JPH0243558A - Electrophotographic sensitive body - Google Patents
Electrophotographic sensitive bodyInfo
- Publication number
- JPH0243558A JPH0243558A JP63194842A JP19484288A JPH0243558A JP H0243558 A JPH0243558 A JP H0243558A JP 63194842 A JP63194842 A JP 63194842A JP 19484288 A JP19484288 A JP 19484288A JP H0243558 A JPH0243558 A JP H0243558A
- Authority
- JP
- Japan
- Prior art keywords
- group
- general formula
- carrier
- formula
- substituted
- 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
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 16
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 14
- 125000005843 halogen group Chemical group 0.000 claims abstract description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 8
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 7
- 125000003118 aryl group Chemical group 0.000 claims abstract description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims description 50
- 108091008695 photoreceptors Proteins 0.000 claims description 43
- 239000000126 substance Substances 0.000 claims description 36
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 4
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 2
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 230000035945 sensitivity Effects 0.000 abstract description 18
- 230000006866 deterioration Effects 0.000 abstract description 3
- 230000003252 repetitive effect Effects 0.000 abstract 2
- 239000010410 layer Substances 0.000 description 60
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 24
- 239000011230 binding agent Substances 0.000 description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052711 selenium Inorganic materials 0.000 description 4
- 239000011669 selenium Substances 0.000 description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 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
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- PWEBUXCTKOWPCW-UHFFFAOYSA-N squaric acid Chemical compound OC1=C(O)C(=O)C1=O PWEBUXCTKOWPCW-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
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 2
- 229920000180 alkyd Polymers 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 125000004663 dialkyl amino group Chemical group 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- -1 dry with a sieve Substances 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 2
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- UBOXGVDOUJQMTN-UHFFFAOYSA-N 1,1,2-trichloroethane Chemical compound ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 description 1
- FKNIDKXOANSRCS-UHFFFAOYSA-N 2,3,4-trinitrofluoren-1-one Chemical compound C1=CC=C2C3=C([N+](=O)[O-])C([N+]([O-])=O)=C([N+]([O-])=O)C(=O)C3=CC2=C1 FKNIDKXOANSRCS-UHFFFAOYSA-N 0.000 description 1
- JOERSAVCLPYNIZ-UHFFFAOYSA-N 2,4,5,7-tetranitrofluoren-9-one Chemical compound O=C1C2=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C2C2=C1C=C([N+](=O)[O-])C=C2[N+]([O-])=O JOERSAVCLPYNIZ-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
- SXOQOOQUBDERIZ-UHFFFAOYSA-N 3,4-dichlorocyclobut-3-ene-1,2-dione Chemical compound ClC1=C(Cl)C(=O)C1=O SXOQOOQUBDERIZ-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical class C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 206010034972 Photosensitivity reaction Diseases 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
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical class C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- 239000002262 Schiff base Chemical class 0.000 description 1
- 150000004753 Schiff bases Chemical class 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000004414 alkyl thio group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000002490 anilino group Chemical class [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 125000005427 anthranyl group Chemical group 0.000 description 1
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- 150000001716 carbazoles Chemical class 0.000 description 1
- 150000001721 carbon Chemical group 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
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 125000004986 diarylamino group Chemical group 0.000 description 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 125000000623 heterocyclic group Chemical group 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
- 150000007857 hydrazones Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 229940079865 intestinal antiinfectives imidazole derivative Drugs 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 229940102253 isopropanolamine Drugs 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000113 methacrylic resin Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- KKFHAJHLJHVUDM-UHFFFAOYSA-N n-vinylcarbazole Chemical compound C1=CC=C2N(C=C)C3=CC=CC=C3C2=C1 KKFHAJHLJHVUDM-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 230000003287 optical effect Effects 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
- 150000004866 oxadiazoles Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 125000001484 phenothiazinyl group Chemical class C1(=CC=CC=2SC3=CC=CC=C3NC12)* 0.000 description 1
- 150000004986 phenylenediamines Chemical class 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920000647 polyepoxide Polymers 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
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003219 pyrazolines Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical class [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical class C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229940066767 systemic antihistamines phenothiazine derivative Drugs 0.000 description 1
- 229940042055 systemic antimycotics triazole derivative Drugs 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 125000005259 triarylamine group Chemical class 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005550 wet granulation Methods 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
- G03G5/02—Charge-receiving layers
- G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
- G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
- G03G5/0622—Heterocyclic compounds
- G03G5/0624—Heterocyclic compounds containing one hetero ring
- G03G5/0627—Heterocyclic compounds containing one hetero ring being five-membered
- G03G5/0629—Heterocyclic compounds containing one hetero ring being five-membered containing one hetero atom
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
- G03G5/02—Charge-receiving layers
- G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
- G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
- G03G5/0601—Acyclic or carbocyclic compounds
- G03G5/0609—Acyclic or carbocyclic compounds containing oxygen
- G03G5/0611—Squaric acid
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、詳しくは特定の非対称
スクェアリウム化合物を含有する感光層を有する電子写
真感光体に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to an electrophotographic photoreceptor, and more particularly to an electrophotographic photoreceptor having a photosensitive layer containing a specific asymmetric squareium compound.
［従来の技術］
従来、電子写真感光体としては、セレン、酸化亜鉛、硫
化カドミウム、シリコン等の無機光導電性化合物を主成
分とする感光層を有する無機感光体が広く用いられてき
た。しかし、これらは感度、熱安定性、耐湿性、耐久性
、製造コスト等において必ずしも満足し得るものではな
い。例えば、セレンは結晶化すると感光体としての特性
が劣化してしまうため、製造上も難しく、また熱や指紋
等が原因となり結晶化し、感光体としての性能が劣化し
てしまう。また硫化カドミウムでは耐湿性や耐久性、酸
化亜鉛でも耐久性等に問題がある。[Prior Art] Conventionally, inorganic photoreceptors having a photosensitive layer containing an inorganic photoconductive compound such as selenium, zinc oxide, cadmium sulfide, or silicon as a main component have been widely used as electrophotographic photoreceptors. However, these are not necessarily satisfactory in terms of sensitivity, thermal stability, moisture resistance, durability, manufacturing cost, etc. For example, when selenium crystallizes, its properties as a photoreceptor deteriorate, making it difficult to manufacture.Also, selenium crystallizes due to heat, fingerprints, etc., and its performance as a photoreceptor deteriorates. In addition, cadmium sulfide has problems with moisture resistance and durability, and zinc oxide has problems with durability, etc.
これら無機感光体の持つ欠点を克服する目的で様々な有
機光導電性化合物を主成分とする感光層を有する有機感
光体の研究・開発が近年盛んに行なわれている。例えば
特公昭５０−１０４９６号公報には、ポリ−Ｎ−ビニル
カルバゾール
リニトロー９−フルオレノンを含有する感光層を有する
有機感光体の記載がある。しかし、この感光体は、感度
及び耐久性において必ずしも満足できるものではない。In order to overcome these drawbacks of inorganic photoreceptors, research and development have been actively conducted in recent years on organic photoreceptors having photosensitive layers containing various organic photoconductive compounds as main components. For example, Japanese Patent Publication No. 50-10496 describes an organic photoreceptor having a photosensitive layer containing poly-N-vinylcarbazole lintro-9-fluorenone. However, this photoreceptor is not necessarily satisfactory in sensitivity and durability.
このような欠点を改良するためにキャリア発生機能とキ
ャリア輸送機能とを異なる物質に分担させ、より高性能
の有機感光体を開発する試みがなされている。このよう
ないわゆる機能分離型の感光体は、それぞれの材料を広
い範囲から選択することができ、任意の性能を有する感
光体を比較的容易に作成し得ることから多くの研究がな
されてきた。In order to improve these drawbacks, attempts have been made to develop organic photoreceptors with higher performance by assigning the carrier generation function and the carrier transport function to different substances. Many studies have been conducted on such so-called function-separated type photoreceptors because each material can be selected from a wide range and a photoreceptor having arbitrary performance can be produced relatively easily.
［発明が解決しようとする問題点］
上記のような機能分離型の電子写真感光体において、そ
のキャリア発生物質として、数多くの化合物が提案され
ている。無機化合物をキャリア発生物質として用いる例
としては、たとえば、特公昭４３−１６１９８号公報に
記載された無定形セレンがあり、これは有機光導電性化
合物と組み合わせて使用されるが、無定形セレンからな
るキャリア発生層は熱により結晶化して感光体としての
特性が劣化してしまうという欠点は改良されてはいない
。[Problems to be Solved by the Invention] Many compounds have been proposed as carrier-generating substances in the above-mentioned functionally separated electrophotographic photoreceptor. An example of using an inorganic compound as a carrier generating substance is amorphous selenium described in Japanese Patent Publication No. 43-16198, which is used in combination with an organic photoconductive compound. However, the drawback that the carrier generation layer crystallizes due to heat and deteriorates the characteristics as a photoreceptor has not been improved.
また有機染料や有機顔料をキャリア発生物質として用い
る電子写真感光体も数多く提案されている。代表例とし
ては、ビスアゾ類、トリスアゾ類、フタロシアニン類、
ビリリウム類、スクェアリウム類などが知られており、
可視領域から近赤外領域まで感度を有するものとしてフ
タロシアニン類、トリスアゾ類、スクェアリウム類が報
告されている。Furthermore, many electrophotographic photoreceptors using organic dyes or organic pigments as carrier-generating substances have been proposed. Typical examples include bisazos, trisazos, phthalocyanines,
Viryliums, squareiums, etc. are known.
Phthalocyanines, trisazos, and squaliums have been reported to have sensitivity from the visible region to the near-infrared region.
しかしながら、フタロシアニン類は分光感度が長波長に
片寄り赤色再現性に劣るという欠点を有し、トリスアゾ
類は優れた電気特性と充分な感度を有するに至っていな
い。However, phthalocyanines have the disadvantage that their spectral sensitivity is biased toward long wavelengths and red color reproducibility is poor, and trisazo compounds do not have excellent electrical properties and sufficient sensitivity.
また特開昭４９−１０５５３６号等に示されるスクェア
リウム化合物は、比較的高い感度を有するものの帯電性
、暗減衰等に欠点を有し、高い感度と低い暗減衰を両立
するには至っていない。Although the squalium compounds disclosed in Japanese Patent Application Laid-open No. 49-105536 have relatively high sensitivity, they have drawbacks in chargeability, dark decay, etc., and have not been able to achieve both high sensitivity and low dark decay.
さらに近年電子写真感光体の光源としてＡｒレーザー、
Ｈｆ３−Ｎｅレーザー等の気体レーザーや半導体レーザ
ーが使用され始めている。これらのレーザーはその特徴
として時系列で０Ｎ１０ Ｆ Ｆが可能であり、インテ
リジェントコピアをはじめとする画像処理様能を有する
複写磯やコンピューターのアウトプット用のプリンター
の光源とじて特に有望視されている。中でも半導体レー
ザーはその性質上音響工学素子等の電気信号／光信号の
変換素子が不要であることや小型・軽量化が可能である
ことなどから注目を集めている。しかしこの半導体レー
ザーは気体レーザーに比較して低出力であり、また発振
波長も長波長（約７８０ｎｍ以上）であることから従来
の電子写真感光体では分光感度が短波長側によっている
ものが多く、感度特性において、実用的に満足できるも
のがなかった。Furthermore, in recent years, Ar laser has been used as a light source for electrophotographic photoreceptors.
Gas lasers such as Hf3-Ne lasers and semiconductor lasers are beginning to be used. These lasers are characterized by their ability to perform 0N10 F F in time series, and are particularly promising as light sources for copying machines and computer output printers that have image processing capabilities, including intelligent copiers. . Among these, semiconductor lasers are attracting attention because their nature does not require electrical signal/optical signal conversion elements such as acoustic engineering elements, and they can be made smaller and lighter. However, this semiconductor laser has a low output compared to a gas laser, and the oscillation wavelength is also long (approximately 780 nm or more), so in many conventional electrophotographic photoreceptors, the spectral sensitivity is on the short wavelength side. There were no practically satisfactory sensitivity characteristics.
［発明の目的］
本発明の目的は、キャリア発生能に優れた特定の非対称
スクェアリウム化合物を含有する電子写真感光体を提供
することにある。[Object of the Invention] An object of the present invention is to provide an electrophotographic photoreceptor containing a specific asymmetric squareium compound having excellent carrier generation ability.
本発明の他の目的は、高感度にしてかつ残留電位が小さ
く、また繰り返し使用してもそれらの特性が変化しない
耐久性の浸れた電子写真感光体を提供することにある。Another object of the present invention is to provide a durable electrophotographic photoreceptor that has high sensitivity, a low residual potential, and whose characteristics do not change even after repeated use.
本発明の更に他の目的は、広箱なキャリア輸送物質との
組み合わせにおいても、有効にキャリア発生物質として
作用し得る非対称スクェアリウム化合物を含有する電子
写真感光体を提供することにある。Still another object of the present invention is to provide an electrophotographic photoreceptor containing an asymmetric squareium compound that can effectively act as a carrier generating material even in combination with a wide carrier transporting material.
本発明の更に伯の目的は、半導体レーザー等の長波長光
源に対しても−Ｆ分の実用感度を有する電子写真感光体
を提供することにある。A further object of the present invention is to provide an electrophotographic photoreceptor having a practical sensitivity of -F even to long wavelength light sources such as semiconductor lasers.
本発明の更に他の目的は、明細書中の記載からあきらか
になるであろう。Still other objects of the present invention will become apparent from the description in the specification.
ｃ問題点を解決するための手段１
本発明者等は、以上の目的を達成すべく鋭意研究を重ね
た結果、特定の非対称スクェアリウム化合物が電子写真
感光体の有効成分として動き得ることを見出し、本発明
を完成したものである。cMeans for solving the problem 1 As a result of intensive research to achieve the above object, the present inventors discovered that a specific asymmetric squareium compound can act as an active ingredient of an electrophotographic photoreceptor. , has completed the present invention.
すなわち、本発明の前記目的は、導電性支持体上に、下
記一般式［１］で表わされる非対称スクェアリウム化合
物を含有してなる感光層を有することを特徴とする電子
写真感光体によって達成される。That is, the above object of the present invention is achieved by an electrophotographic photoreceptor characterized by having a photosensitive layer containing an asymmetric squareium compound represented by the following general formula [1] on a conductive support. Ru.
［式中、Ａｒ＋およびＡｒ２は、互に異なり、Ａｒ＋
およびＡｒ２の一方は下記一般式［Ａ］から選ばれ、
（Ｒ＋ 、Ｒ２及びＲ３は、それぞれ水素原子、ハロゲ
ン原子、アルキル基、アルコキシ基、水酸基またはＮ１
−ＩＹを表わす。Ｙは、−Ｃ−ＲａまたハＳ ０２
Ｒｓ （Ｒａ 及ヒＲｓ Ｌｅ＆、それぞｈ水素原子
、置換もしくは非置換のアルキル基、または置換もしく
は非置換のアリール基を表わす。〉を表わす。Ｒ４、Ｒ
５、Ｒ６及びＲ７は、それぞれ水素原子、ハロゲン原子
、又は置換もしくは非置換のアルキル基を表わす。Ａｒ
３は置換若しくは非置換のアリール基を表わす。）
そして、Ａｒ＋ および、Ａｒ２の他方は、下記一般式
［８］、［Ｃ］又は［Ｄ］から選ばれる。[In the formula, Ar+ and Ar2 are different from each other, and Ar+
and Ar2 is selected from the following general formula [A], (R+, R2 and R3 are each a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a hydroxyl group or a N1
-Represents IY. Y is -C-Ra or HaS 02
Rs (Ra and Rs Le&, each representing a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group). R4, R
5, R6 and R7 each represent a hydrogen atom, a halogen atom, or a substituted or unsubstituted alkyl group. Ar
3 represents a substituted or unsubstituted aryl group. ) The other of Ar+ and Ar2 is selected from the following general formula [8], [C], or [D].
一般式［Ｂ］
（式中、Ｒ＋ｏ Ｊ３よびＲｎは、それぞれ互に独立し
たものであるときは、それぞれ、炭素原子数１〜２０の
置換若しくは非置換のアルキル基、置換若しくは非置換
のフェニル基を表わし、又はＲｈ。General formula [B] (wherein, R+o J3 and Rn are each a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted phenyl group, when they are independent of each other) or Rh.
とＲ１１が共同して３ないし７員の含窒素複素環を形成
する場合はアルキレン基を表わす。Ｒｈ２は水素原子、
水酸基、メチル基、トリフルオロメチル基、ハロゲン原
子又はカルボキシル基を表わす、）一般式［Ｃ］
（式中、Ｒｈ３は前記一般式［Ｂ］のＲｈｏおよびＲ＋
＋と同義であり（但しＲｈｏとＲ＋＋とが互に共同して
環を形成する場合を除く）、Ｒ特は前記一般式［Ｂ］の
Ｒｈ２と同義であり、Ｒｈ５は、水素原子、炭素原子数
１〜６のアルキル基、水酸基、炭素原子数１〜４のアル
コキシ基、ハロゲン原子、ニトロ基、シアノ基、カルボ
キシル基、炭素原子数１〜４のアルコキシカルボニル基
又はトリフルオロメチル基を表わす。）
（式中、Ｒｈｏは前記一般式［８］のＲｈ２と同義であ
り、Ｒ１７及びＲｈｏはそれぞれ前記一般式［Ｃ］のＲ
ｈｏと同義である。）］
以下、本発明の非対称のスクェアリウム化合物について
具体的に説明する。When R11 and R11 together form a 3- to 7-membered nitrogen-containing heterocycle, it represents an alkylene group. Rh2 is a hydrogen atom,
General formula [C] (representing a hydroxyl group, methyl group, trifluoromethyl group, halogen atom or carboxyl group) (wherein Rh3 is Rho and R+ of the general formula [B])
+ (except when Rho and R++ jointly form a ring), R has the same meaning as Rh2 in the general formula [B], and Rh5 is a hydrogen atom, a carbon atom It represents an alkyl group having 1 to 6 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, a nitro group, a cyano group, a carboxyl group, an alkoxycarbonyl group having 1 to 4 carbon atoms, or a trifluoromethyl group. ) (wherein, Rho has the same meaning as Rh2 in the general formula [8], and R17 and Rho each have the same meaning as R in the general formula [C])
It is synonymous with ho. )] Hereinafter, the asymmetric squalium compound of the present invention will be specifically explained.
本発明の非対称のスクェアリウム化合物は一般式［Ｉ］
で表わされるが、一般式［Ｉ］におけるＡｒ＋ および
Ａｒ２のどららか一方は前記の一般式［Ａ］から選ばれ
る。The asymmetric squalium compound of the present invention has the general formula [I]
However, one of Ar+ and Ar2 in general formula [I] is selected from the above general formula [A].
一般式［Ａ］において、Ｒｈ 、Ｒ２及びＲ３で表わさ
れるアルキル基としては特に炭素原子数１〜３のものが
好ましく、更に好ましくはメチル基である。また、Ｒｈ
、Ｒ２及びＲ３で表わされるアルコキシ基としてはメ
トキシ基等が好ましく、ハロゲン原子としてはフッ素原
子等が好ましい。In the general formula [A], the alkyl groups represented by Rh, R2 and R3 preferably have 1 to 3 carbon atoms, and more preferably a methyl group. Also, Rh
The alkoxy group represented by , R2 and R3 is preferably a methoxy group, and the halogen atom is preferably a fluorine atom.
Ｒｈ 、Ｒ２及びＲ３で表わされるＮＨＹのＹはＣ−Ｒ
ａ又は−８Ｏ２−Ｒｓを示すが、Ｒ８及びＲ９の置換基
を有してもよいアルキル基の例としては、メチル基、エ
チル基、プロピル基等が挙げられ、またアリール基の例
としてはフェニル基等が挙げられる。また、Ｒ４、Ｒ５
、Ｒ６及びＲ７で表わされるアルキル基としては炭素原
子数１〜３のものが好ましく、特にメチル基が好ましい
。Ｒ４、Ｒｓ 、Ｒｓ及びＲ７で表わされるハロゲン原
子としてはフッ素原子、塩素原子、臭素原子等が好まし
い。Y of NHY represented by Rh, R2 and R3 is C-R
a or -8O2-Rs, but examples of alkyl groups which may have substituents for R8 and R9 include methyl group, ethyl group, propyl group, etc., and examples of aryl groups include phenyl group. Examples include groups. Also, R4, R5
, R6 and R7 preferably have 1 to 3 carbon atoms, particularly preferably a methyl group. The halogen atom represented by R4, Rs, Rs, and R7 is preferably a fluorine atom, a chlorine atom, a bromine atom, or the like.
Ａｒ３は、置換若しくは非置換のアリール基、例えばフ
ェニル基、ナフチル基、アントラニル基、縮合多環等を
表わす。Ａｒ３の置換基としては、たとえばアルキル基
、アルキルチオ基、アルコキシ基、ハロゲン原子、ヒド
ロキシル基、シアン基、エステル基、アシル基、ジアル
キルアミノ基、ジアラルキルアミノ基、ジアリールアミ
ノ基、複素環基、などを挙げることができる。Ar3 represents a substituted or unsubstituted aryl group, such as a phenyl group, a naphthyl group, an anthranyl group, a fused polycyclic group, and the like. Examples of the substituent for Ar3 include an alkyl group, an alkylthio group, an alkoxy group, a halogen atom, a hydroxyl group, a cyan group, an ester group, an acyl group, a dialkylamino group, a dialkylamino group, a diarylamino group, a heterocyclic group, etc. can be mentioned.
そして、本発明の非対称スクェアリウム化合物は、一般
式［Ｉ］におけるＡｒ１およびＡｒ２の他方が前記の一
般式［８］、［Ｃ］又はＣＤ］から選ばれる。In the asymmetric squarium compound of the present invention, the other of Ar1 and Ar2 in general formula [I] is selected from the above general formula [8], [C] or CD].
一般式［８１において、ＲＩＯおよびＲｈで表わされる
アルキル基としては特に炭素原子数１〜７のものが好ま
しく、例えばメチル基、エチル基、プロピル基等が挙げ
られる。In general formula [81, the alkyl group represented by RIO and Rh is preferably one having 1 to 7 carbon atoms, such as a methyl group, an ethyl group, a propyl group, and the like.
以下、本発明に有用な前記非対称スクェアリウム化合物
の具体例を以下に示すが、本発明の非対称スクェアリウ
ム化合物はこれに限定されるものではない。Specific examples of the asymmetric squalium compound useful in the present invention are shown below, but the asymmetric squalium compound of the present invention is not limited thereto.
刀
−船人［Ｉ］で表わされる本発明の非対称スクェアリウ
ム化合物は例えば特開昭６２−２６７７５３号及びテト
ラヘドロン レターズ（ＴｅｔｒａｈｅｄｒｏｎＬｅ！
ｔｔｅｒｓ） ＮＯ，１０，Ｄｐ、７８１−７８２．１
９７０年及びシンセシス（Ｓｙｎｔｈｅｓｉｓ） Ｄｉ
）、９６１．１９８０年の記載に準じて、下記の式で示
すように４段階で合成することができる。The asymmetric squareium compound of the present invention represented by Katana-Funenin [I] is disclosed in, for example, JP-A No. 62-267753 and Tetrahedron Letters (Tetrahedron Le!).
tters) NO, 10, Dp, 781-782.1
970 and Synthesis Di
), 961.1980, it can be synthesized in four steps as shown by the formula below.
′＝−丁
以下余白
ビＬ二ニシー一
第１段階では、式（Ａ＞のスクアリン酸に塩化チオニル
とＮ、Ｎ−ジメチルホルムアミドを加え、約１００℃で
反応させ、３．４−ジクロロ−３−シクロブテン−１，
２−ジオンを得る。In the first step, thionyl chloride and N,N-dimethylformamide are added to the squaric acid of the formula (A>) and reacted at about 100°C to form 3,4-dichloro-3 -cyclobutene-1,
2-dione is obtained.
第２段階では第１段階で得られた式（Ｂ）の３゜４−ジ
クロロ−３−シクロブテン−１，２−ジオンを０．５〜
５モル比の式（Ｃ）のＡｒ２−Ｈと溶媒中、前記Ａｒ２
−Ｈに対して１モル比以上のＡりＣに３の存在下、室温
以下の温度で反応させて式（Ｄ）の化合物を得る。In the second step, the 3゜4-dichloro-3-cyclobutene-1,2-dione of formula (B) obtained in the first step is added to
5 molar ratio of Ar2-H of formula (C) and the above Ar2 in a solvent.
The compound of formula (D) is obtained by reacting A and C in the presence of 3 in a molar ratio of 1 or more to -H at a temperature below room temperature.
前記第２段階において用いられる溶媒の例としてはジク
ロロメタン、四塩化炭素、１．２−ジクロロエタンなど
、通常フリーデル・クラフッ反応で用いられる溶媒を挙
げることができる。また前記ＡｌＣｌ１３の代りに触媒
として、塩化アルミニウム、塩化アンチモン、塩化鉄、
塩化チタン、三フッ化ホウ素、塩化スズ、塩化ビスマス
、塩化亜鉛などのルイス酸を用いてもよい。Examples of the solvent used in the second step include dichloromethane, carbon tetrachloride, 1,2-dichloroethane, and other solvents commonly used in Friedel-Krach reactions. In addition, aluminum chloride, antimony chloride, iron chloride,
Lewis acids such as titanium chloride, boron trifluoride, tin chloride, bismuth chloride, and zinc chloride may also be used.
第３段階では第２段階の反応で得られた式（Ｄ）の化合
物を加水分解して式（Ｅ）の化合物とする。In the third step, the compound of formula (D) obtained in the reaction of the second step is hydrolyzed to form a compound of formula (E).
加水分解は例えば少量の水を含む酢酸中、還流すること
により行なうことができる。Hydrolysis can be carried out, for example, by refluxing in acetic acid containing a small amount of water.
第４段階では第３段階で得られ単離した式（Ｅ）の化合
物を溶媒中還流法または減圧法で式（Ｆ）のＡｒ＋ −
Ｈを反応させて目的とする非対称スクェアリウム化合物
（Ｉ）を得る。ここで用いられる溶媒としては炭素数２
ないし１０の１級または２級アルコール、もしくはそれ
らのアルコールとベンゼン、トルエン、キシレンなどの
芳香族炭化水素との共沸混合物を用いることができる。In the fourth step, the compound of formula (E) obtained and isolated in the third step is refluxed in a solvent or by a reduced pressure method to Ar+ − of formula (F).
The desired asymmetric squalium compound (I) is obtained by reacting with H. The solvent used here has 2 carbon atoms.
1 to 10 primary or secondary alcohols, or azeotropic mixtures of these alcohols and aromatic hydrocarbons such as benzene, toluene, and xylene can be used.
本発明の非対称スクェアリウム化合物はスクェアリウム
化合物の一般的な合成法により得ることもできる。即ち
スクエアリック酸１モルに対し異なる２種類のアミン誘
導体を合計で２モル同時に反応させ得ることができる。The asymmetric squalium compound of the present invention can also be obtained by a general synthesis method for squalium compounds. That is, a total of 2 moles of two different types of amine derivatives can be simultaneously reacted with 1 mole of squaric acid.
しかしながら、この際得られるスクェアリウム化合物は
非対称スクェアリウム化合物と対称スクェアリウム化合
物の混合物であり、生成物の比率のコントロールや、単
品の分離精製が困難であり、電気特性のバラツキが大き
くまた感度の低下をまねく等の問題点を有するので前者
の方法が好ましい。However, the squalium compound obtained in this case is a mixture of an asymmetrical squalium compound and a symmetrical squalium compound, and it is difficult to control the ratio of the products and separate and purify each product, and the electrical properties vary widely and the sensitivity is low. The former method is preferable since it has problems such as lowering the performance.
次に本発明の非対称スクェアリウムの具体的合成法につ
いて下記に示す。Next, a specific method for synthesizing the asymmetric squareium of the present invention will be described below.
合成例（例示化合物Ｉ−５の合成）
（ジシクロブテンジオン（Ｂ）の合成）スクアリン酸１
００ｇにベンゼン５００顧と塩化チオニル１４０戴とＮ
、Ｎ−ジメチルホルムアミド５１ｇを加え、外温１００
℃で２時間撹拌する。溶媒を留去してから、ｎ−ヘキサ
ンで結晶化する。ｎ−ヘキサンで数回デカント洗浄した
後、減圧乾燥し、ジシクロブテンジオン（Ｂ）５８ｇ
（収率４４％）を得た。Synthesis example (synthesis of exemplified compound I-5) (Synthesis of dicyclobutenedione (B)) Squaric acid 1
500 g of benzene, 140 g of thionyl chloride, and N
, add 51 g of N-dimethylformamide, and bring the external temperature to 100
Stir at ℃ for 2 hours. After distilling off the solvent, crystallization is performed from n-hexane. After washing with n-hexane several times by decantation, drying under reduced pressure gave 58 g of dicyclobutenedione (B).
(yield 44%).
以下−余白
′−三三日ミ
ノクロル体（Ｄ）の合成）
塩化メチレン３６０１１２に塩化アルミニウム５３ｇを
加え、約Ｏ℃で撹拌する。ジシクロブテンジオン（Ｂ）
５０ａを加えた後、アニリン誘導体（Ｃ）７７ａを塩化
メチレン１２０ｉ１２に溶かし、内温を０℃に保ちなが
ら、滴下する。内温的０℃で、６時間撹拌する。Below - Margin' - Synthesis of minochlor compound (D)) 53 g of aluminum chloride is added to 360112 methylene chloride and stirred at about 0°C. Dicyclobutenedione (B)
After adding 50a, aniline derivative (C) 77a is dissolved in methylene chloride 120i12 and added dropwise while keeping the internal temperature at 0°C. Stir at internal temperature of 0°C for 6 hours.
塩化メチレン１１と蒸留水１ｆを加え、撹拌後、静置し
て、塩化メチレン層を得る。水洗後、ボウショウで乾燥
し、塩化メチレンを減圧下で留去する。シリカゲルのカ
ラムで精製し、クロル体（Ｄ）を結晶で９４ｇ （収率
８２％）得た。11 methylene chloride and 1 f of distilled water are added, stirred, and then allowed to stand to obtain a methylene chloride layer. After washing with water, dry with a sieve, and methylene chloride is distilled off under reduced pressure. Purification was performed using a silica gel column to obtain 94 g (yield: 82%) of chloride (D) as crystals.
（ＯＨ体（Ｅ）の合成）
クロル体（Ｄ）３１ｇに酢酸１００鶴と蒸留水１０戴を
加え、撹拌下、加熱還流を３時間行う。(Synthesis of OH form (E)) 100 g of acetic acid and 10 g of distilled water are added to 31 g of chlorine form (D), and heated under reflux for 3 hours with stirring.
冷却後、４２の蒸留水を加え、塩酸５０ｔｆｆｉを加え
撹拌、吸引ロートでろ取する。水洗、ｎ−ヘキサン、減
圧乾燥し１．ＯＨ体（Ｅ）２３ａ （収率７８％）を
結晶で得た。After cooling, add 42 ml of distilled water, add 50 tffi of hydrochloric acid, stir, and filter through a suction funnel. Wash with water, n-hexane, dry under reduced pressure 1. The OH form (E) 23a (yield 78%) was obtained in the form of crystals.
（例示化合物Ｉ−５の合成）
０１−１体（Ｅ）２３（Ｉに１−ヘプタツール１りと化
合物（１： ） １６．２（Ｊを加え、減圧下２時間、
撹拌加熱還流を行う。熱時吸引濾過し、アセトン２りで
３回洗浄する。減圧乾燥し、目的とする例示化合物Ｉ−
５を、緑色結晶として２６．４ｇ（収率６４％）得た。(Synthesis of Exemplified Compound I-5) 01-1 body (E) 23 (I added one 1-heptatool and compound (1: ) 16.2 (J), and under reduced pressure for 2 hours,
Stir and heat under reflux. Filter with suction while hot and wash three times with two parts of acetone. Dry under reduced pressure to obtain the desired exemplary compound I-
26.4 g (yield 64%) of 5 was obtained as green crystals.
元素分析
Ｃ）ＩＮ
君１譚値（％） ７６．３５ ５，２５ ５．４
０実測値（％） ７６．３１ ５．２７ ５．３
１分光吸収スペクトル（塩化メチレン中）λｍａｘ ＝
６３６ｎｍ
赤外線吸収スペクトル（ＫＢｒ中）
ｖｍａｘ ＝１５９０ｃｍ−’ （ｃ＝０ ）融点（日
本薬局方融点測定法）
２４３℃
本発明の非対称スクェアリウム化合物は、優れた光導電
性を有し、これを用いて感光体を製造する場合、導電性
支持体上に本発明の非対称スクェアリウム化合物をバイ
ンダー中に分散した感光層を設けることにより製造する
ことができるが、本発明の非対称スクェアリウム化合物
の持つ光導電性のうち、特に優れたキャリア発生能を利
用してキャリア発生物質として用い、これと組み合わせ
て有効に作用し得るキャリア輸送物質と共に用いること
により、いわゆる機能分離型の感光体を構成した場合、
特に優れた結果が得られる。前記機能分離型感光体は分
散型のものであってもよいが、キャリア発生物質を含む
キャリア発生層とキャリア輸送物質を含むキャリア輸送
層を積層した積層型感光体どすることがより好ましい。Elemental analysis C) IN Kimi Tan value (%) 76.35 5,25 5.4
0 Actual value (%) 76.31 5.27 5.3
1-spectrum absorption spectrum (in methylene chloride) λmax =
636 nm Infrared absorption spectrum (in KBr) vmax = 1590 cm-' (c = 0) Melting point (Japanese Pharmacopoeia melting point measurement method) 243°C The asymmetric squareium compound of the present invention has excellent photoconductivity, and it can be used to When manufacturing a photoreceptor, it can be manufactured by providing a photosensitive layer in which the asymmetric squareium compound of the present invention is dispersed in a binder on a conductive support. When a so-called functionally separated photoreceptor is constructed by using it as a carrier-generating substance by taking advantage of its particularly excellent carrier-generating ability out of conductivity, and using it together with a carrier-transporting substance that can effectively act in combination with this,
Particularly good results are obtained. The functionally separated photoreceptor may be of a dispersed type, but it is more preferably a laminated type photoreceptor in which a carrier generation layer containing a carrier generation substance and a carrier transport layer containing a carrier transport substance are laminated.
本発明の非対称スクェアリウム化合物をキャリア発生物
質として用いた場合、これと組み合わせて用いられるキ
ャリア輸送物質としては、トリニトロフルオレノンある
いはテトラニトロフルオレノンなどの電子を輸送しやす
い電子受容性物質のほか、ポリ−Ｎ−ビニルカルバゾー
ルに代表されるような複素環化合物を側鎖に有する重合
体、トリアゾール誘導体、オキサジアゾール誘導体、イ
ミダゾール誘導体、ピラゾリン誘導体、ポリアリールア
ルカン誘導体、フェニレンジアミン誘導体、ヒドラゾン
誘導体、アミノ置換カルゴン誘導体、トリアリールアミ
ン誘導体、カルバゾール誘導体、スチルベン誘導体、フ
ェノチアジン誘導体、アジン誘導体、ブタジェン誘導体
、シッフベース誘導体等の正孔を輸送しやすい電子供与
性物質が挙げられるが、本発明に用いられるキャリア輸
送物質はこれらに限定されるものではない。When the asymmetric squareium compound of the present invention is used as a carrier-generating substance, carrier-transporting substances that can be used in combination with it include electron-accepting substances that easily transport electrons, such as trinitrofluorenone or tetranitrofluorenone, as well as polyesters. - Polymers having heterocyclic compounds in their side chains such as N-vinylcarbazole, triazole derivatives, oxadiazole derivatives, imidazole derivatives, pyrazoline derivatives, polyarylalkane derivatives, phenylenediamine derivatives, hydrazone derivatives, amino-substituted Examples of electron-donating substances that easily transport holes include calgon derivatives, triarylamine derivatives, carbazole derivatives, stilbene derivatives, phenothiazine derivatives, azine derivatives, butadiene derivatives, Schiff base derivatives, etc., and the carrier transporting substance used in the present invention is not limited to these.
感光体の構成は種々の形態が知られているが、本発明の
感光体はそれらのいずれの形態をもとり得る。Various configurations of photoconductors are known, and the photoconductor of the present invention can take any of these configurations.
通常は、第１図〜第６図の形態である。第１図は負帯電
用感光体の例で、導電性支持体１上に前述の非対称スク
ェアリウム化合物を主成分として含有するキャリア発生
層２、その上にキャリア輸送物質を主成分として含有す
るキャリア輸送層３を積層構成に設けた感光層４を有す
る場合である。Usually, the configuration is as shown in FIGS. 1 to 6. FIG. 1 shows an example of a photoreceptor for negative charging, in which a carrier generation layer 2 containing the above-mentioned asymmetric squareium compound as a main component is formed on a conductive support 1, and a carrier containing a carrier transporting substance as a main component is formed on the carrier generation layer 2. This is the case where the photosensitive layer 4 has the transport layer 3 in a laminated configuration.
第２図は正帯電用感光体の例で、キャリア発生ｌ１１２
がキャリア輸送層３の上に設けられている。Figure 2 shows an example of a photoreceptor for positive charging, with carrier generation l112
is provided on the carrier transport layer 3.
この場合、そのキャリア発生層の保護のために、当該キ
ャリア発生層の上にオーバーコート層や中間層を形成す
ることが望ましい。In this case, in order to protect the carrier generation layer, it is desirable to form an overcoat layer or an intermediate layer on the carrier generation layer.
オーバーコート層としては、各種バインダーを用いるこ
とができるが、アクリル樹脂、イソシアネート樹脂等が
望ましい。さらに、酸化スズ、酸化チタン等をバインダ
ー中に分散することもできる。Various binders can be used for the overcoat layer, but acrylic resins, isocyanate resins, etc. are preferable. Furthermore, tin oxide, titanium oxide, etc. can also be dispersed in the binder.
中間層としては、オーバーコート層と同様のバインダー
類や金属酸化物等が使用できる。さらにシリコンやジル
コニウムを含む化合物を用いることもできる。As the intermediate layer, the same binders and metal oxides as those for the overcoat layer can be used. Furthermore, compounds containing silicon or zirconium can also be used.
第３図及び第４図に示すようにこの感光層４は、導電性
支持体上に設けた中間層５を介して設けてもよい。この
ように感光層４を二層構成としたときに最も優れた電子
写真特性を有する感光体が得られる。また本発明におい
ては、第５図および第６図に示すように前記キャリア発
生物質７とキャリア輸送物質を層６中に分散せしめて成
る感光層４を導電性支持体１上に直接、あるいは中間層
５を介して設けてもよい。As shown in FIGS. 3 and 4, this photosensitive layer 4 may be provided via an intermediate layer 5 provided on a conductive support. When the photosensitive layer 4 has a two-layer structure in this manner, a photoreceptor having the most excellent electrophotographic properties can be obtained. Further, in the present invention, as shown in FIGS. 5 and 6, a photosensitive layer 4 comprising a carrier generating substance 7 and a carrier transporting substance dispersed in a layer 6 is formed on the conductive support 1 directly or in an intermediate manner. It may be provided via layer 5.
二層構成の感光層４を構成するキャリア発生層２は導電
性支持体１、もしくはキャリア輸送層３上に直接、ある
いは必要に応じて接着層もしくはバリヤー層などの中間
層を設けた上に例えば次の方法によって形成することが
できる。The carrier generation layer 2 constituting the two-layered photosensitive layer 4 may be applied directly to the conductive support 1 or the carrier transport layer 3, or if necessary, after providing an intermediate layer such as an adhesive layer or a barrier layer, for example. It can be formed by the following method.
Ｍ−１、発明の名称スクェアリウム化合物を適当な溶媒
に溶解した溶液を、あるいは必要に応じてバインダーを
加え混合溶解した溶液を塗布する方法。M-1, Name of the Invention A method of applying a solution in which a squalium compound is dissolved in a suitable solvent, or a solution in which a binder is added and mixed as necessary.
Ｍ−２）本発明の非対称スクェアリウム化合物をボール
ミル、ホモミキサー等によって分散媒中で微細粒子とし
、必要に応じてバインダーをくわえ混合分散した分散液
を塗布する方法。M-2) A method in which the asymmetric squalium compound of the present invention is made into fine particles in a dispersion medium using a ball mill, a homomixer, etc., and a binder is added as necessary to mix and disperse the resulting dispersion.
キャリア発生層の形成に使用される溶媒あるいは分散媒
としては、ｎ−ブヂルアミン、ジエチルアミン、エチレ
ンジアミン、イソプロパツールアミン、トリエタノール
アミン、トリエチレンジアミン、Ｎ、Ｎ−ジメチルホル
ムアミド、アセトン、メチルエチルケトン、シクロヘキ
サノン、ベンゼン、トルエン、キシレン、クロロホルム
、１，２−ジクロロエタン、１，１．２−トリクロロエ
タン、１，１．１−トリクロロエタン、トリクロロエタ
ン、テトラクロロエタン、ジクロロメタン、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
プロパツール、酢酸エチル、酢酸ブチル、ジメチルスル
ホキシド等が挙げられる。Solvents or dispersion media used to form the carrier generation layer include n-butylamine, diethylamine, ethylenediamine, isopropanolamine, triethanolamine, triethylenediamine, N,N-dimethylformamide, acetone, methyl ethyl ketone, cyclohexanone, and benzene. , toluene, xylene, chloroform, 1,2-dichloroethane, 1,1.2-trichloroethane, 1,1.1-trichloroethane, trichloroethane, tetrachloroethane, dichloromethane, tetrahydrofuran, dioxane, methanol, ethanol, isopropanol, ethyl acetate , butyl acetate, dimethyl sulfoxide and the like.
また、キャリア輸送層は上記キャリア発生層と同様にし
て形成することができる。Further, the carrier transport layer can be formed in the same manner as the carrier generation layer described above.
キャリア発生層あるいはキャリア輸送層の形成にバイン
ダー樹脂を用いる場合は任意のものを用いることができ
るが、疎水性で、かつ誘電率が高く、電気絶縁性のフィ
ルム形成性高分子重合体を用いるのが好ましい。このよ
うな高分子重合体としては、例えば次のものを挙げるこ
とができるが、これらに限定されるものではない。When using a binder resin to form the carrier generation layer or the carrier transport layer, any binder resin can be used, but it is preferable to use a film-forming polymer that is hydrophobic, has a high dielectric constant, and is electrically insulating. is preferred. Examples of such high molecular weight polymers include, but are not limited to, the following.
Ｐ−１）ポリカーボネート
Ｐ−２）ポリニスデル
Ｐ−３）メタクリル樹脂
Ｐ−４）アクリル樹脂
Ｐ−５）ポリ塩化ビニル
Ｐ−６）ポリ塩化ビニリデン
Ｐ−７）ポリスチレン
Ｐ−８）ポリビニルアセテート
Ｐ−９）スチレン−ブタジェン共重合体ｐ −ｉｏ）塩
化ビニリデン−アクリロニトリル共重合体
Ｐ −１１）塩化ビニル−酢酸ビニル共重合体Ｐ−１２
）塩化ビニル−酢酸ビニル−無水マレイン酸共重合体
Ｐ −１３）シリコン樹脂
ｐ −１４）シリコン−アルキッド樹脂Ｐ −１５）フ
ェノールホルムアルデヒド樹脂Ｐ −１６）スチレン−
アルキッド樹脂Ｐ −１７）ポリ−Ｎ−ビニルカルバゾ
ールＰ − １８）ポリビニルブチラール
Ｐ − １９）ポリビニルフォルマールＰ−２０）酢酸
ビニル樹脂
Ｐ−２１）エポキシ樹脂
これらのバインダー樹脂は、単独であるいは２種以上の
混合物として用いることができる。P-1) Polycarbonate P-2) Polynisdel P-3) Methacrylic resin P-4) Acrylic resin P-5) Polyvinyl chloride P-6) Polyvinylidene chloride P-7) Polystyrene P-8) Polyvinyl acetate P-9 ) Styrene-butadiene copolymer p -io) Vinylidene chloride-acrylonitrile copolymer P-11) Vinyl chloride-vinyl acetate copolymer P-12
) Vinyl chloride-vinyl acetate-maleic anhydride copolymer P -13) Silicone resin P -14) Silicone-alkyd resin P -15) Phenol formaldehyde resin P -16) Styrene -
Alkyd resin P-17) Poly-N-vinylcarbazole P-18) Polyvinyl butyral P-19) Polyvinyl formal P-20) Vinyl acetate resin P-21) Epoxy resin These binder resins may be used alone or in combination of two or more. It can be used as a mixture of
このようにして形成されるキャリア発生層２の厚さは、
０．０１μ！１〜２０μｍであることが好ましいが、更
に好ましくは０． ０５μｆｆ１〜５μｍである。また
キャリア発生層あるいは感光層が分散系の場合、非対称
スクェアリウム化合物の粒径は５μｍ以下であることが
好ましく、更に好ましくは１μｍ以下である。The thickness of the carrier generation layer 2 formed in this way is
0.01μ! It is preferably 1 to 20 μm, more preferably 0. 05μff1 to 5μm. Further, when the carrier generation layer or the photosensitive layer is a dispersion system, the particle size of the asymmetric squalium compound is preferably 5 μm or less, more preferably 1 μm or less.
キャリア発生層において、キャリア発生物質とバインダ
ーとの重量比は好ましくは１００：Ｑ〜１０００である
。キャリア発生物質の含有割合がこれより少ないと光感
度が低く、残基電位の増加を招き、またこれより多いと
暗減衰及び受容電位が低下する。In the carrier generation layer, the weight ratio of the carrier generation substance to the binder is preferably 100:Q to 1000. If the content of the carrier-generating substance is less than this, the photosensitivity will be low and the residue potential will increase, and if it is more than this, dark decay and acceptance potential will decrease.
また、前記のようにして形成されるキャリア輸送層にお
いて、キャリア輸送物質はキャリア輸送層中のバインダ
ー樹脂１００重量部当り２０〜２００重量部が好ましく
、特に好ましくは３０〜１５０Ｍ量部である。Further, in the carrier transport layer formed as described above, the amount of the carrier transport substance is preferably 20 to 200 parts by weight, particularly preferably 30 to 150 parts by weight, per 100 parts by weight of the binder resin in the carrier transport layer.
また、形成されるキャリア輸送層の厚さは、好ましくは
５〜５０μｆ１特に好ましくは５〜３０μｍである。Further, the thickness of the carrier transport layer to be formed is preferably 5 to 50 μm, particularly preferably 5 to 30 μm.
導電層としては、導電性支持体の上に、酸化チタン、酸
化スズ、ヨウ化銅等の無曙導電性化合物や、カーボン、
有機半導体、導電性ポリマー等の有機導電性化合物をバ
インダーに分散したり、そのままで塗布することによっ
て形成することができる。As a conductive layer, a non-Akebono conductive compound such as titanium oxide, tin oxide, copper iodide, carbon,
It can be formed by dispersing an organic conductive compound such as an organic semiconductor or a conductive polymer in a binder or by applying it as it is.
本発明の非対称スクェアリウム化合物は、粉粒体工学の
見地から、種々の加工をほどこして、分散性を向上させ
ることができる。たとえば、湿式造粒法、スプレードラ
イ、フリーズドライ、乾式粉砕、等が利用できる。The asymmetric squarium compound of the present invention can be subjected to various processes to improve its dispersibility from the viewpoint of powder and granule engineering. For example, wet granulation, spray drying, freeze drying, dry pulverization, etc. can be used.
また、結晶形を変化させることによって、電子写真性能
や分散性を向上させることができる。たとえば、有機ア
ミンで溶解してから酸で中和析出させる方法や、圧力や
温度等で結晶形が変化することがある。Further, by changing the crystal form, electrophotographic performance and dispersibility can be improved. For example, the crystal form may change depending on the method of dissolving with an organic amine and then neutralizing and precipitating with an acid, or depending on pressure, temperature, etc.
本発明の感光体に用いられる導電性支持体としては、合
金を含めた金ｊ板、金属ドラムまたは導電性ポリマー、
酸化インジウム等の導電性化合物や合金を含めたアルミ
ニウム、パラジウム、金等の金属薄層を塗布、蒸着ある
いはラミネートして、導電性化を達成した紙、プラスチ
ックフィルム等が挙げられる。The conductive support used in the photoreceptor of the present invention includes a gold plate including an alloy, a metal drum, a conductive polymer,
Examples include paper, plastic films, etc. that have been made conductive by coating, vapor depositing, or laminating a thin layer of a metal such as aluminum, palladium, or gold containing a conductive compound or alloy such as indium oxide.
接着層あるいはバリヤー層などの中間層としては、前記
バインダーとして用いられる高分子重合体のほか、ポリ
ビニルアルコール、エチルセルロース、カルボキシメチ
ルセルロースなどの有機高分子物質または酸化アルミニ
ウムなどが用いられる。As an intermediate layer such as an adhesive layer or a barrier layer, in addition to the polymer used as the binder, an organic polymer material such as polyvinyl alcohol, ethyl cellulose, carboxymethyl cellulose, or aluminum oxide is used.
本発明の感光体は以上のような構成であって、後述する
ような実施例からも明らかなように、帯電特性、感度特
性、画像形成特性に優れており、特に繰り返し使用した
ときにも疲労劣化が少なく、耐久性が優れたものである
。The photoreceptor of the present invention has the above-described structure, and as is clear from the examples described later, it has excellent charging characteristics, sensitivity characteristics, and image forming characteristics, and is particularly resistant to fatigue even when used repeatedly. It has little deterioration and excellent durability.
［実施例］
以下、本発明の実施例で具体的に説明するが、これによ
り本発明の実施態様が限定されるものではない。[Examples] The present invention will be specifically explained below using Examples, but the embodiments of the present invention are not limited thereto.
実施例１
３００ ｖＱのステンレスボッ１へに、ポリビニルブチ
ラール樹脂（商品名、ＸＹＨＬ）Ｏ，γ５０とテ１〜ラ
ヒドロフラン１５０ｎＥ！と本発明のスクェアリウム化
合物（Ｉ−１）１．５ｃ＋とを入れ、ガラスピーズ１５
〇−を加え、サンドグラインダーで４８時間分散する。Example 1 Into a stainless steel bottle of 300 vQ, polyvinyl butyral resin (trade name, XYHL) O, γ50 and Te1~Rahydrofuran 150 nE! and 1.5c+ of the squalium compound (I-1) of the present invention, and glass beads 15
Add 〇- and disperse with a sand grinder for 48 hours.
この分散液をアルミニウム蒸着ベース上に乾燥後の膜厚
が約０．２μとなる様、ワイヤーバーで塗布し、キャリ
ア発生層（ＣＧＬ）を形成した。次に、ポリカーボネー
ト樹脂（商品名、パンライトに−１３００） ７．５
ｇと塩化エチレン５０ｄと下記キレリア輸送物質に−１
４，０（＋とを磁気撹拌様で混合する。この液を、前記
ＣＧ Ｌの上に、乾燥後の膜厚が２０μとなるように、
アプリケーターによって塗布し、キャリア輸送層（ＣＴ
Ｌ）を形成した。This dispersion was applied onto an aluminum vapor-deposited base using a wire bar so that the film thickness after drying was approximately 0.2 μm to form a carrier generation layer (CGL). Next, polycarbonate resin (trade name, Panlite-1300) 7.5
g, ethylene chloride 50d and the following chyrelia transport substance -1
Mix 4,0(+) with magnetic stirring.Pour this liquid onto the CG L so that the film thickness after drying is 20μ.
Applied by an applicator, the carrier transport layer (CT
L) was formed.
オーブンに入れ、よく乾燥した後、電子写真性能を試験
した。すなわち、川口電気製、静電複写試験装置により
一６ＫＶのコロナ放電を５秒間行なって帯電させた後、
５秒間暗所に放置し、その表面電位ＶＡを測定し、次に
照度１４ルツクスのタングステン・ハロゲンランプを感
光層に照射し、その表面電位が■＾の半分になるまでの
時間を計算して、半減露光ｉ［：１／２を求めた。その
結果Ｖ ＾＝ −１３１０Ｖ、Ｅ １／２ ＝ ２．７
１ｕｘ−ｓｅｃ テあった。After being placed in the oven and thoroughly dried, the electrophotographic performance was tested. That is, after being charged by performing a corona discharge of 16 KV for 5 seconds using an electrostatic copying tester manufactured by Kawaguchi Electric,
Leave it in a dark place for 5 seconds, measure its surface potential VA, then irradiate the photosensitive layer with a tungsten halogen lamp with an illuminance of 14 lux, and calculate the time until the surface potential becomes half of ■^. , half-reduced exposure i[:1/2 was determined. As a result, V ^ = -1310V, E 1/2 = 2.7
It was 1ux-sec.
次に、画像特性及び耐久性を、コニカ■製ＬＤプリンタ
ー（光源７９０ｒ＋ｍ±１Ｏｒ＋ｍの半導体レーザー）
で試験した。１万枚までの絵出しテストで、良好な画像
が得られた。Next, image characteristics and durability were evaluated using a Konica ■ LD printer (semiconductor laser with a light source of 790r+m±1Or+m).
Tested with. Good images were obtained in a picture printing test of up to 10,000 sheets.
実施例２〜１０
実施例１で、キャリア発生物質（ＣＧＭ）Ｉ−１及びキ
ャリア輸送物質（ＣＴＭ）Ｋ−１を表１のようにかえて
感光体を作製し、実施例１と同様に電子写真性能を評価
した。結果を表１に示す。Examples 2 to 10 Photoreceptors were prepared by changing the carrier generating material (CGM) I-1 and the carrier transporting material (CTM) K-1 as shown in Table 1 in Example 1, and the electron Photographic performance was evaluated. The results are shown in Table 1.
表１のＣＴＭを以下に示す。The CTMs in Table 1 are shown below.
Ｋ−６ に−７ に−８ に−９ に−２ に−３ に−４ に−５ しぺ。K-6 ni-7 ni-8 ni-9 ni-2 ni-3 ni-4 ni-5 Shipe.
実施例１１
実施例１で、ＣＧＬとＣＴＬの塗布順序を逆にしたほか
は、実施例１ど同様に感光体を作製し、試験した。（た
だし、コロナ帯電は＋６ＫＶどした。）結果は、Ｖへ＝
１５２０Ｖ 、 Ｅ １／２ ＝ ２．３ ｌｕｘ・
ｓｅｃであった。また、１万枚までの絵出しテストの画
像は良好であった。Example 11 A photoreceptor was produced and tested in the same manner as in Example 1, except that the order of application of CGL and CTL was reversed. (However, the corona charge was +6KV.) The result is V=
1520V, E 1/2 = 2.3 lux・
It was sec. In addition, the images in the image display test of up to 10,000 sheets were good.
実施例１２〜２０
実施例１１で、キャリア発生物質（ＣＧＭ）Ｉ−１及び
キャリア輸送物質（ＣＴＭ）Ｋ−１を、表２のように変
えて感光体を作製し、実施例１１と同様に電子写真性能
を評価した。結果を表２に示す。Examples 12 to 20 In Example 11, photoreceptors were prepared by changing the carrier generating substance (CGM) I-1 and the carrier transporting substance (CTM) K-1 as shown in Table 2, and in the same manner as in Example 11. The electrophotographic performance was evaluated. The results are shown in Table 2.
に−１５
に−１６
に−１７
に−１１
に−１２
に−１３
に−１４
」、り ３−
一−ＬＩ
［発明の効果］
本発明によって、電子写真感光体の感光層を構成する光
導電性物質として前記１般式［Ｉ］で表わされる非対称
スクェアリウム化合物を使用することにより、感度、残
留電位、電荷保持力等の電子写真特性において優れ、ま
た繰返し使用した時の疲労劣化が少なく、熱及び光に対
して安定であり、さらに７８０ｎｍ以上の長波長領域に
おいても十分な感度を有すると同時に、７８０ｎｍ以下
の可視光領域でも十分使用可能な優れた電子写真感光体
を作成することができる。また、本発明の非対称スクェ
アリウム化合物を使用することにより、広範なキャリア
輸送物質との組み合わせにおいても、十分な感度を有す
る感光体を提供することができる。ni-15 ni-16 ni-17 ni-11 ni-12 ni-13 ni-14'', ri 3-1-LI [Effect of the invention] According to the present invention, the photoconductive layer constituting the photosensitive layer of the electrophotographic photoreceptor By using the asymmetric squalium compound represented by the general formula [I] above as a magnetic substance, it has excellent electrophotographic properties such as sensitivity, residual potential, and charge retention, and has little fatigue deterioration when used repeatedly. It is possible to create an excellent electrophotographic photoreceptor that is stable against heat and light, has sufficient sensitivity even in the long wavelength region of 780 nm or more, and can be used satisfactorily even in the visible light region of 780 nm or less. . Further, by using the asymmetric squalium compound of the present invention, it is possible to provide a photoreceptor having sufficient sensitivity even in combination with a wide variety of carrier transport substances.
第１図〜第６図はそれぞれ本発明の電子写真感光体の構
成例について示す断面図であって図中の１〜７はそれぞ
れ以下の事を表わす。
１・・・導電性支持体
２・・・キャリア発生層
３・・・キャリア輸送層
４・・・感光層
５・・・中間層
６・・・キャリア輸送物質を含有づる層７・・・キャリ
ア発生物質FIGS. 1 to 6 are cross-sectional views showing structural examples of the electrophotographic photoreceptor of the present invention, and 1 to 7 in the figures represent the following, respectively. 1... Conductive support 2... Carrier generation layer 3... Carrier transport layer 4... Photosensitive layer 5... Intermediate layer 6... Layer containing carrier transport substance 7... Carrier Generated substance
Claims (3)
れる非対称スクエアリウム化合物の少なくとも１種を含
有してなる感光層を有することを特徴とする電子写真感
光体。 一般式［ I ］ ▲数式、化学式、表等があります▼ 〔式中、Ａｒ＿１およびＡｒ＿２は、互に異なり、Ａｒ
＿１およびＡｒ＿２の一方は下記一般式［Ａ］から選ば
れ、 一般式［Ａ］ ▲数式、化学式、表等があります▼ （Ｒ＿１、Ｒ＿２及びＲ＿３は、それぞれ水素原子、ハ
ロゲン原子、アルキル基、アルコキシ基、水酸基または
ＮＨＹを表わす。Ｙは、▲数式、化学式、表等がありま
す▼または−ＳＯ＿２−Ｒ＿９（Ｒ＿８及びＲ＿９は、
それぞれ水素原子、置換もしくは非置換のアルキル基、
または置換もしくは非置換のアリール基を表わす。）を
表わす。Ｒ＿４、Ｒ＿５、Ｒ＿６及びＲ＿７は、それぞ
れ水素原子、ハロゲン原子、又は置換もしくは非置換の
アルキル基を表わす。Ａｒ＿３は置換若しくは非置換の
アリール基を表わす。） そして、Ａｒ＿１およびＡｒ＿２の他方は、下記一般式
［Ｂ］、［Ｃ］又は［Ｄ］から選ばれる。 一般式［Ｂ］ ▲数式、化学式、表等があります▼ （式中、Ｒ＿１＿０およびＲ＿１＿１は、それぞれ互に
独立したものであるときは、それぞれ、炭素原子数１〜
２０の置換若しくは非置換のアルキル基、置換若しくは
非置換のフェニル基を表わし、又はＲ＿１＿０とＲ＿１
＿１が共同して３ないし７員の含窒素複素環を形成する
場合はアルキレン基を表わす。Ｒ＿１＿２は水素原子、
水酸基、メチル基、トリフルオロメチル基、ハロゲン原
子又はカルボキシル基を表わす。）一般式［Ｃ］ ▲数式、化学式、表等があります▼ （式中、Ｒ＿１＿３は前記一般式［Ｂ］のＲ＿１＿０お
よびＲ＿１＿１と同義であり（但しＲ＿１＿０とＲ＿１
＿１とが互に共同して環を形成する場合を除く）、Ｒ＿
１＿４は前記一般式［Ｂ］のＲ＿１＿２と同義であり、
Ｒ＿１＿５は、水素原子、炭素原子数１〜６のアルキル
基、水酸基、炭素原子数１〜４のアルコキシ基、ハロゲ
ン原子、ニトロ基、シアノ基、カルボキシル基、炭素原
子数１〜４のアルコキシカルボニル基又はトリフルオロ
メチル基を表わす。） 一般式［Ｄ］ ▲数式、化学式、表等があります▼ （式中、Ｒ＿１＿６は前記一般式［Ｂ］のＲ＿１＿２と
同義であり、Ｒ＿１＿７及びＲ＿１＿８はそれぞれ前記
一般式［Ｃ］のＲ＿１＿５と同義である。）］(1) An electrophotographic photoreceptor comprising, on a conductive support, a photosensitive layer containing at least one asymmetric squarium compound represented by the following general formula [I]. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, Ar_1 and Ar_2 are different from each other,
One of _1 and Ar_2 is selected from the general formula [A] below, and the general formula [A] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (R_1, R_2 and R_3 are hydrogen atoms, halogen atoms, alkyl groups, alkoxy represents a group, a hydroxyl group, or NHY.
hydrogen atom, substituted or unsubstituted alkyl group,
Or represents a substituted or unsubstituted aryl group. ). R_4, R_5, R_6 and R_7 each represent a hydrogen atom, a halogen atom, or a substituted or unsubstituted alkyl group. Ar_3 represents a substituted or unsubstituted aryl group. ) The other of Ar_1 and Ar_2 is selected from the following general formula [B], [C], or [D]. General formula [B] ▲ Numerical formulas, chemical formulas, tables, etc.
20 substituted or unsubstituted alkyl groups, substituted or unsubstituted phenyl groups, or R_1_0 and R_1
When _1 together form a 3- to 7-membered nitrogen-containing heterocycle, it represents an alkylene group. R_1_2 is a hydrogen atom,
Represents a hydroxyl group, methyl group, trifluoromethyl group, halogen atom or carboxyl group. ) General formula [C] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1_3 has the same meaning as R_1_0 and R_1_1 in the above general formula [B]
_1), R_
1_4 is synonymous with R_1_2 in the general formula [B],
R_1_5 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, a nitro group, a cyano group, a carboxyl group, an alkoxycarbonyl group having 1 to 4 carbon atoms. Or it represents a trifluoromethyl group. ) General formula [D] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1_6 has the same meaning as R_1_2 in the above general formula [B], and R_1_7 and R_1_8 each have the same meaning as R_1_5 in the above general formula [C] )]
質とを含有し、前記キャリア発生物質の少なくとも１つ
が前記一般式［ I ］で表わされる非対称スクエアリウ
ム化合物である請求項（１）記載の電子写真感光体。(2) The electronic photosensitive layer according to claim (1), wherein the photosensitive layer contains a carrier transporting substance and a carrier generating substance, and at least one of the carrier generating substances is an asymmetric squarium compound represented by the general formula [I]. Photographic photoreceptor.
［ I ］で表わされる非対称スクエアリウム化合物を含
有するキャリア発生層と、キャリア輸送物質を含有する
キャリア輸送層との積層構成からなる請求項（１）また
は（２）記載の電子写真感光体。(3) The photosensitive layer has a laminated structure of a carrier-generating layer containing an asymmetric squarium compound represented by the general formula [I] as a carrier-generating substance, and a carrier-transporting layer containing a carrier-transporting substance. The electrophotographic photoreceptor described in 1) or (2).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63194842A JPH0243558A (en) | 1988-08-04 | 1988-08-04 | Electrophotographic sensitive body |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63194842A JPH0243558A (en) | 1988-08-04 | 1988-08-04 | Electrophotographic sensitive body |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0243558A true JPH0243558A (en) | 1990-02-14 |
Family
ID=16331181
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63194842A Pending JPH0243558A (en) | 1988-08-04 | 1988-08-04 | Electrophotographic sensitive body |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0243558A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005233325A (en) * | 2004-02-20 | 2005-09-02 | Eagle Engineering Aerospace Co Ltd | Sealing device |
| US7736152B2 (en) | 2002-10-24 | 2010-06-15 | International Business Machines Corporation | Land grid array fabrication using elastomer core and conducting metal shell or mesh |
-
1988
- 1988-08-04 JP JP63194842A patent/JPH0243558A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7736152B2 (en) | 2002-10-24 | 2010-06-15 | International Business Machines Corporation | Land grid array fabrication using elastomer core and conducting metal shell or mesh |
| JP2005233325A (en) * | 2004-02-20 | 2005-09-02 | Eagle Engineering Aerospace Co Ltd | Sealing device |
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