EP0233544A2 - Electrophotographical toner - Google Patents
Electrophotographical toner Download PDFInfo
- Publication number
- EP0233544A2 EP0233544A2 EP87101463A EP87101463A EP0233544A2 EP 0233544 A2 EP0233544 A2 EP 0233544A2 EP 87101463 A EP87101463 A EP 87101463A EP 87101463 A EP87101463 A EP 87101463A EP 0233544 A2 EP0233544 A2 EP 0233544A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- alkyl
- single bond
- ethyl
- benzyl
- alkylene
- 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
- 150000001450 anions Chemical class 0.000 claims abstract description 13
- 239000000654 additive Substances 0.000 claims abstract description 9
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims abstract description 8
- 239000002245 particle Substances 0.000 claims abstract description 8
- 229920005989 resin Polymers 0.000 claims abstract description 7
- 239000011347 resin Substances 0.000 claims abstract description 7
- 125000002091 cationic group Chemical group 0.000 claims abstract description 6
- 230000000996 additive effect Effects 0.000 claims abstract description 5
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims abstract description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 4
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 4
- 239000000460 chlorine Substances 0.000 claims abstract description 4
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 4
- 239000001257 hydrogen Substances 0.000 claims abstract description 4
- 239000000049 pigment Substances 0.000 claims abstract description 4
- 125000006833 (C1-C5) alkylene group Chemical group 0.000 claims abstract description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract 2
- 150000001875 compounds Chemical class 0.000 claims description 22
- -1 carbamoylmethyl Chemical group 0.000 claims description 18
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 12
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 claims description 3
- 230000002708 enhancing effect Effects 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 239000007859 condensation product Substances 0.000 claims description 2
- 150000008052 alkyl sulfonates Chemical class 0.000 claims 1
- 229940077388 benzenesulfonate Drugs 0.000 claims 1
- 150000003949 imides Chemical class 0.000 claims 1
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 abstract description 4
- 125000006702 (C1-C18) alkyl group Chemical group 0.000 abstract description 2
- 125000000229 (C1-C4)alkoxy group Chemical group 0.000 abstract description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 13
- 239000000126 substance Substances 0.000 description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 7
- 239000002244 precipitate Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 5
- ZLXYCAQGOXUPPI-UHFFFAOYSA-N n-[3-(dimethylamino)propyl]naphthalene-1-carboxamide Chemical compound C1=CC=C2C(C(=O)NCCCN(C)C)=CC=CC2=C1 ZLXYCAQGOXUPPI-UHFFFAOYSA-N 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 229920005992 thermoplastic resin Polymers 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-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
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- 108091008695 photoreceptors Proteins 0.000 description 3
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000004809 thin layer chromatography Methods 0.000 description 3
- LPMANECYGPQBOX-UHFFFAOYSA-N 2-chloro-n-(2-methylphenyl)acetamide Chemical compound CC1=CC=CC=C1NC(=O)CCl LPMANECYGPQBOX-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical class OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910000464 lead oxide Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 229920000151 polyglycol Polymers 0.000 description 2
- 239000010695 polyglycol Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 229910052711 selenium Inorganic materials 0.000 description 2
- 239000011669 selenium Substances 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- OQMIRQSWHKCKNJ-UHFFFAOYSA-N 1,1-difluoroethene;1,1,2,3,3,3-hexafluoroprop-1-ene Chemical group FC(F)=C.FC(F)=C(F)C(F)(F)F OQMIRQSWHKCKNJ-UHFFFAOYSA-N 0.000 description 1
- AQXYVFBSOOBBQV-UHFFFAOYSA-N 1-amino-4-hydroxyanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(O)=CC=C2N AQXYVFBSOOBBQV-UHFFFAOYSA-N 0.000 description 1
- HNTGIJLWHDPAFN-UHFFFAOYSA-N 1-bromohexadecane Chemical compound CCCCCCCCCCCCCCCCBr HNTGIJLWHDPAFN-UHFFFAOYSA-N 0.000 description 1
- FKNIDKXOANSRCS-UHFFFAOYSA-N 2,3,4-trinitrofluoren-1-one Chemical compound C1=CC=C2C3=C([N+](=O)[O-])C([N+]([O-])=O)=C([N+]([O-])=O)C(=O)C3=CC2=C1 FKNIDKXOANSRCS-UHFFFAOYSA-N 0.000 description 1
- FBNAYEYTRHHEOB-UHFFFAOYSA-N 2,3,5-triphenyl-1,3-dihydropyrazole Chemical compound N1N(C=2C=CC=CC=2)C(C=2C=CC=CC=2)C=C1C1=CC=CC=C1 FBNAYEYTRHHEOB-UHFFFAOYSA-N 0.000 description 1
- TXWSZJSDZKWQAU-UHFFFAOYSA-N 2,9-dimethyl-5,12-dihydroquinolino[2,3-b]acridine-7,14-dione Chemical compound N1C2=CC=C(C)C=C2C(=O)C2=C1C=C(C(=O)C=1C(=CC=C(C=1)C)N1)C1=C2 TXWSZJSDZKWQAU-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- USZXSOMZYDRNPS-UHFFFAOYSA-N 2-benzylidenecarbazol-1-amine Chemical compound NC1=C2N=C3C=CC=CC3=C2C=CC1=CC1=CC=CC=C1 USZXSOMZYDRNPS-UHFFFAOYSA-N 0.000 description 1
- WYCOJIVDCGJKDB-UHFFFAOYSA-N 3,4-dimethylbenzenesulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1C WYCOJIVDCGJKDB-UHFFFAOYSA-N 0.000 description 1
- NLWWHMRHFRTAII-UHFFFAOYSA-N 4-(1,3-benzoxazol-2-yl)-n,n-dimethylaniline Chemical compound C1=CC(N(C)C)=CC=C1C1=NC2=CC=CC=C2O1 NLWWHMRHFRTAII-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- WUMNREMXKHAYJQ-UHFFFAOYSA-N 5-methyl-2,3-diphenyl-1,3-dihydropyrazole Chemical compound N1C(C)=CC(C=2C=CC=CC=2)N1C1=CC=CC=C1 WUMNREMXKHAYJQ-UHFFFAOYSA-N 0.000 description 1
- XCKGFJPFEHHHQA-UHFFFAOYSA-N 5-methyl-2-phenyl-4-phenyldiazenyl-4h-pyrazol-3-one Chemical compound CC1=NN(C=2C=CC=CC=2)C(=O)C1N=NC1=CC=CC=C1 XCKGFJPFEHHHQA-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 0 C*1CC(CCC=C2C(*(C3O)I)O)=C2C3=CC1 Chemical compound C*1CC(CCC=C2C(*(C3O)I)O)=C2C3=CC1 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229920002449 FKM Polymers 0.000 description 1
- 239000004425 Makrolon Substances 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000001825 Polyoxyethene (8) stearate Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- WBFMCDAQUDITAS-UHFFFAOYSA-N arsenic triselenide Chemical compound [Se]=[As][Se][As]=[Se] WBFMCDAQUDITAS-UHFFFAOYSA-N 0.000 description 1
- 125000005228 aryl sulfonate group Chemical group 0.000 description 1
- XJHABGPPCLHLLV-UHFFFAOYSA-N benzo[de]isoquinoline-1,3-dione Chemical class C1=CC(C(=O)NC2=O)=C3C2=CC=CC3=C1 XJHABGPPCLHLLV-UHFFFAOYSA-N 0.000 description 1
- SESFRYSPDFLNCH-UHFFFAOYSA-N benzyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OCC1=CC=CC=C1 SESFRYSPDFLNCH-UHFFFAOYSA-N 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
- YQGOJNYOYNNSMM-UHFFFAOYSA-N eosin Chemical compound [Na+].OC(=O)C1=CC=CC=C1C1=C2C=C(Br)C(=O)C(Br)=C2OC2=C(Br)C(O)=C(Br)C=C21 YQGOJNYOYNNSMM-UHFFFAOYSA-N 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- MOUPNEIJQCETIW-UHFFFAOYSA-N lead chromate Chemical compound [Pb+2].[O-][Cr]([O-])(=O)=O MOUPNEIJQCETIW-UHFFFAOYSA-N 0.000 description 1
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- XLGSXVUJWBCURQ-UHFFFAOYSA-N n-(4-bromophenyl)-1-(2-nitrophenyl)methanimine Chemical compound [O-][N+](=O)C1=CC=CC=C1C=NC1=CC=C(Br)C=C1 XLGSXVUJWBCURQ-UHFFFAOYSA-N 0.000 description 1
- DWXAPYADWDBIII-UHFFFAOYSA-N n-[[4-(dimethylamino)phenyl]methylideneamino]benzamide Chemical compound C1=CC(N(C)C)=CC=C1C=NNC(=O)C1=CC=CC=C1 DWXAPYADWDBIII-UHFFFAOYSA-N 0.000 description 1
- VKWNTWQXVLKCSG-UHFFFAOYSA-N n-ethyl-1-[(4-phenyldiazenylphenyl)diazenyl]naphthalen-2-amine Chemical compound CCNC1=CC=C2C=CC=CC2=C1N=NC(C=C1)=CC=C1N=NC1=CC=CC=C1 VKWNTWQXVLKCSG-UHFFFAOYSA-N 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- GJVFBWCTGUSGDD-UHFFFAOYSA-L pentamethonium bromide Chemical compound [Br-].[Br-].C[N+](C)(C)CCCCC[N+](C)(C)C GJVFBWCTGUSGDD-UHFFFAOYSA-L 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- XOSXWYQMOYSSKB-LDKJGXKFSA-L water blue Chemical compound CC1=CC(/C(\C(C=C2)=CC=C2NC(C=C2)=CC=C2S([O-])(=O)=O)=C(\C=C2)/C=C/C\2=N\C(C=C2)=CC=C2S([O-])(=O)=O)=CC(S(O)(=O)=O)=C1N.[Na+].[Na+] XOSXWYQMOYSSKB-LDKJGXKFSA-L 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/097—Plasticisers; Charge controlling agents
- G03G9/09733—Organic compounds
- G03G9/09741—Organic compounds cationic
Definitions
- R 1 and R 2 are preferably hydrogen.
- C 1 -C 5 alkylene radicals A can be straight-chain or branched.
- C 2 -C S -alkylene radicals and especially the n-propylene radical are preferred.
- Preferred alkyl radicals R 3 are C 1 -C 16 alkyl radicals.
- anions such as halides, for example chloride, bromide and iodide. Tetrafluoroborates and anions of alkyl and aryl sulfonic acids, carboxylic acids, phosphoric acids and phosphonic acids are suitable.
- Anions which lower the water solubility of the compounds (I) and at the same time increase the solubility in organic solvents such as dimethylformamide, acetone, chloroform or toluene are particularly suitable.
- the water solubility can also be reduced by increasing the alkyl radical R 3 , that is to say choosing it in the range of C 5 -C 16 alkyl. In this case, more hydrophilic anions such as halides are also very suitable.
- preferred water solubility of the compounds (I) at 20 ° C. is less than 3% by weight, in particular less than 1% by weight.
- preferred anions are, in particular, aryl sulfonates, such as benzenesulfonates optionally substituted by C 1 -C 12 -alkyl or chlorine, C 5 -C 18 alkyl sulfates, salts of C 5 -C 18 alkyl carboxylic acids and of condensation products of formaldehyde and aryl sulfonic acids and / or optionally sulfonated 4,4'-dihydroxydiphenyl sulfone,
- the compounds of formula (I) can be prepared by known methods, e.g. according to the processes described in DE-A 35 35496.
- the connections themselves are mostly known.
- Charge enhancing additives for electrophotographic toners also called charge control substances, are already known. They are described, for example, in U.S. Patent Nos. 3,893,935, 3,944,493, 4,007,293, 4,079,014, 4,298,672, 4,338,390, 4,394,430 and 4,493,883.
- Latent electrostatic image recordings are developed by inductively depositing the toner on the electrostatic image.
- the charge control substances increase the cationic charge of the toner. This makes the image more vivid and sharper.
- the substances (I) are very suitable as charge control substances in toners.
- the compounds (I) result in a significant increase in the color depth of the developed image and an improvement in the sharpness of the image.
- Another advantage is the much better pH stability, which makes both the production of the compounds and the toner preparations easier.
- the resins contained in the toners are known. They are thermoplastic and have a softening point between 50 and 130 ° C, preferably between 65 and 115 ° C.
- examples of such resins include polystyrene, copolymers of styrene with an acrylate or methacrylate, copolymers of styrene with butadiene and / or acrylonitrile, polyacrylates and polymethacrylates, copolymers of an acrylate or methacrylate with vinyl chloride or vinyl acetate, polyvinyl chloride, copolymers of vinyl chloride with vinylidene chloride, copolymers of Vinyl chloride with vinyl acetate, polyester resins (U.S. Patent 3,590,000), epoxy resins, polyamides and polyurethanes.
- the toners of the present invention contain coloring materials and magnetically attractable material in known amounts.
- the magnetically attractable material can, for example, consist of iron, nickel, chromium oxide, iron oxide or a ferrite of the general formula MFe 2 0 4 , where M is a divalent metal, such as iron, cobalt, zinc, nickel or manganese.
- the toners containing the compounds (I) are prepared by customary processes, e.g. by melting the thermoplastic resin or a mixture of the thermoplastic resins, then finely dividing one or more charge control substances of formula (I), as well as the other additives, if used, into the melted resin using the mixing and kneading machinery known for this purpose Cooling the melt to a solid mass and finally grinding the solid mass into particles of the desired particle size. It is also possible to dissolve the thermoplastic resin and the compound (I) in a common solvent, to incorporate the other additives into the solution and then to spray-dry the liquid in a manner known per se or to evaporate off the solvent or solvents and to add the solid residue To grind particles of the desired particle size. According to a modification of this manufacturing process, the charge control substance of the formula (I) is not dissolved, but finely dispersed in the solution of the thermoplastic resin.
- the toner preparation thus obtained is then used in a xerographic image recording system, for example analogously to US Pat. No. 4,265,990.
- the photoreceptors used for this must have the ability to charge negatively. Examples are those also described in U.S. Patent 4,265,990.
- punches contain: 4-dimethylaminobenzylidene-benzhydrazide, polyvinyl carbazole, 2-benzylidene-aminocarbazole, 2-nitrobenzylidene-p-bromoaniline, 2,4-diphenylehinazoline, 1,5-diphenyl-3-methyl-pyrazoline, 1,3,5-triphenylpyrazoline , Charge transfer complex of polyvinyl carbazole and trinitrofluorenone, 2- (4'-dimethylaminophenyl) benzoxazole, selenium, tellurium and arsenic triselenide.
- the photoreceptors used can also contain sensitizing dyes such as Bengal pink or Eosin G in the charge-generating layer.
- the photoreceptors may contain diamines, as also specified in U.S. Patent 4,265,990.
- the invention also relates to the compounds of the formula (II).
- the substance is practically pure by thin layer chromatography.
- 1 shows fluorescence quenching on the fluorescent silica gel plate.
- Rf value 0.3 (mobile solvent: 45% by volume of butyl acetate, 33% by volume of glacial acetic acid, 9% by volume of formic acid and 13% by volume of water).
- the substance is practically pure by thin layer chromatography.
- the substance is completely pure by thin layer chromatography. It melts at 220-221 ° C.
- 408 g (98% of theory) of the compound of the formula are obtained 408 g (1 mol) of the compound obtained (35 A) are dissolved in 4 l of water at room temperature and 1 l of a 40% aqueous solution of a polycondensation product of sulfonated 4,4'-dihydroxydiphenyl sulfone and formaldehyde is added dropwise while stirring. The crystalline precipitate is filtered off, washed with water and dried at 50 ° C in a vacuum.
- This toner formulation is incorporated into a xerographic imaging system as described in U.S. Patent 4,265,990.
- the procedure for this is to provide a MYLAR® substrate with a charge-generating layer of polyvinylcarbazole in which trigonal selenium is freely dispersed, and a transparent charge-transporting layer is applied over it, which acts as charge-transporting molecules N, N'-diphenyl -N, N'-bis- (3-methylphenyl) -1,1 ⁇ -bisphenyl-4,4'-diamine, dispersed in a MAKROLON® polycarbonate composition.
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Abstract
Positive geladene elektrophotographische Toner enthalten neben üblichen Harz- und Pigmentpartikeln ein die kationische Ladung verstärkendes Additiv der allgemeinen Formel <IMAGE> worin R¹ und R² je für Wasserstoff, Chlor, Brom, Hydroxy, C1-C4-Alkoxy, oder Carboxy, A für C1-C5-Alkylen oder -C6H4-CH2- (m oder p), m für 0 oder 1 n für 1 oder 2 <IMAGE> R³ für C1-C18-Alkyl, Carbamoyl-C1-C2-alkyl, C1-C4-Alkoxycarbonyl-C1-C2-alkyl, Benzyl, Cyclohexyl oder Allyl, R<4> für C1-C4-Alkyl oder eine an D anknüpfende Einfachbindung, R<5> für C1-C4-Alkyl, D für -CH2-, -CH2-CO-, -CH2-CO-NH- oder -CH2-CO-NH-CH2- <IMAGE> oder eine Einfachbindung und An<o> für ein Anion stehen.In addition to conventional resin and pigment particles, positively charged electrophotographic toners contain a cationic charge-increasing additive of the general formula <IMAGE> in which R¹ and R² each represent hydrogen, chlorine, bromine, hydroxyl, C1-C4-alkoxy, or carboxy, A for C1- C5-alkylene or -C6H4-CH2- (m or p), m for 0 or 1 n for 1 or 2 <IMAGE> R³ for C1-C18-alkyl, carbamoyl-C1-C2-alkyl, C1-C4-alkoxycarbonyl- C1-C2-alkyl, benzyl, cyclohexyl or allyl, R <4> for C1-C4-alkyl or a single bond linking to D, R <5> for C1-C4-alkyl, D for -CH2-, -CH2-CO -, -CH2-CO-NH- or -CH2-CO-NH-CH2- <IMAGE> or a single bond and An <o> stand for an anion.
Description
Gegenstand der Erfindung sind positiv geladene elektrophotographische Toner, die neben üblichen Harz- und Pigmentpartikeln ein die kationische Ladung verstärkendes Additiv der allgemeinen Formel
worin
- R 1 und R2 je für Wasserstoff, Chlor, Brom, Hydroxy, C1-C4-Alkoxy, oder Carboxy,
- A für C1-C5-Alkylen oder -C6H4-CH2- (m oder p), m für O oder 1
- n für 1 oder 2
- ⊕
- K für
- R3 für C1-C18-Alkyl, Carbamoyl-C1-C2-alkylg C1-C4-Alkoxycarbonyl-C1-C2-alkyl, Benzyl, Cyclohexyl oder Allyl,
- R4 für C1-C4-Alkyl oder eine an D anknüpfende Einfachbindung,
- R 5 für C1-C4-Alkyl,
- D für -CH2-, -CH2-CO-, -CH2-CO-NH- oder -CH2-CO-NH-CH2-
- W für
- Z für
wherein
- R 1 and R 2 each represent hydrogen, chlorine, bromine, hydroxy, C 1 -C 4 alkoxy or carboxy,
- A for C 1 -C 5 alkylene or -C 6 H 4 -CH 2 - (m or p), m for O or 1
- n for 1 or 2
- ⊕
- K for
- R 3 is C 1 -C 18 alkyl, carbamoyl-C 1 -C 2 alkylg C 1 -C 4 alkoxycarbonyl-C 1 -C 2 alkyl, benzyl, cyclohexyl or allyl,
- R 4 is C 1 -C 4 alkyl or a single bond linking to D,
- R 5 is C 1 -C 4 alkyl,
- D for -CH 2 -, -CH 2 -CO-, -CH 2 -CO-NH- or -CH 2 -CO-NH-CH 2 -
- W for
- Z for
An(-) für ein Anion stehen,
die Verwendung der Verbindungen (I) in elektrographischen Tonern und neue Naphthalsäureimid-Derivate.At (-) stand for an anion,
the use of the compounds (I) in electrographic toners and new naphthalimide derivatives.
Bevorzugt bedeuten R1 und R2 Wasserstoff.R 1 and R 2 are preferably hydrogen.
C1-C5-Alkylenreste A können geradkettig oder verzweigt sind. Dabei sind C2-CS-Alkylenreste und besonders der n-Propylenrest bevorzugt.C 1 -C 5 alkylene radicals A can be straight-chain or branched. C 2 -C S -alkylene radicals and especially the n-propylene radical are preferred.
Bevorzugte Alkylreste R3 sind C1-C16-Alkylreste.Preferred alkyl radicals R 3 are C 1 -C 16 alkyl radicals.
Als Anionen sind übliche Anionen wie Halogenide, z.B. Chlorid, Bromid und Jodid. Tetrafluoroborate und Anionen von Alkyl- und Aryl-sulfonsäuren, -carbonsäuren, -phosphorsäuren und -phosphonsäuren geeignet. Besonders geeignet sind solche Anionen, die die Wasserlöslichkeit der Verbindungen (I) erniedrigen und gleichzeitig die Löslichkeit in organischen Lösungsmitteln wie Dimethylformamid, Aceton, Chloroform oder Toluol erhöhen. Die Verminderung der Wasserlöslichkeit kann aber auch dadurch erfolgen, daß man den Alkylrest R3 vergrößert, also etwa im Bereich von C5-C16-Alkyl wählt. In diesem Falle sind auch hydrophilere Anionen wie Halogenide bestens geeignet.The usual anions are anions, such as halides, for example chloride, bromide and iodide. Tetrafluoroborates and anions of alkyl and aryl sulfonic acids, carboxylic acids, phosphoric acids and phosphonic acids are suitable. Anions which lower the water solubility of the compounds (I) and at the same time increase the solubility in organic solvents such as dimethylformamide, acetone, chloroform or toluene are particularly suitable. However, the water solubility can also be reduced by increasing the alkyl radical R 3 , that is to say choosing it in the range of C 5 -C 16 alkyl. In this case, more hydrophilic anions such as halides are also very suitable.
Die bevorzugte Wasserlöslichkeit der Verbindungen (I) bei 20°C liegt bei unter 3 Gew.X, insbesondere unter 1 Gew.%. Bevorzugte Anionen sind außer Halogeniden und Tetrafluoroboraten insbesondere Arylsulfonate wie gegebenenfalls durch Ci-C12-Alkyl oder Chlor substituierte Benzolsulfonate, C5-C18-Alkylaulfcnate, Salze von C5-C18-Alkylcarbon- säuren und von Kondensationsprodukten aus Formaldehyd und Arylsulfonsäuren und/oder gegebenenfalls sulfoniertem 4,4'-Dihydroxydiphenylsulfon,The preferred water solubility of the compounds (I) at 20 ° C. is less than 3% by weight, in particular less than 1% by weight. In addition to halides and tetrafluoroborates, preferred anions are, in particular, aryl sulfonates, such as benzenesulfonates optionally substituted by C 1 -C 12 -alkyl or chlorine, C 5 -C 18 alkyl sulfates, salts of C 5 -C 18 alkyl carboxylic acids and of condensation products of formaldehyde and aryl sulfonic acids and / or optionally sulfonated 4,4'-dihydroxydiphenyl sulfone,
Bevorzugte Verbindungen der Formel (I) entsprechen der Formel
- A1 für C2-C5-Alkylen,
- e
- K1 für
- R6 für C1-C16-Alkyl, Carbamoylmethyl oder Benzyl,
- R7 für Methyl oder Ethyl oder eine an D anknüpfende Einfachbindung,
- R8 für Methyl oder Ethyl,
- W1 für
- Z1 für
- X für ein Anion stehen, und
- D, m und n die gleiche Bedeutung wie in Formel (I) besitzen.
- A 1 for C 2 -C 5 alkylene,
- e
- K 1 for
- R 6 is C 1 -C 16 alkyl, carbamoylmethyl or benzyl,
- R 7 represents methyl or ethyl or a single bond linked to D,
- R 8 represents methyl or ethyl,
- W 1 for
- Z 1 for
- X stands for an anion, and
- D, m and n have the same meaning as in formula (I).
Die Verbindungen der Formel (I) können nach bekannten Methoden, z.B. nach den in DE-A 35 35496 beschriebenen Verfahren, hergestellt werden. Die Verbindungen selbst sind größtenteils bekannt.The compounds of formula (I) can be prepared by known methods, e.g. according to the processes described in DE-A 35 35496. The connections themselves are mostly known.
Ladungsverstärkende Additive für elektrophotographische Toner, auch Ladungskontroll-Substanzen genannt, sind bereits bekannt. Sie werden beispielsweise in der US-PS 3 893 935, 3 944 493, 4 007 293, 4 079 014, 4 298 672, 4 338 390, 4 394 430 und 4 493 883 beschrieben.Charge enhancing additives for electrophotographic toners, also called charge control substances, are already known. They are described, for example, in U.S. Patent Nos. 3,893,935, 3,944,493, 4,007,293, 4,079,014, 4,298,672, 4,338,390, 4,394,430 and 4,493,883.
Latente elektrostatische Bildaufzeichnungen werden dadurch entwickelt, daß der Toner auf dem elektrostatischen Bild induktiv abgeschieden wird. Die Ladungskontrollsubstanzen verstärken die kationische Ladung des Toners. Dadurch wird das Bild kräftiger und konturenschärfer.Latent electrostatic image recordings are developed by inductively depositing the toner on the electrostatic image. The charge control substances increase the cationic charge of the toner. This makes the image more vivid and sharper.
Derartige Ladungskontrollsubstanzen müssen vielseitige Anforderungen erfüllen.Such charge control substances have to meet diverse requirements.
- 1. Fähigkeit zur Entwicklung des latenten elektrostatischen Bildes zu einem farbstarken sichtbaren Bild.1. Ability to develop the latent electrostatic image into a highly visible color image.
- 2. Leichte Verteilbarkeit in der Tonerzubereitung und gleichmäßige Verteilung auf der Bildoberfläche, um ein störungsfreies, konturenacharfes, gleichförmiges Bild zu erzeugen.2. Easily distributable in the toner preparation and evenly distributed on the image surface in order to produce a trouble-free, contour-accurate, uniform image.
- 3. Unempfindlichkeit gegen Feuchtigkeit.3. Insensitivity to moisture.
- 4. Hohe Thermostabilitat.4. High thermal stability.
- 5. Beständigkeit gegenüber der heißen Mischung aus Bleioxid und einem Vinylidenfluorid-Hexafluoropropylen-Copolymerisat-Harz (z.B. VITON®E-430 von Dupont), mit der das Bild mit Hilfe einer heißen Walze fixiert werden kann. Die Beschichtungsmasse darf sich nicht durch Zersetzungsprodukte schwarz färben.5. Resistance to the hot mixture of lead oxide and a vinylidene fluoride-hexafluoropropylene copolymer resin (e.g. VITON®E-430 from Dupont), with which the image can be fixed with the help of a hot roller. The coating material must not turn black due to decomposition products.
- 6. Ungiftigkeit.6. Non-toxicity.
Die aus den obengenannten US-Patentschriften bekannten Ladungskontrollsubstanzen erfüllen bei weitem nicht alle diese Anforderungen.The charge control substances known from the above-mentioned US patents do not meet all of these requirements by far.
Überraschenderweise zeigte sich nun, daß sich die Substanzen (I) sehr gut als Ladungskontrollsubstanzen in Tonern eignen. Gegenüber den aus der US-PS 4 493 883 bekannten kationischen Phthalimidoverbindungen ergeben die Verbindungen (I) eine deutliche Steigerung der Farbtiefe des entwickelten Bildes und eine Verbesserung der Bildschärfe. Ein weiterer Vorteil ist die wesentlich bessere pH-Stabilität, die sowohl die Herstellung der Verbindungen als auch der Toner-Zubereitungen problemloser gestaltet.Surprisingly, it has now been shown that the substances (I) are very suitable as charge control substances in toners. Compared to the cationic phthalimido compounds known from US Pat. No. 4,493,883, the compounds (I) result in a significant increase in the color depth of the developed image and an improvement in the sharpness of the image. Another advantage is the much better pH stability, which makes both the production of the compounds and the toner preparations easier.
Die in den Tonern enthaltenen Harze sind bekannt. Sie sind thermoplastisch und haben einen Erweichungspunkt zwischen 50 und 130°C, vorzugsweise zwischen 65 und 115°C. Beispiele für derartige Harze umfassen Polystyrol, Copolymere von Styrol mit einem Acrylat oder Methacrylat, Copolymere von Styrol mit Butadien und/oder Acrylnitril, Polyacrylate und Polymethacrylate, Copolymere eines Acrylates oder Methacrylats mit Vinylchlorid oder Vinylacetat, Polyvinylchlorid, Copolymere von Vinylchlorid mit Vinylidenchlorid, Copolymere von Vinylchlorid mit Vinylacetat, Polyesterharze (US-PS 3 590 000), Epoxyharze, Polyamide und Polyurethane.The resins contained in the toners are known. They are thermoplastic and have a softening point between 50 and 130 ° C, preferably between 65 and 115 ° C. Examples of such resins include polystyrene, copolymers of styrene with an acrylate or methacrylate, copolymers of styrene with butadiene and / or acrylonitrile, polyacrylates and polymethacrylates, copolymers of an acrylate or methacrylate with vinyl chloride or vinyl acetate, polyvinyl chloride, copolymers of vinyl chloride with vinylidene chloride, copolymers of Vinyl chloride with vinyl acetate, polyester resins (U.S. Patent 3,590,000), epoxy resins, polyamides and polyurethanes.
Zusätzlich zu den Verbindungen (I) und den thermoplastischen Harzen enthalten die erfindungsgemäßen Toner in bekannten Mengen Färbungsmaterialien und magnetisch anziehbares Material. Das Färbungsmaterial kann aus einem organischen Farbstoff wie Nigrosin, Anilinblau, 2,9-Dimethylchinacridon, C.I. Disperse Red 15 (=C.I. 60 710), C.I. Solvent Red 19 (= C.I. 26 050), C.I. Pigment Blue 15 (=C.I. 74 160), C.I. Pigment Blue 22 (=C.I. 69 810) und C.I. Solvent Yellow 16 (=C.I. 12 700), oder einem anorganischen Pigment, wie Ruß, Rotblei, gelbem Bleioxid oder Chromgelb bestehen. Allgemein überschreitet die Menge des in den Tonern vorhandenen Färbungsmaterials etwa 15 Gew.X nicht.In addition to the compounds (I) and the thermoplastic resins, the toners of the present invention contain coloring materials and magnetically attractable material in known amounts. The coloring material can be made from an organic dye such as nigrosine, aniline blue, 2,9-dimethylquinacridone, CI Disperse Red 15 (= CI 60 710), CI Solvent Red 19 (= CI 26 050), CI Pigment Blue 15 (= C .I. 74 160), CI Pigment Blue 22 (= CI 69 810) and CI Solvent Yellow 16 (= CI 12 700), or an inorganic pigment such as carbon black, red lead, yellow lead oxide or chrome yellow. Generally, the amount of the coloring material present in the toners does not exceed about 15% by weight.
Das magnetisch anziehbare Material kann beispielsweise aus Eisen, Nickel, Chromoxid, Eisenoxid oder einem Ferrit der allgemeinen Formel MFe204, worin M ein zweiwertiges Metall, wie Eisen, Kobalt, Zink, Nickel oder Mangan darstellt, bestehen.The magnetically attractable material can, for example, consist of iron, nickel, chromium oxide, iron oxide or a ferrite of the general formula MFe 2 0 4 , where M is a divalent metal, such as iron, cobalt, zinc, nickel or manganese.
Die Herstellung der die Verbindungen (I) enthaltenden Toner erfolgt nach üblichen Verfahren, z.B. durch Schmelzen des thermoplastischen Harzes oder eines Gemisches der thermoplastischen Harze, anschließend feiner Zerteilung einer oder mehrerer Ladungskontrollsubslanzen der Formel (I), sowie der anderen Zusätze, falls verwendet, in dem geschmolzenen Harz unter Anwendung der für diesen Zweck bekannten Misch- und Knetmaschinerie, anschließende Abkühlung der Schmelze zu einer festen Masse und schließlich Vermahlen der festen Masse zu Teilchen der gewünschten Teilchengröße. Es ist auch möglich, das thermoplastische Harz und die Verbindung (I) in einem gemeinsamen Lösungsmittel zu lösen, die anderen Zusätze in die Lösung einzuverleiben und anschließend die Flüssigkeit in an sich bekannter Weise sprühzutrocknen oder das Lösungsmittel oder die Lösungsmittel abzudampfen und den festen Rückstand zu Teilchen der gewünschten Teilchengröße zu vermahlen. Entsprechend einer Abänderung dieses Herstellungsverfahrens wird die Ladungskontrollsubstanz der Formel (I) nicht gelöst, sondern fein in der Lösung des thermoplastischen Harzes dispergiert.The toners containing the compounds (I) are prepared by customary processes, e.g. by melting the thermoplastic resin or a mixture of the thermoplastic resins, then finely dividing one or more charge control substances of formula (I), as well as the other additives, if used, into the melted resin using the mixing and kneading machinery known for this purpose Cooling the melt to a solid mass and finally grinding the solid mass into particles of the desired particle size. It is also possible to dissolve the thermoplastic resin and the compound (I) in a common solvent, to incorporate the other additives into the solution and then to spray-dry the liquid in a manner known per se or to evaporate off the solvent or solvents and to add the solid residue To grind particles of the desired particle size. According to a modification of this manufacturing process, the charge control substance of the formula (I) is not dissolved, but finely dispersed in the solution of the thermoplastic resin.
Die so erhaltene Tonerzubereitung wird dann, beispielsweise analog US-PS 4 265 990, in einem xerographischen Bildaufzeichnungssystem eingesetzt. Die dafür eingesetzten Photorezeptoren müssen die Fähigkeit haben, sich negativ aufzuladen. Beispiele sind solche, wie sie ebenfalls in US-PS 4 265 990 beschrieben sind. Sie können in der ladungserzeugenden Schicht beispielsweise folgende Substanzen enthalten: 4-Dimethylaminobenzyliden-benzhydrazid, Polyvinylcarbazol, 2-Benzyliden-aminocarbazol, 2-Nitrobenzyliden-p-bromanilin, 2,4-Diphenylehinazolin, 1,5-Diphenyl-3-methyl-pyrazolin, 1,3,5-Triphenylpyrazolin, Charge-Transfer-Komplex aus Polyvinylcarbazol und Trinitrofluorenon, 2-(4'-Dimethylaminophenyl)-benzoxazol, Selen, Tellur und Arsentriselenid.The toner preparation thus obtained is then used in a xerographic image recording system, for example analogously to US Pat. No. 4,265,990. The photoreceptors used for this must have the ability to charge negatively. Examples are those also described in U.S. Patent 4,265,990. You can use the following sub in the charge generating layer, for example punches contain: 4-dimethylaminobenzylidene-benzhydrazide, polyvinyl carbazole, 2-benzylidene-aminocarbazole, 2-nitrobenzylidene-p-bromoaniline, 2,4-diphenylehinazoline, 1,5-diphenyl-3-methyl-pyrazoline, 1,3,5-triphenylpyrazoline , Charge transfer complex of polyvinyl carbazole and trinitrofluorenone, 2- (4'-dimethylaminophenyl) benzoxazole, selenium, tellurium and arsenic triselenide.
Die eingesetzten Photorezeptoren können in der ladungserzeugenden Schicht auch zusätzlich Sensibilisierungsfarbstoffe wie beispielsweise Bengal Rosa oder Eosin G enthalten. In der ladungstransportierenden Schicht können die Photorezeptoren Diamine enthalten, wie sie ebenfalls in US-PS 4 265 990 angegeben sind.The photoreceptors used can also contain sensitizing dyes such as Bengal pink or Eosin G in the charge-generating layer. In the charge transport layer, the photoreceptors may contain diamines, as also specified in U.S. Patent 4,265,990.
Gegenstand der Erfindung sind auch die Verbindungen der Formel (II).The invention also relates to the compounds of the formula (II).
282 g Naphthalsäure-N-(3-dimethylaminopropyl)-imid (1 Mol) und 175,5 g 4,4'-Bis-(chloracetamidophenyl)-methan (0,5 Mol) werden in 1330 g Polyglykol (durchsehn. Molgew. 400) 3 h auf 100°C erhitzt, wobei sich zunächst eine klare viskose Lösung bildet, aus der sich anschließend ein farbloser kristalliner Niederschlag abscheidet. Nach dem Abkühlen auf Raumtemperatur verdünnt man die Reaktionsmischung unter Rühren mit 3,3 1 Isopropanol, saugt den kristallinen Niederschlag ab, wäscht ihn mit Isopropanol bis zum farblosen Ablauf und trocknet ihn bei 60°C im Vakuum. Man erhält 444 g (97% der Theorie) Verbindung der Formel
Die Substanz ist dünnschichtchromatographisch praktisch rein. 1 zeigt auf der fluoreszierenden Kieselgelplatte Fluoreszenzlöschung. Rf-Wert: 0,3 (Laufmittel: 45 Vol-% Essigsäurebutylester, 33 Vol-% Eisessig, 9 Vol-% Ameisensäure und 13 Vol-% Wasser).The substance is practically pure by thin layer chromatography. 1 shows fluorescence quenching on the fluorescent silica gel plate. Rf value: 0.3 (mobile solvent: 45% by volume of butyl acetate, 33% by volume of glacial acetic acid, 9% by volume of formic acid and 13% by volume of water).
In analoger Weise werden die folgenden Verbindungen her- gestellt:
Man setzt in gleicher Weise, wie im Beispiel 1 beschrieben, 282 g Naphthalsäure -N-(3-dimethylaminopropyl)-imid und 175,5 g 4.4'-Bis(chloracetamidophenyl)-methan in 1330 Polyglykol 3h bei 100°C um, setzt 600 ml Ethanol und 225 g p-Toluolsulfonsäure hinzu, erhitzt die Mischung 2 h unter Rückfluß zum Sieden, saugt den farblosen kristallinen Niederschlag ab, wäscht ihn mit 800 ml Ethanol und trocknet ihn bei 60°C im Vakuum.In the same way as described in Example 1, 282 g of naphthalic acid -N- (3-dimethylaminopropyl) imide and 175.5 g of 4,4'-bis (chloroacetamidophenyl) methane are reacted in 1330 polyglycol at 100 ° C. for 3 hours 600 ml of ethanol and 225 g of p-toluenesulfonic acid are added, the mixture is heated to boiling under reflux for 2 hours, the colorless crystalline precipitate is filtered off with suction, washed with 800 ml of ethanol and dried at 60 ° C. in vacuo.
Man erhält 366 g Verbindung der Formel
Schmelzpunkt 186-188° CMelting point 186-188 ° C
Die Substanz ist dünnschichtchromatographisch praktisch rein.The substance is practically pure by thin layer chromatography.
In analoger Weise werden auch die p-Toluol- und Benzolsulfonate der Verbindungen 2 bis 20 hergestellt.The p-toluene and benzenesulfonates of compounds 2 to 20 are also prepared in an analogous manner.
56,5 g (0,2 Mol) Naphthalsäure-N-(3-dimethylaminopropyl)-imid werden in 700 ml Toluol suspendiert, unter Rühren mit 56 g p-Toluolsulfonsäure-methylester versetzt und 1 h bei 60°C verrUhrt. Der farblose kristalline Niederschlag wird abgesaugt, mit 150 ml Isopropanol gewaschen und bei 40°C im Vakuum getrocknet. Man erhält 87 g (93X der Theorie) Verbindung der Formel56.5 g (0.2 mol) of naphthalic acid N- (3-dimethylaminopropyl) imide are suspended in 700 ml of toluene, 56 g of methyl p-toluenesulfonic acid are added with stirring and the mixture is stirred at 60 ° C. for 1 h. The colorless crystalline precipitate is filtered off, washed with 150 ml of isopropanol and dried at 40 ° C in a vacuum. 87 g (93X of theory) of the compound of the formula are obtained
In analoger Weise werden die folgenden Substanzen der Formel
282 g (1 Mol) Naphthalsäure-N-(3-dimethylaminopropyl)-imid werden in 2 1 Acetonitril suspendiert, unter Rühren mit 307 g (1 Mol) 1-Bromhexadecan versetzt und 15 Stunden unter Rückfluß zum Sieden erhitzt. Die Lösung wird 35°C warm von geringen ungelösten Anteilen filtriert. Das Filtrat wird mit 2,5 1 Aceton verrührt und auf -5°C abgekühlt. Der kristalline Niederschlag wird abgesaugt, zuerst mit Aceton, dann mit Petrolether gewaschen und bei 30°C im Vakuum getrocknet. Man erhält 540 g (92 X der Theorie) Verbindung der Formel
289 g (1,02 Mol) Naphthalsäure-N-(3-dimethylaminopropyl)-imid werden in 6,1 1 Toluol suspendiert, bei 60 bis 65°C unter Rühren tropfenweise mit 138 g (1,09 Mol) Dimethylsulfat versetzt und 6 Stunden bei 60 bis 65°C verrührt. Nach dem Kühlen auf Raumtemperatur wird der kristalline Niederschlag abgesaugt, mit Toluol gewaschen und bei 50°C im Vakuum getrocknet. Man erhält 408 g (98 % der Theorie) Verbindung der Formel
2 Gewichtsprozent Verbindung des Beispiels 22, 6 Gewichtsprozent Ruß und 92 Gewichtsprozent eines Styrol-Butadien-Harzes, welches 89 Gewichtsprozent Styrol und 11 Gewichtsprozent Butadien enthält werden im Extruder bei 100°C verschmolzen und verknetet, dann zerkleinert und gemahlen, bis der Partikeldurchmesser kleiner als 5p ist.2 percent by weight of the compound of Example 22, 6 percent by weight of carbon black and 92 percent by weight of a styrene-butadiene resin which contains 89 percent by weight of styrene and 11 percent by weight of butadiene are melted and kneaded in the extruder at 100 ° C., then comminuted and ground until the particle diameter is less than 5p is.
Diese Toner-Zubereitung wird in ein xerographisches Bildaufzeichnungssystem, wie es in US-PS 4 265 990 beschrieben ist, eingearbeitet. Dazu geht man in der Weise vor, daß man ein MYLAR®-Substrat mit einer bei Belichtung ladungserzeugenden Schicht aus Polyvinylcarbazol versieht, in das trigonales Selen frei dispergiert ist, darüber eine transparente ladüngstransportierende Schicht aufbringt, die als ladungstransportierende Moleküle N,N'-Diphenyl-N,N'-bis-(3-Methylphenyl)-1,1`-bisphenyl-4,4'-diamin, dispergiert in eine MAKROLON®-Polycarbonatmasse, enthält.This toner formulation is incorporated into a xerographic imaging system as described in U.S. Patent 4,265,990. The procedure for this is to provide a MYLAR® substrate with a charge-generating layer of polyvinylcarbazole in which trigonal selenium is freely dispersed, and a transparent charge-transporting layer is applied over it, which acts as charge-transporting molecules N, N'-diphenyl -N, N'-bis- (3-methylphenyl) -1,1`-bisphenyl-4,4'-diamine, dispersed in a MAKROLON® polycarbonate composition.
Man erhält gestochen scharfe Bildaufzeichnungen, die denen nach US-PS 4 493 883, Beispiel 1, hergestellten in der Konturenschärfe noch überlegen sind.Razor-sharp image recordings are obtained which are still superior in contour definition to those produced according to US Pat. No. 4,493,883, Example 1.
Claims (5)
worin
wherein
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19863604827 DE3604827A1 (en) | 1986-02-15 | 1986-02-15 | ELECTROPHOTOGRAPHIC TONER |
DE3604827 | 1986-02-15 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0233544A2 true EP0233544A2 (en) | 1987-08-26 |
EP0233544A3 EP0233544A3 (en) | 1990-04-04 |
EP0233544B1 EP0233544B1 (en) | 1993-09-08 |
Family
ID=6294171
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP87101463A Expired - Lifetime EP0233544B1 (en) | 1986-02-15 | 1987-02-03 | Electrophotographical toner |
Country Status (4)
Country | Link |
---|---|
US (2) | US4812379A (en) |
EP (1) | EP0233544B1 (en) |
JP (1) | JPS62192755A (en) |
DE (2) | DE3604827A1 (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0355006A2 (en) * | 1988-08-19 | 1990-02-21 | Bayer Ag | Electrophotographical toner |
EP0501249A1 (en) * | 1991-02-27 | 1992-09-02 | Bayer Ag | Naphthalimides, toners containing them and their use as additive for toners |
WO1993002399A1 (en) * | 1991-07-18 | 1993-02-04 | Eastman Kodak Company | Toners and developers containing amide-containing quaternary ammonium salts as charge control agents |
WO1994011789A1 (en) * | 1992-11-07 | 1994-05-26 | Basf Aktiengesellschaft | Electrostatic toners containing amphiphilic liquid crystals |
US10835453B2 (en) | 2016-12-21 | 2020-11-17 | Voco Gmbh | Storage-stable resin-modified glass ionomer cement |
Families Citing this family (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3738948A1 (en) * | 1987-11-17 | 1989-05-24 | Bayer Ag | COLORLESS SALTS OF HETEROPOLYSAURS AND CATIONIC AROMATIC IMIDES AS CHARGE CONTROL SUBSTANCES IN TONERS |
JPH0814721B2 (en) * | 1988-02-09 | 1996-02-14 | 株式会社巴川製紙所 | Positively chargeable color toner |
EP0388535B1 (en) * | 1989-03-24 | 1994-05-18 | Agfa-Gevaert N.V. | Particulate toner material |
US5086059A (en) * | 1990-06-07 | 1992-02-04 | Du Pont Merck Pharmaceutical Company | Bis-naphthalimides as anticancer agents |
US5206250A (en) * | 1991-03-27 | 1993-04-27 | Du Pont Merck Pharmaceutical Company | Bis-naphthalimides containing amide and thioamide linkers as anticancer agents |
US5329048A (en) * | 1991-03-27 | 1994-07-12 | The Dupont Merck Pharmaceutical Company | Process of preparing tetraamino intermediates |
JPH07501822A (en) * | 1991-12-11 | 1995-02-23 | デュポン・ファーマシュウティカルズ・カンパニー | Highly water-soluble bis-naphthalimide useful as an anticancer agent |
US5376664A (en) * | 1992-07-27 | 1994-12-27 | The Du Pont Merck Pharmaceutical Company | Unsymmetrical mono-3-nitro bis-naphthalimides as anticancer agents |
DE4232739A1 (en) * | 1992-09-30 | 1994-03-31 | Knoll Ag | New asymmetrically substituted bis-naphthalimides |
US5359070A (en) * | 1993-02-11 | 1994-10-25 | The Du Pont Merck Pharmaceutical Company | Unsymmetrical bis-imides as anticancer agents |
US5416089A (en) * | 1993-06-24 | 1995-05-16 | The Du Pont Merck Pharmaceutical Company | Polycyclic and heterocyclic chromophores for bis-imide tumoricidals |
US5358816A (en) * | 1993-08-31 | 1994-10-25 | Eastman Kodak Company | Zinc salt of ortho-benzoic sulfimide as negative charge-controlling additive for toner and developer compositions |
US5358814A (en) * | 1993-08-31 | 1994-10-25 | Eastman Kodak Company | Toner compositions containing as a negative charge-controlling agent a mixture of ortho-benzoic sulfimide and para-anisic acid |
US5358815A (en) * | 1993-08-31 | 1994-10-25 | Eastman Kodak Company | Toner compositions containing negative charge-controlling additive |
US5332637A (en) * | 1993-08-31 | 1994-07-26 | Eastman Kodak Company | Electrostatographic dry toner and developer compositions with hydroxyphthalimide |
US5358818A (en) * | 1993-08-31 | 1994-10-25 | Eastman Kodak Company | Ortho-benzoic sulfimide as charge-controlling agent |
US5358817A (en) * | 1993-08-31 | 1994-10-25 | Eastman Kodak Company | Toner compositions containing as a negative charge-controlling agent the calcium salt of ortho-benzoic sulfimide |
US5561042A (en) * | 1994-07-22 | 1996-10-01 | Cancer Therapy And Research Center | Diamine platinum naphthalimide complexes as antitumor agents |
US5604095A (en) * | 1994-07-22 | 1997-02-18 | Cancer Therapy & Research Center | Unsymmetrically linked bisnaphthalimides as antitumor agents |
US5641782A (en) * | 1995-02-16 | 1997-06-24 | The Dupont Merck Pharmaceutical Company | 3-aromatic and 3-heteroaromatic substituted bisnaphthalimides |
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EP0028777A1 (en) * | 1979-11-07 | 1981-05-20 | Hoechst Aktiengesellschaft | Cationic compounds of the naphthalimide series, process for their preparation and their use |
EP0154740A1 (en) * | 1984-02-21 | 1985-09-18 | Xerox Corporation | Toner compositions |
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US3880859A (en) * | 1971-06-03 | 1975-04-29 | Basf Ag | N-substituted-4-alkoxynaphthalimides |
CH560235A5 (en) * | 1972-02-18 | 1975-03-27 | Ciba Geigy Ag | |
US3953451A (en) * | 1972-06-28 | 1976-04-27 | Basf Aktiengesellschaft | Compounds of the naphthalimide series |
US3940398A (en) * | 1975-01-23 | 1976-02-24 | E. R. Squibb & Sons, Inc. | 2-[[4-(Azine or diazine or triazine)-1-piperazinyl]alkyl]-1H-benz[de]isoquinoline-1,3(2H)-diones |
US4007191A (en) * | 1975-10-14 | 1977-02-08 | E. R. Squibb & Sons, Inc. | 2-(Piperidinyl or tetrahydropyridinyl)-alkyl)-2,3-dihydro-3-hydroxy-1H-benz(DE)isoquinolin-1-ones |
US4139532A (en) * | 1976-05-14 | 1979-02-13 | Basf Aktiengesellschaft | N-Acylaminonaphthalimides |
ES459497A1 (en) * | 1977-06-04 | 1978-04-16 | Made Labor Sa | N(Aminoalkyl)-naphthalimides and their derivatives |
DE2753152A1 (en) * | 1977-11-29 | 1979-06-07 | Basf Ag | NAPHTHALIMIDE DERIVATIVES |
US4508900A (en) * | 1980-11-03 | 1985-04-02 | Hoechst Aktiengesellschaft | Cationic compounds of the naphthalimide series, process for their preparation and their use |
JPS59114546A (en) * | 1982-12-22 | 1984-07-02 | Nippon Kayaku Co Ltd | Electrophotographic printing toner |
US4614820A (en) * | 1983-04-01 | 1986-09-30 | Warner-Lambert Co. | 3,6-disubstituted-1,8-naphthalimides |
US4499266A (en) * | 1983-04-01 | 1985-02-12 | Warner-Lambert Company | 3,6-Dinitro-1,8-naphthalimides |
DE3413833A1 (en) * | 1983-04-12 | 1984-10-18 | Canon K.K., Tokio/Tokyo | DEVELOPMENT PROCESS AND DEVELOPER THEREFOR |
JPH0625874B2 (en) * | 1983-04-23 | 1994-04-06 | キヤノン株式会社 | Triboelectric toner for developing electrostatic image |
US4665071A (en) * | 1984-02-21 | 1987-05-12 | Warner-Lambert Company | 3,6-disubstituted-1,8-naphthalimides and methods for their production and use |
DE3535496A1 (en) * | 1985-10-04 | 1987-04-16 | Bayer Ag | METHOD FOR FLUORESCENT EXTINGUISHING AND NEW CATIONIC NAPHTHALINE PERI DICARBONIC ACID IMID DERIVATIVES |
US4686166A (en) * | 1985-10-07 | 1987-08-11 | Hitachi Chemical Co. | Electrophoto toner comprising imido group monomer unit in polymer |
US4782064A (en) * | 1986-07-21 | 1988-11-01 | American Cyanamid Co. | 2-heteroaryl-alkyl-1H-benz[de]-isoquinoline-1,3(2H)-diones |
-
1986
- 1986-02-15 DE DE19863604827 patent/DE3604827A1/en not_active Withdrawn
-
1987
- 1987-02-03 EP EP87101463A patent/EP0233544B1/en not_active Expired - Lifetime
- 1987-02-03 US US07/010,364 patent/US4812379A/en not_active Expired - Fee Related
- 1987-02-03 DE DE87101463T patent/DE3787297D1/en not_active Expired - Fee Related
- 1987-02-14 JP JP62030718A patent/JPS62192755A/en active Granted
-
1988
- 1988-07-28 US US07/225,329 patent/US4841052A/en not_active Expired - Fee Related
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
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EP0028777A1 (en) * | 1979-11-07 | 1981-05-20 | Hoechst Aktiengesellschaft | Cationic compounds of the naphthalimide series, process for their preparation and their use |
EP0154740A1 (en) * | 1984-02-21 | 1985-09-18 | Xerox Corporation | Toner compositions |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0355006A2 (en) * | 1988-08-19 | 1990-02-21 | Bayer Ag | Electrophotographical toner |
EP0355006A3 (en) * | 1988-08-19 | 1990-03-28 | Bayer Ag | Electrophotographical toner electrophotographical toner |
EP0501249A1 (en) * | 1991-02-27 | 1992-09-02 | Bayer Ag | Naphthalimides, toners containing them and their use as additive for toners |
US5292881A (en) * | 1991-02-27 | 1994-03-08 | Bayer Aktiengesellschaft | New naphthalimides, toners containing these and the use of the new naphthalimides as additives for toners |
WO1993002399A1 (en) * | 1991-07-18 | 1993-02-04 | Eastman Kodak Company | Toners and developers containing amide-containing quaternary ammonium salts as charge control agents |
WO1994011789A1 (en) * | 1992-11-07 | 1994-05-26 | Basf Aktiengesellschaft | Electrostatic toners containing amphiphilic liquid crystals |
US10835453B2 (en) | 2016-12-21 | 2020-11-17 | Voco Gmbh | Storage-stable resin-modified glass ionomer cement |
Also Published As
Publication number | Publication date |
---|---|
EP0233544A3 (en) | 1990-04-04 |
EP0233544B1 (en) | 1993-09-08 |
JPH0431584B2 (en) | 1992-05-26 |
US4812379A (en) | 1989-03-14 |
US4841052A (en) | 1989-06-20 |
DE3787297D1 (en) | 1993-10-14 |
DE3604827A1 (en) | 1987-08-20 |
JPS62192755A (en) | 1987-08-24 |
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