JPH04371962A - Electrophotographic sensitive body - Google Patents
Electrophotographic sensitive bodyInfo
- Publication number
- JPH04371962A JPH04371962A JP14872991A JP14872991A JPH04371962A JP H04371962 A JPH04371962 A JP H04371962A JP 14872991 A JP14872991 A JP 14872991A JP 14872991 A JP14872991 A JP 14872991A JP H04371962 A JPH04371962 A JP H04371962A
- Authority
- JP
- Japan
- Prior art keywords
- crystal
- phthalocyanine
- layer
- titanyl phthalocyanine
- mixed
- 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
- 239000013078 crystal Substances 0.000 claims abstract description 114
- 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 43
- YRZZLAGRKZIJJI-UHFFFAOYSA-N oxyvanadium phthalocyanine Chemical compound [V+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 YRZZLAGRKZIJJI-UHFFFAOYSA-N 0.000 claims abstract description 31
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000000049 pigment Substances 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 125000003367 polycyclic group Chemical group 0.000 claims abstract description 12
- 125000005843 halogen group Chemical group 0.000 claims abstract description 6
- 125000002252 acyl group Chemical group 0.000 claims abstract description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 4
- 125000004093 cyano group Chemical group *C#N 0.000 claims abstract description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims abstract description 4
- 108091008695 photoreceptors Proteins 0.000 claims description 44
- 239000000126 substance Substances 0.000 claims description 33
- 230000035945 sensitivity Effects 0.000 abstract description 25
- 239000000463 material Substances 0.000 abstract description 19
- 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 17
- 239000010410 layer Substances 0.000 description 53
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 27
- 230000015572 biosynthetic process Effects 0.000 description 20
- 238000003786 synthesis reaction Methods 0.000 description 17
- 238000000034 method Methods 0.000 description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 14
- 229920005989 resin Polymers 0.000 description 13
- 239000011347 resin Substances 0.000 description 13
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 9
- -1 polycyclic quinone compounds Chemical class 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 238000001228 spectrum Methods 0.000 description 9
- 238000007600 charging Methods 0.000 description 8
- 239000011230 binding agent Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000010586 diagram Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000011282 treatment Methods 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 230000004888 barrier function Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000010408 film Substances 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 230000003595 spectral effect Effects 0.000 description 5
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- JTPNRXUCIXHOKM-UHFFFAOYSA-N 1-chloronaphthalene Chemical compound C1=CC=C2C(Cl)=CC=CC2=C1 JTPNRXUCIXHOKM-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-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
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 206010034972 Photosensitivity reaction Diseases 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
- 239000012790 adhesive layer Substances 0.000 description 3
- 229920000180 alkyd Polymers 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000003618 dip coating Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000003801 milling Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 230000036211 photosensitivity Effects 0.000 description 3
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000011241 protective layer Substances 0.000 description 3
- 238000011160 research Methods 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
- 238000000926 separation method Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- UBOXGVDOUJQMTN-UHFFFAOYSA-N 1,1,2-trichloroethane Chemical compound ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- RZVCEPSDYHAHLX-UHFFFAOYSA-N 3-iminoisoindol-1-amine Chemical compound C1=CC=C2C(N)=NC(=N)C2=C1 RZVCEPSDYHAHLX-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-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
- ZTWQZJLUUZHJGS-UHFFFAOYSA-N Vat Yellow 4 Chemical compound C12=CC=CC=C2C(=O)C2=CC=C3C4=CC=CC=C4C(=O)C4=C3C2=C1C=C4 ZTWQZJLUUZHJGS-UHFFFAOYSA-N 0.000 description 2
- 238000012644 addition polymerization Methods 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 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
- 238000004458 analytical method Methods 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 125000004104 aryloxy group Chemical group 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 238000007786 electrostatic charging Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- YAFKJTNZIHPYHC-UHFFFAOYSA-N phthalocyanine vanadyl Chemical group [V]=O.C12=CC=CC=C2C(N=C2NC(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2N1 YAFKJTNZIHPYHC-UHFFFAOYSA-N 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 238000012643 polycondensation polymerization Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- LLBIOIRWAYBCKK-UHFFFAOYSA-N pyranthrene-8,16-dione Chemical compound C12=CC=CC=C2C(=O)C2=CC=C3C=C4C5=CC=CC=C5C(=O)C5=C4C4=C3C2=C1C=C4C=C5 LLBIOIRWAYBCKK-UHFFFAOYSA-N 0.000 description 2
- WVIICGIFSIBFOG-UHFFFAOYSA-N pyrylium Chemical class C1=CC=[O+]C=C1 WVIICGIFSIBFOG-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 229920002050 silicone resin Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- SJHPCNCNNSSLPL-CSKARUKUSA-N (4e)-4-(ethoxymethylidene)-2-phenyl-1,3-oxazol-5-one Chemical class O1C(=O)C(=C/OCC)\N=C1C1=CC=CC=C1 SJHPCNCNNSSLPL-CSKARUKUSA-N 0.000 description 1
- FSJSYDFBTIVUFD-SUKNRPLKSA-N (z)-4-hydroxypent-3-en-2-one;oxovanadium Chemical compound [V]=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FSJSYDFBTIVUFD-SUKNRPLKSA-N 0.000 description 1
- MFWFDRBPQDXFRC-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;vanadium Chemical compound [V].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O MFWFDRBPQDXFRC-LNTINUHCSA-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
- KNKRKFALVUDBJE-UHFFFAOYSA-N 1,2-dichloropropane Chemical compound CC(Cl)CCl KNKRKFALVUDBJE-UHFFFAOYSA-N 0.000 description 1
- VZXTWGWHSMCWGA-UHFFFAOYSA-N 1,3,5-triazine-2,4-diamine Chemical compound NC1=NC=NC(N)=N1 VZXTWGWHSMCWGA-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-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
- 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
- BIEFDNUEROKZRA-UHFFFAOYSA-N 2-(2-phenylethenyl)aniline Chemical class NC1=CC=CC=C1C=CC1=CC=CC=C1 BIEFDNUEROKZRA-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-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
- 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
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 102100025474 Carcinoembryonic antigen-related cell adhesion molecule 7 Human genes 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
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- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 101000914321 Homo sapiens Carcinoembryonic antigen-related cell adhesion molecule 7 Proteins 0.000 description 1
- WZELXJBMMZFDDU-UHFFFAOYSA-N Imidazol-2-one Chemical class O=C1N=CC=N1 WZELXJBMMZFDDU-UHFFFAOYSA-N 0.000 description 1
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- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
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- 150000007513 acids Chemical class 0.000 description 1
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- PGEHNUUBUQTUJB-UHFFFAOYSA-N anthanthrone Chemical compound C1=CC=C2C(=O)C3=CC=C4C=CC=C5C(=O)C6=CC=C1C2=C6C3=C54 PGEHNUUBUQTUJB-UHFFFAOYSA-N 0.000 description 1
- RJGDLRCDCYRQOQ-UHFFFAOYSA-N anthrone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3CC2=C1 RJGDLRCDCYRQOQ-UHFFFAOYSA-N 0.000 description 1
- 229940058303 antinematodal benzimidazole derivative Drugs 0.000 description 1
- 229940027998 antiseptic and disinfectant acridine derivative Drugs 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 230000008901 benefit 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
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010549 co-Evaporation Methods 0.000 description 1
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- 150000001907 coumarones Chemical class 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000009837 dry grinding Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 150000002461 imidazolidines Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 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
- 239000012442 inert solvent Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229940079865 intestinal antiinfectives imidazole derivative Drugs 0.000 description 1
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 1
- 229940102253 isopropanolamine Drugs 0.000 description 1
- 229940011051 isopropyl acetate Drugs 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-M isovalerate Chemical compound CC(C)CC([O-])=O GWYFCOCPABKNJV-UHFFFAOYSA-M 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 208000013469 light sensitivity Diseases 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 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
- 239000002245 particle Substances 0.000 description 1
- 125000001791 phenazinyl group Chemical class C1(=CC=CC2=NC3=CC=CC=C3N=C12)* 0.000 description 1
- JYIZNFVTKLARKT-UHFFFAOYSA-N phenol;1,3,5-triazine-2,4,6-triamine Chemical compound OC1=CC=CC=C1.NC1=NC(N)=NC(N)=N1 JYIZNFVTKLARKT-UHFFFAOYSA-N 0.000 description 1
- XQZYPMVTSDWCCE-UHFFFAOYSA-N phthalonitrile Chemical compound N#CC1=CC=CC=C1C#N XQZYPMVTSDWCCE-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 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
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000010298 pulverizing process Methods 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
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000010187 selection method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 125000005504 styryl group Chemical class 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 229940042055 systemic antimycotics triazole derivative Drugs 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
- 239000010409 thin film Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は電子写真感光体に関し、
特に光導電性材料として特定の結晶型を有するチタニル
フタロシアニンとバナジルフタロシアニンの混晶を用い
、プリンタ、複写機等に有効であって、かつ露光手段と
して半導体レーザ光及びＬＥＤ光等を用いて像形成を行
うときにも好適な電子写真感光体に関する。[Industrial Application Field] The present invention relates to an electrophotographic photoreceptor.
In particular, a mixed crystal of titanyl phthalocyanine and vanadyl phthalocyanine having a specific crystal type is used as a photoconductive material, and it is effective for printers, copiers, etc., and image formation is performed using semiconductor laser light, LED light, etc. as an exposure means. The present invention relates to an electrophotographic photoreceptor suitable also for carrying out.
【０００２】0002
【従来技術】近年、光導電性材料の研究が盛んに行われ
ており、電子写真感光体をはじめとして太陽電池、イメ
ージセンサなどの光電変換素子として応用されている。BACKGROUND OF THE INVENTION In recent years, research on photoconductive materials has been actively conducted, and they are being applied as photoelectric conversion elements such as electrophotographic photoreceptors, solar cells, and image sensors.
【０００３】従来、これらの光導電性材料には主として
無機系の材料が用いられ、例えば電子写真感光体におい
てはセレン、酸化亜鉛、硫化カドミウム等の無機光導電
性材料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。Conventionally, inorganic materials have been mainly used as these photoconductive materials. For example, in electrophotographic photoreceptors, photosensitive layers mainly composed of inorganic photoconductive materials such as selenium, zinc oxide, and cadmium sulfide have been used. Inorganic photoreceptors have been widely used.
【０００４】しかしながら、このような無機感光体は、
複写機、プリンタ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た。例えばセレンは熱
や指紋の汚れ等により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。また、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、また、
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
。[0004] However, such inorganic photoreceptors are
The properties required for electrophotographic photoreceptors for copying machines, printers, etc., such as photosensitivity, thermal stability, moisture resistance, and durability, have not always been satisfactory. For example, selenium crystallizes due to heat, fingerprint stains, etc., so its properties as an electrophotographic photoreceptor tend to deteriorate. Additionally, electrophotographic photoreceptors using cadmium sulfide have poor moisture resistance and durability;
Electrophotographic photoreceptors using zinc oxide also have durability problems.
【０００５】更に近年、環境問題が特に重要視されてい
るがセレン、硫化カドミウム等の電子写真感光体は毒性
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。Furthermore, in recent years, environmental issues have become particularly important, but electrophotographic photoreceptors made of selenium, cadmium sulfide, and the like have the disadvantage of being highly restricted in production and handling due to toxicity.
【０００６】このような無機光導電性材料の欠点を改善
するために種々の有機光導電性材料が注目されるように
なり、電子写真感光体の感光層等に使用することが試み
られるなど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。しかしながらこの感光体は感度
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。In order to improve the drawbacks of such inorganic photoconductive materials, various organic photoconductive materials have attracted attention, and in recent years, attempts have been made to use them in photosensitive layers of electrophotographic photoreceptors, etc. Research is being actively conducted. 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.
【０００７】このような電子写真感光体においては、材
料を広い範囲で選択できるので任意の特性を得やすく、
そのため高感度、高耐久の優れた有機感光体が得られる
ことが期待されている。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及びキャリア輸送物質とし
て種々の有機化合物が提案されているが、特にキャリア
発生物質は感光体の基本的な特性を支配する重要な機能
を担っている。そのキャリア発生物質としてはこれまで
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、ピリリウム化合物及びピリリウム化合物の共晶錯体
、スクエアリウム化合物、フタロシアニン化合物、アゾ
化合物などの光導電性物質が実用化されてきた。[0007] In such an electrophotographic photoreceptor, materials can be selected from a wide range, making it easy to obtain desired characteristics.
Therefore, it is expected that an excellent organic photoreceptor with high sensitivity and high durability can be obtained. Various organic compounds have been proposed as carrier-generating substances and carrier-transporting substances for such functionally separated electrophotographic photoreceptors, but carrier-generating substances in particular have important functions that control the basic characteristics of the photoreceptor. I am in charge. As carrier-generating substances, photoconductive substances such as polycyclic quinone compounds typified by dibromuanthanthrone, pyrylium compounds and eutectic complexes of pyrylium compounds, squarium compounds, phthalocyanine compounds, and azo compounds have been put into practical use. It's here.
【０００８】更に電子写真感光体により高い感度を与え
るためには高いキャリア発生効率を持つキャリア発生物
質も必要である。この点について近年、フタロシアニン
化合物は優れた光導電材料として注目され、活発に研究
が行われている。Furthermore, in order to provide higher sensitivity to an electrophotographic photoreceptor, a carrier-generating substance with high carrier-generating efficiency is also required. In this regard, in recent years, phthalocyanine compounds have attracted attention as excellent photoconductive materials, and active research is being conducted.
【０００９】フタロシアニン化合物は中心金属の種類や
結晶型の違いによりスペクトルや光導電性などの各種物
性が変化することが知られている。例えば、銅フタロシ
アニンにはα、β、γ、ε型の結晶型が存在し、これら
の結晶型が異なることにより電子写真特性に大きな差が
あることが報告されている（澤田 学、「染料と薬品
」、２４（６）、１２２（１９７９））。It is known that various physical properties of phthalocyanine compounds, such as spectra and photoconductivity, change depending on the type of central metal and the crystal type. For example, copper phthalocyanine has α, β, γ, and ε crystal forms, and it has been reported that there are large differences in electrophotographic properties depending on these crystal forms (Manabu Sawada, “Dye and Pharmaceuticals,” 24(6), 122 (1979)).
【００１０】また、近年特にチタニルフタロシアニンが
注目されているが、チタニルフタロシアニンについても
Ａ、Ｂ、Ｃ、Ｙ型と呼ばれる４つの主な結晶型が報告さ
れている。しかしながら特開昭６２−６７０９４号のＡ
型、特開昭６１−２３９２４８号記載のＢ型、特開昭６
２−２５６８６５号記載のＣ型チタニルフタロシアニン
は帯電性、電子写真感度ともに未だ不十分な点がある。
また最近発表されたＹ型チタニルフタロシアニン（織田
ら、「電子写真学会誌」、２９（３）、２５０、（１９
９０））は高感度であるが帯電性に関してはまだ不十分
な点もあり、帯電性が良好でかつ高感度なキャリア発生
物質の開発が望まれている。[0010] Furthermore, titanyl phthalocyanine has received particular attention in recent years, and four main crystal forms called A, B, C, and Y types have been reported for titanyl phthalocyanine as well. However, A of JP-A No. 62-67094
type, B type described in JP-A No. 61-239248, JP-A No. 6
The C-type titanyl phthalocyanine described in No. 2-256865 still has insufficient chargeability and electrophotographic sensitivity. In addition, recently announced Y-type titanyl phthalocyanine (Oda et al., "Journal of Electrophotography Society", 29(3), 250, (19
Although 90)) has high sensitivity, there are still some drawbacks in terms of chargeability, and it is desired to develop a carrier-generating substance with good chargeability and high sensitivity.
【００１１】また、バナジルフタロシアニンについても
数多くの報告が有るが感光体としては例えば特開平１−
２１７０７４号に記載されて有るチタニルフタロシアニ
ンのＢ型結晶に相当する結晶型や特開平１−２０４９６
８号に記載のＡ型に相当する結晶型を含んだ感光体が開
示されている。しかしこれらの結晶型では十分な感度は
得られない。更に特開平１−２６８７６３号にはチタニ
ルフタロシアニンの特開昭６２−６７０９４号の比較例
に記載されてある結晶型と類似のブラッグ角２θの２７
．２゜にピークを有する結晶型が記載されているが、こ
の結晶型も感度の点で不十分である。これはバナジルフ
タロシアニンもチタニルフタロシアニンと同様、単に２
７．２゜にピークを有する結晶は三次元的な結晶配列を
考えると９．５゜に明瞭なピークを有する高感度のチタ
ニルフタロシアニンのＹ型結晶の結晶配列とは異なって
いるためである。このようにバナジルフタロシアニンに
ついても高感度な特性の得られる結晶型は報告されてい
ないのが現状である。[0011] Furthermore, there are many reports on vanadyl phthalocyanine, but as a photoreceptor, for example,
Crystal type corresponding to type B crystal of titanyl phthalocyanine described in No. 217074 and JP-A-1-20496
A photoreceptor containing a crystal type corresponding to type A described in No. 8 is disclosed. However, these crystal forms do not provide sufficient sensitivity. Furthermore, in JP-A-1-268763, titanyl phthalocyanine has a Bragg angle of 2θ of 27, which is similar to the crystal type described in the comparative example of JP-A-62-67094.
．． Although a crystal form having a peak at 2° has been described, this crystal form is also insufficient in terms of sensitivity. This means that vanadyl phthalocyanine, like titanyl phthalocyanine, is simply 2
This is because, considering the three-dimensional crystal arrangement, the crystal having a peak at 7.2° is different from the highly sensitive Y-type crystal of titanyl phthalocyanine, which has a clear peak at 9.5°. As described above, at present, no crystal form of vanadyl phthalocyanine that provides highly sensitive characteristics has been reported.
【００１２】また、近年単一のフタロシアニンだけでな
く複数のフタロシアニンを用いて特定の結晶配列を形成
させるというフタロシアニンの混晶が報告されている。
この混晶は単なる複数のフタロシアニンの混合とは異な
り、混晶を形成することによって単一のフタロシアニン
とは異なった特性を得られるという利点がある。このフ
タロシアニンの混晶の例としては例えば特開平２−８４
６６１号には２種以上のフタロシアニンを気相状態を経
て基盤上に再凝集させるフタロシアニンの共蒸着による
混晶の形成が開示されている。しかしながらこれに開示
されている結晶型の銅フタロシアニンと無金属フタロシ
アニンの混晶やチタニルフタロシアニンと無金属フタロ
シアニンの混晶は感度が低いという問題がある。Furthermore, in recent years, mixed crystals of phthalocyanine have been reported in which not only a single phthalocyanine but also a plurality of phthalocyanines are used to form a specific crystal arrangement. This mixed crystal is different from a simple mixture of multiple phthalocyanines, and has the advantage that by forming a mixed crystal, properties different from those of a single phthalocyanine can be obtained. Examples of this phthalocyanine mixed crystal include, for example, JP-A-2-84
No. 661 discloses the formation of a mixed crystal by co-deposition of phthalocyanines, in which two or more phthalocyanines are re-agglomerated on a substrate through a gas phase. However, the mixed crystals of copper phthalocyanine and metal-free phthalocyanine and the mixed crystals of titanyl phthalocyanine and metal-free phthalocyanine disclosed therein have a problem of low sensitivity.
【００１３】また特開平２−７０７６３号に記載されて
いる蒸着によるチタニルフタロシアニンとバナジルフタ
ロシアニンの混晶はチタニルフタロシアニンのＡ型及び
Ｂ型に相当する結晶型を示している。しかしながらこれ
らの結晶型では感度の点で不十分である。このように混
晶においても要求される特性を満足するためには混晶を
構成するフタロシアニンの種類や結晶型の選択が重要で
ある。
そのためには材料の選択だけではなく特定の結晶型を得
るための結晶制御技術も重要で現在知られている蒸着に
よる混晶の形成方法以外の結晶変換技術の開発も望まれ
ている。しかし、このような長波長域に高感度を有する
電子写真感光体は、中波長域から短波長域での光感度が
十分ではなく、白色光源等を光源とする複写機能には対
応できなかった。Further, the mixed crystal of titanyl phthalocyanine and vanadyl phthalocyanine produced by vapor deposition as described in JP-A-2-70763 shows a crystal form corresponding to type A and type B of titanyl phthalocyanine. However, these crystal forms are insufficient in sensitivity. In order to satisfy the required characteristics even in a mixed crystal, it is important to select the type and crystal type of the phthalocyanine constituting the mixed crystal. To this end, not only the selection of materials but also crystal control technology to obtain a specific crystal type is important, and the development of crystal conversion technology other than the currently known method of forming mixed crystals by vapor deposition is also desired. However, such electrophotographic photoreceptors, which have high sensitivity in the long wavelength range, do not have sufficient photosensitivity in the medium to short wavelength range, and cannot support copying functions using white light sources as light sources. .
【００１４】可視光用電子写真感光体及び半導体レーザ
光用電子写真感光体は、それぞれ単独では比較的良好な
性能が得られているが、短波長域から長波長域まで幅広
く感度を有する感光体が求められている。[0014] Electrophotographic photoreceptors for visible light and electrophotographic photoreceptors for semiconductor laser light each have relatively good performance when used alone, but photoreceptors that have sensitivity over a wide range from short wavelength ranges to long wavelength ranges. is required.
【００１５】[0015]
【発明の目的】本発明の目的は、可視光から近赤外領域
に亘って高感度の分光感度特性を有し、プリンタ機能と
白色光を光源とする複写機能との両機能を備えた装置に
適用でき、かつ繰返し特性に優れている複写プロセスの
高速化に対応できるような感光体を提供することである
。[Object of the Invention] The object of the present invention is to provide an apparatus having high spectral sensitivity characteristics ranging from visible light to near infrared light, and having both a printer function and a copying function using white light as a light source. It is an object of the present invention to provide a photoreceptor that can be applied to high-speed copying processes that has excellent repeatability.
【００１６】[0016]
【課題を解決するための手段】本発明の目的は、導電性
支持体上に、電荷発生物質及び電荷輸送物質を含有する
感光層を設けてなる電子写真感光体において、電荷発生
物質としてＣｕＫα特性Ｘ線（波長１．５４１Å）に対
するブラッグ角２θの２７．２゜±０．２゜に主たる明
瞭なピークを有するチタニルフタロシアニンとバナジル
フタロシアニンの混晶を含有し、かつ下記一般式〔Ｑ〕
で表される化合物を含有することを特徴とする電子写真
感光体によって達成される。[Means for Solving the Problems] An object of the present invention is to provide an electrophotographic photoreceptor comprising a photosensitive layer containing a charge-generating substance and a charge-transporting substance on a conductive support. Contains a mixed crystal of titanyl phthalocyanine and vanadyl phthalocyanine that has a main clear peak at a Bragg angle 2θ of 27.2° ± 0.2° with respect to X-rays (wavelength 1.541 Å), and has the following general formula [Q]
This is achieved by an electrophotographic photoreceptor characterized by containing a compound represented by:
【００１７】[0017]
【化２】[Case 2]
【００１８】前記一般式群中、Ｘはハロゲン原子、ニト
ロ基、シアノ基、アシル基又はカルボキシル基を表し、
ｎは０〜４の整数を表し、ｍは０〜６の整数を表す。In the general formula group, X represents a halogen atom, a nitro group, a cyano group, an acyl group or a carboxyl group,
n represents an integer of 0 to 4, and m represents an integer of 0 to 6.
【００１９】以下、本発明を詳細に説明する。The present invention will be explained in detail below.
【００２０】本発明に用いられるフタロシアニンの混晶
について、まず混晶とは一般に２種またはそれ以上の物
質が混合し、均一な溶相となった結晶をつくる場合、そ
の結晶のことをいうが、明礬類に見られるような同形の
塩や結晶格子が類似、或いは原子半径のあまり違わない
金属間においては混晶が形成されることが知られている
。Regarding the mixed crystal of phthalocyanine used in the present invention, firstly, a mixed crystal generally refers to a crystal in which two or more substances are mixed to form a uniform solution phase. It is known that mixed crystals are formed between isomorphic salts such as those found in alums, metals with similar crystal lattices, or metals whose atomic radii do not differ much.
【００２１】本発明の結晶型をとるフタロシアニンの混
晶についても良く似た傾向が見られ、チタニルフタロシ
アニンと比較類似の構造のものが混晶を形成しやすい傾
向が見られた。チタニルフタロシアニンはＷ．Ｈｉｌｌ
ｅｒらによって結晶構造解析がなされており（Ｚ．Ｋｒ
ｉｓｔａｌｌｏｇｒ．，１５９，１７３（１９８２））
、その構造はＴｉ＝Ｏがフタロシアニン環の共役平面に
対して上方に突き出たような構造をしている。A very similar tendency was observed with the mixed crystals of phthalocyanine in the crystal form of the present invention, and those with a relatively similar structure to titanyl phthalocyanine tended to form mixed crystals. Titanyl phthalocyanine is a W. Hill
Crystal structure analysis has been carried out by Z. Kr et al.
istallogr. , 159, 173 (1982))
, its structure is such that Ti=O protrudes upward from the conjugation plane of the phthalocyanine ring.
【００２２】このチタニルフタロシアニンに対して例え
ば平面構造を有する無金属フタロシアニンとの間では結
晶純度の高い本発明の結晶型の混晶を得るのは困難で、
本発明の結晶型に他の結晶が混入してくるなどの問題が
生じ、性能低下の原因となりやすい。一方、バナジルフ
タロシアニンにおいても結晶構造解析がなされており（
Ｒ．Ｚｉｏｌｏ ｅｔ ａｌ．，Ｊ．Ｃｈｅｍ．Ｓｏｃ
．Ｄａｌｔｏｎ，２３００（１９８０））、チタニルフ
タロシアニンとはＴｉ＝Ｏ結合とＶ＝Ｏ結合にわずかに
違いはあるものの良く似た立体構造をとっていることが
報告されている。したがって、バナジルフタロシアニン
はチタニルフタロシアニンと混晶を形成するのに有利な
立体構造を有していると考えられ、実際にバナジルフタ
ロシアニンにおいて他のいくつかのフタロシアニンとは
異なり、本発明の結晶型の混晶を得ることができた。It is difficult to obtain a mixed crystal of the crystal type of the present invention with high crystal purity between titanyl phthalocyanine and metal-free phthalocyanine having a planar structure, for example.
Problems such as contamination of the crystal form of the present invention with other crystals occur, which tends to cause performance deterioration. On the other hand, crystal structure analysis has also been performed on vanadyl phthalocyanine (
R. Ziolo et al. , J. Chem. Soc.
．． Dalton, 2300 (1980)), it has been reported that titanyl phthalocyanine has a very similar three-dimensional structure, although there are slight differences in the Ti=O bond and V=O bond. Therefore, vanadyl phthalocyanine is considered to have a steric structure that is advantageous for forming a mixed crystal with titanyl phthalocyanine, and in fact, vanadyl phthalocyanine, unlike some other phthalocyanines, has a mixed crystal structure of the present invention. I was able to get the crystal.
【００２３】本発明のチタニルフタロシアニンとバナジ
ルフタロシアニンの混晶の結晶型はＣｕＫαの特性Ｘ線
（波長１．５４１Å）に対するブラッグ角２θの２７．
２゜±０．２゜に主たる明瞭なピークを有しているもの
はすべて含まれるが、なかでも２７．２゜±０．２゜以
外にも９．６゜±０．２゜或いは９．０゜±０．２゜に
明瞭なピークを有している結晶型が望ましい。更には９
．６゜±０．２゜及び２７．２゜±０．２゜に明瞭なピ
ークを有するような結晶型が最も望ましい。The crystal type of the mixed crystal of titanyl phthalocyanine and vanadyl phthalocyanine of the present invention has a Bragg angle 2θ of 27.
All those having a clear main peak at 2° ± 0.2° are included, but among them, in addition to 27.2° ± 0.2°, 9.6° ± 0.2° or 9. A crystal form having a clear peak at 0°±0.2° is desirable. Furthermore, 9
．． A crystal form having clear peaks at 6°±0.2° and 27.2°±0.2° is most desirable.
【００２４】本発明で用いられるチタニルフタロシアニ
ン（ＴｉＯＰｃ）は次の一般式〔Ｉ〕で表される。Titanyl phthalocyanine (TiOPc) used in the present invention is represented by the following general formula [I].
【００２５】[0025]
【化３】[Chemical formula 3]
【００２６】但し、Ｘ１，Ｘ２，Ｘ３，Ｘ４は水素原子
、ハロゲン原子、アルキル基、或いはアルコキシ基、ア
リールオキシ基を表し、ｋ，ｌ，ｍ，ｎは０〜４の整数
を表す。また、本発明で用いられるバナジルフタロシア
ニン（ＶＯＰｃ）は次の一般式〔ＩＩ〕で表される。[0026] However, X1, X2, X3, and X4 represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or an aryloxy group, and k, l, m, and n represent integers of 0 to 4. Further, vanadyl phthalocyanine (VOPc) used in the present invention is represented by the following general formula [II].
【００２７】[0027]
【化４】[C4]
【００２８】但し、Ｘ１，Ｘ２，Ｘ３，Ｘ４は水素原子
、ハロゲン原子、アルキル基、或いはアルコキシ基、ア
リールオキシ基を表し、ｋ，ｌ，ｍ，ｎは０〜４の整数
を表す。Ｘ線回折スペクトルは次の条件で測定され、こ
こでいう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。[0028] However, X1, X2, X3, and X4 represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or an aryloxy group, and k, l, m, and n represent integers of 0 to 4. 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.
【００２９】
Ｘ線管球 Ｃｕ
電 圧 ４０．０
ＫＶ電 流 １００
ｍＡスタート角度 ６．００
ｄｅｇ．ストップ角度 ３５．００
ｄｅｇ．ステップ角度 ０．０２０
ｄｅｇ．測定時間 ０．５０
ｓｅｃ．本発明に用いられるチタニルフタロシアニ
ンの合成には種々の方法を用いることができるが、代表
的には次の反応式（１）或いは（２）に従って合成する
ことができる。[0029] X-ray tube Cu voltage 40.0
KV current 100
mA start angle 6.00
deg. Stop angle 35.00
deg. Step angle 0.020
deg. Measurement time 0.50
sec. Although various methods can be used to synthesize titanyl phthalocyanine used in the present invention, it can typically be synthesized according to the following reaction formula (1) or (2).
【００３０】[0030]
【化５】[C5]
【００３１】式中、Ｒ１〜Ｒ４は脱離基を表す。In the formula, R1 to R4 represent a leaving group.
【００３２】又、本発明に用いられるバナジルフタロシ
アニンはチタニルフタロシアニンと同様にｏ−フタロニ
トリルや１，３−ジイノミノイソインドリンと五酸化バ
ナジウム、アセチルアセトンバナジウムに代表されるバ
ナジウム試薬を１−クロルナフタレン等の不活性溶媒中
で反応させることにより得ることができる。[0032] Similarly to titanyl phthalocyanine, the vanadyl phthalocyanine used in the present invention can be prepared by combining o-phthalonitrile, 1,3-diinonominoisoindoline with a vanadium reagent such as vanadium pentoxide or vanadium acetylacetonate with 1-chlornaphthalene or the like. It can be obtained by reacting in an inert solvent.
【００３３】上記のようにして得られたチタニルフタロ
シアニンとバナジルフタロシアニンの混晶の形成は従来
技術としては共蒸着の方法のみが知られているにすぎな
かったが、発明者らによる詳細な検討の結果、そのほか
にも溶媒中に均一に溶解させた後析出させる方法、或い
は固体状態にて混合後、ミリング等の前刀断力を付与す
る方法などによっても混晶の形成が可能であることが判
った。[0033] Formation of the mixed crystal of titanyl phthalocyanine and vanadyl phthalocyanine obtained as described above was only known in the prior art by co-evaporation, but after detailed study by the inventors, As a result, it is possible to form mixed crystals by other methods, such as by dissolving them uniformly in a solvent and then precipitating them, or by applying cutting force such as milling after mixing in a solid state. understood.
【００３４】具体的には再結晶、再沈澱、アッシドペー
スト処理、或いは乾式または湿式によるミリングによる
方法などが挙げられるが、このような混晶の形成法の確
立により本発明の結晶型を得るに至った。しかしながら
混晶を形成させる方法はこれらの方法に限定されるもの
ではない。[0034] Specific methods include recrystallization, reprecipitation, acid paste treatment, and dry or wet milling, but the crystal form of the present invention can be obtained by establishing a method for forming such mixed crystals. reached. However, methods for forming mixed crystals are not limited to these methods.
【００３５】次に本発明に用いられる結晶型のチタニル
フタロシアニン−バナジルフタロシアニン混晶を得る方
法を例示的に示す。例えば通常のアシッドペースト処理
により任意の結晶型のチタニルフタロシアニン及びバナ
ジルフタロシアニンを濃硫酸に溶解し、その硫酸溶液を
水にあけて析出した結晶を濾取する方法、或いは任意の
結晶型のチタニルフタロシアニンとバナジルフタロシア
ニンを混合し、その混合物をミリング等の機械的な力に
より粉砕する方法などによってチタニルフタロシアニン
−バナジルフタロシアニンより構成されるアモルファス
結晶が得られる。ここでアシッドペースト処理によりア
モルファス化を行う場合は一般的な条件にて達成され、
フタロシアニンに対する濃硫酸の重量比は特に限定され
ないが、５倍から２００倍程度が望ましい。また、濃硫
酸に対する水あけに用いる水の量は重量比で通常、５倍
から１００倍程度が望ましい。更に、フタロシアニンを
濃硫酸に溶解する温度は５℃以下、水あけ温度は通常０
℃以上５０℃以下が望ましい。Next, a method for obtaining the crystalline titanyl phthalocyanine-vanadyl phthalocyanine mixed crystal used in the present invention will be exemplified. For example, titanyl phthalocyanine and vanadyl phthalocyanine of any crystal type are dissolved in concentrated sulfuric acid by normal acid paste treatment, the sulfuric acid solution is poured into water, and the precipitated crystals are filtered, or titanyl phthalocyanine of any crystal type and An amorphous crystal composed of titanyl phthalocyanine-vanadyl phthalocyanine can be obtained by mixing vanadyl phthalocyanine and pulverizing the mixture by mechanical force such as milling. Here, when amorphousization is performed by acid paste treatment, it is achieved under general conditions,
The weight ratio of concentrated sulfuric acid to phthalocyanine is not particularly limited, but is preferably about 5 times to 200 times. The amount of water used for draining is preferably about 5 to 100 times the weight of concentrated sulfuric acid. Furthermore, the temperature at which phthalocyanine is dissolved in concentrated sulfuric acid is 5°C or lower, and the water removal temperature is usually 0.
It is desirable that the temperature is 50°C or higher.
【００３６】次いでこのアモルファス結晶を特定の有機
溶媒で処理することによって本発明に用いられる結晶型
を得ることができる。用いられる有機溶媒としては炭化
水素系溶媒、芳香族系溶媒、ハロゲン系溶媒、アルコー
ル、エーテル系溶媒、エステル系溶媒、有機酸、有機ア
ミン類、複素環化合物などが挙げられるが、必要に応じ
てスルホン酸やトリクロル酢酸等の酸を添加してもよい
。一方、アモルファス結晶の状態は水分を含んだウエッ
トペーストの状態或いは水分を含んでいない乾燥状態の
もののどちらも用いることができるが、これは処理する
有機溶媒の種類や目的によって選択する事ができる。
さらにこの溶媒処理においては必要に応じて加熱あるい
はミリング処理等の操作を行うことができる。またこの
ような有機溶媒処理は必要に応じて繰返し行ってもかま
わない。しかしながら結晶変換の方法は必ずしもこのよ
うな方法に限定されるものではない。Next, by treating this amorphous crystal with a specific organic solvent, the crystal form used in the present invention can be obtained. Examples of organic solvents that can be used include hydrocarbon solvents, aromatic solvents, halogen solvents, alcohols, ether solvents, ester solvents, organic acids, organic amines, and heterocyclic compounds. Acids such as sulfonic acid and trichloroacetic acid may also be added. On the other hand, the amorphous crystal can be in either a wet paste state containing moisture or a dry state without moisture, and this can be selected depending on the type of organic solvent to be treated and the purpose. Furthermore, in this solvent treatment, operations such as heating or milling treatment can be performed as necessary. Further, such organic solvent treatment may be repeated as necessary. However, the crystal conversion method is not necessarily limited to this method.
【００３７】本発明のチタニルフタロシアニンとバナジ
ルフタロシアニンの混晶におけるチタニルフタロシアニ
ンとバナジルフタロシアニンの組成比は両方のフタロシ
アニンが存在していれば特に限定されないが、チタニル
フタロシアニンの存在比は５０％以上が望ましい。さら
に望ましくはチタニルフタロシアニンの存在比が８０％
以上である。さらにはチタニルフタロシアニンの存在比
が９０％以上が最も望ましい。ここでいう存在比とは全
重量に対しての含有されているチタニルフタロシアニン
の重量比を表す。The composition ratio of titanyl phthalocyanine and vanadyl phthalocyanine in the mixed crystal of titanyl phthalocyanine and vanadyl phthalocyanine of the present invention is not particularly limited as long as both phthalocyanines are present, but the abundance ratio of titanyl phthalocyanine is preferably 50% or more. More preferably, the abundance ratio of titanyl phthalocyanine is 80%.
That's all. Furthermore, it is most desirable that the abundance ratio of titanyl phthalocyanine is 90% or more. The abundance ratio here refers to the weight ratio of the contained titanyl phthalocyanine to the total weight.
【００３８】次に本発明に係る多環キノン系化合物（以
後多環〔Ｑ〕と表示する）としては、下記一般式〔Ｑ１
〕で示されるアントアントロン系顔料、下記一般式〔Ｑ
２〕で示されるジベンズピレンキノン系顔料及び下記一
般式〔Ｑ３〕で示されるピラントロン系顔料から選ばれ
る少なくとも一種を挙げることができるが、特に一般式
〔Ｑ１〕が好ましい。Next, the polycyclic quinone compound (hereinafter referred to as polycyclic [Q]) according to the present invention has the following general formula [Q1
] An anthrone pigment represented by the following general formula [Q
At least one selected from the dibenzpyrenequinone pigment represented by [2] and the pyranthrone pigment represented by the following general formula [Q3] can be mentioned, and the general formula [Q1] is particularly preferred.
【００３９】[0039]
【化６】[C6]
【００４０】式中、Ｘはハロゲン原子、ニトロ基、シア
ノ基、アシル基又はカルボキシル基を表し、ｎは０〜４
の整数を表し、ｍは０〜６の整数を表す。In the formula, X represents a halogen atom, a nitro group, a cyano group, an acyl group or a carboxyl group, and n is 0 to 4.
represents an integer of 0 to 6, and m represents an integer of 0 to 6.
【００４１】一般式〔Ｑ１〕で示されるアントアントロ
ン系顔料の具体的化合物を挙げると次の通りである。Specific compounds of the anthanthrone pigment represented by the general formula [Q1] are as follows.
【００４２】[0042]
【化７】[C7]
【００４３】[0043]
【化８】[Chemical formula 8]
【００４４】一般式〔Ｑ２〕で示されるジベンズピレン
キノン系顔料の具体的化合物例を挙げると次の通りであ
る。Specific examples of the dibenzpyrenequinone pigment represented by the general formula [Q2] are as follows.
【００４５】[0045]
【化９】[Chemical formula 9]
【００４６】[0046]
【化１０】[Chemical formula 10]
【００４７】一般式〔Ｑ３〕で示されるピラントロン系
顔料の具体的化合物例を挙げると次の通りである。Specific examples of the pyranthrone pigment represented by the general formula [Q3] are as follows.
【００４８】[0048]
【化１１】[Chemical formula 11]
【００４９】[0049]
【化１２】[Chemical formula 12]
【００５０】本発明に係る多環〔Ｑ〕は４５０ｎｍ〜６
００ｎｍの領域で感度が高く、本発明に用いるＴｉＯＰ
ｃとＶＯＰｃの混晶の低感度スペクトル領域の感度を補
うものであり、かつ帯電電位、残留電位などについての
繰返し特性が著しく安定であるという特徴を有する。[0050] The polycyclic [Q] according to the present invention has a wavelength of 450 nm to 6
TiOP has high sensitivity in the 00 nm region and is used in the present invention.
It supplements the sensitivity in the low sensitivity spectral region of the mixed crystal of c and VOPc, and is characterized by extremely stable repeatability with respect to charging potential, residual potential, etc.
【００５１】このような異種のキャリア発生物質の併用
は必ずしも一律的な選択手段があるというものでもなく
、本発明においても数多くの化合物の中から実験の積み
重ねによって前記ＴｉＯＰｃとＶＯＰｃの混晶と多環〔
Ｑ〕の組合せを決定したものである。[0051] There is not necessarily a uniform selection method for using such different types of carrier-generating substances in combination, and in the present invention, the mixed crystal of TiOPc and VOPc and the multi-crystalline compound are selected from a large number of compounds through repeated experiments. ring〔
Q] has been determined.
【００５２】本発明のこの組合せによって長波長から短
波長まで広いスペクトル領域に高感度を保持でき、なお
かつ繰返し使用時も電位の履歴を小さくできた。これに
よれば、可視域で主たる分光感度が必要な複写機（例え
ば蛍光灯、ハロゲンランプ、キセノンランプ等の画像信
号−アナログ信号）として好適となり、かつ可視光領域
中の長波長側あるいは赤外域で主たる分光感度が必要な
プリンタ（例えば発光ダイオード、Ｈｅ−Ｎｅレーザ等
の気体レーザ、半導体レーザ等の画像信号−デジタル信
号）として好適となる。この意味で、アナログ／デジタ
ルの両方式を夫々実現できる。With this combination of the present invention, high sensitivity can be maintained in a wide spectral region from long wavelengths to short wavelengths, and potential history can be reduced even during repeated use. According to this, it is suitable for copying machines that require main spectral sensitivity in the visible range (for example, image signals from fluorescent lamps, halogen lamps, xenon lamps, etc. - analog signals), and is suitable for use in the long wavelength side of the visible light range or in the infrared range. This makes it suitable for printers that require major spectral sensitivity (for example, light emitting diodes, gas lasers such as He-Ne lasers, image signals-digital signals of semiconductor lasers, etc.). In this sense, both analog and digital systems can be realized.
【００５３】次に本発明に用いられるキャリア輸送物質
としては、特に制限はないが、例えばオキサゾール誘導
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、イミダゾロン誘導体、イミダゾリジン誘導体、
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、アミン誘導体、オキサゾ
ロン誘導体、ベンゾチアゾール誘導体、ベンズイミダゾ
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、フェナジン誘導体、アミノスチルベ
ン誘導体、ポリ−Ｎ−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から選
ばれた１種又は２種以上が例示される。Next, the carrier transport substance used in the present invention is not particularly limited, but includes, for example, oxazole derivatives, oxadiazole derivatives, thiazole derivatives, thiadiazole derivatives, triazole derivatives, imidazole derivatives, imidazolone derivatives, imidazolidine derivatives,
Bisimidazolidine derivatives, styryl compounds, hydrazone compounds, pyrazoline derivatives, amine derivatives, oxazolone derivatives, benzothiazole derivatives, benzimidazole derivatives, quinazoline derivatives, benzofuran derivatives,
Acridine derivatives, phenazine derivatives, aminostilbene derivatives, poly-N-vinylcarbazole, poly-1-
Examples include one or more selected from vinylpyrene, poly-9-vinylanthracene, and the like.
【００５４】キャリア発生層或はキャリア輸送層の形成
に用いられるバインダ樹脂は任意のものを用いることが
できるが、疎水性で、かつ誘電率が高く、電気絶縁性の
フィルム形成性高分子重合体で、かつ熱硬化性樹脂であ
ることが好ましい。Any binder resin can be used to form the carrier generation layer or the carrier transport layer, but a film-forming polymer that is hydrophobic, has a high dielectric constant, and is electrically insulating can be used. And it is preferably a thermosetting resin.
【００５５】熱硬化性樹脂としては縮重合型と付加重合
型がある。There are two types of thermosetting resins: condensation polymerization type and addition polymerization type.
【００５６】縮重合型には、フェノール樹脂、尿素樹脂
、メラミン樹脂、メラミン−フェノール樹脂、グアナミ
ン樹脂及びシリコーン樹脂等があり、又付加重合型には
、不飽和ポリエステル樹脂、アルキド樹脂、ジアリルフ
タレート樹脂、エポキシ樹脂及びポリブタジェン樹脂等
がある。Condensation polymerization types include phenolic resins, urea resins, melamine resins, melamine-phenol resins, guanamine resins, and silicone resins, and addition polymerization types include unsaturated polyester resins, alkyd resins, diallyl phthalate resins, etc. , epoxy resins and polybutadiene resins.
【００５７】尚、性能を損わぬ範囲でその他の樹脂を併
用してもよい。Note that other resins may be used in combination as long as the performance is not impaired.
【００５８】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。For example, the following can be mentioned,
It is not limited to these.
【００５９】ポリカーボネート、メタクリル酸樹脂、ア
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、ポリビニルアセテート、スチレン−ブタジ
エン共重合体、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、塩化ビニル−
酢酸ビニル−無水マレイン酸共重合体、シリコーン−ア
ルキッド樹脂、フェノールホルムアルデヒド樹脂、スチ
レン−アルキッド樹脂、ポリ−Ｎ−ビニルカルバゾール
、ポリビニルブチラール、ポリビニルフォルマール。Polycarbonate, methacrylic acid resin, acrylic resin, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyvinyl acetate, styrene-butadiene copolymer, vinylidene chloride-acrylonitrile copolymer, vinyl chloride-vinyl acetate copolymer, chloride vinyl
Vinyl acetate-maleic anhydride copolymer, silicone-alkyd resin, phenol formaldehyde resin, styrene-alkyd resin, poly-N-vinyl carbazole, polyvinyl butyral, polyvinyl formal.
【００６０】これらのバインダ樹脂は、単独であるいは
２種類以上の混合物として用いることができる。These binder resins can be used alone or as a mixture of two or more.
【００６１】本発明に係る感光層には、オゾン劣化防止
の目的で酸化防止剤を添加することができる。酸化防止
剤としては、ヒンダードフェノール、ヒンダードアミン
、パラフェニレンジアミン、アリールアルカン、ハイド
ロキノン、スピロクロマン、スピロインダノン及びそれ
らの誘導体、有機硫黄化合物、有機燐化合物等が挙げら
れる。An antioxidant can be added to the photosensitive layer according to the present invention for the purpose of preventing ozone deterioration. Examples of the antioxidant include hindered phenol, hindered amine, paraphenylene diamine, aryl alkane, hydroquinone, spirochroman, spiroindanone and derivatives thereof, organic sulfur compounds, organic phosphorus compounds, and the like.
【００６２】これらの具体的化合物としては、特開昭６
３−１４１５３号、同６３−１８３５５号、同６３−４
４６６２号、同６３−５０８４８号、同６３−５０８４
９号、同６３−５８４５５号、同６３−７１８５６号、
同６３−７１８５７号及び同６３−１４６０４６号に記
載がある。These specific compounds are described in Japanese Unexamined Patent Publication No. 6
No. 3-14153, No. 63-18355, No. 63-4
No. 4662, No. 63-50848, No. 63-5084
No. 9, No. 63-58455, No. 63-71856,
It is described in No. 63-71857 and No. 63-146046.
【００６３】キャリア発生層には感度の向上、残留電位
及至反復使用時の疲労低減等を目的として、一種又は二
種以上の電子受容性物質を含有せしめることができる。The carrier generation layer may contain one or more electron-accepting substances for the purpose of improving sensitivity, reducing residual potential and reducing fatigue during repeated use.
【００６４】電子受容性物質の添加量は、重量比でキャ
リア発生物質：電子受容性物質＝１００：（０．０１〜
２００）、好ましくは１００：（０．１〜１００）であ
る。The amount of electron-accepting substance to be added is such that the weight ratio of carrier-generating substance:electron-accepting substance is 100:(0.01~
200), preferably 100:(0.1-100).
【００６５】電子受容性物質はキャリア輸送層に添加し
てもよい。かかる層への電子受容性物質の添加量は重量
比でキャリア輸送物質：電子受容性物質＝１００：（０
．０１〜１００）、好ましくは１００：（０．１〜５０
）である。[0065] An electron-accepting substance may be added to the carrier transport layer. The amount of the electron-accepting substance added to this layer is such that the weight ratio of the carrier-transporting substance:electron-accepting substance=100:(0
．． 01-100), preferably 100:(0.1-50
).
【００６６】電子受容性物質の具体例は、特開昭６３−
１６８６５６号等に記載されている。Specific examples of electron-accepting substances are disclosed in JP-A-63-
It is described in No. 168656, etc.
【００６７】また本発明の感光体には、その他、必要に
より感光層を保護する目的で紫外線吸収剤等を含有させ
てもよく、又感色性補正の染料を含有させてもよい。The photoreceptor of the present invention may also contain an ultraviolet absorber or the like for the purpose of protecting the photosensitive layer, if necessary, or a dye for color sensitivity correction.
【００６８】本発明の感光体は支持体上に、キャリア発
生層、キャリア輸送層、更に必要に応じ、保護層、中間
層、バリア層、接着層等の補助層が積層されてもよい。In the photoreceptor of the present invention, a carrier generation layer, a carrier transport layer, and, if necessary, auxiliary layers such as a protective layer, an intermediate layer, a barrier layer, and an adhesive layer may be laminated on the support.
【００６９】キャリア発生層については、下記方法が適
宜用いられる。[0069] Regarding the carrier generation layer, the following method can be used as appropriate.
【００７０】１） キャリア発生物質を適当な溶媒に
溶解した溶液を、あるいは必要に応じてバインダ樹脂を
加え混合溶解した溶液を塗布する方法。1) A method of applying a solution in which a carrier-generating substance is dissolved in a suitable solvent, or a solution in which a binder resin is mixed and dissolved, if necessary.
【００７１】２） キャリア発生物質をボールミル、
ホモミキサ等によって分散媒中で微細粒子（好ましくは
粒径５μｍ以下、更に好ましくは１μｍ以下）とし、必
要に応じてバインダ樹脂を加え混合分散した分散液を塗
布する方法。2) Ball mill the carrier generating material,
A method in which fine particles (preferably particle size of 5 μm or less, more preferably 1 μm or less) are formed in a dispersion medium using a homomixer, etc., and a binder resin is added as necessary to mix and disperse the resulting dispersion and then applied.
【００７２】キャリア発生層の形成に使用される溶媒あ
るいは分散媒としては、ブチルアミン、ジエチルアミン
、エチレンジアミン、イソプロパノールアミン、トリエ
タノールアミン、トリエチレンジアミン、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、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、１，２−ジクロル
プロパン、１，１，２−トリクロルエタン、１，１，１
−トリクロルエタン、トリクロルエチレン、テトラクロ
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、イソプロパノール、
酢酸エチル、酢酸ブチル、ジメチルスルホキシド、メチ
ルセロソルブ、メチルイソブチルケトン等が挙げられる
。Examples of the solvent or dispersion medium used for forming the carrier generation layer include butylamine, diethylamine, ethylenediamine, isopropanolamine, triethanolamine, triethylenediamine, N,N-dimethylformamide, acetone, methyl ethyl ketone, cyclohexanone, benzene, Toluene, xylene, chloroform, 1,2-dichloroethane, 1,2-dichloropropane, 1,1,2-trichloroethane, 1,1,1
- trichloroethane, trichlorethylene, tetrachloroethane, dichloromethane, tetrahydrofuran, dioxane, methanol, ethanol, isopropanol,
Examples include ethyl acetate, butyl acetate, dimethyl sulfoxide, methyl cellosolve, methyl isobutyl ketone, and the like.
【００７３】また、キャリア輸送層は上記キャリア発生
層と同様にして形成することができる。Further, the carrier transport layer can be formed in the same manner as the carrier generation layer described above.
【００７４】感光体に用いられる導電性支持体としては
、合金を含めた金属板、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や合金を含めたアル
ミニウム、パラジウム、金等の金属薄層を塗布、蒸着あ
るいはラミネートして、導電性化された紙、プラスチッ
クフィルム等が挙げられる。接着層あるいはバリヤ層な
どの中間層としては、前記バインダ樹脂として用いられ
る高分子重合体のほか、ポリビニルアルコール、エチル
セルロース、カルボキシメチルセルロースなどの有機高
分子物質又は酸化アルミニウムなどが用いられる。[0074] The conductive support used for the photoreceptor may be a metal plate including an alloy, a metal drum or a conductive polymer, a conductive compound such as indium oxide, or a metal thin film such as aluminum, palladium, or gold including an alloy. Examples include paper, plastic film, etc., which are made conductive by coating, vapor depositing, or laminating layers. As an intermediate layer such as an adhesive layer or a barrier layer, in addition to the polymer used as the binder resin, an organic polymer material such as polyvinyl alcohol, ethyl cellulose, carboxymethyl cellulose, or aluminum oxide is used.
【００７５】次に本発明の感光体の具体的構成について
述べる。Next, the specific structure of the photoreceptor of the present invention will be described.
【００７６】図１及び図２は夫々本発明の感光体の態様
例の断面図である。FIGS. 1 and 2 are sectional views of embodiments of the photoreceptor of the present invention, respectively.
【００７７】図１はキャリア輸送層（ＣＴＬ）がキャリ
ア発生層（ＣＧＬ）の上に積層された態様であって負帯
電用感光体として好ましい態様であり、図２はその逆に
ＣＴＬの上にＣＧＬが積層された態様であって正帯電用
感光体として好ましい態様である。FIG. 1 shows an embodiment in which a carrier transport layer (CTL) is laminated on a carrier generation layer (CGL), which is a preferred embodiment for a negatively charging photoreceptor, and conversely, FIG. This is an embodiment in which CGL is laminated, and is a preferred embodiment as a positive charging photoreceptor.
【００７８】更に本発明においては、キャリア発生物質
（ＣＧＭ）としてＴｉＯＰｃ−ＶＯＰｃの混晶と多環キ
ノン顔料の２種を用いるので、夫々別層のＣＧＬとする
態様が可能である。Furthermore, in the present invention, since two types of carrier generating material (CGM), TiOPc-VOPc mixed crystal and polycyclic quinone pigment, are used, it is possible to form CGL in separate layers.
【００７９】図１（ａ）において、１は支持体、２はＣ
ＧＬでありかつ上下２層のＣＧＬ２Ａ及び２Ｂからなる
。
３はキャリア輸送物質（ＣＴＭ）を含むＣＴＬである。
又図２の場合も同様の構成が可能であり、図１と同記号
は同意味の層である。In FIG. 1(a), 1 is a support, 2 is C
It is a GL and consists of two upper and lower layers of CGL 2A and 2B. 3 is a CTL containing a carrier transport material (CTM). A similar configuration is also possible in the case of FIG. 2, and the same symbols as in FIG. 1 represent layers with the same meaning.
【００８０】ＣＧＬに２層構成を採る場合、イオン化ポ
テンシャル或はＣＴＬのエネルギー注入バリアに原因す
ると思われるが、図１の負帯電用にはＣＴＬに接するＣ
ＧＬ２ＡにＴｉＯＰｃ−ＶＯＰｃの混晶を、支持体に接
するＣＧＬ２Ｂに多環キノン顔料を振当てることが好ま
しい。又、図２の正帯電用の場合にもＣＴＬに接する下
層のＣＧＬ２ＢにＴｉＯＰｃ−ＶＯＰｃの混晶を、上層
のＣＧＬ２Ａに多環キノン顔料を振当てると性能が良好
となる。When a two-layer structure is adopted for the CGL, this is thought to be due to the ionization potential or the energy injection barrier of the CTL, but for the negative charging shown in FIG.
It is preferable to allocate a TiOPc-VOPc mixed crystal to GL2A and a polycyclic quinone pigment to CGL2B in contact with the support. Also, in the case of positive charging shown in FIG. 2, the performance can be improved by allocating a TiOPc-VOPc mixed crystal to the lower layer CGL2B in contact with the CTL and a polycyclic quinone pigment to the upper layer CGL2A.
【００８１】本発明の感光体の層構成は前記図１（ａ）
、図２（ａ）に限らず種々の態様が可能である。The layer structure of the photoreceptor of the present invention is shown in FIG. 1(a).
, various embodiments are possible without being limited to the one shown in FIG. 2(a).
【００８２】図１において、同図（ｂ）の４はＴｉＯＰ
ｃ−ＶＯＰｃの混晶及び多環キノン顔料で混成されたＣ
ＧＬであり、同図（ｃ）の５はＴｉＯＰｃ−ＶＯＰｃの
混晶又は多環キノン顔料のいづれか一方がＣＴＭと混成
されたキャリア発生・輸送複合層（ＣＧＴＬ）であり、
更に同図（ｄ）の７は二種のＣＧＭとＣＴＭで混成され
たＣＧＴＬである。In FIG. 1, 4 in FIG. 1(b) is TiOP.
C mixed with c-VOPc mixed crystal and polycyclic quinone pigment
GL, and 5 in the same figure (c) is a carrier generation/transport composite layer (CGTL) in which either a TiOPc-VOPc mixed crystal or a polycyclic quinone pigment is mixed with CTM,
Furthermore, 7 in the same figure (d) is a CGTL that is a hybrid of two types of CGM and CTM.
【００８３】図２に示される正帯電用の場合にも同様の
構成を与えることができる。A similar configuration can be provided for the case of positive charging shown in FIG.
【００８４】本発明においては補助層が活用されてもよ
く、図１において、保護層８、バリア層（又は接着層）
９、中間層１０を設けた態様例を示した。図２の場合も
同様である。In the present invention, auxiliary layers may be utilized, and in FIG. 1, a protective layer 8, a barrier layer (or adhesive layer)
9. An example of an embodiment in which an intermediate layer 10 is provided is shown. The same applies to the case of FIG.
【００８５】前記ＣＧＬにおいて、ＣＧＭとバインダと
の重量比は好ましくは１００：０〜１０００がよい。Ｃ
ＧＭの含有割合がこれより少ないと光感度が低く、残留
電位の増加を招き、又これより多いと暗減衰及び受容電
位が低下する。[0085] In the CGL, the weight ratio of CGM and binder is preferably 100:0 to 1000. C
If the GM content is less than this, the photosensitivity will be low and the residual potential will increase, and if it is more than this, the dark decay and acceptance potential will decrease.
【００８６】図１、図２において、下側ＣＧＬ２Ｂの膜
層は０．０１〜１０μｍ （更には０．０５〜１μｍ）
とするのが好ましく、上側ＣＧＬ２Ａの膜厚は０．０１
〜１０μｍ（更には０．５〜５μｍ）とするのが好まし
い。In FIGS. 1 and 2, the film layer of the lower CGL 2B has a thickness of 0.01 to 10 μm (even 0.05 to 1 μm).
It is preferable that the film thickness of the upper CGL2A is 0.01
It is preferable to set it as -10 micrometers (furthermore, 0.5-5 micrometers).
【００８７】又ＣＴＬにおいて、ＣＴＭはＣＴＬ中のバ
インダ樹脂１００重量部（ｗｔと標記）当たり２０〜２
００ｗｔが好ましく、特に好ましくは３０〜１５０ｗｔ
である。[0087] In CTL, CTM is 20 to 2 parts by weight per 100 parts by weight (wt) of binder resin in CTL.
00wt is preferred, particularly preferably 30-150wt
It is.
【００８８】又、形成されるＣＴＬの厚さは、好ましく
は５〜５０μｍ、特に好ましくは５〜３０μｍである。The thickness of the formed CTL is preferably 5 to 50 μm, particularly preferably 5 to 30 μm.
【００８９】[0089]
チタニルフタロシアニンの合成
１，３−ジイミノイソインドリン２９．２ｇとｏ−ジク
ロルベンゼン２００ｍｌ及びチタニウムテトラ−ｎ−ブ
トキシドシド２０．４ｇを混合し、窒素気流下にて３時
間還流させた。放冷して室温に戻した後析出した結晶を
濾取し、ｏ−ジクロルベンゼンで洗浄し、更にメタノー
ルで洗浄した。更に得られた結晶を２％塩酸水溶液中室
温にて数回撹拌洗浄し、さらに脱イオン水で数回洗浄を
繰返した。Synthesis of titanyl phthalocyanine 29.2 g of 1,3-diiminoisoindoline, 200 ml of o-dichlorobenzene, and 20.4 g of titanium tetra-n-butoxide were mixed and refluxed for 3 hours under a nitrogen stream. After cooling to room temperature, the precipitated crystals were collected by filtration, washed with o-dichlorobenzene, and further washed with methanol. Furthermore, the obtained crystals were washed several times with stirring in a 2% aqueous hydrochloric acid solution at room temperature, and the washing was repeated several times with deionized water.
【００９０】その後メタノールで洗浄後、乾燥して青紫
色のチタニルフタロシアニン結晶２４．２ｇを得た。After washing with methanol, the mixture was dried to obtain 24.2 g of bluish-purple titanyl phthalocyanine crystals.
【００９１】バナジルフタロシアニンの合成１，３−ジ
イミノイソインドリン２９．２ｇとｏ−ジクロルベンゼ
ン２００ｍｌ及びバナジルアセチルアセトナート８ｇを
混合し、窒素気流下にて５時間還流させた。その後放冷
して室温に戻した後析出した結晶を濾取し、ｏ−ジクロ
ルベンゼンで洗浄し、更にメタノールで洗浄した。更に
得られた結晶を２％塩酸水溶液中室温にて数回撹拌洗浄
し、さらに脱イオン水で数回洗浄を繰返した。乾燥後こ
の結晶を１−クロルナフタレンで再結晶して紫色のバナ
ジルフタロシアニン結晶１８．９ｇを得た。Synthesis of vanadyl phthalocyanine 29.2 g of 1,3-diiminoisoindoline, 200 ml of o-dichlorobenzene and 8 g of vanadyl acetylacetonate were mixed and refluxed for 5 hours under a nitrogen stream. Thereafter, the mixture was allowed to cool to room temperature, and the precipitated crystals were collected by filtration, washed with o-dichlorobenzene, and further washed with methanol. Furthermore, the obtained crystals were washed several times with stirring in a 2% aqueous hydrochloric acid solution at room temperature, and the washing was repeated several times with deionized water. After drying, the crystals were recrystallized from 1-chloronaphthalene to obtain 18.9 g of purple vanadyl phthalocyanine crystals.
【００９２】合成例１
チタニルフタロシアニン４ｇ及びバナジルフタロシアニ
ン１ｇを氷冷下２５０ｇの９６％硫酸に溶解し、この硫
酸溶液を５ｌの水にあけて析出したアモルファス状態の
ウエットペーストを濾取した。更にこのウエットペース
トとｏ−ジクロルベンゼンで５０ｇを混合し、５０℃の
温度で２時間撹拌した。この反応液をメタノールで希釈
後濾過し、更に得られた結晶をメタノールで数回洗浄し
て青色結晶を得た。Synthesis Example 1 4 g of titanyl phthalocyanine and 1 g of vanadyl phthalocyanine were dissolved in 250 g of 96% sulfuric acid under ice cooling, and the sulfuric acid solution was poured into 5 liters of water, and the precipitated amorphous wet paste was collected by filtration. Further, 50 g of this wet paste and o-dichlorobenzene were mixed and stirred at a temperature of 50° C. for 2 hours. The reaction solution was diluted with methanol and filtered, and the resulting crystals were washed several times with methanol to obtain blue crystals.
【００９３】この結晶は図３に示すようにブラッグ角２
θの９．６°及び２７．２°にピークを有する本発明の
チタニルフタロシアニンとバナジルフタロシアニンの混
晶であることが判った。This crystal has a Bragg angle of 2 as shown in FIG.
It was found that this was a mixed crystal of titanyl phthalocyanine and vanadyl phthalocyanine of the present invention having peaks at 9.6° and 27.2° of θ.
【００９４】合成例２
合成例１ウエットペーストを乾燥して得られた粉末５ｇ
及びｐ−トルエンスルホン酸２５ｇを混合し、更に酢酸
５００ｍｌを加えて５時間加熱還流した。反応物を濾取
した後、濾液が完全に中性になるまで水洗を数回繰返し
た。更にメタノール中で３０分間撹拌した後、濾過、乾
燥して青色結晶を得た。この結晶は図４に示すようにブ
ラッグ角２θの９．０゜及び２７．２゜にピークを有す
るチタニルフタロシアニンとバナジルフタロシアニンの
混晶であることが判った。Synthesis Example 2 5g of powder obtained by drying Synthesis Example 1 wet paste
and 25 g of p-toluenesulfonic acid were mixed, and 500 ml of acetic acid was further added, followed by heating under reflux for 5 hours. After the reaction product was collected by filtration, washing with water was repeated several times until the filtrate became completely neutral. After further stirring in methanol for 30 minutes, the mixture was filtered and dried to obtain blue crystals. This crystal was found to be a mixed crystal of titanyl phthalocyanine and vanadyl phthalocyanine having peaks at Bragg angles 2θ of 9.0° and 27.2°, as shown in FIG.
【００９５】合成例３
チタニルフタロシアニン４ｇ及びバナジルフタロシアニ
ン１ｇを氷冷下２５０ｇの９６％硫酸に溶解し、この硫
酸溶液を５ｌの水にあけて析出したアモルファス状態の
ウエットペーストを濾取した。このウエットペーストを
とってメタノール２５０ｍｌ中にて２４時間ミリング処
理を行った。その後、結晶を濾過、乾燥して青紫色の結
晶を得た。Synthesis Example 3 4 g of titanyl phthalocyanine and 1 g of vanadyl phthalocyanine were dissolved in 250 g of 96% sulfuric acid under ice cooling, and the sulfuric acid solution was poured into 5 liters of water, and the precipitated amorphous wet paste was collected by filtration. This wet paste was taken and milled in 250 ml of methanol for 24 hours. Thereafter, the crystals were filtered and dried to obtain blue-purple crystals.
【００９６】この結晶のＸ線回折スペクトルは図５に示
すようにブラッグ角２θの２７．２°に明瞭なピークを
有するが、その他はブロードになっており明瞭なピーク
は観測されなかった。As shown in FIG. 5, the X-ray diffraction spectrum of this crystal has a clear peak at a Bragg angle of 2θ of 27.2°, but the rest is broad and no clear peaks were observed.
【００９７】合成例４
合成例１においてチタニルフタロシアニン２．５ｇ及び
バナジルフタロシアニン２．５ｇを用いた他は合成例１
と同様にして青色結晶を得た。この結晶は図６に示すよ
うにブラッグ角２θの９．６°及び２７．２°にピーク
を有していた。Synthesis Example 4 Synthesis Example 1 except that 2.5 g of titanyl phthalocyanine and 2.5 g of vanadyl phthalocyanine were used in Synthesis Example 1.
Blue crystals were obtained in the same manner as above. As shown in FIG. 6, this crystal had peaks at Bragg angles 2θ of 9.6° and 27.2°.
【００９８】比較合成例１
合成例１のウエットペーストを乾燥して得られた粉末２
ｇを１−クロルナフタレンにより再結晶した。得られた
結晶は図７に示すようにブラッグ角２θの９．２゜、１
０．５゜、１３．１゜、１５．０゜、２６．２゜、２７
．１゜にピークを有するチタニルフタロシアニンとバナ
ジルフタロシアニンの混晶のＡ型結晶であることが判っ
た。Comparative Synthesis Example 1 Powder 2 obtained by drying the wet paste of Synthesis Example 1
g was recrystallized from 1-chloronaphthalene. The obtained crystal has a Bragg angle 2θ of 9.2° and 1 as shown in FIG.
0.5°, 13.1°, 15.0°, 26.2°, 27
．． It was found that it was a type A crystal of a mixed crystal of titanyl phthalocyanine and vanadyl phthalocyanine having a peak at 1°.
【００９９】比較合成例２
合成例１のウエットペーストを乾燥して得られた粉末２
ｇを１５０ｍｌの１，１，２，２−テトラクロルエタン
中で加熱還流して図８のようなブラッグ角２θの７．５
゜及び２８．６゜にピークを有するチタニルフタロシア
ニンとバナジルフタロシアニンの混晶のＢ型結晶を得た
。Comparative Synthesis Example 2 Powder 2 obtained by drying the wet paste of Synthesis Example 1
Heating and refluxing g in 150 ml of 1,1,2,2-tetrachloroethane resulted in a Bragg angle of 2θ of 7.5 as shown in Figure 8.
A type B crystal of a mixed crystal of titanyl phthalocyanine and vanadyl phthalocyanine having peaks at 28.6° and 28.6° was obtained.
【０１００】感光体試料の作成要件は下記の通りであり
、その要件を総括して表１に掲げた。The requirements for preparing the photoreceptor sample are as follows, and the requirements are summarized in Table 1.
【０１０１】〔Ａ〕感光体構成層塗料の調合（１）実施
例１〜２０並びに比較例（１）及び（２） ａ．
下引層（ＯＣＬ）塗料
ポリアミド樹脂（ラッカマイト−５００３
，大日本インキ製） ２５ｇ メ
タノール
１０００ｍｌ
混合溶解し、アルミニウム基体上に膜厚０
．５μｍに塗布した。[A] Preparation of photoconductor constituent layer coating (1) Examples 1 to 20 and Comparative Examples (1) and (2) a.
Undercoat layer (OCL) paint Polyamide resin (Laccamite-5003
, Dainippon Ink) 25g methanol
Mix and dissolve 1000ml to form a film with a thickness of 0 on an aluminum substrate.
．． It was applied to a thickness of 5 μm.
【０１０２】
ｂ．ＣＧＬ塗料
ＣＧＭ（表１掲示化合物）
２０ｇ シリコーン樹脂（固形分）
（ＫＲ５２４０；信越シリコン製） ２
０ｇ 酢酸イソプロピル
１０００ｍｌ
サンドグラインダで１０００ｒｐｍ；２ｈ
ｒ混合し、膜厚０．５μｍ（但し２層構成ＣＧＬの場合
は各層０．２５μｍ宛）に塗布した。b. CGL paint CGM (compounds listed in Table 1)
20g silicone resin (solid content)
(KR5240; manufactured by Shin-Etsu Silicon) 2
0g isopropyl acetate
1000ml sand grinder at 1000rpm; 2h
The mixture was mixed and coated to a film thickness of 0.5 μm (however, in the case of two-layer CGL, each layer was 0.25 μm).
【０１０３】
ｃ．ＣＴＬ塗料
ＣＴＭ（表１掲示化合物）
１３ｇ ポリカーボネート（ユーピロン
Ｚ−２００；三菱瓦斯化学製） ２２ｇ
１，２−ジクロルエタン
１０００ｍｌ
混合、溶解し、２０μｍ膜厚に塗布した。c. CTL paint CTM (compounds listed in Table 1)
13g Polycarbonate (Iupilon Z-200; manufactured by Mitsubishi Gas Chemical) 22g
1,2-dichloroethane
1000 ml was mixed, dissolved, and applied to a film thickness of 20 μm.
【０１０４】尚、表１，表２に記号で掲示したＣＧＭ，
ＣＴＭは下記の通りである。[0104] Furthermore, the CGMs listed with symbols in Tables 1 and 2,
The CTM is as follows.
【０１０５】[0105]
【化１３】[Chemical formula 13]
【０１０６】[0106]
【表１】[Table 1]
【０１０７】[0107]
【表２】[Table 2]
【０１０８】〔Ｂ〕感光体構成層の積層順位構成Ｉ
ＣＧＭ混成系（図１（ｂ）タイプ）構成ＩＩ Ｃ
ＧＭ２層分離系（図１（ａ）タイプ）ＩＩ １；Ｔ
ｉＯＰｃ−ＶＯＰｃの混晶層ＣＴＬ隣接ＩＩ ２；
多環キノン顔料層−ＣＴＬ隣接構成ＩＩＩ ＣＧＭ２
層の分離系（図２（ａ）タイプ）ＩＩＩ １；ＴｉＯ
Ｐｃ−ＶＯＰｃの混晶層ＣＴＬ隣接ＩＩＩ ２；多環
キノン顔料層−ＣＴＬ隣接〔Ｃ〕塗料方法
ＵＣＬ ディップコーティング法
ＣＧＬ 混合系；デップコーティング法２層分離系；
リングコーティング法
ＣＴＬ デップコーティング法
〔Ｄ〕特性評価
こうして得られた感光体試料の特性評価試験を以下のよ
うにして行った。結果を表１，表２に掲げた。[B] Lamination order configuration I of photoreceptor constituent layers
CGM hybrid system (Figure 1(b) type) configuration II C
GM two-layer separation system (Fig. 1(a) type) II 1;T
iOPc-VOPc mixed crystal layer CTL adjacent II 2;
Polycyclic quinone pigment layer - CTL adjacent structure III CGM2
Layer separation system (Fig. 2 (a) type) III 1; TiO
Pc-VOPc mixed crystal layer CTL adjacent III 2; Polycyclic quinone pigment layer-CTL adjacent [C] Coating method UCL Dip coating method CGL Mixing system; Dip coating method 2-layer separation system;
Ring Coating Method CTL Dip Coating Method [D] Characteristic Evaluation Tests for evaluating the characteristics of the thus obtained photoreceptor samples were conducted as follows. The results are listed in Tables 1 and 2.
【０１０９】〔感度試験〕静電帯電試験装置ＥＰＡ―８
１００（川口電機（株）製）を用いて、感光体表面電位
が初期電位から半減するのに必要な露光量Ｅ１／２（ｌ
ｕｘ・ｓｅｃ）を測定した。[Sensitivity test] Electrostatic charging test device EPA-8
100 (manufactured by Kawaguchi Electric Co., Ltd.), the exposure amount E1/2 (l
ux・sec) was measured.
【０１１０】〔繰返し特性試験〕上記静電帯電試験装置
ＥＰＡ―８１００を用いて、帯電→露光→除電を１００
回繰返した時の１回目と１００回目の帯電電位の変化量
Δｏ→１００（Ｖ）を測定した。（｜ΔＶＨ｜として求
めた。）〔長波長光感度測定〕前述のＥＰＡ―８１００
を用いる測定計において光源タングステンランプを使用
し、モノクロメーターを通し特に問題とする７８０ｎｍ
±１ｎｍの波長の光に対するＥ１／２（Ｖｃｍ２／ｅｒ
ｇ）を測定した。これは値の大きい方が感度がよい。[Repetitive characteristic test] Using the above electrostatic charging tester EPA-8100, charging → exposure → static electricity removal was repeated 100 times.
The amount of change in charging potential Δo → 100 (V) between the 1st and 100th repetitions was measured. (Determined as |ΔVH|) [Long wavelength light sensitivity measurement] EPA-8100 mentioned above
A tungsten lamp is used as a light source in a measuring instrument that uses
E1/2 (Vcm2/er) for light with a wavelength of ±1 nm
g) was measured. The larger the value, the better the sensitivity.
【０１１１】[0111]
【発明の効果】表１，表２の結果から明らかなように、
本発明の実施例は白色光、レーザ光に対する感度、繰返
し特性等すべての点で比較例より優れている。[Effect of the invention] As is clear from the results in Tables 1 and 2,
The examples of the present invention are superior to the comparative examples in all respects such as sensitivity to white light and laser light, and repeatability.
【図１】本発明の感光体態様例の断面図FIG. 1 is a sectional view of an embodiment of the photoreceptor of the present invention.
【図２】本発明
の感光体態様例の断面図FIG. 2 is a cross-sectional view of an embodiment of the photoreceptor of the present invention.
【図３】合成例１で得られたＴ
ｉＯＰｃ−ＶＯＰｃのＸ線回折スペクトル図[Figure 3] T obtained in Synthesis Example 1
X-ray diffraction spectrum diagram of iOPc-VOPc
【図４】合成例２で得られたＴｉＯＰｃ−ＶＯＰｃのＸ
線回折スペクトル図FIG. 4: X of TiOPc-VOPc obtained in Synthesis Example 2
Line diffraction spectrum diagram
【図５】合成例３で得られたＴｉＯＰｃ−ＶＯＰｃのＸ
線回折スペクトル図FIG. 5: X of TiOPc-VOPc obtained in Synthesis Example 3
Line diffraction spectrum diagram
【図６】合成例４で得られたＴｉＯＰｃ−ＶＯＰｃのＸ
線回折スペクトル図FIG. 6: X of TiOPc-VOPc obtained in Synthesis Example 4
Line diffraction spectrum diagram
【図７】比較例（１）で得られたＴｉＯＰｃ−ＶＯＰｃ
のＸ線回折スペクトル図FIG. 7: TiOPc-VOPc obtained in Comparative Example (1)
X-ray diffraction spectrum diagram of
【図８】比較例（２）で得られたＴｉＯＰｃ−ＶＯＰｃ
のＸ線回折スペクトル図FIG. 8 TiOPc-VOPc obtained in Comparative Example (2)
X-ray diffraction spectrum diagram of
１ 支持体
２ キャリア発生層（ＣＧＬ）
３ キャリア輸送層（ＣＴＬ）
４ ＴｉＯＰｃ−ＶＯＰｃ混晶及びアゾ化合物を含む
ＣＧＬ５ ＴｉＯＰｃ−ＶＯＰｃ混晶又はアゾ化合物
とＣＴＭを含むキャリア発生・輸送複合層（ＣＧＴＬ）
７ ＣＧＭとＣＴＭからなるＣＧＴＬ８ 保護層
９ バリア層
１０ 中間層1 Support 2 Carrier generation layer (CGL) 3 Carrier transport layer (CTL) 4 CGL containing a TiOPc-VOPc mixed crystal and an azo compound 5 Carrier generation/transport composite layer (CGTL) containing a TiOPc-VOPc mixed crystal or an azo compound and CTM 7 CGTL consisting of CGM and CTM 8 Protective layer 9 Barrier layer 10 Intermediate layer
Claims (1)
電荷輸送物質を含有する感光層を設けてなる電子写真感
光体において、電荷発生物質としてＣｕＫα特性Ｘ線（
波長１．５４１Å）に対するブラッグ角２θの２７．２
゜±０．２°に主たる明瞭なピークを有するチタニルフ
タロシアニンとバナジルフタロシアニンの混晶を含有し
、かつ下記一般式〔Ｑ〕で表される多環キノン顔料とを
別個に又は混合して含有する層を設けた電子写真感光体
。 【化１】 〔式中、Ｘはハロゲン原子、ニトロ基、シアノ基、アシ
ル基又はカルボキシル基を表し、ｎは０〜４の整数を表
し、ｍは０〜６の整数を表す。〕1. An electrophotographic photoreceptor comprising a photosensitive layer containing a charge-generating substance and a charge-transporting substance on a conductive support, in which CuKα characteristic X-rays (
Bragg angle 2θ for wavelength 1.541 Å) is 27.2
Contains a mixed crystal of titanyl phthalocyanine and vanadyl phthalocyanine having a main clear peak at ±0.2°, and contains a polycyclic quinone pigment represented by the following general formula [Q], either separately or in a mixture. An electrophotographic photoreceptor with layers. [Formula, X represents a halogen atom, a nitro group, a cyano group, an acyl group, or a carboxyl group, n represents an integer of 0 to 4, and m represents an integer of 0 to 6. ]
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14872991A JPH04371962A (en) | 1991-06-20 | 1991-06-20 | Electrophotographic sensitive body |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14872991A JPH04371962A (en) | 1991-06-20 | 1991-06-20 | Electrophotographic sensitive body |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04371962A true JPH04371962A (en) | 1992-12-24 |
Family
ID=15459307
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14872991A Pending JPH04371962A (en) | 1991-06-20 | 1991-06-20 | Electrophotographic sensitive body |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04371962A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07128889A (en) * | 1993-11-01 | 1995-05-19 | Fuji Xerox Co Ltd | Electrophotographic photoreceptor |
| US7358016B2 (en) | 2002-07-23 | 2008-04-15 | Osaka Gas Co., Ltd. | Electrophotographic photoreceptor and electrophoto-graphic apparatus equipped with the same |
-
1991
- 1991-06-20 JP JP14872991A patent/JPH04371962A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07128889A (en) * | 1993-11-01 | 1995-05-19 | Fuji Xerox Co Ltd | Electrophotographic photoreceptor |
| US7358016B2 (en) | 2002-07-23 | 2008-04-15 | Osaka Gas Co., Ltd. | Electrophotographic photoreceptor and electrophoto-graphic apparatus equipped with the same |
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