JPS6122301B2 - - Google Patents
Info
- Publication number
- JPS6122301B2 JPS6122301B2 JP53026604A JP2660478A JPS6122301B2 JP S6122301 B2 JPS6122301 B2 JP S6122301B2 JP 53026604 A JP53026604 A JP 53026604A JP 2660478 A JP2660478 A JP 2660478A JP S6122301 B2 JPS6122301 B2 JP S6122301B2
- Authority
- JP
- Japan
- Prior art keywords
- photoreceptor
- weight
- disazo pigment
- disazo
- charge
- 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.)
- Expired
Links
- 239000000049 pigment Substances 0.000 claims description 63
- 108091008695 photoreceptors Proteins 0.000 claims description 57
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 claims description 50
- 239000004480 active ingredient Substances 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- 125000001624 naphthyl group Chemical group 0.000 claims description 2
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 claims 1
- 239000010410 layer Substances 0.000 description 39
- 239000002800 charge carrier Substances 0.000 description 22
- 238000012546 transfer Methods 0.000 description 17
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 14
- 239000000126 substance Substances 0.000 description 12
- 239000011230 binding agent Substances 0.000 description 9
- 239000002609 medium Substances 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- 239000006185 dispersion Substances 0.000 description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 229920006267 polyester film Polymers 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000006163 transport media Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- VHQGURIJMFPBKS-UHFFFAOYSA-N 2,4,7-trinitrofluoren-9-one Chemical compound [O-][N+](=O)C1=CC([N+]([O-])=O)=C2C3=CC=C([N+](=O)[O-])C=C3C(=O)C2=C1 VHQGURIJMFPBKS-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229920000515 polycarbonate Polymers 0.000 description 3
- 239000004417 polycarbonate Substances 0.000 description 3
- 229920001225 polyester resin Polymers 0.000 description 3
- 239000004645 polyester resin Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- QNLZIZAQLLYXTC-UHFFFAOYSA-N 1,2-dimethylnaphthalene Chemical compound C1=CC=CC2=C(C)C(C)=CC=C21 QNLZIZAQLLYXTC-UHFFFAOYSA-N 0.000 description 2
- TURIHPLQSRVWHU-UHFFFAOYSA-N 2-phenylnaphthalene Chemical compound C1=CC=CC=C1C1=CC=C(C=CC=C2)C2=C1 TURIHPLQSRVWHU-UHFFFAOYSA-N 0.000 description 2
- UZGVMZRBRRYLIP-UHFFFAOYSA-N 4-[5-[4-(diethylamino)phenyl]-1,3,4-oxadiazol-2-yl]-n,n-diethylaniline Chemical compound C1=CC(N(CC)CC)=CC=C1C1=NN=C(C=2C=CC(=CC=2)N(CC)CC)O1 UZGVMZRBRRYLIP-UHFFFAOYSA-N 0.000 description 2
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- -1 disazo compound Chemical class 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- PMBBBTMBKMPOQF-UHFFFAOYSA-N 1,3,7-trinitrodibenzothiophene 5,5-dioxide Chemical compound O=S1(=O)C2=CC([N+](=O)[O-])=CC=C2C2=C1C=C([N+]([O-])=O)C=C2[N+]([O-])=O PMBBBTMBKMPOQF-UHFFFAOYSA-N 0.000 description 1
- WQGWMEKAPOBYFV-UHFFFAOYSA-N 1,5,7-trinitrothioxanthen-9-one Chemical compound C1=CC([N+]([O-])=O)=C2C(=O)C3=CC([N+](=O)[O-])=CC([N+]([O-])=O)=C3SC2=C1 WQGWMEKAPOBYFV-UHFFFAOYSA-N 0.000 description 1
- HYGLETVERPVXOS-UHFFFAOYSA-N 1-bromopyrene Chemical compound C1=C2C(Br)=CC=C(C=C3)C2=C2C3=CC=CC2=C1 HYGLETVERPVXOS-UHFFFAOYSA-N 0.000 description 1
- ZWAMZDRREBOHIO-UHFFFAOYSA-N 1-ethylpyrene Chemical compound C1=C2C(CC)=CC=C(C=C3)C2=C2C3=CC=CC2=C1 ZWAMZDRREBOHIO-UHFFFAOYSA-N 0.000 description 1
- KCIJNJVCFPSUBQ-UHFFFAOYSA-N 1-pyren-1-ylethanone Chemical compound C1=C2C(C(=O)C)=CC=C(C=C3)C2=C2C3=CC=CC2=C1 KCIJNJVCFPSUBQ-UHFFFAOYSA-N 0.000 description 1
- VEUMBMHMMCOFAG-UHFFFAOYSA-N 2,3-dihydrooxadiazole Chemical compound N1NC=CO1 VEUMBMHMMCOFAG-UHFFFAOYSA-N 0.000 description 1
- TYUPTZLMOSZOAV-UHFFFAOYSA-N 2,4,10-trinitro-6-oxidobenzo[c]cinnolin-6-ium Chemical compound C1=CC([N+]([O-])=O)=C2C3=CC([N+](=O)[O-])=CC([N+]([O-])=O)=C3N=[N+]([O-])C2=C1 TYUPTZLMOSZOAV-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
- RBFUXCYPJKXNMP-UHFFFAOYSA-N 2,4,7-trinitrophenanthrene-9,10-dione Chemical compound [O-][N+](=O)C1=CC([N+]([O-])=O)=C2C3=CC=C([N+](=O)[O-])C=C3C(=O)C(=O)C2=C1 RBFUXCYPJKXNMP-UHFFFAOYSA-N 0.000 description 1
- HJCNIHXYINVVFF-UHFFFAOYSA-N 2,6,8-trinitroindeno[1,2-b]thiophen-4-one Chemical compound O=C1C2=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C2C2=C1C=C([N+](=O)[O-])S2 HJCNIHXYINVVFF-UHFFFAOYSA-N 0.000 description 1
- HDVGAFBXTXDYIB-UHFFFAOYSA-N 2,7-dinitrofluoren-9-one Chemical compound C1=C([N+]([O-])=O)C=C2C(=O)C3=CC([N+](=O)[O-])=CC=C3C2=C1 HDVGAFBXTXDYIB-UHFFFAOYSA-N 0.000 description 1
- VMQHOWOVMXIROE-UHFFFAOYSA-N 2,8-dinitrodibenzothiophene Chemical compound C1=C([N+]([O-])=O)C=C2C3=CC([N+](=O)[O-])=CC=C3SC2=C1 VMQHOWOVMXIROE-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical group C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- MFAWABLKXSRSOR-UHFFFAOYSA-N 2-(6,8-dinitroindeno[1,2-b]thiophen-4-ylidene)propanedinitrile Chemical compound [O-][N+](=O)C1=CC([N+](=O)[O-])=CC2=C1C(SC=C1)=C1C2=C(C#N)C#N MFAWABLKXSRSOR-UHFFFAOYSA-N 0.000 description 1
- IIKVAWLYHHZRGV-UHFFFAOYSA-N 2-carbazol-9-ylethanol Chemical compound C1=CC=C2N(CCO)C3=CC=CC=C3C2=C1 IIKVAWLYHHZRGV-UHFFFAOYSA-N 0.000 description 1
- WGRSVHBSCVGKDP-UHFFFAOYSA-N 2-ethyl-9h-carbazole-1-carbaldehyde Chemical compound C1=CC=C2C3=CC=C(CC)C(C=O)=C3NC2=C1 WGRSVHBSCVGKDP-UHFFFAOYSA-N 0.000 description 1
- XMPQJGTYEXSTIY-UHFFFAOYSA-N 2-indeno[1,2-b]thiophen-4-ylidenepropanedinitrile Chemical compound C12=CC=CC=C2C(=C(C#N)C#N)C2=C1SC=C2 XMPQJGTYEXSTIY-UHFFFAOYSA-N 0.000 description 1
- GXLYVLHWXVRVKI-UHFFFAOYSA-N 2-nitrodibenzothiophene Chemical compound C1=CC=C2C3=CC([N+](=O)[O-])=CC=C3SC2=C1 GXLYVLHWXVRVKI-UHFFFAOYSA-N 0.000 description 1
- AJEAHBZZHSLIQP-UHFFFAOYSA-N 2-nitrofluoren-9-one Chemical compound C1=CC=C2C(=O)C3=CC([N+](=O)[O-])=CC=C3C2=C1 AJEAHBZZHSLIQP-UHFFFAOYSA-N 0.000 description 1
- YOCSZWYTDFWNMT-UHFFFAOYSA-N 2-nitroindeno[1,2-b]thiophen-4-one Chemical compound O=C1C2=CC=CC=C2C2=C1C=C([N+](=O)[O-])S2 YOCSZWYTDFWNMT-UHFFFAOYSA-N 0.000 description 1
- KEHIOHQUZQSPCO-UHFFFAOYSA-N 2-nitroindeno[2,1-b]thiophen-4-one Chemical compound C12=CC=CC=C2C(=O)C2=C1C=C([N+](=O)[O-])S2 KEHIOHQUZQSPCO-UHFFFAOYSA-N 0.000 description 1
- KLLLJCACIRKBDT-UHFFFAOYSA-N 2-phenyl-1H-indole Chemical compound N1C2=CC=CC=C2C=C1C1=CC=CC=C1 KLLLJCACIRKBDT-UHFFFAOYSA-N 0.000 description 1
- NOXSEPQGTKXPOK-UHFFFAOYSA-N 3,7,9-trinitro-5-oxidobenzo[c]cinnolin-5-ium Chemical compound C1=C([N+]([O-])=O)C=C2C3=CC=C([N+](=O)[O-])C=C3[N+]([O-])=NC2=C1[N+]([O-])=O NOXSEPQGTKXPOK-UHFFFAOYSA-N 0.000 description 1
- YRXRGRLSHSSUNF-UHFFFAOYSA-N 3,7-dinitrodibenzothiophene 5,5-dioxide Chemical compound C1=C([N+]([O-])=O)C=C2S(=O)(=O)C3=CC([N+](=O)[O-])=CC=C3C2=C1 YRXRGRLSHSSUNF-UHFFFAOYSA-N 0.000 description 1
- AEFDIOODLJMOML-UHFFFAOYSA-N 3,7-dinitrodibenzothiophene 5-oxide Chemical compound C1=C([N+]([O-])=O)C=C2S(=O)C3=CC([N+](=O)[O-])=CC=C3C2=C1 AEFDIOODLJMOML-UHFFFAOYSA-N 0.000 description 1
- JFGQHAHJWJBOPD-UHFFFAOYSA-N 3-hydroxy-n-phenylnaphthalene-2-carboxamide Chemical compound OC1=CC2=CC=CC=C2C=C1C(=O)NC1=CC=CC=C1 JFGQHAHJWJBOPD-UHFFFAOYSA-N 0.000 description 1
- PAEVCXCHJVISEP-UHFFFAOYSA-N 3-n,3-n,6-n,6-n-tetrabenzyl-9-ethylcarbazole-3,6-diamine Chemical compound C=1C=C2N(CC)C3=CC=C(N(CC=4C=CC=CC=4)CC=4C=CC=CC=4)C=C3C2=CC=1N(CC=1C=CC=CC=1)CC1=CC=CC=C1 PAEVCXCHJVISEP-UHFFFAOYSA-N 0.000 description 1
- YPRJLDUOGDQQAK-UHFFFAOYSA-N 3-nitrodibenzothiophene 5,5-dioxide Chemical compound C1=CC=C2S(=O)(=O)C3=CC([N+](=O)[O-])=CC=C3C2=C1 YPRJLDUOGDQQAK-UHFFFAOYSA-N 0.000 description 1
- BBSNLPXHXFJCJE-UHFFFAOYSA-N 3-nitrodibenzothiophene 5-oxide Chemical compound C1=CC=C2S(=O)C3=CC([N+](=O)[O-])=CC=C3C2=C1 BBSNLPXHXFJCJE-UHFFFAOYSA-N 0.000 description 1
- MLEBCZSWVARRML-UHFFFAOYSA-N 4-(2,5-diphenyl-1,3-oxazol-4-yl)-n,n-diethylaniline Chemical compound C1=CC(N(CC)CC)=CC=C1C1=C(C=2C=CC=CC=2)OC(C=2C=CC=CC=2)=N1 MLEBCZSWVARRML-UHFFFAOYSA-N 0.000 description 1
- RWUOXSKITRZJNC-UHFFFAOYSA-N 4-(4-amino-5-methoxy-2-nitrophenyl)-2-methoxy-5-nitroaniline Chemical compound C1=C(N)C(OC)=CC(C=2C(=CC(N)=C(OC)C=2)[N+]([O-])=O)=C1[N+]([O-])=O RWUOXSKITRZJNC-UHFFFAOYSA-N 0.000 description 1
- BZKRKPGZABEOSM-XMHGGMMESA-N 4-[(e)-2-[3-[4-(diethylamino)phenyl]-2-phenyl-3,4-dihydropyrazol-5-yl]ethenyl]-n,n-diethylaniline Chemical compound C1=CC(N(CC)CC)=CC=C1\C=C\C1=NN(C=2C=CC=CC=2)C(C=2C=CC(=CC=2)N(CC)CC)C1 BZKRKPGZABEOSM-XMHGGMMESA-N 0.000 description 1
- YCHDSDSNBXYNHE-UHFFFAOYSA-N 4-[3-[4-(diethylamino)phenyl]-1h-1,2,4-triazol-5-yl]-n,n-diethylaniline Chemical compound C1=CC(N(CC)CC)=CC=C1C1=NN=C(C=2C=CC(=CC=2)N(CC)CC)N1 YCHDSDSNBXYNHE-UHFFFAOYSA-N 0.000 description 1
- SBMCZDLOXDWNIN-UHFFFAOYSA-N 4-[bis[4-(diethylamino)phenyl]methyl]-n,n-diethylaniline Chemical compound C1=CC(N(CC)CC)=CC=C1C(C=1C=CC(=CC=1)N(CC)CC)C1=CC=C(N(CC)CC)C=C1 SBMCZDLOXDWNIN-UHFFFAOYSA-N 0.000 description 1
- QXOYFCJDRWUAMR-UHFFFAOYSA-N 4-hydroxy-n-phenylnaphthalene-2-carboxamide Chemical compound C=1C2=CC=CC=C2C(O)=CC=1C(=O)NC1=CC=CC=C1 QXOYFCJDRWUAMR-UHFFFAOYSA-N 0.000 description 1
- SLXTUFROUKJXGO-UHFFFAOYSA-N 6,8-dinitroindeno[1,2-b]thiophen-4-one Chemical compound [O-][N+](=O)C1=CC([N+](=O)[O-])=CC2=C1C(SC=C1)=C1C2=O SLXTUFROUKJXGO-UHFFFAOYSA-N 0.000 description 1
- CVSBRGRSQUGIKO-UHFFFAOYSA-N 9-(2-chloroethyl)carbazole Chemical compound C1=CC=C2N(CCCl)C3=CC=CC=C3C2=C1 CVSBRGRSQUGIKO-UHFFFAOYSA-N 0.000 description 1
- PLAZXGNBGZYJSA-UHFFFAOYSA-N 9-ethylcarbazole Chemical compound C1=CC=C2N(CC)C3=CC=CC=C3C2=C1 PLAZXGNBGZYJSA-UHFFFAOYSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 239000004419 Panlite Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- YLQWCDOCJODRMT-UHFFFAOYSA-N fluoren-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C2=C1 YLQWCDOCJODRMT-UHFFFAOYSA-N 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Substances O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- WSOJIQBCVMSHLB-UHFFFAOYSA-N indeno[1,2-b]thiophen-4-one Chemical compound C12=CC=CC=C2C(=O)C2=C1SC=C2 WSOJIQBCVMSHLB-UHFFFAOYSA-N 0.000 description 1
- FFQQXIVOSCLQKP-UHFFFAOYSA-N indeno[2,1-b]thiophen-4-one Chemical compound O=C1C2=CC=CC=C2C2=C1SC=C2 FFQQXIVOSCLQKP-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- NYGZLYXAPMMJTE-UHFFFAOYSA-M metanil yellow Chemical group [Na+].[O-]S(=O)(=O)C1=CC=CC(N=NC=2C=CC(NC=3C=CC=CC=3)=CC=2)=C1 NYGZLYXAPMMJTE-UHFFFAOYSA-M 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 150000003071 polychlorinated biphenyls Chemical group 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001470 polyketone Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920006215 polyvinyl ketone Polymers 0.000 description 1
- RCYFOPUXRMOLQM-UHFFFAOYSA-N pyrene-1-carbaldehyde Chemical compound C1=C2C(C=O)=CC=C(C=C3)C2=C2C3=CC=CC2=C1 RCYFOPUXRMOLQM-UHFFFAOYSA-N 0.000 description 1
- 150000003334 secondary amides Chemical class 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 239000007858 starting material Substances 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
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Landscapes
- Photoreceptors In Electrophotography (AREA)
- Light Receiving Elements (AREA)
Description
本発明は電子写真用の感光体に関し、更に詳し
くは有効成分としてジスアゾ顔料を含有する感光
層を有する新規な感光体に関する。
従来、導電性支持体上にアゾ顔料を有効成分と
して含有する感光層を設けた電子写真用感光体が
知られている。例えば特公昭44−16474号公報に
はモノアゾ顔料を用いたものが、また特開昭47−
37543号公報にはジスアゾ顔料を用いたものが開
示されている。これらのアゾ顔料は感光体の有効
成分として確かに有用な材料ではあるが、電子写
真プロセスの点から感光体に対する種々の要求を
考慮すると、未だこれらの要求を充分に満足する
ものが得られていないのが実情である。従つてア
ゾ顔料に限らず有効成分として働く顔料を電子写
真プロセスに応じて広範囲に選択し得るように多
種類にすることは更に重要なことであり、それに
よつて初めてある種のプロセスに適切な感光体を
提供することが可能となる。即ち電子写真プロセ
スにおいては感光体の有効成分として働き得る顔
料の種類はできるだけ多いことが望ましい。
本発明の第一の目的は各種の電子写真プロセス
に有効成分として働き得る新規なジスアゾ顔料を
含む電子写真感光体を提供することである。
本発明の第二の目的は有効成分として働き得る
ジスアゾ顔料を広範に選択し得る電子写真用感光
体を提供することである。
本発明の第三の目的はこのようなジスアゾ顔料
を含む新たな高感度、高可撓性の電子写真感光体
を提供することである。
本発明者らは一群のジスアゾ顔料を製造し、そ
れらの感光体への応用を検討した結果、下記一般
式で表わされる５・5′−ジメトキシ−２・2′−ジ
ニトロビフエニル骨格を有するジスアゾ顔料が感
光体のすぐれた有効成分として働き得ることを知
見し、本発明を完成したものである。
即ち本発明は導電性支持体上に一般式
〔但しＡは
The present invention relates to a photoreceptor for electrophotography, and more particularly to a novel photoreceptor having a photosensitive layer containing a disazo pigment as an active ingredient. Conventionally, electrophotographic photoreceptors are known in which a photosensitive layer containing an azo pigment as an active ingredient is provided on a conductive support. For example, Japanese Patent Publication No. 44-16474 uses a monoazo pigment;
Publication No. 37543 discloses one using a disazo pigment. Although these azo pigments are certainly useful materials as active ingredients for photoreceptors, considering the various requirements for photoreceptors from the point of view of electrophotographic processes, it has not yet been possible to obtain one that fully satisfies these requirements. The reality is that there is not. Therefore, it is even more important to have a wide variety of pigments that act as active ingredients, not just azo pigments, so that a wide range of pigments can be selected depending on the electrophotographic process. It becomes possible to provide a photoreceptor. That is, in the electrophotographic process, it is desirable to have as many types of pigments as possible that can act as active ingredients in the photoreceptor. A first object of the present invention is to provide an electrophotographic photoreceptor containing a novel disazo pigment that can serve as an active ingredient in various electrophotographic processes. A second object of the present invention is to provide an electrophotographic photoreceptor that allows a wide selection of disazo pigments that can serve as active ingredients. A third object of the present invention is to provide a new highly sensitive and highly flexible electrophotographic photoreceptor containing such a disazo pigment. The present inventors produced a group of disazo pigments and studied their application to photoreceptors. The present invention was completed based on the discovery that pigments can serve as excellent active ingredients for photoreceptors. That is, the present invention provides a structure in which the general formula [However, A is
【式】【formula】
【式】 又は【formula】 or
【式】
（ここでＸはベンゼン環、ナフタレン環、インド
ール環、カルバゾール環、ベンゾフラン環又はそ
れらの置換体、Ar1はベンゼン環、ナフタレン
環、ジベンゾフラン環、カルバゾール環又はそれ
らの置換体、Ar2及びAr3はベンゼン環、ナフタ
レン環又はそれらの置換体、R1及びR3は水素、
低級アルキル基、フエニル基又はその置換体、
R2は低級アルキル基、カルボキシル基又はその
エステル）を表わす。〕
で示されるジスアゾ顔料を有効成分として含有す
る感光層を有することを特徴とする電子写真用感
光体を提供するものである。
以下に本発明で使用される前記一般式の化合物
の具体例を構造式で示す。なお式中
については以後[Formula ] (where , and Ar 3 is a benzene ring, naphthalene ring or a substituted product thereof, R 1 and R 3 are hydrogen,
lower alkyl group, phenyl group or substituted product thereof,
R 2 represents a lower alkyl group, a carboxyl group, or an ester thereof. ] The present invention provides an electrophotographic photoreceptor characterized by having a photosensitive layer containing a disazo pigment represented by the following as an active ingredient. Specific examples of the compounds of the above general formula used in the present invention are shown below in terms of structural formulas. During the ceremony About this later
【式】と略
記する。
これらのジスアゾ顔料は、５・5′−ジメトキシ
−２・2′−ジニニトロベンジジンを出発原料と
し、これをまず常法によりジアゾ化し、テトラゾ
ニウム塩として単離した後、適当な有機溶媒、例
えばＮ・Ｎ−ジメチルホルムアミド中で前記一般
式のＡに対応する化合物（ナフトールAS系等の
カツプラー）とアルカリの存在下カツプリングさ
せることにより容易に製造することができる。例
えば前記No.1の顔料の製造法は下記の通りであ
る。なおその他のジスアゾ顔料もカツプラーを変
える他はこの製造例に従つて製造することができ
る。
製造例
（ジスアゾ顔料No.1の製造）
５・5′−ジメトキシ−２・2′−ジニトロベンジ
ジン8.6ｇを、濃塩酸80ml及び水60mlから調製し
た希塩酸に加え、室温で約30分間よく撹拌する。
次にこの混合物を約０℃に冷却し、亜硝酸ナトリ
ウム4.4ｇを水15mlに溶解した溶液を、−３゜〜２
℃の温度で約20分間に亘つて滴下する。その後、
同温度で約１時間撹拌し、微量の未反応物を濾別
し、濾液に42％硼弗化水素酸水溶液40mlを加え、
析出する沈澱を濾取し水洗した後、乾燥して10.4
ｇ（収率76％）のヘキサゾニウムトリフルオロポ
レートを黄色結晶として得た。次にこのヘキサゾ
ニウム塩3.4ｇと、カツプリング成分として２−
ヒドロキシ−３−ナフトエ酸アニリド7.4ｇと
を、冷却したＮ・Ｎ−ジメチルホルムアミド800
mlに溶解し、これに酢酸ナトリウム12.6ｇ及び水
200mlからなる溶液を５〜15℃の温度で約30分間
に亘つて滴下した後、室温で更に４時間撹拌し
た。その後沈澱を濾取し、１の水で２回洗浄し
てから、Ｎ・Ｎ−ジメチルホルムアミド１で３
回洗浄した後、100℃、２mmHgの減圧下に乾燥し
て化合物No.1のジスアゾ化合物4.9ｇ（収率88
％）を得た。
融点：250℃以上
赤外線吸収スペクトル（KBr錠剤）1680cm-1
（第２アミドの吸収）
元素分析
計算値 実測値
Ｃ（％） 65.30 65.60
Ｈ（％） 3.88 3.60
Ｎ（％） 12.69 12.90
本発明の感光体は以上のようなジスアゾ顔料を
含むものであるが、これら顔料の応用の仕方によ
つて第１〜３図の形態をとることができる。第１
図の感光体は導電性支持体１上にジスアゾ顔料４
（ここでは光導電性物質として使用される）〜樹
脂結着剤３系感光層２を設けたものである。第２
図の感光体は導電性支持体１上にジスアゾ顔料４
（ここでは電荷担体発生物質として使用される）
〜電荷移動媒体（電荷移動性物質及び樹脂結着剤
の混合物）５系感光層２′を設けたものである。
また第３図の感光体は第２図の感光体の変形で、
感光層２″はジスアゾ顔料４を主体とする電荷担
体発生層６と電荷移動媒体の層７とからなつてい
る。
第１図の感光体においてジスアゾ顔料は光導電
性物質として作用し、光減衰に必要な電荷担体の
生成及び移動は顔料粒子を介して行なわれる。第
２図の感光体の場合は電荷移動性物質は結着剤
（及び場合により可塑剤）と共に電荷移動媒体を
形成し、一方ジスアゾ顔料は電荷担体発生物質と
して作用する。この電荷移動媒体はジスアゾ顔料
のような電荷担体の生成能力はないが、ジスアゾ
顔料から発生した電荷担体を受け入れ、これを移
動する能力を持つている。即ち第２図の感光体で
は光減衰に必要な電荷担体の生成はジスアゾ顔料
によつて行なわれ、一方、電荷担体の移動は主に
電荷移動媒体により行なわれる。ここで電荷移動
媒体の吸収波長領域がジスアゾ顔料の主に可視部
の吸収波長領域と重ならないことが好ましい。こ
れはジスアゾ顔料に効率良く電荷担体を発生させ
るために顔料表面まで光を透過させる必要がある
からである。しかし例えばある特定波長だけに感
度を有する感光体の場合はこの限りではない。従
つて電荷移動媒体及びジスアゾ顔料の両者の吸収
波長は完全に重複しなければよい。次に第３図の
感光体では電荷移動媒体層を透過して来た光が電
荷担体発生層である感光層２″に到達し、その部
分のジスアゾ顔料で電荷担体の生成が起こり、一
方、電荷移動媒体層は電荷担体の注入を受けその
移動を行なうもので、光減衰に必要な電荷担体の
生成はジスアゾ顔料で、また電荷担体の移動は電
荷移動媒体で行うというメカニズムは第２図に示
した感光体の場合と同様である。ここでもジスア
ゾ顔料は電荷担体発生物質である。
第１図の感光体を作成するにはジスアゾ顔料の
微粒子を結着剤溶液中に分散した分散液を導電性
支持体上に塗布乾燥すればよい。第２図の感光体
を作成するにはジスアゾ顔料の微粒子を電荷移動
性物質及び結着剤を溶解した溶液中にジスアゾ顔
料の微粒子を分散せしめ、これを導電性支持体上
に塗布乾燥すればよい。また第３図の感光体は導
電性支持体上にジスアゾ顔料を真空蒸着するか、
アミン溶媒に溶解せしめて塗布するか、或いはジ
スアゾ顔料の微粒子を必要あれば結着剤を溶解し
た適当な溶媒中に分散し、これを導電性支持体上
に塗布乾燥し、更に必要あれば例えばバフ研摩等
の方法により表面仕上げするか膜厚を調整した
後、その上に電荷移動性物質及び結着剤を含む溶
液を塗布乾燥して得られる。いずれにしても本発
明で使用されるジスアゾ顔料はボールミル等によ
り粒径５μ以下、好ましくは２μ以下に粉砕して
用いられる。塗布法は通常の手段、例えばドクタ
ーブレード、ワイヤーバーなどで行なう。感光層
の厚さは第１図及び第２図のものでは約３〜50
μ、好ましくは５〜20μである。また第３図のも
のでは電荷担体発生層の厚みは、５μ以下、好ま
しくは２μ以下がよく、電荷移動媒体層の厚さは
約３〜50μ、好ましくは５〜20μである。また第
１図の感光体において感光層中のジスアゾ顔料の
割合は感光体に対し30〜70重量％好ましくは約50
重量％が適当である（前述のように第１図の感光
体の場合は、ジスアゾ顔料は光導電物質として作
用し、光減衰に必要な電荷担体の生成及び移動は
顔料粒子を介して行なわれるので、顔料粒子間の
接触は感光層表面から支持体まで連続しているこ
とが好ましい。このため感光層に占める顔料の割
合は比較的多い方が好ましいが、感光層の強度及
び感度を考慮すると、約50重量％がよい）。第２
図の感光体において、感光層中のジスアゾ顔料の
占める割合は50重量％以下、好ましくは20重量％
以下であり、１重量％でも充分有効である。また
電荷移動性物質の割合は10〜95重量％、好ましく
は30〜90重量％である。また第３図の感光体にお
ける電荷移動媒体層中の電荷移動性物質の割合は
第２図の感光体の感光層の場合と同様、10〜95重
量％、好ましくは30〜90重量％である。なお第１
〜３図のいずれの感光体の作成においても結着剤
と共に可塑剤を併用することができる。
本発明の感光体において導電性支持体としては
アルミニウム等の金属板又は金属箔、アルミニウ
ムなどの金属を蒸着したプラスチツクフイルム、
或いは導電処理を施した紙等が使用される。結着
剤としてはポリアミド、ポリウレタン、ポリエス
テル、エポキシ樹脂、ポリケトン、ポリカーボネ
ートなどの縮合樹脂やポリビニルケトン、ポリス
チレン、ポリ−Ｎ−ビニルカルパゾール、ポリア
クリルアミド等のビニル重合体等が挙げられる
が、絶縁性で且つ接着性のある樹脂は全て使用で
きる。可塑剤としてはハロゲン化パラフイン、ポ
リ塩化ビフエニル、ジメチルナフタレン、ジブチ
ルフタレート等が挙げられる。また電荷移動性物
質としては現在まで多くの物質が提案され、例え
ば、特開昭47−30332、同48−52235、同49−
71941、同49−105537、同50−39952、同50−
99142、同51−96329及び同51−105075号公報或い
は特願昭52−68183、同52−70252、同52−
76802、同52−125183、同52−126945、同52−
126946、同52−128448及び同52−151025号で提案
され、そのいずれもが本発明において使用可能で
ある。次に電荷移動性物質の具体例を挙げると、
高分子のものではポリ−Ｎ−ビニルカルバゾー
ル、ハロゲン化ポリ−Ｎ−ビニルカルバゾール、
ポリビニルピレン、ポリビニルインドロキノキサ
リン、ポリビニルジベンゾチオフエン、ポリビニ
ルアントラセン、ポリビニルアクリジン等のビニ
ル重合体やピレン〜ホルムアルデヒド樹脂、プロ
ムピレン〜ホルムアルデヒド樹脂、エチルカルバ
ゾール〜ホルムアルデヒド樹脂、クロロエチルカ
ルバゾールホルムアルデヒド樹脂等の縮合樹脂
が、また低分子（単量体）のものではフルオレノ
ン、２−ニトロ−９−フルオレノン、２・７−ジ
ニトロ−９−フルオレノン、２・４・７−トリニ
トロ−９−フルオレノン、２・４・５・７−テト
ラニトロ−９−フルオレノン、4H−インデノ
〔１・２−ｂ〕チオフエン−４−オン、２−ニト
ロ−4H−インデノ〔１・２−ｂ〕チオフエン−
４−オン、２・６・８−トリニトロ−4H−イン
デノ〔１・２−ｂ〕チオフエン−４−オン、8H
−インデノ〔２・１−ｂ〕チオフエン−８−オ
ン、２−ニトロ−8H−インデノ〔２・１−ｂ〕−
チオフエン−８−オン、２−プロム−６・８−ジ
ニトロ−4H−インデノ〔１・２−ｂ〕チオフエ
ン−４−オン、６・８−ジニトロ−4H−インデ
ノ〔１・２−ｂ〕チオフエン−４−オン、２−ニ
トロジベンゾチオフエン、２・８−ジニトロジベ
ンゾチオフエン、３−ニトロジベンゾチオフエン
−５−オキサイド、３・７−ジニトロジベンゾチ
オフエン−５−オキサイド、１・３・７−トリニ
トロジベンゾチオフエン−５・５−ジオキサイ
ド、３−ニトロジベンゾチオフエン−５・５−ジ
オキサイド、３・７−ジニトロジベンゾチオフエ
ン−５・５−ジオキサイド、４−ジシアノメチレ
ン−4H−インデノ〔１・２−ｂ〕チオフエン、
６・８−ジニトロ−４−ジシアノメチレン−4H
−インデノ〔１・２−ｂ〕チオフエン、１・３・
７・９−テトラニトロベンゾ〔ｃ〕シンノリン−
５−オキサイド、２・４・10−トリニトロベンゾ
〔ｃ〕シンノリン−６−オキサイド、２・４・８
−トリニトロベンゾ〔ｃ〕シンノリン−６−オキ
サイド、２・４・８−トリニトロチオキサント
ン、２・４・７−トリニトロ−９・10−フエナン
スレンキノン、１・４−ナフトキノンベンゾ
〔ａ〕アンスラセン−７・12−ジオン、２・４・
７−トリニトロ−９−ジシアノメチレンフルオレ
ン、テトラクロル無水フタル酸、１−ブロムピレ
ン、トメチルピレン、１−エチルピレン、１−ア
セチルピレン、カルバゾール、Ｎ−エチルカルバ
ゾール、Ｎ−β−クロロエチルカルバゾール、Ｎ
−β−ヒドロキシエチルカルバゾール、２−フエ
ニルインドール、２−フエニルナフタレン、２・
５−ビス（４−ジエチルアミノフエニル）−１・
３・４−オキサジアゾール、２・５−ビス（４−
ジエチルアミノフエニル）１・３・４−トリアゾ
ール、１−フエニル−３−（４−ジエチルアミノ
スチリル）−５−（４−ジエチルアミノフエニル）
ピラゾリン、２−フエニル−４−（４−ジエチル
アミノフエニル）−５−フエニルオキサゾール、
トリフエニルアミン、トリス（４−ジエチルアミ
ノフエニル）メタン、３・６−ビス（ジベンジル
アミノ）−９−エチルカルバゾール等が挙げられ
る。これらの電荷移動性物質は単独又は２種以上
混合して用いられる。
なお以上のようにして得られる感光体にはいず
れも導電性支持体と感光層の間に必要に応じて接
着層又はバリヤ層を設けることができる。これら
の層に用いられる材料としてはポリアミド、ニト
ロセルロース、酸化アルミニウム等が適当で、ま
た膜厚は１μ以下が好ましい。
本発明の感光体を用いて複写を行なうには、感
光層面に帯電、露光を施した後、現像を行ない、
必要によつて、紙等へ転写を行なうことにより達
成される。
本発明の感光体は一般に感度が高く、また可撓
性に富む等のすぐれた利点を有する。
以下に実施例を示す。
実施例 １
ポリエステル樹脂（デユポン社製、ポリエステ
ルアドヒーシブ49000）１重量部、No.1のジスア
ゾ顔料１重量部及びテトラヒドロフラン26重量部
をポールミル中で粉砕混合し、得られた分散液
を、アルミニウム蒸着したポリエステルフイルム
上にドクターブレードを用いて塗布し100℃で10
分間乾燥して厚さ７μの感光層を持つた第１図の
形態の感光体を得た。
次にこの感光体の感光層面に市販の静電複写紙
試験装置により＋6KVのコロナ放電を20秒間行な
つて正帯電させた後、20秒間暗所に放置し、その
時の表面電位Vpo（ボルト）を測定し、ついでタ
ングステンランプから、その表面が照度20ルツク
スになるよう感光層に光照射を施し、その表面電
位がVpoの1/2になる迄の時間（秒）を求めて露
光量Ｅ1/2（ルツクス・秒）とした。その結果は
Vpo＝590V、Ｅ1/23.8ルツクス・秒であつた。
実施例 ２〜10
実施例１においてNo.1のジスアゾ顔料の代り
に下記表−１に示す番号のジスアゾ顔料を夫々用
いた他は実施例１と同じ感光体作成法に従つて感
光体を作成し、以下これらの感光体について実施
例１と同じ測定を行ない表−１の結果を得た。It is abbreviated as [formula]. These disazo pigments use 5,5'-dimethoxy-2,2'-dininitrobenzidine as a starting material, which is first diazotized by a conventional method and isolated as a tetrazonium salt, and then treated with a suitable organic solvent, such as N - It can be easily produced by coupling a compound corresponding to A in the general formula (a coupler such as naphthol AS type) in N-dimethylformamide in the presence of an alkali. For example, the method for producing the pigment No. 1 is as follows. Note that other disazo pigments can also be produced according to this production example, except for changing the coupler. Production example (Production of disazo pigment No. 1) Add 8.6 g of 5,5'-dimethoxy-2,2'-dinitrobenzidine to dilute hydrochloric acid prepared from 80 ml of concentrated hydrochloric acid and 60 ml of water, and stir well at room temperature for about 30 minutes. .
Next, this mixture was cooled to about 0°C, and a solution of 4.4 g of sodium nitrite dissolved in 15 ml of water was added to the temperature between -3° and 2°C.
The mixture is added dropwise over a period of about 20 minutes at a temperature of °C. after that,
Stir at the same temperature for about 1 hour, remove trace amounts of unreacted materials by filtration, add 40 ml of 42% borohydrofluoric acid aqueous solution to the filtrate,
The precipitate is collected by filtration, washed with water, and dried.
g (yield 76%) of hexazonium trifluoroporate was obtained as yellow crystals. Next, 3.4 g of this hexazonium salt and 2-
7.4 g of hydroxy-3-naphthoic acid anilide was added to 800 g of cooled N.N-dimethylformamide.
ml and add 12.6 g of sodium acetate and water to this.
200 ml of the solution was added dropwise over a period of about 30 minutes at a temperature of 5 to 15°C, and then stirred for an additional 4 hours at room temperature. Thereafter, the precipitate was collected by filtration, washed twice with 1 part of water, and then 3 times with 1 part of N.N-dimethylformamide.
After washing twice, it was dried at 100°C under a reduced pressure of 2 mmHg to produce 4.9 g of compound No. 1, a disazo compound (yield: 88
%) was obtained. Melting point: 250℃ or higher Infrared absorption spectrum (KBr tablet) 1680cm -1
(Absorption of secondary amide) Elemental analysis Calculated value Actual value C (%) 65.30 65.60 H (%) 3.88 3.60 N (%) 12.69 12.90 The photoreceptor of the present invention contains the above-mentioned disazo pigments. Depending on how it is applied, it can take the form shown in FIGS. 1 to 3. 1st
The photoreceptor in the figure has a disazo pigment 4 on a conductive support 1.
(Here, it is used as a photoconductive substance.) A photosensitive layer 2 containing three resin binders is provided. Second
The photoreceptor in the figure has a disazo pigment 4 on a conductive support 1.
(here used as charge carrier generating material)
-A charge transfer medium (a mixture of a charge transfer substance and a resin binder) 5-based photosensitive layer 2' is provided.
The photoreceptor shown in Figure 3 is a modification of the photoreceptor shown in Figure 2.
The photosensitive layer 2'' consists of a charge carrier generation layer 6 mainly composed of a disazo pigment 4 and a layer 7 of a charge transport medium. In the photoreceptor of FIG. The generation and transfer of the charge carriers necessary for On the other hand, disazo pigments act as charge carrier generating substances.This charge transfer medium does not have the ability to generate charge carriers like disazo pigments, but it has the ability to accept and transfer charge carriers generated from disazo pigments. That is, in the photoreceptor shown in Fig. 2, the generation of charge carriers necessary for light attenuation is carried out by the disazo pigment, while the transfer of charge carriers is mainly carried out by the charge transfer medium. It is preferable that the wavelength region does not overlap with the absorption wavelength region of the disazo pigment, which is mainly in the visible region. This is because it is necessary to transmit light to the surface of the pigment in order to efficiently generate charge carriers in the disazo pigment. However, For example, this does not apply to a photoconductor that is sensitive only to a specific wavelength.Therefore, the absorption wavelengths of both the charge transfer medium and the disazo pigment need not completely overlap.Next, in the case of the photoconductor shown in FIG. The light that has passed through the charge transfer medium layer reaches the photosensitive layer 2'', which is the charge carrier generation layer, and charge carriers are generated in the disazo pigment in that area, while the charge transfer medium layer is injected with charge carriers. The mechanism in which the charge carriers necessary for light attenuation are generated by a disazo pigment and the charge carriers are transferred by a charge transfer medium is similar to that of the photoreceptor shown in Figure 2. be. Here again, the disazo pigment is a charge carrier generating substance. In order to produce the photoreceptor shown in FIG. 1, a dispersion of disazo pigment particles dispersed in a binder solution may be coated on a conductive support and dried. To create the photoreceptor shown in Figure 2, fine particles of disazo pigment are dispersed in a solution containing a charge transporting substance and a binder, and the particles are coated on a conductive support and dried. good. The photoreceptor shown in Fig. 3 is made by vacuum-depositing a disazo pigment on a conductive support, or
The disazo pigment can be dissolved in an amine solvent and applied, or fine particles of the disazo pigment can be dispersed in an appropriate solvent in which a binder is dissolved if necessary, and this can be applied and dried on a conductive support, and if necessary, e.g. After the surface is finished by a method such as buffing or the film thickness is adjusted, a solution containing a charge transfer substance and a binder is applied thereon and dried. In any case, the disazo pigment used in the present invention is used after being ground to a particle size of 5 μm or less, preferably 2 μm or less using a ball mill or the like. Application is carried out by conventional means, such as a doctor blade or wire bar. The thickness of the photosensitive layer is approximately 3 to 50 mm for those in Figures 1 and 2.
μ, preferably 5 to 20 μ. In the case of FIG. 3, the thickness of the charge carrier generation layer is preferably 5 microns or less, preferably 2 microns or less, and the thickness of the charge transport medium layer is about 3 to 50 microns, preferably 5 to 20 microns. Further, in the photoreceptor shown in FIG. 1, the proportion of the disazo pigment in the photoreceptor layer is 30 to 70% by weight, preferably about 50% by weight based on the photoreceptor.
(As mentioned above, in the case of the photoreceptor of FIG. 1, the disazo pigment acts as a photoconductive material, and the generation and transfer of charge carriers necessary for light attenuation takes place through the pigment particles. Therefore, it is preferable that the contact between the pigment particles be continuous from the surface of the photosensitive layer to the support.For this reason, it is preferable that the proportion of the pigment in the photosensitive layer be relatively large, but considering the strength and sensitivity of the photosensitive layer, , about 50% by weight is good). Second
In the photoreceptor shown in the figure, the proportion of the disazo pigment in the photosensitive layer is 50% by weight or less, preferably 20% by weight.
or less, and even 1% by weight is sufficiently effective. The proportion of the charge-transfer substance is 10 to 95% by weight, preferably 30 to 90% by weight. Further, the proportion of the charge transporting substance in the charge transport medium layer of the photoreceptor shown in FIG. 3 is 10 to 95% by weight, preferably 30 to 90% by weight, as in the case of the photosensitive layer of the photoreceptor shown in FIG. . Note that the first
In producing any of the photoreceptors shown in Figures 1 to 3, a plasticizer can be used in combination with a binder. In the photoreceptor of the present invention, the conductive support may be a metal plate or metal foil such as aluminum, a plastic film on which metal such as aluminum is vapor-deposited,
Alternatively, paper or the like that has been subjected to conductive treatment may be used. Examples of the binder include condensation resins such as polyamide, polyurethane, polyester, epoxy resin, polyketone, and polycarbonate, and vinyl polymers such as polyvinyl ketone, polystyrene, poly-N-vinylcarpazole, and polyacrylamide. Any resin that has adhesive properties can be used. Examples of the plasticizer include halogenated paraffin, polychlorinated biphenyl, dimethylnaphthalene, and dibutyl phthalate. In addition, many substances have been proposed as charge-mobile substances to date, such as JP-A No. 47-30332, JP-A No. 48-52235, JP-A No. 49-49-
71941, 49-105537, 50-39952, 50-
99142, No. 51-96329 and No. 51-105075 or Japanese Patent Application No. 52-68183, No. 52-70252, No. 52-
76802, 52-125183, 52-126945, 52-
No. 126946, No. 52-128448, and No. 52-151025, all of which can be used in the present invention. Next, specific examples of charge-mobile substances are:
Polymers include poly-N-vinylcarbazole, halogenated poly-N-vinylcarbazole,
Vinyl polymers such as polyvinylpyrene, polyvinylindoquinoxaline, polyvinyldibenzothiophene, polyvinylanthracene, polyvinylacridine, etc., and condensation resins such as pyrene-formaldehyde resin, propylene-formaldehyde resin, ethylcarbazole-formaldehyde resin, chloroethylcarbazole-formaldehyde resin, etc. , and low molecular weight (monomer) ones such as fluorenone, 2-nitro-9-fluorenone, 2,7-dinitro-9-fluorenone, 2,4,7-trinitro-9-fluorenone, 2,4,5, 7-tetranitro-9-fluorenone, 4H-indeno[1,2-b]thiophene-4-one, 2-nitro-4H-indeno[1,2-b]thiophene-
4-one, 2,6,8-trinitro-4H-indeno[1,2-b]thiophen-4-one, 8H
-indeno[2.1-b]thiophen-8-one, 2-nitro-8H-indeno[2.1-b]-
Thiophen-8-one, 2-prom-6,8-dinitro-4H-indeno[1,2-b]thiophen-4-one, 6,8-dinitro-4H-indeno[1,2-b]thiophene- 4-one, 2-nitrodibenzothiophene, 2,8-dinitrodibenzothiophene, 3-nitrodibenzothiophene-5-oxide, 3,7-dinitrodibenzothiophene-5-oxide, 1,3,7- Trinitrodibenzothiophene-5,5-dioxide, 3-nitrodibenzothiophene-5,5-dioxide, 3,7-dinitrodibenzothiophene-5,5-dioxide, 4-dicyanomethylene-4H- indeno[1,2-b]thiophene,
6,8-dinitro-4-dicyanomethylene-4H
-Indeno[1.2-b]thiophene, 1.3.
7,9-Tetranitrobenzo[c]cinnoline-
5-oxide, 2,4,10-trinitrobenzo[c]cinnoline-6-oxide, 2,4,8
-trinitrobenzo[c]cinnoline-6-oxide, 2,4,8-trinitrothioxanthone, 2,4,7-trinitro-9,10-phenanthrenequinone, 1,4-naphthoquinonebenzo[a]anthracene -7・12-dione, 2・4・
7-trinitro-9-dicyanomethylenefluorene, tetrachlorophthalic anhydride, 1-bromopyrene, tomethylpyrene, 1-ethylpyrene, 1-acetylpyrene, carbazole, N-ethylcarbazole, N-β-chloroethylcarbazole, N
-β-hydroxyethylcarbazole, 2-phenylindole, 2-phenylnaphthalene, 2.
5-bis(4-diethylaminophenyl)-1.
3,4-oxadiazole, 2,5-bis(4-
diethylaminophenyl) 1,3,4-triazole, 1-phenyl-3-(4-diethylaminostyryl)-5-(4-diethylaminophenyl)
Pyrazoline, 2-phenyl-4-(4-diethylaminophenyl)-5-phenyloxazole,
Examples include triphenylamine, tris(4-diethylaminophenyl)methane, 3,6-bis(dibenzylamino)-9-ethylcarbazole, and the like. These charge transfer substances may be used alone or in combination of two or more. In any of the photoreceptors obtained as described above, an adhesive layer or a barrier layer may be provided between the conductive support and the photosensitive layer, if necessary. Suitable materials for these layers include polyamide, nitrocellulose, aluminum oxide, etc., and the film thickness is preferably 1 μm or less. To perform copying using the photoreceptor of the present invention, the surface of the photosensitive layer is charged and exposed, and then developed.
This can be achieved by transferring to paper or the like, if necessary. The photoreceptor of the present invention generally has excellent advantages such as high sensitivity and flexibility. Examples are shown below. Example 1 1 part by weight of polyester resin (manufactured by DuPont, Polyester Adhesive 49000), 1 part by weight of No. 1 disazo pigment, and 26 parts by weight of tetrahydrofuran were pulverized and mixed in a Pall mill, and the resulting dispersion was mixed with aluminum. Apply it on the vapor-deposited polyester film using a doctor blade and heat it for 10 minutes at 100℃.
After drying for a minute, a photoreceptor having a photoreceptor layer having a thickness of 7 .mu.m as shown in FIG. 1 was obtained. Next, a +6KV corona discharge was applied to the photosensitive layer surface of this photoreceptor using a commercially available electrostatic copying paper tester for 20 seconds to positively charge it, and then it was left in a dark place for 20 seconds, and the surface potential at that time was Vpo (volts). Then, the photosensitive layer is irradiated with light from a tungsten lamp so that the surface has an illumination intensity of 20 lux, and the time (seconds) until the surface potential becomes 1/2 of Vpo is determined and the exposure amount E1/ 2 (lux seconds). The result is
Vpo=590V, E1/23.8 Lux・sec. Examples 2 to 10 Photoreceptors were produced according to the same photoreceptor production method as in Example 1, except that disazo pigments with the numbers shown in Table 1 below were used instead of disazo pigment No. 1 in Example 1. However, the same measurements as in Example 1 were carried out on these photoreceptors, and the results shown in Table 1 were obtained.
【表】
実施例 11
ポリエステル樹脂（実施例１と同じ）10重量
部、２・４・７−トリニトロ−９−フルオレノン
10重量部、No.2のジスアゾ顔料２重量部及びテ
トラヒドロフラン198重量部をボールミル中で粉
砕混合し、得られた分散液を、アルミニウムを蒸
着したポリエステルフイルム上にドクターブレー
ドを用いて塗布し、100℃で10分間乾燥して厚さ
10μの感光層を持つた第２図の形態の感光体を作
成した。次にこの感光体のVpo及びＥ1/2を実施
例１で＋6KVのコロナ放電を行なつた代りに−
6KVののコロナ放電を行なつた以外は全く同様に
測定し、Vpo＝740ボルト、Ｅ1/2＝5.1ルツク
ス・秒の結果を得た。
実施例 12〜20
実施例11においてNo.2のジスアゾ顔料の代り
に下記表−２に示す番号のジスアゾ顔料を夫々用
いて第２図の形態の感光体を作成し、以下実施例
11と同じ方法でVpo及びＥ1/2を求め表−２の結
果を得た。[Table] Example 11 10 parts by weight of polyester resin (same as Example 1), 2,4,7-trinitro-9-fluorenone
10 parts by weight, 2 parts by weight of No. 2 disazo pigment, and 198 parts by weight of tetrahydrofuran were pulverized and mixed in a ball mill, and the resulting dispersion was applied onto a polyester film coated with aluminum using a doctor blade. Dry for 10 minutes at ℃ to thick
A photoreceptor having a photosensitive layer having a thickness of 10μ and having the configuration shown in FIG. 2 was prepared. Next, Vpo and E1/2 of this photoconductor were changed to - instead of +6KV corona discharge in Example 1.
Measurements were made in exactly the same manner except that a 6KV corona discharge was performed, and results were obtained of Vpo = 740 volts and E1/2 = 5.1 Lux·sec. Examples 12 to 20 In Example 11, the disazo pigments shown in the numbers shown in Table 2 below were used in place of the disazo pigment No. 2 to prepare photoreceptors in the form shown in Fig. 2, and the following examples were used.
Vpo and E1/2 were determined using the same method as in No. 11, and the results shown in Table 2 were obtained.
【表】【table】
【表】
実施例 21
ポリエステル樹脂（実施例１と同じ）10重量
部、２・５−ビス（４−ジエチルアミノフエニ
ル）−１・３・４−オキサジアゾール10重量部、
No.3のジスアゾ顔料２重量部及びテトラヒドロ
フラン198重量部をボールミル中で粉砕混合し、
得られた分散液を、アルミニウムを蒸着したポリ
エステルフイルム上にドクターブレードを用いて
塗布し、120℃で10分間乾燥して厚さ10μの感光
層を持つ第２図の形態の感光体を作成した。以下
この感光体について実施例１と同じ測定を行な
い、Vpo＝930ボルト、Ｅ1/2＝9.7ルツクス・秒
の結果を得た。
実施例 22〜30
実施例21においてNo.3のジスアゾ顔料の代り
に夫々下記表−３のジスアゾ顔料を用いた他は実
施例21と同じ方法で第２図の形態の感光体を作成
し、以下実施例１と同じ測定を行ない、表−３の
結果を得た。[Table] Example 21 10 parts by weight of polyester resin (same as Example 1), 10 parts by weight of 2,5-bis(4-diethylaminophenyl)-1,3,4-oxadiazole,
2 parts by weight of No. 3 disazo pigment and 198 parts by weight of tetrahydrofuran were ground and mixed in a ball mill,
The resulting dispersion was applied onto a polyester film coated with aluminum using a doctor blade, and dried at 120°C for 10 minutes to produce a photoreceptor with a photosensitive layer having a thickness of 10μ as shown in Figure 2. . The same measurements as in Example 1 were carried out on this photoreceptor, and the results were that Vpo=930 volts and E1/2=9.7 lux·sec. Examples 22 to 30 A photoreceptor having the form shown in FIG. 2 was prepared in the same manner as in Example 21 except that disazo pigments shown in Table 3 below were used in place of disazo pigment No. 3 in Example 21. The same measurements as in Example 1 were then carried out, and the results shown in Table 3 were obtained.
【表】
実施例 31
No.5のジスアゾ顔料２重量部及びテトラヒド
ロフラン98重量部をボールミル中で粉砕混合し、
得られた分散液を、アルミニウム蒸着ポリエステ
ルフイルム上にドクターブレードで塗布し、自然
乾燥して厚さ１μの電荷担体発生層を形成せしめ
た。一方、２・４・７−トリニトロ−９−フルオ
レノン２重量部、ポリカーボネート〔(株)テイジン
製、パンライトＬ〕２重量部及びテトラヒドロフ
ラン46重量部を混合して分散液とし、これを前記
電荷担体発生層上にドクターブレードで塗布し、
100℃で10分間乾燥して厚さ10μの電荷移動媒体
質を形成せしめ、第３図の形態の感光体を得た。
上記のようにして得た感光体について、実施例１
と同様に測定し、Vpo＝1080ボルト、Ｅ1/2＝6.0
ルツクス・秒の結果を得た。
実施例 32〜40
実施例31においてNo.5のジスアゾ顔料の代り
に下記表−４のジスアゾ顔料を夫々用いた他は同
じ方法で第３図の形態の感光体を形成した。これ
ら感光体のVpo及びＥ1/2を表−４に示す。[Table] Example 31 2 parts by weight of No. 5 disazo pigment and 98 parts by weight of tetrahydrofuran were ground and mixed in a ball mill.
The resulting dispersion was applied onto an aluminum-deposited polyester film using a doctor blade and air-dried to form a charge carrier generation layer with a thickness of 1 μm. On the other hand, 2 parts by weight of 2,4,7-trinitro-9-fluorenone, 2 parts by weight of polycarbonate [Panlite L, manufactured by Teijin Co., Ltd.], and 46 parts by weight of tetrahydrofuran were mixed to prepare a dispersion, and this was used as the charge carrier. Apply it on the generation layer with a doctor blade,
The mixture was dried at 100° C. for 10 minutes to form a charge transfer medium having a thickness of 10 μm, thereby obtaining a photoreceptor having the form shown in FIG.
Example 1 Regarding the photoreceptor obtained as described above
Measured in the same way, Vpo = 1080 volts, E1/2 = 6.0
I got the result of lux sec. Examples 32 to 40 Photoreceptors having the form shown in FIG. 3 were formed in the same manner as in Example 31, except that the disazo pigments shown in Table 4 below were used in place of disazo pigment No. 5. Table 4 shows the Vpo and E1/2 of these photoreceptors.
【表】
実施例 41
No.6のジスアゾ顔料２重量部及びテトラヒド
ロフラン98重量部をボールミル中で粉砕混合し、
得られた分散液をアルミニウム蒸着ポリエステル
フイルム上にドクターブレードで塗布し自然乾燥
して厚さ１μの電荷担体発生層を形成した。一
方、２・５−ビス（４−ジエチルアミノフエニ
ル）−１・３・４−オキサジアゾール２重量部、
ポリカーボネート（実施例31に同じ）２重量部及
びテトラヒドロフラン46重量部を混合して分散液
とし、これを前記電荷担体発生層上にドクターブ
レードで塗布し、120℃で10分間乾燥して厚さ10
μの電荷移動媒体層を形成せしめ、第３図の積層
型感光体を得た。上記のようにして得た感光体に
ついて、−6KVのコロナ放電を行なつた以外は、
実施例１と同様に測定を行ない、このもののVpo
＝760ボルト、Ｅ1/2＝4.1ルツクス・秒の結果を
得た。
実施例 42〜50
実施例41においてNo.6のジスアゾ顔料の代り
に下記表−５ののジスアゾ顔料を夫々用いて同様
な感光体を作成した。これらの感光体のVpo及び
Ｅ1/2は表−５の通りである。[Table] Example 41 2 parts by weight of disazo pigment No. 6 and 98 parts by weight of tetrahydrofuran were pulverized and mixed in a ball mill.
The resulting dispersion was applied onto an aluminum-deposited polyester film using a doctor blade and air-dried to form a charge carrier generation layer having a thickness of 1 μm. On the other hand, 2 parts by weight of 2,5-bis(4-diethylaminophenyl)-1,3,4-oxadiazole,
2 parts by weight of polycarbonate (same as in Example 31) and 46 parts by weight of tetrahydrofuran were mixed to form a dispersion, which was applied onto the charge carrier generation layer using a doctor blade and dried at 120°C for 10 minutes to a thickness of 10%.
A charge transfer medium layer of .mu. was formed to obtain the laminated photoreceptor shown in FIG. The photoreceptor obtained as described above was subjected to -6KV corona discharge.
Measurement was carried out in the same manner as in Example 1, and the Vpo of this product was
= 760 volts, E1/2 = 4.1 lux·sec. Examples 42 to 50 Photoreceptors similar to Example 41 were prepared using the disazo pigments listed in Table 5 below in place of disazo pigment No. 6. The Vpo and E1/2 of these photoreceptors are shown in Table-5.
第１〜３図は夫々本発明感光体の拡大断面図で
ある。
１……導電性支持体、２，２′，２″……感光
層、３……結着剤、４……ジスアゾ顔料、５……
電荷移動媒体、６……電荷担体発生層、７……電
荷移動媒体層。
1 to 3 are enlarged sectional views of the photoreceptor of the present invention, respectively. DESCRIPTION OF SYMBOLS 1... Conductive support, 2, 2', 2''... Photosensitive layer, 3... Binder, 4... Disazo pigment, 5...
Charge transport medium, 6... Charge carrier generation layer, 7... Charge transport medium layer.
Claims (1)
ール環、カルバゾール環、ベンゾフラン環又はそ
れらの置換体、Ar1はベンゼン環、ナフタレン
環、ジベンゾフラン環、カルバゾール環又はそれ
らの置換体、Ar2及びAr3はベンゼン環、ナフタ
レン環又はそれらの置換体、R1及びR3は水素、
低級アルキル基、フエニル基又はその置換体、
R2は低級アルキル基、カルボキシル基又はその
エステル）を表わす。〕 で示されるジスアゾ顔料を有効成分として含有す
る感光層を有することを特徴とする電子写真用感
光体。[Claims] 1. General formula on a conductive support [However, A is [Formula] [Formula] or [Formula] ( where , , a carbazole ring or a substituted product thereof, Ar 2 and Ar 3 are a benzene ring, a naphthalene ring or a substituted product thereof, R 1 and R 3 are hydrogen,
lower alkyl group, phenyl group or substituted product thereof,
R 2 represents a lower alkyl group, a carboxyl group, or an ester thereof. ] A photoreceptor for electrophotography, characterized in that it has a photosensitive layer containing a disazo pigment represented by the following as an active ingredient.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2660478A JPS54119927A (en) | 1978-03-10 | 1978-03-10 | Photosensitive material for electrophotography |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2660478A JPS54119927A (en) | 1978-03-10 | 1978-03-10 | Photosensitive material for electrophotography |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS54119927A JPS54119927A (en) | 1979-09-18 |
| JPS6122301B2 true JPS6122301B2 (en) | 1986-05-31 |
Family
ID=12198106
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2660478A Granted JPS54119927A (en) | 1978-03-10 | 1978-03-10 | Photosensitive material for electrophotography |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS54119927A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61107250A (en) * | 1984-10-31 | 1986-05-26 | Canon Inc | Electrophotographic sensitive body |
| JPS61185752A (en) * | 1985-02-13 | 1986-08-19 | Mitsubishi Paper Mills Ltd | Electrophotographic sensitive body |
| JP2009128587A (en) * | 2007-11-22 | 2009-06-11 | Mitsubishi Chemicals Corp | Electrophotographic photoreceptor, image forming apparatus and electrophotographic photoreceptor cartridge |
-
1978
- 1978-03-10 JP JP2660478A patent/JPS54119927A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS54119927A (en) | 1979-09-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4260672A (en) | Electrophotographic sensitive element having a photoconductive disazo pigment | |
| US4293492A (en) | Disazo compounds derived from 3,6-bis(styryl)-9-ethylcarbazole | |
| JPS6029109B2 (en) | Electrophotographic photoreceptor | |
| JPS6027013B2 (en) | Electrophotographic photoreceptor | |
| JPS6027014B2 (en) | Electrophotographic photoreceptor | |
| JPS6027018B2 (en) | Electrophotographic photoreceptor | |
| JPS6027015B2 (en) | Electrophotographic photoreceptor | |
| JPS6027016B2 (en) | electrophotographic photoreceptor | |
| JPS6129498B2 (en) | ||
| JPS6219745B2 (en) | ||
| JPS6129499B2 (en) | ||
| JPS6243175B2 (en) | ||
| JPS6029108B2 (en) | Electrophotographic photoreceptor | |
| JPH0452459B2 (en) | ||
| JPS6219736B2 (en) | ||
| JPS6122301B2 (en) | ||
| JPS6122300B2 (en) | ||
| US4426327A (en) | 3,6-Disazo-9-ethyl carbazole compounds | |
| JPS6029107B2 (en) | Electrophotographic photoreceptor | |
| JPS6219738B2 (en) | ||
| JPS6219746B2 (en) | ||
| JPS6129497B2 (en) | ||
| JPS6219743B2 (en) | ||
| JPS6219744B2 (en) | ||
| JPS6219742B2 (en) |