JPH02165156A - Electrophotographic sensitive body - Google Patents
Electrophotographic sensitive bodyInfo
- Publication number
- JPH02165156A JPH02165156A JP32090188A JP32090188A JPH02165156A JP H02165156 A JPH02165156 A JP H02165156A JP 32090188 A JP32090188 A JP 32090188A JP 32090188 A JP32090188 A JP 32090188A JP H02165156 A JPH02165156 A JP H02165156A
- Authority
- JP
- Japan
- Prior art keywords
- layer
- carrier
- ti0pc
- photoreceptor
- derivatives
- 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.)
- Granted
Links
- SJHHDDDGXWOYOE-UHFFFAOYSA-N oxytitamium phthalocyanine Chemical compound [Ti+2]=O.C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 SJHHDDDGXWOYOE-UHFFFAOYSA-N 0.000 claims abstract description 34
- 108091008695 photoreceptors Proteins 0.000 claims description 45
- 230000035945 sensitivity Effects 0.000 abstract description 11
- -1 titanyl phthalocyanine compound Chemical class 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 10
- 239000000758 substrate Substances 0.000 abstract description 2
- 238000010030 laminating Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 71
- 239000000126 substance Substances 0.000 description 35
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 230000015572 biosynthetic process Effects 0.000 description 15
- 238000003786 synthesis reaction Methods 0.000 description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 12
- 238000000862 absorption spectrum Methods 0.000 description 11
- 239000011230 binding agent Substances 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 10
- 239000013078 crystal Substances 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 9
- 239000006185 dispersion Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 239000000049 pigment Substances 0.000 description 6
- 229910052711 selenium Inorganic materials 0.000 description 6
- 239000011669 selenium Substances 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000002612 dispersion medium Substances 0.000 description 5
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical class 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 5
- 239000000243 solution Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229920000642 polymer Polymers 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
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000008064 anhydrides Chemical class 0.000 description 3
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000003618 dip coating Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 239000004417 polycarbonate Substances 0.000 description 3
- 229920000515 polycarbonate Polymers 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- JTPNRXUCIXHOKM-UHFFFAOYSA-N 1-chloronaphthalene Chemical compound C1=CC=C2C(Cl)=CC=CC2=C1 JTPNRXUCIXHOKM-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229920000180 alkyd Polymers 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- YDSWCNNOKPMOTP-UHFFFAOYSA-N mellitic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(O)=O)=C(C(O)=O)C(C(O)=O)=C1C(O)=O YDSWCNNOKPMOTP-UHFFFAOYSA-N 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- XQZYPMVTSDWCCE-UHFFFAOYSA-N phthalonitrile Chemical compound N#CC1=CC=CC=C1C#N XQZYPMVTSDWCCE-UHFFFAOYSA-N 0.000 description 2
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 2
- 229920005668 polycarbonate resin Polymers 0.000 description 2
- 239000004431 polycarbonate resin Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229920002050 silicone resin Polymers 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 229940014800 succinic anhydride Drugs 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- ZWYDDDAMNQQZHD-UHFFFAOYSA-L titanium(ii) chloride Chemical compound [Cl-].[Cl-].[Ti+2] ZWYDDDAMNQQZHD-UHFFFAOYSA-L 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- NMNSBFYYVHREEE-UHFFFAOYSA-N 1,2-dinitroanthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=C([N+]([O-])=O)C([N+](=O)[O-])=CC=C3C(=O)C2=C1 NMNSBFYYVHREEE-UHFFFAOYSA-N 0.000 description 1
- XVMIKRZPDSXBTP-UHFFFAOYSA-N 1,3-dibromobutan-2-one Chemical compound CC(Br)C(=O)CBr XVMIKRZPDSXBTP-UHFFFAOYSA-N 0.000 description 1
- WDCYWAQPCXBPJA-UHFFFAOYSA-N 1,3-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC([N+]([O-])=O)=C1 WDCYWAQPCXBPJA-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- WPMHMYHJGDAHKX-UHFFFAOYSA-N 1-ethenylpyrene Chemical compound C1=C2C(C=C)=CC=C(C=C3)C2=C2C3=CC=CC2=C1 WPMHMYHJGDAHKX-UHFFFAOYSA-N 0.000 description 1
- BIEFDNUEROKZRA-UHFFFAOYSA-N 2-(2-phenylethenyl)aniline Chemical class NC1=CC=CC=C1C=CC1=CC=CC=C1 BIEFDNUEROKZRA-UHFFFAOYSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- 229940093475 2-ethoxyethanol Drugs 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- SEBPXHSZHLFWRL-UHFFFAOYSA-N 3,4-dihydro-2,2,5,7,8-pentamethyl-2h-1-benzopyran-6-ol Chemical class O1C(C)(C)CCC2=C1C(C)=C(C)C(O)=C2C SEBPXHSZHLFWRL-UHFFFAOYSA-N 0.000 description 1
- ITUYMTWJWYTELW-UHFFFAOYSA-N 4-chloroiminocyclohexa-2,5-dien-1-one Chemical compound ClN=C1C=CC(=O)C=C1 ITUYMTWJWYTELW-UHFFFAOYSA-N 0.000 description 1
- OTLNPYWUJOZPPA-UHFFFAOYSA-N 4-nitrobenzoic acid Chemical compound OC(=O)C1=CC=C([N+]([O-])=O)C=C1 OTLNPYWUJOZPPA-UHFFFAOYSA-N 0.000 description 1
- MEXUTNIFSHFQRG-UHFFFAOYSA-N 6,7,12,13-tetrahydro-5h-indolo[2,3-a]pyrrolo[3,4-c]carbazol-5-one Chemical compound C12=C3C=CC=C[C]3NC2=C2NC3=CC=C[CH]C3=C2C2=C1C(=O)NC2 MEXUTNIFSHFQRG-UHFFFAOYSA-N 0.000 description 1
- OGOYZCQQQFAGRI-UHFFFAOYSA-N 9-ethenylanthracene Chemical compound C1=CC=C2C(C=C)=C(C=CC=C3)C3=CC2=C1 OGOYZCQQQFAGRI-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 206010011878 Deafness Diseases 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004419 Panlite Substances 0.000 description 1
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001251 acridines Chemical class 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 229940058303 antinematodal benzimidazole derivative Drugs 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 229940027998 antiseptic and disinfectant acridine derivative Drugs 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000000498 ball milling Methods 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
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical class C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 1
- 150000001565 benzotriazoles Chemical class 0.000 description 1
- XITRBUPOXXBIJN-UHFFFAOYSA-N bis(2,2,6,6-tetramethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)NC(C)(C)C1 XITRBUPOXXBIJN-UHFFFAOYSA-N 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
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- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 1
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- 239000002285 corn oil Substances 0.000 description 1
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- 150000001907 coumarones Chemical class 0.000 description 1
- GVJHHUAWPYXKBD-UHFFFAOYSA-N d-alpha-tocopherol Natural products OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 description 1
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- 239000008367 deionised water Substances 0.000 description 1
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- 208000016354 hearing loss disease Diseases 0.000 description 1
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- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
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- 125000000687 hydroquinonyl group Chemical class C1(O)=C(C=C(O)C=C1)* 0.000 description 1
- 150000002460 imidazoles Chemical class 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
- 239000003112 inhibitor Substances 0.000 description 1
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- 229940079865 intestinal antiinfectives imidazole derivative Drugs 0.000 description 1
- 208000017169 kidney disease Diseases 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 150000002668 lysine derivatives Chemical class 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000113 methacrylic resin Substances 0.000 description 1
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- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
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- 150000004866 oxadiazoles Chemical class 0.000 description 1
- 150000007978 oxazole derivatives Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 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
- 229920001568 phenolic resin Polymers 0.000 description 1
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- 150000003008 phosphonic acid esters Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- OXNIZHLAWKMVMX-UHFFFAOYSA-N picric acid Chemical compound OC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O OXNIZHLAWKMVMX-UHFFFAOYSA-N 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002689 polyvinyl acetate 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
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 150000003219 pyrazolines Chemical class 0.000 description 1
- 125000002294 quinazolinyl group Chemical class N1=C(N=CC2=CC=CC=C12)* 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229960005265 selenium sulfide Drugs 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- PWEBUXCTKOWPCW-UHFFFAOYSA-N squaric acid Chemical compound OC1=C(O)C(=O)C1=O PWEBUXCTKOWPCW-UHFFFAOYSA-N 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 229920001909 styrene-acrylic polymer Polymers 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 229940042055 systemic antimycotics triazole derivative Drugs 0.000 description 1
- UGNWTBMOAKPKBL-UHFFFAOYSA-N tetrachloro-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(Cl)=C(Cl)C1=O UGNWTBMOAKPKBL-UHFFFAOYSA-N 0.000 description 1
- AUHHYELHRWCWEZ-UHFFFAOYSA-N tetrachlorophthalic anhydride Chemical compound ClC1=C(Cl)C(Cl)=C2C(=O)OC(=O)C2=C1Cl AUHHYELHRWCWEZ-UHFFFAOYSA-N 0.000 description 1
- NLDYACGHTUPAQU-UHFFFAOYSA-N tetracyanoethylene Chemical group N#CC(C#N)=C(C#N)C#N NLDYACGHTUPAQU-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 150000004867 thiadiazoles Chemical class 0.000 description 1
- 150000007979 thiazole derivatives Chemical class 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229960001295 tocopherol Drugs 0.000 description 1
- 229930003799 tocopherol Natural products 0.000 description 1
- 235000010384 tocopherol Nutrition 0.000 description 1
- 239000011732 tocopherol Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- GVJHHUAWPYXKBD-IEOSBIPESA-N α-tocopherol Chemical compound OC1=C(C)C(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-IEOSBIPESA-N 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
- G03G5/0664—Dyes
- G03G5/0696—Phthalocyanines
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Photoreceptors In Electrophotography (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、電子写真感光体に関し、特にプリンタ、複写
機等に使用され、特にＬＥＤ光及び半導体レーザ光に対
して有効な電子写真感光体に関するものである。Detailed Description of the Invention [Field of Industrial Application] The present invention relates to an electrophotographic photoreceptor, and an electrophotographic photoreceptor that is particularly used in printers, copiers, etc. and is particularly effective against LED light and semiconductor laser light. It is related to.
従来、可視光に光感度を有する電子写真感光体は複写機
、プリンタ等に広く使用されている。Conventionally, electrophotographic photoreceptors sensitive to visible light have been widely used in copying machines, printers, and the like.
このような電子写真感光体としては、セレン、酸化亜鉛
、硫化カドミウム等の無機光導電性物質を主成分とする
感光層を設けた無機感光体が広く使用されている。しか
しながら、このような無機感光体は複写機等の電子写真
感光体として要求される光感度、熱安定性、耐湿性、耐
久性等の特性において必ずしも満足できるものではない
。As such electrophotographic photoreceptors, inorganic photoreceptors provided with a photosensitive layer mainly composed of an inorganic photoconductive substance such as selenium, zinc oxide, or cadmium sulfide are widely used. However, such inorganic photoreceptors do not necessarily satisfy the characteristics such as photosensitivity, thermal stability, moisture resistance, and durability required of electrophotographic photoreceptors for copying machines and the like.
例えば、セレンは熱や手で触ったときの指紋の汚れ等に
より結晶化するため、電子写真感光体としての上記特性
が劣化し易い。For example, since selenium crystallizes due to heat or fingerprint stains when touched, the above-mentioned characteristics as an electrophotographic photoreceptor tend to deteriorate.
又硫化カドミウムを用いた電子写真感光体は耐湿度性、
耐久性に劣り、又酸化亜鉛を用いた電子写真感光体は耐
久性に問題がある。又、セレン、硫化カドミウムの電子
写真感光体は製造上、取扱い上の制約が大きい。In addition, electrophotographic photoreceptors using cadmium sulfide are moisture resistant,
Durability is poor, and electrophotographic photoreceptors using zinc oxide have durability problems. Furthermore, electrophotographic photoreceptors made of selenium or cadmium sulfide have significant restrictions in manufacturing and handling.
このような無機光導電性物質の問題点を改善するために
、種々の有機の光導電性物質を電子写真感光体の感光層
に使用することが試みられ、近年活発に研究、開発が行
なわれている。In order to improve these problems with inorganic photoconductive materials, attempts have been made to use various organic photoconductive materials in the photosensitive layer of electrophotographic photoreceptors, and active research and development has been conducted in recent years. ing.
例えば、特公昭５０−１０４９８号には、ポリ−Ｎ−ビ
ニルカルバゾールと２．４．７−ドリニトロー９−フル
オレノンを含有した感光層を有する有機感光体が記載さ
れ（いる。しかし、この感光体も感度及び耐久性におい
て十分でない。そのため、感光層を二層に分けてキャリ
ア発生層と４ヤリア輸送層全別々に構成し、それぞれに
キャリア発生物質、キャリア輸送物質を含有さゼた機能
分離型の電子・写真感光体が開発された。For example, Japanese Patent Publication No. 50-10498 describes an organic photoreceptor having a photosensitive layer containing poly-N-vinylcarbazole and 2,4,7-dolinitro-9-fluorenone. Sensitivity and durability are not sufficient. Therefore, the photosensitive layer is divided into two layers, a carrier generation layer and four carrier transport layers, each containing a carrier generation substance and a carrier transport substance. Electronic/photographic photoreceptors were developed.
これは、キャリア発生機能とキャリア輸送機能を異なる
物質に個別に分担させることができるため、各機能を発
揮する物質を広い範囲のものから選択することができる
ので、任意の特性を有する電子写真感光体を比較的容易
に得られる。そのため、感度が高く、耐久性の大きい有
機感光体が得られることが期待されている。This is because the carrier generation function and the carrier transport function can be assigned to different substances, and the substances that exhibit each function can be selected from a wide range of materials. The body can be obtained relatively easily. Therefore, it is expected that organic photoreceptors with high sensitivity and durability can be obtained.
このような機能分離型の電子写真感光体のキャリア発生
層に有効なキャリア発生物質としては、従来数多くの物
質が提案されている。Many substances have been proposed as carrier-generating substances effective for the carrier-generating layer of such functionally separated electrophotographic photoreceptors.
無機物質を用いる例としては、例えば特公昭４３−１６
１９８号に記載されているように無定形セレンが挙げら
れる。この無定形セレンを含有するキャリア発生層は有
蒙ギヤリア輸送物質を含有するキャリア輸送層と組合さ
れて使用される３、Ｌ５かし、ご。Examples of using inorganic substances include, for example, Japanese Patent Publication No. 43-16
Examples include amorphous selenium as described in No. 198. This carrier generation layer containing amorphous selenium is used in combination with a carrier transport layer containing a monolayer gear transport material.
の無定形セレンからなるキャリア発生層は、上記したよ
うに熱等により結晶化してその特性が劣化するという問
題点がある。As mentioned above, the carrier generation layer made of amorphous selenium has the problem that it is crystallized by heat or the like and its properties deteriorate.
■、有機物質を上記のギヤ０１発生物質として用いる例
どしては、有機染料や有機顔料が挙げられる。(2) Examples of using an organic substance as the gear 01 generating substance include organic dyes and organic pigments.
これらのうちで、有機系光導電材料の一つであるフタロ
シアニン系化合物は、他のものに比べ感光域が長波長に
拡っていることが知られている。Among these, phthalocyanine compounds, which are one of the organic photoconductive materials, are known to have a photosensitive range extending to longer wavelengths than other compounds.
これらの光導電性を示すフタロシアニン系化合物と１．
、ては例えば特開昭６１−２３９２４８号に記載されて
いるα型チタニルフタロシアニンが挙げられる。These phthalocyanine compounds exhibiting photoconductivity and 1.
Examples include α-type titanyl phthalocyanine described in JP-A-61-239248.
このα型チタニルフタロシアニンは、 Ｃｕ Ｋα！、
５４１人のＸ線に対するブラッグ角度は、７．５゜、１
２．３゜、 １６．３＠、 ２５．３゜、 ２８．７’
にピークを有する。This α-type titanyl phthalocyanine is Cu Kα! ,
The Bragg angle for X-rays of 541 people is 7.5°, 1
2.3°, 16.3@, 25.3°, 28.7'
It has a peak at
しかし、このα型チタニルフタロシアニンは感度が低く
、繰返し使用に対する電位安定性が劣−）ており、反転
現像を用いる電子写真プロ七スではカブリを起こし易い
などの問題がある。However, this α-type titanyl phthalocyanine has low sensitivity and poor potential stability for repeated use, and has problems such as being prone to fog in electrophotographic processing using reversal development.
従って本発明の目的は、帯電性が良好で、高い感度を有
し、繰返し使用時の電位安定性の高いチタニル７タロシ
アニンを用いた電子写真感光体を提供することにある。Therefore, an object of the present invention is to provide an electrophotographic photoreceptor using titanyl-7-thalocyanine that has good charging properties, high sensitivity, and high potential stability during repeated use.
本発明の電子写真感光体は、ＣｕＫａの特性Ｘ線（波長
１．５４１人）に対するブラッグ角２θの主要ピークが
７．４″±０．２″、 １１．０゜±０．２．１７．９
゜±０．２’。The electrophotographic photoreceptor of the present invention has a main peak of Bragg angle 2θ of 7.4″±0.2″ and 11.0°±0.2.17. 9
゜±0.2'.
２０．１’″±０．２．２６．４°：ｌ二層、２６．２
９．０″±０．２６にあるチタ：：ル７りロシアニンを
含有する電子写真感光体、又特に望ｊニジ＜はブラッグ
角２θの７．４°土０゜２°、 ８．９６ｆ０．２゜、
１１．Ｄ゜±０゜２＠、 １７．３″１０−２゜、１
７．９゜±０．２°、 ２０．１６±０６２°、 ２
６．４゜±０，２゜、２９．０゜±０．２ににピークが
あるチタニルフタロシアニンを感光層に含有して構成さ
れる。20.1'''±0.2.26.4°: l double layer, 26.2
An electrophotographic photoreceptor containing a titanium cyanocyanine having a Bragg angle of 2θ of 7.4° and 0.2°, 8.96f0. 2゜,
11. D゜±0゜2@, 17.3″10-2゜, 1
7.9°±0.2°, 20.16±062°, 2
The photosensitive layer contains titanyl phthalocyanine having peaks at 6.4°±0.2° and 29.0°±0.2.
ただし本発明におけるピークとは、ノイズとは異なった
明瞭な鋭角の突出部のことである。However, the peak in the present invention refers to a distinct acute-angled protrusion that is different from noise.
本発明のチタニル７タロシアニンの基本構造は次の一般
式で表ざ４する。The basic structure of the titanyl 7-thalocyanine of the present invention is represented by the following general formula.
般式
但し、Ｘ １．＞（１，＞（３，）（４は水素原子、）
１０ゲン原子、アルキル基、或いはアルコキシ基を表し
、ｎ 、 ｍ 、Ｑ 、 ｋは０〜４の整数を表す。General formula However, X1. >(1,>(3,) (4 is a hydrogen atom,)
10 represents an atom, an alkyl group, or an alkoxy group, and n, m, Q, and k represent integers of 0 to 4.
上記のＸ線回折スペクトルは次の条件で測定し２だもの
である。The above X-ray diffraction spectrum was measured under the following conditions.
Ｘ線管球 Ｃｕ
電 圧 ４０．ＯＫＶｔ 流
１００ ｍＡ
スター］・角度 ６．００ ｄｅｇ。X-ray tube Cu voltage 40. OKVt style
100 mA star]・Angle 6.00 deg.
ストップ角度 ３５．θＱ ｄｅｇ。Stop angle 35. θQ deg.
ステップ角度 ０．０２０ ｄｅｇ。Step angle 0.020 deg.
測定時間 ０．５０ ｓｅｃ。Measurement time: 0.50 sec.
更に上記チタニルフタロシアニンを含有する本発明の電
子写真感光体は、吸収スペクトルにおいて５００ｎｍ
〜９００ｎａ＋領域での最大吸収波長が６２０〜８６０
ｎ１こ位置することが望ましく、更に望ましくは７２６
ｎｎ＋〜８２０ｎｍの範囲に位置するものである。Further, the electrophotographic photoreceptor of the present invention containing the titanyl phthalocyanine has an absorption spectrum of 500 nm.
The maximum absorption wavelength in the ~900na+ region is 620-860
It is desirable that the location be n1, more preferably 726.
It is located in the range of nn+ to 820 nm.
上記の吸収スペクトルは、後述の実施例１の方法で作成
した感光体を「３２０形自記記録分光光度計（日立製作
新製）」を用いて測定した反射型の吸収スペクトルであ
る。The above absorption spectrum is a reflection type absorption spectrum obtained by measuring a photoreceptor prepared by the method of Example 1 described later using a "320 type self-recording spectrophotometer (manufactured by Hitachi Seisakusho)".
次に本発明のチタニルフタロシアニンの製造方法を例示
的に説明する。Next, the method for producing titanyl phthalocyanine of the present invention will be exemplified.
まず、例えば四塩化チタンとフタロジニトリルとをａ−
クロルナフタレン溶媒中で反応させて、チタニルフタロ
シアニン（Ｔｉ０Ｐｃ） ヲ得６゜この後、反応を完結
させるために、アンモニア水等による加水分解の操作を
入れてもよい。First, for example, titanium tetrachloride and phthalodinitrile are mixed into a-
The reaction is carried out in a chlornaphthalene solvent to obtain titanyl phthalocyanine (Ti0Pc). Thereafter, in order to complete the reaction, a hydrolysis operation using aqueous ammonia or the like may be performed.
又引続いて２−エトキシエタノール、ジオキサン、テト
ラヒトミフラン、アセトン、Ｎ、Ｎ−ジメチルホルムア
ミド、Ｎ−メチルピロリドン、ａ−クロルナフタレン等
の溶媒で処理することが好ましい。It is also preferable to subsequently treat with a solvent such as 2-ethoxyethanol, dioxane, tetrahytomifuran, acetone, N,N-dimethylformamide, N-methylpyrrolidone, a-chlornaphthalene, or the like.
次にこのＴｉ０Ｐｃをモザー及びトーマス著の「７りロ
シアニン化合物」に記載されているようなアシッドペー
スト法で処理した後、芳昏族系溶媒或いはハロゲン系溶
媒等の溶媒中、２０℃〜１００℃の温度で結晶変換する
のに十分な時間撹拌もしくは機械的剪断力をもってミリ
ングし、本発明のＴｉ０Ｐｃが製造される。又、この場
合に用いられる溶媒は水、アルコール系溶媒、エーテル
系溶媒等の溶媒と混合しても用いることができる。Next, this Ti0Pc is treated with an acid paste method as described in "7 Lycyanine Compounds" by Moser and Thomas, and then heated at 20 to 100 °C in a solvent such as an aromatic solvent or a halogen solvent. The Ti0Pc of the present invention is produced by milling at a temperature of 100 mL with stirring or mechanical shear for a time sufficient to effect crystal conversion. Further, the solvent used in this case can be used in combination with a solvent such as water, an alcohol solvent, or an ether solvent.
結晶転移工程において使用される装置として代表的なも
のを挙げると、一般的な撹拌装置、例えばホモミキサー
ディスパーサ、アジター スターク、或いはニーダ、
パンバリミキサー、ボールミル、サンドミル、アトライ
タ等がある。Typical devices used in the crystal transition process include general stirring devices, such as homomixers, dispersers, agitators, and kneaders.
There are Pan Bali mixers, ball mills, sand mills, attritors, etc.
本発明では上記Ｔｉ０Ｐｃのほかに更に他のキャリア発
生物質を併用してもよい。他のキャリア発生物質の含有
量は特に制限はないが、好ましくはＴｉ０Ｐｃ １００
重量部に対し、ｉｏｏ重量部以下、特に好ましくは５０
重量部以下である。併用できるキャリア発生物質として
は本発明のフタロシアニンと異更に代表的には次の化合
物が挙げられる。In the present invention, other carrier-generating substances may be used in combination with Ti0Pc. The content of other carrier-generating substances is not particularly limited, but preferably Ti0Pc 100
less than ioo parts by weight, particularly preferably 50 parts by weight
Parts by weight or less. Examples of carrier-generating substances that can be used in combination with the phthalocyanine of the present invention include the following compounds.
なる結晶形を有するＴ ｉＯＰＣｓ具体的にはａ型、β
型、ａβ混合型、アモルファス型等の結晶形を有 （１
）するＴｉ０Ｐｃが挙げられる。又、上記以外の７タロ
シアニン顔料、アゾ顔料、アントラキノン顔料、ペリレ
ン顔料、多環キノン顔料、スクアリック酸メチン顔料が
挙げられる。TiOPCs have crystal forms such as a-type, β-type
It has crystal forms such as type, aβ mixed type, and amorphous type (1
) Ti0Pc is mentioned. Other examples include heptalocyanine pigments, azo pigments, anthraquinone pigments, perylene pigments, polycyclic quinone pigments, and methine squaric acid pigments other than the above.
本発明の感光体において、機能分離聾とする場 （２）
合に使用されるキャリア輸送物質は特に制限はないが代
表的なものとして、オキサゾール誘導体、オキサジアゾ
ール誘導体、チアゾール誘導体、チアジアゾール誘導体
、トリアゾール誘導体、イミダゾール誘導体、イミダシ
ロン誘導体、イミダゾ （３）リジン誘導体、ビスイミ
ダゾリジン誘導体、スチリル化合物、ヒドラゾン化合物
、ピラゾリン誘導体、オキサシロン誘導体、ベンゾチア
ゾール誘導体、ベンゾイミダゾール誘導体、キナゾリン
誘導体、ベンゾフラン誘導体、アクリジン誘導体、７エ
（４）ナジン誘導体、アミノスチルベン誘導体、ポリ−
Ｎルビニルカルバゾール、ポリ−１−ビニルピレン、ポ
リ−９−ビニルアントラセン等が挙げられる。In the photoreceptor of the present invention, a place for functionally separated deafness (2)
There are no particular restrictions on carrier transport substances used in this case, but representative examples include oxazole derivatives, oxadiazole derivatives, thiazole derivatives, thiadiazole derivatives, triazole derivatives, imidazole derivatives, imidasilone derivatives, imidazo (3) lysine derivatives, Bisimidazolidine derivatives, styryl compounds, hydrazone compounds, pyrazoline derivatives, oxacilone derivatives, benzothiazole derivatives, benzimidazole derivatives, quinazoline derivatives, benzofuran derivatives, acridine derivatives, 7e(4) nadine derivatives, aminostilbene derivatives, poly-
Examples include N-ruvinylcarbazole, poly-1-vinylpyrene, and poly-9-vinylanthracene.
曾
Ｃ！Ｈ！
本発明の感光体の感光層を構成するためには、上記キャ
リア発生物質をバインダ中に分散せしめた層を導電性支
持体上に設ければよい１．或はこのキャリア発生物質と
ギヤリア輸送物質とを組合せ、積層型もしくは単層型の
いわゆる機能分離型感光層を設けてもよい。Zeng C! H! In order to constitute the photosensitive layer of the photoreceptor of the present invention, a layer in which the carrier-generating substance described above is dispersed in a binder may be provided on a conductive support.1. Alternatively, the carrier generating substance and the gear transporting substance may be combined to provide a so-called functionally separated photosensitive layer of a laminated type or a single layer type.
機能分離型感光層とする場合、通常は、第９図〜第１４
図のようにする。即ち、第９図に示す層構成は、導電性
支持体１上に本発明に係るＴ １ＯＰｃを含むキャリア
発生層２を形成し、これに上記キャリア輸送物質を含有
するキャリア輸送層３を積層して感光層４を形成したも
のであり、第１θ図はこれらのキャリア発生層２とキャ
リア輸送層３を逆にした感光層４′を形成したものであ
り、第１１図の層構成は第９図の層構成の感光層４と導
電性支持体１の間に中間層５を設け、第１２図は第１θ
図の層構成の感光層４′と導電性支持体ｌとの間に中間
層５を設け、それぞれ導電性支持体１の７り−エレクト
ロンの注入を防止するようにしたものであり、第１３図
の層構成は本発明に係るＴｉ０Ｐｃを主とするキャリア
発生物質６とこれと組合されるキャリア輸送物質７を含
有する感光層４“を形成したものであり、第１４図の層
構成はこの感光層４“と導電性支持体ｌとの間に上記の
中間層５を設けたものである。In the case of a functionally separated photosensitive layer, the steps in FIGS. 9 to 14 are usually used.
Do as shown. That is, in the layer structure shown in FIG. 9, a carrier generation layer 2 containing T1OPc according to the present invention is formed on a conductive support 1, and a carrier transport layer 3 containing the above carrier transport substance is laminated thereon. Figure 1θ shows a photosensitive layer 4' formed by reversing the carrier generation layer 2 and carrier transport layer 3, and the layer structure in Figure 11 is the same as the layer structure shown in Figure 11. An intermediate layer 5 is provided between the photosensitive layer 4 and the conductive support 1 having the layer structure shown in the figure.
An intermediate layer 5 is provided between the photosensitive layer 4' having the layer structure shown in the figure and the conductive support 1 to prevent the injection of electrons into the conductive support 1. The layer structure shown in the figure forms a photosensitive layer 4'' containing a carrier-generating material 6 mainly composed of Ti0Pc according to the present invention and a carrier-transporting material 7 combined therewith, and the layer structure shown in FIG. The above intermediate layer 5 is provided between the photosensitive layer 4'' and the conductive support l.
二層構成の感光層を形成する場合におけるキャリア発生
層２及びキャリア輸送層３は、次のごとき方法によって
設けることができる。In the case of forming a photosensitive layer having a two-layer structure, the carrier generation layer 2 and the carrier transport layer 3 can be provided by the following method.
（イ）キャリア発生物質、キャリア輸送物質を適当な溶
剤に夫々溶解した溶液或いはこれにバインダを加えて混
合溶解した溶液を塗布する方法。(a) A method of applying a solution in which a carrier-generating substance and a carrier-transporting substance are respectively dissolved in an appropriate solvent, or a solution in which a binder is added and mixed and dissolved therein.
（ロ）ギヤリア発生物質、キャリア輸送物質をボールミ
ル、ホモミキサー、超音波等によって夫々分散媒中で微
細粒子とし、必要に応じてバインダを加えて混合分散し
て得られる分散液を塗布する方法。(b) A method in which a gear-generating substance and a carrier-transporting substance are made into fine particles in a dispersion medium using a ball mill, a homomixer, an ultrasonic wave, etc., and a binder is added as necessary to mix and disperse the obtained dispersion, and the resulting dispersion is applied.
キャリア発生層及びキャリア輸送層の形成に使用される
溶剤或は分散媒としては、ブチルアミン、Ｎ、Ｎ−ジメ
チルホルムアミド、アセトン、メチルエチルケトン、シ
クロヘキサノン、ベンゼン、トルエン、キシレン、クロ
ロホルム、１．２−ジクロルエタン、ジクロルメタン、
テトラヒドロフラン、ジオキサン、メタノール、エタノ
ール、イングロパノール、酢酸エチル、酢酸ブチル、ジ
メチルスルホキシド等を挙げることができる。 キャリ
ア発生層若しくはキャリア輸送層の形成にバインダを用
いる場合に、このバインダとしては任意のものを用いる
ことができるが、特に疎水性でかつ誘電率が高い電気絶
縁性のフィルム形成能を有する高分子重合体が好ましい
。こうした重合体としては、例えば次のものを挙げるこ
とができるが、勿論これらに限定されるものではない。Examples of the solvent or dispersion medium used to form the carrier generation layer and the carrier transport layer include butylamine, N,N-dimethylformamide, acetone, methyl ethyl ketone, cyclohexanone, benzene, toluene, xylene, chloroform, 1,2-dichloroethane, dichloromethane,
Examples include tetrahydrofuran, dioxane, methanol, ethanol, ingropanol, ethyl acetate, butyl acetate, dimethyl sulfoxide, and the like. When a binder is used to form a carrier generation layer or a carrier transport layer, any binder can be used, but in particular, a polymer that is hydrophobic, has a high dielectric constant, and has the ability to form an electrically insulating film. Polymers are preferred. Examples of such polymers include, but are not limited to, the following:
１）ポリカーボネート
２）ポリエステル
３）メタクリル樹脂
４）アクリル樹脂
５）ポリ塩化ビニル
６）ポリ塩化ビニリデン
７）ポリスチレン
８）ポリビニルアセテート
９）スチレン−ブタジェン共重合体
１０）塩化ビニリデン−アクリロニトリル共重合体１１
）塩化ビニル−酢酸ビニル共重合体１２） 塩化ビニル
−酢酸ビニル−無水マレイン酸共重合体
１３）シリコーン樹脂
１４）シリコーン−アルキッド樹脂
１５）フェノール−ホルムアルデヒド樹脂１６）スチレ
ン−アクリル共重合樹脂
１７）スチレン−アルキッド樹脂
＋８）ポリ−Ｎ−ビニルカルバゾール
１９）ポリビニルブチラール
２０）ポリカーボネートＺ樹脂
これらのバインダは、単独或いは２種以上の混合物とし
て用いることができる。又バインダｌｏ。1) Polycarbonate 2) Polyester 3) Methacrylic resin 4) Acrylic resin 5) Polyvinyl chloride 6) Polyvinylidene chloride 7) Polystyrene 8) Polyvinyl acetate 9) Styrene-butadiene copolymer 10) Vinylidene chloride-acrylonitrile copolymer 11
) Vinyl chloride-vinyl acetate copolymer 12) Vinyl chloride-vinyl acetate-maleic anhydride copolymer 13) Silicone resin 14) Silicone-alkyd resin 15) Phenol-formaldehyde resin 16) Styrene-acrylic copolymer resin 17) Styrene - Alkyd resin + 8) Poly-N-vinyl carbazole 19) Polyvinyl butyral 20) Polycarbonate Z resin These binders can be used alone or as a mixture of two or more. Also binder lo.
に対するキャリア発生物質の割合は１０〜６００ｗｉ／
ｗｔ、好ましくは５０〜４００ｗｔ／曹【、キャリア輸
送物質はｌ。The ratio of carrier-generating substances to
wt, preferably 50 to 400 wt/carbonate, and the carrier transport material is l.
〜５００ｗｔ／ｗｔとするのがよい。It is preferable to set it to ~500wt/wt.
このようにして形成されるキャリア発生層２の厚さは０
．０１〜２０μｍであることが好ましいが、更に好まし
くは０．０５〜５μｍである。キャリア輸送層の厚みは
２〜ｉｏｏμ１１好ましくは５〜３０ｐｗｓである。The thickness of the carrier generation layer 2 formed in this way is 0.
．． The thickness is preferably 0.01 to 20 μm, more preferably 0.05 to 5 μm. The carrier transport layer has a thickness of 2 to 11 μm, preferably 5 to 30 pws.
上記キャリア発生物質を分散せしめて感光層を形成する
場合においでは、ギヤリア発生物質は２μＩ以下、好ま
しくは１μｍ以下の平均粒径の粉粒体とされるのが好ま
しい。即ち、粒径が糸り大きいと層中への分散が悪くな
るとともに、粒子が表面に一部突出して表面の平滑性が
悪くなり、場合によっては粒子の突出部分で放電が生じ
たり、或いはそこ６ニトナ一粒子が付着してトナーフィ
ルミング現象が生じ易い７
更に、上記感光層には感度の向上、残留電位乃至反復使
用時の疲労低減等を目的として、一種又は二種以上の電
子受容物質を含有せしめることができる。ここに用いる
ことのできる電子受容性物質としては、例えば無水琥珀
酸、無水マレイン酸、ジブロム無水琥珀酸、無水フタル
酸、テトラクロル無水フタル酸、テ［・ラブ【コム無水
フタル酸、３ニトロ無水７タル酸、４−ニトロ無水７タ
ル酸、無水ピロメリット酸、無水メリッｈａ、テトラシ
アノエチレン、デトラシアノキノジメタン、０−ジニト
ロベンゼン、回−ジニトロベンゼン、１．３．５−１り
ニトロベンゼン、パラニトロベンゾニ］・リル、ビクリ
ルクｃｒ ｆイド、キノンクロルイミド、クロラニル、
ブルマニル、ジクロルジシアノバラベンゾキノン、アノ
トラキノン、ジニトロアントラキノン、９−フルオｌ−
ニリデン〔ジシアノメチレンマロノジニトリル〕、ポリ
ニトロ−９−フルオレニリデン−〔ジシアノメチレンマ
ロノジニトリル〕、ピクリン酸、０−二１・口安息嘗酸
、ｐ−ニトロ安息香酸、３、ｓ−ジニトロ安息香酸、ペ
ンタフルオロ安息香酸、５−ニトロサリチル酸、３，５
−ダニ１〜ロサリヂル酸、フタル酸、メリット酸、その
他の電子親和力の大きい化合物を挙げることができる。When the photosensitive layer is formed by dispersing the carrier-generating substance, the gear-generating substance is preferably in the form of powder having an average particle size of 2 μI or less, preferably 1 μm or less. In other words, if the particle diameter is too large, dispersion in the layer will be poor, and some of the particles will protrude from the surface, resulting in poor surface smoothness. 6. Toner filming phenomenon is likely to occur due to adhesion of a single nitona particle. 7. In addition, one or more electron-accepting substances may be added to the photosensitive layer for the purpose of improving sensitivity, reducing residual potential or fatigue during repeated use, etc. can be made to contain. Examples of electron-accepting substances that can be used here include succinic anhydride, maleic anhydride, dibrominosuccinic anhydride, phthalic anhydride, tetrachlorophthalic anhydride, te[·lab[comb]phthalic anhydride, 3-nitro succinic anhydride, Talic acid, 4-nitro-7-talic anhydride, pyromellitic anhydride, meliha anhydride, tetracyanoethylene, detracyanoquinodimethane, 0-dinitrobenzene, di-dinitrobenzene, 1.3.5-1 dinitrobenzene , paranitrobenzoni] ril, vicrylic cr f-ide, quinone chlorimide, chloranil,
Brumanil, dichlordicyanobarabenzoquinone, anothraquinone, dinitroanthraquinone, 9-fluoro-l-
Nylidene [dicyanomethylenemalonodinitrile], polynitro-9-fluorenylidene-[dicyanomethylenemalonodinitrile], picric acid, 0-21-benzoic acid, p-nitrobenzoic acid, 3, s-dinitrobenzoic acid, Pentafluorobenzoic acid, 5-nitrosalicylic acid, 3,5
-Dani 1 - Examples include rosalidylic acid, phthalic acid, mellitic acid, and other compounds with high electron affinity.
又、電子受容性物質の添加割合は、重量比でキ腎リア発
生物質 ：電子受容物質は１００：０．旧〜２００、好
ましくはｉｏｏ ： ０．１−１００である。Further, the addition ratio of the electron-accepting substance is 100:0 by weight of the nephropathy-generating substance:electron-accepting substance. old to 200, preferably ioo: 0.1-100.
又、Ｊ：記感光層中には保存性、耐久性、耐環境依存性
を向上させる目的で酸化防止剤や光安定剤等の劣化防止
剤を含有させることができる。そのＪ、うな目的に用い
られる化合物としては例えば、トコフェロール等のクロ
マノール誘導体及びそのエーテル化化合物もしくはエス
テル化化合物、ボリアリールアルカン化合物、ハイドロ
キノン誘導体及びそのモノ及びジエーデル化化合物、ベ
ンゾ７ｚノン誘導体、ベンゾトリアゾール誘導体、チオ
エーテル化合物、ホスホン酸エステル、亜燐酸エステル
、フエニ１／ンジアミン誘導体、フェノール化合物、ヒ
ンダードフェノ−・ル化合物、直鎖アミン化合物、環状
アミン化合物、ヒンダードアミン化合物、などが有効で
ある。特に有効な化合物の具体例、！：Ｉ、４１：ｉ、
ｒｌＲＧＡＮＯＸ ｌ０ＩＯＪ 、 ｒｌＲＧＡＮＯＸ
５６５」チバ・ガイキー社製）「スミライザーＢＨＴＪ
、［スミライザーＭＤＰＪ （住友化学工寮社製）等の
ヒンダ ドフェノール化合物、「サノー＝ル１．．５＝
２６２６Ｊ、［サノー・ル１．５６２２ＬＤＪ（三４（
社製）等のヒンダードアミン化合物が挙げられる。Further, in the photosensitive layer (J), deterioration inhibitors such as antioxidants and light stabilizers may be contained in order to improve storage stability, durability, and environmental dependence resistance. Examples of compounds used for this purpose include chromanol derivatives such as tocopherol and their etherified or esterified compounds, polyarylalkane compounds, hydroquinone derivatives and their mono- and diederlated compounds, benzo-7zone derivatives, and benzotriazoles. Derivatives, thioether compounds, phosphonic acid esters, phosphorous acid esters, phenylene diamine derivatives, phenol compounds, hindered phenol compounds, linear amine compounds, cyclic amine compounds, hindered amine compounds, and the like are effective. Specific examples of particularly effective compounds! :I, 41:i,
rlRGANOX l0IOJ, rlRGANOX
565" manufactured by Ciba Gaikie) "Sumilizer BHTJ
, [Hindered phenol compounds such as Sumilizer MDPJ (manufactured by Sumitomo Chemical Co., Ltd.), "Sanol 1..5 =
2626J, [Sanoru 1.5622LDJ (34 (
Examples of hindered amine compounds include:
中間層、侃−護層等に用いられるバインダとし７ては、
上記のキャリア発生層及びキャリア輸送層用ｌご挙げｔ
−ものを用いることがＣさるが、その他にボリア“ミド
樹脂、ナイロン樹脂、エチレン−酢酸ビニル共重合体、
ポリビニルアルコール、セルロース誘導体等が有効であ
る。１
尚、」−記の感光層を設けるべき支持体ｌは金属板、金
属ドラム又は導電性ポリマー、酸化インジウム等の導電
性化合物もしくはアルミニウム、パラジウム、金等の金
属よりなる導電性薄層を塗布、蒸着、ラミネート等の手
段により、紙、グラスチックフィルム等の基体に設けて
成るものが用いられる。As a binder 7 used for the intermediate layer, protective layer, etc.,
For the above carrier generation layer and carrier transport layer, please refer to the following.
- In addition, boria amide resin, nylon resin, ethylene-vinyl acetate copolymer,
Polyvinyl alcohol, cellulose derivatives, etc. are effective. 1. The support l on which the photosensitive layer is to be provided is a metal plate, metal drum, or coated with a conductive thin layer made of a conductive polymer, a conductive compound such as indium oxide, or a metal such as aluminum, palladium, or gold. A material that is provided on a substrate such as paper or a glass film by means such as vapor deposition, lamination, etc. is used.
接着層或いはバリヤ層等として機能する中間層としては
、上記のバインダ樹脂として説明したような高分子重合
体、ポリビニルアルコール、エチルモノ１０−ス、カル
ボキシメチルセルｌコースなどの有機高分子物質又は酸
化アルミニウムなどより成るものが用いられる。The intermediate layer that functions as an adhesive layer or barrier layer may be made of a polymer as described above as the binder resin, an organic polymer material such as polyvinyl alcohol, ethyl mono-10-acetate, carboxymethyl cellulose, or aluminum oxide. Something consisting of the following is used.
本発明は、以上説明したように上記Ｔｉ０Ｐｃを用いる
ことにＪ：り特ｌごＬＥＤ光及び半導体レーザ光に対し
て有効な電子感光体を得ることができる。In the present invention, as described above, by using the Ti0Pc described above, it is possible to obtain an electron photoreceptor that is particularly effective for LED light and semiconductor laser light.
更に本発明の電子写真感光体は感度、帯！能、電位安定
性に優れるという特長を有するものである。Furthermore, the electrophotographic photoreceptor of the present invention has excellent sensitivity and band! It has the features of excellent electrical potential and potential stability.
（実施例〕
（合成例１）
フタロジニトリル４０ｇとα−クロルナフタレン５００
＋ｌ＋４の混合物中に窒素気流下１８ｇの四塩化チタン
を滴下した後、徐々に昇温して、２００℃〜２３０℃の
温度範囲で３時間撹拌して反応を完結させた。(Example) (Synthesis Example 1) 40 g of phthalodinitrile and 500 g of α-chlornaphthalene
After 18 g of titanium tetrachloride was dropped into the mixture of +l+4 under a nitrogen stream, the temperature was gradually raised and the reaction was completed by stirring in a temperature range of 200°C to 230°C for 3 hours.
その後室温まで放置冷却し、濾過して生成物であるジク
ロロチタニウムフタロシアニン（ＴｉＣＬＰｃ）を得た
。Thereafter, the mixture was allowed to cool to room temperature and filtered to obtain a product, dichlorotitanium phthalocyanine (TiCLPc).
得られたジクロロチタニウムフタロシアニンを濃アンモ
ニア水３００ｍｇで加水分解した後、アセトン、０・ジ
クロルベンゼンで洗浄した。The obtained dichlorotitanium phthalocyanine was hydrolyzed with 300 mg of concentrated ammonia water, and then washed with acetone and 0.dichlorobenzene.
次に得られたＴｉ０Ｐｃ ５ｇを３〜５℃の温度で９６
％硫酸１００ｇ中で２時間撹拌した後濾過し、得られた
硫酸溶液を水３Ｉ２中に滴下して析出した結晶を濾取し
た。この結晶を脱イオン水で濾液が中性となるまで洗浄
を繰返し、十分に乾燥した。Next, 5 g of the obtained Ti0Pc was heated to 96°C at a temperature of 3 to 5°C.
After stirring in 100 g of % sulfuric acid for 2 hours, the mixture was filtered, and the resulting sulfuric acid solution was dropped into water 3I2, and the precipitated crystals were collected by filtration. The crystals were washed repeatedly with deionized water until the filtrate became neutral and thoroughly dried.
更に硫酸処理したＴｉ０Ｐｃ ２ｇをエチレングリコー
ル１２０ｃｃ中、１８０℃〜１９０℃の温度で３時間撹
拌した後濾過し、メタノールで十分に洗浄した。このよ
うにして得られた結晶は第１図に示すようなブラッグ角
２θの７．４゜、１１．０°、１７．９°、 ２０．１
゜、 ２６．４゜、２９．０°にピークを有する本発明
のＴｉ０Ｐｃであることが判った。Further, 2 g of Ti0Pc treated with sulfuric acid was stirred in 120 cc of ethylene glycol at a temperature of 180° C. to 190° C. for 3 hours, filtered, and thoroughly washed with methanol. The crystals thus obtained have Bragg angles of 2θ of 7.4°, 11.0°, 17.9°, and 20.1 as shown in Figure 1.
It was found that the Ti0Pc of the present invention has peaks at 26.4°, 29.0°.
（合成例２）
合成例１において硫酸処理したＴｉ０Ｐｃ ２ｇを２−
ブトキシェタノール１２０ｃｃ中、１６０℃の温度で３
時間撹拌した後、濾過し、メタノールで十分に洗浄した
。このようにして得られた結晶は、第２図に示すような
ブラッグ角２θの７．４＠、 １１．０°、 １７．９
”。(Synthesis Example 2) 2g of Ti0Pc treated with sulfuric acid in Synthesis Example 1 was
3 at a temperature of 160°C in 120cc of butoxethanol.
After stirring for an hour, it was filtered and thoroughly washed with methanol. The crystal thus obtained has Bragg angles 2θ of 7.4 @, 11.0°, and 17.9 as shown in Figure 2.
”.
２０．１°、 ２６．４＠、 ２９．０’にピークを有
する本発明のＴｉ０Ｐｃであることが判った。It was found that the Ti0Pc of the present invention has peaks at 20.1°, 26.4@, and 29.0'.
（合成例３）
合成例１において硫酸処理したＴｉ０Ｐｃ ２．５ｇに
分散媒としてエチレングリコール３５ｇ１更にＯ−ジク
ロルベンゼン３５ｇを加え、サンドグラインダで４０℃
〜８０℃の温度範囲でミリングを行った。統いて分散媒
を除去し、アセトン、メタノールで洗浄を行った。得ら
れた結晶は、第３図に示すようなブラッグ角２θの７．
４°、１１．０゜、１７．９゜、２０．１゜、 ２６．
０゜、２９．０”にピークを有する本発明のＴｉ０Ｐｃ
であることが判った。(Synthesis Example 3) To 2.5 g of Ti0Pc treated with sulfuric acid in Synthesis Example 1, 35 g of ethylene glycol and 35 g of O-dichlorobenzene were added as a dispersion medium, and the mixture was heated at 40°C using a sand grinder.
Milling was carried out at a temperature range of ~80°C. The dispersion medium was removed and washed with acetone and methanol. The obtained crystal has a Bragg angle of 2θ of 7.0 as shown in FIG.
4°, 11.0°, 17.9°, 20.1°, 26.
Ti0Pc of the present invention having a peak at 0°, 29.0”
It turned out to be.
（比較合成例）
合成例１において硫酸処理したＴｉ０Ｐｃ ２ｇを２−
メトキシエタノール１２０ｍＱ中で３時間加熱還流を行
った後、濾過してメタノールで十分に洗浄した。このよ
うにして得られた結晶は、第４図に示すようなブラッグ
角２θの７．５°、 １２．４゜、 １６．３°、 ２
５．３’。(Comparative Synthesis Example) 2g of Ti0Pc treated with sulfuric acid in Synthesis Example 1 was
After heating under reflux for 3 hours in 120 mQ of methoxyethanol, the mixture was filtered and thoroughly washed with methanol. The crystals thus obtained have Bragg angles of 2θ of 7.5°, 12.4°, 16.3°, and 2 as shown in FIG.
5.3'.
２８．６’にピークを有するσ型Ｔ １ＯＰｃであるこ
とが判った。It was found to be σ-type T 1OPc having a peak at 28.6'.
（実施例１）
合成例１で得た第１図のＸ線回折パターンを有するＴｉ
０Ｐｃ３部（ｗｔ）、シリコーン樹脂（ｒ ＫＲ−５２
４０。(Example 1) Ti having the X-ray diffraction pattern shown in Figure 1 obtained in Synthesis Example 1
0Pc 3 parts (wt), silicone resin (r KR-52
40.
１５％キシレンブタノール溶液」信越化学社製）２０部
、メチルエチルケトン１００部（ｗｔ）をサンドグライ
ンダで粉砕分散して分散液を得た。得られた分散液をア
ルミニウム板にデイツプ（浸漬）塗布法により塗布して
、膜厚約０．２μｍのキャリア発生層を形成した。A dispersion was obtained by grinding and dispersing 20 parts of 15% xylene butanol solution (manufactured by Shin-Etsu Chemical Co., Ltd.) and 100 parts (wt) of methyl ethyl ketone using a sand grinder. The resulting dispersion was applied to an aluminum plate by dip coating to form a carrier generation layer with a thickness of about 0.2 μm.
一方、キャリア輸送物質（１）１部とポリカーボネート
樹脂（「ニーピロンＺ ２００Ｊ三菱瓦斯化学社製）２
部（曹ｔ）及びンリコーンオイル（「にＦ−５４Ｊ 信
越化学社製）を１．２・ジクロルエタン１５部（ｗｔ）
に溶解し、デイツプ塗布法により、前記キャリア発生層
上に塗布し、１００℃で３０分間乾燥して膜厚１８μＩ
のキャリア輸送層を形成し、感光体を作成した。On the other hand, 1 part of carrier transport substance (1) and 2 parts of polycarbonate resin ("Nipilon Z 200J manufactured by Mitsubishi Gas Chemical Co., Ltd.")
1.2 parts (soda t) and corn oil (F-54J, manufactured by Shin-Etsu Chemical Co., Ltd.) and 15 parts (wt) of dichloroethane.
was dissolved in the above carrier generation layer using a dip coating method, and dried at 100°C for 30 minutes to obtain a film thickness of 18μI.
A carrier transport layer was formed to prepare a photoreceptor.
この感孝体をサンプル１とする。又この感光体の吸収ス
ペクトルを第５図に示す。This susceptor will be referred to as sample 1. Further, the absorption spectrum of this photoreceptor is shown in FIG.
（実施例２）
実施例１における合成例１のＴｉ０Ｐｃの代りに合成例
２で得た第２図のＴｉ０Ｐｃを用いた他は、実施例１と
同様にして感光体を作成した。これをサンプル２とする
。又この感光体の吸収スペクトルを第６図に示す。(Example 2) A photoreceptor was produced in the same manner as in Example 1, except that Ti0Pc shown in FIG. 2 obtained in Synthesis Example 2 was used in place of Ti0Pc of Synthesis Example 1 in Example 1. This is called sample 2. Further, the absorption spectrum of this photoreceptor is shown in FIG.
（実施例３）
実施例１における合成例１のＴｉ０Ｐｃの代りに合成例
３で得た第３図のＴｉ０Ｐｃを用いｔ；他は、実施例１
と同様にして感光体を作成した。これをサンプル３とす
る。又この感光体の吸収スペクトルを第７図に示す。(Example 3) Ti0Pc shown in FIG. 3 obtained in Synthesis Example 3 was used instead of Ti0Pc of Synthesis Example 1 in Example 1; the rest was as in Example 1.
A photoreceptor was prepared in the same manner as described above. This is called sample 3. Further, the absorption spectrum of this photoreceptor is shown in FIG.
（比較例１）
実施例１におけ？）合成倒ｌのＴｉ０Ｐｅの代りに、比
較合成例１で得た第４図のα型Ｔｉ０Ｐｃを用いた他は
、実施例１と同様にして感光体を作成し、た。(Comparative Example 1) In Example 1? ) A photoreceptor was prepared in the same manner as in Example 1, except that the α-type Ti0Pc shown in FIG. 4 obtained in Comparative Synthesis Example 1 was used in place of the synthesized Ti0Pe.
これを比較づンプル（１）とする。This is called comparison sample (1).
又この感光体の吸収スペクトルを第８図に示１′。The absorption spectrum of this photoreceptor is shown in FIG. 1'.
（評価）
以上で得られたそれぞれのザンプルを次のようにして評
価し、た。ペーパアナライザＥＰＡ −８１００（川口
電機社製）を用い、−８０μＡの放電条件で５秒間帯電
し、帯電直後の表面電位（Ｖａ）、５秒間暗中放置しｊ
−後の表面電位（Ｖｉ）、表面照度が２（Ｊ２ｕｘ）に
なるように露光し、表面電位が１／２Ｖ ｉになるまで
の霞光量（Ｅ ｌ／２） （１２ＬＩＸ−ｓｅｅ）を求
め、更にの式より暗減衰率（Ｄ：］ ８−求めた。(Evaluation) Each sample obtained above was evaluated as follows. Using Paper Analyzer EPA-8100 (manufactured by Kawaguchi Electric Co., Ltd.), it was charged for 5 seconds under a -80 μA discharge condition, and the surface potential (Va) immediately after charging was maintained in the dark for 5 seconds.
- Expose so that the subsequent surface potential (Vi) and surface illuminance are 2 (J2ux), and calculate the amount of haze light (E 1/2) (12LIX-see) until the surface potential becomes 1/2 Vi, Furthermore, the dark decay rate (D:] 8- was determined from the formula.
これらの結果を表−１に示す。These results are shown in Table-1.
以下余白
表−１
この結果から本発明のＴｉ０Ｐｃは特に高い感度を有し
−〔おり、帯電性も良好であることが判る。Margin Table-1 The results show that the Ti0Pc of the present invention has particularly high sensitivity and good chargeability.
一方、比較（〕゛ンンブル）のα型Ｔ １ＯＰｅは感度
が低く、暗減衰率も大きく、帯電性においても本発明の
電子写真感光体に比べて劣っている。On the other hand, the comparative α-type T 1OPe has low sensitivity, a large dark decay rate, and is inferior to the electrophotographic photoreceptor of the present invention in chargeability.
次にこれらの感光体を用い、通常のカールソンプロセス
を行い、初期とｉｏ、ｏｏｏ回後の帯電直後の表面電位
の差〔Δｖｂ：＋ 、 ｉｏ、ｏｏｏ回後の残留電位〔
Ｖ「〕を求めＩ；。Next, using these photoreceptors, a normal Carlson process is performed, and the difference in surface potential immediately after charging between the initial stage and after io, ooo cycles [Δvb: +, residual potential after io, ooo cycles] is determined.
Find V ``]I;.
又、一定光量照射役の表面電位（Ｖｗ）について、初期
及びｉｏ、ｏｏｏ回後の値を求めた。In addition, the initial value and the value after io and ooo times were determined for the surface potential (Vw) of the constant light irradiation role.
これらの結果を表−２に示す。These results are shown in Table-2.
表−２ この結果から本発明の電子写真感光体は繰返り。Table-2 Based on this result, the electrophotographic photoreceptor of the present invention was repeatedly developed.
使用時の電位安定性６．．１憂れでいることが判る。Potential stability during use6. ．． I can see that you are feeling depressed.
以上のことから、本発明の電ｊ”写真感光体は高い感度
を何し、帯電性も良好で繰返し使用時の電位安定性に優
れでいる。From the above, the electrophotographic photoreceptor of the present invention has high sensitivity, good chargeability, and excellent potential stability during repeated use.
（！ｍＮ ４ ）
キャリア輸送物質（１）１部とポリニスプル樹脂［バイ
ロン２００Ｊ （東洋紡社製）１．５部、をｌ、２−ジ
クロルエタン１５部１．−溶解１．た液をアルミニウム
ドラムＬに、険漬塗布法によって塗布１．゛〔、乾燥の
後、膜厚１５μあのギヤリア輸送層を形成し２゛。(!mN 4 ) 1 part of carrier transport substance (1), 1.5 parts of Polynisple resin [Vylon 200J (manufactured by Toyobo), and 15 parts of l,2-dichloroethane 1. -Dissolution 1. 1. Apply the solution to the aluminum drum L by dip coating method. After drying, a gear transport layer with a thickness of 15 μm was formed.
〜・刀、本発明１７） ？、成例３のＴ＋Ｏ＋’ｅ ｉ
部、パイ〕・ダ樹脂としてポリカーボネート「パンライ
ト■。~・Sword, present invention 17)? , T+O+'e i of Example 3
Part, Pie] - Polycarbonate ``Panlite■'' as resin.
１２５０Ｊ （量大化成２ｆ： Ｉ ） ３部、分散媒
としてモノクロルベ〉・セフ１５部と、ｌ、２−ジクロ
ルブタン３５部をボールミルを用いて分散した後、更に
、キャリア輸送物質（＋）をバインダ樹脂に対し７て７
５ｖｒｔ％の割合となるように添加した。こうして得ら
れた分散液を先のキャリア輸送層の上に、スプレー塗布
法によって塗布して、膜４５μｍのキャリア発生層を形
成した。After dispersing 3 parts of 1250J (large-volume chemical formation 2f: I), 15 parts of monochlorbe>/Cef as a dispersion medium, and 35 parts of l,2-dichlorobutane using a ball mill, the carrier transport substance (+) was further added to the binder resin. 7 against 7
It was added at a ratio of 5vrt%. The thus obtained dispersion was applied onto the carrier transport layer by a spray coating method to form a carrier generation layer having a thickness of 45 μm.
こうして得られた感光体台・、帯電極性をプラス極性と
した他１ま評価ｌど同様にして評価し、た。The photoreceptor stand thus obtained was evaluated in the same manner except that the charging polarity was changed to positive polarity.
Ｖａ ＝ １４００ （Ｖ）
Ｖｉ ＝ １Ｉ２ｆｌ ぐＶ）Ｄ
＝ ２０．０ （％）
Ｅ ！４＝ １．３７ （１＋、＋ｘ ８ｓｅｃ）
（実施例５）
アル二ニウムドラムトに、塩化ビニル−酢酸ビニル−無
水マｌ、 （ン酸共重合体１−よスＩ／ツク ＭＦ−１
ｉＪＪ（覆水化学社製）からなる庁さ０．１μｍの中間
層を形成ｔ、 ｆニー 。Va = 1400 (V) Vi = 1I2fl guV)D
= 20.0 (%) E! 4= 1.37 (1+, +x 8sec)
(Example 5) Vinyl chloride-vinyl acetate-anhydride, (phosphoric acid copolymer 1-Yosu I/Tsuku MF-1) was placed on an aluminum drum.
An intermediate layer with a thickness of 0.1 μm consisting of iJJ (manufactured by Okisui Kagaku Co., Ltd.) was formed.
一方、本発明の合成例３のＴｉ０Ｐｃ １部、をボール
ミル粉砕した後、ポリカーボネート樹脂［パンライトＬ
−１２５０Ｊ ３部、モノクロルベンゼン１５部、１．
２−ジクロルエタン３５部の液を加えて分散を行った。On the other hand, after ball milling 1 part of Ti0Pc of Synthesis Example 3 of the present invention, polycarbonate resin [Panlite L
-1250J 3 parts, monochlorobenzene 15 parts, 1.
Dispersion was carried out by adding 35 parts of 2-dichloroethane.
得られた分散液に、更にキャリア輸送物質（１）２部を
添加して、先の中間層の上に、スプレー塗布法により塗
布し乾燥して、厚さ２０μｍの感光層を形成した。To the resulting dispersion, 2 parts of carrier transport substance (1) was further added, and the mixture was coated onto the intermediate layer by spray coating and dried to form a photosensitive layer with a thickness of 20 μm.
こうして得られた感光体を、帯電極性をプラス極性とし
た他は評価ｌと同様にして評価した。The thus obtained photoreceptor was evaluated in the same manner as Evaluation 1 except that the charging polarity was changed to positive polarity.
Ｖａ −１３７５（Ｖ） Ｖｉ ＝ １０９５ （Ｖ） Ｄ −２０，４（％） Ｅ ％ ＝ １．５９ （ｌｕｘ−ｓｅｃ）Va -1375 (V) Vi = 1095 (V) D -20.4 (%) E% = 1.59 (lux-sec)
第１図、第５図はそれぞれ実施例１で用いたＴ １ＯＰ
ｃのＸ線回折図とその感光体の吸収スペクトル。
第２図、第６図はそれぞれ実施例２で用いたＴｉ０Ｐｃ
のＸ線回折図とその感光体の吸収スペクトル。
第３図、第７図はそれぞれ実施例３で用いたＴｉ０Ｐｃ
のＸ線回折図とその感光体の吸収スペクトル。
′＄４図、１８図はそれぞれ比較例１で用いたσｆｉＴ
ｉＯＰｃのＸ線回折図とその感光体の吸収スペクトルで
ある。
第９図〜第１４図は本発明の電子写真感光体の層構成の
具体例を示した各断面図である。
ｌ・・・導電性支持体
２・・・キャリア発生層
３・・・キャリア輸送層
４．４゜、４“・・・感光層
５・・・中間層Figures 1 and 5 are T 1OP used in Example 1, respectively.
X-ray diffraction diagram of c and absorption spectrum of the photoreceptor. Figures 2 and 6 show the Ti0Pc used in Example 2, respectively.
X-ray diffraction diagram and absorption spectrum of the photoreceptor. Figures 3 and 7 show the Ti0Pc used in Example 3, respectively.
X-ray diffraction diagram and absorption spectrum of the photoreceptor. '$4 Figure and 18 figure are the σfiT used in Comparative Example 1, respectively.
These are an X-ray diffraction diagram of iOPc and an absorption spectrum of its photoreceptor. 9 to 14 are cross-sectional views showing specific examples of the layer structure of the electrophotographic photoreceptor of the present invention. l... Conductive support 2... Carrier generation layer 3... Carrier transport layer 4.4°, 4''... Photosensitive layer 5... Intermediate layer
Claims (1)
ッグ角２θの、少なくとも７．４゜±０．２゜、１１．
０゜±０．２゜、１７．９゜±０．２゜、２０．１゜±
０．２゜、２６．４゜±０．２゜、２９．０゜±０．２
゜に主要ピークを与える結晶型のチタニルフタロシアニ
ンを含有する電子写真感光体。Bragg angle 2θ of at least 7.4° ± 0.2° with respect to the characteristic X-ray (wavelength 1.541 Å) of CuKα; 11.
0゜±0.2゜, 17.9゜±0.2゜, 20.1゜±
0.2°, 26.4°±0.2°, 29.0°±0.2
An electrophotographic photoreceptor containing crystalline titanyl phthalocyanine that gives a main peak at °.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32090188A JP2657839B2 (en) | 1988-12-20 | 1988-12-20 | Electrophotographic photoreceptor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32090188A JP2657839B2 (en) | 1988-12-20 | 1988-12-20 | Electrophotographic photoreceptor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02165156A true JPH02165156A (en) | 1990-06-26 |
| JP2657839B2 JP2657839B2 (en) | 1997-09-30 |
Family
ID=18126533
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP32090188A Expired - Lifetime JP2657839B2 (en) | 1988-12-20 | 1988-12-20 | Electrophotographic photoreceptor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2657839B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0354264A (en) * | 1989-07-21 | 1991-03-08 | Canon Inc | Lowly crystalline oxytitaniumphthalocyanine, production of crystalline oxytitaniumphthalocyanine therefrom, oxytitaniumphthalocyanine of new crystal form, and electrophotographic photoreceptor prepared therefrom |
-
1988
- 1988-12-20 JP JP32090188A patent/JP2657839B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0354264A (en) * | 1989-07-21 | 1991-03-08 | Canon Inc | Lowly crystalline oxytitaniumphthalocyanine, production of crystalline oxytitaniumphthalocyanine therefrom, oxytitaniumphthalocyanine of new crystal form, and electrophotographic photoreceptor prepared therefrom |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2657839B2 (en) | 1997-09-30 |
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