US3711280A - Metallocene photoconductors used in electrophotography - Google Patents
Metallocene photoconductors used in electrophotography Download PDFInfo
- Publication number
- US3711280A US3711280A US00116208A US3711280DA US3711280A US 3711280 A US3711280 A US 3711280A US 00116208 A US00116208 A US 00116208A US 3711280D A US3711280D A US 3711280DA US 3711280 A US3711280 A US 3711280A
- Authority
- US
- United States
- Prior art keywords
- group
- photoconductive
- electrophotographic
- photoconductors
- poly
- 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
- 150000001875 compounds Chemical class 0.000 abstract description 19
- -1 e.g. Chemical group 0.000 description 104
- 239000010410 layer Substances 0.000 description 39
- 238000000034 method Methods 0.000 description 22
- 239000000203 mixture Substances 0.000 description 20
- 239000000463 material Substances 0.000 description 16
- 239000011230 binding agent Substances 0.000 description 13
- 125000004432 carbon atom Chemical group C* 0.000 description 13
- 239000008199 coating composition Substances 0.000 description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- 125000003118 aryl group Chemical group 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 10
- 238000000576 coating method Methods 0.000 description 10
- 230000001235 sensitizing effect Effects 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 239000000975 dye Substances 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 7
- 125000000217 alkyl group Chemical group 0.000 description 6
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 229920002554 vinyl polymer Polymers 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 125000001624 naphthyl group Chemical group 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 125000003545 alkoxy group Chemical group 0.000 description 4
- 125000004104 aryloxy group Chemical group 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 239000001257 hydrogen Chemical group 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 230000005855 radiation Effects 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- 229920000180 alkyd Polymers 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 3
- 125000000623 heterocyclic group Chemical group 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 239000004417 polycarbonate Substances 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- WVIICGIFSIBFOG-UHFFFAOYSA-N pyrylium Chemical compound C1=CC=[O+]C=C1 WVIICGIFSIBFOG-UHFFFAOYSA-N 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- QGKMIGUHVLGJBR-UHFFFAOYSA-M (4z)-1-(3-methylbutyl)-4-[[1-(3-methylbutyl)quinolin-1-ium-4-yl]methylidene]quinoline;iodide Chemical compound [I-].C12=CC=CC=C2N(CCC(C)C)C=CC1=CC1=CC=[N+](CCC(C)C)C2=CC=CC=C12 QGKMIGUHVLGJBR-UHFFFAOYSA-M 0.000 description 2
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 2
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- DZBUGLKDJFMEHC-UHFFFAOYSA-N acridine Chemical compound C1=CC=CC2=CC3=CC=CC=C3N=C21 DZBUGLKDJFMEHC-UHFFFAOYSA-N 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 239000000298 carbocyanine Substances 0.000 description 2
- 125000005587 carbonate group Chemical group 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- ILZSSCVGGYJLOG-UHFFFAOYSA-N cobaltocene Chemical compound [Co+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 ILZSSCVGGYJLOG-UHFFFAOYSA-N 0.000 description 2
- TXCDCPKCNAJMEE-UHFFFAOYSA-N dibenzofuran Chemical compound C1=CC=C2C3=CC=CC=C3OC2=C1 TXCDCPKCNAJMEE-UHFFFAOYSA-N 0.000 description 2
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 2
- JXTHNDFMNIQAHM-UHFFFAOYSA-N dichloroacetic acid Chemical compound OC(=O)C(Cl)Cl JXTHNDFMNIQAHM-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical group 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000000123 paper Substances 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- XSCHRSMBECNVNS-UHFFFAOYSA-N quinoxaline Chemical compound N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 229910052711 selenium Inorganic materials 0.000 description 2
- 239000011669 selenium Substances 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
- 229940117958 vinyl acetate Drugs 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 description 1
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical compound N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 description 1
- AGIJRRREJXSQJR-UHFFFAOYSA-N 2h-thiazine Chemical compound N1SC=CC=C1 AGIJRRREJXSQJR-UHFFFAOYSA-N 0.000 description 1
- 125000004860 4-ethylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- GJCOSYZMQJWQCA-UHFFFAOYSA-N 9H-xanthene Chemical compound C1=CC=C2CC3=CC=CC=C3OC2=C1 GJCOSYZMQJWQCA-UHFFFAOYSA-N 0.000 description 1
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229920006385 Geon Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 229920004142 LEXAN™ Polymers 0.000 description 1
- 229920004315 LEXAN™ RESIN 105 Polymers 0.000 description 1
- 239000004418 Lexan Substances 0.000 description 1
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- 229910001370 Se alloy Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 229920001986 Vinylidene chloride-vinyl chloride copolymer Polymers 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- MUBKMWFYVHYZAI-UHFFFAOYSA-N [Al].[Cu].[Zn] Chemical compound [Al].[Cu].[Zn] MUBKMWFYVHYZAI-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000000641 acridinyl group Chemical group C1(=CC=CC2=NC3=CC=CC=C3C=C12)* 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 125000006383 alkylpyridyl group Chemical group 0.000 description 1
- 125000005124 aminocycloalkyl group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000001000 anthraquinone dye Substances 0.000 description 1
- 150000008425 anthrones Chemical class 0.000 description 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 125000004350 aryl cycloalkyl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- RFRXIWQYSOIBDI-UHFFFAOYSA-N benzarone Chemical compound CCC=1OC2=CC=CC=C2C=1C(=O)C1=CC=C(O)C=C1 RFRXIWQYSOIBDI-UHFFFAOYSA-N 0.000 description 1
- JKOSHCYVZPCHSJ-UHFFFAOYSA-N benzene;toluene Chemical compound C1=CC=CC=C1.C1=CC=CC=C1.CC1=CC=CC=C1 JKOSHCYVZPCHSJ-UHFFFAOYSA-N 0.000 description 1
- 125000004618 benzofuryl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 125000004619 benzopyranyl group Chemical group O1C(C=CC2=C1C=CC=C2)* 0.000 description 1
- 125000004196 benzothienyl group Chemical group S1C(=CC2=C1C=CC=C2)* 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 1
- 125000002837 carbocyclic group Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000002508 contact lithography Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 1
- 125000004966 cyanoalkyl group Chemical group 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- HEWFKXVSWQSSAT-UHFFFAOYSA-M cyclopenta-1,3-diene;cyclopenta-2,4-dien-1-ylidenemethanolate;iron(2+) Chemical compound [Fe+2].C=1C=C[CH-]C=1.[O-]C=C1C=CC=C1 HEWFKXVSWQSSAT-UHFFFAOYSA-M 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 125000004986 diarylamino group Chemical group 0.000 description 1
- 229960005215 dichloroacetic acid Drugs 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000005670 electromagnetic radiation Effects 0.000 description 1
- KRWWZDVIEFSIOT-UHFFFAOYSA-N ethenyl acetate;furan-2,5-dione Chemical compound CC(=O)OC=C.O=C1OC(=O)C=C1 KRWWZDVIEFSIOT-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 150000002220 fluorenes Chemical class 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000002425 furfuryl group Chemical group C(C1=CC=CO1)* 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 125000003800 germyl group Chemical group [H][Ge]([H])([H])[*] 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 125000005347 halocycloalkyl group Chemical group 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000006377 halopyridyl group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000005350 hydroxycycloalkyl group Chemical group 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 1
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 1
- 125000001041 indolyl group Chemical group 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- QDLAGTHXVHQKRE-UHFFFAOYSA-N lichenxanthone Natural products COC1=CC(O)=C2C(=O)C3=C(C)C=C(OC)C=C3OC2=C1 QDLAGTHXVHQKRE-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- DZVCFNFOPIZQKX-LTHRDKTGSA-M merocyanine Chemical compound [Na+].O=C1N(CCCC)C(=O)N(CCCC)C(=O)C1=C\C=C\C=C/1N(CCCS([O-])(=O)=O)C2=CC=CC=C2O\1 DZVCFNFOPIZQKX-LTHRDKTGSA-M 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000012184 mineral wax Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- JNMWNOFTCDEJHU-UHFFFAOYSA-N n,n-diethyl-3,4-dimethylaniline Chemical compound CCN(CC)C1=CC=C(C)C(C)=C1 JNMWNOFTCDEJHU-UHFFFAOYSA-N 0.000 description 1
- CIPVVROJHKLHJI-UHFFFAOYSA-N n,n-diethyl-3-methylaniline Chemical compound CCN(CC)C1=CC=CC(C)=C1 CIPVVROJHKLHJI-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 125000004971 nitroalkyl group Chemical group 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 239000011101 paper laminate Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 125000004351 phenylcyclohexyl group Chemical group C1(=CC=CC=C1)C1(CCCCC1)* 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- QWYZFXLSWMXLDM-UHFFFAOYSA-M pinacyanol iodide Chemical compound [I-].C1=CC2=CC=CC=C2N(CC)C1=CC=CC1=CC=C(C=CC=C2)C2=[N+]1CC QWYZFXLSWMXLDM-UHFFFAOYSA-M 0.000 description 1
- 125000005936 piperidyl group Chemical group 0.000 description 1
- 229920001490 poly(butyl methacrylate) polymer Polymers 0.000 description 1
- 229920000205 poly(isobutyl methacrylate) Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 125000001500 prolyl group Chemical group [H]N1C([H])(C(=O)[*])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- BKIKRRUKWYJTEU-UHFFFAOYSA-N propane terephthalic acid Chemical compound CCC.OC(=O)c1ccc(cc1)C(O)=O BKIKRRUKWYJTEU-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 125000004309 pyranyl group Chemical group O1C(C=CC=C1)* 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000719 pyrrolidinyl group Chemical group 0.000 description 1
- 125000001422 pyrrolinyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- NTQLADLBRQMNQJ-UHFFFAOYSA-M pyrylium;perchlorate Chemical compound [O-]Cl(=O)(=O)=O.C1=CC=[O+]C=C1 NTQLADLBRQMNQJ-UHFFFAOYSA-M 0.000 description 1
- 125000005493 quinolyl group Chemical group 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 230000011514 reflex Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical group [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010008 shearing Methods 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
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- 125000005346 substituted cycloalkyl group Chemical group 0.000 description 1
- 230000000153 supplemental effect Effects 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 150000003557 thiazoles Chemical class 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 125000006617 triphenylamine group Chemical class 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F17/00—Metallocenes
-
- 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
- G03G5/0662—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic containing metal elements
Definitions
- This invention relates to electrophotography and more particularly to a novel compound and to a class of photoconductive materials and the compositions and elements produced therefrom.
- Electrophotographic imaging processes and techniques are based on the discovery that certain materials which are normally insulating become conductive during exposure to electromagnetic radiation of certain wave lengths after being electrically charged. Such materials, which may be either organic or inorganic, are termed photoconductors. They are conveniently formed into usable imageforming elements by coating a layer of the photoconductive composition, together with an electrically insulating resinous binder where necessary or desirable, onto a suitable support. Such an element will accept and retain an electrostatic charge in the absence of actinic radiation. In use, the surface of the element is charged in the dark to a uniform potential and exposed to an imagewise pattern of actirnc radiation, which selectively reduces the surface potential to produce a charge pattern corresponding to the imagewise radiation pattern.
- the resultant charge pattern or electrostatic latent image may be developed by contacting it with suitable charged marking particles which adhere in accordance with the charge pattern, or it may be transferred to another insulating surface upon which it is developed.
- the particles may then be fused or fixed to the surface by known means such as heat or solvent vapor, or they may be transferred to another surface to which they may similarly be fixed, to produce a permanent reproduction of the original radiation pattern.
- Various photoconductive insulating materials have been employed in the manufacture of electrophotographic elements. For example, vapors of selenium and vapors of selenium alloys deposited on a suitable support and particles of photoconductive zinc oxide held in a resinous, film-forming binder have found wide application in pre'sent-day document copying applications.
- electrophotographic elements having coated thereon photoconductive compositions containing as photoconductors metallocenes derived from first row transition metals.
- the metals from which these metallocenes are derived are those in the first row of Groups IVb, Vb, VII), VIII) and VIII in accordance with the Periodic Table of the Elements (Handbook of Chemistry and Physics, 38th edition, pp. 394-) and include titanium, vanadium, chromium, manganese, iron, cobalt and nickel. Similarly, vinyl polymers containing the metallocenes 3J8 side chains can be used.
- the metallocene can be substituted on one or both of its aromatic nuclei with a wide variety of substituents, such as those hereinafter set forth.
- M represents an atom of titanium, vanadium, chromium
- R represents any of the following:
- An aliphatic group having 1 to 18 carbon atoms e.g., methyl, ethyl, propyl, butyl, isobutyl, octyl, dodecyl, etc., including a substituted alkyl group having 1 to 18 carbon atoms, such as:
- nitroalkyl e.g., nitrobutyl, nitroethyl
- cyanoalkyl e.g., cyanopropyl, cyanobutyl
- alkaryl e.g., tolyl, ethylphenyl, propylnaththyl, etc.
- a cycloalkyl group having 4 to 8 carbon atoms in the cyclic nucleus e.g., cyclobutyl, cyclohexyl, cyclopentyl, etc., including a substituted cycloalkyl group such (a) alkoxycycloalkyl, e.g., ethoxycyclohexyl, methoxycyclobutyl, propoxycyclohexyl, etc., (b) aryloxycycloalkyl, e.g., iphenoxycyclohexyl, naphthoxycyclohexyl, phenoxycyclopentyl, etc, (c) aminocycloalkyl, e.g., aminocyclobutyl, aminocyclohexyl, aminocyclopentyl, etc., (d) hydroxycycloalkyl, e.g., hydroxycyclohexyl, hy-
- droxycyclopentyl, hydroxycyclobutyl, etc. (e) arylcycloalkyl, e.g., phenylcyclohexyl, phenylcyclobutyl, etc., (f) alkylaminocycloalkyl, e.g., rnethylaminocyclohcxyl, methylaminocyclopentyl, etc., and also including dialkyla-minocycloalkyl, e.g., diethylamiuocyclohexyl,
- arylarninocycloalkyl e.g., phenylarninocyclohexyl, diphenylaminocyclohexyl, N-pheuyl-N-ethylaminocyclopentyl, N-phenyl-N-methylaminocyclohexyl, naphthylarninocyclopentyl, etc.
- nitrocycloalkyl e.g., nitrocyclobutyl, nitrocyclohexyl, nitrocyclopentyl, etc.
- cyanocycloalkyl e.g., cyanocyclohexyl, cyanocyclobutyl, cyanocyclopentyl, etc.
- halocycloalkyl e.g., chlorocyclohexyl, bromocyclopentyl, chlorocyclooctyl, etc.
- R is hydroxy, hydrogen, aryl, e.g., phenyl, naphthyl, etc., amino, including substituted amino, cg, diloweralkylamino, lower alkoxy having 1 to 8 carbon atoms, e.g., butoxy, methoxy, etc., aryloxy, e.g., phenoxy, naphthoxy, etc., lower alkyl having 1 to 8 carbon atoms, e.g., methyl, ethyl, propyl, butyl, etc.;
- a heterocyclic group including a substituted heterocyclic group containing 5 to 6 members in the hetero nucleus and including at least one sulfur, selenium, oxygen or nitrogen atom such as a thienyl group, e.g., a benzothienyl group, a pyrrolyl group, e.g., a nitropyrrolyl group, a pyrrolidinyl group, e.g., a prolyl group, a pyr rolinyl group, a benzopyrrolyl group, e.g., an indolyl group, a carbazolyl group, a furyl group, e.g., a furfuryl group, a benzofuryl group, etc., a pyridyl group, e.g., a halopyridyl group, an aminopyridyl group, a hydroxypyridyl group, an alkylpyridyl group, a
- alkoxy having 1 to 18 carbon atoms e.g,, methoxy, ethoxy, propoxy, butoxy, etc.'
- aryloxy e.g., phenoxy, naphthoxy, etc.
- R and R are the same or difierent including lower alkyl having 1 to about 8 carbon atoms such as methyl, isopropyl, hexyl, octyl, etc., and aryl such as phenyl, naphthyl, etc.;
- halogen such as chlorine, bromine, fluorine or iodine
- Z represents any of the following:
- n is a positive integer having a value of about 3 to 1000 and n and n are positive integers each having a value of about 1 to 999 with 3n +n 1000
- aromatic nuclei are carbazole, indole, quinoline, quinoxaline, benzofuran, dibenzofuran, benzothiophene, dibenzothiophene, pyrazole, fluorene, anthracene and the like.
- Additional aromatic nuclei are those derived from organometallic compounds having at least one aminoaryl substituent attached to a Group IIIa, Group IVa or Group Va metal atom, as described in copending Goldman and Johnson U.S. Ser. No. 650,664, filed July 3, 1967 now U.S. Pat. No. 3,647,429, issued Mar. 7, 1972; and Johnson U.S. Ser. No. 755,711, filed Aug. 28, 1968 now U.S. Pat. No. 3,607,257, issued Sept. 21, 1971.
- R include hydrogen atoms, halogen atoms, lower alkyl groups having from 1 to about 8 carbon atoms, aryl groups and amino groups
- Z include diarylamino, dialkylaminopheuyl, diarylaminophenyl, and bis- (dialkylaminophenyl)methylene.
- R and R are amino substituted aryl groups, said aryl s preferably being substituted in the para position.
- the particularly preferred photoconductor is ferrocenylbis(2-methyl 4 diethylaminophenyl)methane, corresponding to the formula:
- Some typical metallocene photoconductors according to the invention include the following:
- the monomeric photoconductors of this invention are generally prepared by reacting in an inert atmosphere the aldehyde of the ferrocene or analogous metallocene with the desired aromatic compound in solution. Separation and purification are accomplished by conventional methods.
- the polymeric photoconductors of the invention are prepared by first making the vinyl monomers containing the photoconductive groups and then poly
- Electrophotographic elements of the invention can be prepared with the photoconducting compounds of the invention in the usual manner, i.e., by blending a dispersion or solution of a photoconductive compound together with a. binder, when necessary or desirable, and coating or forming a self-supporting layer with the photoconductorcontaining material. Mixtures of the photoconductors described herein can be employed. Likewise, other photoconductors known in the art can be combined with the present photoconductors. In addition, supplemental matcrials useful for changing the spectral sensitivity or electrophotosensitivity of the element can be added to the composition of the element when it is desirable to produce the characteristic effect of such materials.
- the photoconductive layers of the invention can also be sensitized by the addition of effective amounts of sensitizing compounds to exhibit improved electrophotosensitivity.
- Sensitizing compounds useful with the photoconductive compounds of the present invention can be selected from a wide variety of materials, including such materials as pyrylium dye salts including thiapyrylium dye salts and selenapyrylium dye salts disclosed in Vanv Allan et al. U.S. Pat.
- cyanine including carbocyanine
- merocyanine diarylmethane
- thiazine azine
- oxazine xanthene
- phthalein acridine
- azo anthraquinone dyes and the like and mixtures thereof.
- the sensitizers preferred for use with the compounds of this invention are selected from pyrylium salts including selenapyrylium salts and thiapyrylium salts, and cyanine dyes including carbocyanine dyes.
- sensitizing compound is employed with the binder and organic photoconductor to form a sensitized electrophotographic element
- Other methods of incorporating the sensitizer or the effect of the sensitizer may, however, be employed consistent with the practice of this invention.
- no sensitizing compound is required to give photoconductivity in the layers which contain the photoconducting substances, therefore, no sensitizer is required in a particular photoconductive layer.
- relatively minor amounts of sensitizing compound give substantial improvement in speed of such layers, the use of a sensitizer is preferred.
- the amount of sensitizer that can be added to a photoconductor-incorporating layer to give effective increases in speed can vary widely.
- the optimum concentration in any given case will vary with the specific photoconductor and sensitizing compound used.
- substantial speed gains can be obtained where an appropriate sensitizer is added in a concentration range from about 0.0001 to about 30 percent by weight based on the Weight of the film-forming coating composition.
- a sensitizer is added to the coating composition in an amount by weight from about 0.005 to about 5.0 percent by weight of the total coating composition.
- Preferred binders for use in preparing the present photoconductive layers are film-forming, hydrophobic polymeric binders having fairly high dielectric strength which are good electrically insulating, film-forming vehicles.
- Materials of this type comprise styrene-butadiene compolymers; silicone resins; styrene-alkyd resins; siliconealkyd resins; soya-alkyd resins; poly(vinyl chloride); poly- (vinylidene chloride); vinylidene chloride-vinyl chloride copolymers; vinylidene chloride-acrylonitrile copolymers; poly(vinyl acetate); vinyl acetate-vinyl chloride copolymers; poly(vinyl acetals), such as poly(vinyl butyral); polyacrylic and methacrylic esters, such as poly(rnethylmethacrylate), poly(n-butylmethacrylate), poly(isobutylmethacrylate), etc; poly
- styrene-alkyd resins can be prepared according to the method described in US. Pats. 2,361,019 by Gerhart, issued Oct. 24, 1944 and 2,258,423 by Rust, issued Oct. 7, 1941.
- Suitable resins of the type contemplated for use in the photoconductive layers of the invention are sold under such trademarks as Geon 222, Vitel PE-101, Cymac, Piccopale 100, Saran F-220, Lexan 105 and Lexan 145.
- Other types of binders which can be used in the photoconductive layers of the invention include such materials as paraffin, mineral waxes, etc.
- Solvents useful for preparing coating compositions with the photoconductors of the present invention can include a wide variety of organic solvents for the components of the coating composition.
- organic solvents for the components of the coating composition.
- benzene; toluene; acetone; Z-butanone; chlorinated hydrocarbons such as methylene chloride, ethylene chloride, and the like; ethers, such as tetrahydrofuran and the like, or mixtures of such solvents can advantageously be employed in the practice of this invention.
- the photoconductive substance is present in an amount equal to at least about 1 weight percent of the coating composition.
- the upper limit in the amount of photoconductive material present can be Widely varied in accordance with usual practice. It is normally required that the photoconductive material be present in an amount ranging from about 1 Weight percent of the coating composition to about 99 weight percent of the coating composition.
- a preferred Weight range for the photoconductive material in the coating composition is from about 10 weight percent to about 60 weight percent.
- Coating thicknesses of the photoconductive composition on a support can vary widely. Normally, a wet coating thickness in the range of about 25 microns to about 500 microns is useful in the practice of the invention A preferred range of coating thickness is from about 50 microns to about microns before drying although such thicknesses can vary Widely depending on the particular application desired for the electrophotographic element.
- Suitable supporting materials for coating the photoconductive layers of the present invention can include any of the electrically conducting supports, for example, paper (at a relative humidity above 20 percent); aluminum-paper laminates; metal foils, such as aluminum foil, zinc foil, etc.; metal plates, such as aluminum, copper, Zinc, brass, and galvanized plates; vapor deposited metal layers such as silver, nickel or aluminum on conventional film supports such as cellulose acetate, poly- (ethylene terephthalate), polystyrene and the like conducting supports.
- the electrically conducting supports for example, paper (at a relative humidity above 20 percent); aluminum-paper laminates; metal foils, such as aluminum foil, zinc foil, etc.; metal plates, such as aluminum, copper, Zinc, brass, and galvanized plates; vapor deposited metal layers such as silver, nickel or aluminum on conventional film supports such as cellulose acetate, poly- (ethylene terephthalate), polystyrene and the like conducting supports.
- An especially useful conducting support can be repared by coating a transparent film support material such as poly(ethylene terephthalate) with a layer containing a semiconductor.
- a suitable conducting coating can be prepared from the sodium salt of a carboxyester lactone of a maleic anhydride-vinyl acetate copolyrner, cuprous iodide and the like.
- Such conductive layers and methods for their optimum preparation and use are disclosed in US. 3,007,901 by Minsk, issued Nov. 11, 1961, 3,245,833 by Trevoy, issued Apr. 12, 1966 and 3,262,807 by Sterman at al., issued July 26, 1966.
- compositions of the present invention can be employed in photocond-uctive elements useful in any of the well-known electrophotographic processes which require photoconductive layers.
- One such process is the xerographic process.
- an electrophotographic element held in the dark is given a blanket electrostatic charge by placing it under a corona discharge to give a uniform charge to the surface of the photoconductive layer. This charge is retained by the layer owing to the substantial dark insulating property of the layer, i.e., the low conductivity of the layer in the dark.
- the electrostatic charge formed on the surface of the photoconductive layer is then selectively dissipated from the surface of the layer by imagewise exposure to light by means of a conventional exposure operation such as, for example, by a contact-printing technique, or by lens projection of an image, or reflex or bireflex technique and the like, to thereby form a latent electrostatic image in the photoconductive layer.
- Exposing the surface in this manner forms a pattern of electrostatic charge by virtue of the fact that light energy striking the photoconductor causes the electrostatic charge in the light-struck areas to be conducted away from the surface in proportion to the intensity of the illumination in a particular area.
- the charge pattern produced by exposure is then developed or transferred to another surface and developed there, i.e., either the charge or uncharged areas rendered visible, by treatment with a medium comprising electrostatically responsive particles having optical density.
- the developing electrostatically responsive particles can be in the form of a dust, or powder and generally comprise a pigment in a resinous carrier called a toner.
- a preferred method of applying such a toner to a latent electrostatic image for solid area development is by the use of a magnetic brush. Methods of forming and using a magnetic brush toner applicator are described in the following U.S. patents: 2,786,439 by Young, issued Mar. 26, 1957; 2,786,440 by Giairno, issued Mar. 26, 1957; 2,786,441 by Young, issued Mar.
- Liquid development of the latent electrostatic image may also be used.
- the developing particles are carried to the imagebearing surface in an electrically insulating liquid carrier.
- Methods of development of this type are widely known and have been described in the patent literature, for example, U.S. Pat. 2,907,674 by Metcalfe et al., issued Oct. 6, 1959.
- dry developing processes the most widely used method of obtaining a permanent record is achieved by selecting a developing particle which has as one of its components a low-melting resin. Heating the powder image then causes the resin to melt or fuse into or on the element. The powder is, therefore, caused to adhere permanently to the surface of the photoconductive layer.
- a transfer of the charge image or powder image formed on the photoconductive layer can be made to a second support such as paper which would then become the final print after developing and fusing or fusing, respectively.
- a second support such as paper which would then become the final print after developing and fusing or fusing, respectively.
- compositions of the present invention can be used in electrophotographic elements having many structural variations.
- the photoconductive composition can be coated in the form of single layers or multiple layers on a suitable opaque or transparent conducting support.
- the layers can be contiguous or spaced having layers of insulating material or other photoconductive material between layers or overcoated or interposed between the photoconductive layer or sensitizing layer and the conducting layer. It is also possible to adjust the position of the support and the conducting layer by placing a photoconductor layer over a support and coating the exposed face of the support or the exposed or overcoated face of the photoconductor with a conducting layer. Configurations differing from those contained in the example can be useful or even preferred for the same or different application for the electrophotographic element.
- EXAMPLE 2 The ferrocene compound prepared as in Example 1 is incorporated into a coating dope having the following composition.
- Organic photoconductor g 0.25 Polymeric binder g 1.0 Sensitizer g 0.0 1 Dichloromethane ml 7.2
- the exposure causes reduction of the surface potential of the element under each step of the gray scale from its initial potential, V to some lower potential, V, whose exact value depends on the actual amount of exposure received by the areas.
- the results of the measurements are plotted on a graph of surface potential V vs. log exposure for each step.
- the speed is the numerical expression of 10 multiplied by the reciprocal of the exposure required to reduce the 600 volt charged surface potential by 100 volts.
- the speed of the element thus produced is 34 when charged positively and 57 when charged negatively.
- the speed of a control element containing no photoconductor is 22 when charged positively and 40 when charged negatively.
- the sensitizer in each case is 2,6-bis(4-ethylphenyl) 4 (4-n-amyloxyphenyl) thiapyrylium perchlorate. Similar improvements in speed are obtained when the sensitizer is Rhodamine B (CI. 45170) or 4-(n-butylamino)-2(4-methoxyphenyl)-benzo [b] pyrylium perchlorate.
- a photoconductor-containing coating composition is made which contains the photoconductor of Example 1 together with other components as listed below:
- Sensitizer D solution contains 0.0029 gram of the dye 4 (4 dimethylaminophenyl)-2, fi-diphenylthiapyrylium perchlorate per milliliter of dichloromethane.
- the aggregate solution is made by combining 3.92 grams of the polycarbonate listed in the table above with 0.08 gram of Sensitizer D in 26.8 ml. of dichloromethane and subjecting the solution to high-speed shearing for several hours according to the procedure of copending Gramza application U.S. Ser. No. 821,513, filed May 2, 1969, entitled Method for the Preparation of Photoconductive Compositions, now U.S. Pat. No. 3,615,413, issued Oct. 26, 1971.
- the coating composition is then made by mixing the ingredients with moderate stirring for about one-half hour at room temperature.
- the resultant composition is coated at a wet thickness of 150 microns onto a piece of the support employed in Example 2 in the manner described there, and similarly dried to form a usable electrophotographic element.
- the element is tested as described in Example 2, except that the speed is measured at a point at 100 volts above the zero volt base line with both positive and negative charging.
- the element of this example has a speed as thus determined of when charged positively, compared to a speed of 25 for a control element identically prepared except that the photoconductor of the invention is omitted. When charged negatively, the
- R and R are amino substituted aryl groups.
- An electrophotographic element as described in claim 1 additionally comprising a sensitizer selected from the group consisting of pyryliurn and thiapyrylium dye salts and wherein said binder is a carbonate polymer.
- a photoconductive element for use in electrophotography comprising a conductive support bearing a photoconductive layer comprising ferrocenylbis(2-methyl-4- diethylaminophenyDmethane, a pyrylium dye sensitizer and a polymeric film-forming electrically insulating binder.
- said photoconductive element has a photoconductive layer comprising a ferrocenylbis(2-methyl-4-diethylaminophenyDmethane photoconductor and an electrically insulating film-forming polymeric binder.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Photoreceptors In Electrophotography (AREA)
Abstract
A CLASS OF METALLOCENE COMPOUNDS ARE DISCLOSED WHICH EXHIBIT PHOTOCONDUCTIVE PROPERTIES USEFUL IN ELECTROPHOTOGRAPHY.
Description
United States Patent 3,711,280 METALLOCENE PHOTOCONDUCTORS USED IN ELECTROPHOTOGRAPHY Arthur L. Johnson, Rochester, N.Y., assignor to Eastman Kodak Company, Rochester, N.Y. No Drawing. Filed Feb. 17, 1971, Ser. No. 116,208 Int. Cl. G03g 5/06 U.S. Cl. 961.6 6 Claims ABSTRACT OF THE DISCLOSURE A class of metallocene compounds are disclosed which exhibit photoconductive properties useful in electrophotography.
This invention relates to electrophotography and more particularly to a novel compound and to a class of photoconductive materials and the compositions and elements produced therefrom.
Electrophotographic imaging processes and techniques are based on the discovery that certain materials which are normally insulating become conductive during exposure to electromagnetic radiation of certain wave lengths after being electrically charged. Such materials, which may be either organic or inorganic, are termed photoconductors. They are conveniently formed into usable imageforming elements by coating a layer of the photoconductive composition, together with an electrically insulating resinous binder where necessary or desirable, onto a suitable support. Such an element will accept and retain an electrostatic charge in the absence of actinic radiation. In use, the surface of the element is charged in the dark to a uniform potential and exposed to an imagewise pattern of actirnc radiation, which selectively reduces the surface potential to produce a charge pattern corresponding to the imagewise radiation pattern. The resultant charge pattern or electrostatic latent image may be developed by contacting it with suitable charged marking particles which adhere in accordance with the charge pattern, or it may be transferred to another insulating surface upon which it is developed. The particles may then be fused or fixed to the surface by known means such as heat or solvent vapor, or they may be transferred to another surface to which they may similarly be fixed, to produce a permanent reproduction of the original radiation pattern.
Various photoconductive insulating materials have been employed in the manufacture of electrophotographic elements. For example, vapors of selenium and vapors of selenium alloys deposited on a suitable support and particles of photoconductive zinc oxide held in a resinous, film-forming binder have found wide application in pre'sent-day document copying applications.
Since the introduction of electrophotography, a great many organic compounds have been found to possess some degree of photoconductivity. Many organic compounds have revealed a useful level of photoconduction and have been incorporated into photoconductive compositions. As a result, a large number of organic compounds have been known to possess some degree of photoconductivity. Typical of these organic photoconductors are the triphenylamines and the triarylmethane leuco bases. Optically clear photoconductor-containing elements having desirable electrophotographic properties can be especially useful in electrophotography. Such electrophotographic elements can be exposed through a transparent base if desired, thereby providing flexibility in equipment design. Such compositions, when coated as a film or layer on a suitable support, also yield an element which is reusable;
that is, it can be used to form subsequent images after Patented Jan. 16, .1973
residual toner from prior images has been removed by transfer and/ or cleaning. Thus far, the selection of various compounds for incorporation into photoconductive compositions to form electrophotographic layers has proceeded on a compound-by-compound basis. Nothing as yet has been discovered from the la ge number of different photoconductive substances tested which permits effective prediction, and therefore selection of the particular compounds exhibiting the desired electrophotographic properties.
It is, therefore, an object of this invention to provide a novel class of photoconductive compounds.
It is another object of this invention to provide a novel class of photoconductors having useful photosensitivity when electrically charged.
It is yet another object of this invention to provide novel photoconductor-containing compositions which exhibit useful electrical speeds when positively or negatively charged.
It is still another object of this invention to provide novel transparent electrophotographic elements having useful electrophotographic speeds.
It is a further object of this invention to provide an improved process utilizing the novel photoconductors described herein.
These and other objects of this invention are accomplished with electrophotographic elements having coated thereon photoconductive compositions containing as photoconductors metallocenes derived from first row transition metals.
The metals from which these metallocenes are derived are those in the first row of Groups IVb, Vb, VII), VIII) and VIII in accordance with the Periodic Table of the Elements (Handbook of Chemistry and Physics, 38th edition, pp. 394-) and include titanium, vanadium, chromium, manganese, iron, cobalt and nickel. Similarly, vinyl polymers containing the metallocenes 3J8 side chains can be used. The metallocene can be substituted on one or both of its aromatic nuclei with a wide variety of substituents, such as those hereinafter set forth.
Illustrative photoconductors of this invention are represented by the following structure:
M represents an atom of titanium, vanadium, chromium,
manganese, iron, cobalt or nickel;
R represents any of the following:
(1) An aliphatic group having 1 to 18 carbon atoms, e.g., methyl, ethyl, propyl, butyl, isobutyl, octyl, dodecyl, etc., including a substituted alkyl group having 1 to 18 carbon atoms, such as:
(h) nitroalkyl, e.g., nitrobutyl, nitroethyl,
nitropentyl, etc.,
(i) cyanoalkyl, e.g., cyanopropyl, cyanobutyl,
cyanoethyl, etc.,
(j) haloalkyl, e.g., chloromethyl, bromopentyl,
chlorooctyl, etc.,
' (k) alkyl substituted with an acyl group having the formula wherein R is hydroxy, hydrogen, aryl, e.g., phenyl, naphthyl, etc., lower alkyl having 1 to 8 carbon atoms, e.g., methyl, ethyl, propyl, etc., amino, including substituted amino, e.g., diloweralkylamino, lower alkoxy having 1 to 8 carbon atoms, e.g., butoxy, methoxy, etc., aryloxy, e.g., phenoxy, naphthoxy, etc.;
(2) An aryl group, e.g., phenyl, naphthyl, anthryl, fiuorenyl, etc., including a substituted aryl group such as wherein R is hydroxy, halogen, e.g., chlorine, hydrogen, aryl, e.g., phenyl, naphthyl, etc., amino, including substituted amino, e.g., diloweralkylamino, lower alkoxy having 1 to 8 carbon atoms, e.g., butoxy, methoxy, etc., aryloxy, e.g., phenoxy, naphthoxy, etc., lower alkyl having 1 to ,8 carbon atoms, e.g., methyl, ethyl, propyl, butyl, etc.,
(1) alkaryl, e.g., tolyl, ethylphenyl, propylnaththyl, etc.
(3) a cycloalkyl group having 4 to 8 carbon atoms in the cyclic nucleus, e.g., cyclobutyl, cyclohexyl, cyclopentyl, etc., including a substituted cycloalkyl group such (a) alkoxycycloalkyl, e.g., ethoxycyclohexyl, methoxycyclobutyl, propoxycyclohexyl, etc., (b) aryloxycycloalkyl, e.g., iphenoxycyclohexyl, naphthoxycyclohexyl, phenoxycyclopentyl, etc, (c) aminocycloalkyl, e.g., aminocyclobutyl, aminocyclohexyl, aminocyclopentyl, etc., (d) hydroxycycloalkyl, e.g., hydroxycyclohexyl, hy-
droxycyclopentyl, hydroxycyclobutyl, etc., (e) arylcycloalkyl, e.g., phenylcyclohexyl, phenylcyclobutyl, etc., (f) alkylaminocycloalkyl, e.g., rnethylaminocyclohcxyl, methylaminocyclopentyl, etc., and also including dialkyla-minocycloalkyl, e.g., diethylamiuocyclohexyl,
dimethylaminocyclobutyl, dipropylarninocyclooctyl, etc.,
(g) arylarninocycloalkyl, e.g., phenylarninocyclohexyl, diphenylaminocyclohexyl, N-pheuyl-N-ethylaminocyclopentyl, N-phenyl-N-methylaminocyclohexyl, naphthylarninocyclopentyl, etc.,
(h) nitrocycloalkyl, e.g., nitrocyclobutyl, nitrocyclohexyl, nitrocyclopentyl, etc.,
(i) cyanocycloalkyl, e.g., cyanocyclohexyl, cyanocyclobutyl, cyanocyclopentyl, etc.,
(j) halocycloalkyl, e.g., chlorocyclohexyl, bromocyclopentyl, chlorocyclooctyl, etc.,
(k) cycloalkyl-substituted with an acyl group having the formula:
wherein R is hydroxy, hydrogen, aryl, e.g., phenyl, naphthyl, etc., amino, including substituted amino, cg, diloweralkylamino, lower alkoxy having 1 to 8 carbon atoms, e.g., butoxy, methoxy, etc., aryloxy, e.g., phenoxy, naphthoxy, etc., lower alkyl having 1 to 8 carbon atoms, e.g., methyl, ethyl, propyl, butyl, etc.;
(4) a heterocyclic group including a substituted heterocyclic group containing 5 to 6 members in the hetero nucleus and including at least one sulfur, selenium, oxygen or nitrogen atom such as a thienyl group, e.g., a benzothienyl group, a pyrrolyl group, e.g., a nitropyrrolyl group, a pyrrolidinyl group, e.g., a prolyl group, a pyr rolinyl group, a benzopyrrolyl group, e.g., an indolyl group, a carbazolyl group, a furyl group, e.g., a furfuryl group, a benzofuryl group, etc., a pyridyl group, e.g., a halopyridyl group, an aminopyridyl group, a hydroxypyridyl group, an alkylpyridyl group, a nitropyridyl group, etc., a piperidyl group, a quinolyl group, an acridinyl group, a pyranyl group, a benzopyranyl group, a pyrazolyl group, an oxaz'olyl group, a thiazolyl group, etc.;
(5) hydrogen;
(6) alkoxy having 1 to 18 carbon atoms, e.g,, methoxy, ethoxy, propoxy, butoxy, etc.',
(7) aryloxy, e.g., phenoxy, naphthoxy, etc.;
(8) vinyl;
(9) amino having the formula:
wherein R and R are the same or difierent including lower alkyl having 1 to about 8 carbon atoms such as methyl, isopropyl, hexyl, octyl, etc., and aryl such as phenyl, naphthyl, etc.;
(10) nitro; and
(11) halogen such as chlorine, bromine, fluorine or iodine; and Z represents any of the following:
is an integer having a value equal to the valence of. the metal M minus 1;
(7) a group corresponding to the formula:
(8) a group corresponding to the formula:
(9) a group corresponding to the formula:
(10) a group corresponding to the formula:
and
and
wherein M and Z have the same meanings hereinabove set forth, A is a nitrogen atom or a carbon atom, X represents the atoms required to complete a monoor polycyclic aromatic nucleus which may be carbocyclic or heterocyclic having such hetero atoms as oxygen, sulfur, nitrogen, etc., and containing up to 19 atoms. The symbol n is a positive integer having a value of about 3 to 1000 and n and n are positive integers each having a value of about 1 to 999 with 3n +n 1000 Typical of such aromatic nuclei are carbazole, indole, quinoline, quinoxaline, benzofuran, dibenzofuran, benzothiophene, dibenzothiophene, pyrazole, fluorene, anthracene and the like. Additional aromatic nuclei are those derived from organometallic compounds having at least one aminoaryl substituent attached to a Group IIIa, Group IVa or Group Va metal atom, as described in copending Goldman and Johnson U.S. Ser. No. 650,664, filed July 3, 1967 now U.S. Pat. No. 3,647,429, issued Mar. 7, 1972; and Johnson U.S. Ser. No. 755,711, filed Aug. 28, 1968 now U.S. Pat. No. 3,607,257, issued Sept. 21, 1971.
The preferred substituents for R include hydrogen atoms, halogen atoms, lower alkyl groups having from 1 to about 8 carbon atoms, aryl groups and amino groups, while the preferred substituents for Z include diarylamino, dialkylaminopheuyl, diarylaminophenyl, and bis- (dialkylaminophenyl)methylene.
Preferred metallocene photoconductors according to the invention are ferrocenes corresponding to the general structure:
wherein R and R are amino substituted aryl groups, said aryl grups preferably being substituted in the para position. The particularly preferred photoconductor is ferrocenylbis(2-methyl 4 diethylaminophenyl)methane, corresponding to the formula:
I Me
Some typical metallocene photoconductors according to the invention include the following:
( l l,l-bis(p-diphenylaminophenyl)ferrocene (2) p-diphenylaminophenylferrocene (3 p-diethylaminophenyltitanocene (4) 1- [tris (p-diethylaminophenyl) germyl] cobaltocene (5) diethylaminonickelocene (6) poly(vinylferrocene-co-3-bromo-N-vinylcarbazole) (7) poly (vinylferrocene-co-4-vinyl-4',4"-dimethyltri'phenylamine) The monomeric photoconductors of this invention are generally prepared by reacting in an inert atmosphere the aldehyde of the ferrocene or analogous metallocene with the desired aromatic compound in solution. Separation and purification are accomplished by conventional methods. The polymeric photoconductors of the invention are prepared by first making the vinyl monomers containing the photoconductive groups and then polymerizing in a conventional manner.
Electrophotographic elements of the invention can be prepared with the photoconducting compounds of the invention in the usual manner, i.e., by blending a dispersion or solution of a photoconductive compound together with a. binder, when necessary or desirable, and coating or forming a self-supporting layer with the photoconductorcontaining material. Mixtures of the photoconductors described herein can be employed. Likewise, other photoconductors known in the art can be combined with the present photoconductors. In addition, supplemental matcrials useful for changing the spectral sensitivity or electrophotosensitivity of the element can be added to the composition of the element when it is desirable to produce the characteristic effect of such materials.
The photoconductive layers of the invention can also be sensitized by the addition of effective amounts of sensitizing compounds to exhibit improved electrophotosensitivity. Sensitizing compounds useful with the photoconductive compounds of the present invention can be selected from a wide variety of materials, including such materials as pyrylium dye salts including thiapyrylium dye salts and selenapyrylium dye salts disclosed in Vanv Allan et al. U.S. Pat. 3,250,615, issued May 10, 1966; fluorenes, such as 7,12-dioxo 13 dibenzo(a,h)fiuorene, 5,10 dioxo 4a,1l diabenzo(b)fluorene, 3,13-dioxo-7- oxadibenzo(b,g)fluorene, and the like; aromatic nitro compounds of the kinds described in U.S. Pat. 2,610,120 by Minsk, issued Sept. 9, 1952; anthrones like those disclosed in US. Pat. 2,670,284 by Zvanut, issued Feb. 23, 1954; quinones, U.S. Pat. 2,670,286 by Minsk, issued Feb. 23, 1954; benzophenones, U.S. Pat. 2,670,287 by Minsk, issued Feb. 23, 1954; thiazoles, U.S. Pat. 2,732,- 301 by Robertson, issued Jan. 24, 1956; mineral acids; carboxylic acids, such as maleic acid, dichloroacetic acid,
and salicylic acid; sulfoinic and phosphoric acids; and various dyes, such as cyanine (including carbocyanine), merocyanine, diarylmethane, thiazine, azine, oxazine, xanthene, phthalein, acridine, azo, anthraquinone dyes and the like and mixtures thereof. The sensitizers preferred for use with the compounds of this invention are selected from pyrylium salts including selenapyrylium salts and thiapyrylium salts, and cyanine dyes including carbocyanine dyes.
Where a sensitizing compound is employed with the binder and organic photoconductor to form a sensitized electrophotographic element, it is the normal practice to mix a suitable amount of the sensitizing compound with the coating composition so that, after thorough mixing, the sensitizing compound is uniformly distributed in the coated element. Other methods of incorporating the sensitizer or the effect of the sensitizer may, however, be employed consistent with the practice of this invention. In preparing the photoconductive layers, no sensitizing compound is required to give photoconductivity in the layers which contain the photoconducting substances, therefore, no sensitizer is required in a particular photoconductive layer. However, since relatively minor amounts of sensitizing compound give substantial improvement in speed of such layers, the use of a sensitizer is preferred. The amount of sensitizer that can be added to a photoconductor-incorporating layer to give effective increases in speed can vary widely. The optimum concentration in any given case will vary with the specific photoconductor and sensitizing compound used. In general, substantial speed gains can be obtained where an appropriate sensitizer is added in a concentration range from about 0.0001 to about 30 percent by weight based on the Weight of the film-forming coating composition. Normally, a sensitizer is added to the coating composition in an amount by weight from about 0.005 to about 5.0 percent by weight of the total coating composition.
Preferred binders for use in preparing the present photoconductive layers are film-forming, hydrophobic polymeric binders having fairly high dielectric strength which are good electrically insulating, film-forming vehicles. Materials of this type comprise styrene-butadiene compolymers; silicone resins; styrene-alkyd resins; siliconealkyd resins; soya-alkyd resins; poly(vinyl chloride); poly- (vinylidene chloride); vinylidene chloride-vinyl chloride copolymers; vinylidene chloride-acrylonitrile copolymers; poly(vinyl acetate); vinyl acetate-vinyl chloride copolymers; poly(vinyl acetals), such as poly(vinyl butyral); polyacrylic and methacrylic esters, such as poly(rnethylmethacrylate), poly(n-butylmethacrylate), poly(isobutylmethacrylate), etc; polystyrene; nitrated polystyrene; polymethylstyrene; polyvinyl toluene-styrene copolymers; isobutylene polymers; polyesters, such as poly(ethylenealkaryloxyalkylene terephthalate); phenolformaldehyde resins; ketone resins; polyamides; polycarbonate; polythiocarbonates; poly(ethyleneglycol co bis hydroxyethoxyphenyl) propane terephthalate; copolyrners of vinyl haloarylates and vinyl acetate such as poly(vinyl-mbromobenzoate-co-vinylacetate); etc. Methods of making resins of this type have been described in the prior art, for example, styrene-alkyd resins can be prepared according to the method described in US. Pats. 2,361,019 by Gerhart, issued Oct. 24, 1944 and 2,258,423 by Rust, issued Oct. 7, 1941. Suitable resins of the type contemplated for use in the photoconductive layers of the invention are sold under such trademarks as Geon 222, Vitel PE-101, Cymac, Piccopale 100, Saran F-220, Lexan 105 and Lexan 145. Other types of binders which can be used in the photoconductive layers of the invention include such materials as paraffin, mineral waxes, etc.
Solvents useful for preparing coating compositions with the photoconductors of the present invention can include a wide variety of organic solvents for the components of the coating composition. For example, benzene; toluene; acetone; Z-butanone; chlorinated hydrocarbons such as methylene chloride, ethylene chloride, and the like; ethers, such as tetrahydrofuran and the like, or mixtures of such solvents can advantageously be employed in the practice of this invention.
In preparing the coating compositions utilizing the 'photoconductors disclosed herein, useful results are obtained where the photoconductive substance is present in an amount equal to at least about 1 weight percent of the coating composition. The upper limit in the amount of photoconductive material present can be Widely varied in accordance with usual practice. It is normally required that the photoconductive material be present in an amount ranging from about 1 Weight percent of the coating composition to about 99 weight percent of the coating composition. A preferred Weight range for the photoconductive material in the coating composition is from about 10 weight percent to about 60 weight percent.
Coating thicknesses of the photoconductive composition on a support can vary widely. Normally, a wet coating thickness in the range of about 25 microns to about 500 microns is useful in the practice of the invention A preferred range of coating thickness is from about 50 microns to about microns before drying although such thicknesses can vary Widely depending on the particular application desired for the electrophotographic element.
Suitable supporting materials for coating the photoconductive layers of the present invention can include any of the electrically conducting supports, for example, paper (at a relative humidity above 20 percent); aluminum-paper laminates; metal foils, such as aluminum foil, zinc foil, etc.; metal plates, such as aluminum, copper, Zinc, brass, and galvanized plates; vapor deposited metal layers such as silver, nickel or aluminum on conventional film supports such as cellulose acetate, poly- (ethylene terephthalate), polystyrene and the like conducting supports.
An especially useful conducting support can be repared by coating a transparent film support material such as poly(ethylene terephthalate) with a layer containing a semiconductor. A suitable conducting coating can be prepared from the sodium salt of a carboxyester lactone of a maleic anhydride-vinyl acetate copolyrner, cuprous iodide and the like. Such conductive layers and methods for their optimum preparation and use are disclosed in US. 3,007,901 by Minsk, issued Nov. 11, 1961, 3,245,833 by Trevoy, issued Apr. 12, 1966 and 3,262,807 by Sterman at al., issued July 26, 1966.
The compositions of the present invention can be employed in photocond-uctive elements useful in any of the well-known electrophotographic processes which require photoconductive layers. One such process is the xerographic process. In a process of this type, an electrophotographic element held in the dark, is given a blanket electrostatic charge by placing it under a corona discharge to give a uniform charge to the surface of the photoconductive layer. This charge is retained by the layer owing to the substantial dark insulating property of the layer, i.e., the low conductivity of the layer in the dark. The electrostatic charge formed on the surface of the photoconductive layer is then selectively dissipated from the surface of the layer by imagewise exposure to light by means of a conventional exposure operation such as, for example, by a contact-printing technique, or by lens projection of an image, or reflex or bireflex technique and the like, to thereby form a latent electrostatic image in the photoconductive layer. Exposing the surface in this manner forms a pattern of electrostatic charge by virtue of the fact that light energy striking the photoconductor causes the electrostatic charge in the light-struck areas to be conducted away from the surface in proportion to the intensity of the illumination in a particular area.
The charge pattern produced by exposure is then developed or transferred to another surface and developed there, i.e., either the charge or uncharged areas rendered visible, by treatment with a medium comprising electrostatically responsive particles having optical density. The developing electrostatically responsive particles can be in the form of a dust, or powder and generally comprise a pigment in a resinous carrier called a toner. A preferred method of applying such a toner to a latent electrostatic image for solid area development is by the use of a magnetic brush. Methods of forming and using a magnetic brush toner applicator are described in the following U.S. patents: 2,786,439 by Young, issued Mar. 26, 1957; 2,786,440 by Giairno, issued Mar. 26, 1957; 2,786,441 by Young, issued Mar. 26, 1957; and 2,874,063 by Greig, issued Feb. 17, 1959. Liquid development of the latent electrostatic image may also be used. In liquid development, the developing particles are carried to the imagebearing surface in an electrically insulating liquid carrier. Methods of development of this type are widely known and have been described in the patent literature, for example, U.S. Pat. 2,907,674 by Metcalfe et al., issued Oct. 6, 1959. In dry developing processes, the most widely used method of obtaining a permanent record is achieved by selecting a developing particle which has as one of its components a low-melting resin. Heating the powder image then causes the resin to melt or fuse into or on the element. The powder is, therefore, caused to adhere permanently to the surface of the photoconductive layer. In other cases, a transfer of the charge image or powder image formed on the photoconductive layer can be made to a second support such as paper which would then become the final print after developing and fusing or fusing, respectively. Techniques of the type indicated are well known in the art and have been described in the literature such as in RCA 'Review, volume (1954), pages 469- 484.
The compositions of the present invention can be used in electrophotographic elements having many structural variations. For example, the photoconductive composition can be coated in the form of single layers or multiple layers on a suitable opaque or transparent conducting support. Likewise, the layers can be contiguous or spaced having layers of insulating material or other photoconductive material between layers or overcoated or interposed between the photoconductive layer or sensitizing layer and the conducting layer. It is also possible to adjust the position of the support and the conducting layer by placing a photoconductor layer over a support and coating the exposed face of the support or the exposed or overcoated face of the photoconductor with a conducting layer. Configurations differing from those contained in the example can be useful or even preferred for the same or different application for the electrophotographic element.
The following examples are included for a further understanding of the invention.
EXAMPLE 1 Preparation of ferrocenyl-bis(2-methyl- 4-diethylaminophenyl methane A solution of 10.7 grams (0.05 mole) of ferrocene aldehyde, 16.3 grams (0.10 mole) of N,N-diethyl-m-toluidine, 3 grams (0.05 mole) of urea and 4.15 ml. (0.05 mole) of concentrated hydrochloric acid in ml. of methanol is heated under reflux in a nitrogen atmosphere for 18 hours. The mixture is allowed to cool to room temperature (25 C.), after which the solution is stirred in 2.5 l. of ice water. The resulting solid is filtered, washed with water, and dried in air at room temperature. There results a 14. 6 gram yield of yellow solid product having a M.P. of 130'136.5 C. The material is recrystallized from 700 ml. of absolute alcohol to obtain 8.8 grams of reddish-brown crystalline solid having a M.P. 148-15 1 C. The structure of the compound is confirmed by mass spectroscopy.
Analysis.--Calcd for C H FeN (percent): C, 75.8; H, 8.0; Fe, 10.7; N, 5.4. Found (percent): C, 75.9; H, 8.0; Fe, 10.3; N, 5.5.
10 EXAMPLE 2 The ferrocene compound prepared as in Example 1 is incorporated into a coating dope having the following composition.
Organic photoconductor g 0.25 Polymeric binder g 1.0 Sensitizer g 0.0 1 Dichloromethane ml 7.2
Po1y[4,4' isopropylidenebis(phenyleneoxyethylene) coethylene terephthalate]. The resulting composition is coated at a wet thickness of microns onto a poly(ethylene terephthalate) film support bearing a conducting layer comprising metallic nickel vacuum deposited to an optical density of 0.04. The resultant electrophotographic element is charged under a positive or negative corona source until the surface potential, as measured by an electrometer probe reaches about 600 volts. It is then subjected to exposure from behind a stepped density gray scale to a 3000' K. tungsten source. The exposure causes reduction of the surface potential of the element under each step of the gray scale from its initial potential, V to some lower potential, V, whose exact value depends on the actual amount of exposure received by the areas. The results of the measurements are plotted on a graph of surface potential V vs. log exposure for each step. The speed is the numerical expression of 10 multiplied by the reciprocal of the exposure required to reduce the 600 volt charged surface potential by 100 volts. The speed of the element thus produced is 34 when charged positively and 57 when charged negatively. The speed of a control element containing no photoconductor is 22 when charged positively and 40 when charged negatively. The sensitizer in each case is 2,6-bis(4-ethylphenyl) 4 (4-n-amyloxyphenyl) thiapyrylium perchlorate. Similar improvements in speed are obtained when the sensitizer is Rhodamine B (CI. 45170) or 4-(n-butylamino)-2(4-methoxyphenyl)-benzo [b] pyrylium perchlorate.
v EXAMPLE 3 A photoconductor-containing coating composition is made which contains the photoconductor of Example 1 together with other components as listed below:
Polymeric binder poly(4,4-isopropylidenediphenyl ene carbonate) 0.25 Organic photoconductor 0.25 Sensitizer -D solution 4.5 Aggregate solution 7.7
Sensitizer D solution contains 0.0029 gram of the dye 4 (4 dimethylaminophenyl)-2, fi-diphenylthiapyrylium perchlorate per milliliter of dichloromethane. The aggregate solution is made by combining 3.92 grams of the polycarbonate listed in the table above with 0.08 gram of Sensitizer D in 26.8 ml. of dichloromethane and subjecting the solution to high-speed shearing for several hours according to the procedure of copending Gramza application U.S. Ser. No. 821,513, filed May 2, 1969, entitled Method for the Preparation of Photoconductive Compositions, now U.S. Pat. No. 3,615,413, issued Oct. 26, 1971. The coating composition is then made by mixing the ingredients with moderate stirring for about one-half hour at room temperature. The resultant composition is coated at a wet thickness of 150 microns onto a piece of the support employed in Example 2 in the manner described there, and similarly dried to form a usable electrophotographic element. The element is tested as described in Example 2, except that the speed is measured at a point at 100 volts above the zero volt base line with both positive and negative charging. The element of this example has a speed as thus determined of when charged positively, compared to a speed of 25 for a control element identically prepared except that the photoconductor of the invention is omitted. When charged negatively, the
wherein R and R are amino substituted aryl groups.
2. An electrophotographic element as described in claim 1 wherein the ferrocene has the structure:
3. An electrophotographic element as described in claim 1 additionally comprising a sensitizer selected from the group consisting of pyryliurn and thiapyrylium dye salts and wherein said binder is a carbonate polymer.
4. A photoconductive element as described in claim 5 wherein said binder is a carbonate polymer.
5. A photoconductive element for use in electrophotography comprising a conductive support bearing a photoconductive layer comprising ferrocenylbis(2-methyl-4- diethylaminophenyDmethane, a pyrylium dye sensitizer and a polymeric film-forming electrically insulating binder.
6. In an electrophotographic process wherein an electrostatic charge pattern is formed on an electrophotographic element, the improvement characterized in that said photoconductive element has a photoconductive layer comprising a ferrocenylbis(2-methyl-4-diethylaminophenyDmethane photoconductor and an electrically insulating film-forming polymeric binder.
2 References Cited UNITED STATES PATENTS 3,098,864 7/1963 Rausch 260-439 CY 3,352,888 11/1967 Matsunaga 260439 CY 3,379,740 4/1968 Matsunaga 260439 CY X 3,577 ,235 5/ 1971 Contois. 3,335,008 8/1967 Dubose .260439' CY X 3,490,907 1/ 1970 Schenck et a1. 260439' CY X OTHER REFERENCES Metallo-Organic Polymers Open New Field, C & EN News, Sept. 27, 1971, pp. 37-38.
GEORGE F. LESMES, Primary Examiner J. R. MILLER, Assistant Examiner US. Cl. X.R.
96-1 PC, 1.5; 252-501; 260-429 CY, 429.5, 438.5 R, 439 CY
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US11620871A | 1971-02-17 | 1971-02-17 |
Publications (1)
Publication Number | Publication Date |
---|---|
US3711280A true US3711280A (en) | 1973-01-16 |
Family
ID=22365903
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US00116208A Expired - Lifetime US3711280A (en) | 1971-02-17 | 1971-02-17 | Metallocene photoconductors used in electrophotography |
Country Status (1)
Country | Link |
---|---|
US (1) | US3711280A (en) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3960911A (en) * | 1973-11-21 | 1976-06-01 | Frisons Limited | Ferrocene compounds and preparation |
US3980684A (en) * | 1974-11-26 | 1976-09-14 | Exxon Research And Engineering Company | Metallocene intercalates |
US4123268A (en) * | 1977-06-22 | 1978-10-31 | Addressograph-Multigraph Corporation | Boron chelates as acceptor type sensitizers for photoconductive polymers |
DE3202404A1 (en) * | 1982-01-26 | 1983-08-04 | Standard Elektrik Lorenz Ag, 7000 Stuttgart | Photoconductive organic substance and electrophotographic layer containing such a substance |
GB2135068A (en) * | 1983-01-26 | 1984-08-22 | Int Standard Electric Corp | Photoconductive ferrocene derivatives of triphenylamine |
US20050227108A1 (en) * | 2004-04-12 | 2005-10-13 | General Electric Company | Opto-electroactive device comprising a metallocene and method |
-
1971
- 1971-02-17 US US00116208A patent/US3711280A/en not_active Expired - Lifetime
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3960911A (en) * | 1973-11-21 | 1976-06-01 | Frisons Limited | Ferrocene compounds and preparation |
US3980684A (en) * | 1974-11-26 | 1976-09-14 | Exxon Research And Engineering Company | Metallocene intercalates |
US4123268A (en) * | 1977-06-22 | 1978-10-31 | Addressograph-Multigraph Corporation | Boron chelates as acceptor type sensitizers for photoconductive polymers |
DE3202404A1 (en) * | 1982-01-26 | 1983-08-04 | Standard Elektrik Lorenz Ag, 7000 Stuttgart | Photoconductive organic substance and electrophotographic layer containing such a substance |
GB2135068A (en) * | 1983-01-26 | 1984-08-22 | Int Standard Electric Corp | Photoconductive ferrocene derivatives of triphenylamine |
US20050227108A1 (en) * | 2004-04-12 | 2005-10-13 | General Electric Company | Opto-electroactive device comprising a metallocene and method |
EP1587155A3 (en) * | 2004-04-12 | 2005-11-09 | General Electric Company | Opto-electroactive device comprising a metallocene |
US7169483B2 (en) | 2004-04-12 | 2007-01-30 | General Electric Company | Opto-electroactive device comprising a metallocene and method |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US4127412A (en) | Photoconductive compositions and elements | |
US3820989A (en) | Tri-substituted methanes as organic photoconductors | |
US3526501A (en) | 4-diarylamino-substituted chalcone containing photoconductive compositions for use in electrophotography | |
CA1046330A (en) | Photoconductive composition and elements with a styryl amino group containing photoconductor | |
US3240597A (en) | Photoconducting polymers for preparing electrophotographic materials | |
US3488705A (en) | Thermally unstable organic acid salts of triarylmethane dyes as sensitizers for organic photoconductors | |
US4018607A (en) | Crystalline organic pigment sensitizers for photoconductive layers | |
US4365017A (en) | Telluropyrylium electron accepting dye sensitizers for electron donating photoconductive compositions | |
US3677752A (en) | Bis(dialkylaminoaryl)ethylene photoconductors | |
US3719480A (en) | Electrophotographic compositions and elements | |
US3647433A (en) | Dinitroarylmethine dyes as sensitizers in electrophotographic layers | |
US3684502A (en) | Photoconductive co-crystalline complex of pyrylium dye and polymer used in electrophotography | |
US3938994A (en) | Pyrylium dyes for electrophotographic composition and element | |
US4018606A (en) | Organic azo pigment sensitizers for photoconductive layers | |
US3765884A (en) | 1-substituted-2-indoline hydrazone photoconductors | |
US3684548A (en) | Method of preparing a homogeneous dye-sensitized electrophotographic element | |
US4105447A (en) | Photoconductive insulating compositions including polyaryl hydrocarbon photoconductors | |
US4365016A (en) | Benzotelluropyrylium diketonate electron accepting dye sensitizers for electron donating photoconductive compositions | |
US3533783A (en) | Light adapted photoconductive elements | |
US3732180A (en) | Photoconductive composition and method | |
US3711280A (en) | Metallocene photoconductors used in electrophotography | |
US3586500A (en) | Electrophotographic composition and element | |
US3542546A (en) | Organic photoconductors containing the >n-n< nucleus | |
US3719486A (en) | Photoconductive elements containing organo-metallic photoconductors | |
US3652269A (en) | Photoconductive elements containing halogenated polyethylene binders |