JPH0158499B2 - - Google Patents
Info
- Publication number
- JPH0158499B2 JPH0158499B2 JP56151978A JP15197881A JPH0158499B2 JP H0158499 B2 JPH0158499 B2 JP H0158499B2 JP 56151978 A JP56151978 A JP 56151978A JP 15197881 A JP15197881 A JP 15197881A JP H0158499 B2 JPH0158499 B2 JP H0158499B2
- Authority
- JP
- Japan
- Prior art keywords
- layer
- photoreceptor
- dyes
- derivatives
- protective layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 239000010410 layer Substances 0.000 claims description 72
- 108091008695 photoreceptors Proteins 0.000 claims description 44
- 239000011241 protective layer Substances 0.000 claims description 33
- 229910021417 amorphous silicon Inorganic materials 0.000 claims description 7
- 125000001153 fluoro group Chemical group F* 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 6
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 4
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000975 dye Substances 0.000 description 21
- 238000000034 method Methods 0.000 description 20
- 239000007789 gas Substances 0.000 description 15
- 229920005989 resin Polymers 0.000 description 13
- 239000011347 resin Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 11
- -1 polystyrene-acrylic Substances 0.000 description 10
- 239000010408 film Substances 0.000 description 9
- 239000004065 semiconductor Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 8
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 6
- 239000000987 azo dye Substances 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- 229920005668 polycarbonate resin Polymers 0.000 description 5
- 239000004431 polycarbonate resin Substances 0.000 description 5
- 238000012546 transfer 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
- 238000004140 cleaning Methods 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 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 4
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 3
- 239000004419 Panlite Substances 0.000 description 3
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical class [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000001678 irradiating effect Effects 0.000 description 3
- BSIHWSXXPBAGTC-UHFFFAOYSA-N isoviolanthrone Chemical class C12=CC=CC=C2C(=O)C2=CC=C3C(C4=C56)=CC=C5C5=CC=CC=C5C(=O)C6=CC=C4C4=C3C2=C1C=C4 BSIHWSXXPBAGTC-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 229910052711 selenium Inorganic materials 0.000 description 3
- 239000011669 selenium Substances 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- LWHDQPLUIFIFFT-UHFFFAOYSA-N 2,3,5,6-tetrabromocyclohexa-2,5-diene-1,4-dione Chemical compound BrC1=C(Br)C(=O)C(Br)=C(Br)C1=O LWHDQPLUIFIFFT-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 239000001856 Ethyl cellulose Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-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
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- RJGDLRCDCYRQOQ-UHFFFAOYSA-N anthrone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3CC2=C1 RJGDLRCDCYRQOQ-UHFFFAOYSA-N 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000005018 casein Substances 0.000 description 2
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 2
- 235000021240 caseins Nutrition 0.000 description 2
- 229920006026 co-polymeric resin Polymers 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 229920001249 ethyl cellulose Polymers 0.000 description 2
- 235000019325 ethyl cellulose Nutrition 0.000 description 2
- HTENFZMEHKCNMD-UHFFFAOYSA-N helio brilliant orange rk Chemical compound C1=CC=C2C(=O)C(C=C3Br)=C4C5=C2C1=C(Br)C=C5C(=O)C1=CC=CC3=C14 HTENFZMEHKCNMD-UHFFFAOYSA-N 0.000 description 2
- 150000003949 imides Chemical class 0.000 description 2
- 239000001023 inorganic pigment Substances 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- PJQYNUFEEZFYIS-UHFFFAOYSA-N perylene maroon Chemical compound C=12C3=CC=C(C(N(C)C4=O)=O)C2=C4C=CC=1C1=CC=C2C(=O)N(C)C(=O)C4=CC=C3C1=C42 PJQYNUFEEZFYIS-UHFFFAOYSA-N 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
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 2
- 230000003252 repetitive effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 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 2
- 239000010409 thin film Substances 0.000 description 2
- JOUDBUYBGJYFFP-FOCLMDBBSA-N thioindigo Chemical class S\1C2=CC=CC=C2C(=O)C/1=C1/C(=O)C2=CC=CC=C2S1 JOUDBUYBGJYFFP-FOCLMDBBSA-N 0.000 description 2
- SJHPCNCNNSSLPL-CSKARUKUSA-N (4e)-4-(ethoxymethylidene)-2-phenyl-1,3-oxazol-5-one Chemical class O1C(=O)C(=C/OCC)\N=C1C1=CC=CC=C1 SJHPCNCNNSSLPL-CSKARUKUSA-N 0.000 description 1
- ZXBSSAFKXWFUMF-UHFFFAOYSA-N 1,2,3-trinitrofluoren-9-one Chemical compound C12=CC=CC=C2C(=O)C2=C1C=C([N+](=O)[O-])C([N+]([O-])=O)=C2[N+]([O-])=O ZXBSSAFKXWFUMF-UHFFFAOYSA-N 0.000 description 1
- IZUKQUVSCNEFMJ-UHFFFAOYSA-N 1,2-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1[N+]([O-])=O IZUKQUVSCNEFMJ-UHFFFAOYSA-N 0.000 description 1
- FKASFBLJDCHBNZ-UHFFFAOYSA-N 1,3,4-oxadiazole Chemical compound C1=NN=CO1 FKASFBLJDCHBNZ-UHFFFAOYSA-N 0.000 description 1
- 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
- WPMHMYHJGDAHKX-UHFFFAOYSA-N 1-ethenylpyrene Chemical compound C1=C2C(C=C)=CC=C(C=C3)C2=C2C3=CC=CC2=C1 WPMHMYHJGDAHKX-UHFFFAOYSA-N 0.000 description 1
- JOERSAVCLPYNIZ-UHFFFAOYSA-N 2,4,5,7-tetranitrofluoren-9-one Chemical compound O=C1C2=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C2C2=C1C=C([N+](=O)[O-])C=C2[N+]([O-])=O JOERSAVCLPYNIZ-UHFFFAOYSA-N 0.000 description 1
- HDVGAFBXTXDYIB-UHFFFAOYSA-N 2,7-dinitrofluoren-9-one Chemical compound C1=C([N+]([O-])=O)C=C2C(=O)C3=CC([N+](=O)[O-])=CC=C3C2=C1 HDVGAFBXTXDYIB-UHFFFAOYSA-N 0.000 description 1
- BIEFDNUEROKZRA-UHFFFAOYSA-N 2-(2-phenylethenyl)aniline Chemical class NC1=CC=CC=C1C=CC1=CC=CC=C1 BIEFDNUEROKZRA-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
- XQGDNRFLRLSUFQ-UHFFFAOYSA-N 2H-pyranthren-1-one Chemical class C1=C(C2=C3C4=C56)C=CC3=CC5=C3C=CC=CC3=CC6=CC=C4C=C2C2=C1C(=O)CC=C2 XQGDNRFLRLSUFQ-UHFFFAOYSA-N 0.000 description 1
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical compound N1OC=CC=C1 BCHZICNRHXRCHY-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
- ITUYMTWJWYTELW-UHFFFAOYSA-N 4-chloroiminocyclohexa-2,5-dien-1-one Chemical compound ClN=C1C=CC(=O)C=C1 ITUYMTWJWYTELW-UHFFFAOYSA-N 0.000 description 1
- ROFZMKDROVBLNY-UHFFFAOYSA-N 4-nitro-2-benzofuran-1,3-dione Chemical compound [O-][N+](=O)C1=CC=CC2=C1C(=O)OC2=O ROFZMKDROVBLNY-UHFFFAOYSA-N 0.000 description 1
- NKJIFDNZPGLLSH-UHFFFAOYSA-N 4-nitrobenzonitrile Chemical compound [O-][N+](=O)C1=CC=C(C#N)C=C1 NKJIFDNZPGLLSH-UHFFFAOYSA-N 0.000 description 1
- MMVIDXVHQANYAE-UHFFFAOYSA-N 5-nitro-2-benzofuran-1,3-dione Chemical compound [O-][N+](=O)C1=CC=C2C(=O)OC(=O)C2=C1 MMVIDXVHQANYAE-UHFFFAOYSA-N 0.000 description 1
- OGOYZCQQQFAGRI-UHFFFAOYSA-N 9-ethenylanthracene Chemical compound C1=CC=C2C(C=C)=C(C=CC=C3)C3=CC2=C1 OGOYZCQQQFAGRI-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229910000967 As alloy Inorganic materials 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- WZELXJBMMZFDDU-UHFFFAOYSA-N Imidazol-2-one Chemical class O=C1N=CC=N1 WZELXJBMMZFDDU-UHFFFAOYSA-N 0.000 description 1
- 235000000177 Indigofera tinctoria Nutrition 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 229930192627 Naphthoquinone Natural products 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 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
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 1
- 229910001215 Te alloy Inorganic materials 0.000 description 1
- QHWKHLYUUZGSCW-UHFFFAOYSA-N Tetrabromophthalic anhydride Chemical compound BrC1=C(Br)C(Br)=C2C(=O)OC(=O)C2=C1Br QHWKHLYUUZGSCW-UHFFFAOYSA-N 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- UATJOMSPNYCXIX-UHFFFAOYSA-N Trinitrobenzene Chemical compound [O-][N+](=O)C1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1 UATJOMSPNYCXIX-UHFFFAOYSA-N 0.000 description 1
- ZTWQZJLUUZHJGS-UHFFFAOYSA-N Vat Yellow 4 Chemical class C12=CC=CC=C2C(=O)C2=CC=C3C4=CC=CC=C4C(=O)C4=C3C2=C1C=C4 ZTWQZJLUUZHJGS-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QLNFINLXAKOTJB-UHFFFAOYSA-N [As].[Se] Chemical compound [As].[Se] QLNFINLXAKOTJB-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000999 acridine dye Substances 0.000 description 1
- 150000001251 acridines Chemical class 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- XAIKOVRFTSBNNU-UHFFFAOYSA-N anthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C(=O)C2=C1.C1=CC=C2C(=O)C3=CC=CC=C3C(=O)C2=C1 XAIKOVRFTSBNNU-UHFFFAOYSA-N 0.000 description 1
- 229940027998 antiseptic and disinfectant acridine derivative Drugs 0.000 description 1
- XJHABGPPCLHLLV-UHFFFAOYSA-N benzo[de]isoquinoline-1,3-dione Chemical compound C1=CC(C(=O)NC2=O)=C3C2=CC=CC3=C1 XJHABGPPCLHLLV-UHFFFAOYSA-N 0.000 description 1
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical class C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 1
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 1
- JLATXDOZXBEBJX-UHFFFAOYSA-N cadmium(2+);selenium(2-);sulfide Chemical compound [S-2].[Se-2].[Cd+2].[Cd+2] JLATXDOZXBEBJX-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 125000005626 carbonium group Chemical group 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 150000001907 coumarones Chemical class 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 229940097275 indigo Drugs 0.000 description 1
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 description 1
- 229940079865 intestinal antiinfectives imidazole derivative Drugs 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 229910052981 lead sulfide Inorganic materials 0.000 description 1
- 229940056932 lead sulfide Drugs 0.000 description 1
- NNYHMCFMPHPHOQ-UHFFFAOYSA-N mellitic anhydride Chemical compound O=C1OC(=O)C2=C1C(C(OC1=O)=O)=C1C1=C2C(=O)OC1=O NNYHMCFMPHPHOQ-UHFFFAOYSA-N 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- NYGZLYXAPMMJTE-UHFFFAOYSA-M metanil yellow Chemical group [Na+].[O-]S(=O)(=O)C1=CC=CC(N=NC=2C=CC(NC=3C=CC=CC=3)=CC=2)=C1 NYGZLYXAPMMJTE-UHFFFAOYSA-M 0.000 description 1
- 239000000113 methacrylic resin Substances 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 150000002791 naphthoquinones Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000001005 nitro dye Substances 0.000 description 1
- 239000001006 nitroso dye Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical class C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 description 1
- 150000004866 oxadiazoles Chemical class 0.000 description 1
- 150000007978 oxazole derivatives Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
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- 229910052763 palladium Inorganic materials 0.000 description 1
- DGBWPZSGHAXYGK-UHFFFAOYSA-N perinone Chemical compound C12=NC3=CC=CC=C3N2C(=O)C2=CC=C3C4=C2C1=CC=C4C(=O)N1C2=CC=CC=C2N=C13 DGBWPZSGHAXYGK-UHFFFAOYSA-N 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 125000001791 phenazinyl group Chemical class C1(=CC=CC2=NC3=CC=CC=C3N=C12)* 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 239000001007 phthalocyanine dye Substances 0.000 description 1
- INAAIJLSXJJHOZ-UHFFFAOYSA-N pibenzimol Chemical class C1CN(C)CCN1C1=CC=C(N=C(N2)C=3C=C4NC(=NC4=CC=3)C=3C=CC(O)=CC=3)C2=C1 INAAIJLSXJJHOZ-UHFFFAOYSA-N 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- JEXVQSWXXUJEMA-UHFFFAOYSA-N pyrazol-3-one Chemical compound O=C1C=CN=N1 JEXVQSWXXUJEMA-UHFFFAOYSA-N 0.000 description 1
- 150000003219 pyrazolines Chemical class 0.000 description 1
- 125000002294 quinazolinyl group Chemical class N1=C(N=CC2=CC=CC=C12)* 0.000 description 1
- 239000001008 quinone-imine dye Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 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
- 239000002356 single layer Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- QXKXDIKCIPXUPL-UHFFFAOYSA-N sulfanylidenemercury Chemical compound [Hg]=S QXKXDIKCIPXUPL-UHFFFAOYSA-N 0.000 description 1
- 229940042055 systemic antimycotics triazole derivative Drugs 0.000 description 1
- 229910052714 tellurium Inorganic materials 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
- AUHHYELHRWCWEZ-UHFFFAOYSA-N tetrachlorophthalic anhydride Chemical compound ClC1=C(Cl)C(Cl)=C2C(=O)OC(=O)C2=C1Cl AUHHYELHRWCWEZ-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
- 239000001016 thiazine dye Substances 0.000 description 1
- 150000007979 thiazole derivatives Chemical class 0.000 description 1
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 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
- 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
- 238000001771 vacuum deposition Methods 0.000 description 1
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- YKSGNOMLAIJTLT-UHFFFAOYSA-N violanthrone Chemical class C12=C3C4=CC=C2C2=CC=CC=C2C(=O)C1=CC=C3C1=CC=C2C(=O)C3=CC=CC=C3C3=CC=C4C1=C32 YKSGNOMLAIJTLT-UHFFFAOYSA-N 0.000 description 1
- 239000001018 xanthene dye Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
- G03G5/02—Charge-receiving layers
- G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
- G03G5/043—Photoconductive layers characterised by having two or more layers or characterised by their composite structure
- G03G5/0436—Photoconductive layers characterised by having two or more layers or characterised by their composite structure combining organic and inorganic layers
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Photoreceptors In Electrophotography (AREA)
Description
本発明は電子写真感光体、詳しくは、支持体上
に光導電性感光層と該感光層の保護層とを有する
電子写真感光体に関する。
従来、電子写真感光体としてはZnO／樹脂分散
層を感光層とする感光体、フタロシアニン系顔
料／樹脂分散層を感光層とする感光体、Se、Ｓ
−Te又はSe−As等の蒸着層を感光層とする感光
体、Cds／樹脂分散層を感光層とする感光体、ポ
リビニルカルバゾール又は２，４，７−トリニト
ロフルオレノン等の有機半導体層を感光層とする
感光体等が知られており、原稿画像の明暗のパタ
ーンに従つた静電潜像及び顕像を形成する電子写
真法の像支持体として、種々の電子写真プロセ
ス、特に反復転写式電子写真プロセスに用いられ
る。
かかる反復転写式、電子写真プロセスに組込ま
れた感光体は、複数枚の複写物を連続的に得られ
る特性と構造を有することが要請される。
電子写真プロセスの中で繰り返し使用しても、
常に初期の電子写真特性を維持し得るものでなく
てはならず、複数枚の複写物を連続的に得るに充
分なだけの耐久性を有していなければ、実用的な
感光体であるとは言えない。
即ち、電子写真プロセスの工程は、簡単に述べ
ても帯電、露光、現像、転写、クリーニングの工
程を経て１枚の複写物が得られており、複数枚の
複写物を連続的に得る時、感光体は、照射光によ
る光分解、帯電時の電撃破壊、転写紙の剥離ある
いは残留トナーのクリーニング等で損傷を受け易
く、感光体の電子写真特性と感光体の繰り返し特
性の維持には、表面の耐久性、耐摩耗性が特に要
求される。
従来の感光体では、この電子写真特性を向上さ
せるための技術と、表面の耐久性を向上させるた
めの技術とがが相反する傾向に有り、二律背反す
る条件の中から実用的な感光体を技術的に得て、
実用に供していた。
例えば有機半導体から成る電子写真感光体にお
いては、光導電性ポリ−Ｎビニルカルバゾール又
はその誘導体に増感剤を含有させた感光層、ポリ
カーボネート樹脂をバインダーとしこの中に光導
電性有機染料又は顔料を分散した感光層を有する
ものが用いられるが、かかる有機光導性化合物は
機械的強度が弱く、さらには光、熱、電撃、薬品
等に対する抵抗力が弱いため、例えば、反復転写
式複写等の感光体として使用したときは、繰り返
えし使用の過程で電子写真性能が劣化してしま
う。そこで、例えばポリビニルアルコール、カゼ
イン、カルボキシメチルセルローズ、可溶性ナイ
ロン、ポリアミド樹脂等のアルコール又は水可溶
性の保護層を設けて感光層表面の耐久性を向上す
る施策が施されているが、かかる保護層は耐湿性
に難点があり、吸湿して感光層の電子写真性能が
低下する。さらにはポリスチレン−アクリル、ポ
リブタジエン、エチルセルローズ、ポリ醋酸ビニ
ル等の有機溶剤可溶の保護層も知られているが塗
布加工時に感光層を損傷する等のため好ましくな
い。さらにはかかる有機質の保護層は元来薄膜で
は機械的耐久性が少なく、充分な保護層としての
機能を発揮するには例えば20μ以上の厚みが必要
とされる。
しかし保護層の厚みを大ならしめることは通常
の電子写真法による作像は不可能である。即ち、
帯電、露光の繰り返しの過程で残留電位が増大し
て、現像時のカブリが増大し、遂には作像が不可
能になる。そこで、例えばＮ−Ｐシステムの如き
特殊の電子写真プロセスが必要となる。
このＮ−Ｐシステムは感光層表面に例えば
100μの厚い絶縁層を設けたものが用いられ、例
えば一次帯電→逆極性二次帯電及び同時像露光→
全面露光で代表されるプロセスをへて静電荷像が
形成されるので極めて複雑な作像工程が必要とな
り、装置も高価となるなどの問題がある。このよ
うに有機半導体を用いた感光体を反復転写式電子
写真法に適用するには多くの欠点を有していた。
このように有機半導体から成る電子写真用感光
体を得るには多くの困難と欠点が伴つていた。
本発明者等は鋭意研究の結果新規な有機半導体
電子写真用感光体を見い出した。
本発明の目的は、電子写真プロセス、いわゆる
カールソンプロセスで用い得る、保護膜を有する
有機半導体から成る感光体を提供するものであ
り、繰り返し使用による残留電位の蓄積もなく、
変化する環境条件にも安定であり、膜厚が数ミク
ロン以下と言つた比較的薄い膜厚で充分満足し得
る機械的強度を有しており、好ましい電子写真の
光学的特性を有する事等の従来の欠点を解決した
有機半導体から成る感光体を提供することにあ
る。
かかる目的は、支持体上に有機光導電性材料を
含有する光導電性感光層と該感光層の保護層とを
有する有機電子写真感光体において、前記保護層
が、水素原子および／または弗素原子を含む非晶
質炭化シリコン又は水素原子および／または弗素
原子を含む非晶質窒化シリコンからなる膜厚が
0.05μ〜1μの層から成ることを特徴とする有機電
子写真感光体によつて達成される。
本発明において、保護層は、光導電性層が感光
性を有する光の波長に対し、実質的に透明でなく
てはならない。
しかし、従来、保護層が高抵抗を有する場合に
は、複写の繰り返しに伴い、保護層へ残留電荷が
蓄積し、残留電位が高くなり、複数枚の複写物を
連続して得ようとすれば、複写画像に地肌汚れが
生じていた。
本発明は、この問題を解決する為に、保護層が
可視域ではほぼ透明であるが可視短波長光
（500μｍ以下）及び紫外光に対しては光導電性を
有する素材で構成されている。即ち、像露光と同
時又はその前後のクリーニング時に可視短波長光
（500μｍ以下）及び紫外光を照射することによ
り、保護層に蓄積した残留電荷が中和され、地肌
部の残留電位は除去される。
残留電荷除去手段を用いたプロセスでは複数枚
の複写物を連続して複写しても、複写の繰り返し
に伴う電荷の蓄積がなく、地肌汚れのない鮮明な
画像が得られる。
更に、通常の有機感光体においては紫外光照射
によつて、感光体の経時劣化が有り、感度劣化お
よび残留電位上昇等の問題が生じていたが、この
点からも、本発明は、保護層が紫外光吸収能を有
するので、感光体の劣化を防止する利点を有す
る。
本発明の保護層を有機半導体化合物からなる光
導電性材料を含有する層上に形成する方法として
は、イオンプレーテイング法、スパツターリング
法及びグロー放電法等が挙げられる。なお、大面
積に亘つて均一な膜を形成する方法としてはグロ
ー放電法が好ましい。
本発明の保護層は、水素原子および／または弗
素原子を含む非晶質炭化シリコン膜又は、水素原
子および／または弗素原子を含む非晶質窒化シリ
コン膜で構成される。グロー放電法による場合に
は、グロー放電装置内にSiH4ガスもしくは、
SiH4とSiF4ガス、SiH4ガスとC2H4ガス等の炭化
水素ガスとを含むArガス等を導入し、0.1〜
1Torrの範囲の圧力でグロー放電分解を行い、水
素原子および／またはフツ素原子を含む非晶質炭
化シリコン膜を得ることが出来る。一般にSi1-x
Cx：Ｈ又はSi1-xCx：Ｈ：Ｆで、0.2＜ｘ≦0.4にお
ける構造を有する。一方、非晶質窒化シリコン膜
は、SiH4もしくはSiH4、SiF4とNH4ガスとを含
む、Arガス等を導入し、0.1〜1Torrの範囲の圧
力でグロー放電分解を行うことにより得られる。
この時、SiH4／NH4が0.05〜0.15であることが望
ましい。保護層膜厚は、0.05〜1μである。
本発明の保護層は機械的強度が高く、有機半導
体表面の耐摩耗性、耐久性を著しく向上させる。
また、保護層膜厚の薄膜化が容易に行なえること
に加えて、繰り返し使用によつても安定した帯電
特性が得られる。
更に上記保護層は、可視光に対して透明であ
り、原稿照明ランプの出力を増加させる必要はな
く、光学的特性も維持される。
また上記保護層の紫外線吸収能により、光導電
性層表面の酸化が防止できるため感光体の経時安
定性が極めて良好となる。
特に上記保護層は、光導電性を有する為、像露
光の前後に紫外光ないしは可視短波長光（500n
ｍ以下）照射を行なうことにより残留電荷の消去
が可能であり、残留電荷除去手段を設けること
で、地肌部への現像剤付着がなくなり、クリーニ
ングブレードの負荷を低減することが出来るの
で、感光体表面の摩耗を極めて少くすることがで
きるとともに縦筋汚れの発生も防ぐことができ
る。
又光源としてレーザー光（例えば発光波長域
6328ÅHe−Neレーザー光）を用いて像露光を行
い短波長の光により像露光の前后に全面露光を組
合せて施すことにより、保護層に電荷の残留を伴
うことのない解像力の高い静電荷像が形成され、
現像後鮮明な可視像が得られるので、実用上有効
である。
本発明の光導電性層としてはポリ−Ｎ−ビニル
カルバゾール（以下PVKと略す）／２，４，７
−トリニトロ−９−フルオレノン（以下TNFと
略す）、ポリビニルピレン、ニトロ化ポリアセナ
フチレン、ニトロ化ポリビニルナフタリン、テト
ラシアノキノジメタン錯体等の単層からなるも
の、あるいはPVK／無定形セレン、オキザジア
ゾール誘導体／ペリレン誘導体（米国特許第
3871882号明細書参照）等のキヤリア発生層とキ
ヤリア輸送層の二層構成をなす有機光導電体を使
用することができる。
キヤリア発生物質としては可視光を吸収してフ
リーキヤリアを発生するものであれば、無機顔料
及び有機色素の何れをも用いることができる。無
定形セレン、三方晶系セレン、セレン−砒素合
金、セレン−テルル合金、硫化カドミウム、セレ
ン化カドミウム、硫セレン化カドミウム、硫化水
銀、酸化鉛、硫化鉛等の無機顔料の外、次の代表
例で示されるような有機色素を用いてもよい。
(1) モノアゾ色素、ポリアゾ色素、金属錯塩アゾ
色素、ピラゾロンアゾ色素、スチルベンアゾ色
素及びチアゾールアゾ色素等のアゾ系色素
(2) ペリレン酸無水物及びペリレン酸イミド等の
ペリレン系色素
(3) アントラキノン誘導体、アントアントロン誘
導体、ジベンズピレンキノン誘導体、ピラント
ロン誘導体、ビオラントロン誘導体及びイソビ
オラントロン誘導体等のアントラキノン系乃至
多環キノン系色素
(4) インジゴ誘導体及びチオインジゴ誘導体等の
インジゴイド系色素
(5) 金属フタロシアニン及び無金属フタロシアニ
ン等のフタロシアニン系色素
(6) ジフエニルメタン色素、トリフエニルメタン
色素、キサンテン色素及びアクリジン色素等の
カルボニウム系色素
(7) アジン色素、オキサジン色素及びチアジン色
素等のキノンイミン系色素
(8) シアニン色素及びアゾメチン色素等のメチン
系色素
(9) キノリン系色素
(10) ニトロ系色素
(11) ニトロソ系色素
(12) ベンゾキノン及びナフトキノン系色素
(13) ナフタルイミド系色素
(14) ビスベンズイミダゾール誘導体等のペリノ
ン系色素
(15) キナクリドン系色素
かかるキヤリア発生層３は後記実施例１および
４に示されるような真空蒸着法によつても良い
し、また後記実施例２に示されるような塗布法に
よつても良い。そして、この塗布法による場合に
用いられるバインダー樹脂としては、例えばポリ
エチレン、ポリプロピレン、アクリル樹脂、メタ
クリル樹脂、塩化ビニル樹脂、酢酸ビニル樹脂、
エポキシ樹脂、ポリウレタン樹脂、フエノール樹
脂、ポリエステル樹脂、アルキツド樹脂、ポリカ
ーボネート樹脂、シリコン樹脂、メラミン樹脂等
の付加重合型樹脂、重付加型樹脂、重縮合型樹脂
並びにこれらの樹脂の繰返し単位のうちの２つ以
上を含む共重合体樹脂、例えば塩化ビニル−酢酸
ビニル共重合体樹脂、塩化ビニル−酢酸ビニル−
無水マレイン酸共重合体樹脂等を挙げることがで
きる。しかしバインダー樹脂はこれらに限定され
るものではなく、斯かる用途に一般に用いられる
すべての樹脂を使用することができる。
前記キヤリア発生層に加えることのできる特定
乃至非特定の極性のキヤリアに対する移動度の大
きいキヤリア輸送物質としては、本発明において
キヤリア輸送層４等の構成に用いる、後述する特
定のキヤリア輸送物質をその一部又は全部として
用いることもできるが、電子写真感光体としての
性能を考慮して他のキヤリア輸送物質を用いても
よい。
更にこのキヤリア発生層３には感度の向上、残
留電位乃至反復使用時の疲労低減等を目的として
一種又は二種以上の電子受容性物質を含有せしめ
ることができる。
ここに用いることのできる電子受容性物質とし
ては、例えば、無水コハク酸、無水マレイン酸、
ジブロム無水マレイン酸、無水フタル酸、テトラ
クロル無水フタル酸、テトラブロム無水フタル
酸、３−ニトロ無水フタル酸、４−ニトロ無水フ
タル酸、無水ピロメリツト酸、無水メリツト酸、
テトラシアノエチレン、テトラシアノキノジメタ
ン、ｏ−ジニトロベンゼン、ｍ−ジニトロベンゼ
ン、１，３，５−トリニトロベンゼン、パラニト
ロベンゾニトリル、ビクリルクロライド、キノン
クロルイミド、クロラニル、ブロマニルを挙げる
ことができる。
本発明においてキヤリア輸送層４に使用される
キヤリア輸送物質としてはオキサゾール誘導体、
オキサジアゾール誘導体、チアゾール誘導体、チ
アシアゾール誘導体、トリアゾール誘導体、イミ
ダゾール誘導体、イミダゾロン誘導体、イミタゾ
リジン誘導体、ビスイミダゾリジン誘導体、ピラ
ゾリン誘導体、オキサゾロン誘導体、ベンゾチア
ゾール誘導体、ベンズイミタゾール誘導体、キナ
ゾリン誘導体、ベンゾフラン誘導体、アクリジン
誘導体、フエナジン誘導体、アミノスチルベン誘
導体、ポリ−Ｎ−ビニルカルバゾール、ポリ−１
−ビニルピレン、ポリ−９−ビニルアントラセ
ン、２，４，７−トリニトロフルオレノン、２，
４，５，７−テトラニトロフルオレノン、２，７
−ジニトロフルオレノン等が挙げられる。
次に本発明に有効な支持体としては、アルミニ
ウム、パラジウム、銅、鉄、ニツケル、ステンレ
ス、金、銀、錫、亜鉛などの金属または酸化錫な
どの金属酸化物を蒸着またはラミネートして得ら
れる支持体または紙もしくはプラスチツクフイル
ムに前記金属、金属酸化物もしくはカーボンブラ
ツクの粉末を樹脂中に分散含有せしめた層を塗布
して得られる支持体などの種々の導電性支持体が
用いられる。
また本発明においては、前記導電性支持体と感
光層との間に塩化ビニル−酢酸ビニル−無水マレ
イン酸共重合体、カゼイン、ポリビニルアルコー
ル、エチルセルローズまたは酢酸ビニルなどから
なる中間層を前記支持体と感光層の接着性または
感光層の静電特性を改良する目的で設けることが
できる。
以下、実施例を挙げて本発明を例証するが、本
発明の実施態様はこれらに限定されない。
実施例 １
厚さ75μのポリエチレンテレフタレートフイル
ム上にアルミニウム薄層をラミネートした導電性
支持体上に、塩化ビニル−酢酸ビニル−無水マレ
イン酸共重合体「エスレツクMF−10」（積水化
学工業製）より成る厚さ約0.1μの中間層を設け、
次に、キヤリア発生層としてＮ，N′−ジメチル
−ペリレン−３，４，９，10−テトラカルボン酸
ジイミド（パリオゲンマルーン3920、C.I.No.
71130）を真空蒸着法により前記中間層上に厚さ
約0.3μに形成した。次に、キヤリア輸送層として
２，５−ビス（４−ジエチルアミノフエニル）−
１，３，４−オキサジアゾールの５ｇとポリカー
ボネート樹脂「パンライトＬ−1250」（帝人化成
社製）10ｇとを１，２−ジクロルエタン100mlに
溶解した溶液を前記キヤリア輸送層上に塗布し、
温度70℃で１時間乾燥せしめて厚さ13μに形成し
た。次に13.56MHzの高周波グロー放電装置に
3vol％のSiH4ガスと17vol％のC2H4ガスとを含む
Arガスを導入し、0.5Torrの圧力でグロー放電分
解を行い前記キヤリア発生層上に厚さ0.4μの保護
層を有する感光体（試料１）を作成した。比較の
為、前記保護層を有していない他は本実施例と同
様の感光体（比較品１）を作成した。
この試料１の感光体を市販の複写機「Ｕ−
Bix2000R」〔小西六写真工業(株)製〕に装着し、
３万回コピーに亘る実写試験を行つたところ、全
て鮮明な画像が得られた。一方、比較品１を用い
て、同様の実験を行つたところ、15000回コピー
を行つた時点で画像の一部に縦筋が生じ、鮮明な
画像が得られなかつた。
実施例 ２
75μ厚ポリエチレンテレフタレートフイルム上
にアルミニウム薄層をラミネートした導電性支持
体上に塩化ビニル−酢酸ビニル−無水マレイン酸
共重合体「エスレツクMF−10」（積水化学工業
製）よりなる厚さ約0.1μの中間層を設け、次に前
記中間層上にアントアントロン系試料「モノライ
トレツド2Y」（C.I.No.59300）を、２〜３×
10-4Torrの真空雰囲気中において蒸着源温度350
℃で３分間蒸着せしめ、厚さ約0.5μのキヤリア発
生層を形成した。
次に下記構造を有するヒドラゾン化合物の５ｇ
と
ポリカーボネート樹脂「パンライトＬ−1250」
（帝人化成社製）10ｇとを１，２−ジクロルエタ
ン100mlに溶解した溶液をドクターブレードを用
いて前記キヤリア発生層上に塗布し、温度70℃で
１時間乾燥せしめて厚さ12μのキヤリア輸送層を
形成した。次に13.56MHzの高周波グロー放電装
置に18vol％のNH3と2vol％のSiH4とを含むArガ
スを導入し0.2Torrの圧力でグロー放電分解を行
い、前記キヤリア輸送層上に厚さ0.2μの保護層を
有する感光体（試料２）を作成した。比較の為、
保護層を有していないこと以外は本実施例と同様
の感光体（比較品２）を作成した。
この試料１の感光体を市販の複写機「Ｕ−
Bix2000R」に装着し、40000回複写を行つたと
ころ、全て鮮明な画像が得られた。一方、比較品
２を用いて同様の方法で複写を行つた所、15000
回複写を行つた時点で画像の一部に縦筋が生じ、
鮮明な画像が得られなかつた。
実施例 ３
前記試料１と同様のキヤリア発生層とキヤリア
輸送層からなる２層構造感光体上に、エステルア
クリレート樹脂「アロニツクスＭ−8060」（東亜
合成化学工業製）をトルエンで希釈し、ドクター
ブレードを用いて塗布し、温度80℃で６時間乾燥
せしめて、厚さ2μの保護層を有する感光体（比
較品３）を作成した。試料１と比較品３とを市販
の複写機「Ｕ−Bix2000R」に装着して連続複
写テストを行ない、露光絞り値2.5における感光
層の画像地肌部の電位を「エレクトロスタテイツ
クボルトメーター144D−1D型」（モンローエレ
クトロニクスインコーポレーテツド社製）を用い
て測定した。その結果は第１表に示す通りであつ
た。
The present invention relates to an electrophotographic photoreceptor, and more particularly, to an electrophotographic photoreceptor having a photoconductive photosensitive layer and a protective layer for the photosensitive layer on a support. Conventionally, electrophotographic photoreceptors include photoreceptors with a ZnO/resin dispersion layer as a photoreceptor layer, photoreceptors with a phthalocyanine pigment/resin dispersion layer as a photoreceptor layer, Se, S
A photoreceptor with a vapor deposited layer such as -Te or Se-As as a photoreceptor layer, a photoreceptor with a Cds/resin dispersion layer as a photoreceptor layer, an organic semiconductor layer such as polyvinylcarbazole or 2,4,7-trinitrofluorenone, etc. Photoreceptors with layers are known, and are used as image supports for electrophotography to form electrostatic latent images and developed images that follow the light-dark pattern of the original image, and are used in various electrophotographic processes, especially repetitive transfer type Used in electrophotographic processes. A photoreceptor incorporated in such a repetitive transfer type electrophotographic process is required to have characteristics and structure that allow a plurality of copies to be continuously obtained. Even after repeated use in the electrophotographic process,
It must be able to maintain its initial electrophotographic properties at all times, and must be durable enough to produce multiple copies in succession to be considered a practical photoreceptor. I can't say that. In other words, in the electrophotographic process, a single copy is obtained through the steps of charging, exposure, development, transfer, and cleaning, and when multiple copies are obtained in succession, Photoreceptors are susceptible to damage due to photodecomposition caused by irradiation light, electric shock damage during charging, peeling of transfer paper, and cleaning of residual toner. Durability and abrasion resistance are particularly required. In conventional photoreceptors, the techniques for improving the electrophotographic properties and the techniques for improving the surface durability tend to conflict with each other. get the point,
It was put to practical use. For example, in an electrophotographic photoreceptor made of an organic semiconductor, a photosensitive layer is made of a photoconductive poly-N vinyl carbazole or a derivative thereof containing a sensitizer, a polycarbonate resin is used as a binder, and a photoconductive organic dye or pigment is contained in the photosensitive layer. A compound having a dispersed photosensitive layer is used, but such an organic photoconductive compound has low mechanical strength and also has low resistance to light, heat, electric shock, chemicals, etc. When used as a body, the electrophotographic performance deteriorates with repeated use. Therefore, measures have been taken to improve the durability of the photosensitive layer surface by providing an alcohol- or water-soluble protective layer such as polyvinyl alcohol, casein, carboxymethyl cellulose, soluble nylon, or polyamide resin. It has a problem with moisture resistance, and absorbs moisture, which deteriorates the electrophotographic performance of the photosensitive layer. Furthermore, protective layers soluble in organic solvents such as polystyrene-acrylic, polybutadiene, ethyl cellulose, and polyvinyl acetate are known, but these are not preferred because they damage the photosensitive layer during coating. Furthermore, such an organic protective layer originally has low mechanical durability as a thin film, and requires a thickness of, for example, 20 μm or more in order to function as a sufficient protective layer. However, it is impossible to increase the thickness of the protective layer by forming an image by ordinary electrophotography. That is,
During the process of repeated charging and exposure, the residual potential increases, and fog during development increases, eventually making it impossible to form an image. Therefore, a special electrophotographic process such as the NP system is required. This N-P system is applied to the surface of the photosensitive layer, for example.
A device with a 100μ thick insulating layer is used, for example, primary charging → reverse polarity secondary charging and simultaneous image exposure →
Since an electrostatic charge image is formed through a process typified by full-surface exposure, an extremely complicated image forming process is required, and the apparatus becomes expensive. As described above, there are many drawbacks to applying a photoreceptor using an organic semiconductor to repeated transfer electrophotography. As described above, many difficulties and drawbacks have been involved in obtaining electrophotographic photoreceptors made of organic semiconductors. As a result of intensive research, the present inventors have discovered a novel organic semiconductor electrophotographic photoreceptor. An object of the present invention is to provide a photoreceptor made of an organic semiconductor having a protective film, which can be used in an electrophotographic process, the so-called Carlson process, and which does not accumulate residual potential due to repeated use.
It is stable under changing environmental conditions, has sufficient mechanical strength even with a relatively thin film thickness of several microns or less, and has favorable optical properties for electrophotography. An object of the present invention is to provide a photoreceptor made of an organic semiconductor that solves the conventional drawbacks. This object is an organic electrophotographic photoreceptor having a photoconductive photosensitive layer containing an organic photoconductive material on a support and a protective layer for the photosensitive layer, in which the protective layer contains hydrogen atoms and/or fluorine atoms. or amorphous silicon nitride containing hydrogen atoms and/or fluorine atoms.
This is achieved by an organic electrophotographic photoreceptor characterized by comprising a layer of 0.05μ to 1μ. In the present invention, the protective layer must be substantially transparent to the wavelength of light to which the photoconductive layer is sensitive. However, conventionally, when the protective layer has a high resistance, residual charges accumulate in the protective layer with repeated copying, and the residual potential becomes high. , The copied image had background stains. In the present invention, in order to solve this problem, the protective layer is made of a material that is almost transparent in the visible range but photoconductive to visible short wavelength light (500 μm or less) and ultraviolet light. That is, by irradiating visible short wavelength light (500 μm or less) and ultraviolet light during cleaning at the same time as or before and after image exposure, residual charges accumulated in the protective layer are neutralized and residual potential in the background area is removed. . In the process using the residual charge removing means, even if a plurality of copies are successively copied, there is no charge accumulation due to repeated copying, and a clear image without background stains can be obtained. Furthermore, in conventional organic photoreceptors, irradiation with ultraviolet light causes deterioration of the photoreceptor over time, resulting in problems such as deterioration of sensitivity and increase in residual potential. has the ability to absorb ultraviolet light, so it has the advantage of preventing deterioration of the photoreceptor. Examples of methods for forming the protective layer of the present invention on a layer containing a photoconductive material made of an organic semiconductor compound include an ion plating method, a sputtering method, and a glow discharge method. Note that a glow discharge method is preferable as a method for forming a uniform film over a large area. The protective layer of the present invention is composed of an amorphous silicon carbide film containing hydrogen atoms and/or fluorine atoms, or an amorphous silicon nitride film containing hydrogen atoms and/or fluorine atoms. When using the glow discharge method, SiH 4 gas or
Introduce Ar gas containing SiH 4 and SiF 4 gas, SiH 4 gas and hydrocarbon gas such as C 2 H 4 gas, and
Glow discharge decomposition is performed at a pressure in the range of 1 Torr to obtain an amorphous silicon carbide film containing hydrogen atoms and/or fluorine atoms. Generally Si 1-x
It has a structure in which C x :H or Si 1-x C x :H:F satisfies 0.2<x≦0.4. On the other hand, an amorphous silicon nitride film can be obtained by introducing Ar gas, etc. containing SiH 4 or SiH 4 , SiF 4 and NH 4 gas, and performing glow discharge decomposition at a pressure in the range of 0.1 to 1 Torr. .
At this time, it is desirable that SiH 4 /NH 4 is 0.05 to 0.15. The thickness of the protective layer is 0.05 to 1μ. The protective layer of the present invention has high mechanical strength and significantly improves the abrasion resistance and durability of the organic semiconductor surface.
Further, in addition to being able to easily reduce the thickness of the protective layer, stable charging characteristics can be obtained even after repeated use. Moreover, the protective layer is transparent to visible light, so there is no need to increase the output of the document illumination lamp, and the optical properties are maintained. Furthermore, the ultraviolet absorbing ability of the protective layer prevents oxidation of the surface of the photoconductive layer, resulting in extremely good stability of the photoreceptor over time. In particular, since the above protective layer has photoconductivity, it is necessary to use ultraviolet light or visible short wavelength light (500n) before and after image exposure.
The residual charge can be erased by irradiating the photoreceptor (less than 100 m), and by providing a residual charge removal means, developer adhesion to the background part is eliminated and the load on the cleaning blade can be reduced. Abrasion on the surface can be extremely reduced, and the occurrence of vertical streak stains can also be prevented. Laser light (e.g. emission wavelength range) can also be used as a light source.
By performing imagewise exposure using a 6328Å He-Ne laser beam (6328Å He-Ne laser beam) and then performing full-body exposure before and after the imagewise exposure using short-wavelength light, a high-resolution electrostatic charge image with no charge remaining on the protective layer can be created. formed,
It is practically effective because a clear visible image can be obtained after development. The photoconductive layer of the present invention is poly-N-vinylcarbazole (hereinafter abbreviated as PVK)/2,4,7
-Those consisting of a single layer of trinitro-9-fluorenone (hereinafter abbreviated as TNF), polyvinylpyrene, nitrated polyacenaphthylene, nitrated polyvinylnaphthalene, tetracyanoquinodimethane complex, or PVK/amorphous selenium, oxadiazole Derivatives/perylene derivatives (U.S. Patent No.
An organic photoconductor having a two-layer structure consisting of a carrier generation layer and a carrier transport layer, such as JP 3871882, etc., can be used. As the carrier generating substance, any inorganic pigment or organic dye can be used as long as it absorbs visible light and generates free carriers. In addition to inorganic pigments such as amorphous selenium, trigonal selenium, selenium-arsenic alloy, selenium-tellurium alloy, cadmium sulfide, cadmium selenide, cadmium selenide sulfide, mercury sulfide, lead oxide, lead sulfide, the following representative examples Organic dyes such as those shown in may also be used. (1) Azo dyes such as monoazo dyes, polyazo dyes, metal complex azo dyes, pyrazolone azo dyes, stilbene azo dyes, and thiazole azo dyes (2) Perylene dyes such as perylenic anhydride and perylenic acid imide (3) Anthraquinone Anthraquinone or polycyclic quinone dyes such as derivatives, anthorone derivatives, dibenzpyrenequinone derivatives, pyranthrone derivatives, violanthrone derivatives and isoviolanthrone derivatives (4) Indigoid dyes such as indigo derivatives and thioindigo derivatives (5) Metals Phthalocyanine dyes such as phthalocyanine and metal-free phthalocyanine (6) Carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes, xanthene dyes and acridine dyes (7) Quinoneimine dyes such as azine dyes, oxazine dyes and thiazine dyes (8) Methine dyes such as cyanine dyes and azomethine dyes (9) Quinoline dyes (10) Nitro dyes (11) Nitroso dyes (12) Benzoquinone and naphthoquinone dyes (13) Naphthalimide dyes (14) Bisbenzimidazole derivatives Perinone dyes (15), quinacridone dyes, etc. The carrier generation layer 3 may be formed by a vacuum deposition method as shown in Examples 1 and 4 below, or by a coating method as shown in Example 2 below. You can also depend on it. Binder resins used in this coating method include, for example, polyethylene, polypropylene, acrylic resin, methacrylic resin, vinyl chloride resin, vinyl acetate resin,
Addition polymerization type resins, polyaddition type resins, polycondensation type resins such as epoxy resins, polyurethane resins, phenolic resins, polyester resins, alkyd resins, polycarbonate resins, silicone resins, melamine resins, and two of the repeating units of these resins. Copolymer resins containing at least
Examples include maleic anhydride copolymer resin. However, the binder resin is not limited to these, and all resins commonly used for such purposes can be used. As carrier transport substances having high mobility for carriers of specific or non-specific polarity that can be added to the carrier generation layer, specific carrier transport substances to be described later, which are used in the construction of the carrier transport layer 4 etc. in the present invention, may be used. Although it can be used in part or in whole, other carrier transport materials may be used in consideration of the performance as an electrophotographic photoreceptor. Further, the carrier generation layer 3 may contain one or more electron-accepting substances for the purpose of improving sensitivity, reducing residual potential or fatigue during repeated use, and the like. Examples of electron-accepting substances that can be used here include succinic anhydride, maleic anhydride,
Dibromaleic anhydride, phthalic anhydride, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, 3-nitrophthalic anhydride, 4-nitrophthalic anhydride, pyromellitic anhydride, mellitic anhydride,
Mention may be made of tetracyanoethylene, tetracyanoquinodimethane, o-dinitrobenzene, m-dinitrobenzene, 1,3,5-trinitrobenzene, paranitrobenzonitrile, vicryl chloride, quinone chlorimide, chloranil, bromanil. . In the present invention, carrier transport materials used in the carrier transport layer 4 include oxazole derivatives,
Oxadiazole derivatives, thiazole derivatives, thiasiazole derivatives, triazole derivatives, imidazole derivatives, imidazolone derivatives, imitazolidine derivatives, bisimidazolidine derivatives, pyrazoline derivatives, oxazolone derivatives, benzothiazole derivatives, benzimitazole derivatives, quinazoline derivatives, benzofuran derivatives, Acridine derivatives, phenazine derivatives, aminostilbene derivatives, poly-N-vinylcarbazole, poly-1
-vinylpyrene, poly-9-vinylanthracene, 2,4,7-trinitrofluorenone, 2,
4,5,7-tetranitrofluorenone, 2,7
-dinitrofluorenone and the like. Next, as a support that is effective in the present invention, metals such as aluminum, palladium, copper, iron, nickel, stainless steel, gold, silver, tin, and zinc, or metal oxides such as tin oxide are deposited or laminated. Various conductive supports can be used, such as a support obtained by applying a layer containing the metal, metal oxide, or carbon black powder dispersed in a resin to a support or paper or plastic film. Further, in the present invention, an intermediate layer made of vinyl chloride-vinyl acetate-maleic anhydride copolymer, casein, polyvinyl alcohol, ethyl cellulose, vinyl acetate, etc. is provided between the conductive support and the photosensitive layer. It can be provided for the purpose of improving the adhesion of the photosensitive layer or the electrostatic properties of the photosensitive layer. The present invention will be illustrated below with reference to examples, but the embodiments of the present invention are not limited thereto. Example 1 A vinyl chloride-vinyl acetate-maleic anhydride copolymer "Eslec MF-10" (manufactured by Sekisui Chemical Co., Ltd.) was coated on a conductive support consisting of a thin aluminum layer laminated on a 75μ thick polyethylene terephthalate film. An intermediate layer with a thickness of about 0.1μ is provided,
Next, N,N'-dimethyl-perylene-3,4,9,10-tetracarboxylic acid diimide (Paliogen Maroon 3920, CI No.
71130) was formed to a thickness of about 0.3 μm on the intermediate layer by vacuum evaporation. Next, 2,5-bis(4-diethylaminophenyl)-
A solution prepared by dissolving 5 g of 1,3,4-oxadiazole and 10 g of polycarbonate resin "Panlite L-1250" (manufactured by Teijin Chemicals) in 100 ml of 1,2-dichloroethane is applied on the carrier transport layer,
It was dried at a temperature of 70°C for 1 hour and formed to a thickness of 13μ. Next, a 13.56MHz high frequency glow discharge device
Contains 3vol% SiH4 gas and 17vol% C2H4 gas
Ar gas was introduced and glow discharge decomposition was performed at a pressure of 0.5 Torr to produce a photoreceptor (sample 1) having a protective layer of 0.4 μm in thickness on the carrier generation layer. For comparison, a photoreceptor (comparative product 1) similar to this example was prepared except that it did not have the protective layer. The photoconductor of Sample 1 was transferred to a commercially available copying machine "U-
Bix2000R” [manufactured by Konishiroku Photo Industry Co., Ltd.].
When a live-action test was conducted over 30,000 copies, clear images were obtained in all cases. On the other hand, when a similar experiment was conducted using Comparative Product 1, vertical streaks appeared in a portion of the image after 15,000 copies were made, and a clear image could not be obtained. Example 2 A thin layer of vinyl chloride-vinyl acetate-maleic anhydride copolymer "Eslec MF-10" (manufactured by Sekisui Chemical Co., Ltd.) was coated on a conductive support consisting of a thin aluminum layer laminated on a 75μ thick polyethylene terephthalate film. An intermediate layer of about 0.1 μm is provided, and then an anthrone-based sample “Monolite Red 2Y” (CI No. 59300) is applied 2 to 3× on the intermediate layer.
Deposition source temperature 350 in a vacuum atmosphere of 10 -4 Torr
Deposition was carried out for 3 minutes at 0.degree. C. to form a carrier generation layer with a thickness of about 0.5 .mu.m. Next, 5g of a hydrazone compound having the following structure
and Polycarbonate resin “Panlite L-1250”
(manufactured by Teijin Kasei Co., Ltd.) and dissolved in 100 ml of 1,2-dichloroethane, a solution was applied onto the carrier generation layer using a doctor blade and dried at a temperature of 70°C for 1 hour to form a carrier transport layer with a thickness of 12μ. was formed. Next, Ar gas containing 18 vol% NH 3 and 2 vol% SiH 4 was introduced into a 13.56 MHz high frequency glow discharge device, and glow discharge decomposition was performed at a pressure of 0.2 Torr, and a thickness of 0.2 μm was formed on the carrier transport layer. A photoreceptor (Sample 2) having a protective layer of For comparison,
A photoreceptor (comparative product 2) similar to this example was prepared except that it did not have a protective layer. The photoconductor of Sample 1 was transferred to a commercially available copying machine "U-
Bix2000R" and made 40,000 copies, all of which produced clear images. On the other hand, when copying was carried out in the same manner using comparative product 2, 15,000
Vertical streaks appear in some parts of the image after multiple copies are made,
A clear image could not be obtained. Example 3 Ester acrylate resin "Aronix M-8060" (manufactured by Toagosei Chemical Industry Co., Ltd.) was diluted with toluene on a photoreceptor with a two-layer structure consisting of a carrier generation layer and a carrier transport layer similar to Sample 1, and a doctor blade was applied. A photoreceptor (comparative product 3) having a protective layer with a thickness of 2 μm was prepared by coating the photoreceptor using a 2 μm thick protective layer and drying it at a temperature of 80° C. for 6 hours. Sample 1 and comparative product 3 were installed in a commercially available copying machine "U-Bix2000R" and a continuous copying test was carried out. The measurements were made using a mold (manufactured by Monroe Electronics Incorporated). The results were as shown in Table 1.
【表】
この第１表の結果から判断されるように、比較
品３による場合には、多数回に亘る連続コピーに
よる画像地肌部の電位の増加が著しく、得られた
複写画像は地肌汚れが大きくて実用に供すること
のできないものであつた。
実施例 ４
90μ厚ポリエチレンテレフタレートフイルム上
にアルミニウム薄層をラミネートした導電性支持
体上に塩化ビニル−酢酸ビニル−無水マレイン酸
共重合体「エスレツクMF−10」（積水化学工業
製）より成る厚さ約0.1μの中間層を設け、アント
アントロン系顔料「モノライトレツド2Y」（C.I.
No.59300）を、２〜３×10-4Torrの真空雰囲気中
において蒸着源温度350℃で３分間蒸着せしめ厚
さ0.5μのキヤリア発生層を形成した。次に下記構
造を有するヒドラゾン化合物の５ｇと
ポリカーボネート樹脂「パンライトＬ−1250」
（帝人化成社製）10ｇとを１，２−ジクロルエタ
ン100mlに溶解した溶液をドクターブレードを用
いて前記キヤリア発生層上に塗布し、温度70℃で
１時間乾燥せしめて厚さ13μのキヤリア輸送層を
形成した。次に13.56MHzの高周波グロー放電装
置に3vol％のSiH4ガスと17vol％のC2H4ガスとを
含むArガスを導入し、0.5Torrの圧力でグロー放
電分解を行い前記キヤリア発生層上に厚さ0.4μの
保護層を有する感光体（試料３）を作製した。比
較の為、保護層を有していない他は本実施例と同
様の感光体（比較品４）を作製した。
試料３及び比較品４をエレクトロメーターSD
−428型（(株)川口電機製作所製）に装着し、帯電
器放電極に対する印加電圧を−6KVとして５秒
間帯電操作を行ない、この帯電操作直後における
感光層表面の帯電電位Vo（Ｖ）と、この帯電電位
Voを1/2に減衰せしめるために必要な照射光量Ｅ
１／２（lx・sec）とを測定した。また試料３及び比
較品４に超電圧水銀灯「SHL−100UV」〔(株)東京
芝浦電気製〕を距離５cmで30秒間照射して、同様
な測定を行なつた。その結果は第２表に示す通り
であつた。[Table] As judged from the results in Table 1, in the case of Comparative Product 3, the potential of the image background area increased significantly due to continuous copying many times, and the resulting copied image had background stains. It was too large to be put to practical use. Example 4 A thin layer of vinyl chloride-vinyl acetate-maleic anhydride copolymer "Eslec MF-10" (manufactured by Sekisui Chemical Co., Ltd.) was coated on a conductive support consisting of a thin aluminum layer laminated on a 90μ thick polyethylene terephthalate film. An intermediate layer of approximately 0.1μ is provided, and an anthrone-based pigment "Monolite Red 2Y" (CI
No. 59300) was evaporated for 3 minutes at a evaporation source temperature of 350° C. in a vacuum atmosphere of 2 to 3×10 −4 Torr to form a carrier generation layer with a thickness of 0.5 μm. Next, 5g of a hydrazone compound having the following structure and Polycarbonate resin “Panlite L-1250”
(manufactured by Teijin Kasei) and dissolved in 100 ml of 1,2-dichloroethane, a solution was applied onto the carrier generation layer using a doctor blade and dried at a temperature of 70°C for 1 hour to form a carrier transport layer with a thickness of 13μ. was formed. Next, Ar gas containing 3 vol% SiH 4 gas and 17 vol% C 2 H 4 gas was introduced into a 13.56 MHz high-frequency glow discharge device, and glow discharge decomposition was performed at a pressure of 0.5 Torr on the carrier generation layer. A photoreceptor (Sample 3) having a protective layer with a thickness of 0.4 μm was produced. For comparison, a photoreceptor (comparative product 4) similar to that of this example was produced except that it did not have a protective layer. Sample 3 and comparative product 4 were measured using an electrometer SD.
-428 type (manufactured by Kawaguchi Electric Seisakusho Co., Ltd.), the voltage applied to the charger discharge electrode was set to -6KV, and the charging operation was performed for 5 seconds, and the charged potential Vo (V) on the surface of the photosensitive layer immediately after this charging operation was , this charging potential
Amount of irradiation light E required to attenuate Vo to 1/2
1/2 (lx·sec) was measured. Similar measurements were also carried out by irradiating Sample 3 and Comparative Product 4 with a supervoltage mercury lamp "SHL-100UV" (manufactured by Tokyo Shibaura Electric Co., Ltd.) at a distance of 5 cm for 30 seconds. The results were as shown in Table 2.
【表】
この第２表の結果から判断されるように、比較
品４は紫外光照射により感度が著しく低下し、試
料３の紫外光に対する安定性が認められた。[Table] As judged from the results in Table 2, the sensitivity of Comparative Product 4 decreased significantly when irradiated with ultraviolet light, and the stability of Sample 3 against ultraviolet light was observed.
図は本発明に係る電子写真感光体の構成の一例
を示す慨略拡大断面図である。
図中、１は感光体、２は導電性支持体、３はキ
ヤリア発生層、４はキヤリア輸送層、５は保護層
を示す。
The figure is a schematic enlarged sectional view showing an example of the structure of an electrophotographic photoreceptor according to the present invention. In the figure, 1 is a photoreceptor, 2 is a conductive support, 3 is a carrier generation layer, 4 is a carrier transport layer, and 5 is a protective layer.
Claims (1)
電性感光層と該感光層の保護層とを有する有機電
子写真感光体において、前記保護層が、水素原子
および／または弗素原子を含む非晶質炭化シリコ
ン又は水素原子および／または弗素原子を含む非
晶質窒化シリコンからなる膜厚が0.05μ〜1μの層
から成ることを特徴とする有機電子写真感光体。 ２ 前記感光層がキヤリア発生層とキヤリア輸送
層とから構成されることを特徴とする特許請求の
範囲第１項記載の有機電子写真感光体。[Scope of Claims] 1. An organic electrophotographic photoreceptor having a photoconductive photosensitive layer containing an organic photoconductive material on a support and a protective layer for the photosensitive layer, wherein the protective layer contains hydrogen atoms and/or Alternatively, an organic electrophotographic photoreceptor comprising a layer of amorphous silicon carbide containing fluorine atoms or amorphous silicon nitride containing hydrogen atoms and/or fluorine atoms and having a thickness of 0.05 μm to 1 μm. 2. The organic electrophotographic photoreceptor according to claim 1, wherein the photosensitive layer is composed of a carrier generation layer and a carrier transport layer.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15197881A JPS5854347A (en) | 1981-09-28 | 1981-09-28 | Electrophotographic receptor |
| US06/422,728 US4477549A (en) | 1981-09-28 | 1982-09-24 | Photoreceptor for electrophotography, method of forming an electrostatic latent image, and electrophotographic process |
| DE3235887A DE3235887C2 (en) | 1981-09-28 | 1982-09-28 | Electrophotographic process and electrophotographic recording material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15197881A JPS5854347A (en) | 1981-09-28 | 1981-09-28 | Electrophotographic receptor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5854347A JPS5854347A (en) | 1983-03-31 |
| JPH0158499B2 true JPH0158499B2 (en) | 1989-12-12 |
Family
ID=15530382
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15197881A Granted JPS5854347A (en) | 1981-09-28 | 1981-09-28 | Electrophotographic receptor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5854347A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05778Y2 (en) * | 1984-12-28 | 1993-01-11 | ||
| JPS648176U (en) * | 1987-07-01 | 1989-01-18 | ||
| JP6503928B2 (en) * | 2015-06-29 | 2019-04-24 | コニカミノルタ株式会社 | Electrophotographic photosensitive member, image forming apparatus and image forming method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5630133A (en) * | 1979-08-20 | 1981-03-26 | Canon Inc | Electrophotographic receptor |
| JPS56115573A (en) * | 1980-02-15 | 1981-09-10 | Matsushita Electric Ind Co Ltd | Photoconductive element |
-
1981
- 1981-09-28 JP JP15197881A patent/JPS5854347A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5630133A (en) * | 1979-08-20 | 1981-03-26 | Canon Inc | Electrophotographic receptor |
| JPS56115573A (en) * | 1980-02-15 | 1981-09-10 | Matsushita Electric Ind Co Ltd | Photoconductive element |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5854347A (en) | 1983-03-31 |
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