JPH0333862A - Electrophotographic sensitive body - Google Patents
Electrophotographic sensitive bodyInfo
- Publication number
- JPH0333862A JPH0333862A JP16859889A JP16859889A JPH0333862A JP H0333862 A JPH0333862 A JP H0333862A JP 16859889 A JP16859889 A JP 16859889A JP 16859889 A JP16859889 A JP 16859889A JP H0333862 A JPH0333862 A JP H0333862A
- Authority
- JP
- Japan
- Prior art keywords
- photosensitive layer
- titanyl phthalocyanine
- layer
- photoreceptor
- binder
- 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
- 239000000049 pigment Substances 0.000 claims abstract description 36
- 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 31
- 239000011230 binding agent Substances 0.000 claims abstract description 18
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 6
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 5
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 claims abstract description 5
- 229920001225 polyester resin Polymers 0.000 claims abstract description 4
- 229920005990 polystyrene resin Polymers 0.000 claims abstract description 4
- 239000005038 ethylene vinyl acetate Substances 0.000 claims abstract description 3
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims abstract description 3
- 108091008695 photoreceptors Proteins 0.000 claims description 40
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 8
- 239000006185 dispersion Substances 0.000 claims description 6
- 239000004645 polyester resin Substances 0.000 claims description 3
- 238000010030 laminating Methods 0.000 claims 1
- 229920000642 polymer Polymers 0.000 claims 1
- 230000035945 sensitivity Effects 0.000 abstract description 21
- 230000007547 defect Effects 0.000 abstract description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 51
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 27
- 239000000126 substance Substances 0.000 description 22
- 229920005989 resin Polymers 0.000 description 18
- 239000011347 resin Substances 0.000 description 18
- 239000000463 material Substances 0.000 description 13
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 11
- 239000013078 crystal Substances 0.000 description 10
- 238000001228 spectrum Methods 0.000 description 10
- 238000001914 filtration Methods 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- -1 methylethyl Chemical group 0.000 description 6
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- JTPNRXUCIXHOKM-UHFFFAOYSA-N 1-chloronaphthalene Chemical compound C1=CC=C2C(Cl)=CC=CC2=C1 JTPNRXUCIXHOKM-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-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
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229920000515 polycarbonate Polymers 0.000 description 4
- 239000004417 polycarbonate Substances 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- RZVCEPSDYHAHLX-UHFFFAOYSA-N 3-iminoisoindol-1-amine Chemical compound C1=CC=C2C(N)=NC(=N)C2=C1 RZVCEPSDYHAHLX-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
- 238000010521 absorption reaction Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 125000003367 polycyclic group Chemical group 0.000 description 3
- 239000002356 single layer Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 3
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- LWHDQPLUIFIFFT-UHFFFAOYSA-N 2,3,5,6-tetrabromocyclohexa-2,5-diene-1,4-dione Chemical compound BrC1=C(Br)C(=O)C(Br)=C(Br)C1=O LWHDQPLUIFIFFT-UHFFFAOYSA-N 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-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
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 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
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-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
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- YDSWCNNOKPMOTP-UHFFFAOYSA-N mellitic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(O)=O)=C(C(O)=O)C(C(O)=O)=C1C(O)=O YDSWCNNOKPMOTP-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- XQZYPMVTSDWCCE-UHFFFAOYSA-N phthalonitrile Chemical compound N#CC1=CC=CC=C1C#N XQZYPMVTSDWCCE-UHFFFAOYSA-N 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- 239000008096 xylene 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
- 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
- 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
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-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
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- SNOJPWLNAMAYSX-UHFFFAOYSA-N 2-methylpropan-1-ol;titanium Chemical compound [Ti].CC(C)CO.CC(C)CO.CC(C)CO.CC(C)CO SNOJPWLNAMAYSX-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
- ITUYMTWJWYTELW-UHFFFAOYSA-N 4-chloroiminocyclohexa-2,5-dien-1-one Chemical compound ClN=C1C=CC(=O)C=C1 ITUYMTWJWYTELW-UHFFFAOYSA-N 0.000 description 1
- OTLNPYWUJOZPPA-UHFFFAOYSA-N 4-nitrobenzoic acid Chemical compound OC(=O)C1=CC=C([N+]([O-])=O)C=C1 OTLNPYWUJOZPPA-UHFFFAOYSA-N 0.000 description 1
- 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
- 241000283690 Bos taurus Species 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical class C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 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
- 206010027146 Melanoderma Diseases 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 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
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 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
- 239000003963 antioxidant agent Substances 0.000 description 1
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- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 125000000609 carbazolyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 1
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- QJNYIFMVIUOUSU-UHFFFAOYSA-N chloroethene;ethenyl acetate;furan-2,5-dione Chemical compound ClC=C.CC(=O)OC=C.O=C1OC(=O)C=C1 QJNYIFMVIUOUSU-UHFFFAOYSA-N 0.000 description 1
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- 230000000149 penetrating effect Effects 0.000 description 1
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- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
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- 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
- 239000002985 plastic film Substances 0.000 description 1
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- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 1
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- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
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- 229920002635 polyurethane Polymers 0.000 description 1
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- 239000011118 polyvinyl acetate Substances 0.000 description 1
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- 230000002250 progressing effect Effects 0.000 description 1
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 description 1
- 150000003219 pyrazolines Chemical class 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229920002050 silicone resin 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
- UGNWTBMOAKPKBL-UHFFFAOYSA-N tetrachloro-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(Cl)=C(Cl)C1=O UGNWTBMOAKPKBL-UHFFFAOYSA-N 0.000 description 1
- AUHHYELHRWCWEZ-UHFFFAOYSA-N tetrachlorophthalic anhydride Chemical compound ClC1=C(Cl)C(Cl)=C2C(=O)OC(=O)C2=C1Cl AUHHYELHRWCWEZ-UHFFFAOYSA-N 0.000 description 1
- NLDYACGHTUPAQU-UHFFFAOYSA-N tetracyanoethylene Chemical group N#CC(C#N)=C(C#N)C#N NLDYACGHTUPAQU-UHFFFAOYSA-N 0.000 description 1
- 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
- VLLMWSRANPNYQX-UHFFFAOYSA-N thiadiazole Chemical compound C1=CSN=N1.C1=CSN=N1 VLLMWSRANPNYQX-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 125000005259 triarylamine group Chemical group 0.000 description 1
Landscapes
- Photoreceptors In Electrophotography (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は電子写真感光体に関し、特に光導電性材料とし
て特定のチタニルフタロシアニン顔料を用い、プリンタ
、複写機等に有効であって、露光手段として半導体レー
ザー光及び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ものである。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to an electrophotographic photoreceptor, in particular, it uses a specific titanyl phthalocyanine pigment as a photoconductive material, and is effective for printers, copying machines, etc. The present invention relates to an electrophotographic photoreceptor which is also suitable for image formation using semiconductor laser light, LED light, or the like.
［従来の技術］
近年、電子写真感光体に用いられる光導電性林料として
、無機光導電性材料に代えて有機光導電性材料が多く用
いられるようになった。その理由は、有機光導電性材料
においては、合成物質及び合成条件の組合せにより多種
多様の材料を得ることができ、材料の選択の自由度が大
きく、目的に応じて所望の感光体を容易に作製できるか
らである。[Prior Art] In recent years, organic photoconductive materials have been increasingly used instead of inorganic photoconductive materials as photoconductive materials used in electrophotographic photoreceptors. The reason for this is that a wide variety of organic photoconductive materials can be obtained by combining synthetic substances and synthesis conditions, and there is a large degree of freedom in selecting materials, making it easy to create the desired photoreceptor depending on the purpose. This is because it can be manufactured.
更にまた、前記有機光導電性林料を用いた感光体におい
ては、キャリア発生機能とキレリア輸送機能とを異なる
材料に分担させた機能分離型とすることにより、林料の
選択の自由度が一層拡大され、帯電能、感度及び耐久性
等の電子写真特性の改善が期待されるようになった。Furthermore, in the photoreceptor using the organic photoconductive forest material, the degree of freedom in selecting the forest material is further increased by making the photoreceptor a functionally separated type in which the carrier generation function and the chirelia transport function are shared by different materials. As a result, improvements in electrophotographic properties such as chargeability, sensitivity, and durability are expected.
他方、複写業界において、−ｍの画質の改善及びｍｅの
＆Ｉ集機能が要請され、これに対応したデジタル方式の
複写機又はプリンター等の記録装置の開発が進められて
おり、そのための記録媒体としての感光体の改善かの望
されている。前記デジタル方式の記録装置においては、
一般に、画像信号により変調されたレーザー光を用いて
ドツト状に露光して感光体上にドツト潜像を形成し、こ
れを反転現像方式により現像して像形成を行うようにし
ている。この場合、前記レーザー光としては、露光袋ｄ
の単純化、小型化及び低価格化が可能な半導体レー１Ｆ
−装置が好ましく用いられ、その発振波長はｙｓｏｎｍ
以上の赤外ｆｔ１ＩｔＪ、とされている。従って、用い
られる感光体としては、少なくとも１５０〜８５０ｒｖ
の波長領域に高感度を有することが要求される。On the other hand, in the copying industry, improvements in the image quality of the -m and the &I collection function of the me are required, and the development of digital copying machines, printers, and other recording devices to meet these demands is progressing, and as a recording medium for this purpose, Improvements in photoreceptors are desired. In the digital recording device,
Generally, a latent dot image is formed on a photoreceptor by exposing it in dots using a laser beam modulated by an image signal, and this is developed by a reversal development method to form an image. In this case, as the laser beam, the exposure bag d
Semiconductor Ray 1F that can be simplified, downsized, and lowered in price
- device is preferably used, the oscillation wavelength of which is ysonm
The above infrared ft1ItJ. Therefore, the photoreceptor used should have at least 150 to 850 rv.
It is required to have high sensitivity in the wavelength range of .
ところで、前記機能弁ｌＩ！ｉ型の感光体に用いられる
主１１９フ発生物質として、種々の有機染料又は有機顔
料が提案されており、例えば、ジブロムアンスアンスロ
ンに代表される多環キノン顔料、ビリリウム染料、及び
該ビリリウム染料とポリカーボネートとの共晶錯体、ス
クェアリウム顔料、フタロシアニン顔料、アゾ顔料等が
実用化されている。これらのうち、特開昭（３１−２３
９２４８号公報、同６１−２１７０５０号公報、同６２
−６７０９４号公報及び同６３−２１８７６８号公報等
には、７５０ｎ１１以上の長波長領域に主感度を有する
チタニル系フタロシアニン顔料が記載されている。こう
したチタニル系フタロシアニン顔料はいずれも、特定の
凝集構造もしくは結晶構造をもだしることによって、主
吸収を長波長化させ、高感度化を図ったものであるが、
前記したｉｎの製造条件の設定が難しく、このため、帯
電能、感度、繰り返し特性等の特性全般を満足するもの
が得られず、また、感度の点では一層の高感度化が望ま
れる。By the way, the function valve lI! Various organic dyes or organic pigments have been proposed as the main 119-fluorescent material used in I-type photoreceptors, such as polycyclic quinone pigments represented by dibromoanthurone, biryllium dyes, and biryllium dyes. Eutectic complexes of polycarbonate and polycarbonate, squareium pigments, phthalocyanine pigments, azo pigments, etc. have been put into practical use. Among these, Tokukai Sho (31-23
No. 9248, No. 61-217050, No. 62
JP-67094, JP-63-218768, and the like describe titanyl-based phthalocyanine pigments having main sensitivity in a long wavelength region of 750n11 or more. All of these titanyl-based phthalocyanine pigments have a specific agglomerated or crystalline structure, which increases the wavelength of the main absorption and increases sensitivity.
It is difficult to set the manufacturing conditions for the above-mentioned in, and for this reason, it is not possible to obtain a product that satisfies all the characteristics such as charging ability, sensitivity, and repeatability.In addition, in terms of sensitivity, even higher sensitivity is desired.
本出願人は先に、前記高感度化の要望に対応するものと
して、特開昭６４−１７０６８＠明１１１５１及び特願
昭６３−２８６５３７号明ＩＩＩ（昭和６３年１１月１
１日出ＷＩ）により高感度チタニル系フタロシアニン感
光体を提案した。この感光体は、キャリア発生物質とし
てＣｏ−Ｋａ特性Ｘ線（波長１．５４ Ａ ＞ ニ対１
ｔ６ブラツグ角度２θの主要ピークが少なくとも２７．
２゜±０．２°及び９．６゜±０．２°にあるチタニル
フタロシアニン顔料を用いた点に特徴がある。The present applicant previously proposed Japanese Patent Application Laid-Open No. 17068/1988@Mei 11151 and Japanese Patent Application No. 286537/1986 Mei III (November 1, 1988) as a response to the above-mentioned demand for higher sensitivity.
1) proposed a highly sensitive titanyl-based phthalocyanine photoreceptor. This photoreceptor uses Co-Ka characteristic X-rays (wavelength: 1.54 A > 2:1) as a carrier-generating substance.
The main peak of t6 bragg angle 2θ is at least 27.
It is characterized by the use of titanyl phthalocyanine pigments at angles of 2°±0.2° and 9.6°±0.2°.
即ち、この顔料は、従来公知のチタニル系フタロシアニ
ン顔料とは全く異なった前記ｘｍ回折スペクトルを有し
ていて、可視及び近赤外の吸収スペクトルが７８０ｎ−
〜８Ｂ０ｎｌに最大吸収を示す凝集状態を有し、前記レ
ーザー光に対して極めて高感度な特性を発揮しうるちの
である。That is, this pigment has the above-mentioned xm diffraction spectrum that is completely different from that of conventionally known titanyl-based phthalocyanine pigments, and has a visible and near-infrared absorption spectrum of 780n-
It has an agglomerated state showing maximum absorption at ~8B0nl, and exhibits extremely high sensitivity to the laser beam.
〔発明が解決しようとする課Ｍ］
本出願人が先に提案した上記チタニルフタロシアニン顔
料は前記のように優れた感度特性を有し、また、感光体
上への像形成に際し゛〔、画像信号により変調されたレ
ーザー光によりドツト露光して前記感光体上にドツト潜
像を形成し、該ｌｆ＆のドツト露光部を反転現像してド
ツト状のトナー画像を良好に得ることができる。ところ
が、このようなチタニルフタロシアニン顔料を用いた感
光体の感度特性や電荷保持性は、その分散方法によって
左右されることがあり、分散方法の確立によって安定し
た特性を得ることが望まれている。[Problem M to be Solved by the Invention] The titanyl phthalocyanine pigment previously proposed by the present applicant has excellent sensitivity characteristics as described above, and also has excellent sensitivity characteristics when forming an image on a photoreceptor. A dot latent image is formed on the photoconductor by dot exposure with a laser beam modulated by a signal, and the dot-exposed area of lf& is reversely developed to obtain a good dot-shaped toner image. However, the sensitivity characteristics and charge retention properties of photoreceptors using such titanyl phthalocyanine pigments may be affected by the dispersion method, and it is desired to obtain stable characteristics by establishing a dispersion method.
他方、通常の電子写真感光体においては、接地されたＩ
ＪＩＷＩ！ｍと感光層との間のＮ魚釣接触は微視的には
均一ではなく、例えば４１１層側からのキャリア注入が
場所によって異なるために、感光体表面に保持される電
荷分布に、局所的な差異が生じる。これは、現像の後に
、画像欠陥として顕在化し、ポジ型現像方式においては
黒地に白色斑点、ネガ型の反転現像方式においては白地
に黒色斑点となる。特に反転現像方式における黒色斑点
は、地かぶりと同様に、画像品質を著しく損なうもので
ある。この問題は、前記の高感度化された感光体におい
ては特に鋭敏に生じ、前記反転現像方式における黒色斑
点の発生が顕著となる。On the other hand, in a normal electrophotographic photoreceptor, the grounded I
JIWI! The contact between the photoreceptor and the photoreceptor layer is not microscopically uniform; for example, carrier injection from the 411 layer side differs depending on the location. There will be significant differences. This becomes apparent as an image defect after development, and becomes a white spot on a black background in a positive type development system, and a black spot on a white background in a negative type reversal development system. In particular, black spots in the reversal development system significantly impair image quality, similar to background fog. This problem occurs particularly acutely in the above-mentioned highly sensitive photoreceptor, and the occurrence of black spots in the above-mentioned reversal development method becomes conspicuous.
本発明は上記従来の課題に鑑みなされたもので、その口
開は、特に半導体レーザー等の長波長光に対して高感度
特性を右し、電荷保持性が良好で、さらに、画像欠陥、
特に反転現像時における黒色斑点の少ない電子写真感光
体を提供することにある。The present invention has been made in view of the above-mentioned conventional problems, and the aperture has high sensitivity characteristics, especially to long wavelength light such as semiconductor lasers, good charge retention, and furthermore, has the advantage of preventing image defects.
The object of the present invention is to provide an electrophotographic photoreceptor with fewer black spots especially during reversal development.
［Ｎ題を解決するための手段］
上記目的を達成するために、本発明は、導電性支持体上
に感光層を有する電子写真感光体において、前記感光層
がＣｕ−にα特性Ｘ線（波長１．５４Ａ＞に対するブラ
ッグ角２θの主要ピークが少なくとも９．６゜±０．２
°及び２１．２゜±０２゜にあり且つ９．６′″±０．
２°のピーク強度が２７．２’″±０，２°のピーク強
度の４０％以上であるチタニルフタロシアニン顔料を含
有し、前記感光層はさらにバインダーとしてアクリル樹
脂、ポリエステル樹脂、ポリスチレン樹脂、エチレン−
酢酸ビニル共重合体及び塩化ビニル−酢酸ビニル共瓜合
体から選ばれる少なくとも１種を含有することを特徴と
する。[Means for Solving Problem N] In order to achieve the above object, the present invention provides an electrophotographic photoreceptor having a photosensitive layer on a conductive support, in which the photosensitive layer is exposed to α characteristic X-rays ( The main peak of the Bragg angle 2θ for a wavelength of 1.54 A> is at least 9.6° ± 0.2
° and 21.2°±02° and 9.6′″±0.
The photosensitive layer contains a titanyl phthalocyanine pigment whose peak intensity at 2° is 40% or more of the peak intensity at 27.2'''±0.2°, and the photosensitive layer further contains acrylic resin, polyester resin, polystyrene resin, ethylene resin, etc. as a binder.
It is characterized by containing at least one member selected from a vinyl acetate copolymer and a vinyl chloride-vinyl acetate copolymer.
本発明に係る前記チタニルフタロシアニン顔料は、前記
した各公報で知られたチタニル系フタロシアニン顔料と
は顔料結晶の凝集状態が異なり、後記の実施例の第３図
〜第５図に示されるような独特のＸ線回折スペクトルを
右していて、可視及び近赤外の吸収スベク１−ルが７８
０ｎｍ〜８６０ｎｍに最大吸収を示す凝集状態を有し、
半導体レーザー光等に対して極めて高感ＩＪ！な特性を
発揮しうるものである。本発明に係る前記チタニルフタ
ロシアニン顔料の基本構造は次の一般式で表される。The titanyl phthalocyanine pigment according to the present invention is different from the titanyl phthalocyanine pigments known in the above-mentioned publications in the agglomeration state of pigment crystals, and has unique characteristics as shown in FIGS. 3 to 5 of Examples described later. The X-ray diffraction spectrum of the visible and near-infrared absorption spectrum is 78
It has an agglomerated state that exhibits maximum absorption between 0 nm and 860 nm,
Extremely sensitive IJ to semiconductor laser light, etc.! It can exhibit unique characteristics. The basic structure of the titanyl phthalocyanine pigment according to the present invention is represented by the following general formula.
式中、ＸＩ 、Ｘ２ 、Ｘ３及び×４はそれぞれ水素原
子、ハロゲン原子、アルキル基又はアルコキシ基を表し
、ｎ、ｍ、ｌ及びｋはそれぞれＯ〜４の整数を表す。In the formula, XI, X2, X3 and x4 each represent a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group, and n, m, l and k each represent an integer of O to 4.
また、上記のＸ線回折スペクトルは次の条件で測定した
もの（以下同様）である。Moreover, the above X-ray diffraction spectrum was measured under the following conditions (the same applies hereinafter).
Ｘ線管球 Ｃｕ 電圧 ４０．０ ＫＶ 雷電流 １００．０ ｍＡ スタート角＠ ６．００ ｄｅｇ。X-ray tube Cu Voltage 40.0 KV Lightning current 100.0 mA Starting angle @ 6.00 deg.
ストップ角度 ３５．００ ｄｅｇ。Stop angle 35.00 deg.
ステップ角度 ０．０２０ ｄｃｇ。Step angle: 0.020 dcg.
測定時ｌ１ａＩ０．５０ ｓｅｃ。During measurement l1aI0.50 sec.
また、上記のＸ線回折スペクトルは「３２０型自記記録
分光光度計」 （日立製作新製）を用いて測定され、反
射壁の回折スペクトルとされる。Moreover, the above-mentioned X-ray diffraction spectrum is measured using a "320 type self-recording spectrophotometer" (manufactured by Hitachi Seisakusho), and is taken as the diffraction spectrum of the reflecting wall.
本発明に係るチタニルフタロシアニン顔料は前記ブラッ
グ角２θの主要ピークが９，６゜±０．２゜及び２７．
２゜±０．２°にあるが、これらの特徴的なピークの他
に、１１．７’″± ０．２°、１５．０”± ０．２
′″２３．５”±０．２°及び２４．１゜±０．２°に
もピークを有している。The titanyl phthalocyanine pigment according to the present invention has the main peaks of the Bragg angle 2θ of 9.6°±0.2° and 27.0°.
2° ± 0.2°, but in addition to these characteristic peaks, 11.7'" ± 0.2°, 15.0" ± 0.2
It also has peaks at '23.5'±0.2° and 24.1°±0.2°.
さらに本発明に係るチタニルフタロシアニン顔料は、前
記ブラッグ角２θの９，６゛±０．２°のピーク強度が
２７．２゜±０．２°のピーク強度の４０％以上のもの
であり、感度、帯電性等の点から特に好ましい。Furthermore, the titanyl phthalocyanine pigment according to the present invention has a peak intensity at 9.6° ± 0.2° of the Bragg angle 2θ that is 40% or more of the peak intensity at 27.2° ± 0.2°, and has sensitivity. , is particularly preferable from the viewpoint of charging properties and the like.
本発明に係る前記チタニルフタロシアニンの製造方法を
次に説明する。例えば、１，３−ジイミノイソインドリ
ンとスルホランを混合し、これにチタニウムテトラプロ
ポキシドを加え、窒素雰囲気下に反応させる。反応温度
は８０℃〜３００℃で、特に１００℃〜２６０℃が好ま
しい。反応終了後、放冷した後析出物を濾取し、チタニ
ルフタロシアニンを得ることができる。次にこれを溶媒
処理することによって、第３図〜第５図に示す目的の結
晶型のチタニルフタロシアニン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攪拌装置の他に
、ホモミキサ、ディスパーサ、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
。The method for producing the titanyl phthalocyanine according to the present invention will be explained next. For example, 1,3-diiminoisoindoline and sulfolane are mixed, titanium tetrapropoxide is added thereto, and the mixture is reacted under a nitrogen atmosphere. The reaction temperature is 80°C to 300°C, particularly preferably 100°C to 260°C. After the reaction is completed, the precipitate is collected by filtration after being left to cool to obtain titanyl phthalocyanine. Next, by treating this with a solvent, the desired crystalline titanyl phthalocyanine shown in FIGS. 3 to 5 can be obtained.
As the apparatus used for the treatment, in addition to a general stirring apparatus, a homomixer, a disperser, an agitator, a ball mill, a sand mill, an attritor, etc. can be used.
本発明では、キャリア発生物質として上記のチタニルフ
タロシアニンの他に、本発明の効果を損わない範囲で他
の主１９フ発生物質をＯｆ用してもよい。そのようなり
１用可能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α
型、β型、α、β混台型台型モルファス型等のチタニル
フタロシアニンをはじめ、他のフタロシアニン顔料、ア
ゾ顔料、アントラキノン顔料、ペリレン顔料、多環牛ノ
ン顔料、スクェアリウム顔料等が挙げられる。In the present invention, in addition to the above-mentioned titanyl phthalocyanine, other carrier-generating substances may be used as carrier-generating substances to the extent that the effects of the present invention are not impaired. Examples of carrier generating substances that can be used in this way include those that differ in crystal form from the titanyl phthalocyanine of the present invention, such as α
In addition to titanyl phthalocyanine of type, β type, α, β mixed table type, trapezoid type, and amorphous type, other phthalocyanine pigments, azo pigments, anthraquinone pigments, perylene pigments, polycyclic bovine pigments, squareium pigments, etc.
本発明の感光体を作製するには、例えば、溶媒にバイン
ダー樹脂を溶解した溶液中に本発明に係る前記チタニル
フタロシアニン顔料を混合分散し、かつこれに後述する
キャリア輸送物質を溶解してなる塗布液を、必要に応じ
て予め下引層を設けた導電性支持体上に例えばデイツプ
コーティング、スプレーコーティング、スパイラルコー
ティング等の方法により塗布加工して、第１図の単層構
成の感光体を得る。なお、図中の１は導電性支持体、２
は単層構成の感光層、３は下引層である。To produce the photoreceptor of the present invention, for example, the titanyl phthalocyanine pigment of the present invention is mixed and dispersed in a solution of a binder resin dissolved in a solvent, and a carrier transporting substance described below is dissolved therein. The liquid is coated onto a conductive support on which a subbing layer has been provided in advance, if necessary, by a method such as dip coating, spray coating, or spiral coating to form a photoreceptor having a single layer structure as shown in FIG. obtain. In addition, 1 in the figure is a conductive support, 2
3 is a photosensitive layer having a single layer structure, and 3 is an undercoat layer.
しかしながら、高感度特性及び高耐久性の感光体を得る
上から、機能分離型の第２図の２層構成の感光体とする
のが好ましい。この場合、バインダー樹脂を溶解した溶
液中に前記顔料を混合分散してなる塗布液を、必要に応
じて前記下引層をイｊ゛する支持体１上に塗布してキャ
リア発生１ｉＷ５を形成した後、該キャリア発生層上に
キャリア輸送物質を含む塗布液を塗ず１１加工してキャ
リア輸送層６を積層し、２層構成の感光層４を形成する
。以下、２層構成の感光体を中心として説明する。However, from the viewpoint of obtaining a photoreceptor with high sensitivity and high durability, it is preferable to use a functionally separated photoreceptor having a two-layer structure as shown in FIG. 2. In this case, a coating solution prepared by mixing and dispersing the pigment in a solution containing a binder resin was coated on the support 1 on which the undercoat layer was applied, if necessary, to form carrier generation 1iW5. Thereafter, a coating solution containing a carrier transporting substance is coated on the carrier generating layer and processed 11 to form a carrier transporting layer 6, thereby forming a photosensitive layer 4 having a two-layer structure. The following description focuses on a photoreceptor having a two-layer structure.
前記の２層構成の感光層４のキ１アリア発生ＦｒＪ５を
形成するには、適当な溶剤又は分散媒中にバインダー樹
脂を混合溶解し、得られた溶液中に前記チタニルフタロ
シアニン顔料を混合し、ホモミキサー、ボールミル又は
超合波分子ｌｉ器等により分散して、前記顔料の微細粒
子を含む塗Ｉ５液を作成し、前記導電性支持体１の表面
に設置ノた下引層３上に塗布加工される。In order to form the photosensitive layer 4 having a two-layer structure, the chia-aryl-generating FrJ5 is prepared by mixing and dissolving a binder resin in a suitable solvent or dispersion medium, and mixing the titanyl phthalocyanine pigment into the resulting solution. A coating liquid I5 containing fine particles of the pigment is prepared by dispersing it using a homo mixer, a ball mill, a super-combined molecular lithium-ionizer, etc., and is coated on the subbing layer 3 placed on the surface of the conductive support 1. Processed.
前記２層構成の感光体におけるキャリア発生層を形成す
るに際して、分散含イｉされる前記チタニルフタロシア
ニン顔料の分数液中での、及び層形成後の結晶性及び凝
集性の安定化にとって、シクロヘキサノンに可溶な樹脂
がバインダー樹脂として有利であることが判明した。When forming the carrier generation layer in the two-layered photoreceptor, cyclohexanone is used to stabilize the crystallinity and cohesion of the titanyl phthalocyanine pigment in the fractional solution and after layer formation. It has been found that soluble resins are advantageous as binder resins.
本発明ではシクロヘキサノンに可溶な樹脂として、具体
的には、アクリル樹脂、ポリエステル樹脂、ポリスチレ
ン樹脂、エチレン−酢酸ビニル共重合体及び塩化ビニル
−酢酸ビニル共重合体から選ばれる少なくとも１種が用
いられる。これらの樹脂は市販品として容易に入手する
ことができる。In the present invention, as the cyclohexanone-soluble resin, specifically, at least one selected from acrylic resin, polyester resin, polystyrene resin, ethylene-vinyl acetate copolymer, and vinyl chloride-vinyl acetate copolymer is used. . These resins are easily available as commercial products.
前記キャリア発生層５に用いられるバインダー樹脂は、
単独或いは２Ｆ１以上の混合物として用いることができ
る。またバインダー樹脂に対するキャリア発生物質の割
合は好ましくは１０〜６００重厘％、更に好ましくは５
０〜４ｏｏｎ ｍ％とされる。The binder resin used for the carrier generation layer 5 is:
It can be used alone or as a mixture of 2F1 or more. The ratio of the carrier generating substance to the binder resin is preferably 10 to 600% by weight, more preferably 5% by weight.
It is assumed to be 0-4oon m%.
また、キャリア発生層の形成に使用される溶剤或は分散
媒としてはシクロヘキサノンを用いるのが最も好ましい
が必要に応じて他のｍ ＩＲｅ Ｕｒ用してもよい。併
用可能な溶媒としては、ｎ−ブチルアミン、エチレンジ
アミン、Ｎ、Ｎ−ジメチルボルムアミド、アセトン、メ
チルエチルヶ］・ン、テトラヒドロフラン、ジオ：ｔＵ
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］−フェノン、クロロホルム
、ジクロロメタン、ジクロロエタン、トリクロロエタン
、メタノール、エタノール、プロパノール、ブタノール
等が挙げられる。Further, as the solvent or dispersion medium used for forming the carrier generation layer, it is most preferable to use cyclohexanone, but other m IRe Ur may be used as necessary. Solvents that can be used in combination include n-butylamine, ethylenediamine, N,N-dimethylbormamide, acetone, methylethyl, tetrahydrofuran, and tU.
ethyl acetate, butyl acetate, methyl cellosolve, ethyl cellosolve, ethylene glycol dimethyl ether,
Examples include toluene, xylene, ace]-phenone, chloroform, dichloromethane, dichloroethane, trichloroethane, methanol, ethanol, propanol, butanol, and the like.
このようにして形成されるキャリア発生層５の厚さは０
．０１〜２０μｍであることが好ましいが、更に好まし
くは０．０５〜５μｉｔ”ある。The thickness of the carrier generation layer 5 formed in this way is 0.
．． It is preferably 0.01 to 20 μm, more preferably 0.05 to 5 μm.
上記キャリア発生物質を分散せしめてキャリア発生層５
を形成する場合においては、当該キャリア発生物質は２
μｍ以下、好ましくは１μｍ以下の平均粒径の粉粒体と
されるのが好ましい。即ち、粒径が余り大きいと、層中
への分散が悪くなるとともに、粒子が表面に一部突出し
て表面の平滑性が悪くなり、場合によっては粒子の突出
部分で放電が生じたり、あるいはそこにトナー粒子が付
着してトナーフィルミング現象が生じ易い。The carrier generating layer 5 is made by dispersing the carrier generating substance.
, the carrier-generating substance is 2
It is preferable that the particles have an average particle diameter of 1 μm or less, preferably 1 μm or less. In other words, if the particle size is too large, dispersion in the layer will be poor, and some of the particles will protrude from the surface, resulting in poor surface smoothness. Toner particles tend to adhere to the toner, causing a toner filming phenomenon.
次に、前記キャリア発生層５上にキャリア輸送１１６を
設けて感光体が作製されるが、前記キャリア輸送層６を
形成するための塗布液に用いられる溶剤としては、後述
するバインダー樹脂及びキヤリア輸送層６等を溶解する
が下層のキャリア発生層５を溶解又は浸食しないものが
選択される。Next, a photoreceptor is manufactured by providing a carrier transport layer 116 on the carrier generation layer 5. As for the solvent used in the coating liquid for forming the carrier transport layer 6, the binder resin and the carrier transport layer described below are used as solvents. A material is selected that dissolves the layer 6 etc. but does not dissolve or erode the carrier generation layer 5 below.
前記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、Ａキサゾール、オ
キサジアゾール、チタゾール、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、ボ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−フェニルススチリルトリフエ
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。Various carrier transport substances can be used, but typical examples include nitrogen-containing heterocyclic nuclei and their fused ring nuclei represented by A-xazole, oxadiazole, titazole, thiadiazole, imidazole, etc. , polyarylalkane compounds, pyrazoline compounds, hydrazone compounds, triarylamine compounds, styryl compounds, styryltriphenylamine compounds, β-phenylstyryltriphenylamine compounds, butadiene compounds, Examples include hexatriene compounds, carbazole compounds, and fused polycyclic compounds.
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− ＋ ０７３５ Ｇ ５′−ｉに記載のキャリア
輸送物質を挙げることができるが、
特に代表的なしの
−１
−２
−３
−４
−７
Ｔ−９
Ｔ−１４
−１５
−１７
−１８
−１９
前記キャリア輸送物質と共にキトリアｆａ５ｙｓＭを形
成するためのバインダー樹脂としては、任意のものを選
ぶことができるが、疎水性でかつフィルム形成能を有す
るものとされ、以下のものを挙げることができる。Specific examples of these carrier transport substances include carrier transport substances described in JP-A-61-+0735 G 5'-i, but particularly representative examples include No-1-2-3-4. -7 T-9 T-14 -15 -17 -18 -19 Any binder resin can be selected for forming chitria fa5ysM together with the carrier transporting substance, but it must be hydrophobic and have a film-forming ability. The following can be mentioned.
ポリカーボネート ポリカーボネート２樹脂アクリル樹
脂 メタクリル樹脂
ポリ塩化ごニル ポリ塩化ご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
−酢酸ビニル共項合体
塩化ビニル−酢酸ビニル−無水マレイン酸共重合体
キャリア輸送層の形成に使用される溶剤或は分ｌ！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、
ｎ−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、ジクロロ
メタン、ジクロロエタン、トリクロロエタン、メタノー
ル、エタノール、プロパノール、ブタノール等が挙げら
れる。Polycarbonate Polycarbonate 2 Resin Acrylic Resin Methacrylic Resin Polynylidene Chloride Polystyrene
Styrene-butadiene copolymer polyvinyl acetate polyvinylcarbazole styrene-alkyd resin silicone resin silicone-alkyd resin polyester phenolic resin polyurethane epoxy resin vinylidene chloride-acrylonitrile copolymer vinyl chloride-vinyl acetate copolymer vinyl chloride-vinyl acetate-maleic anhydride Solvent or component used to form the acid copolymer carrier transport layer! A wide variety of media can be used. for example,
n-Butylamine, ethylenediamine, N,N-dimethylformamide, acetone, methyl ethyl ketone, cyclohexanone, tetrahydrofuran, dioxane, ethyl acetate, butyl acetate, methyl cellosolve, ethyl cellosolve, ethylene glycol dimethyl ether, toluene, xylene, acetophenone, chloroform, dichloromethane , dichloroethane, trichloroethane, methanol, ethanol, propanol, butanol and the like.
バインダー樹脂に対するキャリア輸送物質の割合は好ま
しくは１０〜５００重量％とされ、また、キャリア輸送
層の厚みは好ましくは１〜１００μ−１更に好ましくは
５〜３０μ層とされる。The ratio of the carrier transport substance to the binder resin is preferably 10 to 500% by weight, and the thickness of the carrier transport layer is preferably 1 to 100 μ-1, more preferably 5 to 30 μ.
本発明の感光体の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、無水コハク酸、無水マレイ
ン酸、ジブロム無水コハク酸、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７ タルＷ、４−二１・ロ無水フタル酸、無水
ピロメリット酸、無水メリット酸、テｔ−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、諷−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、ブロマニル、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、０−二１へ口安息香酸、ｐ−
二トロ安息香酸、３．５−ジニトロ安息香酸、ペンタフ
ルオロ安息香酸、５−二１へロサリチル酸、３゜５−ジ
ニトロサリチル酸、フタル酸、メリット酸、その他の電
子親和力の大きい化合物を挙げることができる。電子受
容性物質の添加割合はキル９フ発生物質の暖間１００に
対して０．０１〜２００が望ましく、更には０．１〜１
０Ｇが好ましい。The photosensitive layer of the photoreceptor of the present invention can 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-nitroanhydride 7 tal W, 4-21 - Phthalic anhydride, pyromellitic anhydride, mellitic anhydride, tetracyanoethylene, tetracyanoquinodimethane, 0-dinitrobenzene, dinitrobenzene, 1,3.5-trinitrobenzene, p-nitro Benzonitrile, vicryl chloride, quinone chlorimide, chloranil, bromanil, dichlorodicyano-p-benzoquinone, anthraquinone,
Dinitroanthraquinone, 9-fluorenylidene malonodinitrile, polynitro-9-fluorenylidene malonodinitrile, picric acid, 0-21 hebenzoic acid, p-
Nitrobenzoic acid, 3.5-dinitrobenzoic acid, pentafluorobenzoic acid, 5-21-herosalicylic acid, 3゜5-dinitrosalicylic acid, phthalic acid, mellitic acid, and other compounds with high electron affinity may be mentioned. can. The addition ratio of the electron-accepting substance is preferably 0.01 to 200, more preferably 0.1 to 1.
0G is preferred.
また、上記感光層中には、保存性、耐久性、嗣環境依存
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。Further, the photosensitive layer may contain deterioration inhibitors such as antioxidants and light stabilizers for the purpose of improving storage stability, durability, and environmental dependence.
なお、ｍ１図に示した単ｍ構成の感光体においては、感
光層２に用いるキャリア発生物質は本発明に係るチタニ
ルフタロシアニン等であり、キャリア輸送物質は上述し
たものから選択してよい。In the photoreceptor having a single meter structure shown in the m1 diagram, the carrier generating substance used in the photosensitive layer 2 is titanyl phthalocyanine according to the present invention, etc., and the carrier transporting substance may be selected from those mentioned above.
また、感光層２のバインダー樹脂は前記の本発明に係る
バインダー樹脂を少なくとも主成分として使用する。そ
の他、感光層２への添加物質も上述したものと同様であ
ってよい。Further, the binder resin of the photosensitive layer 2 uses the above-mentioned binder resin according to the present invention as at least the main component. Other substances added to the photosensitive layer 2 may also be the same as those mentioned above.
前記導電性支持体としては、金属板、金属ドラム等が用
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上に設けてなるものが用いら
れる。As the conductive support, a metal plate, a metal drum, etc. are used, and a thin layer of a conductive polymer, a conductive compound such as indium oxide, or a metal such as aluminum or palladium is coated, vapor-deposited, laminated, etc. Depending on the situation, a material provided on paper, plastic film, etc. is used.
本発明の感光体の構成は以上に例示したが、以下の実施
例からも明らかなように、レーザー光を露光手段とする
感光体として高感度特性を有し、且つ、反転現像時に黒
色斑点などの欠点を生ずることのない優れた特性を有す
る。The structure of the photoreceptor of the present invention has been exemplified above, but as is clear from the following examples, it has high sensitivity characteristics as a photoreceptor that uses laser light as an exposure means, and also has black spots etc. during reversal development. It has excellent properties without any disadvantages.
［実施例］ 以下、本発明を実施例によって更に詳細に説明する。[Example] Hereinafter, the present invention will be explained in more detail with reference to Examples.
まず、各種のチタニルフタロシアニンｌｌＲｎの合成例
を述べる。First, examples of synthesis of various titanyl phthalocyanines llRn will be described.
（合成例１）
１．３−ジイミノイソインドリン２９．２Ｑとスルホラ
ン２００１ｆｔを混合し、チタニウムテトライソブ０ボ
キシド１７．０（ｌを加え、窒素雰囲気下に１４０℃で
２時間反応させた。放冷した後析出物を濾取し、クロロ
ホルムで洗浄、２％の塩酸水溶液で洗浄、水洗、メタノ
ール洗浄して、乾燥の後２５． ｓｇ（８８，５％）の
チタニルフタロシアニンを得た。(Synthesis Example 1) 29.2 Q of 1,3-diiminoisoindoline and 2001 ft of sulfolane were mixed, 17.0 (l) of titanium tetraisobutoxide was added, and the mixture was reacted at 140° C. for 2 hours under a nitrogen atmosphere. After cooling, the precipitate was collected by filtration, washed with chloroform, 2% aqueous hydrochloric acid, water, and methanol, and after drying, 25.sg (88.5%) of titanyl phthalocyanine was obtained.
生成物は２０倍量の濃硫酸に溶解し、１００００倍量に
あけて析出させて、濾取した後にウェットケーキを１，
２−ジクロルエタンにて５０℃で１０時間加熱して第３
図に示すｘ１６回折スペクトルをもつ結晶型とした。こ
の結晶はブラッグ角２θの９．６°のピーク強度が２７
．２’のそれの１０２％であった。The product was dissolved in 20 times the volume of concentrated sulfuric acid, poured into 10,000 times the volume to precipitate it, and after filtering, the wet cake was dissolved in 1,000 times the volume.
The third mixture was heated in 2-dichloroethane at 50°C for 10 hours.
A crystal form having the x16 diffraction spectrum shown in the figure was obtained. This crystal has a peak intensity of 27° at a Bragg angle of 2θ of 9.6°.
．． It was 102% of that of 2'.
（合成例２）
１．３−ジイミノイソインドリン２９．２（ｌとスルホ
ラン２００１１２を混合し、チタニウムテトライソプロ
ボキジド１７． ｏｇを加え、窒素雰囲気下に１４０℃
で２時間反応させた。放冷した後析出物を濾取し、クロ
ロホルムで洗浄、２％の塩酸水溶液で洗浄、水洗、メタ
ノール洗浄して、乾燥の後２５． ｓｇ＜ ８８．５％
）のチタニルフタロシアニンを得た。(Synthesis Example 2) Mix 29.2 (l) of 1,3-diiminoisoindoline and sulfolane 200112, add 17.0 g of titanium tetraisoproboxide, and heat at 140°C under a nitrogen atmosphere.
The mixture was allowed to react for 2 hours. After cooling, the precipitate was collected by filtration, washed with chloroform, washed with a 2% aqueous hydrochloric acid solution, washed with water, washed with methanol, and dried. 25. sg<88.5%
) titanyl phthalocyanine was obtained.
生成物は２０（８ｆｆｉ＋７）Ｉ！１ｉｔｌ［：溶解り
、、１００倍１の水にあけて析出させて、濾取した後に
ウェットケーキを１，２−ジクロルエタンにて室温で１
時間撹拌して第４図に示すｘｓｉｔ回折スペクトルをも
つ結晶型とした。この結晶はブラッグ角２θの９．６°
のピーク強度が２７．２°のそれの７５％であった。The product is 20(8ffi+7)I! 1 itl [: dissolved, poured into 100 times 1 water to precipitate, collected by filtration, and diluted the wet cake with 1,2-dichloroethane at room temperature.
After stirring for a period of time, a crystal form having an xsit diffraction spectrum shown in FIG. 4 was formed. This crystal has a Bragg angle of 2θ of 9.6°
The peak intensity at 27.2° was 75% of that at 27.2°.
（合成例３）
フタロジニトリル２５．６（Ｊとα−クロルナフタレン
１５０１Ｊ２の混合物中に窒素気流下で６．５ｍ１２の
四塩化チタンを滴下し、２００〜２２０℃の温度で５時
間反応させた。析出物を濾取し、α−クロルナフタレン
で洗浄した後、クロロホルムで洗浄し、続いてメタノー
ルで洗浄した。次いでアンモニア水中で還流して加水分
解を完結させた後、水洗、メタノール洗浄し乾燥の後ゲ
ータニルフタロシアニン２１．８（１（７！ｉ、６％）
を得た。(Synthesis Example 3) 6.5 ml of titanium tetrachloride was added dropwise into a mixture of phthalodinitrile 25.6 (J) and α-chlornaphthalene 1501J2 under a nitrogen stream, and the mixture was reacted at a temperature of 200 to 220°C for 5 hours. The precipitate was collected by filtration, washed with α-chlornaphthalene, then washed with chloroform, and then washed with methanol.Then, the precipitate was refluxed in aqueous ammonia to complete hydrolysis, and then washed with water, methanol, and dried. After getanylphthalocyanine 21.8 (1 (7!i, 6%)
I got it.
生成物は１（Ｈｌｌｆｆｉのａ 硝酸に溶解し、１００
倍色の水にあけて析出させて、濾取した後にウェットケ
ーキを１，２−ジクロルエタンにて室温で１時間撹拌し
て第５図に示すＸ線回折スペクトルをもつ結晶型とした
。この結晶はブラッグ角２θの９．６°のピーク強度が
２７．２°のそれの４５％であった。The product is 1 (Hllffi's a) dissolved in nitric acid, 100
After pouring into double-colored water to precipitate and collecting by filtration, the wet cake was stirred in 1,2-dichloroethane at room temperature for 1 hour to obtain a crystal form having the X-ray diffraction spectrum shown in FIG. In this crystal, the peak intensity at a Bragg angle of 2θ of 9.6° was 45% of that at 27.2°.
（比較合成例１）
フタロジニトリル２５．８ｇとα−クロルナフタレン１
５０ｗｊ２の混合物中に窒素気流下で６．５１１２の四
塩化チタンを滴下し、２００〜２２０℃の温度で５時間
反応させた。析出物を濾取し、α−クロルナフタレンで
洗浄した後、クロロホルムで洗浄し、続いてメタノール
で洗浄した。次いでアンモニア水中で還流して加水分解
を完結させた後、水洗、メタノール洗浄し乾燥の後チタ
ニルフタロシアニン２１．８Ｑ （７５，６％）を得
た。(Comparative synthesis example 1) 25.8 g of phthalodinitrile and 1 α-chlornaphthalene
6.5112 titanium tetrachloride was added dropwise into the 50wj2 mixture under a nitrogen stream, and the mixture was reacted at a temperature of 200 to 220°C for 5 hours. The precipitate was collected by filtration, washed with α-chlornaphthalene, then with chloroform, and then with methanol. The mixture was then refluxed in aqueous ammonia to complete hydrolysis, washed with water, washed with methanol, and dried to obtain titanyl phthalocyanine 21.8Q (75.6%).
生成物は１０倍ｍの濃硫酸に溶解し、１００倍匹の水に
あけて析出させて、濾取した後にウェットケーキを０−
ジクロルベンゼンにて室温で１時間撹拌して第６図に示
すＸｔａ回折スペクトルをもつ結晶型とした。この結晶
はブラッグ角２θの９．６°のピーク強度が２７．２°
のそれの３５％であった。The product was dissolved in 10 times the volume of concentrated sulfuric acid, poured into 100 times the volume of water to precipitate it, and after filtering, the wet cake was dissolved in 0-
The mixture was stirred in dichlorobenzene at room temperature for 1 hour to obtain a crystal form having the Xta diffraction spectrum shown in FIG. This crystal has a peak intensity of 27.2° at a Bragg angle of 2θ of 9.6°.
It was 35% of that of .
（比較合成例２）
合成例１のウェットケーキを乾燥後、α−クロＯナフタ
レンを用いて、加熱撹拌することによって、第７図に示
すようなβ型のチタニルフタロシアニンを得た。(Comparative Synthesis Example 2) After drying the wet cake of Synthesis Example 1, β-type titanyl phthalocyanine as shown in FIG. 7 was obtained by heating and stirring using α-chloroO naphthalene.
（実施例１）
共重合ポリアミド「ラッカマイト５０◇３」 （大日本
インキ社製）３部（部はｌｌｆｌｌ部を示す二以下同じ
）をメタノール１００部に加熱溶解し、０．６μ量フイ
ルタで濾過した後、８！透塗布法によって、アルミニウ
ムドラム上に塗布し、膜厚０．５μ躍の下引層を形成し
た。(Example 1) Copolymerized polyamide "Laccamite 50 ◇ 3" (manufactured by Dainippon Ink Co., Ltd.) 3 parts (where "part" means "llfll" is the same below) were heated and dissolved in 100 parts of methanol, and filtered with a 0.6μ filter. After that, 8! It was coated on an aluminum drum by a transparent coating method to form a subbing layer with a thickness of 0.5 μm.
一方、合成例１において（ｑられた第３図のＸ １２回
折パターンを石するチタニルフタロシアニン３部、バイ
ンダ樹脂としてポリメチルメタクリル酸ンドミルを用い
て分散した液を、先の下引層の上に、浸透塗布法によっ
て塗７Ｇして、膜厚０．２μｍのキャリア発生層を形成
した。次いで、キｔｚリア輸送物質Ｔ−１の１８８、ポ
リカーボネート樹脂「ニーピロンＺ ２００Ｊ （三菱
瓦斯化学社製）１．５部、微量のシリコーンオイルｒＫ
Ｆ−５４Ｊ （信越化学社製〉を、１，２−ジクロロ
エタン１０部に溶解した液を用いて浸透塗布し乾燥の後
、膜厚２５μ−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試料１とする。On the other hand, in Synthesis Example 1, a dispersion of 3 parts of titanyl phthalocyanine, which shows the X12 diffraction pattern in Figure 3, and polymethyl methacrylic acid domil as a binder resin, was applied onto the previous subbing layer. 7G was applied by a penetrating coating method to form a carrier generation layer with a film thickness of 0.2 μm.Next, 188 of Kitz rear transport material T-1 and polycarbonate resin “Nipilon Z 200J (manufactured by Mitsubishi Gas Chemical Co., Ltd.) 1 were applied. .5 parts, trace amount of silicone oil rK
F-54J (manufactured by Shin-Etsu Chemical Co., Ltd.) was applied by penetration using a solution dissolved in 10 parts of 1,2-dichloroethane, and after drying, a carrier transport layer with a thickness of 25 μm was formed. Sample 1 is the photoreceptor.
（実施例２〜７）
キャリア発生物質の種類及びキャリア発生層の樹脂の種
類を表−２に示すものとした他は実施例表−２から、本
発明の感光体は、比較感光体に比して高感度特性を有し
、かつ画像欠陥が少なく、反転現像時の黒斑点が少ない
ことがわかる。しかも分散安定性が良好なため、１ケ月
後の特性が変化しないことがわかる。(Examples 2 to 7) From Table 2 of Examples, except that the type of carrier generating substance and the type of resin of the carrier generating layer were as shown in Table 2, the photoreceptors of the present invention were compared with the comparative photoreceptors. It can be seen that the film has high sensitivity characteristics, fewer image defects, and fewer black spots during reversal development. Moreover, since the dispersion stability is good, it can be seen that the characteristics do not change after one month.
［発明の効果］
以上詳細に説明したように、本発明の感光体によれば、
反転現像時の黒斑点等の発生が少なく、′Ｉｓ感度、高
画質の画像が安定して得られる。[Effects of the Invention] As explained in detail above, according to the photoreceptor of the present invention,
There is little occurrence of black spots during reversal development, and images with high sensitivity and high quality can be stably obtained.
第１図及び第２図はそれぞれ本発明の感光体の層構成を
例示する断面図、第３図〜第５図はそれぞれ本発明の実
施例のチタニルフタロシアニン顔料のＸ線回折スペクト
ル図、第６図及び第７図はそれぞれ比較例のチタニルフ
タロシアニン顔料のＸＰｊ回折スペクトル図である。
１・・・導電性支持体
２・・・単層構成の感光層
３・・・下引層
４・・・２１！Ｊ構成の感光層
５・・・キャリア発生層
６・・・キャリア輸送層1 and 2 are cross-sectional views illustrating the layer structure of the photoreceptor of the present invention, respectively. 7 and 7 are XPj diffraction spectra of titanyl phthalocyanine pigments of comparative examples, respectively. 1... Conductive support 2... Single-layer photosensitive layer 3... Subbing layer 4... 21! J-configuration photosensitive layer 5...carrier generation layer 6...carrier transport layer
Claims (3)
において、前記感光層がＣｕ−Ｋα特性Ｘ線（波長１．
５４Å）に対するブラッグ角２θの主要ピークが少なく
とも９．６゜±０．２゜及び２７．２゜±０．２゜にあ
り且つ９．６゜±０．２゜のピーク強度が２７．２゜±
０．２゜のピーク強度の４０％以上であるチタニルフタ
ロシアニン顔料を含有し、前記感光層はさらにバインダ
ーとしてアクリル樹脂、ポリエステル樹脂、ポリスチレ
ン樹脂、エチレン−酢酸ビニル共重合体及び塩化ビニル
−酢酸ビニル共重合体から選ばれる少なくとも１種を含
有することを特徴とする電子写真感光体。(1) In an electrophotographic photoreceptor having a photosensitive layer on a conductive support, the photosensitive layer is exposed to Cu-Kα characteristic X-rays (wavelength 1.
54 Å), the main peaks of the Bragg angle 2θ are at least 9.6° ± 0.2° and 27.2° ± 0.2°, and the peak intensity at 9.6° ± 0.2° is 27.2° ±
The photosensitive layer contains a titanyl phthalocyanine pigment having a peak intensity of 40% or more at 0.2°, and the photosensitive layer further contains an acrylic resin, a polyester resin, a polystyrene resin, an ethylene-vinyl acetate copolymer, and a vinyl chloride-vinyl acetate copolymer as a binder. An electrophotographic photoreceptor comprising at least one selected from polymers.
ンにて溶解し、これに前記チタニルフタロシアニン顔料
を分散させた分散液を用いて作製されたものであること
を特徴とする請求項１記載の電子写真感光体。(2) The photosensitive layer is produced using a dispersion in which the binder is dissolved in cyclohexanone and the titanyl phthalocyanine pigment is dispersed therein. Photoreceptor.
がこの順に積層されてなり、該キャリア発生層が前記チ
タニルフタロシアニン顔料及びバインダーを含有する請
求項１又は２記載の電子写真感光体。(3) The electrophotographic photoreceptor according to claim 1 or 2, wherein the photosensitive layer is formed by laminating a carrier generation layer and a carrier transport layer in this order, and the carrier generation layer contains the titanyl phthalocyanine pigment and a binder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16859889A JPH0333862A (en) | 1989-06-30 | 1989-06-30 | Electrophotographic sensitive body |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16859889A JPH0333862A (en) | 1989-06-30 | 1989-06-30 | Electrophotographic sensitive body |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0333862A true JPH0333862A (en) | 1991-02-14 |
Family
ID=15871024
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16859889A Pending JPH0333862A (en) | 1989-06-30 | 1989-06-30 | Electrophotographic sensitive body |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0333862A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0414053A (en) * | 1990-05-07 | 1992-01-20 | Ricoh Co Ltd | Manufacture of electrophotographic sensitive body |
| FR2757861A1 (en) * | 1996-12-26 | 1998-07-03 | Sharp Kk | Crystalline titanyl phthalocyanine |
-
1989
- 1989-06-30 JP JP16859889A patent/JPH0333862A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0414053A (en) * | 1990-05-07 | 1992-01-20 | Ricoh Co Ltd | Manufacture of electrophotographic sensitive body |
| FR2757861A1 (en) * | 1996-12-26 | 1998-07-03 | Sharp Kk | Crystalline titanyl phthalocyanine |
| US5972551A (en) * | 1996-12-26 | 1999-10-26 | Sharp Kabushiki Kaisha | Crystalline titanyl phthalocyanines and use thereof |
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