using phenylenediamine derivatives (9) and (10) corresponding to those in which m, n, p, and q are 1 in the substituted aryl group, and a group represented by general formula (1) R 1 to R 4 are all aryl groups substituted at the 4-position of the phenyl group, and m, n, p,
phenylenediamine derivatives corresponding to those wherein q is 1
Comparing Example 11 using (11), the former (Example 5
8) that the latter (Examples 9 to 11) are more excellent in sensitivity characteristics. Examples 12 and 13 (Laminated photoreceptor for digital light source) X-type metal-free phthalocyanine 2 as a charge generating agent
A part by weight and 1 part by weight of polyvinyl butyral as a binder resin were mixed and dispersed in a ball mill together with 120 parts by weight of dichloromethane as a solvent to prepare a coating liquid for a charge generation layer. Then, this coating solution is applied on an aluminum tube as a conductive substrate by a dip coating method, and dried with hot air at 100 ° C. for 60 minutes to form a film having a thickness of 0.1 μm.
A 5 μm charge generation layer was formed.
【００７０】つぎに、電荷輸送剤としてのフェニレンジ
アミン誘導体８０重量部と、結着樹脂としてのポリカボ
ネート１００重量部とを、溶媒である８００重量部のベ
ンゼンととともに、ボールミルにて混合分散させて、電
荷輸送層用の塗布液を作成した。そしてこの塗布液を、
上記電荷発生層上に、ディップコート法にて塗布し、９
０℃で６０分間、熱風乾燥して、膜厚１５μｍの電荷輸
送層を形成して、デジタル光源用の積層型感光体を製造
した。Next, 80 parts by weight of a phenylenediamine derivative as a charge transporting agent and 100 parts by weight of polycarbonate as a binder resin were mixed and dispersed in a ball mill together with 800 parts by weight of benzene as a solvent. A coating solution for the charge transport layer was prepared. And this coating solution,
Apply on the charge generation layer by dip coating,
The resultant was dried with hot air at 0 ° C. for 60 minutes to form a charge transport layer having a thickness of 15 μm, thereby producing a laminated photoconductor for a digital light source.
【００７１】実施例で使用したフェニレンジアミン誘導
体の具体的化合物は、表２中に、前記と同じく化合物番
号を用いて示した。上記両実施例の積層型感光体につい
て、以下に記す初期電気特性試験（II）を行い、その特
性を評価した。初期電気特性試験（II） ジェンテック（ＧＥＮＴＥＣ）社製のドラム感度試験機
を用いて、両実施例の電子写真感光体の表面に印加電圧
を加えて、その表面を−７００Ｖに帯電させた。そし
て、露光光源であるハロゲンランプの白色光からバンド
パスフィルターを用いて取り出した、波長７８０nm（半
値幅２０nm）、光強度１６μＷ／ｃｍ2 の単色光を感光
体の表面に照射（照射時間８０ｍｓｅｃ．）して、上記
表面電位が１／２つまり−３５０Ｖになるのに要した時
間を測定し、半減露光量Ｅ1/2 （μＪ／ｃｍ2 ）を算出
した。また露光開始から３３０ｍｓｅｃ．経過した時点
での表面電位を、露光後電位ＶL （Ｖ）として測定し
た。Specific compounds of the phenylenediamine derivative used in the examples are shown in Table 2 using the same compound numbers as described above. With respect to the laminated photoreceptors of the above Examples, an initial electrical property test (II) described below was performed to evaluate the properties. Initial electrical property test (II) Using a drum sensitivity tester manufactured by GENTEC, an applied voltage was applied to the surfaces of the electrophotographic photosensitive members of both examples, and the surfaces were charged to -700V. Then, the surface of the photoreceptor is irradiated with monochromatic light having a wavelength of 780 nm (half-width 20 nm) and a light intensity of 16 μW / cm 2 extracted from white light of a halogen lamp as an exposure light source using a bandpass filter (irradiation time: 80 msec. Then, the time required for the surface potential to become １ ／, that is, −350 V, was measured, and the half-life exposure amount E 1/2 (μJ / cm 2 ) was calculated. 330 msec. From the start of exposure. The surface potential at the elapse of time was measured as the post-exposure potential V L (V).
【００７２】結果を表２に示す。Table 2 shows the results.
【００７３】[0073]
【表２】 [Table 2]
【００７４】上記表２の結果より、一般式(1) で表され
るフェニレンジアミン誘導体に属するフェニレンジアミ
ン誘導体(5)(11) を用いた実施例１２，１３の感光体は
いずれも、半減露光量Ｅ1/2 （μＪ／ｃｍ2 ）が小さ
く、かつ露光後電位ＶL （Ｖ）が低いことから、感度特
性にすぐれたものであることがわかった。また上記両実
施例を比較すると、一般式(1) 中の基Ｒ1 〜Ｒ4 がフェ
ニル基の４位に置換したアルキル基であるフェニレンジ
アミン誘導体(5) を用いた実施例１２よりも、上記各基
がフェニル基の４位に置換したアリール基であるフェニ
レンジアミン誘導体(11)を用いた実施例１３の方が、感
度特性にすぐれていることもわかった。 実施例１４〜２１、比較例３，４（アナログ光源用単層
型感光体） 電荷発生剤としての式(19)：From the results shown in Table 2, the photoreceptors of Examples 12 and 13 using the phenylenediamine derivatives (5) and (11) belonging to the phenylenediamine derivative represented by the general formula (1) were all half-exposure exposed. Since the amount E 1/2 (μJ / cm 2 ) was small and the post-exposure potential V L (V) was low, it was found that the sensitivity was excellent. Further, when comparing the above Examples, the phenylenediamine derivative (5), in which the groups R 1 to R 4 in the general formula (1) are an alkyl group substituted at the 4-position of a phenyl group, has a higher value than Example 12. It was also found that Example 13 using the phenylenediamine derivative (11) in which each of the above groups was an aryl group substituted at the 4-position of the phenyl group had better sensitivity characteristics. Examples 14 to 21, Comparative Examples 3 and 4 (Single-layer type photoconductor for analog light source) Formula (19) as a charge generating agent:
【００７５】[0075]
【化１５】 Embedded image
【００７６】で表されるアゾ顔料５重量部、電荷輸送剤
のうち正孔輸送剤としてのフェニレンジアミン誘導体７
０重量部、電子輸送剤としての前記式(16)で表される
３，５−ジメチル−３′，５′−ジ−tert−ブチルジフ
ェノキノン２０重量部、ならびに結着樹脂としてのポリ
カーボネート１００重量部を、溶媒である８００重量部
のテトラヒドロフランとともに、ボールミルにて５０時
間混合分散させて、単層型感光層用の塗布液を作成し
た。そしてこの塗布液を、導電性基材としてのアルミニ
ウム素管上に、ディップコート法にて塗布し、１００℃
で６０分間、熱風乾燥して、膜厚１５〜２０μｍの単層
型感光層を有する、アナログ光源用の単層型感光体を製
造した。5 parts by weight of an azo pigment represented by the following formula: phenylenediamine derivative 7 as a hole transporting agent among charge transporting agents
0 parts by weight, 20 parts by weight of 3,5-dimethyl-3 ', 5'-di-tert-butyldiphenoquinone represented by the above formula (16) as an electron transporting agent, and polycarbonate 100 as a binder resin Parts by weight were mixed and dispersed in a ball mill for 50 hours together with 800 parts by weight of tetrahydrofuran as a solvent to prepare a coating solution for a single-layer type photosensitive layer. Then, this coating solution is applied on an aluminum tube as a conductive substrate by a dip coating method,
And dried with hot air for 60 minutes to produce a single-layer photosensitive member for an analog light source having a single-layer photosensitive layer having a thickness of 15 to 20 μm.
【００７７】実施例、比較例で使用したフェニレンジア
ミン誘導体の具体的化合物は、表３中に、前記と同じく
化合物番号を用いて示した。上記各実施例、比較例の電
子写真感光体について、以下に記す初期電気特性試験(I
II) を行い、その特性を評価した。初期電気特性試験(III) ジェンテック（ＧＥＮＴＥＣ）社製のドラム感度試験機
を用いて、各実施例、比較例の電子写真感光体の表面に
印加電圧を加えて、その表面を＋７００Ｖに帯電させ
た。そして、露光光源であるハロゲンランプの白色光
（光強度１４７μＷ／ｃｍ2 ）を感光体の表面に照射
（照射時間５０ｍｓｅｃ．）して、上記表面電位が１／
２つまり３５０Ｖになるのに要した時間を測定し、半減
露光量Ｅ1/2 （μＪ／ｃｍ2 ）を算出した。また露光開
始から３３０ｍｓｅｃ．経過した時点での表面電位を、
露光後電位ＶL （Ｖ）として測定した。Specific compounds of the phenylenediamine derivatives used in Examples and Comparative Examples are shown in Table 3 using the same compound numbers as described above. With respect to the electrophotographic photoreceptors of each of the above Examples and Comparative Examples, an initial electrical property test (I
II) and evaluated its characteristics. Initial electrical property test (III) Using a drum sensitivity tester manufactured by GENTEC, an applied voltage was applied to the surface of the electrophotographic photosensitive member of each of Examples and Comparative Examples to charge the surface to +700 V. Was. Then, the surface of the photoconductor is irradiated with white light (light intensity: 147 μW / cm 2 ) of a halogen lamp as an exposure light source (irradiation time: 50 msec.), And the surface potential is reduced to 1 /
2, ie, the time required to reach 350 V was measured, and the half-life exposure amount E 1/2 (μJ / cm 2 ) was calculated. 330 msec. From the start of exposure. The surface potential at the time
It was measured as the post-exposure potential V L (V).
【００７８】以上の結果を表３に示す。Table 3 shows the above results.
【００７９】[0079]
【表３】 [Table 3]
【００８０】上記表３の結果より、一般式(2) のｍ−フ
ェニレンジアミン誘導体に属するフェニレンジアミン誘
導体(17)を用いた比較例３の感光体、および一般式(3)
のｐ−フェニレンジアミン誘導体に属するフェニレンジ
アミン誘導体(18)を用いた比較例４の感光体は、いずれ
も、半減露光量Ｅ1/2 （μＪ／ｃｍ2 ）が大きく、かつ
露光後電位ＶL （Ｖ）が高いことから感度特性が悪いこ
とがわかった。From the results shown in Table 3, the photoconductor of Comparative Example 3 using the phenylenediamine derivative (17) belonging to the m-phenylenediamine derivative of the general formula (2), and the general formula (3)
Each of the photoconductors of Comparative Example 4 using the phenylenediamine derivative (18) belonging to the p-phenylenediamine derivative of ( 1 ) has a large half-reduction exposure amount E 1/2 (μJ / cm 2 ) and a potential V L after exposure. Since (V) was high, it was found that the sensitivity characteristics were poor.
【００８１】これに対し、一般式(1) で表されるフェニ
レンジアミン誘導体に属するフェニレンジアミン誘導体
(4) 〜(11)を用いた実施例１４〜２１の感光体はいずれ
も、半減露光量Ｅ1/2 （μＪ／ｃｍ2 ）が小さく、かつ
露光後電位ＶL （Ｖ）が低いことから、感度特性にすぐ
れたものであることがわかった。また各実施例のうち、
一般式(1) 中の基Ｒ1 〜Ｒ4 がアルキル基で、ｍ，ｎ，
ｐ，ｑがいずれも１であるものに相当するフエニレンジ
アミン誘導体(4)(5)(6)を用いた実施例１４，１５，１
６を比較すると、上記アルキル基が各フェニル基の４位
に置換したフェニレンジアミン誘導体(5)(6)を用いた実
施例１５，１６の感光体はいずれも、アルキル基が各フ
ェニル基の３位に置換したフェニレンジアミン誘導体
(4) を用いた実施例１４より感度特性にすぐれているこ
とがわかった。On the other hand, a phenylenediamine derivative belonging to the phenylenediamine derivative represented by the general formula (1)
In all of the photoconductors of Examples 14 to 21 using (4) to (11), the half-exposure dose E 1/2 (μJ / cm 2 ) is small and the post-exposure potential V L (V) is low. From this, it was found that the sensitivity characteristics were excellent. In each embodiment,
The groups R 1 to R 4 in the general formula (1) are alkyl groups, and m, n,
Examples 14, 15, and 1 using phenylenediamine derivatives (4), (5), and (6) corresponding to those in which both p and q are 1.
Comparing with No. 6, the photoreceptors of Examples 15 and 16 using the phenylenediamine derivatives (5) and (6) in which the alkyl group was substituted at the 4-position of each phenyl group showed that the alkyl group was 3% of each phenyl group. Substituted phenylenediamine derivative
It was found that the sensitivity characteristic was superior to that of Example 14 using (4).
【００８２】また上記実施例１５，１６と、一般式(1)
中の基Ｒ1 〜Ｒ4 がアルキル基で、ｍ，ｎ，ｐ，ｑがい
ずれも２で、かつ各フェニル基に置換する２つのアルキ
ル基のうちの１つがフェニル基の４位に置換したものに
相当するフェニレンジアミン誘導体(7)(8)を用いた実施
例１７，１８を比較すると、前者（実施例１５，１６）
より後者（実施例１７，１８）の方が感度特性にすぐれ
ていることがわかった。Further, Examples 15 and 16 described above were compared with the general formula (1)
Wherein R 1 to R 4 are alkyl groups, m, n, p and q are all 2, and one of the two alkyl groups substituted for each phenyl group is substituted at the 4-position of the phenyl group. Comparing Examples 17 and 18 using the corresponding phenylenediamine derivatives (7) and (8), the former (Examples 15 and 16)
It was found that the latter (Examples 17 and 18) had better sensitivity characteristics.
【００８３】さらに上記実施例１５〜１８と、一般式
(1) 中の基Ｒ1 ，Ｒ4 がフェニル基の４位に置換したア
ルキル基で、かつ基Ｒ2 ，Ｒ3 がフェニル基の４位に置
換したアリール基で、ｍ，ｎ，ｐ，ｑが１であるものに
相当するフェニレンジアミン誘導体(9)(10) を用いた実
施例１９，２０と、一般式(1) 中の基Ｒ1 〜Ｒ4 がいず
れもフェニル基の４位に置換したアリール基で、ｍ，
ｎ，ｐ，ｑが１であるものに相当するフェニレンジアミ
ン誘導体(11)を用いた実施例２１を比較すると、前者
（実施例１５〜１８）より後者（実施例１９〜２１）の
方が、さらに感度特性にすぐれていることがわかった。 実施例２２〜２９、比較例５，６（アナログ光源用単層
型感光体） 電荷発生剤として、式(20)：Further, the above Examples 15 to 18 and the general formula
The groups R 1 and R 4 in (1) are alkyl groups substituted at the 4-position of the phenyl group, and the groups R 2 and R 3 are aryl groups substituted at the 4-position of the phenyl group, and m, n, p, Examples 19 and 20 using phenylenediamine derivatives (9) and (10) corresponding to those in which q is 1 and the groups R 1 to R 4 in the general formula (1) were all substituted at the 4-position of the phenyl group. A substituted aryl group, m,
Comparing Example 21 using the phenylenediamine derivative (11) corresponding to one in which n, p, and q are 1, the latter (Examples 19 to 21) are better than the former (Examples 15 to 18). Further, it was found that the sensitivity characteristics were excellent. Examples 22 to 29 and Comparative Examples 5 and 6 (Single-layer type photoconductor for analog light source) Formula (20) as a charge generating agent:
【００８４】[0084]
【化１６】 Embedded image
【００８５】で表されるアゾ顔料５重量部を使用したこ
と以外は、実施例１４〜２１、比較例３，４と同様にし
て、膜厚１５〜２０μｍの単層型感光層を有する、アナ
ログ光源用の単層型感光体を製造した。実施例、比較例
で使用したフェニレンジアミン誘導体の具体的化合物
は、表４中に、前記と同じく化合物番号を用いて示し
た。An analog having a single-layer type photosensitive layer having a film thickness of 15 to 20 μm in the same manner as in Examples 14 to 21 and Comparative Examples 3 and 4 except that 5 parts by weight of the azo pigment represented by A single-layer photoreceptor for a light source was manufactured. Specific compounds of the phenylenediamine derivatives used in Examples and Comparative Examples are shown in Table 4 using the same compound numbers as described above.
【００８６】上記各実施例、比較例の電子写真感光体に
ついて、前記初期電気特性試験(III) を行い、その特性
を評価した。以上の結果を表４に示す。The electrophotographic photoreceptors of each of the above Examples and Comparative Examples were subjected to the above-mentioned initial electrical property test (III) to evaluate the properties. Table 4 shows the above results.
【００８７】[0087]
【表４】 [Table 4]
【００８８】上記表４の結果より、一般式(2) のｍ−フ
ェニレンジアミン誘導体に属するフェニレンジアミン誘
導体(17)を用いた比較例５の感光体、および一般式(3)
のｐ−フェニレンジアミン誘導体に属するフェニレンジ
アミン誘導体(18)を用いた比較例６の感光体は、いずれ
も、半減露光量Ｅ1/2 （μＪ／ｃｍ2 ）が大きく、かつ
露光後電位ＶL （Ｖ）が高いことから感度特性が悪いこ
とがわかった。From the results shown in Table 4, the photoreceptor of Comparative Example 5 using the phenylenediamine derivative (17) belonging to the m-phenylenediamine derivative of the general formula (2), and the general formula (3)
Each of the photoconductors of Comparative Example 6 using the phenylenediamine derivative (18) belonging to the p-phenylenediamine derivative of ( 1 ) has a large half-reduction exposure amount E 1/2 (μJ / cm 2 ) and a potential V L after exposure. Since (V) was high, it was found that the sensitivity characteristics were poor.
【００８９】これに対し、一般式(1) で表されるフェニ
レンジアミン誘導体に属するフェニレンジアミン誘導体
(4) 〜(11)を用いた実施例２２〜２９の感光体はいずれ
も、半減露光量Ｅ1/2 （μＪ／ｃｍ2 ）が小さく、かつ
露光後電位ＶL （Ｖ）が低いことから、感度特性にすぐ
れたものであることがわかった。また各実施例のうち、
一般式(1) 中の基Ｒ1 〜Ｒ4 がアルキル基で、ｍ，ｎ，
ｐ，ｑがいずれも１であるものに相当するフエニレンジ
アミン誘導体(4)(5)(6)を用いた実施例２２，２３，２
４を比較すると、上記アルキル基が各フェニル基の４位
に置換したフェニレンジアミン誘導体(5)(6)を用いた実
施例２３，２４の感光体はいずれも、アルキル基が各フ
ェニル基の３位に置換したフェニレンジアミン誘導体
(4) を用いた実施例２２より感度特性にすぐれているこ
とがわかった。On the other hand, a phenylenediamine derivative belonging to the phenylenediamine derivative represented by the general formula (1)
In all of the photoconductors of Examples 22 to 29 using (4) to (11), the half-exposure dose E 1/2 (μJ / cm 2 ) is small and the post-exposure potential V L (V) is low. From this, it was found that the sensitivity characteristics were excellent. In each embodiment,
The groups R 1 to R 4 in the general formula (1) are alkyl groups, and m, n,
Examples 22, 23 and 2 using phenylenediamine derivatives (4), (5) and (6) each corresponding to p and q of 1
Comparison of No. 4 shows that the photoconductors of Examples 23 and 24 using the phenylenediamine derivatives (5) and (6) in which the alkyl group was substituted at the 4-position of each phenyl group showed that the alkyl group had 3 Substituted phenylenediamine derivative
It was found that the sensitivity characteristic was superior to that of Example 22 using (4).
【００９０】また上記実施例２３，２４と、一般式(1)
中の基Ｒ1 〜Ｒ4 がアルキル基で、ｍ，ｎ，ｐ，ｑがい
ずれも２で、かつ各フェニル基に置換する２つのアルキ
ル基のうちの１つがフェニル基の４位に置換したものに
相当するフェニレンジアミン誘導体(7)(8)を用いた実施
例２５，２６を比較すると、フェニレンジアミン誘導体
(7) を用いた実施例２５は、両実施例２３，２４より感
度特性にすぐれており、またフェニレンジアミン誘導体
(8) を用いた実施例２６は、実施例２３と同等で、かつ
実施例２４より感度特性にすぐれていることがわかっ
た。Further, Examples 23 and 24 described above were compared with the general formula (1)
Wherein R 1 to R 4 are alkyl groups, m, n, p and q are all 2, and one of the two alkyl groups substituted for each phenyl group is substituted at the 4-position of the phenyl group. Comparing Examples 25 and 26 using phenylenediamine derivatives (7) and (8) corresponding to the phenylenediamine derivatives,
Example 25 using (7) had better sensitivity characteristics than both Examples 23 and 24, and
It was found that Example 26 using (8) was equivalent to Example 23 and had better sensitivity characteristics than Example 24.
【００９１】さらに上記実施例２３〜２６と、一般式
(1) 中の基Ｒ1 ，Ｒ4 がフェニル基の４位に置換したア
ルキル基で、かつ基Ｒ2 ，Ｒ3 がフェニル基の４位に置
換したアリール基で、ｍ，ｎ，ｐ，ｑが１であるものに
相当するフェニレンジアミン誘導体(9)(10) を用いた実
施例２７，２８と、一般式(1) 中の基Ｒ1 〜Ｒ4 がいず
れもフェニル基の４位に置換したアリール基で、ｍ，
ｎ，ｐ，ｑが１であるものに相当するフェニレンジアミ
ン誘導体(11)を用いた実施例２９を比較すると、前者
（実施例２３〜２６）より後者（実施例２７〜２９）の
方が、さらに感度特性にすぐれていることがわかった。 実施例３０〜３７、比較例７，８（アナログ光源用単層
型感光体） 電荷発生剤として、式(21)：Further, the above Examples 23 to 26 and the general formula
The groups R 1 and R 4 in (1) are alkyl groups substituted at the 4-position of the phenyl group, and the groups R 2 and R 3 are aryl groups substituted at the 4-position of the phenyl group, and m, n, p, Examples 27 and 28 using the phenylenediamine derivatives (9) and (10) corresponding to those in which q is 1 and the groups R 1 to R 4 in the general formula (1) were all substituted at the 4-position of the phenyl group. A substituted aryl group, m,
Comparing Example 29 using a phenylenediamine derivative (11) corresponding to one in which n, p, and q are 1, the latter (Examples 27 to 29) are better than the former (Examples 23 to 26). Further, it was found that the sensitivity characteristics were excellent. Examples 30 to 37 and Comparative Examples 7 and 8 (Single-layer type photoreceptor for analog light source) Formula (21) as a charge generating agent:
【００９２】[0092]
【化１７】 Embedded image
【００９３】で表されるアゾ顔料５重量部を使用したこ
と以外は、実施例１４〜２１、比較例３，４と同様にし
て、膜厚１５〜２０μｍの単層型感光層を有する、アナ
ログ光源用の単層型感光体を製造した。実施例、比較例
で使用したフェニレンジアミン誘導体の具体的化合物
は、表５中に、前記と同じく化合物番号を用いて示し
た。An analog having a single-layer type photosensitive layer having a thickness of 15 to 20 μm in the same manner as in Examples 14 to 21 and Comparative Examples 3 and 4 except that 5 parts by weight of the azo pigment represented by A single-layer photoreceptor for a light source was manufactured. Specific compounds of the phenylenediamine derivatives used in Examples and Comparative Examples are shown in Table 5 using the same compound numbers as described above.
【００９４】上記各実施例、比較例の電子写真感光体に
ついて、前記初期電気特性試験(III) を行い、その特性
を評価した。以上の結果を表５に示す。The electrophotographic photoreceptors of each of the above Examples and Comparative Examples were subjected to the above-mentioned initial electrical property test (III) to evaluate the properties. Table 5 shows the above results.
【００９５】[0095]
【表５】 [Table 5]
【００９６】上記表５の結果より、一般式(2) のｍ−フ
ェニレンジアミン誘導体に属するフェニレンジアミン誘
導体(17)を用いた比較例７の感光体、および一般式(3)
のｐ−フェニレンジアミン誘導体に属するフェニレンジ
アミン誘導体(18)を用いた比較例８の感光体は、いずれ
も、半減露光量Ｅ1/2 （μＪ／ｃｍ2 ）が大きく、かつ
露光後電位ＶL （Ｖ）が高いことから感度特性が悪いこ
とがわかった。From the results shown in Table 5, the photoreceptor of Comparative Example 7 using the phenylenediamine derivative (17) belonging to the m-phenylenediamine derivative of the general formula (2) and the general formula (3)
Each of the photoconductors of Comparative Example 8 using the phenylenediamine derivative (18) belonging to the p-phenylenediamine derivative of ( 1 ) has a large half-reduction exposure amount E 1/2 (μJ / cm 2 ) and a potential V L after exposure. Since (V) was high, it was found that the sensitivity characteristics were poor.
【００９７】これに対し、一般式(1) で表されるフェニ
レンジアミン誘導体に属するフェニレンジアミン誘導体
(4) 〜(11)を用いた実施例３０〜３７の感光体はいずれ
も、半減露光量Ｅ1/2 （μＪ／ｃｍ2 ）が小さく、かつ
露光後電位ＶL （Ｖ）が低いことから、感度特性にすぐ
れたものであることがわかった。また各実施例のうち、
一般式(1) 中の基Ｒ1 〜Ｒ4 がアルキル基で、ｍ，ｎ，
ｐ，ｑがいずれも１であるものに相当するフエニレンジ
アミン誘導体(4)(5)(6)を用いた実施例３０，３１，３
２を比較すると、上記アルキル基が各フェニル基の４位
に置換したフェニレンジアミン誘導体(5) を用いた実施
例３１の感光体は、アルキル基が各フェニル基の３位に
置換したフェニレンジアミン誘導体(4) を用いた実施例
３０と同等であったが、アルキル基が各フェニル基の４
位に置換したフェニレンジアミン誘導体(6) を用いた実
施例３２の感光体は、上記実施例３０より感度特性にす
ぐれていることがわかった。On the other hand, a phenylenediamine derivative belonging to the phenylenediamine derivative represented by the general formula (1)
The photoreceptors of Examples 30 to 37 using (4) to (11) all have a small half-reduction exposure amount E 1/2 (μJ / cm 2 ) and a low post-exposure potential VL (V). From this, it was found that the sensitivity characteristics were excellent. In each embodiment,
The groups R 1 to R 4 in the general formula (1) are alkyl groups, and m, n,
Examples 30, 31, and 3 using phenylenediamine derivatives (4), (5), and (6) corresponding to those in which p and q are both 1.
Comparing the two, the photoreceptor of Example 31 using the phenylenediamine derivative (5) in which the alkyl group was substituted at the 4-position of each phenyl group was found to be a phenylenediamine derivative having the alkyl group substituted at the 3-position of each phenyl group. Example 4 was the same as Example 30 using (4), except that the alkyl group was
The photoreceptor of Example 32 using the phenylenediamine derivative (6) substituted at the 2-position was found to have better sensitivity characteristics than Example 30 described above.
【００９８】また上記実施例３１，３２と、一般式(1)
中の基Ｒ1 〜Ｒ4 がアルキル基で、ｍ，ｎ，ｐ，ｑがい
ずれも２で、かつ各フェニル基に置換する２つのアルキ
ル基のうちの１つがフェニル基の４位に置換したものに
相当するフェニレンジアミン誘導体(7)(8)を用いた実施
例３３，３４を比較すると、フェニレンジアミン誘導体
(7) を用いた実施例３３は、実施例３２と同等で、かつ
実施例３１より感度特性にすぐれており、またフェニレ
ンジアミン誘導体(8) を用いた実施例３４は、実施例３
１，３２より感度特性にすぐれていることがわかった。Further, Examples 31 and 32 described above were compared with the general formula (1)
Wherein R 1 to R 4 are alkyl groups, m, n, p and q are all 2, and one of the two alkyl groups substituted for each phenyl group is substituted at the 4-position of the phenyl group. Comparing Examples 33 and 34 using the corresponding phenylenediamine derivatives (7) and (8),
Example 33 using (7) is equivalent to Example 32 and has better sensitivity characteristics than Example 31, and Example 34 using the phenylenediamine derivative (8) is Example 3
It was found that the sensitivity characteristics were superior to those of Nos. 1 and 32.
【００９９】さらに上記実施例３１〜３４と、一般式
(1) 中の基Ｒ1 ，Ｒ4 がフェニル基の４位に置換したア
ルキル基で、かつ基Ｒ2 ，Ｒ3 がフェニル基の４位に置
換したアリール基で、ｍ，ｎ，ｐ，ｑが１であるものに
相当するフェニレンジアミン誘導体(9)(10) を用いた実
施例３５，３６と、一般式(1) 中の基Ｒ1 〜Ｒ4 がいず
れもフェニル基の４位に置換したアリール基で、ｍ，
ｎ，ｐ，ｑが１であるものに相当するフェニレンジアミ
ン誘導体(11)を用いた実施例３７を比較すると、前者
（実施例３１〜３４）より後者（実施例３５〜３７）の
方が、さらに感度特性にすぐれていることがわかった。Further, in Examples 31 to 34 described above,
The groups R 1 and R 4 in (1) are alkyl groups substituted at the 4-position of the phenyl group, and the groups R 2 and R 3 are aryl groups substituted at the 4-position of the phenyl group, and m, n, p, Examples 35 and 36 using the phenylenediamine derivatives (9) and (10) corresponding to those in which q is 1 and the groups R 1 to R 4 in the general formula (1) were all substituted at the 4-position of the phenyl group. A substituted aryl group, m,
Comparing Example 37 using the phenylenediamine derivative (11) corresponding to one in which n, p, and q are 1, the latter (Examples 35 to 37) are more effective than the former (Examples 31 to 34). Further, it was found that the sensitivity characteristics were excellent.
【０１００】[0100]
【発明の効果】以上、詳述したようにこの発明で使用す
るフェニレンジアミン誘導体は、高い電荷輸送能を有す
るとともに、結着樹脂に対する相溶性にもすぐれてい
る。 As described above, the present invention is not limited to this .
The phenylenediamine derivative has high charge transporting ability and also has excellent compatibility with a binder resin .
【０１０１】したがってこの発明の電子写真感光体は、
上記フェニレンジアミン誘導体を電荷輸送剤として含有
する感光層を備えるため、従来のものに比べて感度特性
にすぐれており、静電式複写機やレーザービームプリン
タ等の各種の画像形成装置の高速化、高性能化に寄与す
るという特有の作用効果を奏する。 Therefore, the electrophotographic photoreceptor of the present invention
Because it has a photosensitive layer containing the phenylenediamine derivative as a charge transporting agent, it has excellent sensitivity characteristics as compared with conventional ones, and can increase the speed of various image forming apparatuses such as an electrostatic copying machine and a laser beam printer. It has a unique effect of contributing to higher performance.
【図１】実施例１のフェニレンジアミン誘導体の赤外分
光分析結果を示すグラフである。1 is a graph showing the infrared spectroscopic analysis of the phenylenediamine derivative of the actual Example 1.
【図２】実施例２のフェニレンジアミン誘導体の赤外分
光分析結果を示すグラフである。2 is a graph showing the infrared spectroscopic analysis of the phenylenediamine derivative of the actual施例2.
【図３】実施例３のフェニレンジアミン誘導体の赤外分
光分析結果を示すグラフである。3 is a graph showing the infrared spectroscopic analysis of the phenylenediamine derivative of the actual施例3.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ Ｈ０１Ｌ 51/00 Ｈ０１Ｌ 31/04 Ｄ (72)発明者 深見 季之 大阪府大阪市中央区玉造１丁目２番28号 三田工業株式会社内 (72)発明者 中森 英雄 大阪府大阪市中央区玉造１丁目２番28号 三田工業株式会社内 (72)発明者 住田 圭介 大阪府大阪市中央区玉造１丁目２番28号 三田工業株式会社内 (72)発明者 斎藤 栄 大阪府大阪市中央区玉造１丁目２番28号 三田工業株式会社内 (56)参考文献 特開 平５−117210（ＪＰ，Ａ) 特開 平５−150481（ＪＰ，Ａ) Ｃｈｅｍ．Ｂｅｒ．（1970），103 （５），1318−1333 (58)調査した分野(Int.Cl.7，ＤＢ名) C07C 211/00 C09K 11/00 G03G 5/00 H01L 31/00 H01L 51/00 ＣＡ（ＳＴＮ) ＲＥＧＩＳＴＲＹ（ＳＴＮ)──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification code FI H01L 51/00 H01L 31/04 D (72) Inventor Kinoyuki Fukami 1-2-28 Tamatsukuri Chuo-ku Osaka City Inside the company (72) Inventor Hideo Nakamori 1-2-28 Tamazuki, Chuo-ku, Osaka-shi, Osaka Inside Mita Kogyo Co., Ltd. In-company (72) Inventor Sakae Saito 1-2-28 Tamazo, Chuo-ku, Osaka-shi, Osaka Mita Kogyo Co., Ltd. (56) References JP-A-5-117210 (JP, A) JP-A-5-150481 ( JP, A) Chem. Ber. (1970), 103 (5), 1318-1333 (58) Fields investigated (Int. Cl. 7 , DB name) C07C 211/00 C09K 11/00 G03G 5/00 H01L 31/00 H01L 51/00 CA ( STN) REGISTRY (STN)
Claims (3)
素数１〜６のアルキル基、炭素数１〜６のアルコキシ
基、もしくは置換基として炭素数１〜６のアルキル基を
有するまたは有さないフェニル基、またはビフェニル基
を示す。ｍ，ｎ，ｐおよびｑは同一または異なって０〜
３の整数を示す。〕で表されるフェニレンジアミン誘導
体を含む感光層を設けたことを特徴とする電子写真感光
体。1. A method according to claim 1, wherein the conductive substrate has the general formula (1): [Wherein R 1, R 2, R 3 and R 4 are the same or different and charcoal
Alkyl group of prime 1-6, alkoxy group having 1 to 6 carbon atoms, even properly represents a phenyl group or a biphenyl group, <br/> with or without an alkyl group having 1 to 6 carbon atoms as a substituent. m, n, p and q are the same or different and
Indicates an integer of 3. An electrophotographic photosensitive member comprising a photosensitive layer containing a phenylenediamine derivative represented by the following formula:
記載の一般式(1) で表されるフェニレンジアミン誘導体
を電荷輸送剤として含有する単層型感光層である請求項
１記載の電子写真感光体。Wherein the photosensitive layer, together with the electric charge generating material, according to claim 1
Claim is a single layer type photosensitive layer containing the phenylenediamine derivative represented by the general formula (1) according as the charge transporting agent
2. The electrophotographic photosensitive member according to 1.
されるフェニレンジアミン誘導体を電荷輸送剤として含
有する電荷輸送層と、電荷発生剤を含有する電荷発生層
とを備えた積層型感光層である請求項１記載の電子写真
感光体。3. A photosensitive layer comprising: a charge transport layer containing the phenylenediamine derivative represented by the general formula (1) according to claim 1 as a charge transport agent; and a charge generation layer containing a charge generator. The electrophotographic photoreceptor according to claim 1, which is a laminated photosensitive layer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17439594A JP3171755B2 (en) | 1993-10-14 | 1994-07-26 | Electrophotographic photoreceptor |
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25720893 | 1993-10-14 | ||
| JP5-257206 | 1993-10-14 | ||
| JP25720693 | 1993-10-14 | ||
| JP5-257208 | 1993-10-14 | ||
| JP17439594A JP3171755B2 (en) | 1993-10-14 | 1994-07-26 | Electrophotographic photoreceptor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07157454A JPH07157454A (en) | 1995-06-20 |
| JP3171755B2 true JP3171755B2 (en) | 2001-06-04 |
Family
ID=27323936
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17439594A Expired - Fee Related JP3171755B2 (en) | 1993-10-14 | 1994-07-26 | Electrophotographic photoreceptor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3171755B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102008050841A1 (en) | 2008-10-08 | 2010-04-15 | Merck Patent Gmbh | New materials for organic electroluminescent devices |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11144773A (en) * | 1997-09-05 | 1999-05-28 | Fuji Photo Film Co Ltd | Photoelectric conversion element and photoregeneration type photoelectrochemical cell |
| JP5010076B2 (en) * | 2001-08-01 | 2012-08-29 | 三井化学株式会社 | Organic electroluminescence device |
| JP4211869B2 (en) * | 2005-12-02 | 2009-01-21 | 東洋インキ製造株式会社 | Diaminoarylene compound having carbazolyl group and use thereof |
| CN109689616A (en) * | 2016-09-09 | 2019-04-26 | 保土谷化学工业株式会社 | Aryl diamine compound and organic electroluminescent device |
| CN115427391A (en) * | 2020-04-03 | 2022-12-02 | 国立大学法人京都大学 | Asymmetric 1,2-bis (diarylamino) benzenes, method for producing same, and use thereof |
-
1994
- 1994-07-26 JP JP17439594A patent/JP3171755B2/en not_active Expired - Fee Related
Non-Patent Citations (1)
| Title |
|---|
| Ｃｈｅｍ．Ｂｅｒ．（１９７０），１０３（５），１３１８−１３３３ |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102008050841A1 (en) | 2008-10-08 | 2010-04-15 | Merck Patent Gmbh | New materials for organic electroluminescent devices |
| DE102008050841B4 (en) | 2008-10-08 | 2019-08-01 | Merck Patent Gmbh | New materials for organic electroluminescent devices |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07157454A (en) | 1995-06-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPH0592936A (en) | Dinaphthoquinone derivative and photosensitizer using the same | |
| JP2504790B2 (en) | Charge transport material for electrophotographic photoreceptor | |
| JP3171755B2 (en) | Electrophotographic photoreceptor | |
| JP3272189B2 (en) | Naphthylenediamine derivatives and electrophotographic photoreceptors using the same | |
| JP3121144B2 (en) | Electrophotographic photoreceptor | |
| JPH01118141A (en) | Electrophotographic sensitive body | |
| JP3653464B2 (en) | Electrophotographic photoreceptor | |
| JP3121142B2 (en) | Electrophotographic photoreceptor | |
| JP3121141B2 (en) | Electrophotographic photoreceptor | |
| JP3121143B2 (en) | Electrophotographic photoreceptor | |
| JP3121145B2 (en) | Electrophotographic photoreceptor | |
| JPH01118143A (en) | Electrophotographic sensitive body | |
| JP3131616B2 (en) | Electrophotographic photoreceptor | |
| JP3131615B2 (en) | Electrophotographic photoreceptor | |
| JP2608930B2 (en) | M-phenylenediamine compound and electrophotographic photoreceptor using the same | |
| JP3121147B2 (en) | Electrophotographic photoreceptor | |
| JP2996487B2 (en) | m-phenylenediamine compound and electrophotographic photoreceptor using the same | |
| JPH01118142A (en) | Electrophotographic sensitive body | |
| JPH08211634A (en) | Electrophotographic photoreceptor | |
| JPH05992A (en) | Quinone compound and light sensitizer for electrophotography | |
| JPH04285670A (en) | Diphenoquinone-based compound and electrophotographic photosensitive sheet using the same compound | |
| JPH07152172A (en) | Electrophotogrpahic photoreceptor | |
| JPH08220789A (en) | Electrophotographic photoreceptor | |
| JPH04285672A (en) | Diphenoquinone-based compound and electrophotographic photosensitive body using the same compound | |
| JPH0592937A (en) | Quinone compound and photosensitizer using the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090323 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100323 Year of fee payment: 9 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100323 Year of fee payment: 9 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110323 Year of fee payment: 10 |
|
| LAPS | Cancellation because of no payment of annual fees |
