JPH05140472A - Production of new dichloro-tin phthalocyanine crystal and electrophotographic photoreceptor made by using the crystal - Google Patents
Production of new dichloro-tin phthalocyanine crystal and electrophotographic photoreceptor made by using the crystalInfo
- Publication number
- JPH05140472A JPH05140472A JP3326721A JP32672191A JPH05140472A JP H05140472 A JPH05140472 A JP H05140472A JP 3326721 A JP3326721 A JP 3326721A JP 32672191 A JP32672191 A JP 32672191A JP H05140472 A JPH05140472 A JP H05140472A
- Authority
- JP
- Japan
- Prior art keywords
- crystal
- dichlorotin phthalocyanine
- type
- crystals
- dichlorotin
- 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.)
- Granted
Links
- 239000013078 crystal Substances 0.000 title claims abstract description 117
- BBRNKSXHHJRNHK-UHFFFAOYSA-L p0997 Chemical compound N1=C(C2=CC=CC=C2C2=NC=3C4=CC=CC=C4C(=N4)N=3)N2[Sn](Cl)(Cl)N2C4=C(C=CC=C3)C3=C2N=C2C3=CC=CC=C3C1=N2 BBRNKSXHHJRNHK-UHFFFAOYSA-L 0.000 title claims abstract description 85
- 108091008695 photoreceptors Proteins 0.000 title claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- 239000003960 organic solvent Substances 0.000 claims abstract description 17
- 238000001228 spectrum Methods 0.000 claims abstract description 16
- 238000002441 X-ray diffraction Methods 0.000 claims abstract description 4
- 229920005989 resin Polymers 0.000 claims description 20
- 239000011347 resin Substances 0.000 claims description 20
- 239000011230 binding agent Substances 0.000 claims description 14
- 125000003923 ethanoic acid ester group Chemical group 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 29
- 238000000034 method Methods 0.000 abstract description 8
- 230000035945 sensitivity Effects 0.000 abstract description 6
- 239000010410 layer Substances 0.000 description 30
- 238000000634 powder X-ray diffraction Methods 0.000 description 25
- 230000015572 biosynthetic process Effects 0.000 description 21
- 238000003786 synthesis reaction Methods 0.000 description 21
- 238000000576 coating method Methods 0.000 description 17
- 238000010586 diagram Methods 0.000 description 16
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 12
- 239000011324 bead Substances 0.000 description 11
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 11
- -1 phthalocyanine compound Chemical class 0.000 description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 6
- 238000002411 thermogravimetry Methods 0.000 description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 238000013329 compounding Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 4
- 229910052721 tungsten Inorganic materials 0.000 description 4
- 239000010937 tungsten Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000003618 dip coating Methods 0.000 description 3
- 150000002168 ethanoic acid esters Chemical class 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- JTPNRXUCIXHOKM-UHFFFAOYSA-N 1-chloronaphthalene Chemical compound C1=CC=C2C(Cl)=CC=CC2=C1 JTPNRXUCIXHOKM-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
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 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
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 239000005018 casein Substances 0.000 description 2
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 2
- 235000021240 caseins Nutrition 0.000 description 2
- 239000013522 chelant Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 229920002382 photo conductive polymer Polymers 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 2
- 229920002401 polyacrylamide Polymers 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 229920002717 polyvinylpyridine Polymers 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 230000004580 weight loss Effects 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical group ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- HOQAPVYOGBLGOC-UHFFFAOYSA-N 1-ethyl-9h-carbazole Chemical compound C12=CC=CC=C2NC2=C1C=CC=C2CC HOQAPVYOGBLGOC-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 108010076119 Caseins Proteins 0.000 description 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical class CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- 108010020346 Polyglutamic Acid Proteins 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- MKRNVBXERAPZOP-UHFFFAOYSA-N Starch acetate Chemical compound O1C(CO)C(OC)C(O)C(O)C1OCC1C(OC2C(C(O)C(OC)C(CO)O2)OC(C)=O)C(O)C(O)C(OC2C(OC(C)C(O)C2O)CO)O1 MKRNVBXERAPZOP-UHFFFAOYSA-N 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 1
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229920006287 phenoxy resin Polymers 0.000 description 1
- 239000013034 phenoxy resin Substances 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- XQZYPMVTSDWCCE-UHFFFAOYSA-N phthalonitrile Chemical compound N#CC1=CC=CC=C1C#N XQZYPMVTSDWCCE-UHFFFAOYSA-N 0.000 description 1
- 229920006391 phthalonitrile polymer Polymers 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920002643 polyglutamic acid Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 150000003219 pyrazolines Chemical class 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
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000003068 static effect Effects 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
- 238000003860 storage Methods 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 150000004961 triphenylmethanes Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Photoreceptors In Electrophotography (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、新規なジクロロスズフ
タロシアニン結晶の製造方法および該新規ジクロロスズ
フタロシアニン結晶を用いた電子写真感光体に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a novel dichlorotin phthalocyanine crystal and an electrophotographic photoreceptor using the novel dichlorotin phthalocyanine crystal.
【０００２】[0002]
【従来の技術】フタロシアニンは、塗料、印刷インキ、
触媒あるいは電子材料として有用な材料であり、特に、
近年、電子写真感光体用材料、光記憶用材料および光電
変換材料として、広範に検討がなされている。BACKGROUND OF THE INVENTION Phthalocyanine is used for paints, printing inks,
It is a material useful as a catalyst or electronic material, and in particular,
In recent years, it has been extensively studied as a material for an electrophotographic photoreceptor, a material for optical storage, and a photoelectric conversion material.
【０００３】電子写真感光体についてみると、近年、従
来提案された有機光導電材料の感光波長域を、近赤外の
半導体レーザーの波長（７８０〜８３０ｎｍ）にまで伸
ばし、レーザープリンター等のデジタル記録用の感光体
として使用することの要求が高まっており、この観点か
ら、スクエアリリウム化合物（特開昭４９−１０５５３
６号及び同５８−２１４１６号公報）、トリフェニルア
ミン系トリスアゾ化合物（特開昭６１−１５１６５９号
公報）、フタロシアニン化合物（特開昭４８−３４１８
９号及び同５７−１４８７４５号公報）等が、半導体レ
ーザー用の光導電材料として提案されている。Regarding electrophotographic photoreceptors, in recent years, the photosensitive wavelength range of conventionally proposed organic photoconductive materials has been extended to the wavelength of the near infrared semiconductor laser (780 to 830 nm), and digital recording for laser printers and the like has been performed. There is an increasing demand for its use as a photoconductor for use, and from this point of view, a squarylium compound (JP-A-49-10553) is used.
6 and 58-21416), triphenylamine-based trisazo compounds (JP-A-61-151659), phthalocyanine compounds (JP-A-48-3418).
No. 9 and No. 57-148745) have been proposed as photoconductive materials for semiconductor lasers.
【０００４】半導体レーザー用の感光材料として、有機
光導電材料を使用する場合は、まず、感光波長域が長波
長まで伸びていること、次に、形成される感光体の感
度、耐久性が良いこと等が要求される。前記の有機光導
電材料は、必ずしも、これらの諸条件を十分に満足する
ものではない。これらの欠点を克服するために、前記の
有機光導電材料について、結晶型と電子写真特性の関係
が検討されており、特に、フタロシアニン化合物につい
ては多くの報告が出されている。When an organic photoconductive material is used as a photosensitive material for a semiconductor laser, first, the photosensitive wavelength range extends to a long wavelength, and then the sensitivity and durability of the formed photoreceptor are good. Things are required. The above-mentioned organic photoconductive material does not always sufficiently satisfy these conditions. In order to overcome these drawbacks, the relationship between the crystal type and the electrophotographic characteristics of the above organic photoconductive material has been studied, and many reports have been made on phthalocyanine compounds.
【０００５】一般に、フタロシアニン化合物は、製造方
法、処理方法の違いにより、幾つかの結晶型を示し、こ
の結晶型の違いは、フタロシアニン化合物の光電変換特
性に大きな影響を及ぼすことが知られている。フタロシ
アニン化合物の結晶型については、例えば、銅フタロシ
アニンについてみると、安定系のβ型以外に、α、π、
ｘ、ρ、γ、δ等の結晶型が知られており、これらの結
晶型は、機械的張力、硫酸処理、有機溶剤処理及び熱処
理等により、相互に転移が可能であることが知られてい
る。（例えば、米国特許第２，７７０，６２９号、同第
３，１０６０，６３５号、同第３，７０８，２９２号及
び３，３５７，９８９号明細書）。また、特開昭５０−
３８５４３号公報には、銅フタロシアニンの結晶型の違
いと電子写真特性について、記載されている。他方、特
開昭６２−１１９５４７号公報には、ジハロゲノスズフ
タロシアニンを電荷発生材料として用いた電子写真感光
体が記載されており、特開平１−１４４０５号公報に
は、Ｘ線回折図上で特定の回折ピークを有するスズフタ
ロシアニン化合物およびそれを用いた電子写真感光体が
記載されている。Generally, phthalocyanine compounds show several crystal forms depending on the difference in production method and treatment method, and it is known that the difference in crystal form has a great influence on the photoelectric conversion characteristics of the phthalocyanine compound. .. Regarding the crystal form of the phthalocyanine compound, for example, looking at copper phthalocyanine, in addition to the stable β form, α, π,
Crystal forms such as x, ρ, γ, and δ are known, and it is known that these crystal forms can mutually transform by mechanical tension, sulfuric acid treatment, organic solvent treatment, heat treatment, or the like. There is. (For example, US Pat. Nos. 2,770,629, 3,1060,635, 3,708,292 and 3,357,989). In addition, JP-A-50-
Japanese Patent No. 38543 describes a difference in crystal type of copper phthalocyanine and electrophotographic characteristics. On the other hand, Japanese Patent Application Laid-Open No. 62-119547 describes an electrophotographic photoreceptor using dihalogenotin phthalocyanine as a charge generating material, and Japanese Patent Application Laid-Open No. 1-140505 discloses an X-ray diffraction diagram. A tin phthalocyanine compound having a specific diffraction peak and an electrophotographic photoreceptor using the same are described.
【０００６】[0006]
【発明が解決しようとする課題】しかしながら、従来開
発されている上記のフタロシアニン化合物は、感光材料
として使用した場合の光感度と耐久性の点でまだ十分満
足のいくものではなかった。本発明は、従来の技術にお
ける上記のような実情に鑑みてなされたものである。す
なわち、本発明の目的は、長波長域に感度を有する光導
電性材料として有用なジクロロスズフタロシアニンの新
規な結晶の製造方法を提供することにある。本発明の他
の目的は、ジクロロスズフタロシアニンの新規な結晶を
光導電材料として用いた高い感度と耐久性を有する電子
写真感光体を提供することにある。However, the above-mentioned phthalocyanine compounds that have been conventionally developed have not been sufficiently satisfactory in terms of photosensitivity and durability when used as a light-sensitive material. The present invention has been made in view of the above-mentioned actual situation in the conventional technique. That is, an object of the present invention is to provide a method for producing a novel dichlorotin phthalocyanine crystal useful as a photoconductive material having sensitivity in a long wavelength region. Another object of the present invention is to provide an electrophotographic photoreceptor having high sensitivity and durability, which uses a novel crystal of dichlorotin phthalocyanine as a photoconductive material.
【０００７】[0007]
【課題を解決するための手段】本発明者等は、ジクロロ
スズフタロシアニンの結晶系について検討した結果、ジ
クロロスズフタロシアニンには、Ｉ〜IV型の４つの結晶
型があること、これらの結晶型は、合成後のジクロロス
ズフタロシアニンを粉砕処理したり、有機溶剤と共にミ
リング処理することによって得られるが、このうち、II
I 型及びIV型結晶は、Ｉ型及びII型に比べて不安定であ
り、適当な有機溶剤で処理することにより、容易にＩ型
結晶に転移することを見出だした。さらに、III 型及び
IV型結晶を経て得られたＩ型結晶は、III 型及びIV型結
晶を経ないで得られたＩ型結晶に比べて、粉末Ｘ線回折
のピークはほぼ一致するものの、ピーク強度比が全く異
なっており、電子写真特性が優れていることを見出だ
し、本発明を完成した。Means for Solving the Problems As a result of investigations on the crystal system of dichlorotin phthalocyanine, the present inventors have found that dichlorotin phthalocyanine has four crystal forms I to IV. It can be obtained by crushing dichlorotin phthalocyanine after synthesis or by milling with an organic solvent. Of these, II
It has been found that the type I and type IV crystals are more unstable than the type I and type II crystals, and can be easily transformed into the type I crystal by treatment with a suitable organic solvent. In addition, type III and
The I-type crystal obtained through the IV-type crystal has almost the same powder X-ray diffraction peaks as those of the I-type crystal obtained without passing through the III-type crystal and the IV-type crystal, but the peak intensity ratio is completely different. They found that they were different and had excellent electrophotographic properties, and completed the present invention.
【０００８】すなわち、本発明のジクロロスズフタロシ
アニンの製造方法は、Ｘ線回折スペクトルにおいて、λ
＝１．５４１８Ａ．Ｕ．のＣｕＫα放射線に対するブラ
ッグ角（以下ブラッグ角という）（２θ±０．２°）＝
８．７°、９．９°、１０．９°、１３．１°、１５．
２°、１６．３°、１７．４°、２１．９°、２５．５
°に強い回折ピークを有するIII 型に属するジクロロス
ズフタロシアニン結晶、または、ブラッグ角（２θ±
０．２°）＝９．２°、１２．２°、１３．４°、１
４．６°、１７．０°、２５．３°に強い回折ピークを
有するIV型に属するジクロロスズフタロシアニン結晶
を、有機溶剤中で処理して、ブラッグ角（２θ±０．２
°）の２５°から３０°の範囲において、２８．２°に
最も強い回折ピークを有するＩ型に属するジクロロスズ
フタロシアニン結晶に転移させることを特徴とする。本
発明の電子写真感光体は、導電性支持体上に、上記のよ
うにして製造されたブラッグ角（２θ±０．２°）の２
５°から３０°の範囲において、２８．２°に最も強い
回折ピークを有するジクロロスズフタロシアニン結晶を
含有する感光層を設けてなることを特徴とする。That is, the method for producing dichlorotin phthalocyanine of the present invention is characterized in that X-ray diffraction spectrum shows λ
= 1.5418A. U. Bragg angle (hereinafter referred to as Bragg angle) of CuKα radiation (2θ ± 0.2 °) =
8.7 °, 9.9 °, 10.9 °, 13.1 °, 15.
2 °, 16.3 °, 17.4 °, 21.9 °, 25.5
Type III dichlorotin phthalocyanine crystal having a strong diffraction peak at ° or Bragg angle (2θ ±
0.2 °) = 9.2 °, 12.2 °, 13.4 °, 1
A dichlorotin phthalocyanine crystal belonging to type IV having strong diffraction peaks at 4.6 °, 17.0 ° and 25.3 ° was treated in an organic solvent to obtain a Bragg angle (2θ ± 0.2).
In the range of 25 ° to 30 ° in (°), the dichlorotin phthalocyanine crystal belonging to Form I having the strongest diffraction peak at 28.2 ° is transferred. The electrophotographic photoreceptor of the present invention has a Bragg angle (2θ ± 0.2 °) of 2 produced as described above on a conductive support.
In the range of 5 ° to 30 °, a photosensitive layer containing a dichlorotin phthalocyanine crystal having a strongest diffraction peak at 28.2 ° is provided.
【０００９】以下、本発明について詳細に説明する。本
発明の製造方法において、出発原料である上記III 型ジ
クロロスズフタロシアニン結晶およびIV型ジクロロスズ
フタロシアニン結晶は、いずれも新規な結晶であり、次
のようにして製造される。すなわち、公知の方法で製造
されたジクロロスズフタロシアニン結晶をボールミル等
を用い、特定の有機溶剤中で粉砕することによって、製
造することができる。また、乾式粉砕の後、溶剤で処理
することによっても得られる。使用する有機溶剤は、II
I 型ジクロロスズフタロシアニン結晶の場合には、トル
エン、キシレン、クロロベンゼン等の芳香族炭化水素が
使用されるが、なかでも、クロロベンゼンが最も好まし
く用いられる。また、IV型ジクロロスズフタロシアニン
結晶の場合には、テトラヒドロフラン、１、４−ジオキ
サン等のエーテル類が使用される。そのなかでも、テト
ラヒドロフランが好ましく用いられる。The present invention will be described in detail below. In the production method of the present invention, the above-mentioned type III dichlorotin phthalocyanine crystal and type IV dichlorotin phthalocyanine crystal, which are starting materials, are both novel crystals and are produced as follows. That is, it can be produced by pulverizing the dichlorotin phthalocyanine crystal produced by a known method using a ball mill or the like in a specific organic solvent. It can also be obtained by treating with a solvent after dry pulverization. The organic solvent used is II
In the case of type I dichlorotin phthalocyanine crystals, aromatic hydrocarbons such as toluene, xylene and chlorobenzene are used, and among them, chlorobenzene is most preferably used. In the case of IV type dichlorotin phthalocyanine crystal, ethers such as tetrahydrofuran and 1,4-dioxane are used. Of these, tetrahydrofuran is preferably used.
【００１０】粉砕には、ボールミルの他、サンドミル、
ニーダー等を用いることができるが、それ等に限定され
るものではない。また、必要に応じて、ガラスビーズ、
スチールビーズ等の磨砕メディア、あるいは食塩、ぼう
硝等の磨砕助剤を用いることができる。粉砕処理は、温
度範囲１０〜５０°Ｃ、通常は室温において、１０〜１
００時間行うことが好ましい。For crushing, in addition to a ball mill, a sand mill,
A kneader or the like can be used, but is not limited thereto. Also, if necessary, glass beads,
A grinding medium such as steel beads, or a grinding aid such as salt or sodium sulfate can be used. The crushing treatment is carried out in the temperature range of 10 to 50 ° C., usually at room temperature in the range of 10 to 1
It is preferably performed for 00 hours.
【００１１】上記のようにして、ブラッグ角（２θ±
０．２°）＝８．７°、９．９°、１０．９°、１３．
１°、１５．２°、１６．３°、１７．４°、２１．９
°、２５．５°に強い回折ピークを有するIII 型のジク
ロロスズフタロシアニン結晶およびブラッグ角（２θ±
０．２°）＝９．２°、１２．２°、１３．４°、１
４．６°、１７．０°、２５．３°に強い回折ピークを
有するIV型のジクロロスズフタロシアニン結晶が製造さ
れる。これらの結晶は、次いで、有機溶剤中で処理する
ことによって、ブラッグ角（２θ±０．２°）の２５°
から３０°の範囲において、２８．２°に最も強い回折
ピークを有するI 型のジクロロスズフタロシアニン結晶
に転移させる。As described above, the Bragg angle (2θ ±
0.2 °) = 8.7 °, 9.9 °, 10.9 °, 13.
1 °, 15.2 °, 16.3 °, 17.4 °, 21.9
Type III dichlorotin phthalocyanine crystal having a strong diffraction peak at 2 ° and 25.5 ° and the Bragg angle (2θ ±
0.2 °) = 9.2 °, 12.2 °, 13.4 °, 1
Type IV dichlorotin phthalocyanine crystals having strong diffraction peaks at 4.6 °, 17.0 °, and 25.3 ° are produced. These crystals were then treated in an organic solvent to give a Bragg angle (2θ ± 0.2 °) of 25 °.
In the range of from 30 ° to 30 °, it is transformed into a type I dichlorotin phthalocyanine crystal having the strongest diffraction peak at 28.2 °.
【００１２】使用される有機溶剤としては、アセトン、
メチルエチルケトン（ＭＥＫ）等のケトン類、塩化メチ
レン、クロロホルム等のハロゲン化炭化水素類、酢酸エ
チル、酢酸ブチル等の酢酸エステル類、ジメチルホルム
アミド（ＤＭＦ）、ピリジン等の種々のものがあげられ
るが、本発明においては、得られるジクロロスズフタロ
シアニン結晶が、ブラッグ角（２θ±０．２°）の２５
°から３０°の範囲において、２８．２°に最も強い回
折ピークを有するI 型の結晶型を有するものになるよう
に、適宜選択して使用する。これらの中でも、酢酸エス
テル類が特に好ましく使用することができる。As the organic solvent used, acetone,
Examples include ketones such as methyl ethyl ketone (MEK), halogenated hydrocarbons such as methylene chloride and chloroform, acetic acid esters such as ethyl acetate and butyl acetate, dimethylformamide (DMF) and pyridine. In the invention, the obtained dichlorotin phthalocyanine crystal has a Bragg angle (2θ ± 0.2 °) of 25.
In the range of 30 ° to 30 °, it is appropriately selected and used so as to have the I-type crystal form having the strongest diffraction peak at 28.2 °. Among these, acetic acid esters can be particularly preferably used.
【００１３】上記結晶転移の際に、有機溶剤中に結着樹
脂を配合してもよい。その場合、分散処理を行うことに
よって、結晶転移が行われると共に、得られた分散液
は、直接、電荷発生層形成用塗布液として使用すること
ができるので、電子写真感光体の製造上有利である。上
記有機溶剤処理に際しては、必要に応じて、ガラスビー
ズ、スチールビーズ等の磨砕メディア等を用いて磨砕を
行いながら処理することも可能である。A binder resin may be blended in an organic solvent at the time of the above crystal transition. In that case, by performing the dispersion treatment, the crystal transition is performed, and the obtained dispersion liquid can be directly used as the charge generation layer forming coating liquid, which is advantageous in the production of the electrophotographic photoreceptor. is there. In the above organic solvent treatment, it is also possible to perform the treatment with grinding media such as glass beads, steel beads, etc. while carrying out the grinding, if necessary.
【００１４】本発明により得られるＩ型結晶は、III 型
及びIV型結晶を経ないで得られたＩ型結晶に比べて、電
子写真特性において優れたものであって、その粉末Ｘ線
回折のピークはIII 型及びIV型結晶を経ないで得られた
Ｉ型結晶とほぼ一致するが、ピーク強度比が全く異なっ
ている。これは、III 型またはIV型結晶からＩ型結晶に
転移する際に、III 型、IV型結晶に取り込まれていた揮
発性成分が抜け出すために結晶格子に歪みがかかり、結
晶の成長軸が異なり、配向性に影響を及ぼすためと推測
される。The type I crystal obtained according to the present invention is superior in electrophotographic characteristics to the type I crystal obtained without passing through the type III and type IV crystals, and its powder X-ray diffraction The peaks are almost the same as the type I crystals obtained without passing through the type III and type IV crystals, but the peak intensity ratios are quite different. This is because the crystal lattice is distorted because the volatile components taken in the III-type and IV-type crystals escape during the transition from the III-type or IV-type crystals to the I-type crystals, and the crystal growth axis is different. It is presumed that it affects the orientation.
【００１５】次に、本発明の製造方法で得られたジクロ
ロスズフタロシアニン結晶を、感光層における光導電材
料として使用した電子写真感光体について説明する。本
発明の電子写真感光体は、感光層が単層構造のもので
も、電荷発生層と電荷輸送層とに機能分離された積層構
造のものであってもよい。Next, an electrophotographic photosensitive member using the dichlorotin phthalocyanine crystal obtained by the manufacturing method of the present invention as a photoconductive material in the photosensitive layer will be described. The electrophotographic photosensitive member of the present invention may have a single-layered photosensitive layer or a laminated structure in which a charge-generating layer and a charge-transporting layer are functionally separated.
【００１６】感光層が積層構造を有する場合、電荷発生
層は、上記Ｉ型ジクロロスズフタロシアニン結晶及び結
着樹脂から構成される。結着樹脂は、広範な絶縁性樹脂
から選択することができ、また、ポリ−Ｎ−ビニルカル
バゾール、ポリビニルアントラセン、ポリビニルピレン
等の有機光導電性ポリマーから選択することもできる。
好ましい結着樹脂としては、ポリビニルブチラール、ポ
リアリレート（ビスフェノールＡとフタル酸の重縮合体
等）、ポリカーボネート、ポリエステル、フェノキシ樹
脂、塩化ビニル−酢酸ビニル共重合体、ポリ酢酸ビニ
ル、アクリル樹脂、ポリアクリルアミド、ポリアミド、
ポリビニルピリジン、セルロース系樹脂、ウレタン樹
脂、エポキシ樹脂、カゼイン、ポリビニルアルコール、
ポリビニルピロリドン等の絶縁性樹脂をあげることがで
きる。When the photosensitive layer has a laminated structure, the charge generating layer is composed of the above-mentioned I-type dichlorotin phthalocyanine crystal and a binder resin. The binder resin can be selected from a wide range of insulating resins, and can also be selected from organic photoconductive polymers such as poly-N-vinylcarbazole, polyvinylanthracene and polyvinylpyrene.
Preferred binder resins include polyvinyl butyral, polyarylate (polycondensate of bisphenol A and phthalic acid, etc.), polycarbonate, polyester, phenoxy resin, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, acrylic resin, polyacrylamide. ,polyamide,
Polyvinyl pyridine, cellulosic resin, urethane resin, epoxy resin, casein, polyvinyl alcohol,
An insulating resin such as polyvinylpyrrolidone can be used.
【００１７】電荷発生層は、上記結着樹脂を有機溶剤に
溶解した溶液に、上記Ｉ型ジクロロスズフタロシアニン
結晶を分散させて塗布液を調製し、それを導電性支持体
の上に塗布することによって形成することができる。ま
た、III 型、IV型結晶を用い、塗布液中で結晶転移させ
てもよい。その場合、使用するジクロロスズフタロシア
ニン結晶と結着樹脂の配合比は、４０：１〜１：１０、
好ましくは１０：１〜１：４である。ジクロロスズフタ
ロシアニン結晶の比率が高すぎる場合には、塗布液の安
定性が低下し、低すぎる場合には、感度が低下するの
で、上記範囲に設定するのが好ましい。The charge generation layer is prepared by dispersing the above-mentioned type I dichlorotin phthalocyanine crystal in a solution prepared by dissolving the above-mentioned binder resin in an organic solvent to prepare a coating solution, which is then coated on a conductive support. Can be formed by. In addition, crystal transition may be performed in the coating liquid by using type III and type IV crystals. In that case, the compounding ratio of the dichlorotin phthalocyanine crystal and the binder resin used is 40: 1 to 1:10,
It is preferably 10: 1 to 1: 4. If the ratio of the dichlorotin phthalocyanine crystals is too high, the stability of the coating solution will be lowered, and if it is too low, the sensitivity will be lowered, so it is preferable to set the above range.
【００１８】使用する溶剤としては、下引き層あるいは
電荷輸送層を溶解しないものから選択するのが好まし
い。具体的な有機溶剤としては、メタノール、エタノー
ル、イソプロパノール等のアルコール類、アセトン、Ｍ
ＥＫ、シクロヘキサノン等のケトン類、ＤＭＦ、Ｎ，Ｎ
−ジメチルアセトアミド等のアミド類、ジメチルスルホ
キシド類、テトラヒドロフラン、ジオキサン、エチレン
グルコールモノメチルエーテル等のエーテル類、酢酸メ
チル、酢酸エチル等のエステル類、クロロホルム、塩化
メチレン、ジクロルエチレン、四塩化炭素、トリクロル
エチレン等の脂肪族ハロゲン化炭化水素、ベンゼン、ト
ルエン、キシレン、リグロイン、モノクロルベンゼン、
ジクロルベンゼン等の脂肪族、芳香族炭化水素等を用い
ることができる。このうち、酢酸エステル類が特に好ま
しい。The solvent used is preferably selected from those which do not dissolve the undercoat layer or the charge transport layer. Specific organic solvents include alcohols such as methanol, ethanol and isopropanol, acetone, M
EK, ketones such as cyclohexanone, DMF, N, N
-Amids such as dimethylacetamide, dimethylsulfoxides, ethers such as tetrahydrofuran, dioxane, ethylene glycol monomethyl ether, esters such as methyl acetate and ethyl acetate, chloroform, methylene chloride, dichloroethylene, carbon tetrachloride, trichloro Aliphatic halogenated hydrocarbons such as ethylene, benzene, toluene, xylene, ligroin, monochlorobenzene,
Aliphatic or aromatic hydrocarbons such as dichlorobenzene can be used. Of these, acetic acid esters are particularly preferable.
【００１９】塗布液の塗布は、浸漬コーティング法、ス
プレーコーティング法、スピナーコーティング法、ビー
ドコーティング法、ワイパーコーティング法、ブレード
コーティング法、ローラーコーティング法、カーテンコ
ーティング法等のコーティング法を用いることができ
る。また、乾燥は、室温における指触乾燥後、加熱乾燥
する方法が好ましい。加熱乾燥は、３０〜２００°Ｃの
温度で５分〜２時間の範囲で静止または送風下で行うこ
とができる。また、電荷発生層の膜厚は、通常、０．０
５〜５μｍ程度になるように塗布される。The coating liquid can be applied by a coating method such as a dip coating method, a spray coating method, a spinner coating method, a bead coating method, a wiper coating method, a blade coating method, a roller coating method and a curtain coating method. In addition, drying is preferably performed by drying by touching at room temperature and then drying by heating. The heat drying can be performed at a temperature of 30 to 200 ° C. for 5 minutes to 2 hours in a static state or under blowing air. The thickness of the charge generation layer is usually 0.0
It is applied so as to have a thickness of about 5 to 5 μm.
【００２０】電荷輸送層は、電荷輸送材料および結着樹
脂より構成される。電荷輸送材料としては、例えば、ア
ントラセン、ピレン、フェナントレン等の多環芳香族化
合物、インドール、カルバゾール、イミダゾール等の含
窒素複素環を有する化合物、ピラゾリン化合物、ヒドラ
ゾン化合物、トリフェニルメタン化合物、トリフェニル
アミン化合物、エナミン化合物、スチルベン化合物等、
公知のものならば如何なるものでも使用することができ
る。更にまた、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、ポリビニルアント
ラセン、ポリ−Ｎ−ビニルフェニルアントラセン、ポリ
ビニルピレン、ポリビニルアセナフチレン、ポリグリシ
ジカルバゾール、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等の光導電性ポ
リマーがあげられ、これ等はそれ自体で層を形成しても
よい。また、結着樹脂としては、上記した電荷発生層に
使用されるものと同様な絶縁性樹脂が使用できる。The charge transport layer is composed of a charge transport material and a binder resin. Examples of the charge transport material include polycyclic aromatic compounds such as anthracene, pyrene, and phenanthrene, compounds having a nitrogen-containing heterocyclic ring such as indole, carbazole, and imidazole, pyrazoline compounds, hydrazone compounds, triphenylmethane compounds, triphenylamine. Compounds, enamine compounds, stilbene compounds, etc.
Any known material can be used. Furthermore, poly-N-vinylcarbazole, halogenated poly-N-vinylcarbazole, polyvinylanthracene, poly-N-vinylphenylanthracene, polyvinylpyrene, polyvinylacenaphthylene, polyglycidicarbazole, pyrene-formaldehyde resin, ethylcarbazole. -Photoconductive polymers such as formaldehyde resins are mentioned, which may themselves form the layer. Further, as the binder resin, the same insulating resin as that used for the charge generation layer can be used.
【００２１】電荷輸送層は、上記電荷輸送材料と結着樹
脂および上記と同様な有機溶剤とを用いて塗布液を調製
したあと、同様に塗布して形成することができる。電荷
輸送材料と結着樹脂との配合比（重量部）は、通常５：
１〜１：５の範囲で設定される。また、電荷輸送層の膜
厚は、通常１０〜３０μｍ程度に設定される。The charge transport layer can be formed by preparing a coating solution using the above charge transport material, a binder resin and the same organic solvent as described above, and then applying the same. The compounding ratio (parts by weight) of the charge transport material and the binder resin is usually 5:
It is set in the range of 1 to 1: 5. The thickness of the charge transport layer is usually set to about 10 to 30 μm.
【００２２】電子写真感光体が、単層構造を有する場合
においては、感光層は上記のジクロロスズフタロシアニ
ン結晶が電荷輸送材料および結着樹脂よりなる層に分散
された構成を有する光導電層よりなる。その場合、電荷
輸送材料と結着樹脂との配合比は、１：２０〜５：１、
ジクロロスズフタロシアニン結晶と電荷輸送材料との配
合比は、１：１０〜１０：１程度に設定するのが好まし
い。電荷輸送材料および結着樹脂は、上記と同様なもの
が使用され、上記と同様にして光導電層が形成される。When the electrophotographic photoreceptor has a single-layer structure, the photosensitive layer is composed of a photoconductive layer having a structure in which the above-mentioned dichlorotin phthalocyanine crystal is dispersed in a layer composed of a charge transport material and a binder resin. .. In that case, the compounding ratio of the charge transport material and the binder resin is 1:20 to 5: 1,
The compounding ratio of the dichlorotin phthalocyanine crystal and the charge transport material is preferably set to about 1:10 to 10: 1. As the charge transport material and the binder resin, those similar to the above are used, and the photoconductive layer is formed in the same manner as above.
【００２３】導電性支持体としては、電子写真感光体と
して使用することが公知のものならば、如何なるもので
も使用することができる。本発明において、導電性支持
体上に下引き層が設けられてもよい。下引き層は、導電
性支持体からの不必要な電荷の注入を阻止するために有
効であり、感光層の帯電性を高める作用がある。さら
に、感光層と導電性支持体との密着性を高める作用もあ
る。下引き層を構成する材料としては、ポリビニルアル
コール、ポリビニルピロリドン、ポリビニルピリジン、
セルロースエーテル類、セルロースエステル類、ポリア
ミド、ポリウレタン、カゼイン、ゼラチン、ポリグルタ
ミン酸、澱粉、スターチアセテート、アミノ澱粉、ポリ
アクリル酸、ポリアクリルアミド、ジルコニウムキレー
ト化合物、ジルコニウムアルコキシド化合物、有機ジル
コニウム化合物、チタニルキレート化合物、チタニルア
ルコキシド化合物、有機チタニル化合物、シランカップ
リング剤等があげられる。下引き層の膜厚は、０．０５
〜２μｍ程度に設定するのが好ましい。As the conductive support, any material can be used as long as it is known to be used as an electrophotographic photoreceptor. In the present invention, an undercoat layer may be provided on the conductive support. The undercoat layer is effective in preventing unnecessary injection of charges from the conductive support, and has the function of enhancing the chargeability of the photosensitive layer. Further, it also has the function of enhancing the adhesion between the photosensitive layer and the conductive support. As a material forming the undercoat layer, polyvinyl alcohol, polyvinylpyrrolidone, polyvinylpyridine,
Cellulose ether, cellulose ester, polyamide, polyurethane, casein, gelatin, polyglutamic acid, starch, starch acetate, amino starch, polyacrylic acid, polyacrylamide, zirconium chelate compound, zirconium alkoxide compound, organic zirconium compound, titanyl chelate compound, Examples include titanyl alkoxide compounds, organic titanyl compounds, silane coupling agents and the like. The thickness of the undercoat layer is 0.05
It is preferably set to about 2 μm.
【００２４】[0024]
【実施例】以下、実施例によって本発明を説明する。 合成例１（ジクロロスズフタロシアニンの合成） フタロニトリル５０ｇ及び無水塩化第２スズ２７ｇを、
１−クロルナフタレン３５０ｍｌ中に加え、１９５°Ｃ
において５時間反応させた後、生成物を濾別し、１−ク
ロルナフタレン、アセトン、メタノール、次いで水で洗
浄した後、減圧乾燥して、ジクロロスズフタロシアニン
結晶１８．３ｇ（２７％）を得た。得られたジクロロス
ズフタロシアニン結晶の粉末Ｘ線回折図を、図１に示
す。EXAMPLES The present invention will be described below with reference to examples. Synthesis Example 1 (Synthesis of dichlorotin phthalocyanine) 50 g of phthalonitrile and 27 g of anhydrous stannic chloride,
1-Chlornaphthalene was added to 350 ml and added at 195 ° C.
After 5 hours of reaction, the product was filtered off, washed with 1-chloronaphthalene, acetone, methanol, then water and dried under reduced pressure to give 18.3 g (27%) of dichlorotin phthalocyanine crystals. .. The powder X-ray diffraction pattern of the obtained dichlorotin phthalocyanine crystal is shown in FIG.
【００２５】合成例２ 合成例１で得られたジクロロスズフタロシアニン結晶１
ｇを、ガラスビーズ（１ｍｍφ）１００ｇとともにクロ
ロベンゼン（以下ＭＣＢという）３０ｍｌ中で、ボール
ミルを用いて室温にて７２時間粉砕し、得られたスラリ
ーを濾過し、メタノールで繰り返し洗浄した後、減圧乾
燥して、ジクロロスズフタロシアニンのIII 結晶０．９
７ｇを得た。得られたジクロロスズフタロシアニンのII
I 型結晶の粉末Ｘ線回折図を、図２に示す。熱重量分析
の結果を、図１４に示す。約１３０℃で約１１％の重量
減少が見られた（試料量は９．３９ｍｇ）。Synthesis Example 2 Dichlorotin phthalocyanine crystal 1 obtained in Synthesis Example 1
g was crushed with 100 g of glass beads (1 mmφ) in 30 ml of chlorobenzene (hereinafter referred to as MCB) using a ball mill at room temperature for 72 hours, and the obtained slurry was filtered, repeatedly washed with methanol, and then dried under reduced pressure. III crystal of dichlorotin phthalocyanine 0.9
7 g was obtained. II of the obtained dichlorotin phthalocyanine
The powder X-ray diffraction pattern of the type I crystal is shown in FIG. The results of thermogravimetric analysis are shown in FIG. A weight loss of about 11% was observed at about 130 ° C (sample amount: 9.39 mg).
【００２６】合成例３ 合成例２において、粉砕時の溶剤として、テトラヒドロ
フラン（以下ＴＨＦという）を用いた以外は、同様に処
理して、ジクロロスズフタロシアニンのIV型結晶０．９
３ｇを得た。得られたジクロロスズフタロシアニンのIV
型結晶の粉末Ｘ線回折図を、図３に示す。熱重量分析の
結果を、図１５に示す。約１５０℃で約７％の重量減少
が見られた（試料量は９．７９ｍｇ）Synthetic Example 3 The same treatment as in Synthetic Example 2 except that tetrahydrofuran (hereinafter referred to as THF) was used as the solvent at the time of pulverization, and dichlorotin phthalocyanine IV type crystal 0.9
3 g was obtained. IV of the obtained dichlorotin phthalocyanine
The powder X-ray diffraction pattern of the shaped crystal is shown in FIG. The results of thermogravimetric analysis are shown in FIG. Weight loss of about 7% was observed at about 150 ° C (sample amount: 9.79 mg)
【００２７】合成例４ 合成例１で得たジクロロスズフタロシアニン５ｇをメノ
ウボール（２０ｍｍφ）５００ｇとともにメノウ製ポッ
ト（５００ｍｌ）に入れ、遊星型ボールミル（フリッチ
ュ社製：Ｐ−５製）にて、４００ｒｐｍで１時間粉砕し
た。得られたジクロロスズフタロシアニン結晶の粉末Ｘ
線回折図を、図４に示す。Synthetic Example 4 5 g of dichlorotin phthalocyanine obtained in Synthetic Example 1 was put together with 500 g of agate balls (20 mmφ) in an agate pot (500 ml) and 400 rpm in a planetary ball mill (Fritsch company: P-5). Crushed for 1 hour. Obtained powder X of dichlorotin phthalocyanine crystal
The line diffraction pattern is shown in FIG.
【００２８】合成例５ 合成例４で得たジクロロスズフタロシアニン結晶０．５
ｇをＭＣＢ１５ｍｌ、ガラスビーズ３０ｇと共に室温下
２４時間ミリング処理した後、ガラスビーズを濾別、乾
燥して、ジクロロスズフタロシアニンのIII 型結晶０．
４５ｇを得た。（Ｘ線は図２と同様）Synthesis Example 5 Dichlorotin phthalocyanine crystal 0.5 obtained in Synthesis Example 4
Milling treatment with 15 ml of MCB and 30 g of glass beads at room temperature for 24 hours, the glass beads were separated by filtration and dried to form dichlorotin phthalocyanine type III crystal.
45 g were obtained. (X-ray is the same as in Fig. 2)
【００２９】合成例６ 合成例５のＭＣＢをＴＨＦにかえて同様に処理し、ジク
ロロスズフタロシアニンのIV型結晶を０．４３ｇ得た。
（Ｘ線は図３と同様）Synthesis Example 6 MCB of Synthesis Example 5 was replaced with THF and treated in the same manner to obtain 0.43 g of type IV crystal of dichlorotin phthalocyanine.
(X-ray is the same as in Fig. 3)
【００３０】実施例１ 合成例２で得たジクロロスズフタロシアニンのIII 型結
晶０．５ｇをｎ−酢酸ブチル１５ｍｌを用いて、合成例
５と同様に処理して、ジクロロスズフタロシアニンのＩ
型結晶０．４０ｇを得た。得られたジクロロスズフタロ
シアニンのＩ型結晶の粉末Ｘ線回折図を、図５に示す。
熱重量分析の結果を、図１６に示す。０〜２００℃の間
で重量変化はほとんど見られなかった（試料量は９．７
８ｍｇ）。Example 1 0.5 g of the type III crystal of dichlorotin phthalocyanine obtained in Synthesis Example 2 was treated with 15 ml of n-butyl acetate in the same manner as in Synthesis Example 5 to give I of dichlorotin phthalocyanine I.
0.40 g of mold crystals were obtained. The powder X-ray diffraction pattern of the obtained I-type crystal of dichlorotin phthalocyanine is shown in FIG.
The results of thermogravimetric analysis are shown in FIG. Almost no weight change was observed between 0 and 200 ° C (sample amount was 9.7).
8 mg).
【００３１】実施例２ 合成例３で得たジクロロスズフタロシアニンのIV型結晶
０．５ｇを用いた他は、実施例１と同様にして、本発明
のジクロロスズフタロシアニンのＩ型結晶０．４２ｇを
得た。得られたジクロロスズフタロシアニンのＩ型結晶
の粉末Ｘ線回折図を、図６に示す。Example 2 0.42 g of dichlorotin phthalocyanine type I crystal of the present invention was prepared in the same manner as in Example 1 except that 0.5 g of dichlorotin phthalocyanine type IV crystal obtained in Synthesis Example 3 was used. Obtained. The powder X-ray diffraction pattern of the obtained dichlorotin phthalocyanine type I crystal is shown in FIG.
【００３２】比較例１ 合成例４で得たジクロロスズフタロシアニン結晶０．５
ｇを酢酸ブチル１５ｍｌ、ガラスビーズ３０ｇと共に室
温下２４時間ミリング処理した後、ガラスビーズを濾
別、乾燥して、ジクロロスズフタロシアニンのＩ型結晶
０．４５ｇを得た。得られたジクロロスズフタロシアニ
ンのＩ型結晶の粉末Ｘ線回折図を、図７に示す。Comparative Example 1 0.5 g of dichlorotin phthalocyanine crystal obtained in Synthesis Example 4
After 15 g of butyl acetate and 30 g of glass beads were milled at room temperature for 24 hours, the glass beads were separated by filtration and dried to obtain 0.45 g of dichlorotin phthalocyanine type I crystal. The powder X-ray diffraction pattern of the obtained dichlorotin phthalocyanine type I crystal is shown in FIG. 7.
【００３３】実施例３ 合成例２で得られたジクロロスズフタロシアニン結晶１
部をポリビニルブチラール（商品名：エスレックＢＭ−
１、積水化学社製）１部及びｎ−酢酸ブチル１００部と
混合し、ガラスビーズと共にペイントシェーカーで１時
間処理して分散した後、得られた塗布液を浸漬コーティ
ング法でアルミニウム基板上に塗布し、１００°Ｃにお
いて５分間加熱乾燥し、膜厚０．２μｍの電荷発生層を
形成した。また、この溶液を乾燥し、粉末Ｘ線回折を測
定したところ、図８に示すように本発明のジクロロスズ
フタロシアニンのＩ型結晶であった。Example 3 Dichlorotin phthalocyanine crystal 1 obtained in Synthesis Example 2
Polyvinyl butyral (brand name: S-REC BM-
1, manufactured by Sekisui Chemical Co., Ltd.) and 100 parts of n-butyl acetate, mixed with glass beads for 1 hour by a paint shaker and dispersed, and then the obtained coating solution is applied on an aluminum substrate by a dip coating method. Then, it was heated and dried at 100 ° C. for 5 minutes to form a charge generation layer having a thickness of 0.2 μm. Further, when this solution was dried and powder X-ray diffraction was measured, it was found to be the I-type crystal of dichlorotin phthalocyanine of the present invention as shown in FIG.
【００３４】次に下記構造式Next, the following structural formula
【化１】 [Chemical 1]
【００３５】下記構造式The following structural formula
【化２】 で示されるポリ（４，４−シクロヘキシリデンジフェニ
レンカーボネート）３部を、モノクロロベンゼン２０部
に溶解し、得られた塗布液を、電荷発生層が形成された
アルミニウム基板上に浸漬コーティング法で塗布し、１
２０°Ｃにおいて１時間加熱乾燥し、膜厚２０μｍの電
荷発生層を形成した。[Chemical 2] 3 parts of poly (4,4-cyclohexylidenediphenylene carbonate) represented by are dissolved in 20 parts of monochlorobenzene, and the obtained coating solution is applied onto an aluminum substrate having a charge generation layer formed thereon by a dip coating method. Then 1
It was heated and dried at 20 ° C. for 1 hour to form a charge generation layer having a film thickness of 20 μm.
【００３６】得られた電子写真感光体を、常温常湿（２
０°Ｃ、５０％ＲＨ）の環境の中で、静電複写試験装置
（ＥＰＡ−８１００、川口電気（株）製）を用いて、−
６ＫＶのコロナ放電を行い、帯電させた後、タングステ
ンランプの光を、モノクロメーターを用いて８００ｎｍ
の単色光にし、感光体表面上で１μＷ／ｃｍ2 になるよ
うに調整し、照射した。そしてその表面電位が初期ＶO
（ボルト）の１／２になるまでの露光量Ｅ1/2 （ｅｒｇ
／ｃｍ2 ）を測定し、その後１０ルックスのタングステ
ン光を１秒間感光体表面上に照射し、残留電位ＶR を測
定した。さらに、上記の帯電、露光を１０００回繰り返
した後のＶO 、Ｅ1/2 、ＶR を測定した。その結果を表
１に示す。The obtained electrophotographic photosensitive member was subjected to normal temperature and normal humidity (2
Using an electrostatic copying tester (EPA-8100, manufactured by Kawaguchi Electric Co., Ltd.) in an environment of 0 ° C. and 50% RH,
After performing a 6 KV corona discharge and charging, the light of a tungsten lamp is used to 800 nm using a monochromator.
The monochromatic light was adjusted to 1 μW / cm 2 on the surface of the photoreceptor, and irradiation was performed. And the surface potential is the initial V O
Exposure amount to 1/2 of (volt) E 1/2 (erg
/ Cm 2 ), and then 10 lux of tungsten light was irradiated onto the surface of the photoconductor for 1 second to measure the residual potential V R. Further, after repeating the above charging and exposure 1000 times, V O , E 1/2 and V R were measured. The results are shown in Table 1.
【００３７】実施例４ 合成例３で得られたジクロロスズフタロシアニンを用い
た以外は、実施例３と同様にして感光体を作製し、評価
した。結果を表１に示す。また、ＣＧＬ塗布液を乾燥
し、粉末Ｘ線回折を測定したところ図９に示すように本
発明のジクロロスズフタロシアニンのＩ型結晶であっ
た。Example 4 A photoconductor was prepared and evaluated in the same manner as in Example 3 except that the dichlorotin phthalocyanine obtained in Synthesis Example 3 was used. The results are shown in Table 1. Further, the CGL coating solution was dried and powder X-ray diffraction was measured to find that it was an I-type crystal of dichlorotin phthalocyanine of the present invention as shown in FIG.
【００３８】比較例２ 比較例１で得られたジクロロスズフタロシアニンのＩ型
結晶を用いたほかは、実施例４と同様にして感光体を作
製し、評価した。結果を表１に示す。また、ＣＧＬ塗布
液を乾燥し、粉末Ｘ線回折を測定したところ図１０に示
すようにＩ型結晶のままであった。Comparative Example 2 A photoconductor was prepared and evaluated in the same manner as in Example 4 except that the type I crystal of dichlorotin phthalocyanine obtained in Comparative Example 1 was used. The results are shown in Table 1. Further, when the CGL coating liquid was dried and powder X-ray diffraction was measured, it remained as an I-type crystal as shown in FIG.
【００３９】比較例３〜５ ＣＧＬ塗布溶剤としてｎ−酢酸ブチルの代わりに、ｎ−
ブタノールを用い表１に示した顔料（電荷発生材）用い
た他は、実施例４と同様にして感光体を作製し、評価し
た。またそれぞれのＣＧＬ塗布液を乾燥し、粉末Ｘ線回
折を測定した。結果を表１にまとめた。Comparative Examples 3 to 5 Instead of n-butyl acetate as the CGL coating solvent, n-
A photoreceptor was prepared and evaluated in the same manner as in Example 4 except that butanol was used and the pigment (charge generating material) shown in Table 1 was used. Further, each CGL coating liquid was dried, and powder X-ray diffraction was measured. The results are summarized in Table 1.
【００４０】[0040]
【表１】 [Table 1]
【００４１】[0041]
【発明の効果】本発明によれば、簡単な処理で、ブラッ
グ角（２θ±０．２°）の２５°から３０°の範囲にお
いて、２８．２°に最も強い回折ピークを有するジクロ
ロスズフタロシアニンの新規な結晶が得られる。本発明
によって得られるジクロロスズフタロシアニン結晶は、
半導体レーザーを利用するプリンター等の電子写真感光
体用の光導電材料として非常に有用であり、得られた本
発明の電子写真感光体は、優れた感度および耐久性を有
している。According to the present invention, dichlorotin phthalocyanine having the strongest diffraction peak at 28.2 ° in a Bragg angle (2θ ± 0.2 °) range of 25 ° to 30 ° can be obtained by a simple treatment. A new crystal of is obtained. The dichlorotin phthalocyanine crystal obtained by the present invention,
It is very useful as a photoconductive material for an electrophotographic photoreceptor such as a printer using a semiconductor laser, and the obtained electrophotographic photoreceptor of the present invention has excellent sensitivity and durability.
【図１】 合成例１によって得られたジクロロスズフタ
ロシアニン結晶の粉末Ｘ線回折スペクトル図である。FIG. 1 is a powder X-ray diffraction spectrum diagram of a dichlorotin phthalocyanine crystal obtained in Synthesis Example 1.
【図２】 合成例２によって得られたジクロロスズフタ
ロシアニンのIII 型結晶の粉末Ｘ線回折スペクトル図で
ある。FIG. 2 is a powder X-ray diffraction spectrum diagram of a type III crystal of dichlorotin phthalocyanine obtained in Synthesis Example 2.
【図３】 合成例３によって得られたジクロロスズフタ
ロシアニンのIV型結晶の粉末Ｘ線回折スペクトル図であ
る。FIG. 3 is a powder X-ray diffraction spectrum diagram of a type IV crystal of dichlorotin phthalocyanine obtained in Synthesis Example 3.
【図４】 合成例４によって得られたジクロロスズフタ
ロシアニン結晶の粉末Ｘ線回折スペクトル図である。FIG. 4 is a powder X-ray diffraction spectrum diagram of a dichlorotin phthalocyanine crystal obtained in Synthesis Example 4.
【図５】 実施例１によって得られたジクロロスズフタ
ロシアニンのＩ型結晶の粉末Ｘ線回折スペクトル図であ
る。5 is a powder X-ray diffraction spectrum diagram of the I-type crystal of dichlorotin phthalocyanine obtained in Example 1. FIG.
【図６】 実施例２によって得られたジクロロスズフタ
ロシアニンのＩ型結晶の粉末Ｘ線回折スペクトル図であ
る。6 is a powder X-ray diffraction spectrum diagram of the I-type crystal of dichlorotin phthalocyanine obtained in Example 2. FIG.
【図７】 比較例１によって得られたジクロロスズフタ
ロシアニンのＩ型結晶の粉末Ｘ線回折スペクトル図であ
る。7 is a powder X-ray diffraction spectrum diagram of the I-type crystal of dichlorotin phthalocyanine obtained in Comparative Example 1. FIG.
【図８】 実施例３によって得られたジクロロスズフタ
ロシアニンのＩ型結晶の粉末Ｘ線回折スペクトル図であ
る。8 is a powder X-ray diffraction spectrum diagram of the I-type crystal of dichlorotin phthalocyanine obtained in Example 3. FIG.
【図９】 実施例４によって得られたジクロロスズフタ
ロシアニンのＩ型結晶の粉末Ｘ線回折スペクトル図であ
る。9 is a powder X-ray diffraction spectrum diagram of the I-type crystal of dichlorotin phthalocyanine obtained in Example 4. FIG.
【図１０】 比較例２及び５によって得られたジクロロ
スズフタロシアニンのＩ型結晶の粉末Ｘ線回折スペクト
ル図である。FIG. 10 is a powder X-ray diffraction spectrum diagram of I-type crystals of dichlorotin phthalocyanine obtained in Comparative Examples 2 and 5.
【図１１】 比較例３によって得られたジクロロスズフ
タロシアニン結晶の粉末Ｘ線回折スペクトル図である。11 is a powder X-ray diffraction spectrum diagram of the dichlorotin phthalocyanine crystal obtained in Comparative Example 3. FIG.
【図１２】 比較例４によって得られたジクロロスズフ
タロシアニン結晶の粉末Ｘ線回折スペクトル図である。12 is a powder X-ray diffraction spectrum diagram of the dichlorotin phthalocyanine crystal obtained in Comparative Example 4. FIG.
【図１３】ジクロロスズフタロシアニンのＩＩ型結晶の
粉末Ｘ線回折スペクトル図である。FIG. 13 is a powder X-ray diffraction spectrum diagram of a type II crystal of dichlorotin phthalocyanine.
【図１４】 合成例２によって得られたジクロロスズフ
タロシアニンのIII型結晶の熱重量分析図である。FIG. 14 is a thermogravimetric analysis chart of the type III crystal of dichlorotin phthalocyanine obtained in Synthesis Example 2.
【図１５】 合成例３によって得られたジクロロスズフ
タロシアニンのIV型結晶の熱重量分析図である。FIG. 15 is a thermogravimetric analysis diagram of the type IV crystal of dichlorotin phthalocyanine obtained in Synthesis Example 3.
【図１６】 実施例１によって得られたジクロロスズフ
タロシアニンのI 型結晶の熱重量分析図である。16 is a thermogravimetric analysis diagram of the I-type crystal of dichlorotin phthalocyanine obtained in Example 1. FIG.
─────────────────────────────────────────────────────
─────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成４年１１月９日[Submission date] November 9, 1992
【手続補正１】[Procedure Amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００３６[Correction target item name] 0036
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００３６】得られた電子写真感光体を、常温常湿（２
０℃、４０％ＲＨ）の環境の中で、静電複写試験装置
（ＥＰＡ−８１００、川口電気（株）製）を用いて、−
６ＫＶのコロナ放電を行い、帯電させた後、タングステ
ンランプの光を、モノクロメーターを用いて８００ｎｍ
の単色光にし、感光体表面上で１μＷ／ｃｍ2 になるよ
うに調整し、照射した。そしてその表面電位が初期Ｖ0
（ボルト）の１／２になるまでの露光量Ｅ1/2 （ｅｒｇ
／ｃｍ2 ）を測定し、その後１０ルックスのタングステ
ン光を１秒間感光体表面上に照射し、残留電位ＶR を測
定した。さらに、上記の帯電、露光を１０００回繰り返
した後のＶ0 、Ｅ1/2 、ＶR を測定した。その結果を表
１に示す。The obtained electrophotographic photosensitive member was subjected to normal temperature and normal humidity (2
Using an electrostatic copying tester (EPA-8100, manufactured by Kawaguchi Electric Co., Ltd.) in an environment of 0 ° C. and 40 % RH,
After performing a 6 KV corona discharge and charging, the light of a tungsten lamp is used to 800 nm using a monochromator.
The monochromatic light was adjusted to 1 μW / cm 2 on the surface of the photoreceptor, and irradiation was performed. Then, the surface potential is the initial V 0.
Exposure amount to 1/2 of (volt) E 1/2 (erg
/ Cm 2 ), and then 10 lux of tungsten light was irradiated onto the surface of the photoconductor for 1 second to measure the residual potential V R. Further, V 0 , E 1/2 and V R were measured after the above charging and exposure were repeated 1000 times. The results are shown in Table 1.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 大門 克己 神奈川県南足柄市竹松1600番地 富士ゼロ ツクス株式会社竹松事業所内 (72)発明者 飯島 正和 神奈川県南足柄市竹松1600番地 富士ゼロ ツクス株式会社竹松事業所内 (72)発明者 真下 清和 神奈川県南足柄市竹松1600番地 富士ゼロ ツクス株式会社竹松事業所内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Katsumi Daimon 1600 Takematsu, Minamiashigara-shi, Kanagawa Fuji Zero Tsux Co., Ltd. Takematsu Plant (72) Inventor Masakazu Iijima 1600 Takematsu, Minamiashigara-shi, Kanagawa Fujizero Tsukus Corporation Takematsu Business In-house (72) Inventor Seiwa Mashita 1600 Takematsu, Minamiashigara City, Kanagawa Prefecture Fuji Zero Tsukusu Co., Ltd. Takematsu Office
Claims (4)
角（２θ±０．２°）＝８．７°、９．９°、１０．９
°、１３．１°、１５．２°、１６．３°、１７．４
°、２１．９°、２５．５°に強い回折ピークを有する
ジクロロスズフタロシアニン結晶、または、ブラッグ角
（２θ±０．２°）＝９．２°、１２．２°、１３．４
°、１４．６°、１７．０°、２５．３°に強い回折ピ
ークを有するジクロロスズフタロシアニン結晶を、有機
溶剤中で処理し、ブラッグ角（２θ±０．２°）の２５
°から３０°の範囲において、２８．２°に最も強い回
折ピークを有するジクロロスズフタロシアニン結晶に転
移させることを特徴とするブラッグ角（２θ±０．２
°）の２５°から３０°の範囲において、２８．２°に
最も強い回折ピークを有するジクロロスズフタロシアニ
ン結晶の製造方法。1. In X-ray diffraction spectrum, Bragg angle (2θ ± 0.2 °) = 8.7 °, 9.9 °, 10.9
°, 13.1 °, 15.2 °, 16.3 °, 17.4
Dichlorotin phthalocyanine crystal having strong diffraction peaks at 2 °, 21.9 °, 25.5 °, or Bragg angle (2θ ± 0.2 °) = 9.2 °, 12.2 °, 13.4
Dichlorotin phthalocyanine crystals having strong diffraction peaks at °, 14.6 °, 17.0 °, and 25.3 ° were treated in an organic solvent to give a Bragg angle (2θ ± 0.2 °) of 25.
In the range of 30 ° to 30 °, the Bragg angle (2θ ± 0.2) is characterized in that the crystal is transferred to the dichlorotin phthalocyanine crystal having the strongest diffraction peak at 28.2 °.
The production method of the dichlorotin phthalocyanine crystal having the strongest diffraction peak at 28.2 ° in the range of 25 ° to 30 °.
特徴とする請求項１記載のブラッグ角（２θ±０．２
°）の２５°から３０°の範囲において、２８．２°に
最も強い回折ピークを有するジクロロスズフタロシアニ
ン結晶の製造方法。2. The Bragg angle (2θ ± 0.2) according to claim 1, wherein the organic solvent contains a binder resin.
The production method of the dichlorotin phthalocyanine crystal having the strongest diffraction peak at 28.2 ° in the range of 25 ° to 30 °.
を特徴とする請求項１記載のブラッグ角（２θ±０．２
°）の２５°から３０°の範囲において、２８．２°に
最も強い回折ピークを有するジクロロスズフタロシアニ
ン結晶の製造方法。3. The Bragg angle (2θ ± 0.2) according to claim 1, wherein the organic solvent is an acetic acid ester.
The production method of the dichlorotin phthalocyanine crystal having the strongest diffraction peak at 28.2 ° in the range of 25 ° to 30 °.
グ角（２θ±０．２°）の２５°から３０°の範囲にお
いて、２８．２°に最も強い回折ピークを有するジクロ
ロスズフタロシアニン結晶を含有する感光層を設けてな
ることを特徴とする電子写真感光体。4. A dichlorotin phthalocyanine having a strongest diffraction peak at 28.2 ° in a Bragg angle (2θ ± 0.2 °) range of 25 ° to 30 ° according to claim 1 on a conductive support. An electrophotographic photoreceptor comprising a photosensitive layer containing crystals.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03326721A JP3092270B2 (en) | 1991-11-15 | 1991-11-15 | Method for producing novel dichlorotin phthalocyanine crystal and electrophotographic photoreceptor using the crystal |
| US07/874,093 US5283145A (en) | 1991-05-01 | 1992-04-27 | Crystals of dichlorotin phthalocyanine, method of preparing the crystal, and electrophotographic photoreceptor comprising the crystal |
| US07/927,961 US5308728A (en) | 1991-08-16 | 1992-08-11 | Dichlorotin phthalocyanine crystal, process for producing the same, and electrophotographic photoreceptor using the same |
| US08/144,012 US5416207A (en) | 1991-08-16 | 1993-11-01 | Dichlorotin phthalocyanine crystal, process for producing the same, and electrophotographic photoreceptor using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03326721A JP3092270B2 (en) | 1991-11-15 | 1991-11-15 | Method for producing novel dichlorotin phthalocyanine crystal and electrophotographic photoreceptor using the crystal |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05140472A true JPH05140472A (en) | 1993-06-08 |
| JP3092270B2 JP3092270B2 (en) | 2000-09-25 |
Family
ID=18190938
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP03326721A Expired - Fee Related JP3092270B2 (en) | 1991-05-01 | 1991-11-15 | Method for producing novel dichlorotin phthalocyanine crystal and electrophotographic photoreceptor using the crystal |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3092270B2 (en) |
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-
1991
- 1991-11-15 JP JP03326721A patent/JP3092270B2/en not_active Expired - Fee Related
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