JPH0424698B2 - - Google Patents
Info
- Publication number
- JPH0424698B2 JPH0424698B2 JP59091844A JP9184484A JPH0424698B2 JP H0424698 B2 JPH0424698 B2 JP H0424698B2 JP 59091844 A JP59091844 A JP 59091844A JP 9184484 A JP9184484 A JP 9184484A JP H0424698 B2 JPH0424698 B2 JP H0424698B2
- Authority
- JP
- Japan
- Prior art keywords
- parts
- group
- charge
- compound
- photoreceptor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 108091008695 photoreceptors Proteins 0.000 claims description 46
- 150000001875 compounds Chemical group 0.000 claims description 30
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 125000000623 heterocyclic group Chemical group 0.000 claims description 7
- 125000001424 substituent group Chemical group 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000003277 amino group Chemical group 0.000 claims description 4
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 125000004434 sulfur atom Chemical group 0.000 claims description 2
- 239000010410 layer Substances 0.000 description 43
- 239000000126 substance Substances 0.000 description 25
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 24
- -1 hydrazone compound Chemical class 0.000 description 19
- 239000000463 material Substances 0.000 description 18
- 230000035945 sensitivity Effects 0.000 description 15
- 230000015572 biosynthetic process Effects 0.000 description 14
- 238000003786 synthesis reaction Methods 0.000 description 14
- 239000000203 mixture Substances 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000011230 binding agent Substances 0.000 description 11
- 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 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-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
- 239000000049 pigment Substances 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 239000000975 dye Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 5
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 4
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000005457 ice water Substances 0.000 description 4
- 229920005668 polycarbonate resin Polymers 0.000 description 4
- 239000004431 polycarbonate resin Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 238000001953 recrystallisation Methods 0.000 description 4
- 229910052711 selenium Inorganic materials 0.000 description 4
- 239000011669 selenium Substances 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004419 Panlite Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 230000006698 induction Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- VEFLKXRACNJHOV-UHFFFAOYSA-N 1,3-dibromopropane Chemical compound BrCCCBr VEFLKXRACNJHOV-UHFFFAOYSA-N 0.000 description 2
- WRBOHOGDAJPJOQ-UHFFFAOYSA-N 3-Formylcarbazole Natural products C1=CC=C2C3=CC(C=O)=CC=C3NC2=C1 WRBOHOGDAJPJOQ-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 206010034972 Photosensitivity reaction Diseases 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- 229920006026 co-polymeric resin Polymers 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 230000005496 eutectics Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000036211 photosensitivity Effects 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920006267 polyester film Polymers 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920005596 polymer binder Polymers 0.000 description 2
- 239000002491 polymer binding agent Substances 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- WVIICGIFSIBFOG-UHFFFAOYSA-N pyrylium Chemical class C1=CC=[O+]C=C1 WVIICGIFSIBFOG-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 239000012312 sodium hydride Substances 0.000 description 2
- 229910000104 sodium hydride Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 description 1
- YBQZXXMEJHZYMB-UHFFFAOYSA-N 1,2-diphenylhydrazine Chemical compound C=1C=CC=CC=1NNC1=CC=CC=C1 YBQZXXMEJHZYMB-UHFFFAOYSA-N 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical compound C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 description 1
- MWOODERJGVWYJE-UHFFFAOYSA-N 1-methyl-1-phenylhydrazine Chemical compound CN(N)C1=CC=CC=C1 MWOODERJGVWYJE-UHFFFAOYSA-N 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical group C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- KUBDPQJOLOUJRM-UHFFFAOYSA-N 2-(chloromethyl)oxirane;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound ClCC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 KUBDPQJOLOUJRM-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 235000000177 Indigofera tinctoria Nutrition 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 1
- 229910001370 Se alloy Inorganic materials 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000005874 Vilsmeier-Haack formylation reaction Methods 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 125000003785 benzimidazolyl group Chemical class N1=C(NC2=C1C=CC=C2)* 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000012461 cellulose resin Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 125000000490 cinnamyl group Chemical group C(C=CC1=CC=CC=C1)* 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000007857 hydrazones Chemical class 0.000 description 1
- 235000019239 indanthrene blue RS Nutrition 0.000 description 1
- UHOKSCJSTAHBSO-UHFFFAOYSA-N indanthrone blue Chemical compound C1=CC=C2C(=O)C3=CC=C4NC5=C6C(=O)C7=CC=CC=C7C(=O)C6=CC=C5NC4=C3C(=O)C2=C1 UHOKSCJSTAHBSO-UHFFFAOYSA-N 0.000 description 1
- 229940097275 indigo Drugs 0.000 description 1
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000005001 laminate film Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- NYGZLYXAPMMJTE-UHFFFAOYSA-M metanil yellow Chemical group [Na+].[O-]S(=O)(=O)C1=CC=CC(N=NC=2C=CC(NC=3C=CC=CC=3)=CC=2)=C1 NYGZLYXAPMMJTE-UHFFFAOYSA-M 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000004923 naphthylmethyl group Chemical group C1(=CC=CC2=CC=CC=C12)C* 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 125000001484 phenothiazinyl group Chemical group C1(=CC=CC=2SC3=CC=CC=C3NC12)* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 229920001184 polypeptide Polymers 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 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
- 239000000843 powder Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 150000003219 pyrazolines Chemical class 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- ODZPKZBBUMBTMG-UHFFFAOYSA-N sodium amide Chemical compound [NH2-].[Na+] ODZPKZBBUMBTMG-UHFFFAOYSA-N 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- 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
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000001018 xanthene dye Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
- G03G5/02—Charge-receiving layers
- G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
- G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
- G03G5/0622—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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Photoreceptors In Electrophotography (AREA)
- Photovoltaic Devices (AREA)
Description
【発明の詳細な説明】
本発明は電子写真感光体に関するものであり、
更に詳しくは、導電性支持体上に形成せしめた光
導電層の中に、新規なヒドラゾン化合物を含有せ
しめることにより、優れた光感度、耐久性を有す
る電子写真感光体を提供するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an electrophotographic photoreceptor,
More specifically, the present invention provides an electrophotographic photoreceptor having excellent photosensitivity and durability by incorporating a novel hydrazone compound into a photoconductive layer formed on a conductive support.
電子写真法は既にカールソンが米国特許第
2297691号に明らかにしたように、この写真法は
静電現象と光導電現象とを巧妙に組合せしたもの
であり、光導電性感光体を暗所でコロナ放電等に
より、表面を一様に帯電させた後、光導電性を利
用して光像を静電潜像に変え、これに着色した電
荷粉体（トナー）を付着させて可視像に変える画
像形成法の一つである。 Electrophotography has already been covered by Carlson's U.S. Patent No.
As disclosed in No. 2297691, this photographic method is a clever combination of electrostatic and photoconductive phenomena, in which the surface of a photoconductive photoreceptor is uniformly charged by corona discharge etc. in a dark place. This is an image forming method in which the optical image is converted into an electrostatic latent image using photoconductivity, and colored charged powder (toner) is attached to the image to convert it into a visible image.
このような電子写真法における感光体に要求さ
れる基本的な電気的および光電気的特性として、
暗所において適当な電位に帯電できること、この
電位が適当な時間保持できること、更に、光照射
により速やかに電荷が逸散することができること
などがあげられる。 The basic electrical and photoelectric properties required of the photoreceptor in such electrophotography are as follows:
The characteristics include being able to be charged to an appropriate potential in a dark place, being able to maintain this potential for an appropriate amount of time, and being able to quickly dissipate the charge by light irradiation.
このような感光体において、従来より、無定形
セレン、硫化カドミウム、酸化亜鉛等の無機光導
電性物質が広く使用されてきた。これらの無機物
質は上記条件は満足するが、いくつかの欠点も同
時に有する。例えば硫化カドミウムや酸化亜鉛は
結着剤としての樹脂に分散させて感光体として用
いられるが、平滑性、可撓性、硬度、引張り強
度、耐摩擦性などの機械的な欠点を有するため、
そのままでは反復使用に耐えることができない。
更に硫化カドミウムにおいては衛生性の問題にも
考慮が必要である。 In such photoreceptors, inorganic photoconductive substances such as amorphous selenium, cadmium sulfide, and zinc oxide have been widely used. Although these inorganic materials satisfy the above conditions, they also have some drawbacks. For example, cadmium sulfide and zinc oxide are used as photoreceptors by being dispersed in resin as a binder, but they have mechanical drawbacks such as smoothness, flexibility, hardness, tensile strength, and abrasion resistance.
As it is, it cannot withstand repeated use.
Furthermore, when using cadmium sulfide, consideration must also be given to hygiene issues.
また、無定形セレンにおいては、製法が蒸着に
よらなくてはならず、製造コストが高価となるば
かりでなく、可撓性がなく、ベルト状に加工する
ことが困難である他、セレンの毒性および熱や機
械的衝撃に対して鋭敏なため取り扱いには注意を
要するなどの欠点を有する。 In addition, amorphous selenium must be manufactured by vapor deposition, which not only increases the manufacturing cost but also makes it difficult to process into a belt shape due to lack of flexibility, as well as the toxicity of selenium. It also has disadvantages such as being sensitive to heat and mechanical shock and requiring careful handling.
近年、これらの無機系感光体の欠点を排除する
ために、有機系感光体の研究がすすみ、有機系感
光体における、皮膜の容易性、製造の容易性、軽
量、可撓性、分光感度の多変性の多くの利点を有
するため、種々の有機系感光体が提案され、実用
に供されているものもある。 In recent years, in order to eliminate the drawbacks of these inorganic photoreceptors, research on organic photoreceptors has progressed, and organic photoreceptors have improved ease of coating, ease of manufacture, light weight, flexibility, and spectral sensitivity. Since they have many advantages of polymorphism, various organic photoreceptors have been proposed, and some are in practical use.
例えば、ポリ−Ｎ−ビニルカルバゾールと２，
４，７−トリニトロフルオレン−９−オンとから
なる感光体（米国特許第3484237）、ポリ−Ｎ−ビ
ニルカルバゾールをピリリウム塩系色素で増感し
たもの（特公昭48−25658号公報）、染料と樹脂と
からなる共晶錯体を主成分とする感光体（特開昭
47−10735号公報）などである。 For example, poly-N-vinylcarbazole and 2,
Photoreceptor consisting of 4,7-trinitrofluoren-9-one (US Patent No. 3484237), poly-N-vinylcarbazole sensitized with pyrylium salt dye (Japanese Patent Publication No. 25658/1989), dye A photoreceptor whose main component is a eutectic complex consisting of
47-10735).
また、更に光により電荷を発生する物質（電荷
発生物質と呼ぶ）と、この発生した電荷を輸送す
ることのできる物質（電荷輸送物質と呼ぶ）とを
組合せた電子写真感光体が提案されている。例え
ば、米国特許第3791826号明細書には電荷発生層
上に電荷輸送層を設けた感光体が、また、米国特
許第3764315号明細書には電荷発生物質を電荷輸
送物質中に分散せしめた感光層を持つ感光体が記
載されている。この種の電荷の発生と電荷の輸送
とを、それぞれ別の物質により機能を分担させる
ことにより、すなわち電荷発生物質と電荷輸送物
質の組合せにより、その特性はより良好となり、
有用な感光体が提供される。 Additionally, an electrophotographic photoreceptor has been proposed that combines a substance that generates electric charge when exposed to light (called a charge-generating substance) and a substance that can transport the generated electric charge (called a charge-transporting substance). . For example, US Pat. No. 3,791,826 discloses a photoreceptor in which a charge transport layer is provided on a charge generating layer, and US Pat. No. 3,764,315 discloses a photoreceptor in which a charge generating material is dispersed in a charge transport material. Photoreceptors with layers are described. By assigning the functions of this kind of charge generation and charge transport to different substances, that is, by combining the charge generation material and the charge transport material, the characteristics can be improved.
Useful photoreceptors are provided.
そして、これまで、この種の感光体において、
有用な電荷発生物質は多く知られている。一方、
電荷輸送物質としては種々の物質が提案されてい
るが、必ずしも満足し得るものとは言い難いのが
現状である。優れた電荷輸送物質とは、基本的特
性として、帯電せしめた時、十分に電位を保持で
きること、電荷発生物質から電荷を発生されるよ
うな有効な波長の光を電荷発生物質にまで十分透
過させること、更には、電荷発生物質より発生さ
れた電荷を速やかに輸送する能力を有するもので
ある。また、実用上の要求特性としては、単独も
しくは、結着剤に溶解し、皮膜を形成するうえで
均一な皮膜を形成し得ること、温度、湿度および
コロナ放電の際発生されるオゾン、NOx等によ
る過酷な環境条件下において、静電特性の劣化、
変化をもたらさないことが必要である。これまで
に、この種の電荷輸送物質として、化学構造式別
に分類すればトリフエニルの如きポリフエニル化
合物、米国特許第3717462号、米国特許第4150987
号、特開昭55−52064号明細書に記載されている
ヒドラゾン化合物、米国特許第3820989号明細書
に記載されているジアリールアルカン化合物、米
国特許第3189477号明細書に記載されている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、米国特許第3837851
号明細書に記載されているピラゾリン化合物等
が、近年提案されている比較的優れた電荷輸送物
質である。しかし、これらの電荷輸送物質に関し
ても、前記条件に関して、全て満足しているもの
とはいえないのが現状である。 Until now, in this type of photoreceptor,
Many useful charge generating materials are known. on the other hand,
Various materials have been proposed as charge transport materials, but at present it is difficult to say that they are necessarily satisfactory. The basic characteristics of an excellent charge transport material are that when it is charged, it can hold a sufficient potential, and that it can sufficiently transmit light of an effective wavelength that allows the charge to be generated from the charge-generating material. Furthermore, it has the ability to quickly transport the charges generated by the charge generating substance. Practical requirements include the ability to form a uniform film either alone or when dissolved in a binder, temperature, humidity, ozone and NOx generated during corona discharge, etc. Deterioration of electrostatic properties under harsh environmental conditions due to
It is necessary not to bring about change. So far, as this type of charge transport material, polyphenyl compounds such as triphenyl have been classified by chemical structural formula, US Pat. No. 3,717,462, and US Pat. No. 4,150,987.
No., hydrazone compound described in JP-A No. 55-52064, diarylalkane compound described in U.S. Pat. No. 3,820,989, 2, described in U.S. Pat. No. 3,189,477,
5-bis(P-diethylaminophenyl)-1,
3,4-Oxadiazole, U.S. Patent No. 3837851
Pyrazoline compounds and the like described in the specification are relatively excellent charge transport materials that have been proposed in recent years. However, the current situation is that these charge transport materials do not satisfy all of the above conditions.
本発明者等は鋭意研究を行つた結果、特定の構
造のヒドラゾン化合物が、電子写真感光体の真に
有用な電荷輸送物質であることを発見し、更にこ
の電荷輸送材を用いた電子写真感光体が優れた性
質を有することを見出し、本発明を完成したもの
である。 As a result of intensive research, the present inventors have discovered that a hydrazone compound with a specific structure is a truly useful charge transport material for electrophotographic photoreceptors, and furthermore, they have discovered that a hydrazone compound with a specific structure is a truly useful charge transport material for electrophotographic photoreceptors. He discovered that the human body has excellent properties and completed the present invention.
即ち、本発明は優れた特性を有する電子写真感
光体に関して、新規な構造のヒドラゾン誘導体を
用いて提供するものである。 That is, the present invention provides an electrophotographic photoreceptor having excellent properties using a hydrazone derivative with a novel structure.
本発明の目的は、新規な電荷輸送物質を含有せ
しめることにより高感度にて残留電位の少ない電
子写真感光体を提供することである。本発明の他
の目的は、帯電露光、現像、転写工程が繰り返し
て行われる反復転写式電子写真用の感光体として
用いた時、繰り返し使用による疲労劣化が少な
く、更に低温より高温、低湿度より高湿度下にお
ける種々の過酷な環境下において、安定した特性
を維持する耐久性および環境性の優れた電子写真
感光体を提供することにある。 An object of the present invention is to provide an electrophotographic photoreceptor with high sensitivity and low residual potential by containing a novel charge transporting substance. Another object of the present invention is that when used as a photoreceptor for repetitive transfer type electrophotography in which charging exposure, development, and transfer steps are repeated, fatigue deterioration due to repeated use is small, and furthermore, the present invention is more effective than low temperatures, high temperatures, and low humidity. The object of the present invention is to provide an electrophotographic photoreceptor that maintains stable characteristics under high humidity and various harsh environments and has excellent durability and environmental friendliness.
本発明のかかる目的は、電荷輸送物質として下
記一般式（）で示されるヒドラゾン化合物の少
なくとも１種を含有させることによつて達成され
る。 This object of the present invention can be achieved by containing at least one hydrazone compound represented by the following general formula () as a charge transport material.
一般式（）
但し、式中、
Ｘは直接結合、酸素原子、イオウ原子、または
カルボニル基；
R1は水素原子、ハロゲン原子またはニトロ基、
あるいは置換基を有してもよいアルキル基、アル
コキシ基またはアミノ基；
R2，R3は置換基を有してもよいアルキル基、
アラルキル基、アリール基または複素環残基、あ
るいはR2とR3とで複素環残基を形成してもよ
い；
ｎは１〜10の整数を示す。）
R1は水素原子；塩素原子、臭素原子等のハロ
ゲン原子；ニトロ基；メチル基、エチル基、プロ
ピル基等のアルキル基；メトキシ基、エトキシ基
等のアルコキシ基；またはアミノ基、ジメチルア
ミノ基、ジエチルアミノ基、ジベンジルアミノ基
等のアミノ基である。 General formula () However, in the formula, X is a direct bond, an oxygen atom, a sulfur atom, or a carbonyl group; R1 is a hydrogen atom, a halogen atom, or a nitro group;
Or an alkyl group, an alkoxy group or an amino group which may have a substituent; R 2 and R 3 are an alkyl group which may have a substituent,
An aralkyl group, an aryl group, a heterocyclic residue, or R 2 and R 3 may form a heterocyclic residue; n represents an integer of 1 to 10. ) R 1 is a hydrogen atom; a halogen atom such as a chlorine atom or a bromine atom; a nitro group; an alkyl group such as a methyl group, an ethyl group, or a propyl group; an alkoxy group such as a methoxy group or an ethoxy group; or an amino group or a dimethylamino group , diethylamino group, dibenzylamino group, etc.
R2，R3は、メチル基、エチル基、直鎖状ない
し分岐状のプロピル基、ブチル基、ペンチル基、
ヘキシル基等のアルキル基；ベンジル基、ナフチ
ルメチル基、シンナミル基、フエネチル基等のア
ラルキル基；フエニル基、ナフチル基等のアリー
ル基；ピリジン、ベンゾチアゾール、ベンゾオキ
サゾール、カルバゾール、フエノチアジン等の複
素環残基であり、あるいはR2.R3で複素環残基を
形成してもよい。 R 2 and R 3 are a methyl group, an ethyl group, a linear or branched propyl group, a butyl group, a pentyl group,
Alkyl groups such as hexyl; aralkyl groups such as benzyl, naphthylmethyl, cinnamyl, and phenethyl; aryl groups such as phenyl and naphthyl; heterocyclic residues such as pyridine, benzothiazole, benzoxazole, carbazole, and phenothiazine group, or R 2 .R 3 may form a heterocyclic residue.
前記アルキル基、アラルキル基、アリール基、
複素環残基は置換基を有していてもよく、置換基
としては、アルキル基、ハロゲン原子、アルコキ
シ基、アリールオキシ基、アミノ基等が挙げられ
る。 The alkyl group, aralkyl group, aryl group,
The heterocyclic residue may have a substituent, and examples of the substituent include an alkyl group, a halogen atom, an alkoxy group, an aryloxy group, and an amino group.
なお、前記一般式〔〕で表わされる本発明の
ヒドラゾン化合物は、例えば次に示す方法により
製造することができる。 The hydrazone compound of the present invention represented by the general formula [] can be produced, for example, by the method shown below.
まず次に示す一般式〔〕の化合物２モル相当
とジハロアルカン１モル相当をトルエン、キシレ
ン、ジオキサン、ジメチルホルムアミド等の有機
溶剤中で水酸化ナトリウム、水酸化カリウム、ナ
トリウムアミド、水素化ナトリウム等の存在下に
一般式〔〕
〔式中Ｘ，R1は一般式〔〕と同様〕
反応させることにより、一般式〔〕の化合物
を得る。 First, the equivalent of 2 moles of the compound of the following general formula [] and the equivalent of 1 mole of dihaloalkane are dissolved in sodium hydroxide, potassium hydroxide, sodium amide, sodium hydride, etc. in an organic solvent such as toluene, xylene, dioxane, dimethylformamide, etc. in the presence General formula [] [In the formula, X and R 1 are the same as in the general formula []] By reacting, a compound of the general formula [] is obtained.
一般式〔〕
〔式中Ｘ，R1，ｎは一般式〔〕と同様〕
ついで一般式〔〕の化合物に常法に従つてア
ルデヒド基を導入して一般式〔〕の化合物が得
られる。例えば、一般式〔〕の化合物をジメチ
ルホルムアミドに溶解し、オキシ塩化リンを反応
させるビルスマイヤー反応でホルミル化すること
ができる。 General formula [] [In the formula, X, R 1 and n are the same as in the general formula []] Next, an aldehyde group is introduced into the compound of the general formula [] according to a conventional method to obtain a compound of the general formula []. For example, the compound of general formula [] can be dissolved in dimethylformamide and formylated by Vilsmeier reaction in which phosphorus oxychloride is reacted.
一般式〔〕
〔式中Ｘ，R1，ｎは一般式〔〕と同様〕
次に一般式〔〕のアルデヒド類と一般式
〔〕で示されるヒドラジン又はその鉱酸塩とを
通常の有機溶媒例えばメタノール、エタノール、
ジオキサン、キシロール、ジメチルホルムアミド
中
一般式〔〕
〔式中、R2，R3は一般式〔〕と同様〕
で、場合によつては酢酸等の触媒を使用して反
応させて一般式〔〕で表わされるヒドラゾン化
合物が得られる。 General formula [] [In the formula, X, R 1 , and n are the same as in the general formula []] Next, the aldehyde of the general formula [] and the hydrazine or its mineral salt represented by the general formula [] are mixed in a normal organic solvent. For example, methanol, ethanol,
In dioxane, xylol, dimethylformamide A hydrazone compound represented by the general formula [] [wherein R 2 and R 3 are the same as the general formula []] can be obtained by reaction using a catalyst such as acetic acid in some cases. It will be done.
また、別法として例えば一般式〔〕で示され
るヒドラゾン化合物２モル相当にジハロアルカン
１モル相当を一般式〔〕を合成する方法と同様
の方法で反応させて一般式〔〕のヒドラゾン化
合物を得ることができる。 Alternatively, for example, a hydrazone compound of the general formula [] can be obtained by reacting 2 moles of the hydrazone compound represented by the general formula [] with 1 mole of dihaloalkane in the same manner as the method for synthesizing the general formula []. be able to.
一般式〔〕
〔式中、Ｘ，R1，R2，R3は一般式〔〕と同
様〕
この様な合成法にて、本発明で用いられる一般
式〔〕で表わされるヒドラゾン化合物の代表例
を以下に列挙する。 General formula [ ] [ In the formula , Examples are listed below.
これらの化合物は、１種または２種以上組合せ
て用いることができる。 These compounds can be used alone or in combination of two or more.
本発明の感光体は以上のようなヒドラゾン化合
物を含有するものであるが、これらヒドラゾン化
合物の応用の仕方によつて種々の特性の感光体が
得られる。例えば、本発明における電荷輸送物質
としてのヒドラゾン化合物を電荷発生物質と同一
層中にて導電性支持基体に設けた、通常単層型感
光体と称せられる構成、もしくは、主として電荷
発生物質を含有する第１層と、主として電荷輸送
物質を含有する第２層を導電性支持基体上にて２
積層構成することによつてなされる通常積層型感
光体と称せられる構成にて使用することができ
る。これらの構成の選択は感光体の使用する極性
により適宜選ばれる。また、本発明で用いられる
電荷発生物質として、例えば次のものがある。無
機化合物として、セレン、セレン合金、CdS、
ZnO、CdSe、アモルフアスシリコン等の無機光
半導体も用いることができるが、好ましくは有機
系電荷発生物質を用いるのが好ましい。有機の電
荷発生物質としては、例えば、金属フタロシアニ
ンおよび無金属フタロシアニンなどのフタロシア
ニン顔料、モノアゾ色素およびジスアゾ色素など
のアゾ系色素、インジゴ系顔料、キナクリドン顔
料、インダンスレン系顔料、キサンテン染料、ベ
ンズイミダゾール顔料、ペリレン顔料、スクアリ
ツクメナン染料等の染顔料、あるいはピリリウム
塩染料とポリカーボネート樹脂から形成される共
晶錯体、ポリビニルカルバゾール等の電子供与性
物質とTNF等の電子受容性物質からなる電荷移
動錯体などがあがられるが、特にフタロシアニン
顔料を用いることが好ましい。 The photoreceptor of the present invention contains the hydrazone compound as described above, and photoreceptors with various characteristics can be obtained depending on how these hydrazone compounds are applied. For example, in the present invention, a hydrazone compound as a charge transporting substance is provided on a conductive support substrate in the same layer as a charge generating substance, which is usually called a single layer type photoreceptor, or a structure mainly containing a charge generating substance. A first layer and a second layer containing primarily a charge transport material are deposited on an electrically conductive support substrate.
It can be used in a structure usually called a laminated type photoreceptor, which is formed by laminating layers. These configurations are appropriately selected depending on the polarity of the photoreceptor used. Furthermore, examples of charge generating substances used in the present invention include the following. Inorganic compounds include selenium, selenium alloys, CdS,
Although inorganic optical semiconductors such as ZnO, CdSe, and amorphous silicon can also be used, it is preferable to use organic charge-generating substances. Examples of organic charge-generating substances include phthalocyanine pigments such as metal phthalocyanine and metal-free phthalocyanine, azo dyes such as monoazo dyes and disazo dyes, indigo pigments, quinacridone pigments, indanthrene pigments, xanthene dyes, and benzimidazoles. Pigments, perylene pigments, dyes and pigments such as squalizumenan dyes, eutectic complexes formed from pyrylium salt dyes and polycarbonate resins, and charge transfer complexes consisting of electron-donating substances such as polyvinylcarbazole and electron-accepting substances such as TNF. Among them, it is particularly preferable to use phthalocyanine pigments.
本発明におけるヒドラゾン化合物はそれ自身で
は皮膜形成能を有しない為、感光層として形成せ
しめるには結着剤樹脂を用いる。また、電荷発生
物質に関してもポリビニルカルバゾールの如き高
分子樹脂を除いてそれ自身では皮膜を形成し得な
い為、必要に応じて結着剤を用いてもよい。 Since the hydrazone compound in the present invention does not have film-forming ability by itself, a binder resin is used to form it as a photosensitive layer. Further, since charge generating substances cannot form a film by themselves except for polymeric resins such as polyvinylcarbazole, a binder may be used as necessary.
本発明において好ましく用いられる結着剤は、
高い電気絶縁性のフイルム形成性高分子重合体、
あるいは共重合体である。このような高分子重合
体、共重合体であり、本発明において好ましく用
いられる結着剤はフエノール樹脂、ポリエステル
樹脂、酢酸ビニル樹脂、ポリカーボネート樹脂、
ポリペプチド樹脂、セルロース系樹脂、ポリビニ
ルピロリドン、ポリエチレンオキサイド、ポリ塩
化ビニル樹脂、でん粉類、ポリビニルアルコー
ル、アクリル系共重合体樹脂、メタクリル系共重
合樹脂、シリコーン樹脂、ポリアクリロニトリル
系共重合樹脂、ポリアクリルアミド、ポリビニル
ブチラール、ポリビニルカルバゾール、ポリ塩化
ビニリデン樹脂、ポリウレタン樹脂等が挙げられ
る。これらの高分子バインダーは、単独あるいは
２種以上混合して用いられるが、本発明に使用で
きる結着剤は、これらに限定されるものではな
い。更に本発明の感光体は導電性支持体上に必要
に応じて中間層を介して電荷発生物質を主成分と
する電荷発生層を設け、該層に隣接して電荷輸送
物質を主成分とする電荷輸送物質を設けた積層構
成としてもよい。また、このような積層構成にし
た場合、電荷発生層と電荷輸送層のどちらを上層
にするかは帯電性を正負にどちらかを選ぶかによ
つて決定される。一般に負帯電の時は電荷輸送層
を上層にした方が特性上有利である。また、本発
明の感光体において、電荷発生層と電荷輸送層の
それぞれの別個の層からなる積層構成とする場
合、電荷発生層は導電性支持体上に直接あるいは
必要に応じて接着層あるいはバリアー層などの中
間層を設けた上に真空蒸着するか、電荷発生
物質を適当な溶剤に溶解した溶液を塗布するか、
電荷発生物質をボールミル、アトライター等で
分散溶媒中にて微細化し、必要に応じて高分子バ
インダーと混合分散して得られる分散液を塗布す
る等の方法によつて設けることができる。このと
き用いられる高分子バインダーは電荷輸送層に用
いられるものと同様なものであつてもよい。 The binder preferably used in the present invention is
Highly electrically insulating film-forming polymer,
Alternatively, it is a copolymer. Among such polymers and copolymers, binders preferably used in the present invention include phenol resins, polyester resins, vinyl acetate resins, polycarbonate resins,
Polypeptide resin, cellulose resin, polyvinylpyrrolidone, polyethylene oxide, polyvinyl chloride resin, starch, polyvinyl alcohol, acrylic copolymer resin, methacrylic copolymer resin, silicone resin, polyacrylonitrile copolymer resin, polyacrylamide , polyvinyl butyral, polyvinyl carbazole, polyvinylidene chloride resin, polyurethane resin, and the like. These polymer binders may be used alone or in combination of two or more, but the binder that can be used in the present invention is not limited to these. Further, in the photoreceptor of the present invention, a charge generation layer containing a charge generation substance as a main component is provided on the conductive support via an intermediate layer if necessary, and adjacent to the charge generation layer the charge generation layer containing a charge transport substance as a main component is provided. A laminated structure including a charge transport material may also be used. In addition, when such a laminated structure is adopted, which of the charge generation layer and the charge transport layer is to be the upper layer is determined by selecting whether the chargeability is positive or negative. Generally, when negatively charged, it is advantageous in terms of characteristics to have a charge transport layer as an upper layer. In addition, when the photoreceptor of the present invention has a laminated structure consisting of separate layers of a charge generation layer and a charge transport layer, the charge generation layer is placed directly on the conductive support or optionally with an adhesive layer or barrier layer. Either vacuum evaporation is performed on an intermediate layer such as a layer, or a solution of a charge-generating substance dissolved in a suitable solvent is applied.
It can be provided by a method such as micronizing the charge-generating substance in a dispersion solvent using a ball mill, attritor, etc., and applying a dispersion obtained by mixing and dispersing it with a polymeric binder if necessary. The polymer binder used at this time may be the same as that used for the charge transport layer.
また、本発明に係わるヒドラゾン化合物と結着
剤とからなる単層の感光層であつてもよい。ま
た、電荷輸送物質は、結着剤100重量部当り電荷
輸送物質を10〜300重量部が好ましい。ただし、
本発明はこの範囲のみに制限されるものではな
い。また、この感光層の厚さは、要求される光感
度や耐久性および、電荷発生物質、電荷輸送物質
の結着剤に対する混合割合によつて決定されるが
単層型、積層型、何れにしても、支持導電性基体
上の感光層の厚さは50ミクロン以下、好ましくは
７〜30ミクロンぐらいが皮膜の可撓性の点からし
ても適当である。 Further, it may be a single-layer photosensitive layer comprising the hydrazone compound according to the present invention and a binder. Further, the charge transport material is preferably 10 to 300 parts by weight per 100 parts by weight of the binder. however,
The present invention is not limited to this range only. The thickness of this photosensitive layer is determined by the required photosensitivity and durability, as well as the mixing ratio of the charge-generating substance and the charge-transporting substance to the binder. However, the thickness of the photosensitive layer on the supporting conductive substrate is preferably 50 microns or less, preferably about 7 to 30 microns, from the viewpoint of film flexibility.
また、感光層には必要に応じて、保護層として
役立つ層を被覆することもできる。 The photosensitive layer can also be coated with a layer that serves as a protective layer, if necessary.
本発明の電子写真感光体に用いる支持体として
は、導電性が付与されていれば何れのものでも良
く、従来用いられているいずれのタイプの導電層
であつてもさしつかえない。具体的には、アルミ
ニウム、銅、ステンレス、真鍮などの金属、アル
ミニウム、酸化インジウムや酸化錫などを蒸着ま
たはラミネートしたプラスチツクあるいは導電性
粒子、例えばカーボンブラツク、錫粒子、アルミ
ニウム粒子を分散したプラスチツクなどを挙げる
ことができる。また、その型状については、シー
ト状あるいはシリンダー状、その他のものであつ
ても差しつかえない。なお、本発明による電子写
真感光体を使用する際に、光源は通常、ハロゲン
ランプ等の他、電荷発生物質がフタロシアニンの
ような場合、感度が750nm以上にもあるために、
ガリウム−アルミニウム−ヒ素半導体レーザー
（発振波長780nm）の様なレーザー光を用いるこ
ともできる。 The support used in the electrophotographic photoreceptor of the present invention may be any support as long as it is endowed with conductivity, and any type of conductive layer conventionally used may be used. Specifically, metals such as aluminum, copper, stainless steel, and brass, plastics on which aluminum, indium oxide, tin oxide, etc. are vapor-deposited or laminated, and conductive particles such as carbon black, tin particles, and aluminum particles dispersed therein are used. can be mentioned. Moreover, the shape may be sheet-like, cylindrical, or other shapes. In addition, when using the electrophotographic photoreceptor according to the present invention, the light source is usually a halogen lamp or the like, and if the charge generating substance is phthalocyanine, it has a sensitivity of 750 nm or more.
Laser light such as a gallium-aluminum-arsenic semiconductor laser (oscillation wavelength: 780 nm) can also be used.
本発明は以上のような構成よりなり、その使用
に際し、正帯電、および負帯電においても高感度
にして、また、繰り返しによる感光体の劣化も少
なく、また実用上において、低温から高温度ま
で、また、低湿度から高湿度下までにおける帯電
保持力、感度変化における環境性、耐久性の優れ
た特徴を有する。 The present invention has the above-mentioned structure, and when used, it has high sensitivity in both positive and negative charging, and there is little deterioration of the photoreceptor due to repeated use. In addition, it has excellent characteristics such as charge retention ability under conditions of low humidity to high humidity, environmental friendliness with respect to sensitivity changes, and durability.
次に本発明を合成例と実施例とにより、更に具
体的に説明するが、本発明は以下の実施例に限定
されるものではない。以下、実施例において例中
「部」とあるのは重量部を示す。 Next, the present invention will be explained in more detail with reference to synthesis examples and examples, but the present invention is not limited to the following examples. In the following examples, "parts" refer to parts by weight.
合成例 １ 本発明の化合物(1)の合成例を示す。Synthesis example 1 An example of synthesis of compound (1) of the present invention is shown.
ジメチルホルムアミド150部にフエノチアジン
19.9部、水素化ナトリウム５部を20℃以下で加
え、ついで１，２−ジブロムエタン9.4部を冷却
しながら20℃以下で滴下する。滴下終了後、50〜
60℃まで昇温して、同温度で２時間撹拌する。反
応液を冷却後、氷水2000部に注入し、沈殿物をろ
過、水洗、乾燥して下記の構造を有する化合物
〔ａ〕が８部得られる。 Phenothiazine in 150 parts of dimethylformamide
19.9 parts and 5 parts of sodium hydride were added at below 20°C, and then 9.4 parts of 1,2-dibromoethane was added dropwise at below 20°C while cooling. After dripping, 50~
Raise the temperature to 60°C and stir at the same temperature for 2 hours. After cooling the reaction solution, it is poured into 2000 parts of ice water, and the precipitate is filtered, washed with water, and dried to obtain 8 parts of compound [a] having the following structure.
つぎに、ジメチルホルムアミド100部にオキシ
塩化リン30部を冷却しつつ加え、ついで化合物
〔ａ〕を17部を20℃以下で加えて、20〜30℃で１
時間撹拌した後、50〜60℃で３時間撹拌する。冷
却して氷水1000部に注入し、水酸化ナトリウム水
溶液で中和してPH８〜９とする。ろ過、水洗して
下記の構造を有する化合物〔ｂ〕が16部得られ
る。 Next, 30 parts of phosphorus oxychloride was added to 100 parts of dimethylformamide while cooling, then 17 parts of compound [a] were added at 20°C or lower, and 1
After stirring for an hour, stir at 50-60°C for 3 hours. Cool, pour into 1000 parts of ice water, and neutralize with aqueous sodium hydroxide solution to pH 8-9. After filtering and washing with water, 16 parts of compound [b] having the following structure are obtained.
次にエタノール100部に化合物〔ｂ〕9.6部、ジ
フエニルヒドラジン9.2部および酢酸３部を加え
て70〜80℃で３時間撹拌する。冷却してろ過、水
洗し、ついでアンモニア水にリスラリーして再び
ろ過、水洗し、乾燥して化合物〔１〕が15部得ら
れる。ジオキサンから再結晶精製して純品13部が
得られる。 Next, 9.6 parts of compound [b], 9.2 parts of diphenylhydrazine and 3 parts of acetic acid were added to 100 parts of ethanol, and the mixture was stirred at 70-80°C for 3 hours. The mixture is cooled, filtered, washed with water, reslurried in aqueous ammonia, filtered again, washed with water, and dried to obtain 15 parts of compound [1]. Recrystallization purification from dioxane yields 13 parts of pure product.
合成例 ２ 本発明の化合物(2)の合成例を示す。Synthesis example 2 An example of synthesis of compound (2) of the present invention is shown.
ジメチルホルムアミド260部に水酸化ナトリウ
ム15部を加えて20℃以下でカルバゾール33部を加
える。ついで15〜20℃で１，３−ジブロムプロパ
ン20部を滴下する。滴下終了後、60〜70℃まで昇
温して同温度で２時間撹拌する。反応液を冷却
後、氷水3000部に注入し、沈殿物をろ過、水洗、
乾燥して下記の構造の化合物〔ｃ〕が35部得られ
る。 Add 15 parts of sodium hydroxide to 260 parts of dimethylformamide, and add 33 parts of carbazole at 20°C or below. Then, 20 parts of 1,3-dibromopropane is added dropwise at 15-20°C. After the addition is complete, the temperature is raised to 60-70°C and stirred at the same temperature for 2 hours. After cooling the reaction solution, it was poured into 3000 parts of ice water, and the precipitate was filtered, washed with water,
After drying, 35 parts of a compound [c] having the following structure is obtained.
つぎに、ジメチルホルムアミド100部にオキシ
塩化リン20部を冷却しつつ加え、ついで化合物
〔ｃ〕を15部を20℃以下で加え、20〜30℃で１時
間撹拌した後、40〜50℃で２時間撹拌する。合成
例〔１〕と同様の後処理を行つて下記の構造を有
する化合物〔ｄ〕が14部得られる。 Next, 20 parts of phosphorus oxychloride was added to 100 parts of dimethylformamide while cooling, then 15 parts of compound [c] was added at 20°C or lower, stirred at 20-30°C for 1 hour, and then heated at 40-50°C. Stir for 2 hours. By performing the same post-treatment as in Synthesis Example [1], 14 parts of compound [d] having the following structure are obtained.
次にジオキサン100部に化合物〔ｄ〕8.6部、メ
チルフエニルヒドラジン6.1部および酢酸３部を
加えて90〜100℃で３時間撹拌する。冷却してろ
過、水洗し、ついで結晶をアンモニアアルカリ水
にリスラリーして再びろ過、水洗する。乾燥して
化合物〔２〕が11部得られる。ベンゼンから再結
晶精製して純品９部が得られる。 Next, 8.6 parts of compound [d], 6.1 parts of methylphenylhydrazine and 3 parts of acetic acid were added to 100 parts of dioxane, and the mixture was stirred at 90-100°C for 3 hours. Cool, filter, and wash with water, then reslurry the crystals in ammonia-alkaline water, filter again, and wash with water. After drying, 11 parts of compound [2] is obtained. Recrystallization purification from benzene yields 9 parts of pure product.
合成例 ３ 本発明の化合物(3)の合成例を示す。Synthesis example 3 A synthesis example of compound (3) of the present invention is shown.
合成例２のメチルフエニルヒドラゾン6.1部の
代りに下記の構造を有するヒドラジン９部を使用
して全く
同様に反応を行い化合物(3)が13部得られる。ジ
オキサンから再結晶精製して11部の純品が得られ
る。 Using 9 parts of hydrazine having the following structure in place of 6.1 parts of methylphenylhydrazone in Synthesis Example 2, A similar reaction is carried out to obtain 13 parts of compound (3). Recrystallization purification from dioxane yields 11 parts of pure product.
合成例 ４ 本発明の化合物(4)の合成例を示す。Synthesis example 4 A synthesis example of compound (4) of the present invention is shown.
カルバゾール−３−カルボアルデヒドとＮ−ｐ
−メトキシベンジル−Ｎ−フエニルヒドラジンか
ら得られる下記の構造を有するヒドラゾン
20部をジメチルホルムアミド100部に加えつい
で水酸化ナトリウム４部を加え、ついで20℃以下
で１，３−ジブロムプロパン５部を滴下する。滴
下終了後、50〜60℃で１時間撹拌した後、冷却し
氷水1000部に注入する。ろ過、水洗して化合物(4)
が18部得られる。ジオキサンから再結晶精製して
純品15部が得られる。 Carbazole-3-carbaldehyde and N-p
-Hydrazone having the following structure obtained from methoxybenzyl-N-phenylhydrazine Add 20 parts to 100 parts of dimethylformamide, then add 4 parts of sodium hydroxide, and then add 5 parts of 1,3-dibromopropane dropwise at below 20°C. After the addition was completed, the mixture was stirred at 50 to 60°C for 1 hour, cooled, and poured into 1000 parts of ice water. Compound (4) after filtration and washing with water
You will get 18 copies. Recrystallization purification from dioxane yields 15 parts of pure product.
実施例 １
銅フタロシアニン40部、テトラニトロ銅フタロ
シアニン0.5部を98％濃硫酸500部に十分撹拌しな
がら溶解する。溶解した液を水5000部にあけ、銅
フタロシアニン、テトラニトロ銅フタロシアニン
の組成物を析出させた後、ロ過、水洗し、減圧下
120℃で乾燥する。Example 1 40 parts of copper phthalocyanine and 0.5 parts of tetranitrocopper phthalocyanine are dissolved in 500 parts of 98% concentrated sulfuric acid with thorough stirring. Pour the dissolved solution into 5,000 parts of water to precipitate a composition of copper phthalocyanine and tetranitrocopper phthalocyanine, then filter, wash with water, and remove under reduced pressure.
Dry at 120℃.
次に、この組成物１部、化合物(1)2.5部、アク
リルポリオール（武田薬品工業(株)製、タケラツク
Ａ−702）3.6部、エポキシ樹脂（シエル化学社
製、エポン1007）0.5部、メチルエチルケトン1.2
部およびセロソルブアセテート1.2部からなる組
成物を磁性ボールミルにて48時間練肉を行ない光
導電性組成物を得る。 Next, 1 part of this composition, 2.5 parts of compound (1), 3.6 parts of acrylic polyol (manufactured by Takeda Pharmaceutical Co., Ltd., Takerakku A-702), 0.5 parts of epoxy resin (manufactured by Ciel Chemical Co., Ltd., Epon 1007), and methyl ethyl ketone. 1.2
1.2 parts of Cellosolve acetate and 1.2 parts of cellosolve acetate were milled for 48 hours in a magnetic ball mill to obtain a photoconductive composition.
次に、この光導電性組成物を厚さ５ミクロンの
アルミニウム箔と75ミクロンのポリエステルフイ
ルムとのラミネートフイルムのアルミニウム上に
乾燥膜厚が８ミクロンになるようにロールコート
し、110℃に均一加熱されたオーブン中に１時間
置き、電子写真感光体とした。こうして得られた
サンプルに対して＋5.7KV、コロナギヤツプ10
mm、10m／minの帯電スピードでコロナ放電を与
え、放電停止後、10秒後に2854Kのタングステン
光源にて10Luxの照度で露光する。この時の露光
直前の電位が50％低下するのに要した光の照射量
を感度とした。この様にして測定したサンプルは
最大表面帯電量570V、暗減衰率12％、感度
1.2Lux.sec、残留電位20Vであり、帯電性、感度
ともに実用に十分な値であり、その光減衰曲線を
見ると、帯電露光に際し、表面電位減衰において
インダクシヨンは見られず、Ｊ曲線の光減衰曲線
を示した。またこの感光体を複写機にて正帯電に
て10000枚のコピーを連続してとつたが、得られ
た画像は階調性に優れ、通常の写真を原稿にして
複写を行つても、その細部中間色濃度に関しても
美しい画像が得られ、また、感度変化がなく、更
に、感光体にキズを生じているものの、複写画像
には全くそのキズが出ていない鮮明な画像が得ら
れた。 Next, this photoconductive composition was roll coated onto the aluminum of a laminate film of 5 micron thick aluminum foil and 75 micron polyester film to a dry film thickness of 8 microns, and uniformly heated to 110°C. The sample was placed in a heated oven for 1 hour to prepare an electrophotographic photoreceptor. +5.7KV for the sample thus obtained, corona gap 10
Corona discharge is applied at a charging speed of mm and 10 m/min, and after 10 seconds after the discharge stops, exposure is performed with a 2854K tungsten light source at an illuminance of 10 Lux. The amount of light irradiation required for the potential immediately before exposure to decrease by 50% at this time was defined as the sensitivity. The sample measured in this way had a maximum surface charge of 570V, a dark decay rate of 12%, and a sensitivity.
1.2Lux.sec, residual potential 20V, which is sufficient for practical use in both chargeability and sensitivity. Looking at the light attenuation curve, there is no induction in the surface potential attenuation upon charging exposure, and the J curve. The light attenuation curve is shown. We also made 10,000 copies of this photoreceptor in a row using a copying machine with positive charging, but the resulting images had excellent gradation, and even when copies were made using an ordinary photograph as the original, A beautiful image was obtained in terms of detail intermediate color density, and there was no change in sensitivity.Furthermore, although there were scratches on the photoreceptor, a clear image without any scratches was obtained in the copied image.
実施例 ２
銅フタロシアニン40部、ジニトロメタルフリー
フタロシアニン1.5部を98％濃硫酸100部に十分撹
拌しながら溶解する。溶解した液を水1000部に注
入し、フタロシアニン系組成物を析出させた後、
ロ過、水洗し、減圧下120℃で乾燥する。この組
成物を１部、化合物(2)３部をポリカーボネート樹
脂（帝人(株)パンライトＬ−1250）４部をテトラヒ
ドロフラン10部とともにボールミルにて分散し、
この液をスプレーにて厚さ10μmにアルミニウム
円筒に塗布した後、乾燥し、電子写真感光体とし
た。こうして得られたサンプルに対し、実施例１
と同様にして電子写真特性を測定した。このよう
にして測定したサンプルは最大表面帯電量560V、
感度1.1Lux.secであり、その光減衰曲線におい
て、インダクシヨンのない、Ｊ曲線を示し、複写
機による正帯電による繰り返し実写テストにおい
ても、10000枚のコピーにて、初期、最終画像に
おいても階調性が優れ、感度変化がなく、鮮明な
画像が得られた。Example 2 40 parts of copper phthalocyanine and 1.5 parts of dinitrometal-free phthalocyanine are dissolved in 100 parts of 98% concentrated sulfuric acid with thorough stirring. After pouring the dissolved liquid into 1000 parts of water and precipitating the phthalocyanine composition,
Filter, wash with water, and dry at 120°C under reduced pressure. 1 part of this composition, 3 parts of compound (2), 4 parts of polycarbonate resin (Teijin Ltd. Panlite L-1250) and 10 parts of tetrahydrofuran were dispersed in a ball mill,
This liquid was sprayed onto an aluminum cylinder to a thickness of 10 μm, and then dried to form an electrophotographic photoreceptor. Example 1
The electrophotographic properties were measured in the same manner as above. The sample measured in this way has a maximum surface charge of 560V,
It has a sensitivity of 1.1 Lux.sec, and its optical attenuation curve shows a J curve with no induction.Even in repeated live-photographing tests using positive charging with a copier, there was no difference in initial and final images after 10,000 copies. The tonality was excellent, there was no change in sensitivity, and clear images were obtained.
実施例 ３
ε型銅フタロシアニン１部に対し、合成例１に
準じて合成した化合物(3)２部、トリフエニルメタ
ン0.8部、アクリル樹脂４部、セロソルブアセテ
ート20部をボールミルにて分散せしめ、以下実施
例１と同様にして、サンプルの測定を行つた。得
られた光減衰曲線はインダクシヨンがなくＪ曲線
であり、この時の最大表面電位は600V、暗減衰
率９％、感度3.0Lux.sec、残留電位15Vであり、
また、実写テストにおいても、実施例１と同じ結
果が得られた。Example 3 2 parts of compound (3) synthesized according to Synthesis Example 1, 0.8 parts of triphenylmethane, 4 parts of acrylic resin, and 20 parts of cellosolve acetate were dispersed in a ball mill to 1 part of ε-type copper phthalocyanine. The samples were measured in the same manner as in Example 1. The obtained light attenuation curve is a J curve with no induction, the maximum surface potential at this time is 600V, the dark attenuation rate is 9%, the sensitivity is 3.0Lux.sec, and the residual potential is 15V.
Furthermore, the same results as in Example 1 were obtained in the actual photographic test.
実施例 ４
実施例１にて得られた銅フタロシアニン10部、
アクリルポリオール（タケラツクＡ−702）36部、
エポキシ樹脂（シエル化学社製）５部およびメチ
ルエチルケトン：セロソルブアセテート（１：
１）50部からなる組成物をボールミルにより、24
時間混練して、光導電性塗料を調整し、この塗料
をアルミニウム支持体上に約1μとなるように塗
布し、電荷発生層を形成した。Example 4 10 parts of copper phthalocyanine obtained in Example 1,
36 parts of acrylic polyol (Takerakatsu A-702),
5 parts of epoxy resin (manufactured by Ciel Chemical Co., Ltd.) and methyl ethyl ketone: cellosolve acetate (1:
1) A composition consisting of 50 parts was milled using a ball mill for 24 parts.
A photoconductive paint was prepared by kneading for a period of time, and this paint was coated on an aluminum support to a thickness of about 1 μm to form a charge generating layer.
次に、ポリカーボネート樹脂（パンライトＬ−
1250）10部、ポリエステル樹脂（グツドイヤー
製）３部をテトラヒドロフランおよびトルエン溶
媒100部で混合した。溶媒の重量比は９：１であ
る。次に合成例２に準じて合成した化合物(5)９部
をシリコンオイル0.02部と共に添加した。この液
を電荷発生層の上に約15μとなるように塗布し、
80℃で乾燥して電荷輸送層を形成し、積層感光体
を得た。 Next, polycarbonate resin (Panlite L-
1250) and 3 parts of polyester resin (manufactured by Gutdeyer) were mixed with tetrahydrofuran and 100 parts of toluene solvent. The weight ratio of solvents is 9:1. Next, 9 parts of compound (5) synthesized according to Synthesis Example 2 were added together with 0.02 part of silicone oil. Apply this liquid on the charge generation layer to a thickness of about 15μ,
A charge transport layer was formed by drying at 80°C, and a laminated photoreceptor was obtained.
この感光体を−6.5KVのコロナ帯電を0.2秒行
つた時の表面電位は−610Vであり、更に感度は
1.2Lux.secであり、極めて高感度の感光体であつ
た。 When this photoreceptor was corona charged to -6.5KV for 0.2 seconds, the surface potential was -610V, and the sensitivity was
1.2 Lux.sec, making it an extremely sensitive photoreceptor.
実施例 ５
Ｘ型メタルフリーフタロシアニン10部と熱硬化
性アクリル樹脂32部、メラミン樹脂８部および酢
酸ブチル：セロソルブアセテート（１：１）50部
からなる組成物をボールミルにより24時間混練し
て光導電性塗料を調整し、この塗料をアルミニウ
ム支持体上に約1μとなるように塗布し、電荷発
生層を形成した。Example 5 A composition consisting of 10 parts of X-type metal-free phthalocyanine, 32 parts of thermosetting acrylic resin, 8 parts of melamine resin, and 50 parts of butyl acetate:cellosolve acetate (1:1) was kneaded in a ball mill for 24 hours to produce photoconductivity. A charge-generating layer was formed by preparing a static paint and coating it on an aluminum support to a thickness of about 1 μm.
次に、実施例４の電荷輸送層と同様にして、電
荷発生層の上に約15μとなるように塗布し、80℃
で乾燥し、電荷輸送層を形成し、積層型感光体を
得た。 Next, in the same manner as the charge transport layer of Example 4, it was coated on the charge generation layer to a thickness of about 15μ, and heated to 80°C.
A charge transport layer was formed and a laminated photoreceptor was obtained.
この感光体を−6.5KVのコロナ帯電を0.2秒行
つた時の表面電位は−1200Vであり、また感度Ｅ
１／２は1.1Lux.secであつた。 When this photoreceptor was corona charged at -6.5KV for 0.2 seconds, the surface potential was -1200V, and the sensitivity E
1/2 was 1.1 Lux.sec.
実施例 ６
ダイアンブルー（CI21180）２部にテトラヒド
ロフラン98部を加え、これをボールミル中で分砕
混合して電荷発生顔料塗液を得る。これをアルミ
ニウムを蒸着したポリエステルフイルム上にドク
ターブレードを用いて塗布し、自然乾燥して厚さ
0.5μの電荷発生層を形成せしめる。次いで、合成
例２に準じて合成した化合物(7)２部、ポリカーボ
ネート（パンライトＬ）２部およびテトラヒドロ
フラン45部を混合して得た電荷輸送層形成塗液
を、上記電荷発生層上にドクターブレードを用い
て塗布し、100℃で30分間乾燥して厚さ10μの電
荷発生層を形成せしめて、本発明の感光体を作つ
た。Example 6 98 parts of tetrahydrofuran was added to 2 parts of Diane Blue (CI21180), and the mixture was crushed and mixed in a ball mill to obtain a charge-generating pigment coating liquid. This was applied using a doctor blade onto a polyester film coated with aluminum, dried naturally, and the thickness
A charge generation layer of 0.5μ is formed. Next, a charge transport layer forming coating liquid obtained by mixing 2 parts of compound (7) synthesized according to Synthesis Example 2, 2 parts of polycarbonate (Panlite L), and 45 parts of tetrahydrofuran was applied to the charge generation layer with a doctor. The photoreceptor of the present invention was prepared by coating with a blade and drying at 100° C. for 30 minutes to form a charge generating layer with a thickness of 10 μm.
この感光体を−6.5KVのコロナ帯電を0.2秒行
つた時の表面電位は−960Vであり、また感度Ｅ
１／２は6.8Lux.secであつた。 When this photoreceptor was corona charged at -6.5KV for 0.2 seconds, the surface potential was -960V, and the sensitivity E
1/2 was 6.8 Lux.sec.
Claims (1)
とも１種を含有する感光層を有することを特徴と
する電子写真感光体。 一般式（） （但し、式中、 Ｘは直接結合、酸素原子、イオウ原子、または
カルボニル基； R1は水素原子、ハロゲン原子またはニトロ基、
あるいは置換基を有してもよいアルキル基、アル
コキシ基またはアミノ基； R2，R3は置換基を有してもよいアルキル基、
アラルキル基、アリール基または複素環残基、あ
るいはR2とR3とで複素環残基を形成してもよ
い； ｎは１〜10の整数を示す。）[Scope of Claims] 1. An electrophotographic photoreceptor comprising a photosensitive layer containing at least one compound represented by the following general formula (). General formula () (However, in the formula, X is a direct bond, an oxygen atom, a sulfur atom, or a carbonyl group; R1 is a hydrogen atom, a halogen atom, or a nitro group,
Or an alkyl group, an alkoxy group or an amino group which may have a substituent; R 2 and R 3 are an alkyl group which may have a substituent,
An aralkyl group, an aryl group, a heterocyclic residue, or R 2 and R 3 may form a heterocyclic residue; n represents an integer of 1 to 10. )
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59091844A JPS60237453A (en) | 1984-05-10 | 1984-05-10 | Electrophotographic sensitive body |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59091844A JPS60237453A (en) | 1984-05-10 | 1984-05-10 | Electrophotographic sensitive body |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60237453A JPS60237453A (en) | 1985-11-26 |
| JPH0424698B2 true JPH0424698B2 (en) | 1992-04-27 |
Family
ID=14037887
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59091844A Granted JPS60237453A (en) | 1984-05-10 | 1984-05-10 | Electrophotographic sensitive body |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60237453A (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0727230B2 (en) * | 1986-05-21 | 1995-03-29 | ミノルタ株式会社 | Photoconductor |
| US6066426A (en) * | 1998-10-14 | 2000-05-23 | Imation Corp. | Organophotoreceptors for electrophotography featuring novel charge transport compounds |
| US6340548B1 (en) * | 2000-03-16 | 2002-01-22 | Imation Corp. | Organophotoreceptors for electrophotography featuring novel charge transport compounds |
| US7118839B2 (en) * | 2001-09-28 | 2006-10-10 | Samsung Electronics Co., Ltd. | Electrophotographic organophotoreceptors with novel charge transport materials |
| KR100532845B1 (en) * | 2002-10-02 | 2005-12-05 | 삼성전자주식회사 | Multi-layered electro photographic positive charged organic photoconductor and manufacturing method thereof |
| KR100462622B1 (en) | 2002-10-28 | 2004-12-23 | 삼성전자주식회사 | Double-layered positive type organic photoreceptor |
| KR100679724B1 (en) * | 2004-10-13 | 2007-02-07 | 주식회사 두산 | Chromophore compounds and organic electroluminescence display device comprising the same |
| JP5734093B2 (en) * | 2010-06-30 | 2015-06-10 | キヤノン株式会社 | Electrophotographic photosensitive member, process cartridge, and electrophotographic apparatus |
-
1984
- 1984-05-10 JP JP59091844A patent/JPS60237453A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60237453A (en) | 1985-11-26 |
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