JPH0477908B2 - - Google Patents
Info
- Publication number
- JPH0477908B2 JPH0477908B2 JP59196860A JP19686084A JPH0477908B2 JP H0477908 B2 JPH0477908 B2 JP H0477908B2 JP 59196860 A JP59196860 A JP 59196860A JP 19686084 A JP19686084 A JP 19686084A JP H0477908 B2 JPH0477908 B2 JP H0477908B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- layer
- charge
- charge transport
- coating
- 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 - Lifetime
Links
- 108091008695 photoreceptors Proteins 0.000 claims description 37
- 239000000758 substrate Substances 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical class [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 claims description 7
- 125000000623 heterocyclic group Chemical group 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 3
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 125000005427 anthranyl group Chemical group 0.000 claims description 2
- 125000001624 naphthyl group Chemical group 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000000168 pyrrolyl group Chemical group 0.000 claims description 2
- 125000000129 anionic group Chemical group 0.000 claims 1
- WINTXHPCODMMRI-UHFFFAOYSA-N benzene naphthalene Chemical compound C1=CC=CC=C1.C1=CC=CC=C1.C1=CC=CC2=CC=CC=C21 WINTXHPCODMMRI-UHFFFAOYSA-N 0.000 claims 1
- 125000000524 functional group Chemical group 0.000 claims 1
- 230000032258 transport Effects 0.000 description 40
- -1 1 Chemical class 0.000 description 36
- 239000010408 film Substances 0.000 description 24
- 238000000576 coating method Methods 0.000 description 21
- 239000011248 coating agent Substances 0.000 description 19
- 239000000463 material Substances 0.000 description 17
- 239000011347 resin Substances 0.000 description 16
- 229920005989 resin Polymers 0.000 description 16
- 239000000126 substance Substances 0.000 description 16
- 238000001035 drying Methods 0.000 description 13
- 238000000034 method Methods 0.000 description 13
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 229910052782 aluminium Inorganic materials 0.000 description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 9
- 239000000975 dye Substances 0.000 description 9
- DNXIASIHZYFFRO-UHFFFAOYSA-N pyrazoline Chemical compound C1CN=NC1 DNXIASIHZYFFRO-UHFFFAOYSA-N 0.000 description 9
- 239000002800 charge carrier Substances 0.000 description 8
- 239000011230 binding agent Substances 0.000 description 7
- 239000005018 casein Substances 0.000 description 7
- 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 7
- 235000021240 caseins Nutrition 0.000 description 7
- 230000035945 sensitivity Effects 0.000 description 7
- 239000004372 Polyvinyl alcohol Substances 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 5
- 239000000049 pigment Substances 0.000 description 5
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- 238000012546 transfer Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920001230 polyarylate Polymers 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 229920000178 Acrylic resin Polymers 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-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
- 230000000052 comparative effect Effects 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 230000005525 hole transport Effects 0.000 description 3
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 125000004076 pyridyl group Chemical group 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical group ClCCCl WSLDOOZREJYCGB-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
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- MGIAHHJRDZCTHG-UHFFFAOYSA-N benzene-1,3-dicarboxylic acid;terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1.OC(=O)C1=CC=CC(C(O)=O)=C1 MGIAHHJRDZCTHG-UHFFFAOYSA-N 0.000 description 2
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 229920002382 photo conductive polymer Polymers 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920002401 polyacrylamide Polymers 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 150000003219 pyrazolines Chemical class 0.000 description 2
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 2
- 229910052711 selenium Inorganic materials 0.000 description 2
- 239000011669 selenium Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 150000003557 thiazoles Chemical class 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- WQGWMEKAPOBYFV-UHFFFAOYSA-N 1,5,7-trinitrothioxanthen-9-one Chemical compound C1=CC([N+]([O-])=O)=C2C(=O)C3=CC([N+](=O)[O-])=CC([N+]([O-])=O)=C3SC2=C1 WQGWMEKAPOBYFV-UHFFFAOYSA-N 0.000 description 1
- LFKNYYQRWMMFSM-UHFFFAOYSA-N 1-ethyl-9h-carbazole;formaldehyde Chemical compound O=C.N1C2=CC=CC=C2C2=C1C(CC)=CC=C2 LFKNYYQRWMMFSM-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
- 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
- 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
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- XXWVEJFXXLLAIB-UHFFFAOYSA-N 4-[[4-(diethylamino)-2-methylphenyl]-phenylmethyl]-n,n-diethyl-3-methylaniline Chemical compound CC1=CC(N(CC)CC)=CC=C1C(C=1C(=CC(=CC=1)N(CC)CC)C)C1=CC=CC=C1 XXWVEJFXXLLAIB-UHFFFAOYSA-N 0.000 description 1
- PLAZXGNBGZYJSA-UHFFFAOYSA-N 9-ethylcarbazole Chemical compound C1=CC=C2N(CC)C3=CC=CC=C3C2=C1 PLAZXGNBGZYJSA-UHFFFAOYSA-N 0.000 description 1
- LSZJZNNASZFXKN-UHFFFAOYSA-N 9-propan-2-ylcarbazole Chemical compound C1=CC=C2N(C(C)C)C3=CC=CC=C3C2=C1 LSZJZNNASZFXKN-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920000305 Nylon 6,10 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229920001893 acrylonitrile styrene Polymers 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000009125 cardiac resynchronization therapy Methods 0.000 description 1
- 239000012461 cellulose resin Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 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
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000007857 hydrazones Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 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
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000007760 metering rod coating Methods 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- KKFHAJHLJHVUDM-UHFFFAOYSA-N n-vinylcarbazole Chemical compound C1=CC=C2N(C=C)C3=CC=CC=C3C2=C1 KKFHAJHLJHVUDM-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002916 oxazoles Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920006287 phenoxy resin Polymers 0.000 description 1
- 239000013034 phenoxy resin Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 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
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 229920002717 polyvinylpyridine Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 1
- RCYFOPUXRMOLQM-UHFFFAOYSA-N pyrene-1-carbaldehyde Chemical compound C1=C2C(C=O)=CC=C(C=C3)C2=C2C3=CC=CC2=C1 RCYFOPUXRMOLQM-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- WVIICGIFSIBFOG-UHFFFAOYSA-N pyrylium Chemical compound C1=CC=[O+]C=C1 WVIICGIFSIBFOG-UHFFFAOYSA-N 0.000 description 1
- 125000005493 quinolyl group Chemical group 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 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
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
- 125000006617 triphenylamine group Chemical class 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene 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
- G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
- G03G5/0622—Heterocyclic compounds
- G03G5/0644—Heterocyclic compounds containing two or more hetero rings
- G03G5/0661—Heterocyclic compounds containing two or more hetero rings in different ring systems, each system containing at least one hetero ring
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
- G03G5/02—Charge-receiving layers
- G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
- G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
- G03G5/0664—Dyes
- G03G5/0666—Dyes containing a methine or polymethine group
- G03G5/0672—Dyes containing a methine or polymethine group containing two or more methine or polymethine groups
- G03G5/0674—Dyes containing a methine or polymethine group containing two or more methine or polymethine groups containing hetero rings
Description
産業上の利用分野
本発明は新規な電子写真感光材料を使用した電
子写真感光体に関するものであり更に詳しくは特
定の分子構造を有するシアニン色素を光導電層中
に含有する高感度の電子写真用感光材料を使用し
た電子写真感光体に関するものである。
従来の技術
従来より、光導電性を示す顔料や染料について
は、数多くの文献等で発表されている。
例えば、“RCA Review”Vol.23，P.413〜
P.419（1962.9）ではフタロシアニン顔料の光導電
性についての発表がなされており、又このフタロ
シアニン顔料を用いた電子写真感光体が米国特許
第3397086号公報や米国特許第3816118号公報等に
示されている。その他に、電子写真感光体に用い
る有機半導体としては、例えば米国特許第
4315983号公報、米国特許第4327169号公報や
“Reseach Disclosure”20517（1981.5）に示され
ているピリリウム系染料、米国特許第3824099号
公報に示されているスクエアリツク酸メチン染
料、米国特許第3898084号公報、米国特許第
4251613号公報等に示されたジスアゾ顔料などが
挙げられる。
この様な有機半導体は、無機半導体に較べて合
成が容易で、しかも要求する波長域の光に対して
光導電性をもつ様な化合物として合成することが
でき、この様な有機半導体の被膜を導電性支持体
に形成した電子写真感光体は、感色性が良くなる
という利点を有しているが、感度および耐久性に
おいて実用できるものは、ごく僅かである。
発明が解決しようとする問題点
本発明者らは有機半導体材料の諸欠点を改良し
優れた電子写真特性を備えた光導電性材料を得べ
く鋭意研究の結果本発明を完成するに至つた。
本発明の第一の目的は、新規な有機半導体被膜
を提供することである。
本発明の第２の目的は現存するすべての電子写
真プロセスにおいても使用可能でありかつ従来の
欠点を改善してより高い電子写真応答利得の得ら
れる電子写真感光体を提供することにある。
問題点を解決するための手段作用
すなわち本発明の感光体は導電性支持体上に一
般式（）で示されるシアニン色素及び樹脂より
なる光導電層を設けてなることを特徴とするもの
である。
〔式中、ｋ、ｌ、ｍ、ｎは０、１、２から選ばれ
る整数を示し、Ｘはヨウ素、塩素、臭素、過塩素
酸、フツ化ホウ素酸パラトルエンスルホン酸等の
アニオン官能基を示し、ZYは置換基を有しても
よい５ないし６員の複素環あるいは置換基を有し
てもよいベンゼン、ナフタレン等の芳香環と縮合
した５ないし６員の複素環を形成するための残基
を表わす。具体的には
INDUSTRIAL APPLICATION FIELD The present invention relates to an electrophotographic photoreceptor using a new electrophotographic photosensitive material, and more specifically to a highly sensitive electrophotographic photoreceptor containing a cyanine dye having a specific molecular structure in a photoconductive layer. This invention relates to an electrophotographic photoreceptor using a photosensitive material. BACKGROUND ART Conventionally, pigments and dyes exhibiting photoconductivity have been published in numerous publications. For example, “RCA Review” Vol.23, P.413~
P.419 (September 1962), there was a presentation on the photoconductivity of phthalocyanine pigments, and electrophotographic photoreceptors using this phthalocyanine pigment were shown in U.S. Pat. No. 3,397,086, U.S. Pat. No. 3,816,118, etc. ing. In addition, as organic semiconductors used in electrophotographic photoreceptors, for example, US Pat.
4315983, U.S. Patent No. 4327169 and “Reseach Disclosure” 20517 (May 1981), pyrylium dyes, U.S. Patent No. 3824099, methine squaritate dyes, U.S. Patent No. 3898084 Publication, U.S. Patent No.
Examples include disazo pigments disclosed in Publication No. 4251613 and the like. Such organic semiconductors are easier to synthesize than inorganic semiconductors, and can be synthesized as compounds that have photoconductivity for light in the required wavelength range. An electrophotographic photoreceptor formed on a conductive support has the advantage of improved color sensitivity, but only a few of them are practical in terms of sensitivity and durability. Problems to be Solved by the Invention The present inventors have completed the present invention as a result of intensive research aimed at improving the various drawbacks of organic semiconductor materials and obtaining a photoconductive material with excellent electrophotographic properties. The first object of the present invention is to provide a novel organic semiconductor coating. A second object of the present invention is to provide an electrophotographic photoreceptor that can be used in all existing electrophotographic processes, improves the conventional drawbacks, and provides higher electrophotographic response gain. Means for Solving the Problems The photoreceptor of the present invention is characterized in that a photoconductive layer comprising a cyanine dye represented by the general formula () and a resin is provided on a conductive support. . [In the formula, k, l, m, and n represent integers selected from 0, 1, and 2, and and ZY is a 5- to 6-membered heterocycle that may have a substituent or a 5- to 6-membered heterocycle fused with an aromatic ring such as benzene or naphthalene that may have a substituent. Represents a residue. in particular
【式】【formula】
【式】【formula】
【式】【formula】
【式】【formula】
【式】【formula】
【式】【formula】
【式】
等を示す（式中ＡはＯ、Ｓ、Se、Ｎ−R9
[Formula] etc. (In the formula, A is O, S, Se, N-R 9
【式】を示しR3〜R6、R9〜R11は水素または
メチル、エチル等のアルキル基または置換されて
もよいフエニル基を示し、R7、R8は水素または
メチル、エチル、メトキシ等の脂肪族基またはク
ロル、ブロム等のハロゲン基を示す。）Ｑは置換
され得るフエニル基、ナフチル基、アントラニル
基、フラン基、チオフエン基、ピロール基を示
す。〕
上記一般式で表わされるシアニン色素の具体
例を以下に示す。
上記構造を有するシアニン色素は本発明の特許
請求の範囲を限定するものではない。
これらのシアニン色素は文献既知の方法で合成
できる。
すなわち、Zh.Org.Kim、1968、４、1089−94、
2207−12に記載の方法を応用することにより得ら
れる。
たとえば化合物(1)は以下のようにして得られ
る。
化合物（28）は以下の合成ルートで得られる
前述のシアニン化合物を有する被膜は光導電性
を示し、従つて下述する電子写真感光体の感光層
に用いることができる。
すなわち、本発明の具体例では導電性支持体の
上に前述のシアニン化合物を真空蒸着法により被
膜形成するか、あるいは適当なバインダー中に分
散含有させて被膜形成することにより電子写真感
光体を調製することができる。
本発明の好ましい具体例では、電子写真感光体
の感光層を電荷発生層と電荷輸送層に機能分離し
た電子写真感光体における電荷発生層として、前
述の光導電性被膜を適用することができる。
電荷発生層は、十分な吸光度を得るために、で
きる限り多くの前述の光導電性を示す化合物を含
有し、且つ発生した電荷キヤリアの飛程を短かく
するために薄膜層、例えば5μ以下、好ましくは
0.01〜1μの膜厚をもつ薄膜層とすることが好まし
い。このことは、入射光量の大部分が電荷発生層
で吸収されて、多くの電荷キヤリアを生成するこ
と、さらに発生した電荷キヤリアを再結合や捕獲
（トラツプ）により失活することなく電荷輸送層
に注入する必要があることに帰因している。
電荷発生層は、前述の化合物を適当なバインダ
ーに分散させ、これを基体の上に塗工することに
よつて形成でき、また真空蒸着装置により蒸着膜
を形成することによつて得ることができる。電荷
発生層を塗工によつて形成する際に用いうるバイ
ンダーとしては広範な絶縁性樹脂から選択でき、
またポリ−Ｎ−ビニルカルバゾール、ポリビニル
アントラセンやポリビニルピレンなどの有機光導
電性ポリマーから選択できる。好ましくは、ポリ
ビニルブチラール、ポリアリレート（ビスフエノ
ールＡとフタル酸の縮重合体など。）ポリカーボ
ネート、ポリエステル、フエノキシ樹脂、ポリ酢
酸ビニル、アクリル樹脂、ポリアクリルアミド樹
脂、ポリアミド、ポリビニルピリジン、セルロー
ス系樹脂、ウレタン樹脂、エポキシ樹脂、カゼイ
ン、ポリビニルアルコール、ポリビニルピロリド
ンなどの絶縁性樹脂を挙げることができる。電荷
発生層中に含有する樹脂は、80重量％以下、好ま
しくは40重量％以上が適している。
これらの樹脂を溶解する溶剤は、樹脂の種類に
よつて異なり、また下述の電荷輸送層や下引層を
溶解しないものから選択することが好ましい。具
体的な有機溶剤としては、メタノール、エタノー
ル、イソプロパノールなどのアルコール類、アセ
トン、メチルエチルケトン、シクロヘキサノンな
どのケトン類、Ｎ，Ｎ−ジメチルホルムアミド、
Ｎ，Ｎ−ジメチルアセトアミドなどのアミド類、
ジメチルスルホキシドなどのスルホキシド類、テ
トラヒドロフラン、ジオキサン、エチレングリコ
ールモノメチルエーテルなどのエーテル類、酢酸
メチル、酢酸エチルなどのエステル類、クロロホ
ルム、塩化メチレン、ジクロルエチレン、四塩化
炭素、トリクロルエチレンなどの脂肪族ハロゲン
化炭化水素類あるいはベンゼン、トルエン、キシ
レン、リグロイン、モノクロルベンゼン、ジクロ
ルベンゼンなどの芳香族類などを用いることがで
きる。
塗工は、浸漬コーテイング法、スプレーコーテ
イング法、スピンナーコーテイング法、ビードコ
ーテイング法、マイヤーバーコーテイング法、ブ
レードコーテイング法、ローラーコーテイング
法、カーテンコーテイング法などのコーテイング
法を用いて行なうことができる。乾燥は、室温に
おける指触乾燥後、加熱乾燥する方法が好まし
い。加熱乾燥は、30℃〜200℃の温度で５分〜２
時間の範囲の時間で、静止または送風下で行なう
ことができる。
電荷輸送層は、前述の電荷発生層と電気的に接
続されており、電界の存在下で電荷発生層から注
入された電荷キヤリアを受け取るとともに、これ
らの電荷キヤリアを表面まで輸送できる機能を有
している。この際、この電荷輸送層は、電荷発生
層の上に積層されていてもよくまたその下に積層
されていてもよい。
電荷輸送層における電荷キヤリアを輸送する物
質（以下、単に電荷輸送物質という）は、前述の
電荷発生層が感応する電磁波の波長域に実質的に
非感応性であることが好ましい。ここで言う「電
磁波」とは、γ線、Ｘ線、紫外線、可視光線、近
赤外線、赤外線、遠赤外線などを包含する広義の
「光線」の定義を包含する。電荷輸送層の光感応
性波長域が電荷発生層のそれと一致またはオーバ
ーラツプする時には、両者で発生した電荷キヤリ
アが相互に捕獲し合い、結果的には感度の低下の
原因となる。
電荷輸送物質としては電子輸送性物質と正孔輸
送性物質があり、電子輸送性物質としては、クロ
ルアニル、ブロモアニル、テトラシアノエチレ
ン、テトラシアノキノジメタン、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等の電子
吸引性物質やこれら電子吸引性物質を高分子化し
たもの等がある。
正孔輸送性物質としては、ピレン、Ｎ−エチル
カルバゾール、Ｎ−イソプロピルカルバゾール、
Ｎ−メチル−Ｎ−フエニルヒドラジノ−３−メチ
リデン−９−エチルカルバゾール、Ｎ，Ｎ−ジフ
エニルヒドラジノ−３−メチリデン−９−エチル
カルバゾール、Ｎ，Ｎ−ジフエニルヒドラジノ−
３−メチリデン−10−エチルフエノチアジン、
Ｎ，Ｎ−ジフエニルヒドラジノ−３−メチリデン
−10−エチルフエノキサジン、Ｐ−ジエチルアミ
ノベンズアルデヒド−Ｎ，Ｎ−ジフエニルヒドラ
ゾン、Ｐ−ジエチルアミノベンズアルデヒド−Ｎ
−α−ナフチル−Ｎ−フエニルヒドラゾン、Ｐ−
ピロリジノベンズアルデヒド−Ｎ，Ｎ−ジフエニ
ルヒドラゾン、１，３，３−トリメチルインドレ
ニン−ω−アルデヒド−Ｎ，Ｎ−ジフエニルヒド
ラゾン、Ｐ−ジエチルベンズアルデヒド−３−メ
チルベンズチアゾリノン−２−ヒドラゾン等のヒ
ドラゾン類、２，５−ビス（Ｐ−ジエチルアミノ
フエニル）−１，３，４−オキサジアゾール、１
−フエニル−３−（Ｐ−ジエチルアミノスチリル）
−５−（Ｐ−ジエチルアミノフエニル）ピラリゾ
ン、１−〔キノリル(2)〕−３−（Ｐ−ジエチルアミ
ノスチリル）−５−（Ｐ−ジエチルアミノフエニ
ル）ピラゾリン、１−〔ピリジル(2)〕−３−（Ｐ−
ジエチルアミノスチリル）−５−（Ｐ−ジエチルア
ミノフエニル）ピラゾリン、１−〔６−メトキシ
−ピリジル(2)〕−３−（Ｐ−ジエチルアミノスチリ
ル）−５−（Ｐ−ジエチルアミノフエニル）ピラゾ
リン、１−〔ピリジル(3)〕−３−（Ｐ−ジエチルア
ミノスチリル）−５−（Ｐ−ジエチルアミノフエニ
ル）ピラゾリン、１−〔レピジル(2)〕−３−（Ｐ−
ジエチルアミノスチリル）−５−（Ｐ−ジエチルア
ミノフエニル）ピラゾリン、１−〔ピリジン(2)〕−
３−（Ｐ−ジエチルアミノスチリル）−４−メチル
−５−（Ｐ−ジエチルアミノフエニル）ピラゾリ
ン、１−〔ピリジル(2)〕−３−（α−メチル−Ｐ−
ジエチルアミノスチリル）−５−（Ｐ−ジエチルア
ミノフエニル）ピラゾリン、１−フエニル−３−
（Ｐ−ジエチルアミノスチリル）−４−メチル−５
−（Ｐ−ジエチルアミノフエニル）ピラゾリン、
１−フエニル−３−（α−ベンジル−Ｐ−ジエチ
ルアミノスチリル）−５−（Ｐ−ジエチルアミノフ
エニル）ピラゾリン、スピロピラゾリンなどのピ
ラゾリン類、２−（Ｐ−ジエチルアミノスチリル）
−６−ジエチルアミノベンズオキサゾール、２−
（Ｐ−ジエチルアミノフエニル）−４−（Ｐ−ジメ
チルアミノフエニル）−５−（２−クロロフエニ
ル）オキサゾール等のオキサゾール系化合物、２
−（Ｐ−ジエチルアミノスチリル）−６−ジエチル
アミノベンゾチアゾール等のチアゾール系化合
物、ビス（４−ジエチルアミノ−２−メチルフエ
ニル）−フエニルメタン等のトリアリールメタン
系化合物、１，１−ビス（４−Ｎ，Ｎ−ジエチル
アミノ−２−メチルフエニル）ヘプタン、１，
１，２，２−テトラキス（４−Ｎ，Ｎ−ジメチル
アミノ−２−メチルフエニル）エタン等のポリア
リールアルカン類、トリフエニルアミン、ポリ−
Ｎ−ビニルカルバゾール、ポリビニルピレン、ポ
リビニルアントラセン、ポリビニルアクリジン、
ポリ−９−ビニルフエニルアントラセン、ピレン
−ホルムアルデヒド樹脂、エチルカルバゾールホ
ルムアルデヒト樹脂等がある。
これらの有機電荷輸送物質の他に、セレン、セ
レン−テルルアモルフアスシリコン、硫化カドミ
ウムなどの無機材料も用いることができる。
また、これらの電荷輸送物質は、１種または２
種以上組合せて用いることができる。
電荷輸送物質に成膜性を有していない時には、
適当なバインダーを選択することによつて被膜形
成できる。バインダーとして使用できる樹脂は、
例えばアクリル樹脂、ポリアリレート、ポリエス
テル、ポリカーボネート、ポリスチレン、アクリ
ロニトリル−スチレンコポリマー、アクリロニト
リル−ブタジエンコポリマー、ポリビニルブチラ
ール、ポリビニルホルマール、ポリスルホン、ポ
リアクリルアミド、ポリアミド、塩素化ゴムなど
の絶縁性樹脂、あるいはポリ−Ｎ−ビニルカルバ
ゾール、ポリビニルアントラセン、ポリビニルピ
レンなどの有機光導電性ポリマーを挙げることが
できる。
電荷輸送層は、電荷キヤリアを輸送できる限界
があるので、必要以上に膜厚を厚くすることがで
きない。一般的には、５〜30μであるが、好まし
い範囲は８〜20μである。塗工によつて電荷輸送
層を形成する際には、前述した様な適当なコーテ
イング法を用いることができる。
この様な電荷発生層と電荷輸送層の積層構造か
らなる感光層は、導電層を有する基体の上に設け
られる。導電層を有する基体としては、基体自体
が導電性をもつもの、例えばアルミニウム、アル
ミニウム合金、銅、亜鉛、ステンレス、バナジウ
ム、モリブデン、クロム、チタン、ニツケル、イ
ンジウム、金や白金などを用いることができ、そ
の他にアルミニウム、アルミニウム合金、酸化イ
ンジウム、酸化錫、酸化インジウム−酸化錫合金
などを真空蒸着法によつて被膜形成された層を有
するプラスチツク（例えばポリエチレン、ポリプ
ロピレン、ポリ塩化ビニル、ポリエチレンテレフ
タレート、アクリル樹脂、ポリフツ化エチレンな
ど）、導電性粒子（例えば、カーボンブラツク、
銀粒子など）を適当なバインダーとともにプラス
チツクの上に被覆した基体、導電性粒子をプラス
チツクや紙に含浸した基体や導電性ポリマーを有
するプラスチツクなどを用いることができる。
導電層と感光層の中間に、バリヤー機能と接着
機能をもつ下引層を設けることもできる。下引層
は、カゼイン、ポリビニルアルコール、ニトロセ
ルロース、エチレン−アクリル酸コポリマー、ポ
リアミド（ナイロン６、ナイロン66、ナイロン
610、共重合ナイロン、アルコキシメチル化ナイ
ロンなど）、ポリウレタン、ゼラチン、酸化アル
ミニウムなどによつて形成できる。
下引層の膜厚は、0.1〜5μ、好ましくは0.5〜3μ
が適当である。
導電層、電荷発生層、電荷輸送層の順に積層し
た感光体を使用する場合において電荷輸送物質が
電子輸送性物質からなるときは、電荷輸送層表面
を正に帯電する必要があり、帯電後露光すると露
光部では電荷発生層において生成した電子が電荷
輸送層に注入され、そのあと表面に達して正電荷
を中和し、表面電位の減衰が生じ未露光部との間
に静電コントラストが生じる。この様にしてでき
た静電潜像を負荷電性のトナーで現像すれば可視
像が得られる。これを直接定着するか、あるいは
トナー像を紙やプラスチツクフイルム等に転写
後、現像し定着することができる。
また、感光体上の静電潜像を転写紙の絶縁層上
に転写後現像し、定着する方法もとれる。現像剤
の種類や現像方法、定着方法は公知のものや公知
の方法のいずれを採用しても良く、特定のものに
限定されるものではない。
一方、電荷輸送物質が正孔輸送物質から成る場
合、電荷輸送層表面を負に帯電する必要があり、
帯電後、露光すると露光部では電荷発生層におい
て生成した正孔が電荷輸送層に注入され、その後
表面に達して負電荷を中和し、表面電位の減衰が
生じ未露光部との間に静電コントラストが生じ
る。現像時には電子輸送性物質を用いた場合とは
逆に正電荷性トナーを用いる必要がある。
導電層、電荷輸送層、電荷発生層の順に積層し
た感光体を使用する場合において電荷輸送物質が
電子輸送性物質からなるときは、電荷発生層表面
を負に帯電する必要があり帯電後露光すると露光
部では電荷発生層において生成した電子は電荷輸
送層に注入されそのあと基盤に達する一方電荷発
生層において生成した正孔は表面に達し表面電位
の減衰が生じ未露光部との間に静電コントラスト
が生じる。この様にしてできた静電潜像を正荷電
性のトナーで現像すれば可視像が得られる。これ
を直接定着するか、あるいはトナー像を紙やプラ
スチツクフイルム等に転写後現像し定着すること
ができる。
また、感光体上の静電潜像を転写紙の絶縁層上
に転写後現像し、定着する方法もとれる。現像剤
の種類や現像方法、定着方法は公知のものや公知
の方法のいずれを採用しても良く、特定のものに
限定されるものではない。
一方、電荷輸送物質が正孔輸送正物質からなる
ときは、電荷発生層表面を正に帯電する必要があ
り帯電後露光すると露光部では電荷発生層におい
て生成した正孔は電荷輸送層に注入されそのあと
基盤に達する一方電荷発生層において生成した電
子は表面に達し表面電位の減衰が生じ未露光部と
の間に静電コントラストが生じる。
現像時には電子輸送性物質を用いた場合とは逆
に負電荷性トナーを用いる必要がある。
また、本発明の別の具体例では、前述のヒドラ
ゾン類、ピラゾリン類、オキサゾール類、チアゾ
ール類、トリアリールメタン類、ポリアリールア
ルカン類、トリフエニルアミン、ポリ−Ｎ−ビニ
ルカルバゾール類など有機光導電性物質や酸化亜
鉛、硫化カドミウム、セレンなどの無機光導電性
物質の増感剤として前述のシアニン化合物を含有
させた感光被膜とすることができる。この感光被
膜は、これらの光導電性物質と前述のシアニン化
合物をバインダーとともに塗工によつて被膜形成
される。
また本発明の別の具体例としては特開昭49−
916483号公報（光導電性部材）に開示されている
様な電荷移動錯体中に電荷発生材料を添加したタ
イプの感光体として使用することもできる。いず
れの感光体においても、一般式（）で示される
化合物から選ばれる少なくとも１種類のシアニン
化合物を含有し、必要に応じて光吸収の異なる他
の光導電性顔料や染料を組合せて使用することに
よつて、この感光体の感度を高めたり、あるいは
パンクロマチツクな感光体として調整することも
可能である。
本発明の電子写真感光体は電子写真複写機に利
用するのみならず、レーザープリンターやCRT
プリンターなどの電子写真応用分野にも広く用い
ることができる。
以下、本発明を実施例に従つて説明する。
実施例 １〜30
アルミ板上にカゼインのアンモニア水溶液（カ
ゼイン11.2ｇ、28％アンモニア水１ｇ、水222ml）
をマイヤーバーで、乾燥後の膜厚が1.0ミクロン
となる様に塗布し、乾燥した。
次に、ブチラール樹脂（ブチラール化度63モル
％）２ｇをイソプロピルアルコール95mlで溶かし
た溶液に、具体例に挙げた30種のシアニン化合物
５ｇを各々加えて30種の溶工液を調製した。
各塗工液をサンドミル分散した後、それぞれ前
述のカゼイン下引層の上に乾燥後の膜厚が0.1μと
なる様にマイヤーバーで塗布し、乾燥して電荷発
生層を形成させた。
次いて、構造式
のヒドラゾン化合物５ｇとポリメチルメタクリレ
ート樹脂（数平均分子量100000）５ｇをベンゼン
70mlに溶解し、これを電荷発生層の上に乾燥後の
膜厚が12μとなる様にマイヤーバーで塗布し、乾
燥して電荷輸送層を形成した。
この様にして作成した30種の電子写真感光体を
川口電機(株)製静電複写紙試験装置ModelSP−428
を用いてダイナミツク方式で−5KVでコロナ帯
電し、暗所で１秒間保持した後、照度5luxで４秒
間露光し帯電特性を調べた。
帯電特性としては、初期帯電電位（VO）と１
秒間暗減衰させた時の電位を1/2に減衰するに必
要な露光量（Ｅ１／２）を測定した。この結果を
第１表に示す。又、20lux.sec露光後の残留電位
をVRで表わした。 [ Formula : _ _ _ This represents an aliphatic group such as chloro, bromo, or a halogen group. ) Q represents a phenyl group, a naphthyl group, an anthranyl group, a furan group, a thiophene group, or a pyrrole group, which may be substituted. ] Specific examples of the cyanine dye represented by the above general formula are shown below. The cyanine dye having the above structure does not limit the scope of the claims of the present invention. These cyanine dyes can be synthesized by methods known in the literature. Namely, Zh.Org.Kim, 1968, 4, 1089-94,
It can be obtained by applying the method described in 2207-12. For example, compound (1) can be obtained as follows. Compound (28) can be obtained by the following synthetic route The coating containing the cyanine compound described above exhibits photoconductivity and can therefore be used in the photosensitive layer of the electrophotographic photoreceptor described below. That is, in a specific example of the present invention, an electrophotographic photoreceptor is prepared by forming a film of the above-mentioned cyanine compound on a conductive support by a vacuum evaporation method, or by dispersing and containing the cyanine compound in a suitable binder to form a film. can do. In a preferred embodiment of the present invention, the photoconductive coating described above can be applied as a charge generation layer in an electrophotographic photoreceptor in which the photosensitive layer is functionally separated into a charge generation layer and a charge transport layer. The charge generation layer contains as much of the above-mentioned photoconductive compound as possible in order to obtain sufficient absorbance, and is a thin film layer, for example, 5μ or less, in order to shorten the range of the generated charge carriers. Preferably
A thin film layer having a thickness of 0.01 to 1 μm is preferable. This means that most of the incident light is absorbed by the charge generation layer, generating many charge carriers, and that the generated charge carriers are not deactivated by recombination or trapping, but are transferred to the charge transport layer. This is due to the need for injection. The charge generation layer can be formed by dispersing the above-mentioned compound in a suitable binder and coating it on the substrate, or it can be obtained by forming a vapor deposited film using a vacuum vapor deposition apparatus. . The binder that can be used when forming the charge generation layer by coating can be selected from a wide range of insulating resins.
It can also be selected from organic photoconductive polymers such as poly-N-vinylcarbazole, polyvinylanthracene and polyvinylpyrene. Preferably, polyvinyl butyral, polyarylate (condensation polymer of bisphenol A and phthalic acid, etc.), polycarbonate, polyester, phenoxy resin, polyvinyl acetate, acrylic resin, polyacrylamide resin, polyamide, polyvinylpyridine, cellulose resin, urethane. Examples include insulating resins such as resin, epoxy resin, casein, polyvinyl alcohol, and polyvinylpyrrolidone. The resin contained in the charge generation layer is suitably 80% by weight or less, preferably 40% by weight or more. The solvent that dissolves these resins varies depending on the type of resin, and is preferably selected from those that do not dissolve the charge transport layer or undercoat layer described below. Specific organic solvents include alcohols such as methanol, ethanol, and isopropanol, ketones such as acetone, methyl ethyl ketone, and cyclohexanone, N,N-dimethylformamide,
Amides such as N,N-dimethylacetamide,
Sulfoxides such as dimethyl sulfoxide, ethers such as tetrahydrofuran, dioxane, and ethylene glycol monomethyl ether, esters such as methyl acetate and ethyl acetate, aliphatic halogens such as chloroform, methylene chloride, dichloroethylene, carbon tetrachloride, and trichloroethylene. Hydrocarbons or aromatics such as benzene, toluene, xylene, ligroin, monochlorobenzene, dichlorobenzene, etc. can be used. Coating can be carried out using coating methods such as dip coating, spray coating, spinner coating, bead coating, Meyer bar coating, blade coating, roller coating, and curtain coating. For drying, it is preferable to dry to the touch at room temperature and then heat dry. Heat drying at a temperature of 30℃ to 200℃ for 5 minutes to 2
It can be carried out stationary or under blown air for a period of time within a range of hours. The charge transport layer is electrically connected to the charge generation layer described above, and has the function of receiving charge carriers injected from the charge generation layer in the presence of an electric field and transporting these charge carriers to the surface. ing. At this time, this charge transport layer may be laminated on or under the charge generation layer. The substance that transports charge carriers in the charge transport layer (hereinafter simply referred to as charge transport substance) is preferably substantially insensitive to the wavelength range of electromagnetic waves to which the charge generation layer is sensitive. The term "electromagnetic waves" used herein includes a broad definition of "light rays" that includes gamma rays, X-rays, ultraviolet rays, visible light, near infrared rays, infrared rays, far infrared rays, and the like. When the photosensitive wavelength range of the charge transport layer coincides with or overlaps that of the charge generation layer, charge carriers generated in both trap each other, resulting in a decrease in sensitivity. Charge transport substances include electron transport substances and hole transport substances, and electron transport substances include chloranil, bromoanil, tetracyanoethylene, tetracyanoquinodimethane, and 2,4,7-trinitro-9-fluorenone. , 2, 4, 5, 7-
Tetranitro-9-fluorenone, 2,4,7-
trinitro-9-dicyanomethylenefluorenone, 2,4,5,7-tetranitroxanthone,
Examples include electron-withdrawing substances such as 2,4,8-trinitrothioxanthone, and polymerization of these electron-withdrawing substances. Examples of hole-transporting substances include pyrene, N-ethylcarbazole, N-isopropylcarbazole,
N-Methyl-N-phenylhydrazino-3-methylidene-9-ethylcarbazole, N,N-diphenylhydrazino-3-methylidene-9-ethylcarbazole, N,N-diphenylhydrazino-
3-methylidene-10-ethylphenothiazine,
N,N-diphenylhydrazino-3-methylidene-10-ethylphenoxazine, P-diethylaminobenzaldehyde-N,N-diphenylhydrazone, P-diethylaminobenzaldehyde-N
-α-Naphthyl-N-phenylhydrazone, P-
Pyrrolidinobenzaldehyde-N,N-diphenylhydrazone, 1,3,3-trimethylindolenine-ω-aldehyde-N,N-diphenylhydrazone, P-diethylbenzaldehyde-3-methylbenzthiazolinone-2-hydrazone hydrazones such as 2,5-bis(P-diethylaminophenyl)-1,3,4-oxadiazole, 1
-Phenyl-3-(P-diethylaminostyryl)
-5-(P-diethylaminophenyl)pyralizone, 1-[quinolyl(2)]-3-(P-diethylaminostyryl)-5-(P-diethylaminophenyl)pyrazoline, 1-[pyridyl(2)]- 3-(P-
diethylaminostyryl)-5-(P-diethylaminophenyl)pyrazoline, 1-[6-methoxy-pyridyl(2)]-3-(P-diethylaminostyryl)-5-(P-diethylaminophenyl)pyrazoline, 1- [Pyridyl(3)]-3-(P-diethylaminostyryl)-5-(P-diethylaminophenyl)pyrazoline, 1-[Lepidyl(2)]-3-(P-
diethylaminostyryl)-5-(P-diethylaminophenyl)pyrazoline, 1-[pyridine(2)]-
3-(P-diethylaminostyryl)-4-methyl-5-(P-diethylaminophenyl)pyrazoline, 1-[pyridyl(2)]-3-(α-methyl-P-
diethylaminostyryl)-5-(P-diethylaminophenyl)pyrazoline, 1-phenyl-3-
(P-diethylaminostyryl)-4-methyl-5
-(P-diethylaminophenyl)pyrazoline,
1-Phenyl-3-(α-benzyl-P-diethylaminostyryl)-5-(P-diethylaminophenyl)pyrazoline, spiropyrazoline and other pyrazolines, 2-(P-diethylaminostyryl)
-6-diethylaminobenzoxazole, 2-
Oxazole compounds such as (P-diethylaminophenyl)-4-(P-dimethylaminophenyl)-5-(2-chlorophenyl)oxazole, 2
Thiazole compounds such as -(P-diethylaminostyryl)-6-diethylaminobenzothiazole, triarylmethane compounds such as bis(4-diethylamino-2-methylphenyl)-phenylmethane, 1,1-bis(4-N,N -diethylamino-2-methylphenyl)heptane, 1,
Polyarylalkanes such as 1,2,2-tetrakis(4-N,N-dimethylamino-2-methylphenyl)ethane, triphenylamine, poly-
N-vinylcarbazole, polyvinylpyrene, polyvinylanthracene, polyvinylacridine,
Examples include poly-9-vinylphenylanthracene, pyrene-formaldehyde resin, and ethylcarbazole formaldehyde resin. In addition to these organic charge transport materials, inorganic materials such as selenium, selenium-tellurium amorphous silicon, and cadmium sulfide can also be used. Moreover, these charge transport substances may be one or two types.
More than one species can be used in combination. When the charge transport material does not have film-forming properties,
A film can be formed by selecting an appropriate binder. Resins that can be used as binders are:
For example, insulating resins such as acrylic resin, polyarylate, polyester, polycarbonate, polystyrene, acrylonitrile-styrene copolymer, acrylonitrile-butadiene copolymer, polyvinyl butyral, polyvinyl formal, polysulfone, polyacrylamide, polyamide, chlorinated rubber, or poly-N- Mention may be made of organic photoconductive polymers such as vinylcarbazole, polyvinylanthracene, polyvinylpyrene. Since the charge transport layer has a limit in its ability to transport charge carriers, it cannot be made thicker than necessary. Generally, it is 5-30μ, but the preferred range is 8-20μ. When forming the charge transport layer by coating, an appropriate coating method as described above can be used. A photosensitive layer having such a laminated structure of a charge generation layer and a charge transport layer is provided on a substrate having a conductive layer. As the substrate having the conductive layer, materials that are themselves conductive can be used, such as aluminum, aluminum alloy, copper, zinc, stainless steel, vanadium, molybdenum, chromium, titanium, nickel, indium, gold, and platinum. In addition, plastics (such as polyethylene, polypropylene, polyvinyl chloride, polyethylene terephthalate, acrylic, resin, polyethylene fluoride, etc.), conductive particles (e.g. carbon black,
A substrate made of plastic coated with silver particles (silver particles, etc.) together with a suitable binder, a substrate made of plastic or paper impregnated with conductive particles, a plastic containing a conductive polymer, etc. can be used. A subbing layer having barrier and adhesive functions can also be provided between the conductive layer and the photosensitive layer. The subbing layer is made of casein, polyvinyl alcohol, nitrocellulose, ethylene-acrylic acid copolymer, polyamide (nylon 6, nylon 66, nylon
610, copolymerized nylon, alkoxymethylated nylon, etc.), polyurethane, gelatin, aluminum oxide, etc. The thickness of the undercoat layer is 0.1 to 5μ, preferably 0.5 to 3μ.
is appropriate. When using a photoreceptor in which a conductive layer, a charge generation layer, and a charge transport layer are laminated in this order, and the charge transport material is an electron transport material, the surface of the charge transport layer must be positively charged, and exposure after charging is required. Then, in the exposed area, electrons generated in the charge generation layer are injected into the charge transport layer, and then reach the surface and neutralize the positive charge, causing a decrease in surface potential and creating an electrostatic contrast with the unexposed area. . A visible image can be obtained by developing the electrostatic latent image thus formed with a negatively charged toner. This can be directly fixed, or the toner image can be transferred to paper, plastic film, etc. and then developed and fixed. Alternatively, a method may be used in which the electrostatic latent image on the photoreceptor is transferred onto an insulating layer of transfer paper, then developed and fixed. The type of developer, the developing method, and the fixing method may be any known ones or known methods, and are not limited to specific ones. On the other hand, when the charge transport material consists of a hole transport material, the surface of the charge transport layer must be negatively charged.
After charging, when exposed to light, holes generated in the charge generation layer in the exposed area are injected into the charge transport layer, and then reach the surface and neutralize the negative charge, causing a decrease in surface potential and static electricity between the exposed area and the unexposed area. Electrocontrast occurs. During development, it is necessary to use a positively charged toner, contrary to the case where an electron transporting substance is used. When using a photoreceptor in which a conductive layer, a charge transport layer, and a charge generation layer are laminated in this order, and the charge transport material is an electron transport material, it is necessary to charge the surface of the charge generation layer negatively, and when exposed to light after charging, In the exposed area, electrons generated in the charge generation layer are injected into the charge transport layer and then reach the substrate, while holes generated in the charge generation layer reach the surface and the surface potential attenuates, creating an electrostatic charge between it and the unexposed area. Contrast occurs. A visible image can be obtained by developing the electrostatic latent image thus formed with a positively charged toner. This can be directly fixed, or the toner image can be transferred to paper, plastic film, etc. and then developed and fixed. Alternatively, a method may be used in which the electrostatic latent image on the photoreceptor is transferred onto an insulating layer of transfer paper, then developed and fixed. The type of developer, the developing method, and the fixing method may be any known ones or known methods, and are not limited to specific ones. On the other hand, when the charge transport material consists of a positive hole transport material, it is necessary to charge the surface of the charge generation layer positively, and when exposed to light after charging, the holes generated in the charge generation layer are injected into the charge transport layer in the exposed area. After that, the electrons generated in the charge generation layer reach the substrate, and the surface potential attenuates, creating an electrostatic contrast with the unexposed area. During development, it is necessary to use a negatively charged toner, contrary to the case where an electron transporting substance is used. In another specific example of the present invention, organic photoconductive materials such as the aforementioned hydrazones, pyrazolines, oxazoles, thiazoles, triarylmethanes, polyarylalkanes, triphenylamines, poly-N-vinylcarbazoles, etc. The photosensitive film may contain the above-mentioned cyanine compound as a sensitizer for photoconductive substances or inorganic photoconductive substances such as zinc oxide, cadmium sulfide, and selenium. This photosensitive film is formed by coating these photoconductive substances and the above-mentioned cyanine compound together with a binder. Further, as another specific example of the present invention, JP-A-49-
It can also be used as a type of photoreceptor in which a charge generating material is added to a charge transfer complex as disclosed in Japanese Patent No. 916483 (photoconductive member). Any photoreceptor should contain at least one cyanine compound selected from the compounds represented by the general formula (), and if necessary, other photoconductive pigments or dyes with different light absorptions may be used in combination. It is also possible to increase the sensitivity of this photoreceptor or to adjust it as a panchromatic photoreceptor. The electrophotographic photoreceptor of the present invention can be used not only for electrophotographic copying machines, but also for laser printers and CRTs.
It can also be widely used in electrophotographic applications such as printers. Hereinafter, the present invention will be explained according to examples. Examples 1 to 30 Ammonia aqueous solution of casein (11.2 g of casein, 1 g of 28% ammonia water, 222 ml of water) on an aluminum plate
was applied with a Mayer bar so that the film thickness after drying was 1.0 microns, and dried. Next, 5 g of each of the 30 types of cyanine compounds mentioned in the specific examples were added to a solution of 2 g of butyral resin (degree of butyralization: 63 mol %) dissolved in 95 ml of isopropyl alcohol to prepare 30 types of eluent. After dispersing each coating solution in a sand mill, each coating solution was coated on the casein undercoat layer using a Mayer bar so that the film thickness after drying was 0.1 μm, and dried to form a charge generation layer. Then, the structural formula 5 g of hydrazone compound and 5 g of polymethyl methacrylate resin (number average molecular weight 100,000) were added to benzene.
The solution was dissolved in 70 ml and applied onto the charge generation layer using a Mayer bar so that the film thickness after drying was 12μ, and dried to form a charge transport layer. The 30 types of electrophotographic photoreceptors prepared in this way were tested using an electrostatic copying paper tester Model SP-428 manufactured by Kawaguchi Electric Co., Ltd.
The sample was corona-charged dynamically at -5KV using a 1000V, held in a dark place for 1 second, and then exposed to light for 4 seconds at an illuminance of 5lux to examine its charging characteristics. The charging characteristics are initial charging potential (VO) and 1
The exposure amount (E1/2) required to attenuate the potential to 1/2 when dark decaying for a second was measured. The results are shown in Table 1. Further, the residual potential after 20 lux.sec exposure was expressed as VR .
【表】【table】
【表】【table】
【表】【table】
【表】
上記比較化合物を実施例１のシアニン化合物に
代え実施例１と全く同様に感光体を作成し特性を
調べその結果を表２に示した。[Table] A photoreceptor was prepared in exactly the same manner as in Example 1 except that the above comparative compound was replaced with the cyanine compound of Example 1, and the characteristics were investigated and the results are shown in Table 2.
【表】
比較例はいずれも感度が実施例よりも低く残留
電位が大きい。更に実施例１の帯電測定装置を用
いダイナミツク方式で実施例１と同じ帯電露光操
作を5000回繰り返し帯電初期電位VOと露光後の
残留電位VRの変化を調べ結果を表３に示した。
なお実施例１、５、８、27、30の感光体について
も同じ測定を行つた。[Table] All comparative examples have lower sensitivity and higher residual potential than the examples. Furthermore, using the charge measuring device of Example 1, the same charge exposure operation as in Example 1 was repeated 5000 times in a dynamic manner, and the changes in the initial charging potential VO and the residual potential VR after exposure were examined, and the results are shown in Table 3.
Note that the same measurements were performed on the photoreceptors of Examples 1, 5, 8, 27, and 30.
【表】
比較例の感光体がいずれも表２の初期残留電位
が高いのに対応して繰り返し使用時の残留電位が
著しく高く、それに押上げられてVDも高く実用
上電位安定性に欠け大きな問題である。それに反
し本発明による実施例は繰り返し使用後の特性も
極めて安定であり、実用上極めてすぐれた特性を
具備している異は明白である。
実用例 31〜35
実施例１と同様にしてアルミ板上にカゼインの
下引き層を塗布した。
次に実施例１で用いたヒドラゾン化合物を電荷
輸送物質とする電荷輸送層を乾燥後の膜厚が12μ
となるようにマイヤーバーで塗布し乾燥して電荷
輸送層を形成させた。
次いで実施例１、４、11、20、30種の塗工液を
電荷輸送層の上に乾燥後の膜厚が0.1μとなる様に
マイヤーバーで塗布し、乾燥して電荷発生層を形
成した。
この様にして作成した５種の電子写真感光体を
実施例１と同様にして帯電特性を調べた。この場
合＋5KVでコロナ帯電した。この結果を表４に
示す。[Table] Corresponding to the high initial residual potential shown in Table 2, the photoreceptors of the comparative examples all had extremely high residual potentials during repeated use, and as a result, V D was also high and lacked potential stability in practical use. This is a big problem. On the other hand, the properties of the embodiments according to the present invention are extremely stable even after repeated use, and it is obvious that they have extremely excellent properties in practical use. Practical Examples 31 to 35 A casein subbing layer was coated on an aluminum plate in the same manner as in Example 1. Next, a charge transport layer containing the hydrazone compound used in Example 1 as a charge transport substance had a film thickness of 12 μm after drying.
A charge transport layer was formed by coating with a Mayer bar and drying. Next, the coating solutions of Examples 1, 4, 11, 20, and 30 were applied onto the charge transport layer using a Meyer bar so that the film thickness after drying was 0.1μ, and dried to form a charge generation layer. did. The charging characteristics of the five types of electrophotographic photoreceptors prepared in this manner were examined in the same manner as in Example 1. In this case, it was corona charged at +5KV. The results are shown in Table 4.
【表】
実施例 36
ポリ−Ｎ−ビニルカルバゾール１ｇと前述のシ
アニン化合物(1)５mgを１，２−ジクロルエタン10
ｇに加えた後、十分に撹拌した。こうして調製し
た塗工液をアルミニウム蒸着したポリエチレンテ
レフタレートフイルムの上に乾燥膜厚が15μとな
る様にドクターブレードにより塗布した。
この感光体の帯電特性を実施例１と同様の方法
によつて測定した。但し、帯電極性はとした。
この結果を下記に示す。
VO：590
Ｅ１／２：3.0luv.sec
前記実施例36の電子写真感光体を調製した時に
用いたシアニン化合物(1)に代えて、前述のシアニ
ン化合物（13）用いたほかは、実施例36と全く同
様の方法で感光体を調製した後、この感光体の帯
電特性を測定した。この結果を下記に示す。但
し、帯電極性をとした。
VO：＋590
Ｅ１／２：3.4luv.sec
実施例 37
微粒子酸化亜鉛（堺化学(株)製Sazex2000）10
ｇ、アクリル系樹脂（三菱レーヨン(株)製ダイヤナ
ールLR009）４ｇ、トルエン10ｇおよび前記例示
のシアニン化合物（19）10mgをボールミル中で十
分に混合し、得られた塗工液をアルミニウム蒸着
したポリエチレンテレフタレートフイルムの上に
ドクターブレードにより乾燥膜厚が21μになる様
に塗布し、乾燥して電子写真感光体を調製した。
この電子写真感光体の分光感度を電子写真法の
分光写真により測定したところ、前述のシアニン
化合物を含有していない酸化亜鉛被膜に較べて、
本実施例の感光体は長波長側に感度を有している
ことが判明した。
実施例 38
アルミ蒸着ポリエチレンテレフタレートフイル
ムのアルミ面上に膜厚1.1ミクロンのポリビニル
アルコーアールの被膜を形成した。
次に、実施例10と同じシアニン化合物を含有し
た塗光液を先に形成したポリビニルアルコール層
の上に、乾燥後の膜厚が0.1μとなる様にマイヤー
バーで塗布し、乾燥して電荷発生層を形成した。
次いで、構造式
のピラゾリン化合物５ｇとポリアレート樹脂（ビ
スフエノールＡとテレフタル酸−イソフタル酸の
縮重合体）５ｇをテトラヒドロフラン70mlに溶か
した液を電荷発生層の上に乾燥後の膜厚が10μと
なる様に塗布し、乾燥して電荷輸送層を形成し
た。
こうして調製した感光体の帯電特性を実施例１
と同様の方法によつて測定した。この結果を下記
に示す。
VO：−600V
Ｅ１／２：4.0luv.sec
実施例 39
厚さ100μ厚のアルミ板上にカゼインのアンモ
ニア水溶液を塗布し、乾燥して膜厚1.1μの下引層
を形成した。
次に、２，４，７−トリニトロ−９−フルオレ
ノン５ｇとポリ−Ｎ−ビニルカルバゾール（数平
均分子量300000）５ｇをテトラヒドロフラン70ml
に溶かして電荷移動錯化合物を形成した。この電
荷移動錯化合物と前述のシアニン化合物１ｇをポ
リエステル樹脂（バイロン：東洋紡製）５ｇをテ
トラヒドロフラン70mlに溶かした液に加え、分散
した。この分散液を下引層の上に乾燥後の膜厚が
12μとなる様に塗布し、乾燥した。こうして調製
した感光体の帯電特性を実施例１と同様の方法で
測定した。これらの結果は、次のとおりであつ
た。但し、帯電極性はとした。
VO：＋570V
Ｅ１／２：3.0luv.sec
実施例 40
アルミ蒸着ポリエチレンテレフタレートフイル
ムのアルミ面上に膜厚1.1μのポリビニルアルコー
ルの被膜を形成した。
次に、実施例12で用いた前述のシアニン化合物
（12）の分散液を先に形成したポリビニルアルコ
ール層の上に、乾燥後の膜厚が0.5μとなる様にマ
イヤーバーで塗布し、乾燥して電荷発生層を形成
した。
次に、構造式
のピラゾリン化合物５ｇとポリアリレート樹脂
（ビスフエノールＡとテレフタル酸−イソフタル
酸の縮重合体）５ｇをテトラヒドロフラン70mlに
溶かした液を電荷発生層の上に乾燥後の膜厚が
10μとなる様に塗布し、乾燥して電荷輸送層を形
成した。
こうして調製した感光体の帯電特性を実施例１
と同様の方法によつて測定した。これの結果は次
のとおりであつた。
VO：−610V
Ｅ１／２：4.0luv.sec
発明の効果
本発明によれば、繰り返し使用後の特性も極め
て安定であり、実用上極めてすぐれた特性を具備
した電子写真感光体を得ることができる。[Table] Example 36 1 g of poly-N-vinylcarbazole and 5 mg of the above-mentioned cyanine compound (1) were added to 10% of 1,2-dichloroethane.
g and stirred thoroughly. The coating solution thus prepared was applied onto a polyethylene terephthalate film on which aluminum was vapor-deposited using a doctor blade so that the dry film thickness was 15 μm. The charging characteristics of this photoreceptor were measured in the same manner as in Example 1. However, the charging polarity was determined.
The results are shown below. VO: 590 E1/2: 3.0luv.sec Example 36 except that the cyanine compound (13) described above was used in place of the cyanine compound (1) used when preparing the electrophotographic photoreceptor of Example 36. After preparing a photoreceptor in exactly the same manner as described above, the charging characteristics of this photoreceptor were measured. The results are shown below. However, the charging polarity was taken into account. VO: +590 E1/2: 3.4luv.sec Example 37 Fine particle zinc oxide (Sazex2000 manufactured by Sakai Chemical Co., Ltd.) 10
g, 4 g of acrylic resin (Dyanal LR009 manufactured by Mitsubishi Rayon Co., Ltd.), 10 g of toluene, and 10 mg of the above-mentioned cyanine compound (19) were thoroughly mixed in a ball mill, and the resulting coating solution was applied to aluminum-deposited polyethylene. It was applied onto a terephthalate film using a doctor blade to a dry film thickness of 21 μm, and dried to prepare an electrophotographic photoreceptor. When the spectral sensitivity of this electrophotographic photoreceptor was measured by spectrophotography using electrophotography, it was found that compared to the zinc oxide coating that does not contain the cyanine compound mentioned above,
It was found that the photoreceptor of this example had sensitivity on the long wavelength side. Example 38 A polyvinyl alcohol film having a thickness of 1.1 microns was formed on the aluminum surface of an aluminum vapor-deposited polyethylene terephthalate film. Next, a coating liquid containing the same cyanine compound as in Example 10 was applied onto the previously formed polyvinyl alcohol layer using a Mayer bar so that the film thickness after drying was 0.1μ, dried and charged. A generation layer was formed. Then, the structural formula A solution prepared by dissolving 5 g of pyrazoline compound and 5 g of polyarylate resin (condensation polymer of bisphenol A and terephthalic acid-isophthalic acid) in 70 ml of tetrahydrofuran was applied onto the charge generation layer so that the film thickness after drying was 10 μm. , and dried to form a charge transport layer. Example 1 shows the charging characteristics of the photoreceptor thus prepared.
It was measured using the same method as above. The results are shown below. VO: -600V E1/2: 4.0luv.sec Example 39 An ammonia aqueous solution of casein was coated on an aluminum plate with a thickness of 100 μm and dried to form a subbing layer with a thickness of 1.1 μm. Next, 5 g of 2,4,7-trinitro-9-fluorenone and 5 g of poly-N-vinylcarbazole (number average molecular weight 300,000) were added to 70 ml of tetrahydrofuran.
to form a charge transfer complex. This charge transfer complex compound and 1 g of the aforementioned cyanine compound were added to a solution in which 5 g of polyester resin (Vylon, manufactured by Toyobo) was dissolved in 70 ml of tetrahydrofuran, and dispersed. This dispersion is applied onto the undercoat layer so that the film thickness after drying is
It was applied to a thickness of 12μ and dried. The charging characteristics of the photoreceptor thus prepared were measured in the same manner as in Example 1. These results were as follows. However, the charging polarity was determined. VO: +570V E1/2: 3.0luv.sec Example 40 A polyvinyl alcohol film with a thickness of 1.1 μm was formed on the aluminum surface of an aluminum vapor-deposited polyethylene terephthalate film. Next, the above-mentioned dispersion of cyanine compound (12) used in Example 12 was applied onto the polyvinyl alcohol layer formed previously using a Mayer bar so that the film thickness after drying was 0.5μ, and then dried. A charge generation layer was formed. Next, the structural formula A solution prepared by dissolving 5 g of pyrazoline compound and 5 g of polyarylate resin (condensation polymer of bisphenol A and terephthalic acid-isophthalic acid) in 70 ml of tetrahydrofuran was placed on the charge generation layer to determine the film thickness after drying.
It was applied to a thickness of 10μ and dried to form a charge transport layer. Example 1 shows the charging characteristics of the photoreceptor thus prepared.
It was measured using the same method as above. The results were as follows. VO: -610V E1/2: 4.0luv.sec Effects of the Invention According to the present invention, the characteristics after repeated use are extremely stable, and an electrophotographic photoreceptor having extremely excellent characteristics in practical use can be obtained. .
Claims (1)
光体において光導電層に下記一般式（）で示さ
れるシアニン誘導体を含有することを特徴とする
電子写真感光体。 （式中ｋ、ｌ、ｍ、ｎは０、１、２から選ばれる
整数を示し、Ｘはアニオン官能基を示し、Ｚ、Ｙ
は置換基を有してもよいし５ないし６員の複素
環、あるいは置換基を有してもよいベンゼンナフ
タレン等の芳香環と縮合した５ないし６員の複素
環を形成するための残基を表わす。R1およびR2
は置換され得る脂肪族基またはアリール基を示
す。Ｑは置換され得るフエニル基、ナフチル基、
アントラニル基、フラン基、チオフエン基、ピロ
ール基を示す。）[Scope of Claims] 1. An electrophotographic photoreceptor having a photoconductive layer on a conductive substrate, characterized in that the photoconductive layer contains a cyanine derivative represented by the following general formula (). (In the formula, k, l, m, n represent integers selected from 0, 1, 2, X represents an anionic functional group, Z, Y
is a 5- to 6-membered heterocycle which may have a substituent, or a residue for forming a 5- to 6-membered heterocycle fused with an aromatic ring such as benzenenaphthalene which may have a substituent represents. R1 and R2
represents an aliphatic group or an aryl group that may be substituted. Q is a substituted phenyl group, a naphthyl group,
Indicates anthranyl group, furan group, thiophene group, and pyrrole group. )
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59196860A JPS6175358A (en) | 1984-09-21 | 1984-09-21 | Electrophotographic sensitive body |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59196860A JPS6175358A (en) | 1984-09-21 | 1984-09-21 | Electrophotographic sensitive body |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6175358A JPS6175358A (en) | 1986-04-17 |
| JPH0477908B2 true JPH0477908B2 (en) | 1992-12-09 |
Family
ID=16364857
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59196860A Granted JPS6175358A (en) | 1984-09-21 | 1984-09-21 | Electrophotographic sensitive body |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6175358A (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54121742A (en) * | 1978-03-14 | 1979-09-21 | Fuji Xerox Co Ltd | Photosensitive material for electrophotography |
| JPS5714556A (en) * | 1980-06-27 | 1982-01-25 | Chisso Corp | Improved arndt-elstert synthesis |
| JPS57144559A (en) * | 1981-03-02 | 1982-09-07 | Fuji Xerox Co Ltd | Electrophotographic receptor |
| JPS57157254A (en) * | 1981-02-23 | 1982-09-28 | Minnesota Mining & Mfg | Photosensitive layer and electronic photographic article |
| JPS57188043A (en) * | 1981-05-14 | 1982-11-18 | Hitachi Chem Co Ltd | Electrophotographic receptor |
| JPS58118650A (en) * | 1982-01-07 | 1983-07-14 | Canon Inc | Electrophotographic receptor |
| JPS58120256A (en) * | 1982-01-12 | 1983-07-18 | Hitachi Chem Co Ltd | Electrophotographic receptor |
| JPS59146063A (en) * | 1983-02-09 | 1984-08-21 | Canon Inc | Organic film |
-
1984
- 1984-09-21 JP JP59196860A patent/JPS6175358A/en active Granted
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54121742A (en) * | 1978-03-14 | 1979-09-21 | Fuji Xerox Co Ltd | Photosensitive material for electrophotography |
| JPS5714556A (en) * | 1980-06-27 | 1982-01-25 | Chisso Corp | Improved arndt-elstert synthesis |
| JPS57157254A (en) * | 1981-02-23 | 1982-09-28 | Minnesota Mining & Mfg | Photosensitive layer and electronic photographic article |
| JPS57144559A (en) * | 1981-03-02 | 1982-09-07 | Fuji Xerox Co Ltd | Electrophotographic receptor |
| JPS57188043A (en) * | 1981-05-14 | 1982-11-18 | Hitachi Chem Co Ltd | Electrophotographic receptor |
| JPS58118650A (en) * | 1982-01-07 | 1983-07-14 | Canon Inc | Electrophotographic receptor |
| JPS58120256A (en) * | 1982-01-12 | 1983-07-18 | Hitachi Chem Co Ltd | Electrophotographic receptor |
| JPS59146063A (en) * | 1983-02-09 | 1984-08-21 | Canon Inc | Organic film |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6175358A (en) | 1986-04-17 |
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