JPH02297560A - Electrophotographic sensitive body - Google Patents
Electrophotographic sensitive bodyInfo
- Publication number
- JPH02297560A JPH02297560A JP11984489A JP11984489A JPH02297560A JP H02297560 A JPH02297560 A JP H02297560A JP 11984489 A JP11984489 A JP 11984489A JP 11984489 A JP11984489 A JP 11984489A JP H02297560 A JPH02297560 A JP H02297560A
- Authority
- JP
- Japan
- Prior art keywords
- compounds
- titanyl phthalocyanine
- obtd
- carrier
- layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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 17
- 238000002441 X-ray diffraction Methods 0.000 claims abstract description 8
- 108091008695 photoreceptors Proteins 0.000 claims description 31
- 238000001228 spectrum Methods 0.000 claims description 2
- 239000013078 crystal Substances 0.000 abstract description 10
- 230000035945 sensitivity Effects 0.000 abstract description 10
- 239000002904 solvent Substances 0.000 abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- JTPNRXUCIXHOKM-UHFFFAOYSA-N 1-chloronaphthalene Chemical compound C1=CC=C2C(Cl)=CC=CC2=C1 JTPNRXUCIXHOKM-UHFFFAOYSA-N 0.000 abstract description 3
- 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 abstract description 3
- XQZYPMVTSDWCCE-UHFFFAOYSA-N phthalonitrile Chemical compound N#CC1=CC=CC=C1C#N XQZYPMVTSDWCCE-UHFFFAOYSA-N 0.000 abstract description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 abstract description 3
- 238000009835 boiling Methods 0.000 abstract description 2
- ZWYDDDAMNQQZHD-UHFFFAOYSA-L titanium(ii) chloride Chemical compound [Cl-].[Cl-].[Ti+2] ZWYDDDAMNQQZHD-UHFFFAOYSA-L 0.000 abstract description 2
- 230000003252 repetitive effect Effects 0.000 abstract 2
- 230000003301 hydrolyzing effect Effects 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 43
- 239000000126 substance Substances 0.000 description 24
- 150000001875 compounds Chemical class 0.000 description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- -1 polycyclic quinone compounds Chemical class 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 239000011230 binding agent Substances 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- 239000000049 pigment Substances 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 239000002612 dispersion medium Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 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
- 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
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000203 mixture 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
- 229910052711 selenium Inorganic materials 0.000 description 3
- 239000011669 selenium Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-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
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229920000180 alkyd Polymers 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 150000004056 anthraquinones Chemical class 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 2
- 239000004431 polycarbonate resin Substances 0.000 description 2
- 229920005668 polycarbonate resin Polymers 0.000 description 2
- 125000003367 polycyclic group Chemical group 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920002050 silicone resin Polymers 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 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 2
- 239000011787 zinc oxide Substances 0.000 description 2
- AFVDZBIIBXWASR-AATRIKPKSA-N (E)-1,3,5-hexatriene Chemical class C=C\C=C\C=C AFVDZBIIBXWASR-AATRIKPKSA-N 0.000 description 1
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-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
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- LVGLBCQZYRCDFB-UHFFFAOYSA-N 10,10-dibromoanthracen-9-one Chemical compound C1=CC=C2C(Br)(Br)C3=CC=CC=C3C(=O)C2=C1 LVGLBCQZYRCDFB-UHFFFAOYSA-N 0.000 description 1
- FKNIDKXOANSRCS-UHFFFAOYSA-N 2,3,4-trinitrofluoren-1-one Chemical compound C1=CC=C2C3=C([N+](=O)[O-])C([N+]([O-])=O)=C([N+]([O-])=O)C(=O)C3=CC2=C1 FKNIDKXOANSRCS-UHFFFAOYSA-N 0.000 description 1
- HZNVUJQVZSTENZ-UHFFFAOYSA-N 2,3-dichloro-5,6-dicyano-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(C#N)=C(C#N)C1=O HZNVUJQVZSTENZ-UHFFFAOYSA-N 0.000 description 1
- TZGYEOFGLJPLEL-UHFFFAOYSA-N 2-(2,2-diphenylethenyl)-n,n-diphenylaniline Chemical class C=1C=CC=C(N(C=2C=CC=CC=2)C=2C=CC=CC=2)C=1C=C(C=1C=CC=CC=1)C1=CC=CC=C1 TZGYEOFGLJPLEL-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
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 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
- UKYNESNNFCHAEV-UHFFFAOYSA-N 3,4-dibromooxolane-2,5-dione Chemical compound BrC1C(Br)C(=O)OC1=O UKYNESNNFCHAEV-UHFFFAOYSA-N 0.000 description 1
- VYWYYJYRVSBHJQ-UHFFFAOYSA-N 3,5-dinitrobenzoic acid Chemical compound OC(=O)C1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1 VYWYYJYRVSBHJQ-UHFFFAOYSA-N 0.000 description 1
- ITUYMTWJWYTELW-UHFFFAOYSA-N 4-chloroiminocyclohexa-2,5-dien-1-one Chemical compound ClN=C1C=CC(=O)C=C1 ITUYMTWJWYTELW-UHFFFAOYSA-N 0.000 description 1
- ROFZMKDROVBLNY-UHFFFAOYSA-N 4-nitro-2-benzofuran-1,3-dione Chemical compound [O-][N+](=O)C1=CC=CC2=C1C(=O)OC2=O ROFZMKDROVBLNY-UHFFFAOYSA-N 0.000 description 1
- 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
- NKJIFDNZPGLLSH-UHFFFAOYSA-N 4-nitrobenzonitrile Chemical compound [O-][N+](=O)C1=CC=C(C#N)C=C1 NKJIFDNZPGLLSH-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
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical class C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-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
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 1
- 239000004419 Panlite Substances 0.000 description 1
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
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- QHWKHLYUUZGSCW-UHFFFAOYSA-N Tetrabromophthalic anhydride Chemical compound BrC1=C(Br)C(Br)=C2C(=O)OC(=O)C2=C1Br QHWKHLYUUZGSCW-UHFFFAOYSA-N 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
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- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 1
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- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
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- 125000003354 benzotriazolyl group Chemical class N1N=NC2=C1C=CC=C2* 0.000 description 1
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- 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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- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229920001600 hydrophobic polymer Polymers 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
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- 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
- NNYHMCFMPHPHOQ-UHFFFAOYSA-N mellitic anhydride Chemical compound O=C1OC(=O)C2=C1C(C(OC1=O)=O)=C1C1=C2C(=O)OC1=O NNYHMCFMPHPHOQ-UHFFFAOYSA-N 0.000 description 1
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- CVKIMZDUDFGOLC-UHFFFAOYSA-N n,n-diphenyl-2-(2-phenylethenyl)aniline Chemical class C=1C=CC=CC=1C=CC1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 CVKIMZDUDFGOLC-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical compound C1=CON=N1 WCPAKWJPBJAGKN-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
- 239000005011 phenolic resin Substances 0.000 description 1
- 150000004986 phenylenediamines Chemical class 0.000 description 1
- 150000003008 phosphonic acid esters Chemical class 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
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 150000003219 pyrazolines Chemical class 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229960005265 selenium sulfide Drugs 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 229940014800 succinic anhydride Drugs 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
- PCCVSPMFGIFTHU-UHFFFAOYSA-N tetracyanoquinodimethane Chemical compound N#CC(C#N)=C1C=CC(=C(C#N)C#N)C=C1 PCCVSPMFGIFTHU-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- VLLMWSRANPNYQX-UHFFFAOYSA-N thiadiazole Chemical compound C1=CSN=N1.C1=CSN=N1 VLLMWSRANPNYQX-UHFFFAOYSA-N 0.000 description 1
- 150000003568 thioethers Chemical class 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
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 125000005259 triarylamine group Chemical group 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000005406 washing Methods 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
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するものであり、特にプリ
ンタ、複写機等に有効に用いることができ、半導体レー
ザ光及びLED光に対して高感度を示す電子写真感光体
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, which can be particularly effectively used in printers, copiers, etc., and is highly resistant to semiconductor laser light and LED light. The present invention relates to an electrophotographic photoreceptor exhibiting sensitivity.
従来、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きた。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かっt
;。例えば、セレンは熱や指紋の汚れ等によって結晶化
するために電子写真感光体としての特性が劣化しやすい
。又、硫化カドミウムを用いた電子写真感光体は耐湿性
、耐久性に劣り、又、酸化亜鉛を用いた電子写真感光体
も耐久性に問題がある。セレン、硫化カドミウムの電子
写真感光体は又毒性の点で製造上、取扱上の制約が大き
いという欠点を有している。Conventionally, inorganic photoreceptors provided with a photosensitive layer containing an inorganic photoconductive substance such as selenium, zinc oxide, or cadmium sulfide as a main component have been widely used as electrophotographic photoreceptors. 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.
;. For example, selenium crystallizes due to heat, fingerprint stains, etc., so its properties as an electrophotographic photoreceptor tend to deteriorate. Further, electrophotographic photoreceptors using cadmium sulfide have poor moisture resistance and durability, and electrophotographic photoreceptors using zinc oxide also have problems in durability. Electrophotographic photoreceptors made of selenium or cadmium sulfide also have the drawback of severe restrictions in manufacturing and handling due to toxicity.
このような無機光導電性物質の欠点を改善するために、
種々の有機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、活発に研究が行われてい
る。例えば、特公昭50−10496号には、ポリビニ
ルカルバゾールとトリニトロ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ている。しかし、こ
の感光体は感度及び耐久性において十分なものではない
。そのため、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た機能分離型の電子写真感光
体が開発された。このような電子写真感光体においては
物質を広い範囲のものから選択することができるので、
任意の特性を得やすく、そのため感度が高く、耐久性の
優れた有機感光体が得られることが期待されている。In order to improve the drawbacks of such inorganic photoconductive materials,
Attempts have been made to use various organic photoconductive substances in photosensitive layers of electrophotographic photoreceptors, and research has been actively conducted in recent years. For example, Japanese Patent Publication No. 50-10496 describes an organic photoreceptor having a photosensitive layer containing polyvinylcarbazole and trinitrofluorenone. However, this photoreceptor does not have sufficient sensitivity and durability. Therefore, a functionally separated electrophotographic photoreceptor has been developed in which the carrier generation function and the carrier transport function are assigned to different substances. In such electrophotographic photoreceptors, materials can be selected from a wide range, so
It is expected that organic photoreceptors with arbitrary characteristics can be easily obtained, and therefore have high sensitivity and excellent durability.
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
物質としては種々の有機染料及び有機顔料が提案されて
おり、ジブロムアンスアンスロンに代表される多環キノ
ン化合物、ビリリウム化合物及びビリリウム化合物とポ
リカーボネートとの共結晶錯体、スクェアリウム化合物
、7りロシアニン化合物、アゾ化合物などが実用化され
てきた。Various organic dyes and organic pigments have been proposed as carrier-generating substances for such functionally separated electrophotographic photoreceptors, including polycyclic quinone compounds such as dibromoanthrone, biryllium compounds, and biryllium compounds and polycarbonates. Co-crystal complexes, squalium compounds, 7-lycyanine compounds, azo compounds, etc. have been put into practical use.
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.
特に近年、チタニル7タロシアニンが注目されているが
、例えば特開昭62−256865号に記載されていル
C型チタニル7タロシアニンや特開昭63・19806
7号記載のチタニルフタロシアニンはCu−にσ1.5
41人に対するブラッグ角2θ7.0±0.2゜、 1
5.5゜±0.2゜及び23.4゜±0.2°に明瞭な
ピークを有している。Particularly in recent years, titanyl-7 thalocyanine has attracted attention.
The titanyl phthalocyanine described in No. 7 has a Cu- σ1.5
Bragg angle 2θ7.0±0.2° for 41 people, 1
It has clear peaks at 5.5°±0.2° and 23.4°±0.2°.
しかしながらこれらのチタニルフタロシアニンは帯電性
が劣り、繰返し使用に対する電位安定性が劣るなどの問
題がある。However, these titanyl phthalocyanines have problems such as poor chargeability and poor potential stability for repeated use.
本発明の目的は、高感度にしてかつ残留電位が小さく、
また繰返し使用においても電位特性が安定しているよう
な優れた電子写真感光体を提供することにある。The purpose of the present invention is to achieve high sensitivity and low residual potential.
Another object of the present invention is to provide an excellent electrophotographic photoreceptor whose potential characteristics are stable even after repeated use.
本発明の他の目的は半導体レーザ等の長波長光源に対し
ても十分な感度を有する電子写真感光体を提供すること
にある。Another object of the present invention is to provide an electrophotographic photoreceptor having sufficient sensitivity even to long wavelength light sources such as semiconductor lasers.
(発明の構成及び作用効果〕
本発明の上記の目的は、Cu−にαの特性X線(波長1
.541A )に対する回折パターンにおいてブラッグ
角2θの6.8゜±0.2゜、9.7゜±0.2゜、
15.4゜±0.26にピークを有するチタニル7タロ
シアニンを感光層中に含有させることによって達成する
ことができる。(Structure and Effects of the Invention) The above object of the present invention is to
.. In the diffraction pattern for 541A), the Bragg angle 2θ is 6.8° ± 0.2°, 9.7° ± 0.2°,
This can be achieved by incorporating titanyl 7-thalocyanine having a peak at 15.4°±0.26 into the photosensitive layer.
本発明のチタニル7タロシアニンの基本構造ハ次の一般
式で表される。The basic structure of the titanyl 7-thalocyanine of the present invention is represented by the following general formula.
一般式
但シ、X 1.X2.x3.X4は水素原子、ノ10ゲ
ン原子、アルキル基、或いはアルコキシ基を表し、n、
m、12.には0〜4の整数を表す。General formula, X1. X2. x3. X4 represents a hydrogen atom, a hydrogen atom, an alkyl group, or an alkoxy group, n,
m, 12. represents an integer from 0 to 4.
X線回折スペクトルは次の条件で測定され、ここでのピ
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。The X-ray diffraction spectrum is measured under the following conditions, and the peak here refers to a distinct acute-angled protrusion that is different from noise.
X線管球 Cu
電 圧 40.OKV電 流
100 mAスタート角度 6.O
deg。X-ray tube Cu voltage 40. OKV current
100 mA start angle 6. O
deg.
ストップ角度 35.Odeg。Stop angle 35. Odeg.
ステップ角度 0.02 deg。Step angle 0.02 deg.
測定時間 0.50 sec。Measurement time: 0.50 sec.
本発明のチタニル7りロシアニンの製造方法会例示的に
説明する。例えば、四塩化チタンとフタロジニトリルと
をα・クロルナフタレン等の不活性高沸点溶媒中で反応
させる。反応温度は160〜300°Cで、特に160
〜260℃が好ましい。これによって得られるジクロロ
チタニウムフタロシアニンを塩基もしくは水で加水分解
することによってチタニルフタロシアニンが得られる。The method for producing titanyl 7-lyrosyanine of the present invention will be exemplarily explained. For example, titanium tetrachloride and phthalodinitrile are reacted in an inert high-boiling solvent such as α-chlornaphthalene. The reaction temperature is 160-300°C, especially 160°C.
~260°C is preferred. The dichlorotitanium phthalocyanine thus obtained is hydrolyzed with a base or water to obtain titanyl phthalocyanine.
次にこれを溶媒処理することによって、目的の結晶型を
得ることができるが、処理に用いられる装置としては一
般的な撹拌装置の他に、ホモミキサー、ディスパーザ、
アジター、或いはボールミル、サンドミル、アトライタ
等を用いることができる。Next, by treating this with a solvent, the desired crystal form can be obtained, but in addition to the general stirring device, the equipment used for the treatment is a homomixer, a disperser,
An agitator, ball mill, sand mill, attritor, etc. can be used.
本発明では上記のチタニルフタロシアニンの外に他のキ
ャリア発生物質を併用してもよい。そのようなキャリア
発生物質としては本発明のチタニルフタロシアニンとは
結晶型において異なる。例えばa型、β型、σββ置台
型アモルファス型等のチタニルフタロシアニンをはじめ
、他の7りロシアニン顔料、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、スクェアリウム
顔料等が挙げられる。In the present invention, other carrier-generating substances may be used in combination with the above titanyl phthalocyanine. Such a carrier generating substance differs in crystal form from the titanyl phthalocyanine of the present invention. Examples include a-type, β-type, σββ-mounted amorphous titanyl phthalocyanine, other 7-lycyanine pigments, azo pigments, anthraquinone pigments, perylene pigments, polycyclic quinone pigments, squareium pigments, and the like.
本発明の感光体におけるキャリア輸送物質としては、種
々のものが使用できるが、代表的なものとしては例えば
、オキサゾール、オキサジアゾール、チアゾール、チア
ジアゾール、イミダゾール等に代表される含窒素複素環
核及びその縮合環核を有する化合物、ポリアリールアル
カン系の化合物、ピラゾリン系化合物、ヒドラゾン系化
合物、トリアリールアミン系化合物、スチリル系化合物
、スチリルトリフェニルアミン系化合物、β−フェニル
スチリルトリフェニルアミン系化合物、ブタジェン系化
合物、ヘキサトリエン系化合物、カルバゾール系化合物
、縮合多環系化合物、等が挙げられる。これらのキャリ
ア輸送物質の具体例としては、例えば特開昭61−10
735.6号に記載のキャリア輸送物質を挙げることが
できるが、特に代表的なものの構造を次に示す。Various carrier transport substances can be used in the photoreceptor of the present invention, but representative examples include nitrogen-containing heterocyclic nuclei represented by oxazole, oxadiazole, thiazole, thiadiazole, imidazole, etc. Compounds having such condensed ring nuclei, polyarylalkane compounds, pyrazoline compounds, hydrazone compounds, triarylamine compounds, styryl compounds, styryltriphenylamine compounds, β-phenylstyryltriphenylamine compounds, Examples include butadiene compounds, hexatriene compounds, carbazole compounds, fused polycyclic compounds, and the like. Specific examples of these carrier transport substances include, for example, JP-A-61-10
The carrier transport substances described in No. 735.6 can be mentioned, and the structures of particularly typical ones are shown below.
C,H。C, H.
感光体の構成は種々の形態が知られている。本発明の感
光体はそれらのいずれの形態をもとりうるが、積層型も
しくは分散型の機能分離型感光体とするのが望ましい。Various configurations of photoreceptors are known. Although the photoreceptor of the present invention can take any of these forms, it is preferably a layered or dispersed functionally separated photoreceptor.
この場合、通常は第1図から第6図のような構成となる
。第1図に示す層構成は、導電性支持体l上にキャリア
発生層2を形成し、これにキャリア輸送層3を積層して
感光層4を形成したものであり、第2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る。第3図は第1図の層構成の感光
層4と導電性支持体lの間に中間層5を設け、第4図は
第2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を設けたものである。第5図の層構成はキャリ
ア発生物質6とキャリア輸送物質7を含有する感光層4
″を形成したものであり、第6図はこのような感光層4
″と導電性支持体lとの間に中間層5を設けたものであ
る。In this case, the configuration is usually as shown in FIGS. 1 to 6. The layer structure shown in FIG. 1 is such that a carrier generation layer 2 is formed on a conductive support l, and a carrier transport layer 3 is laminated thereon to form a photosensitive layer 4. Photosensitive layer 4' with carrier generation layer 2 and carrier transport layer 3 reversed
was formed. 3, an intermediate layer 5 is provided between the photosensitive layer 4 and the conductive support l having the layer structure shown in FIG. 1, and FIG. 4 shows the photosensitive layer 4' and the conductive support l having the layer structure shown in FIG. An intermediate layer 5 is provided between the two. The layer structure shown in FIG. 5 is a photosensitive layer 4 containing a carrier-generating substance 6 and a carrier-transporting substance 7.
'', and FIG. 6 shows such a photosensitive layer 4.
An intermediate layer 5 is provided between the conductive support l and the conductive support l.
感光層の形成においては、キャリア発生物質或いはキャ
リア輸送物質を単独で、もしくはバインダや添加剤とと
もに溶解させた溶液を塗布する方法が有効である。しか
しまた、一般にキャリア発生物質の溶解度は低いため、
そのような場合キャリア発生物質を、超音波分散機、ボ
ールミル、サンドミル、ホモミキサー等の分散装置を用
いて適当な分散媒中に微粒子分散させた液を塗布する方
法が有効となる。この場合、バインダや添加剤は分散液
中に添加して用いられるのが通常である。In forming the photosensitive layer, it is effective to apply a solution in which a carrier-generating substance or a carrier-transporting substance is dissolved alone or together with a binder or an additive. However, because the solubility of carrier-generating substances is generally low,
In such a case, it is effective to apply a solution in which fine particles of a carrier-generating substance are dispersed in a suitable dispersion medium using a dispersion device such as an ultrasonic dispersion machine, a ball mill, a sand mill, or a homomixer. In this case, the binder and additives are usually added to the dispersion.
感光層の形成に使用される溶剤或いは分散媒としては広
く任意のものを用いることができる。例えばブチルアミ
ン、エチレンジアミン、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、
テトラヒドロフラン、ジオキサン、酢酸エチル、酢酸ブ
チル、メチルセルソルブ、エチルセルソルブ、エチレン
グリコールジメチルエーテル、トルエン、キシレン、ア
セトフェノン、クロロホルム、ジクロルメタン、ジクロ
ルエタン、トリクロルエタン、メタノール、エタノール
、クロルノール、ブタノール等が挙げられる。A wide variety of solvents or dispersion media can be used to form the photosensitive layer. For example, butylamine, ethylenediamine, N,N-dimethylformamide, acetone, methyl ethyl ketone, cyclohexanone,
Examples include tetrahydrofuran, dioxane, ethyl acetate, butyl acetate, methyl cellosolve, ethyl cellosolve, ethylene glycol dimethyl ether, toluene, xylene, acetophenone, chloroform, dichloromethane, dichloroethane, trichloroethane, methanol, ethanol, chloronol, butanol, and the like.
キャリア発生層も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、バインダとして任意のものを選ぶこ
とができるが、特に疎水性でかつフィルム形成能を有す
る高分子重合体が望ましい。When a binder is used to form a carrier generation layer or a carrier transport layer, any binder can be selected as the binder, but a hydrophobic polymer having film-forming ability is particularly desirable.
このような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、これらに限定されるものではない。Examples of such polymers include, but are not limited to, the following:
ポリカーボネート ポリカーボネートZ樹脂ア
クリル樹脂 メタクリル樹脂ポリ塩化ビニ
ル ポリ塩化ビニリデンポリスチレン
スチレン−ブタジェン共重合体ポリ酢酸ビニル
ポリビニルホルマールポリビニルブチラー
ル ポリビニルアセタールポリビニルカルバゾール
スチレン−アルキッド樹脂シリコーン樹脂
シリコーン−アルキッド樹脂ポリエステル
フェノール樹脂ポリウレタン エポ
キシ樹脂塩化ビニリデン−アクリロニトリル共重合体塩
化ビニル−酢酸ビニル共重合体。Polycarbonate Polycarbonate Z resin Acrylic resin Methacrylic resin Polyvinyl chloride Polyvinylidene chloride Polystyrene
Styrene-butadiene copolymer polyvinyl acetate polyvinyl formal polyvinyl butyral polyvinyl acetal polyvinyl carbazole styrene-alkyd resin silicone resin
Silicone-alkyd resin polyester
Phenolic resin polyurethane Epoxy resin Vinylidene chloride-acrylonitrile copolymer Vinyl chloride-vinyl acetate copolymer.
塩化ビニル−酢酸ビニル−無水マレイン酸共重合体バイ
ンダに対するキャリア発生物質の割合は10〜600%
が望ましく、さらには50〜400wt%が好ましい。The ratio of the carrier generating substance to the vinyl chloride-vinyl acetate-maleic anhydride copolymer binder is 10 to 600%.
is desirable, and more preferably 50 to 400 wt%.
バインダに対するキャリア輸送物質の割合は10〜50
0w t%とするのが望ましい。キャリア発生層の厚さ
は0.01〜20μmとされるが、さらには0.05〜
5μmが好ましい。キャリア輸送層の厚みは1〜100
μmであるが、さらには5〜30μ−が好ましい。The ratio of carrier transport substance to binder is 10-50
It is desirable to set it to 0wt%. The thickness of the carrier generation layer is 0.01 to 20 μm, and more preferably 0.05 to 20 μm.
5 μm is preferred. The thickness of the carrier transport layer is 1 to 100
The thickness is preferably 5 to 30 μm.
上記感光層には感度の向上や残留電位の減少、或いは反
復使用時の疲労の低減を目的として、電子受容性物質を
含有させることができる。このような電子受容性物質と
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
、テトラブロム無水フタル酸、3−ニトロ無水フタル酸
、4−ニトロ無水7タル酸、無水ピロメリット酸、無水
メリット酸、テトラシアノエチレン、テトラシアノキノ
ジメタン、0−ジニトロベンゼン、m−ジニトロベンゼ
ン、1,3.5−トリニトロベンゼン、p−ニトロベン
ゾニトリル、ビクリルクロライド、キノンクロルイミド
、クロラニル、クロラニル、ジクロルジシアノ−p−ベ
ンゾキノン、アントラキノン、ジニトロアントラキノン
、9−フルオレニリデンマロノジニトリル、ポリニトロ
−9−フルオレニリデンマロノジニトリル、ピクリン酸
、0−ニトロ安息香酸、p−ニトロ安息香酸、3,5−
ジニトロ安息香酸、ペンタフルオル安息香酸、5−ニト
ロサリチル酸、3.5−ジニトロサリチル酸、7タル酸
、メリット厳、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。電子受容性物質の添加割合はキャリ
ア発生物質の重量100に対して0.01〜200が望
ましく、さらには0.1〜【00が好ましい。The photosensitive layer may contain an electron-accepting substance for the purpose of improving sensitivity, reducing residual potential, or reducing fatigue during repeated use. Examples of such electron-accepting substances include succinic anhydride, maleic anhydride, dibromo succinic anhydride, phthalic anhydride, tetrachlorophthalic anhydride, tetrabromo phthalic anhydride, 3-nitro-phthalic anhydride, 4-nitro-7 Talic acid, pyromellitic anhydride, mellitic anhydride, tetracyanoethylene, tetracyanoquinodimethane, 0-dinitrobenzene, m-dinitrobenzene, 1,3.5-trinitrobenzene, p-nitrobenzonitrile, vicryl chloride , quinone chlorimide, chloranil, chloranil, dichlordicyano-p-benzoquinone, anthraquinone, dinitroanthraquinone, 9-fluorenylidenemalonodinitrile, polynitro-9-fluorenylidenemalonodinitrile, picric acid, 0-nitrobenzoic acid , p-nitrobenzoic acid, 3,5-
Examples include dinitrobenzoic acid, pentafluorobenzoic acid, 5-nitrosalicylic acid, 3.5-dinitrosalicylic acid, heptatalic acid, Merritt, and other compounds with high electron affinity. The addition ratio of the electron-accepting substance is desirably 0.01 to 200, more preferably 0.1 to 0.00, per 100 of the weight of the carrier generating substance.
まI;、上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。そのような目的に用い
られる化合物として例えば、トコフェロール等のタロマ
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、ポリアリールアルカン化合物、ハイドロキ
ノンNi体及びそのモノ及びジエーテル化化合物、ベン
ゾフェノン誘導体、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、
フェニレンジアミン誘導体、フェノール化合物、ヒンダ
ードフェノール化合物、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としては、rlRGANOX
l0IOJ 、 rlRGANOX565J (チバ
・ガイギー社製)、[スミライザーBHT」、[スミラ
イザーMDPJ (住良化学工業社製)等のヒンダード
フェノール化合物、「サノールLS−2626J 、
rサノールLS−622LDJ (三共社製)等のヒン
ダードアミン化合物が挙げられる。中間層、保護層等に
用いられるバインダとしては、上記のキャリア発生層及
びキャリア輸送層用に挙げたものを用いることができる
が、その他にポリアミド樹脂、ナイロン樹脂、エチレン
−酢酸ビニル共重合体、エチレン−酢酸ビニル−無水マ
レイン酸共重合体、エチレン−酢酸ビニル−メタクリル
酸共重合体等のエチレン系樹脂、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。Also, deterioration inhibitors such as antioxidants and light stabilizers can be contained in the photosensitive layer for the purpose of improving storage stability, durability, and environmental dependence resistance. Compounds used for such purposes include, for example, talomanol derivatives such as tocopherol and their etherified or esterified compounds, polyarylalkane compounds, hydroquinone Ni forms and their mono- and dietherized compounds, benzophenone derivatives, benzotriazole derivatives, and thioethers. compounds, phosphonic acid esters, phosphorous esters,
Effective examples include phenylenediamine derivatives, phenol compounds, hindered phenol compounds, linear amine compounds, cyclic amine compounds, and hindered amine compounds. Specific examples of particularly effective compounds include rlRGANOX
Hindered phenol compounds such as l0IOJ, rlRGANOX565J (manufactured by Ciba Geigy), [Sumilizer BHT], [Sumilizer MDPJ (manufactured by Sumira Chemical Industries, Ltd.), "Sanol LS-2626J,
Examples include hindered amine compounds such as rSanol LS-622LDJ (manufactured by Sankyo Co., Ltd.). As the binder used for the intermediate layer, protective layer, etc., those listed for the carrier generation layer and carrier transport layer can be used, but in addition, polyamide resin, nylon resin, ethylene-vinyl acetate copolymer, Ethylene resins such as ethylene-vinyl acetate-maleic anhydride copolymer and ethylene-vinyl acetate-methacrylic acid copolymer, polyvinyl alcohol, cellulose derivatives, and the like are effective.
導電性支持体としては、金属板、金属ドラムが用いられ
る他、導電性ポリマーや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、パラジウム等の金属の薄層
を塗布、蒸着、ラミネート等の手段により紙やプラスチ
ックフィルムなどの基体の上に設けてなるものを用いる
ことができる。As the conductive support, a metal plate or a metal drum is used, or a thin layer of a conductive polymer, a conductive compound such as indium oxide, or a metal such as aluminum or palladium is coated on paper by means such as coating, vapor deposition, or lamination. It is possible to use a substrate provided on a substrate such as a plastic film or a plastic film.
本発明の感光体は以上のような構成であって、以下の実
施例からも明かなように、帯電特性、感度特性、繰返し
特性に優れたものである。The photoreceptor of the present invention has the above-mentioned structure, and as is clear from the following examples, it has excellent charging characteristics, sensitivity characteristics, and repeatability characteristics.
(合成例1)
フタロジニトリル65gとα−クロルナフタレン500
mQの混合物中に窒素気流下で14.7m12の四塩化
チタンを滴下した後、徐々に200°Cまで昇温し、反
応温度を200°C〜220℃の間に保って3時間撹拌
して反応を完結させた。その後放冷し130℃になった
ところで熱時濾過し、a−クロルナフタレンで洗浄した
後、メタノールで数回洗浄しさらに80℃の熱水で数回
洗浄した。得られた結晶を乾燥し、その5gを96%硫
酸long中で3〜5℃で撹拌した徒、濾過して、得ら
れた硫酸溶液を水1,5リットル中に注いだ。析出した
結晶を濾取し、洗浄液が中性となるまで水洗を繰返した
後、150m4のメチルセロソルブを加えて50°C〜
70℃の温度で20時間ミリングを行った。続いて分散
媒を除去し、アセトン、メタノールで洗浄した後、乾燥
して本発明の結晶を得た。この結晶は第7図に示すよう
にブラッグ角2θの6.8゜、9.7゜、 15.4°
に特徴的なピークを示した。(Synthesis Example 1) 65 g of phthalodinitrile and 500 g of α-chlornaphthalene
After dropping 14.7 mL of titanium tetrachloride into the mQ mixture under a nitrogen stream, the temperature was gradually raised to 200 °C, and the reaction temperature was maintained between 200 °C and 220 °C and stirred for 3 hours. The reaction was completed. Thereafter, it was allowed to cool, and when the temperature reached 130°C, it was filtered while hot, washed with a-chlornaphthalene, washed several times with methanol, and further washed several times with hot water at 80°C. The obtained crystals were dried, 5 g of them were stirred in a long glass of 96% sulfuric acid at 3 to 5°C, filtered, and the obtained sulfuric acid solution was poured into 1.5 liters of water. The precipitated crystals were collected by filtration, washed with water repeatedly until the washing solution became neutral, and then 150 m4 of methyl cellosolve was added and heated at 50°C.
Milling was carried out at a temperature of 70°C for 20 hours. Subsequently, the dispersion medium was removed, washed with acetone and methanol, and then dried to obtain crystals of the present invention. As shown in Figure 7, this crystal has Bragg angles of 2θ of 6.8°, 9.7°, and 15.4°.
showed a characteristic peak.
(比較合成例1)
合成例1の硫酸処理によって得られたチタニルフタロシ
アニン5gを150mQのジメチルスルホキシド中、1
50°Cの温度で8時間加熱処理を行なった。このよう
にして得られた結晶は第8図に示すようにブラッグ角度
2θの6.8゜、 15.5゜、 23.4゜、25.
4°にピークを示した。(Comparative Synthesis Example 1) 5 g of titanyl phthalocyanine obtained by the sulfuric acid treatment in Synthesis Example 1 was dissolved in 150 mQ of dimethyl sulfoxide.
Heat treatment was performed at a temperature of 50°C for 8 hours. The thus obtained crystals have Bragg angles of 2θ of 6.8°, 15.5°, 23.4°, and 25°, as shown in FIG.
A peak was observed at 4°.
(比較合成例2)
合成例1の硫酸処理によって得られたチタニルフタロシ
アニン5gに150o+12のメタノールを加え撹拌し
ながら8時間加熱還流処理を行なった。このようにして
得られた結晶は第9図に示すようにブラッグ角2θの6
.9゜、 15.5゜、 23.4’にピークを示し
tこ 。(Comparative Synthesis Example 2) 150°+12 methanol was added to 5 g of titanyl phthalocyanine obtained by the sulfuric acid treatment in Synthesis Example 1, and the mixture was heated under reflux for 8 hours with stirring. The crystal thus obtained has a Bragg angle of 2θ of 6 as shown in FIG.
.. Showing peaks at 9°, 15.5°, and 23.4'
tko.
(実施例1)
合成例1において得られた第7図のX線回折パターンを
有するチタニルフタロシアニン3部、バインダ樹脂とし
てシリコーン樹脂(rKR−5240,15%キシレン
ブタノール溶液」信越化学社製)2部m、分散媒として
、メチルエチルケトン100部ヲサンドミルを用いて分
散し、これをアルミニウムを蒸着したポリエステルベー
ス上にワイヤバーヲ用いて塗布して、膜厚0.2μmの
キャリア発生層を形成した。次いで、キャリア輸送物質
lの1部とポリカーボネート樹脂「ニーピロンZ200
J (三菱瓦斯化学社11)1.3部及び微量のシリコ
ーンオイルrKF−54J (信越化学社製)を、l、
2−ジクロルエタン10部に溶解した液をブレード塗布
機を用いて塗布し乾燥の後、膜厚20μmのキャリア輸
送層を形成した。このようにして得られた感光体をサン
プルlとする。(Example 1) 3 parts of titanyl phthalocyanine having the X-ray diffraction pattern shown in FIG. 7 obtained in Synthesis Example 1, 2 parts of silicone resin (rKR-5240, 15% xylene butanol solution, manufactured by Shin-Etsu Chemical Co., Ltd.) as a binder resin. As a dispersion medium, 100 parts of methyl ethyl ketone was dispersed using a sand mill, and this was applied onto a polyester base coated with aluminum using a wire bar to form a carrier generation layer having a thickness of 0.2 μm. Next, one part of the carrier transport substance and polycarbonate resin "Nipilon Z200" were added.
1.3 parts of J (Mitsubishi Gas Chemical Co., Ltd. 11) and a trace amount of silicone oil rKF-54J (manufactured by Shin-Etsu Chemical Co., Ltd.),
A solution dissolved in 10 parts of 2-dichloroethane was applied using a blade coater, and after drying, a carrier transport layer having a thickness of 20 μm was formed. The photoreceptor thus obtained is referred to as sample 1.
(比較例1)
実施例1における、第7図のチタニルフタロシアニンを
比較合成例2で得た第8図のX線回折パターンを持つ比
較のチタニルフタロシアニンに代えた他は実施例1と同
様にして比較用の感光体を得た。これを比較サンプル(
1)とする。(Comparative Example 1) The same procedure as in Example 1 was carried out except that the titanyl phthalocyanine shown in FIG. 7 in Example 1 was replaced with the comparative titanyl phthalocyanine having the X-ray diffraction pattern shown in FIG. A photoreceptor for comparison was obtained. This is a comparison sample (
1).
(比較例2)
実施例1における、第7図のチタニルフタロンアニンを
比較合成例3で得た第9図のX線回折パターンを持つ比
較のチタニルフタロシアニンに代えた他は実施例1と同
様にして比較用の感光体を得た。これを比較サンプル(
2)とする。(Comparative Example 2) Same as Example 1 except that the titanyl phthalonanine shown in FIG. 7 in Example 1 was replaced with the comparative titanyl phthalocyanine having the X-ray diffraction pattern shown in FIG. 9 obtained in Comparative Synthesis Example 3. A comparative photoreceptor was obtained. This is a comparison sample (
2).
(評価l)
以上のようにして得られたサンプルは、ベーパアナライ
ザーEPA−8100(川口電気社製)を用いて、以下
のような評価を行った。まず、−80μへの条件で5秒
間のコロナ帯電を行い、帯電直後の表面電位Va及び、
5秒間放置後の表面電位Viを求め、続いて表面照度が
21uxとなるような露光を行ない、表面電位を1/2
Viとするのに必要な露光*E+yz表面電位を一60
0vから一100Vまで低下させるのに必要な露光量E
@Go/lGoを求めた。又D = 100(Va−
Vi)/ Va(%)の式より暗減衰率りを求めた。結
果は表1に示した。(Evaluation 1) The sample obtained as described above was evaluated as follows using a vapor analyzer EPA-8100 (manufactured by Kawaguchi Electric Co., Ltd.). First, corona charging was performed for 5 seconds under the condition of -80μ, and the surface potential Va immediately after charging was
Determine the surface potential Vi after leaving it for 5 seconds, then perform exposure so that the surface illuminance is 21ux, and reduce the surface potential to 1/2.
Exposure required to make Vi * E + yz surface potential - 60
Exposure amount E required to lower the voltage from 0V to -100V
@Go/lGo was calculated. Also, D = 100 (Va-
The dark decay rate was determined from the formula Vi)/Va (%). The results are shown in Table 1.
(評価2)
得られたサンプルは又、プリンタLP−3010(コニ
カ社tS)に半導体レーザ光源を装着した改造機を用い
て評価した。未露光部電位v14、露光部電位vLを求
め、さらに1万回繰返しの後でのV8とvLを求めた。(Evaluation 2) The obtained sample was also evaluated using a modified printer LP-3010 (Konica tS) equipped with a semiconductor laser light source. The unexposed area potential v14 and the exposed area potential vL were determined, and V8 and vL after repeating 10,000 times were determined.
結果は表2に示した。The results are shown in Table 2.
表 1
表 2
実施例(2)
アルミニウムドラム上に、塩化ビニル−酢酸ビニル−無
水マレイン酸共重合体[エスレック MFiOJ(It
水化学社製)からなる厚さ0.1.unの中間層を形成
した。一方、合成例1で得た第7図のチタニルフタロシ
アニン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 −1250J3部、モノクロ
ルベンゼン 15部、l、2−ジクロルエタン35部の
液を加えて分散を行った。得られた分散液に、さらにキ
ャリア輸送物質lの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。Table 1 Table 2 Example (2) Vinyl chloride-vinyl acetate-maleic anhydride copolymer [S-LEC MFiOJ (It
(manufactured by Suikagaku Co., Ltd.) with a thickness of 0.1. An intermediate layer of un was formed. On the other hand, 1 part of the titanyl phthalocyanine shown in Figure 7 obtained in Synthesis Example 1 was ground in a ball mill, and then a solution of 3 parts of polycarbonate resin "Panlite L-1250J, 15 parts of monochlorobenzene, and 35 parts of l,2-dichloroethane was added. Dispersion was carried out. 2 parts of the carrier transport substance 1 was further added to the obtained dispersion, and the mixture was applied onto the intermediate layer by spray coating and dried to form a photosensitive layer with a thickness of 20 μm. did.
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 1500 (V)
Vi =l160 (V)
D −22,7(%)
E l/2 −1.42 (Iux+5ec)E
@00/+00−4−09 C1ux#5ec)以上
の実施例から明らかなように本発明の電子写真感光体は
高感度でかつ帯電性に優れ、また繰返し使用時の電位安
定性に優れていることが判る。Va 1500 (V) Vi =l160 (V) D -22,7(%) E l/2 -1.42 (Iux+5ec)E
@00/+00-4-09 C1ux#5ec) As is clear from the above examples, the electrophotographic photoreceptor of the present invention has high sensitivity and excellent chargeability, and also has excellent potential stability during repeated use. I understand that.
第1図〜第6図は本発明の感光体の層構成の具体例を示
しt;各断面図である。
第7図は合成例1によって得られる本発明のチタニルフ
タロシアニンのX線回折図、第8図、第9図はそれぞれ
比較合成例11比較合成例2で得られるナタニルフタロ
ンアニンのX線回折図である。
1−一一一導電性支持体
2−一一一キャリア発生層
3−一−−キャリア輸送層
4.4 ’、4“−−m−感光層
5−−一中間層FIGS. 1 to 6 are cross-sectional views showing specific examples of the layer structure of the photoreceptor of the present invention. FIG. 7 is an X-ray diffraction diagram of titanyl phthalocyanine of the present invention obtained in Synthesis Example 1, and FIGS. 8 and 9 are X-ray diffraction diagrams of natanyl phthalonanine obtained in Comparative Synthesis Example 11 and Comparative Synthesis Example 2, respectively. It is. 1-111 conductive support 2-111 carrier generation layer 3-1-carrier transport layer 4.4', 4''--m-photosensitive layer 5--1 intermediate layer
Claims (1)
ペクトルにおいて、ブラック角2θの6.8゜±0.2
゜、9.7゜±0.2゜、15.4゜±0.2゜にピー
クを有するチタニルフタロシアニンを含有することを特
徴とする電子写真感光体。In the X-ray diffraction spectrum for Cu-Kα rays (wavelength 1.541 Å), the Black angle 2θ is 6.8° ± 0.2
1. An electrophotographic photoreceptor comprising titanyl phthalocyanine having peaks at 15.4°±0.2°, 9.7°±0.2°, and 15.4°±0.2°.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP11984489A JPH02297560A (en) | 1989-05-11 | 1989-05-11 | Electrophotographic sensitive body |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP11984489A JPH02297560A (en) | 1989-05-11 | 1989-05-11 | Electrophotographic sensitive body |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH02297560A true JPH02297560A (en) | 1990-12-10 |
Family
ID=14771664
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP11984489A Pending JPH02297560A (en) | 1989-05-11 | 1989-05-11 | Electrophotographic sensitive body |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH02297560A (en) |
-
1989
- 1989-05-11 JP JP11984489A patent/JPH02297560A/en active Pending
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