JPH04338968A - Electrophotographic sensitive body - Google Patents
Electrophotographic sensitive bodyInfo
- Publication number
- JPH04338968A JPH04338968A JP16871491A JP16871491A JPH04338968A JP H04338968 A JPH04338968 A JP H04338968A JP 16871491 A JP16871491 A JP 16871491A JP 16871491 A JP16871491 A JP 16871491A JP H04338968 A JPH04338968 A JP H04338968A
- Authority
- JP
- Japan
- Prior art keywords
- titanyl phthalocyanine
- photoreceptor
- present
- phthalocyanine pigment
- synthesis example
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- SJHHDDDGXWOYOE-UHFFFAOYSA-N oxytitamium phthalocyanine Chemical compound [Ti+2]=O.C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 SJHHDDDGXWOYOE-UHFFFAOYSA-N 0.000 claims abstract description 55
- 239000000049 pigment Substances 0.000 claims abstract description 38
- 229910001868 water Inorganic materials 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000004458 analytical method Methods 0.000 claims abstract description 7
- 238000004455 differential thermal analysis Methods 0.000 claims abstract description 7
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- 125000003118 aryl group Chemical group 0.000 claims abstract description 5
- 125000005103 alkyl silyl group Chemical group 0.000 claims abstract description 4
- 125000005104 aryl silyl group Chemical group 0.000 claims abstract description 4
- 108091008695 photoreceptors Proteins 0.000 claims description 45
- 150000001875 compounds Chemical class 0.000 claims description 13
- 230000035945 sensitivity Effects 0.000 abstract description 14
- 239000013078 crystal Substances 0.000 abstract description 13
- 239000004065 semiconductor Substances 0.000 abstract description 6
- 238000010521 absorption reaction Methods 0.000 abstract description 3
- 238000000862 absorption spectrum Methods 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 47
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 45
- 230000015572 biosynthetic process Effects 0.000 description 42
- 238000003786 synthesis reaction Methods 0.000 description 42
- 239000000126 substance Substances 0.000 description 27
- 230000000052 comparative effect Effects 0.000 description 15
- 239000000463 material Substances 0.000 description 14
- 239000011230 binding agent Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- 229920000548 poly(silane) polymer Polymers 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 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 9
- 238000000576 coating method Methods 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000012046 mixed solvent Substances 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 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
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000003708 ampul Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- GNEPOXWQWFSSOU-UHFFFAOYSA-N dichloro-methyl-phenylsilane Chemical compound C[Si](Cl)(Cl)C1=CC=CC=C1 GNEPOXWQWFSSOU-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000002612 dispersion medium Substances 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000004417 polycarbonate Substances 0.000 description 3
- 229920000515 polycarbonate Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- 239000002356 single layer Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 3
- 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
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-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
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N Vilsmeier-Haack reagent Natural products CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- 229920000180 alkyd Polymers 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
- 239000011521 glass Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 239000007788 liquid Substances 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
- 238000002156 mixing Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000000149 penetrating effect Effects 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
- 125000003367 polycyclic group Chemical group 0.000 description 2
- WVIICGIFSIBFOG-UHFFFAOYSA-N pyrylium Chemical compound C1=CC=[O+]C=C1 WVIICGIFSIBFOG-UHFFFAOYSA-N 0.000 description 2
- 229920002050 silicone resin Polymers 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 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
- IZUKQUVSCNEFMJ-UHFFFAOYSA-N 1,2-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1[N+]([O-])=O IZUKQUVSCNEFMJ-UHFFFAOYSA-N 0.000 description 1
- XVMIKRZPDSXBTP-UHFFFAOYSA-N 1,3-dibromobutan-2-one Chemical compound CC(Br)C(=O)CBr XVMIKRZPDSXBTP-UHFFFAOYSA-N 0.000 description 1
- WDCYWAQPCXBPJA-UHFFFAOYSA-N 1,3-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC([N+]([O-])=O)=C1 WDCYWAQPCXBPJA-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- HJRJRUMKQCMYDL-UHFFFAOYSA-N 1-chloro-2,4,6-trinitrobenzene Chemical compound [O-][N+](=O)C1=CC([N+]([O-])=O)=C(Cl)C([N+]([O-])=O)=C1 HJRJRUMKQCMYDL-UHFFFAOYSA-N 0.000 description 1
- JTPNRXUCIXHOKM-UHFFFAOYSA-N 1-chloronaphthalene Chemical compound C1=CC=C2C(Cl)=CC=CC2=C1 JTPNRXUCIXHOKM-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
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 1
- WDMUXYQIMRDWRC-UHFFFAOYSA-N 2-hydroxy-3,4-dinitrobenzoic acid Chemical compound OC(=O)C1=CC=C([N+]([O-])=O)C([N+]([O-])=O)=C1O WDMUXYQIMRDWRC-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
- SLAMLWHELXOEJZ-UHFFFAOYSA-N 2-nitrobenzoic acid Chemical compound OC(=O)C1=CC=CC=C1[N+]([O-])=O SLAMLWHELXOEJZ-UHFFFAOYSA-N 0.000 description 1
- UKYNESNNFCHAEV-UHFFFAOYSA-N 3,4-dibromooxolane-2,5-dione Chemical compound BrC1C(Br)C(=O)OC1=O UKYNESNNFCHAEV-UHFFFAOYSA-N 0.000 description 1
- VYWYYJYRVSBHJQ-UHFFFAOYSA-N 3,5-dinitrobenzoic acid Chemical compound OC(=O)C1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1 VYWYYJYRVSBHJQ-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- ITUYMTWJWYTELW-UHFFFAOYSA-N 4-chloroiminocyclohexa-2,5-dien-1-one Chemical compound ClN=C1C=CC(=O)C=C1 ITUYMTWJWYTELW-UHFFFAOYSA-N 0.000 description 1
- ROFZMKDROVBLNY-UHFFFAOYSA-N 4-nitro-2-benzofuran-1,3-dione Chemical compound [O-][N+](=O)C1=CC=CC2=C1C(=O)OC2=O ROFZMKDROVBLNY-UHFFFAOYSA-N 0.000 description 1
- OTLNPYWUJOZPPA-UHFFFAOYSA-N 4-nitrobenzoic acid Chemical compound OC(=O)C1=CC=C([N+]([O-])=O)C=C1 OTLNPYWUJOZPPA-UHFFFAOYSA-N 0.000 description 1
- NKJIFDNZPGLLSH-UHFFFAOYSA-N 4-nitrobenzonitrile Chemical compound [O-][N+](=O)C1=CC=C(C#N)C=C1 NKJIFDNZPGLLSH-UHFFFAOYSA-N 0.000 description 1
- MMVIDXVHQANYAE-UHFFFAOYSA-N 5-nitro-2-benzofuran-1,3-dione Chemical compound [O-][N+](=O)C1=CC=C2C(=O)OC(=O)C2=C1 MMVIDXVHQANYAE-UHFFFAOYSA-N 0.000 description 1
- MEXUTNIFSHFQRG-UHFFFAOYSA-N 6,7,12,13-tetrahydro-5h-indolo[2,3-a]pyrrolo[3,4-c]carbazol-5-one Chemical compound C12=C3C=CC=C[C]3NC2=C2NC3=CC=C[CH]C3=C2C2=C1C(=O)NC2 MEXUTNIFSHFQRG-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000004420 Iupilon Substances 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 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
- UATJOMSPNYCXIX-UHFFFAOYSA-N Trinitrobenzene Chemical compound [O-][N+](=O)C1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1 UATJOMSPNYCXIX-UHFFFAOYSA-N 0.000 description 1
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
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- 125000003545 alkoxy group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- WLVCKQCYPRKQMH-UHFFFAOYSA-N bis(chloromethyl)silane Chemical compound ClC[SiH2]CCl WLVCKQCYPRKQMH-UHFFFAOYSA-N 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 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
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- VIRVTHOOZABTPR-UHFFFAOYSA-N dichloro(phenyl)silane Chemical compound Cl[SiH](Cl)C1=CC=CC=C1 VIRVTHOOZABTPR-UHFFFAOYSA-N 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 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 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- -1 indium oxide Chemical class 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- APHGZSBLRQFRCA-UHFFFAOYSA-M indium(1+);chloride Chemical compound [In]Cl APHGZSBLRQFRCA-UHFFFAOYSA-M 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
- 239000004611 light stabiliser Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- NNYHMCFMPHPHOQ-UHFFFAOYSA-N mellitic anhydride Chemical compound O=C1OC(=O)C2=C1C(C(OC1=O)=O)=C1C1=C2C(=O)OC1=O NNYHMCFMPHPHOQ-UHFFFAOYSA-N 0.000 description 1
- 239000000113 methacrylic resin Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- OXNIZHLAWKMVMX-UHFFFAOYSA-N picric acid Chemical compound OC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O OXNIZHLAWKMVMX-UHFFFAOYSA-N 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 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
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003595 spectral effect Effects 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
- 229920001909 styrene-acrylic polymer Polymers 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- WMOVHXAZOJBABW-UHFFFAOYSA-N tert-butyl acetate Chemical compound CC(=O)OC(C)(C)C WMOVHXAZOJBABW-UHFFFAOYSA-N 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
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Photoreceptors In Electrophotography (AREA)
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チタニルフタロシアニン
顔料と特定の化合物とを用い、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LE
D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。[Industrial Application Field] The present invention relates to an electrophotographic photoreceptor.
In particular, it uses a specific titanyl phthalocyanine pigment and a specific compound as a photoconductive material, and is effective for printers, copiers, etc., and uses semiconductor laser light and LE as an exposure means.
The present invention relates to an electrophotographic photoreceptor that is also suitable for forming images using D light or the like.
【0002】0002
【従来の技術】近年、電子写真感光体に用いられる光導
電性材料として、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。2. Description of the Related Art In recent years, organic photoconductive materials have been increasingly used in place 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.
【0003】更にまた、前記有機光導電性材料を用いた
感光体においては、キャリア発生機能とキャリア輸送機
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、材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 material, the degree of freedom in material selection is increased by making the photoreceptor a functionally separated type in which the carrier generation function and carrier transport function are shared by different materials. As a result, improvements in electrophotographic properties such as charging ability, sensitivity, and durability are expected.
【0004】他方、複写業界において、一層の画質の改
善及び画像の編集機能が要請され、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
改善が切望されている。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
光を用いてドット状に露光して感光体上にドット潜像を
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
、露光装置の単純化、小型化及び低価格化が可能な半導
体レーザー装置が好ましく用いられ、その発振波長は7
50nm以上の赤外領域とされている。従って、用いら
れる感光体としては、少なくとも750〜850nm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, there is a demand for further improvement in image quality and image editing functions, and development of recording devices such as digital copiers or printers to meet this demand is progressing, and recording media for this purpose are being developed. There is a strong need for improvements in photoreceptors for use as photoreceptors. In the digital recording apparatus, generally, a dot latent 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. I try to do this. In this case, as the laser beam, it is preferable to use a semiconductor laser device which can simplify, downsize and reduce the cost of the exposure device, and its oscillation wavelength is 7.
It is said to be in the infrared region of 50 nm or more. Therefore, the photoreceptor used is required to have high sensitivity at least in the wavelength range of 750 to 850 nm.
【0005】ところで、前記機能分離型の感光体に用い
られるキャリア発生物質として、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、ピリリウム染料、
及び該ピ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。なかでもフタロシアニン顔料は
光電変換の量子効率が高く、また近赤外領域まで高い分
光感度を示すため、特に半導体レーザ光源に対応する電
子写真感光体用として注目されてきた。By the way, various organic dyes or organic pigments have been proposed as carrier-generating substances used in the functionally separated photoreceptor, such as polycyclic quinone pigments represented by dibromuanthurone, pyrylium dyes, etc. ,
Also, eutectic complexes of the pyrylium dye and polycarbonate, squareium pigments, phthalocyanine pigments, azo pigments, etc. have been put into practical use. Among them, phthalocyanine pigments have high photoelectric conversion quantum efficiency and exhibit high spectral sensitivity up to the near-infrared region, so they have attracted attention, especially for use in electrophotographic photoreceptors compatible with semiconductor laser light sources.
【0006】そのような目的に対して、銅フタロシアニ
ン、無金属フタロシアニン、クロルインジウムフタロシ
アニン、クロルガリウムフタロシアニンなどを用いた電
子写真感光体が報告されているが、近年特にチタニルフ
タロシアニンが注目されるようになり、例えば特開昭6
1−239248号、同62−670943号、同62
−272272号、同63−116158号のようにチ
タニルフタロシアニンの種々の結晶型を用いた電子写真
感光体が開示されている。For such purposes, electrophotographic photoreceptors using copper phthalocyanine, metal-free phthalocyanine, chlorindium phthalocyanine, chlorgallium phthalocyanine, etc. have been reported, but titanyl phthalocyanine has recently attracted particular attention. For example, JP-A No. 6
No. 1-239248, No. 62-670943, No. 62
Electrophotographic photoreceptors using various crystal forms of titanyl phthalocyanine have been disclosed, such as No. 272272 and No. 63-116158.
【0007】[0007]
【発明が解決しようとする課題】一般にフタロシアニン
を電子写真感光体に用いる場合、その結晶型によって特
性は著しく変化することは良く知られている。従って、
電子写真感光体用のフタロシアニンとしては高感度で帯
電能に優れた安定な結晶型が必要である。しかしながら
、従来開示されているチタニルフタロシアニンは、高感
度で、かつ高温高湿環境下における繰り返し使用の安定
性のよいものがない。すなわち、α型チタニルフタロシ
アニンは高感度ではあるが、安定性が悪く、またβ型チ
タニルフタロシアニンは感度が劣るという欠点を有して
いる。It is well known that when phthalocyanine is used in an electrophotographic photoreceptor, its properties vary significantly depending on its crystal type. Therefore,
As a phthalocyanine for electrophotographic photoreceptors, a stable crystal type with high sensitivity and excellent charging ability is required. However, none of the previously disclosed titanyl phthalocyanines has high sensitivity and good stability in repeated use under high temperature and high humidity environments. That is, although α-type titanyl phthalocyanine has high sensitivity, it has poor stability, and β-type titanyl phthalocyanine has the disadvantage of poor sensitivity.
【0008】本発明はこのような従来の課題に鑑みなさ
れたもので、高感度でしかも外部環境の影響を受けにく
く、繰り返し使用特性も良好な電子写真感光体を提供す
ることを目的とする。The present invention has been made in view of the above-mentioned problems in the prior art, and it is an object of the present invention to provide an electrophotographic photoreceptor that is highly sensitive, less susceptible to the influence of the external environment, and has good repeated use characteristics.
【0009】[0009]
【課題を解決するための手段】上記目的を達成するため
に、本発明の電子写真感光体は、真空中での吸着ガスの
成分分析において分子数で水分子が最も多く含まれてい
るチタニルフタロシアニン顔料と、下記一般式[I]で
表わされる繰返し単位を有する化合物とを含有する構成
を特徴としたものである。[Means for Solving the Problems] In order to achieve the above object, the electrophotographic photoreceptor of the present invention is a titanyl phthalocyanine containing the largest number of water molecules in the component analysis of adsorbed gas in vacuum. It is characterized by a structure containing a pigment and a compound having a repeating unit represented by the following general formula [I].
【0010】0010
【化2】
式中、R1及びR2はそれぞれアルキル基、アリール基
、アルキルシリル基又はアリールシリル基を表わす。embedded image In the formula, R1 and R2 each represent an alkyl group, an aryl group, an alkylsilyl group or an arylsilyl group.
【0011】以下、本発明を詳細に説明する。The present invention will be explained in detail below.
【0012】本発明に係る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フタロシアニン
顔料とは顔料結晶の凝集状態が異なり、さらに真空中で
の吸着ガスの成分分析において分子数で水分子が最も多
く含まれているという特徴を有していて、可視及び近赤
外の吸収スペクトルが780nm〜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
極めて高感度な特性を発揮しうるものである。The titanyl phthalocyanine pigment according to the present invention differs from the titanyl phthalocyanine pigments known in the above-mentioned publications in the aggregation state of the pigment crystals, and furthermore, in the component analysis of the adsorbed gas in vacuum, the number of water molecules is It has the characteristic of being the most abundant, and has an agglomerated state in which the visible and near-infrared absorption spectrum shows maximum absorption in the range of 780 nm to 860 nm, and has the property of being extremely sensitive to semiconductor laser light, etc. It is something that can be demonstrated.
【0013】本発明において、上記の吸着ガスの成分分
析は次の方法で測定することができる。In the present invention, the component analysis of the adsorbed gas described above can be performed by the following method.
【0014】チタニルフタロシアニン顔料0.5gを大
気下湿度60%の条件にて内容積3.0cm3のガラス
管に封入したアンプルを測定室に装着し、真空度2×1
0−8Torrの測定室中にてアンプルの破断を行ない
、四重極質量分析管にてアンプル中より放出されるガス
の分子量を検出して成分分析を行なう。[0014] An ampoule containing 0.5 g of titanyl phthalocyanine pigment sealed in a glass tube with an internal volume of 3.0 cm3 under atmospheric conditions of 60% humidity was placed in the measurement chamber, and the degree of vacuum was 2 x 1.
The ampoule is broken in a measurement chamber at 0-8 Torr, and the molecular weight of the gas released from the ampoule is detected using a quadrupole mass spectrometer tube for component analysis.
【0015】また、感光ドラムからのキャリア発生物質
中のチタニルフタロシアニン顔料の水分子量を測定でき
る。Furthermore, the water molecular weight of the titanyl phthalocyanine pigment in the carrier-generating material from the photosensitive drum can be measured.
【0016】すなわち、感光ドラムをメタノール(純度
98%以上)中に常温で浸漬し、感光層をアルミニウム
基体から分離する。次に基体から分離した感光層をメチ
レンクロライド中で溶解し、濾紙を用いてメチレンクロ
ライド(純度98%以上)の洗浄を繰り返しながらろ過
する。ろ紙上の析出物を酢酸−t−ブチル(純度98%
以上)に溶解し、得られた液を遠心分離器により沈澱物
を分離する。That is, the photosensitive drum is immersed in methanol (purity of 98% or more) at room temperature to separate the photosensitive layer from the aluminum substrate. Next, the photosensitive layer separated from the substrate is dissolved in methylene chloride, and filtered using filter paper while repeatedly washing with methylene chloride (purity of 98% or more). The precipitate on the filter paper was treated with t-butyl acetate (purity 98%).
(above) and separate the precipitate from the resulting solution using a centrifuge.
【0017】このようにして得られたチタニルフタロシ
アニンを洗浄し、120℃で乾燥後、前述の方法により
吸着分子の定量を行う事ができる。After washing the thus obtained titanyl phthalocyanine and drying at 120° C., the amount of adsorbed molecules can be determined by the method described above.
【0018】この成分分析の結果、チタニルフタロシア
ニン顔料では、水、水素、窒素、酸素、二酸化炭素等の
各分子が検出されるが、本発明に係るチタニルフタロシ
アニン顔料は水分子が最も多く含まれていることが特徴
である。As a result of this component analysis, various molecules such as water, hydrogen, nitrogen, oxygen, and carbon dioxide are detected in the titanyl phthalocyanine pigment, but the titanyl phthalocyanine pigment according to the present invention contains the largest amount of water molecules. It is characterized by the presence of
【0019】また、本発明に係るチタニルフタロシアニ
ン顔料は示差熱分析において80℃から120℃の間に
吸熱ピークを有することが感度、繰り返し特性の点から
好ましい。Further, it is preferable that the titanyl phthalocyanine pigment according to the present invention has an endothermic peak between 80° C. and 120° C. in differential thermal analysis from the viewpoint of sensitivity and repeatability.
【0020】ここで、上記示差熱分析は、チタニルフタ
ロシアニン顔料10mgを大気下湿度60%、昇温速度
毎分10℃の条件にて行ない、上記吸熱ピークは半値幅
30度以上の吸熱ピークをいう。[0020] Here, the above-mentioned differential thermal analysis was carried out on 10 mg of the titanyl phthalocyanine pigment under conditions of an atmospheric humidity of 60% and a temperature increase rate of 10°C per minute, and the above-mentioned endothermic peak refers to an endothermic peak with a half-width of 30 degrees or more. .
【0021】本発明に係るチタニルフタロシアニン顔料
として特に好ましくは、Cu−Kα線に対するX線回折
スペクトルが、ブラッグ角2θの9.5°±0.2°,
27.2°±0.2°にピークを持つチタニルフタロシ
アニン顔料である。Particularly preferably, the titanyl phthalocyanine pigment according to the present invention has an X-ray diffraction spectrum for Cu-Kα radiation of 9.5°±0.2° of Bragg angle 2θ,
It is a titanyl phthalocyanine pigment with a peak at 27.2°±0.2°.
【0022】本発明に用いられる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 basic structure of the titanyl phthalocyanine pigment used in the present invention is represented by the following general formula.
【0023】[0023]
【化3】
式中、X1、X2、X3及びX4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0〜4の整数を表す。[Image Omitted] In the formula, X1, X2, X3 and X4 are each a hydrogen atom,
Represents a halogen atom, alkyl group or alkoxy group, n
, m, l and k each represent an integer of 0 to 4.
【0024】本発明に用いられ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。次にこれを混合溶媒処理することによって、目的の
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 used in the present invention will be explained below. 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, especially 100°C.
C to 260C is preferred. 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 mixed solvent, the desired titanyl phthalocyanine can be obtained. In addition to a general stirring device, the equipment used for the treatment is a homomixer, disperser, agitator, or ball mill.
A sand mill, attritor, etc. can be used.
【0025】本発明では、キャリア発生物質として本発
明のチタニルフタロシアニン顔料の他に、本発明の効果
を損わない範囲で他のキャリア発生物質を併用してもよ
い。そのような併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混合型、アモルファス
型等のチタニルフタロシアニンをはじめ、アゾ顔料、ア
ントラキノン顔料、ペリレン顔料、多環キノン顔料、ス
クエアリウム顔料等が挙げられる。In the present invention, other carrier-generating substances may be used in combination with the titanyl phthalocyanine pigment of the present invention as long as the effects of the present invention are not impaired. Carrier generating substances that can be used in combination include:
The titanyl phthalocyanine of the present invention differs in crystal form, such as α type, β type, α, β mixed type, amorphous type, etc., as well as azo pigments, anthraquinone pigments, perylene pigments, polycyclic quinone pigments, and squarium. Examples include pigments.
【0026】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
、必要に応じて予め中間層(下引層)を設けた導電性支
持体上に例えばディップコーティング、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、図1又は図2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、4″は単層構成の感光層、
5は中間層である。To produce the photoreceptor of the present invention, for example,
A coating solution prepared by mixing and dispersing the titanyl phthalocyanine pigment according to the present invention in a solution of a binder resin dissolved in a solvent and dissolving a carrier transport substance described later in this is applied to an intermediate layer (undercoat) in advance, if necessary. A photoreceptor having a single layer structure as shown in FIG. 1 or 2 is obtained by coating the conductive support provided with the above-mentioned conductive layer by, for example, dip coating, spray coating, spiral coating, or the like. In addition, 1 in the figure is a conductive support, 4'' is a photosensitive layer with a single layer structure,
5 is the middle layer.
【0027】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、機能分離型の図3乃至図6の積層
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、必要に応じて前記中間層5を有する導電性支
持体1上に塗布してキャリア発生層2を形成した後、該
キャリア発生層2上にキャリア輸送物質を含む塗布液を
塗布加工してキャリア輸送層3を積層して、2層構成の
感光層4(図3、図5)、もしくはこれとは逆層構成の
感光層4′(図4、図6)を形成する。以下、二層構成
の感光層を有する感光体を中心に説明する。However, from the viewpoint of obtaining a photoreceptor with high sensitivity characteristics and high durability, it is preferable to use a functionally separated photoreceptor having the laminated structure shown in FIGS. 3 to 6. In this case, a coating solution prepared by mixing and dispersing the pigment in a solution containing a binder resin was applied onto the conductive support 1 having the intermediate layer 5 as necessary to form the carrier generation layer 2. After that, a coating liquid containing a carrier transporting substance is applied onto the carrier generation layer 2, and a carrier transporting layer 3 is laminated to form a photosensitive layer 4 having a two-layer structure (FIGS. 3 and 5), or vice versa. A photosensitive layer 4' (FIGS. 4 and 6) having a layered structure is formed. Hereinafter, a photoreceptor having a two-layered photosensitive layer will be mainly described.
【0028】二層構成の感光層を形成する場合における
キャリア発生層2及びキャリア輸送層3は、次のごとき
方法によって設けることができる。
(イ)キャリア発生物質、キャリア輸送物質を適当な溶
剤に夫々溶解した溶液或いはこれにバインダを加えて混
合溶解した溶液を塗布する方法。
(ロ)キャリア発生物質、キャリア輸送物質をボールミ
ル、ホモミキサー、超音波等によって夫々分散媒中で微
細粒子とし、必要に応じてバインダを加えて混合分散し
て得られる分散液を塗布する方法。In the case of forming a photosensitive layer having a two-layer structure, the carrier generation layer 2 and the carrier transport layer 3 can be provided by the following method. (a) A method of applying a solution in which a carrier-generating substance and a carrier-transporting substance are respectively dissolved in an appropriate solvent, or a solution in which a binder is added and mixed and dissolved therein. (b) A method in which a carrier-generating substance and a carrier-transporting substance are made into fine particles in a dispersion medium using a ball mill, a homomixer, an ultrasonic wave, etc., and a binder is added as necessary to mix and disperse the obtained dispersion, and the resulting dispersion is applied.
【0029】キャリア発生層及びキャリア輸送層の形成
に使用される溶剤或は分散媒としては、ブチルアミン、
N,N−ジメチルホルムアミド、アセトン、メチルエチ
ルケトン、シクロヘキサノン、ベンゼン、トルエン、キ
シレン、クロロホルム、1,2−ジクロルエタン、ジク
ロルメタン、テトラヒドロフラン、ジオキサン、メタノ
ール、エタノール、イソプロパノール、酢酸エチル、酢
酸ブチル、ジメチルスルホキシド等を挙げることができ
る。キャリア発生層若しくはキャリア輸送層の形成にバ
インダを用いる場合に、このバインダとしては任意のも
のを用いることができるが、特に疎水性でかつ誘電率が
高い電気絶縁性のフィルム形成能を有する高分子重合体
が好ましい。こうした重合体としては、例えば次のもの
を挙げることができるが、勿論これらに限定されるもの
ではない。As the solvent or dispersion medium used for forming the carrier generation layer and the carrier transport layer, butylamine,
N,N-dimethylformamide, acetone, methyl ethyl ketone, cyclohexanone, benzene, toluene, xylene, chloroform, 1,2-dichloroethane, dichloromethane, tetrahydrofuran, dioxane, methanol, ethanol, isopropanol, ethyl acetate, butyl acetate, dimethyl sulfoxide, etc. be able to. When a binder is used to form a carrier generation layer or a carrier transport layer, any binder can be used, but in particular, a polymer that is hydrophobic, has a high dielectric constant, and has the ability to form an electrically insulating film. Polymers are preferred. Examples of such polymers include, but are not limited to, the following:
【0030】1)ポリカーボネート
2)ポリエステル
3)メタクリル樹脂
4)アクリル樹脂
5)ポリ塩化ビニル
6)ポリ塩化ビニリデン
7)ポリスチレン
8)ポリビニルアセテート
9)スチレン−ブタジエン共重合体
10)塩化ビニリデン−アクリロニトリル共重合体11
)塩化ビニル−酢酸ビニル共重合体12)塩化ビニル−
酢酸ビニル−無水マレイン酸共重合体13)シリコーン
樹脂
14)シリコーン−アルキッド樹脂
15)フェノール−ホルムアルデヒド樹脂16)スチレ
ン−アクリル共重合樹脂
17)スチレン−アルキッド樹脂
18)ポリ−N−ビニルカルバゾール
19)ポリビニルブチラール
20)ポリカーボネートZ樹脂
これらのバインダは、単独或いは2種以上の混合物とし
て用いることができる。1) Polycarbonate 2) Polyester 3) Methacrylic resin 4) Acrylic resin 5) Polyvinyl chloride 6) Polyvinylidene chloride 7) Polystyrene 8) Polyvinyl acetate 9) Styrene-butadiene copolymer 10) Vinylidene chloride-acrylonitrile copolymer Combine 11
) Vinyl chloride-vinyl acetate copolymer 12) Vinyl chloride-
Vinyl acetate-maleic anhydride copolymer 13) Silicone resin 14) Silicone-alkyd resin 15) Phenol-formaldehyde resin 16) Styrene-acrylic copolymer resin 17) Styrene-alkyd resin 18) Poly-N-vinylcarbazole 19) Polyvinyl Butyral 20) Polycarbonate Z resin These binders can be used alone or as a mixture of two or more.
【0031】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重量%、更に好ま
しくは50〜400重量%とされる。The ratio of the carrier generating substance to the binder resin is preferably 10 to 600% by weight, more preferably 50 to 400% by weight.
【0032】このようにして形成されるキャリア発生層
2の厚さは0.01〜20μmであることが好ましいが
、更に好ましくは0.05〜5μmである。The thickness of the carrier generation layer 2 thus formed is preferably 0.01 to 20 μm, more preferably 0.05 to 5 μm.
【0033】上記キャリア発生物質を分散せしめてキャ
リア発生層2を形成する場合においては、当該キャリア
発生物質は2μm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
。When the carrier generating layer 2 is formed by dispersing the carrier generating substance, the carrier generating substance is preferably in the form of powder having an average particle size of 2 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.
【0034】本発明では、キャリア輸送物質として、前
記一般式[I]で表わされる繰返し単位を有する化合物
の少なくとも一種が用いられる。In the present invention, at least one compound having a repeating unit represented by the above general formula [I] is used as the carrier transporting substance.
【0035】以下、前記一般式[I]で表わされる繰返
し単位を有する化合物(以下、本発明のポリシラン化合
物と称する。)について説明する。The compound having a repeating unit represented by the general formula [I] (hereinafter referred to as the polysilane compound of the present invention) will be explained below.
【0036】前記一般式[I]において、R1,R2で
表わされるアルキル基は例えばメチル基、エチル基、プ
ロピル基等であり、アリール基は例えばフェニル基等で
ある。また、R1,R2で表わされるアルキルシリル基
又はアリールシリル基におけるアルキル基又はアリール
基の具体例も上述と同様のものが挙げられる。これらR
1,R2で表わされる基はさらに置換基を有していても
よい。In the general formula [I], the alkyl group represented by R1 and R2 is, for example, a methyl group, ethyl group, propyl group, etc., and the aryl group is, for example, a phenyl group. Further, specific examples of the alkyl group or aryl group in the alkylsilyl group or arylsilyl group represented by R1 and R2 are the same as those mentioned above. These R
The group represented by 1 and R2 may further have a substituent.
【0037】本発明のポリシラン化合物は前記一般式で
表わされる同一の繰返し単位からなる単独重合体であっ
ても、或は異なる繰返し単位を有する共重合体であって
もよい。The polysilane compound of the present invention may be a homopolymer consisting of the same repeating units represented by the above general formula, or a copolymer having different repeating units.
【0038】本発明のポリシラン化合物の分子量は好ま
しくは103〜106であり、さらに好ましくは105
〜106である。The molecular weight of the polysilane compound of the present invention is preferably 103 to 106, more preferably 105
~106.
【0039】以下に本発明のポリシラン化合物の代表的
具体例を示すが、本発明はこれらに限定するものではな
い。Typical specific examples of the polysilane compound of the present invention are shown below, but the present invention is not limited thereto.
【0040】[0040]
【化4】[C4]
【0041】[0041]
【化5】[C5]
【0042】次に、本発明のポリシラン化合物の合成例
を説明する。Next, a synthesis example of the polysilane compound of the present invention will be explained.
【0043】合成例1(ポリシランI−3の合成)乾燥
トルエン200ml中にジクロルメチルフェニルシラン
19.1gを加え、窒素気流下において金属ナトリウム
の分散液を加え、3時間加熱還流させた。Synthesis Example 1 (Synthesis of Polysilane I-3) 19.1 g of dichloromethylphenylsilane was added to 200 ml of dry toluene, a dispersion of sodium metal was added under a nitrogen stream, and the mixture was heated under reflux for 3 hours.
【0044】放冷後、少量のメタノールを加えて残存す
るナトリウムを分解した。After cooling, a small amount of methanol was added to decompose the remaining sodium.
【0045】次いで水洗を繰返した後、トルエン相を減
圧留去し、ヘキサンに注いで沈澱を濾取した。再沈澱を
繰返して目的とするポリシランI−3 1.5gを得
た。After repeated washing with water, the toluene phase was distilled off under reduced pressure, poured into hexane, and the precipitate was collected by filtration. The reprecipitation was repeated to obtain 1.5 g of the desired polysilane I-3.
【0046】合成例2(ポリシランI−8の合成)上述
の合成例1のジクロルメチルフェニルシランの代りに1
,1−ジクロルメチルシラン10g、ジクロルメチルフ
ェニルシラン5g、ジクロルフェニルシラン10gの混
合を使い、同様にしてポリシランI−8(コポリマー)
の1.3gを得た。Synthesis Example 2 (Synthesis of Polysilane I-8) In place of dichloromethylphenylsilane in Synthesis Example 1 above, 1
, 1-dichloromethylsilane, 5 g of dichloromethylphenylsilane, and 10 g of dichlorophenylsilane were used to prepare polysilane I-8 (copolymer) in the same manner.
1.3g of was obtained.
【0047】本発明では、キャリア輸送物質として前記
本発明のポリシラン化合物の他に、本発明の効果を損わ
ない範囲で他のキャリア輸送物質を併用してもよい。In the present invention, in addition to the above-mentioned polysilane compound of the present invention, other carrier transport substances may be used in combination as carrier transport substances within a range that does not impair the effects of the present invention.
【0048】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1〜100μm、更
に好ましくは5〜30μm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 μm, more preferably 5 to 30 μm.
【0049】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−ニトロ無水フタル酸、4−ニトロ無水フタル
酸、無水ピロメリット酸、無水メリット酸、テトラシア
ノエチレン、テトラシアノキノジメタン、o−ジニトロ
ベンゼン、m−ジニトロベンゼン、1,3,5−トリニ
トロベンゼン、p−ニトロベンゾニトリル、ピクリルク
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、o−ニトロ安息香酸、
p−ニトロ安息香酸、3,5−ジニトロ安息香酸、ペン
タフルオロ安息香酸、5−ニトロサリチル酸、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ャリア発生物質の重量1
00に対して0.01〜200が望ましく、更には0.
1〜100が好ましい。The photosensitive layer of the photoreceptor of the present invention may contain an electron-accepting substance for the purpose of improving sensitivity, reducing residual potential, or reducing fatigue during repeated use. Examples of such electron-accepting substances include succinic anhydride, maleic anhydride, dibromo succinic anhydride, phthalic anhydride, tetrachlorophthalic anhydride, tetrabromo phthalic anhydride, 3-nitro-phthalic anhydride, and 4-nitro-phthalic anhydride. Acid, pyromellitic anhydride, mellitic anhydride, tetracyanoethylene, tetracyanoquinodimethane, o-dinitrobenzene, m-dinitrobenzene, 1,3,5-trinitrobenzene, p-nitrobenzonitrile, picryl chloride, Quinone chlorimide, chloranil, bromanil, dichlordicyano-p-benzoquinone, anthraquinone, dinitroanthraquinone, 9-fluorenylidenemalonodinitrile, polynitro-9-fluorenylidenemalonodinitrile, picric acid, o-nitrobenzoic acid,
p-Nitrobenzoic acid, 3,5-dinitrobenzoic acid, pentafluorobenzoic acid, 5-nitrosalicylic acid, 3,5-
Examples include dinitrosalicylic acid, phthalic acid, mellitic acid, and other compounds with high electron affinity. The addition ratio of the electron-accepting substance is 1 weight of the carrier-generating substance.
00 to 0.01 to 200, more preferably 0.01 to 200.
1 to 100 is preferred.
【0050】また、上記感光層中には、保存性、耐久性
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 anti-deterioration agents such as antioxidants and light stabilizers for the purpose of improving storage stability and durability.
【0051】なお、図1及び図2に示した単層構成の感
光体においては、感光層4″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顔料等であり、
キャリア輸送物質は上述したものから選択してよい。ま
た、感光層4″のバインダー樹脂、その他の添加物質も
上述したものと同様であってよい。In the single-layer photoreceptor shown in FIGS. 1 and 2, the carrier-generating substance used in the photosensitive layer 4'' is the titanyl phthalocyanine pigment of the present invention, etc.
The carrier transport material may be selected from those mentioned above. Further, the binder resin and other additives of the photosensitive layer 4'' may be the same as those described above.
【0052】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, or laminated. A material provided on paper, plastic film, etc. by means such as the above is used.
【0053】また、接着層或いはバリヤ層等として機能
する前記中間層5としては、上記のバインダ樹脂として
説明したような高分子重合体、ポリビニルアルコール、
エチルセルロース、カルボキシメチルセルロース、ポリ
アミドなどの有機高分子物質又は酸化アルミニウムなど
より成るものが用いられる。The intermediate layer 5, which functions as an adhesive layer or a barrier layer, may be made of a high molecular weight polymer, polyvinyl alcohol, etc. as explained above as the binder resin.
Organic polymer materials such as ethyl cellulose, carboxymethyl cellulose, polyamide, or aluminum oxide are used.
【0054】[0054]
【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。EXAMPLES The present invention will now be explained in more detail by way of examples.
【0055】まず、各種のチタニルフタロシアニン顔料
の合成例を述べる。First, examples of synthesis of various titanyl phthalocyanine pigments will be described.
【0056】(合成例1)1,3−ジイミノイソインド
リン29.2gとスルホラン200mlを混合し、チタ
ニウムテトライソプロポキシド17.0g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25.5
g(88.5%)のチタニルフタロシアニンを得た。生
成物100gを2kgの濃硫酸に溶解し、20リットル
の水にあけて析出させて濾取し、アモルファス状態のウ
ェットペーストを得た。(Synthesis Example 1) 29.2 g of 1,3-diiminoisoindoline and 200 ml of sulfolane were mixed, 17.0 g of titanium tetraisopropoxide 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, washed with a 2% aqueous hydrochloric acid solution, washed with water, washed with methanol, and dried.
g (88.5%) of titanyl phthalocyanine was obtained. 100 g of the product was dissolved in 2 kg of concentrated sulfuric acid, poured into 20 liters of water, precipitated and collected by filtration to obtain an amorphous wet paste.
【0057】このウェットペースト2gに、1,2−ジ
クロロエタン200mlとメタノール100mlの混合
溶媒を加え、室温下で3時間撹拌を行なった。メタノー
ルで希釈して濾過し、メタノール洗浄後、乾燥して、ブ
ラッグ角2θの9.5°±0.2°,27.2°±0.
2°にピークを有するX線回折スペクトルをもつ結晶を
得た。なお、X線回折スペクトルはX線回折装置JDX
−8200(日本電子社製)を用い、次の条件で測定し
たもの(以下同様)である。A mixed solvent of 200 ml of 1,2-dichloroethane and 100 ml of methanol was added to 2 g of this wet paste, and the mixture was stirred at room temperature for 3 hours. Diluted with methanol, filtered, washed with methanol and dried to obtain Bragg angle 2θ of 9.5°±0.2°, 27.2°±0.
A crystal with an X-ray diffraction spectrum having a peak at 2° was obtained. Note that the X-ray diffraction spectrum was obtained using an X-ray diffraction device JDX.
-8200 (manufactured by JEOL Ltd.) under the following conditions (the same applies hereinafter).
【0058】
X線管球 Cu(Cu−Kα線)電圧
40.0 KV電流
100.0 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 d
eg.X-ray tube Cu (Cu-Kα ray) voltage
40.0 KV current
100.0 mA starting angle
6.00 deg. Stop angle 35
.. 00 deg. Step angle 0.020
deg. Measurement time 0.50 d
eg.
【0059】また、この結晶の示差熱分析におい
て図7に示す示差熱曲線が得られ、99.6℃に吸熱ピ
ークが認められた。示差熱分析は前述の方法に従った(
以下同様)。Further, in differential thermal analysis of this crystal, a differential thermal curve shown in FIG. 7 was obtained, and an endothermic peak was observed at 99.6°C. Differential thermal analysis followed the method previously described (
Same below).
【0060】(合成例2)1,3−ジイミノイソインド
リン29.2gとスルホラン200mlを混合し、チタ
ニウムテトライソプロポキシド17.0g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25.5
g(88.5%)のチタニルフタロシアニンを得た。(Synthesis Example 2) 29.2 g of 1,3-diiminoisoindoline and 200 ml of sulfolane were mixed, 17.0 g of titanium tetraisopropoxide 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, washed with a 2% aqueous hydrochloric acid solution, washed with water, washed with methanol, and dried.
g (88.5%) of titanyl phthalocyanine was obtained.
【0061】生成物100gを2kgの濃硫酸に溶解し
、20リットルの水にあけて析出させて濾取し、アモル
ファス状態のウェットペーストを得た。100 g of the product was dissolved in 2 kg of concentrated sulfuric acid, poured into 20 liters of water, precipitated and collected by filtration to obtain an amorphous wet paste.
【0062】このウェットペースト2gに1,2−ジク
ロロエタン200mlとアセトン100mlの混合溶媒
を加え、室温下で3時間撹拌を行なった。メタノールで
希釈して濾過し、メタノール洗浄後乾燥して、ブラッグ
角2θの9.5°±0.2°,27.2°±0.2°に
ピークを有するX線回折スペクトルをもつ結晶を得た。
また、この結晶の示差熱分析において図8に示す示差熱
曲線が得られた。A mixed solvent of 200 ml of 1,2-dichloroethane and 100 ml of acetone was added to 2 g of this wet paste, and the mixture was stirred at room temperature for 3 hours. Dilute with methanol, filter, wash with methanol and dry to obtain crystals with an X-ray diffraction spectrum having peaks at 9.5° ± 0.2° and 27.2° ± 0.2° of Bragg angle 2θ. Obtained. Further, in differential thermal analysis of this crystal, a differential thermal curve shown in FIG. 8 was obtained.
【0063】(比較合成例1)合成例1のウェットペー
ストを乾燥後、α−クロロナフタレンを用いて、加熱撹
拌することによって、β型のチタニルフタロシアニンを
得た。X線回折スペクトルはブラッグ角2θの9.3°
±0.2°,10.6°±0.2°,13.2°±0.
2°,15.1°±0.2°,15.7°±0.2°,
16.1°±0.2°,20.8°±0.2°,23.
3°±0.2°,26.3°±0.2°,27.1°±
0.2°にピークを有していた。また示差熱曲線を図9
に示した。(Comparative Synthesis Example 1) After drying the wet paste of Synthesis Example 1, β-type titanyl phthalocyanine was obtained by heating and stirring using α-chloronaphthalene. The X-ray diffraction spectrum has a Bragg angle of 2θ of 9.3°.
±0.2°, 10.6°±0.2°, 13.2°±0.
2°, 15.1°±0.2°, 15.7°±0.2°,
16.1°±0.2°, 20.8°±0.2°, 23.
3°±0.2°, 26.3°±0.2°, 27.1°±
It had a peak at 0.2°. In addition, the differential thermal curve is shown in Figure 9.
It was shown to.
【0064】上記合成例1,2及び比較合成例1で得ら
れた各々のチタニルフタロシアニンを前述の方法に従っ
て真空中での吸着ガスの成分分析を行なったところ、以
下の結果が得られた。When the adsorbed gas components of each titanyl phthalocyanine obtained in Synthesis Examples 1 and 2 and Comparative Synthesis Example 1 were analyzed in vacuum according to the method described above, the following results were obtained.
【0065】
分子数%
H2 H2O
CO N2 O2 CO2
合成例1 2.2 68.
5 0.0 23.3 4.2
1.8 合成例2 2
.0 59.3 0.0 3
1.3 5.6 1.8 比較合成
例1 0.0 2.6
0.0 79.5 13.9 4
.0合成例1,2において得られたチタニルフタロシア
ニンは水分子が最も多く含まれていることがわかる。[0065]
Number of molecules%
H2 H2O
CO N2 O2 CO2
Synthesis Example 1 2.2 68.
5 0.0 23.3 4.2
1.8 Synthesis Example 2 2
.. 0 59.3 0.0 3
1.3 5.6 1.8 Comparative synthesis example 1 0.0 2.6
0.0 79.5 13.9 4
.. It can be seen that the titanyl phthalocyanine obtained in Synthesis Examples 1 and 2 contains the largest amount of water molecules.
【0066】(合成例3)合成例2と同様にしてチタニ
ルフタロシアニンのアモルファス状態のウェットペース
ト2g に1,2−ジクロロエタン200mlとH2O
50mlの混合溶媒を加え、60℃で4時間攪拌を行っ
た。次にメタノールで希釈してろ過し、メタノール洗浄
後乾燥して結晶を得た。(Synthesis Example 3) In the same manner as in Synthesis Example 2, 200 ml of 1,2-dichloroethane and H2O were added to 2 g of amorphous wet paste of titanyl phthalocyanine.
50 ml of mixed solvent was added and stirred at 60°C for 4 hours. Next, the mixture was diluted with methanol, filtered, washed with methanol, and dried to obtain crystals.
【0067】(合成例4)合成例2と同様にしてチタニ
ルフタロシアニンのアモルファス状態のウェットペース
トを水洗乾燥後、チタニルフタロシアニン12部と塩化
ナトリウム18部とジエチレングリコール8部を混合し
、80℃の加熱下で自動乳鉢により60時間ミリングし
た。次に上記処理品を水洗し、減圧乾燥した後に乾燥品
1部にシクロヘキサノン20部とガラスビーズ2部を加
えて1時間サンドグラインダーにより分散を行なった。
その後ろ過、乾燥を行い結晶を得た。(Synthesis Example 4) After washing and drying an amorphous wet paste of titanyl phthalocyanine in the same manner as in Synthesis Example 2, 12 parts of titanyl phthalocyanine, 18 parts of sodium chloride, and 8 parts of diethylene glycol were mixed, and the mixture was heated at 80°C. Milling was carried out in an automatic mortar for 60 hours. Next, the treated product was washed with water and dried under reduced pressure, and then 20 parts of cyclohexanone and 2 parts of glass beads were added to 1 part of the dried product and dispersed using a sand grinder for 1 hour. Thereafter, it was filtered and dried to obtain crystals.
【0068】(比較合成例2)合成例2と同様にしてチ
タニルフタロシアニンのアモルファス状態のウェットペ
ースト2gに1,2−ジクロロエタン200mlとH2
O100mlの混合溶媒を加え、80℃で4時間半攪拌
を行った。次にメタノールで希釈してろ過し、メタノー
ル洗浄後乾燥して結晶を得た。(Comparative Synthesis Example 2) In the same manner as in Synthesis Example 2, 200 ml of 1,2-dichloroethane and H2 were added to 2 g of amorphous wet paste of titanyl phthalocyanine.
A mixed solvent of 100 ml of O was added, and the mixture was stirred at 80° C. for 4.5 hours. Next, the mixture was diluted with methanol, filtered, washed with methanol, and dried to obtain crystals.
【0069】上記合成例3,4及び比較合成例2で得ら
れた各々のチタニルフタロシアニンをこれを用いて作製
した感光ドラムから前述の方法に従って真空中での吸着
ガスの成分分析を行なったところ、以下の結果が得られ
た。[0069] When the adsorbed gas components were analyzed in vacuum according to the method described above from photosensitive drums prepared using each of the titanyl phthalocyanines obtained in Synthesis Examples 3 and 4 and Comparative Synthesis Example 2, the following results were obtained. The following results were obtained.
【0070】
分子数%
H2 H2O
CO N2 O2 CO2
合成例3 2.3 43.
5 0.0 42.4 9.3
2.5 合成例4 1
.8 63.4 0.0 2
7.5 5.3 2.0 比較合成
例2 2.7 34.7
0.0 47.0 12.2 3
.4[0070]
Number of molecules%
H2 H2O
CO N2 O2 CO2
Synthesis Example 3 2.3 43.
5 0.0 42.4 9.3
2.5 Synthesis Example 4 1
.. 8 63.4 0.0 2
7.5 5.3 2.0 Comparative synthesis example 2 2.7 34.7
0.0 47.0 12.2 3
.. 4
【0071】(実施例1)共重合ポリアミド「ラッ
カマイド5003」(大日本インキ社製)3部(部は重
量部を示す;以下同じ)をメタノール100部に加熱溶
解し、0.6μmフィルタで濾過した後、浸透塗布法に
よって、アルミニウムドラム上に塗布し、膜厚0.5μ
mの下引層を形成した。(Example 1) 3 parts of copolyamide "Laccamide 5003" (manufactured by Dainippon Ink Co., Ltd.) (parts indicate parts by weight; the same applies hereinafter) was dissolved by heating in 100 parts of methanol, and filtered with a 0.6 μm filter. After that, it was coated on an aluminum drum by the penetrating coating method to a film thickness of 0.5 μm.
A subbing layer of m was formed.
【0072】一方、合成例1において得られた本発明に
係るチタニルフタロシアニン3部、バインダ樹脂として
セルロース変性シリコーン樹脂「KR5240」(信越
化学社製)固形分3部、分散媒としてメチルイソブチル
ケトン100部、をサ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布して、膜厚
0.2μmのキャリア発生層を形成した。次いで、前記
例示キャリア輸送物質I−2の1部、ポリカーボネート
樹脂「ユーピロンZ200」(三菱瓦斯化学社製)1.
5部、微量のシリコーンオイル「KF−54」(信越化
学社製)を、1,2−ジクロロエタン10部に溶解した
液を用いて先のキャリア発生層の上に浸透塗布し乾燥の
後、膜厚25μmのキャリア輸送層を形成して本発明の
感光体試料を得た。On the other hand, 3 parts of the titanyl phthalocyanine according to the present invention obtained in Synthesis Example 1, 3 parts of cellulose-modified silicone resin "KR5240" (manufactured by Shin-Etsu Chemical Co., Ltd.) solid content as a binder resin, and 100 parts of methyl isobutyl ketone as a dispersion medium. , using a sand mill to disperse the liquid,
A carrier generation layer having a thickness of 0.2 μm was formed by coating on the previous subbing layer by a penetrating coating method. Next, one part of the above-mentioned exemplary carrier transport substance I-2, polycarbonate resin "Iupilon Z200" (manufactured by Mitsubishi Gas Chemical Co., Ltd.)1.
A solution obtained by dissolving 5 parts of silicone oil "KF-54" (manufactured by Shin-Etsu Chemical Co., Ltd.) in 10 parts of 1,2-dichloroethane is used to penetrate and coat the carrier generation layer, and after drying, the film is coated. A carrier transport layer having a thickness of 25 μm was formed to obtain a photoreceptor sample of the present invention.
【0073】(実施例2)キャリア輸送物質I−2の代
わりに前記例示キャリア輸送物質I−3を用いた以外は
実施例1と同様にして感光体試料を作製した。(Example 2) A photoreceptor sample was prepared in the same manner as in Example 1 except that the above-mentioned exemplary carrier transport material I-3 was used instead of carrier transport material I-2.
【0074】(実施例3)合成例1のチタニルフタロシ
アニンの代わりに合成例2のチタニルフタロシアニンを
用い、キャリア輸送物質I−2の代わりに前記例示キャ
リア輸送物質I−6を用いた以外は実施例1と同様にし
て感光体試料を作製した。(Example 3) Example except that the titanyl phthalocyanine of Synthesis Example 2 was used in place of the titanyl phthalocyanine of Synthesis Example 1, and the exemplified carrier transport substance I-6 was used in place of the carrier transport substance I-2. A photoreceptor sample was prepared in the same manner as in Example 1.
【0075】(実施例4)合成例1のチタニルフタロシ
アニンの代わりに合成例3のチタニルフタロシアニンを
用いた以外は実施例1と同様にして感光体試料を作製し
た。(Example 4) A photoreceptor sample was prepared in the same manner as in Example 1 except that the titanyl phthalocyanine of Synthesis Example 3 was used instead of the titanyl phthalocyanine of Synthesis Example 1.
【0076】(実施例5)合成例1のチタニルフタロシ
アニンの代わりに合成例4のチタニルフタロシアニンを
用いた以外は実施例1と同様にして感光体試料を作製し
た。(Example 5) A photoreceptor sample was prepared in the same manner as in Example 1 except that the titanyl phthalocyanine of Synthesis Example 4 was used instead of the titanyl phthalocyanine of Synthesis Example 1.
【0077】(比較例1)合成例1のチタニルフタロシ
アニンの代わりに比較合成例1のチタニルフタロシアニ
ンを用いた以外は実施例1と同様にして感光体試料を作
製した。(Comparative Example 1) A photoreceptor sample was prepared in the same manner as in Example 1 except that the titanyl phthalocyanine of Comparative Synthesis Example 1 was used instead of the titanyl phthalocyanine of Synthesis Example 1.
【0078】(比較例2)合成例2のチタニルフタロシ
アニンの代わりに比較合成例1のチタニルフタロシアニ
ンを用いた以外は実施例3と同様にして感光体試料を作
製した。(Comparative Example 2) A photoreceptor sample was prepared in the same manner as in Example 3 except that the titanyl phthalocyanine of Comparative Synthesis Example 1 was used in place of the titanyl phthalocyanine of Synthesis Example 2.
【0079】(比較例3)キャリア輸送物質I−2の代
わりに下記キャリア輸送物質を用いた以外は実施例1と
同様にして感光体試料を作製した。(Comparative Example 3) A photoreceptor sample was prepared in the same manner as in Example 1 except that the following carrier transport substance was used instead of carrier transport substance I-2.
【0080】[0080]
【化6】[C6]
【0081】(比較例4)合成例1のチタニルフタロシ
アニンの代わりに比較合成例2のチタニルフタロシアニ
ンを用いた以外は実施例1と同様にして感光体試料を作
製した。(Comparative Example 4) A photoreceptor sample was prepared in the same manner as in Example 1 except that the titanyl phthalocyanine of Comparative Synthesis Example 2 was used in place of the titanyl phthalocyanine of Synthesis Example 1.
【0082】(評価)前記本発明の試料及び比較試料を
「U−Bix1550」(コニカ社製)(半導体レーザ
光源搭載)改造機に搭載し、グリッド電圧VGを600
[V]に調節し、未露光部電位VH及び0.7mWの照
射時の露光部の電位VLを測定した。また、33℃80
%RHの環境下において、5万プリント後のVH及びV
Lについても合わせて測定し、その結果を下記表1に示
す。(Evaluation) The sample of the present invention and the comparative sample were mounted on a modified machine "U-Bix1550" (manufactured by Konica) (equipped with a semiconductor laser light source), and the grid voltage VG was set to 600.
[V], and the potential VH of the unexposed part and the potential VL of the exposed part when irradiated with 0.7 mW were measured. Also, 33℃80
%RH environment, VH and V after 50,000 prints
L was also measured and the results are shown in Table 1 below.
【0083】[0083]
【表1】[Table 1]
【0084】上記の結果から、本発明の感光体は高感度
で、しかも高温高湿環境下において繰り返し使用による
安定性が良好であることがわかる。これに対し比較感光
体は低感度で繰り返し使用による安定性が著しく劣って
いる。From the above results, it can be seen that the photoreceptor of the present invention has high sensitivity and good stability when repeatedly used in a high temperature and high humidity environment. In contrast, the comparative photoreceptor has low sensitivity and is significantly inferior in stability after repeated use.
【0085】[0085]
【発明の効果】以上詳細に説明したように、本発明の電
子写真感光体によれば、高感度でしかも外部環境の影響
を受けにくく、繰り返し使用特性が非常に良好であると
いう優れた効果を奏する。[Effects of the Invention] As explained in detail above, the electrophotographic photoreceptor of the present invention has the excellent effects of being highly sensitive, less susceptible to the effects of the external environment, and having very good repeated use characteristics. play.
【図1】本発明の感光体の層構成を例示する断面図であ
る。FIG. 1 is a cross-sectional view illustrating the layer structure of a photoreceptor of the present invention.
【図2】本発明の感光体の層構成を例示する断面図であ
る。FIG. 2 is a cross-sectional view illustrating the layer structure of the photoreceptor of the present invention.
【図3】本発明の感光体の層構成を例示する断面図であ
る。FIG. 3 is a cross-sectional view illustrating the layer structure of the photoreceptor of the present invention.
【図4】本発明の感光体の層構成を例示する断面図であ
る。FIG. 4 is a cross-sectional view illustrating the layer structure of the photoreceptor of the present invention.
【図5】本発明の感光体の層構成を例示する断面図であ
る。FIG. 5 is a cross-sectional view illustrating the layer structure of the photoreceptor of the present invention.
【図6】本発明の感光体の層構成を例示する断面図であ
る。FIG. 6 is a cross-sectional view illustrating the layer structure of the photoreceptor of the present invention.
【図7】本発明に係るフタロシアニン顔料の示差熱曲線
図である。FIG. 7 is a differential thermal curve diagram of the phthalocyanine pigment according to the present invention.
【図8】本発明に係るフタロシアニン顔料の示差熱曲線
図である。FIG. 8 is a differential thermal curve diagram of the phthalocyanine pigment according to the present invention.
【図9】β型チタニルフタロシアニン顔料の示差熱曲線
図である。FIG. 9 is a differential thermal curve diagram of a β-type titanyl phthalocyanine pigment.
1 導電性支持体 2 キャリア発生層 3 キャリア輸送層 4,4′,4″ 感光層 5 中間層 1 Conductive support 2 Carrier generation layer 3 Carrier transport layer 4,4′,4″ Photosensitive layer 5 Middle class
Claims (2)
て分子数で水分子が最も多く含まれているチタニルフタ
ロシアニン顔料と、下記一般式[I]で表わされる繰返
し単位を有する化合物とを含有することを特徴とする電
子写真感光体。 【化1】 [式中、R1及びR2はそれぞれアルキル基、アリール
基、アルキルシリル基又はアリールシリル基を表わす。 ][Claim 1] Contains a titanyl phthalocyanine pigment that contains the largest number of water molecules in the component analysis of adsorbed gas in vacuum, and a compound having a repeating unit represented by the following general formula [I]. An electrophotographic photoreceptor characterized by: embedded image In the formula, R1 and R2 each represent an alkyl group, an aryl group, an alkylsilyl group, or an arylsilyl group. ]
差熱分析において80℃から120℃の間に吸熱ピーク
を有す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 electrophotographic photoreceptor according to claim 1, wherein the titanyl phthalocyanine pigment has an endothermic peak between 80° C. and 120° C. in differential thermal analysis.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP16871491A JPH04338968A (en) | 1990-06-13 | 1991-06-13 | Electrophotographic sensitive body |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2-154830 | 1990-06-13 | ||
JP15483090 | 1990-06-13 | ||
JP16871491A JPH04338968A (en) | 1990-06-13 | 1991-06-13 | Electrophotographic sensitive body |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH04338968A true JPH04338968A (en) | 1992-11-26 |
Family
ID=26483002
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP16871491A Pending JPH04338968A (en) | 1990-06-13 | 1991-06-13 | Electrophotographic sensitive body |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH04338968A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005036139A (en) * | 2003-07-17 | 2005-02-10 | Osaka Gas Co Ltd | Copolysilane and method for producing the same |
-
1991
- 1991-06-13 JP JP16871491A patent/JPH04338968A/en active Pending
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005036139A (en) * | 2003-07-17 | 2005-02-10 | Osaka Gas Co Ltd | Copolysilane and method for producing the same |
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