EP0548076A4 - Solvation-based charge direction of liquid electrophotographic developer compositions - Google Patents
Solvation-based charge direction of liquid electrophotographic developer compositionsInfo
- Publication number
- EP0548076A4 EP0548076A4 EP19910902923 EP91902923A EP0548076A4 EP 0548076 A4 EP0548076 A4 EP 0548076A4 EP 19910902923 EP19910902923 EP 19910902923 EP 91902923 A EP91902923 A EP 91902923A EP 0548076 A4 EP0548076 A4 EP 0548076A4
- Authority
- EP
- European Patent Office
- Prior art keywords
- toner
- charge
- solvation
- charge director
- resinous phase
- 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
- 238000007614 solvation Methods 0.000 title claims abstract description 71
- 239000000203 mixture Substances 0.000 title claims abstract description 63
- 239000007788 liquid Substances 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 claims abstract description 75
- 239000002245 particle Substances 0.000 claims abstract description 51
- 239000000463 material Substances 0.000 claims abstract description 29
- 229910052751 metal Inorganic materials 0.000 claims abstract description 23
- 239000002184 metal Substances 0.000 claims abstract description 23
- 150000003839 salts Chemical class 0.000 claims abstract description 15
- 230000008569 process Effects 0.000 claims description 39
- 229920000642 polymer Polymers 0.000 claims description 21
- 239000003086 colorant Substances 0.000 claims description 18
- 229910021645 metal ion Inorganic materials 0.000 claims description 14
- 239000000758 substrate Substances 0.000 claims description 11
- 239000012453 solvate Substances 0.000 claims description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 229920001577 copolymer Polymers 0.000 claims description 6
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 238000010348 incorporation Methods 0.000 claims description 3
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 3
- 229920006217 cellulose acetate butyrate Polymers 0.000 claims description 2
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 claims description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 2
- 229920000554 ionomer Polymers 0.000 claims description 2
- 125000002091 cationic group Chemical group 0.000 abstract description 8
- 229920005989 resin Polymers 0.000 description 20
- 239000011347 resin Substances 0.000 description 20
- 238000011161 development Methods 0.000 description 17
- 241000894007 species Species 0.000 description 12
- 229960001860 salicylate Drugs 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 10
- 229910052782 aluminium Inorganic materials 0.000 description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 10
- 238000010186 staining Methods 0.000 description 10
- -1 sulfoalkyl methacrylate Chemical compound 0.000 description 10
- ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 2,3-dimethylbutane Chemical group CC(C)C(C)C ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 0.000 description 9
- 230000036571 hydration Effects 0.000 description 9
- 238000006703 hydration reaction Methods 0.000 description 9
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 9
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 7
- 239000002253 acid Substances 0.000 description 7
- ALZKMIXVOXRDNL-UHFFFAOYSA-K aluminum 7,7-dimethyloctanoate Chemical compound [Al+3].CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O ALZKMIXVOXRDNL-UHFFFAOYSA-K 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 239000000049 pigment Substances 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 229920000180 alkyd Polymers 0.000 description 6
- 150000001450 anions Chemical class 0.000 description 6
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 6
- 241001441571 Hiodontidae Species 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000011787 zinc oxide Substances 0.000 description 5
- HXISMZRZHNLOHG-UHFFFAOYSA-N 2-hydroxy-3,4-di(propan-2-yl)benzoic acid Chemical compound CC(C)C1=CC=C(C(O)=O)C(O)=C1C(C)C HXISMZRZHNLOHG-UHFFFAOYSA-N 0.000 description 4
- CNPVJWYWYZMPDS-UHFFFAOYSA-N 2-methyldecane Chemical compound CCCCCCCCC(C)C CNPVJWYWYZMPDS-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000002270 dispersing agent Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000001404 mediated effect Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 125000000304 alkynyl group Chemical group 0.000 description 3
- 150000001408 amides Chemical group 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- 125000000753 cycloalkyl group Chemical group 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 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 3
- 230000003993 interaction Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 150000002576 ketones Chemical group 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 3
- 229960004889 salicylic acid Drugs 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 239000001993 wax Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical group CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000002877 alkyl aryl group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
- 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 2
- 230000008021 deposition Effects 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000002170 ethers Chemical group 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 125000001188 haloalkyl group Chemical group 0.000 description 2
- 125000003106 haloaryl group Chemical group 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- BOSAWIQFTJIYIS-UHFFFAOYSA-N 1,1,1-trichloro-2,2,2-trifluoroethane Chemical compound FC(F)(F)C(Cl)(Cl)Cl BOSAWIQFTJIYIS-UHFFFAOYSA-N 0.000 description 1
- OSNILPMOSNGHLC-UHFFFAOYSA-N 1-[4-methoxy-3-(piperidin-1-ylmethyl)phenyl]ethanone Chemical compound COC1=CC=C(C(C)=O)C=C1CN1CCCCC1 OSNILPMOSNGHLC-UHFFFAOYSA-N 0.000 description 1
- IIZPXYDJLKNOIY-JXPKJXOSSA-N 1-palmitoyl-2-arachidonoyl-sn-glycero-3-phosphocholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCC\C=C/C\C=C/C\C=C/C\C=C/CCCCC IIZPXYDJLKNOIY-JXPKJXOSSA-N 0.000 description 1
- MFYSUUPKMDJYPF-UHFFFAOYSA-N 2-[(4-methyl-2-nitrophenyl)diazenyl]-3-oxo-n-phenylbutanamide Chemical compound C=1C=CC=CC=1NC(=O)C(C(=O)C)N=NC1=CC=C(C)C=C1[N+]([O-])=O MFYSUUPKMDJYPF-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical class [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- XBIUWALDKXACEA-UHFFFAOYSA-N 3-[bis(2,4-dioxopentan-3-yl)alumanyl]pentane-2,4-dione Chemical compound CC(=O)C(C(C)=O)[Al](C(C(C)=O)C(C)=O)C(C(C)=O)C(C)=O XBIUWALDKXACEA-UHFFFAOYSA-N 0.000 description 1
- DKFYMWKWFWBBNE-UHFFFAOYSA-L 7,7-dimethyloctanoate;zirconium(2+) Chemical compound [Zr+2].CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O DKFYMWKWFWBBNE-UHFFFAOYSA-L 0.000 description 1
- 238000012935 Averaging Methods 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- 240000006240 Linum usitatissimum Species 0.000 description 1
- 235000004431 Linum usitatissimum Nutrition 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229930195725 Mannitol Natural products 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 125000002015 acyclic group Chemical group 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- RGPXLIKKJIGEIV-UHFFFAOYSA-K aluminum 2,3-di(nonyl)naphthalene-1-sulfonate Chemical compound [Al+3].CCCCCCCCCc1cc2ccccc2c(c1CCCCCCCCC)S([O-])(=O)=O.CCCCCCCCCc1cc2ccccc2c(c1CCCCCCCCC)S([O-])(=O)=O.CCCCCCCCCc1cc2ccccc2c(c1CCCCCCCCC)S([O-])(=O)=O RGPXLIKKJIGEIV-UHFFFAOYSA-K 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- IRERQBUNZFJFGC-UHFFFAOYSA-L azure blue Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[S-]S[S-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] IRERQBUNZFJFGC-UHFFFAOYSA-L 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 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
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000004203 carnauba wax Substances 0.000 description 1
- 235000013869 carnauba wax Nutrition 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- PZTQVMXMKVTIRC-UHFFFAOYSA-L chembl2028348 Chemical compound [Ca+2].[O-]S(=O)(=O)C1=CC(C)=CC=C1N=NC1=C(O)C(C([O-])=O)=CC2=CC=CC=C12 PZTQVMXMKVTIRC-UHFFFAOYSA-L 0.000 description 1
- VDQQXEISLMTGAB-UHFFFAOYSA-N chloramine T Chemical compound [Na+].CC1=CC=C(S(=O)(=O)[N-]Cl)C=C1 VDQQXEISLMTGAB-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- RPBPCPJJHKASGQ-UHFFFAOYSA-K chromium(3+);octanoate Chemical compound [Cr+3].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O.CCCCCCCC([O-])=O RPBPCPJJHKASGQ-UHFFFAOYSA-K 0.000 description 1
- MYSWGUAQZAJSOK-UHFFFAOYSA-N ciprofloxacin Chemical compound C12=CC(N3CCNCC3)=C(F)C=C2C(=O)C(C(=O)O)=CN1C1CC1 MYSWGUAQZAJSOK-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000009918 complex formation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- VNZQQAVATKSIBR-UHFFFAOYSA-L copper;octanoate Chemical compound [Cu+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O VNZQQAVATKSIBR-UHFFFAOYSA-L 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- DIOQZVSQGTUSAI-NJFSPNSNSA-N decane Chemical compound CCCCCCCCC[14CH3] DIOQZVSQGTUSAI-NJFSPNSNSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- RWYFURDDADFSHT-RBBHPAOJSA-N diane Chemical compound OC1=CC=C2[C@H]3CC[C@](C)([C@](CC4)(O)C#C)[C@@H]4[C@@H]3CCC2=C1.C1=C(Cl)C2=CC(=O)[C@@H]3CC3[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@@](C(C)=O)(OC(=O)C)[C@@]1(C)CC2 RWYFURDDADFSHT-RBBHPAOJSA-N 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- VPWFPZBFBFHIIL-UHFFFAOYSA-L disodium 4-[(4-methyl-2-sulfophenyl)diazenyl]-3-oxidonaphthalene-2-carboxylate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)C1=CC(C)=CC=C1N=NC1=C(O)C(C([O-])=O)=CC2=CC=CC=C12 VPWFPZBFBFHIIL-UHFFFAOYSA-L 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 239000004715 ethylene vinyl alcohol Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 235000004426 flaxseed Nutrition 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- RZXDTJIXPSCHCI-UHFFFAOYSA-N hexa-1,5-diene-2,5-diol Chemical compound OC(=C)CCC(O)=C RZXDTJIXPSCHCI-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- VRWKTAYJTKRVCU-UHFFFAOYSA-N iron(6+);hexacyanide Chemical compound [Fe+6].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] VRWKTAYJTKRVCU-UHFFFAOYSA-N 0.000 description 1
- KNMWLFKLSYMSBR-UHFFFAOYSA-N iron;octanoic acid Chemical compound [Fe].CCCCCCCC(O)=O KNMWLFKLSYMSBR-UHFFFAOYSA-N 0.000 description 1
- 239000000787 lecithin Substances 0.000 description 1
- 229940067606 lecithin Drugs 0.000 description 1
- 235000010445 lecithin Nutrition 0.000 description 1
- 235000010187 litholrubine BK Nutrition 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- WNWZKKBGFYKSGA-UHFFFAOYSA-N n-(4-chloro-2,5-dimethoxyphenyl)-2-[[2,5-dimethoxy-4-(phenylsulfamoyl)phenyl]diazenyl]-3-oxobutanamide Chemical group C1=C(Cl)C(OC)=CC(NC(=O)C(N=NC=2C(=CC(=C(OC)C=2)S(=O)(=O)NC=2C=CC=CC=2)OC)C(C)=O)=C1OC WNWZKKBGFYKSGA-UHFFFAOYSA-N 0.000 description 1
- DIOQZVSQGTUSAI-UHFFFAOYSA-N n-butylhexane Natural products CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 230000010399 physical interaction Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001483 poly(ethyl methacrylate) polymer Polymers 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002717 polyvinylpyridine Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 235000010356 sorbitol Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 229960002317 succinimide Drugs 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 125000004964 sulfoalkyl group Chemical group 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- JOUDBUYBGJYFFP-FOCLMDBBSA-N thioindigo Chemical compound S\1C2=CC=CC=C2C(=O)C/1=C1/C(=O)C2=CC=CC=C2S1 JOUDBUYBGJYFFP-FOCLMDBBSA-N 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 1
- 229940029284 trichlorofluoromethane Drugs 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000000811 xylitol Substances 0.000 description 1
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 1
- 235000010447 xylitol Nutrition 0.000 description 1
- 229960002675 xylitol Drugs 0.000 description 1
- 239000001060 yellow colorant Substances 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
- G03G9/12—Developers with toner particles in liquid developer mixtures
- G03G9/135—Developers with toner particles in liquid developer mixtures characterised by stabiliser or charge-controlling agents
- G03G9/1355—Ionic, organic compounds
-
- 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
- G03G9/12—Developers with toner particles in liquid developer mixtures
- G03G9/13—Developers with toner particles in liquid developer mixtures characterised by polymer components
Definitions
- the present invention relates generally to the field of color electrophotography, and more particularly relates to an improved method for charge directing liquid electrophotographic developer compositions, and to novel toner and developer compositions produced thereby.
- a photoconductive insulating material such as selenium
- a light image is then focused onto the charged surface, which discharges or lowers the potential of the irradiated areas, while leaving the remainder of the surface charged.
- the electrostatic image so formed is then made visible by application of a suitable developing composition, which may be in either dry or liquid form.
- a suitable developing composition which may be in either dry or liquid form.
- Conventional liquid developer compositions comprise a dispersion of pigment particles in an insulating carrier liquid. Application of such a composition to the substrate carrying the electrostatic image results in migration of charged pigment particles to the substrate surface and deposition thereon in conformance with the electrostatic image.
- Liquid developers for use in multicolor image development are relatively recent, and are comprised of colorant embedded in a thermoplastic resin core. These "toner” particles are then dispersed in an insulating carrier medium as above. Like compositions used in black-and-white electrophotography, these developer compositions additionally contain "charge directors”, or “charge control agents”, to control the charge acquired by the toner particles in the insulating liquid.
- each of the color images is transferred from the electrophotographic member to a print substrate after development and prior to formation of the next color image. This process, however, requires extremely accurate registration of the successive color images on the substrate to which they are transferred in order to obtain a high-quality composite image.
- Another color printing process, and the process currently in use commercially, is a four-color liquid electrophotographic process known as "consecutive color toning" or "consecutive multicolor image development".
- This process involves: (l) charging a photoconductive ("pc") surface; (2) impressing a first latent image on the surface by exposure through a colored transparency; (3) developing the image by contacting the pc with a liquid developer composition of a first color, typically yellow; and (4) discharging the pc surface.
- the steps are then repeated in sequence, typically using magenta, cyan, and black developer compositions, i.e., the cyclic process is repeated until the colored image is complete.
- toner instability i.e., the appearance of toner in uncharged, non-image areas (a problem which is ubiquitous in zinc oxide and other positive toner systems) ; poor image resolution (i.e., poor edge acuity); poor image density resulting from insufficient deposition of toner particles in intended image regions; and "image" or "character” staining, where a second process color overtones the first image in regions where portions of the first image should have been discharged but were not.
- An additional problem with current electrophotographic color development processes is the need for multiple washing and drying steps during development, e.g., as described by Alexandrovich et al. in U.S. Patent No. 4,701,387.
- the method is somewhat time-consuming and unwieldy (it is recommended in the '387 patent that "after each development step and before the next developer is applied, the developed image is rinsed.... After rinsing, the rinse liquid is removed from the photoconductive element by drying, wiping or other method."; see column 2, lines 62-67).
- the invention herein now provides a novel method for charge directing liquid electrophotographic developer compositions which addresses the aforementioned problems.
- the invention is premised on the generation of an extremely stable charge director/toner complex, which in turn provides a very stable developer composition of exceptionally high particle-mediated conductivity and charge.
- the present method and associated compositions provide for a streamlined development process and enable preparation of a final electrophotographic print of unex ⁇ pectedly high quality.
- Electrophotographic processing generally: R.M. Schaffert, Electrophotography (London: Focal Press, 1975) , provides a comprehensive overview of electrophotographic processes and techniques.
- Representative references which relate to the field of color electrophotography specifically, include U.S. Patent Nos. 3,060,021 to Greig, 3,253,913 to Smith et al., 3,285,837 to Neber, 3,337,340 to Matkan, 3,553,093 to Putnam et al., 3,672,887 to Matsumoto et al., 3,687,661 to Sato et al. , and 3,849,165 to Stahly et al.
- References which describe electrophotographic toners and developers include U.S. Patent Nos.
- References which relate to charge directors include U.S. Patent Nos. 3,012,969 to van der Minne et al. (polyvalent metal organic salts in combination with an oxygen-containing organic compound) , 3,411,936 to Rots an et al. (metallic soaps), 3,417,019 to Beyer (metallic soaps and organic surface active agents), 3,788,995 to Stahly et al. (various polymeric agents), 4,170,563 to Merrill et al. (phosphonates) ,
- thermosetting binder resins such as polyisocyanate-cured alkyd resins, epoxy ester resins and copolymers of a vinyl monomer and styrene, acrylic and methacrylic esters or the like, alkyd resins cured with mela ine formaldehyde, or benzoguani ine formaldehyde, drying oil modified alkyd resins, and epoxy ester resins cured with a catalyst.
- alkyd and modified alkyd resins e.g., soya oil-modified and linseed oil-modified alkyds
- phenolic and modified phenolic resins phenol formaldehyde resins and derivatives thereof.
- U.S. Patent No. 4,845,003 to Kiriu et al. describes the use of acrylic, styrene-butadiene, epoxy, and polyester resins.
- U.S. Patent No. 3,345,293 to Bartoszewicz et al. describes a rosin-modified phenol- formaldehyde resin, a polystyrene-based resin, and an epoxy resin.
- It is still another object of the invention to provide a solvation-based method for charging toner particles in a liquid electrophotographic developer composition which involves incorporating into the resinous phase of the toner particle a material containing specific solvation sites effective to solvate a selected metal salt used as the charge director. It is a further object of the invention to provide toner for incorporation into a liquid electro ⁇ photographic developer composition, wherein the toner is formulated with a resinous phase containing a material having such specific solvation sites. It is still a further object of the invention to provide a liquid electrophotographic developer composition containing such a toner and charge director dispersed in an insulating carrier liquid.
- solvation sites and the metal salt which serves as the charge director are both selected so that very stable, charged toner complexes are formed, i.e., complexes of (i) the cationic, metal component of the charge director and (ii) the toner particle itself.
- solvation of cations such as metal ions is characterized by the formation of well- known aquo-complexes as
- Equation (3) may indeed proceed according to the equation
- the resinous phase of the toner is formulated so that it contains a polymer having the aforementioned solvation sites, which are then present on the surface of the toner particle and thus exposed to and available to solvate charge director in the liquid developer.
- the resinous phase of the toner is formulated such that it contains monomeric species with such solvation sites, which may or may not be present in combination with a solvating polymer.
- solvation sites are present on a monomeric species, a polymeric species, or both, it must be emphasized that preferred solvating materials are those which will exothermically solvate the cationic component of the charge director so as to aximize the stability of the resulting charged toner complex and minimize the presence of free, unassociated charge director in solution. Solvation may take place without any significant ionization of the solvation sites.
- toner which contains, in its resinous phase, a material containing specific solvation sites as just described.
- a developer composition which contains such toner particles dispersed in an insulating carrier liquid together with a selected metal salt to serve as the charge director.
- Other aspects of the invention include: processes for manufacturing the above-described toner and developer compositions; consecutive color toning processes making use of solvation-based charge direction; and an electrophotographic image constituting a composite color print prepared using the methods and compositions which will be described in detail herein.
- Toner as used herein is intended to denote the resinous, colored particles (referred to sometimes herein as “toner particles”) which ultimately form the electrophotographic image on the photoconductive (pc) surface.
- developer composition as used herein is meant a dispersion of toner and charge director in a selected insulating carrier liquid.
- the developer composition may contain a number of additional components as will be described below.
- Particle-mediated conductivity and charge is intended to mean that virtually all of the conductivity and charge in a developer composition derive from the charged toner particles and not from free, unassociated salts which may be present in solution (i.e., from unassociated charge director or other ionizable species) .
- the developer compositions of the invention display very high particle-mediated conductivity and charge and very low continuous phase conductivity.
- Consecutive color toning as used herein is intended to mean an electrophotographic development process involving repetition of charging and development steps with more than one color (as outlined in the Background Section above) so as to provide a multicolor final image. The process is also sometimes referred to herein as “consecutive multicolor image development”.
- Image staining is a problem which is specific to consecutive color toning, and similarly has its art- recognized meaning as used herein. The problem involves overtoning by a second or subsequent process color of an earlier color image in regions where portions of the earlier image should have been discharged but were not. "Image staining” is also sometimes referred to herein and in the art as “character staining”. By “specific solvation sites” is meant moieties present in a material contained within the toner resin and effective to solvate the metal salt or salts which will serve as the charge director.
- solute unit the charge director, in the present case
- solvent species the solvation sites on the toner surface herein.
- solvation may involve chemical or physical interaction, or both, and may vary in degree from a loose complex to a distinct, tightly complexed structure.
- the solvation sites in the charge director are preferably selected such that solvation of the charge director is a highly exothermic process and gives rise to a very stable, charged toner particle.
- carboxyl as used herein is meant the carboxylic acid moiety -COOH.
- the focus of the present invention is on a solvation-based mechanism for providing charge on toner particles contained in a liquid electrophotographic developer composition.
- the present invention thus involves a novel method of creating very stable charge director/toner complexes.
- the stability of the charge director/toner complex has been found to be of the utmost importance in liquid electrophotography.
- the focus was on the use of toners containing surface ion exchange sites effective to form extremely stable, ionic complexes with the metal salts that serve as the charge director.
- the focus is on a solvation interaction, i.e, the cationic, metal component of the charge director is complexed via solvation to the surface of the toner particle.
- the toner and the cationic component of the charge director are such that complexation between the two components is heavily favored, as here, virtually all of the charge director will be present in complexed form, and there will be substantially no unassociated charge director in solution.
- the solvation sites and the charge director are selected such that solvation is a highly exothermic process, giving rise to an extremely stable complex. Examples of particular toner materials and charge directors which may be used in this manner, to provide an extremely stable charged toner particle, are set out in Part (C) of this section.
- the solvation sites may derive from one or more polymers and/or one or more monomeric species incorporated into the toner resin.
- the toner resin itself may be a polymer containing the desired solvation sites.
- Exceptional solvation sites are those which, as noted above, will not ionize to any significant degree under the conditions of ordinary storage and use of the liquid electrophotographic developer.
- the charge director be either a pH-neutral salt (i.e., a metal salt of a strong acid) or a salt that contains a self-stabilized counterion, as will be described in the next section.
- ionizable moieties are used as solvation sites, it is preferred that a small amount of acid, preferably the acid form of the charge director's counterion, be added into the developer composition to force equilibrium towards the non-ionized form of the species (in the case of a carboxyl group, the added acid will thus give rise to COOH groups as opposed to the ionized C00 ⁇ species) .
- acid preferably the acid form of the charge director's counterion
- the charge director should also be selected with a view towards maximizing the stability of the "solvated" charged toner particle complex. More specifically, the charge director should be a metal salt containing a metal ion which will give rise to a highly exothermic solvation interaction with the aforementioned solvation sites.
- the preferred metals are generally those which have large negative enthalpies of hydration. The following table illustrates the enthalpies of hydration of some ions:
- ⁇ Absolute values are based on the assignment of -1091 ⁇ 10 kJ mol "1 to H + (cf. H.F. Halliwell and S.C. Nyburg, Trans. Faraday Soc. , 1963, 59.:1126). Each value probably has an uncertainty of at least lOn kJ mol "1 , where n is the charge of the ion.
- the present invention involves solvation by materials other than water, and thus does not involve hydration as such. Enthalpies of solvation will, however, typically correlate with these enthalpies of hydration.
- the enthalpy of solvation here i.e., of the cationic, metal component of the charge director by the solvation sites
- the enthalpy of solvation here is generally a large negative value (i.e., the solvation reaction involves an enthalpy of solvation that is more negative than about -50 kJ/mole, preferably more negative than about -100 kJ/mole, most preferably more negative than about -500 J/mole) .
- the present invention encompasses novel toner and developer compositions.
- the novel toner is useful for formulating a liquid developer composition in which conductivity and charge are both substantially particle-mediated, as explained above.
- the toner of the invention includes two basic components: (a) resin; and (b) colorant.
- the present invention involves, as noted above, the incorporation of a material containing specific solvation sites into the resinous phase of the toner particle.
- Materials which may be incorporated into the resinous phase of the toner particle may be either monomeric or polymeric or both.
- Preferred monomeric species are those which contain polar moieties as the solvation sites, e.g., sulfhydryl groups, amines, or oxygenic moieties such as hydroxyl groups, carboxyl groups, ketones, amides, and ethers. Most exceptional, however, are hydroxy1- containing monomeric species. Examples of monomeric species which may be incorporated into the toner resin to provide such specific solvation sites include sugars, e.g., mannitol, sorbitol, xylitol and the like.
- the material containing specific solvation sites be polymeric.
- Preferred polymers like preferred monomers, are those which contain as the specific solvation sites hydroxyl groups, sulfhydryl groups, carboxyl groups, ketones, amides, ethers, and/or amines.
- An example of a class of polymers useful herein which contain ketone moieties as the specific solvation sites are acrylates.
- An example of an amide-containing polymer is nylon, while an exemplary ether-containing polymer is polyethylene oxide.
- An example of an amino-containing polymer for use herein is polyvinyl pyridine.
- Examples of particularly preferred polymers for use herein are ethylene-acrylic acid copolymers, ethylene-vinyl alcohol copolymers, styrene-allyl alcohol copolymers, cellulose acetate- butyrate copolymers, hydroxyalkyl aerylate copolymers, and ionomers and mixtures thereof. It will be appreciated by those skilled in the art, however, that a wide range of polymeric materials may be used herein, so long as the selected material enables solvation of the charge director to give a highly stable toner/charge director complex, and does not interact in a deleterious manner with any of the other components of the developer composition.
- the materials containing specific solvation sites be non-ionized under the conditions used in electrophotographic development, i.e., such that at least about 80%, more preferably at least about 90%, and most preferably at least about 95%, of the solvation sites are not ionized during ordinary conditions of storage and use.
- the solvation sites are readily ionizable species, such as carboxyl groups, again, as noted above, it is preferred that additional acid be included in the developer composition so that the ionization of the carboxyl groups is suppressed. Typically, this will involve adding the acid form of the charge director counterion.
- the charge director counterion is diisopropylsalicylate (DIPS)
- DIPS diisopropylsalicylate
- the metal ion which serves as the cationic component of the charge director is one that will be solvated exothermically by aforementioned material, e.g., aluminum, magnesium, chromium, iron, or the like.
- Preferred metals are those which have very negative enthalpies of hydration and thus, herein, give rise to an enthalpy of solvation that is more negative than about -500 kJ/ ol, more preferably more negative than about -1000 kJ/mol.
- Such values will give rise to a charged toner complex which is extremely stable, in turn enabling preparation of a liquid developer composition having a virtually indefinite shelf-life.
- This aspect of the invention represents a tremendous advantage relative to currently available developer compositions, which can be relatively unstable and have a finite shelf-life.
- the colorants which may be used in the toner can include virtually any pigments, dyes or stains which may be incorporated in the toner resin and which are effective to make visible the electrostatic latent image.
- suitable colorants include: Phthalocyanine blue (C.I. 74160), Diane blue (C.I. 21180), Milori blue (an inorganic pigment equivalent to ultramarine) as cyan colorants; Brilliant carmine 6B (C.I. 15850), Quina- cridone magenta (C.I. Pigment Red 122) and Thio indigo magenta (C.I. 73310) as magenta colorants; benzidine yellow (C.I. 21090 and C.I. 21100) and Hansa Yellow (C.I.
- the developer compositions of the invention contain the aforementioned toner, together with a selected charge director, as described above, dispersed in an insulating carrier liquid.
- charge directors include as a counterion the intramolecularly stabilized anion of an ortho-hydroxy aromatic acid, e.g., salicylic acid or a derivative thereof.
- an ortho-hydroxy aromatic acid e.g., salicylic acid or a derivative thereof.
- derivative intends to include salicylic acid substituted with one to four, typically one to two, substituents independently selected from the group consisting of lower alkyl (1-6C) , lower alkoxy (1-6C) , halogen, amino, hydroxy, nitro and sulfonate.
- substituents independently selected from the group consisting of lower alkyl (1-6C) , lower alkoxy (1-6C) , halogen, amino, hydroxy, nitro and sulfonate.
- charge directors may typically be represented by the formula (RO ) ⁇ 1 (AA ) in which M is a metal atom, AA " represents the anion of the ortho- hydroxy aromatic acid, and R is selected from the group consisting of R-CO-, C 1 ⁇ C 15 alkyl, n is 2, 3 or 4, and x and y are integers the sum of which, clearly, is n.
- the metal atom "M” may be divalent, trivalent or tetravalent, with those metal atoms that will coordinate most strongly with the toner resin being preferred.
- AA ⁇ is diisopropyl salicylate ( DIP S)
- R is c 1 o 21 CO ⁇
- **-••** • •' R ' is C 1 0 H 2 1 ⁇ ' n is 3
- x is 1 or 2
- y is 1 or 2.
- a second class of charge directors useful herein is described in detail in parent U.S. Patent Application Serial No. 07/546,044, also incorporated by reference.
- These charge directors are of the formula (X ⁇ ) a M +n (AA ⁇ ) b in which M is a metal atom as described above, AA " represents the anion of an ortho-hydroxy aromatic acid as described with regard to the charge directors of Serial No. 07/464,906, X ⁇ represents the anion of an a, ⁇ -diketone, n is 2, 3 or 4, and a and b are integers the sum of which is equal to n, with the proviso that neither a nor b is 0.
- the anion X ⁇ represents the anion of an , ⁇ -diketone, one which preferably has the formula:
- R and R" * are independently selected from the group consisting of hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, haloalkyl, aryl, alkaryl, and haloaryl. If alkyl, alkenyl, alkynyl, cycloalkyl, or haloalkyl, the substituent preferably contains from about 1 to about 12 carbon atoms, more preferably from about 1 to about 6 carbon atoms (wherein the latter type of moiety is sometimes referred to herein as "lower” alkyl, akenyl, alkynyl, etc.).
- the substituent preferably contains one to about three rings, more preferably, one to two rings, and most preferably is monocyclic.
- An example of a particularly preferred ⁇ , ⁇ - diketone is acetyl acetone, i.e., wherein R 1 and R2 are both methyl.
- the developer compositions of the invention contain toner and developer dispersed in an electrically insulating carrier liquid as well-known in the art.
- the liquid is typically oleophilic, stable under a variety of conditions, and electrically insulating. That is, the liquid has a low dielectric constant and a high electrical resistivity so as not to interfere with development of the electrostatic charge pattern.
- the carrier liquid has a dielectric constant of less than about 3.5, more preferably less than about 3, and a volume resistivity greater than about 10 9 ohm-cm, more preferably greater than about 10 10 ohm-cm.
- suitable carrier liquids include halogenated hydrocarbon solvents such as carbon tetrachloride, trichloroethylene, and the fluorinated alkanes, e.g., trichloromonofluoromethane and trichlorotrifluoroethane (sold under the trade name "Freon” by the DuPont Company) ; acyclic or cyclic hydrocarbons such as cyclohexane, n-pentane, isooctane, hexane, heptane, decane, dodecane, tetradecane, and the like; aromatic hydrocarbons such as benzene, toluene, xylene, and the like; silicone oils; molten paraffin; and the paraffinic hydrocarbon solvents sold under the names Isopar G, Isopar H, Isopar K and Isopar L (trademarks of Exxon Corporation) .
- Toner is prepared by admixing resin and colorant at an elevated temperature, followed by dry comminution. The intermediate particles so provided are then subjected to liquid attrition to give the final toner particles.
- Resin and colorant are admixed at a temperature in the range of about 70°C to 200°C.
- a two-roll mill, an extruder, an intensive mixer or the like is used to ensure complete mixing.
- the admixture is then comminuted dry, i.e., without addition of liquid, to give intermediate particles typically averaging 30 mils in diameter or less.
- This dry comminution step is carried out in a jet mill, a hammer mill, or the like.
- the intermediate particles so obtained are then subjected to liquid attrition in a selected attrition liquid to give the final toner particles.
- the liquid used for attrition is typically selected from the same class of liquids useful as the carrier liquid for the developer composition, as will be described below.
- the developer compositions of the invention prepared by dispersion of toner and charge director in the insulating carrier liquid — can contain additional materials, e.g., an incompatible phase such as a wax, which is preferably incorporated into the toner at the initial stage of manufacture, i.e., admixed with the colorant, resin, etc., in step (a) (see related application Serial No. 07/464,896).
- the developer can also contain an antistain agent to reduce the problem of background staining, as discussed in the parent application hereto; again, the antistain agent is preferably incorporated into the composition at the stage of toner manufacture.
- the developer composition can also contain other materials as known in the art, e.g., dispersants, stabilizers and the like.
- a consecutive multicolor image development process (or a "consecutive color toning" process) using the materials of the invention may be carried out as follows.
- the surface of a photoconductive insulating layer on a relatively conductive substrate is charged, and an initial electrostatic charge pattern (or "latent image") is formed on that surface by exposure through a colored transparency.
- This latent image is then developed with a liquid developer composition of a first color, i.e., comprising toner formulated with a first colorant, typically yellow.
- the photoconductive layer is then discharged, either optically or non-optically, i.e., via a corona. These steps are then repeated in sequence with developer compositions of different colors, typically (in order) magenta, cyan and black, at which point the developed image may, if desired, be transferred to another substrate, e.g., paper.
- compositions of the invention i.e., compositions which involve a solvation interaction between the surface of the toner particles and the incorporated charge director, it is possible to carry out the aforementioned sequence of steps without any intermediate processing steps, i.e., rinsing, drying or the like. These steps have typically been necessary in the prior art, as exemplified by the Alexandrovich et al. patent, cited supra, to address the problem of image staining.
- compositions and processes of the invention address and overcome a number of significant obstacles heretofore present in color electrophotographic image development.
- RJ-100 a styrene-allyl alcohol copolymer obtained from Allied Chemical Corp. , Morristown, New Jersey
- RJ-100 a styrene-allyl alcohol copolymer obtained from Allied Chemical Corp. , Morristown, New Jersey
- To the polymer melt was added 32 g of Heliogen Blue, 3 g of Pigment Green 7 and 0.9 g of Sicofast Yellow D-1155. Mixing was done in 30 minutes, at which time 10 g of carnauba wax was added. After an additional 15 minutes of mixing the mill was cooled and the resultant product was removed. This mixture was cryogenically comminuted on a hammer mill. Thirty g of this powder were charged into an attritor with 130 g of Isopar G (Exxon). After 45 minutes, the attrition was terminated, discharged from the attritor and diluted with 130 g of Isopar to give a 10% concentrate.
- Isopar G Exxon
- Example 3 The procedure of Example 1 was repeated, except that RJ-100 was replaced with ACX 260, an ethylene vinyl acetate/vinyl alcohol copolymer (obtained from Allied Chemical Corp.). Substantially the same results — with respect to stable conductivity, shelf-life, and image quality — were obtained.
- Example 3
- Example 1 The procedure of Example 1 was repeated, except that the charge director used, instead of aluminum diisopropyl salicylate, was chromium octoate. Substantially the same results — with respect to stable conductivity, shelf-life, and image quality — were obtained.
- Example 1 The procedure of Example 1 was repeated, except that the charge director used, instead of aluminum diisopropyl salicylate, was aluminum tri-neodecanoate (Mooney Chemical) . Substantially the same results — with respect to stable conductivity, shelf-life, and image quality — were obtained.
- the charge director used instead of aluminum diisopropyl salicylate, was aluminum tri-neodecanoate (Mooney Chemical) .
- Mooney Chemical aluminum tri-neodecanoate
- Example 6 The procedure of Example 1 was repeated, except that the charge director used, instead of aluminum diisopropyl salicylate, was copper octoate (Mooney Chemical) . Substantially the same results — with respect to stable conductivity, shelf-life, and image quality — were obtained.
- the charge director used instead of aluminum diisopropyl salicylate, was copper octoate (Mooney Chemical) . Substantially the same results — with respect to stable conductivity, shelf-life, and image quality — were obtained.
- Example 1 The procedure of Example 1 was repeated, except that the charge director used, instead of aluminum diisopropyl salicylate, was ferric octoate (Mooney Chemical) . Substantially the same results — with respect to stable conductivity, shelf-life, and image quality — were obtained.
- Example 1 The procedure of Example 1 was repeated, except that the charge director used, instead of aluminum tri- neodecanoate, was aluminum dinonylnaphthalene sulfonate. Substantially the same results — with respect to stable conductivity, shelf-life, and image quality — were obtained.
- Example 2 The procedure of Example 1 was repeated, except that the charge director used, instead of aluminum diisopropyl salicylate, was Al(AcAc) (DIPS) 2 , wherein
- AcAc represents acetyl acetonate
- DIPS diisopropyl salicylate
- This charge director was prepared as follows. Aluminum acetyl acetonate (Aldrich Chemical Co., 6.4 g; 0.2 mL) and 8.88 g of diisopropyl salicylic acid (Aldrich Chemical Cc.) were dissolved in 100 g of toluene. The resultant solution was heated at 95-100°C for 2 hours. The solvent was removed at 95°C (steambath) in vacuo, leaving 11.3 g of a viscous glass. The latter was dissolved in 25 mL of hot acetone. Upon removal of the acetone in vacuo, a brittle foam resulted which was dried at 70°C for 24 hours.
- ACX 251 an ethylene-vinyl alcohol polymer obtained from Allied Chemical
- ACX 251 an ethylene-vinyl alcohol polymer obtained from Allied Chemical
- Mixing was continued for 30 minutes.
- the mill was cooled and the product removed and processed to a 10% concentrate as described in Example 1.
- To 400 g of 1% working developer was added 0.6 g of a 1% solution of aluminum tri-neodecanoate (Mooney Chemical) .
- the conductivity was 7.8 pmhos.
- the shelf-life of the developer was quite superior. This positively charged developer yielded excellent, dense, high resolution images on ZnO photoconductors.
- Example 10 An ethylene-vinyl alcohol polymer obtained from Allied Chemical
- Example 9 The procedure of Example 9 was repeated, except that the charge director used, instead of aluminum tri- neodecanoate, was aluminum diisopropyl salicylate. Substantially the same results — with respect to stable conductivity, shelf-life, and image quality — were obtained.
- Example 9 The procedure of Example 9 was repeated, except that the charge director used, instead of aluminum tri- neodecanoate, was zirconium di-neodecanoate (Mooney Chemical) . Substantially the same results — with respect to stable conductivity, shelf-life, and image quality — were obtained.
- Example 9 The procedure of Example 9 was repeated, except that the charge director used, instead of aluminum tri- neodecanoate, was ferric tri-naphthenate (Nuodex) .
- Example 9 The procedure of Example 9 was repeated, except that the charge director used, instead of aluminum tri- neodecanoate, was Al(AcAc) (DIPS) 2 , wherein "AcAc” and “DIPS" are defined above.
- the charge director was prepared as described in Example 8.
- AC 201 resin (Allied Chemical) were placed onto a two-roll mill at 100°C. To the polymer melt was added 52 g of Sicofast D-1155. After 30 minutes of mixing, 60 g of AC 540 resin (Allied) and 60 g of AC 7 (Allied) were added. After 15 minutes of mixing, 10 g of Ethomid HT 60 dispersant (obtained from Akzo) and 13 g of WB-17 dispersant (Petrolite) were added. Mixing was continued for 20 minutes and the product was discharged and processed to give a 10% developer as described in Example 1.
- AC 201 resin Allied Chemical
- Example 14 The procedure of Example 14 was repeated, except that the charge director used, instead of aluminum diisopropyl salicylate, was Al(AcAc) (DIPS) - where i n
- Example 14 The procedure of Example 14 is repeated, except that Sicofast D-1155 is replaced with Hostaperm Red E5B- 02. Substantially the same results — with respect to stable conductivity, shelf-life, and image quality — were obtained.
- Example 14 The procedure of Example 14 is repeated, except that Sicofast D-1155 is replaced with Heliogen Blue L- 7080. Substantially the same results — with respect to stable conductivity, shelf-life, and image quality — were obtained.
- Example 14 The procedure of Example 14 is repeated, except that Sicofast D-1155 is replaced with Novaperm Yellow FGL. Substantially the same results — with respect to stable conductivity, shelf-life, and image quality were obtained.
- Example 14 The procedure of Example 14 is repeated, except that Sicofast D-1155 is replaced with Indofast Brilliant Scarlet R-6335. Substantially the same results — with respect to stable conductivity, shelf-life, and image quality — were obtained.
- Example 14 The procedure of Example 14 is repeated, except that Sicofast D-1155 is replaced with Quindo Magenta RV6832. Substantially the same results — with respect to stable conductivity, shelf-life, and image quality — were obtained.
- Example 14 The procedure of Example 14 is repeated, except that Sicofast D-1155 is replaced with Quindo Red 6713.
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Developing Agents For Electrophotography (AREA)
- Liquid Developers In Electrophotography (AREA)
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US58243190A | 1990-09-13 | 1990-09-13 | |
US582431 | 1990-09-13 | ||
PCT/US1990/006837 WO1992005476A1 (en) | 1990-09-13 | 1990-11-21 | Solvation-based charge direction of liquid electrophotographic developer compositions |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0548076A1 EP0548076A1 (en) | 1993-06-30 |
EP0548076A4 true EP0548076A4 (en) | 1993-11-10 |
EP0548076B1 EP0548076B1 (en) | 2001-06-13 |
Family
ID=24329130
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP91902923A Expired - Lifetime EP0548076B1 (en) | 1990-09-13 | 1990-11-21 | Solvation-based charge direction of liquid electrophotographic developer compositions |
Country Status (8)
Country | Link |
---|---|
EP (1) | EP0548076B1 (en) |
JP (1) | JP3238148B2 (en) |
KR (1) | KR100195463B1 (en) |
AT (1) | ATE202220T1 (en) |
AU (1) | AU7151691A (en) |
CA (2) | CA2092707C (en) |
DE (1) | DE69033748T2 (en) |
WO (1) | WO1992005476A1 (en) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE4109086A1 (en) * | 1991-03-20 | 1992-09-24 | Basf Ag | ELECTROSTATIC TONER CONTAINING A KETO CONNECTION AS A CHARGE STABILIZER |
US5445911A (en) * | 1993-07-28 | 1995-08-29 | Hewlett-Packard Company | Chelating positive charge director for liquid electrographic toner |
EP1504312A1 (en) | 2002-01-31 | 2005-02-09 | Hewlett-Packard Indigo B.V. | Image transfer system and liquid toner for use therewith |
JP4937342B2 (en) | 2006-05-10 | 2012-05-23 | ヒューレット−パッカード デベロップメント カンパニー エル.ピー. | Charge director for liquid toner |
JP6609924B2 (en) * | 2015-01-14 | 2019-11-27 | コニカミノルタ株式会社 | Solvent of metal complex compound, toner using the same, method for producing the same, and developer |
JP2019028233A (en) * | 2017-07-28 | 2019-02-21 | 富士ゼロックス株式会社 | Liquid developer, liquid developer cartridge, image forming apparatus, and image forming method |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0376460A1 (en) * | 1988-12-02 | 1990-07-04 | Minnesota Mining And Manufacturing Company | Liquid electrophotographic toner |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3753760A (en) * | 1970-01-30 | 1973-08-21 | Hunt P | Liquid electrostatic development using an amphipathic molecule |
US4156034A (en) * | 1974-03-20 | 1979-05-22 | Hitachi, Ltd. | Liquid developer for electro photography |
JPS5987463A (en) * | 1982-11-10 | 1984-05-21 | Dainippon Printing Co Ltd | Electrophotographic wet type toner |
SE8604684L (en) * | 1986-11-03 | 1988-05-04 | Excorim Kommanditbolag | SET TO COAT SOLID PARTICLES WITH A HYDROPHIL GEL AND THROUGH SEAT COATED PARTICLES |
JPH01211711A (en) * | 1988-02-19 | 1989-08-24 | Asahi Optical Co Ltd | Telephoto lens |
US4957844A (en) * | 1989-03-31 | 1990-09-18 | Dximaging | Liquid electrostatic developer containing multiblock polymers |
-
1990
- 1990-11-21 KR KR1019930700772A patent/KR100195463B1/en not_active IP Right Cessation
- 1990-11-21 AT AT91902923T patent/ATE202220T1/en not_active IP Right Cessation
- 1990-11-21 EP EP91902923A patent/EP0548076B1/en not_active Expired - Lifetime
- 1990-11-21 DE DE69033748T patent/DE69033748T2/en not_active Expired - Fee Related
- 1990-11-21 AU AU71516/91A patent/AU7151691A/en not_active Abandoned
- 1990-11-21 JP JP50320791A patent/JP3238148B2/en not_active Expired - Fee Related
- 1990-11-21 WO PCT/US1990/006837 patent/WO1992005476A1/en active IP Right Grant
- 1990-11-21 CA CA002092707A patent/CA2092707C/en not_active Expired - Fee Related
- 1990-11-23 CA CA002030585A patent/CA2030585A1/en not_active Abandoned
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0376460A1 (en) * | 1988-12-02 | 1990-07-04 | Minnesota Mining And Manufacturing Company | Liquid electrophotographic toner |
Also Published As
Publication number | Publication date |
---|---|
JP3238148B2 (en) | 2001-12-10 |
CA2092707A1 (en) | 1992-03-13 |
AU7151691A (en) | 1992-04-15 |
WO1992005476A1 (en) | 1992-04-02 |
EP0548076B1 (en) | 2001-06-13 |
CA2092707C (en) | 2001-06-12 |
DE69033748D1 (en) | 2001-07-19 |
JPH06503891A (en) | 1994-04-28 |
KR100195463B1 (en) | 1999-06-15 |
CA2030585A1 (en) | 1992-03-14 |
EP0548076A1 (en) | 1993-06-30 |
DE69033748T2 (en) | 2001-09-20 |
ATE202220T1 (en) | 2001-06-15 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US5045425A (en) | Electrophotographic liquid developer composition and novel charge directors for use therein | |
US5366840A (en) | Liquid developer compositions | |
US4760009A (en) | Process for preparation of liquid toner for electrostatic imaging | |
US5308731A (en) | Liquid developer compositions with aluminum hydroxycarboxylic acids | |
US5306591A (en) | Liquid developer compositions having an imine metal complex | |
EP0485391B1 (en) | Electrophotographic toner and developer compositions and color reproduction processes using same | |
EP0435129A1 (en) | Metal salts of beta-diketones as charging adjuvants for electrostatic liquid developers | |
US5397672A (en) | Liquid developer compositions with block copolymers | |
US5069995A (en) | Stain elimination in consecutive color toning | |
US5679492A (en) | Developer compositions | |
EP0548076B1 (en) | Solvation-based charge direction of liquid electrophotographic developer compositions | |
US5153090A (en) | Charge directors for use in electrophotographic compositions and processes | |
US4994341A (en) | Organometallic compounds as mottle prevention additives in liquid electrostatic developers | |
US5840453A (en) | Solvation-based charge direction of electrophotographic developer compositions | |
US5409796A (en) | Liquid developer compositions with quaternized polyamines | |
EP0315117A2 (en) | Process for preparation of liquid electrostatic developer | |
US5411834A (en) | Liquid developer compositions with fluoroalkyl groups | |
EP0889370A1 (en) | Liquid developer compositions | |
US5942365A (en) | Developer compositions and imaging processes | |
US5407775A (en) | Liquid developer compositions with block copolymers | |
US4851316A (en) | Liquid toner compositions with amino acids and polyvalent metal complexes as charge control additives | |
JPH073606B2 (en) | Electrophotographic liquid developer | |
CA2172434C (en) | Electrophotographic toner and developer compositions and color reproduction processes using same | |
US5262266A (en) | Halogenated charge directors for liquid developers | |
US5604075A (en) | Liquid developer compositions and processes |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 19930317 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE CH DE DK ES FR GB GR IT LI LU NL SE |
|
A4 | Supplementary search report drawn up and despatched |
Effective date: 19930920 |
|
AK | Designated contracting states |
Kind code of ref document: A4 Designated state(s): AT BE CH DE DK ES FR GB GR IT LI LU NL SE |
|
17Q | First examination report despatched |
Effective date: 19951002 |
|
GRAG | Despatch of communication of intention to grant |
Free format text: ORIGINAL CODE: EPIDOS AGRA |
|
GRAG | Despatch of communication of intention to grant |
Free format text: ORIGINAL CODE: EPIDOS AGRA |
|
GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE CH DE DK ES FR GB GR IT LI LU NL SE |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20010613 Ref country code: LI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20010613 Ref country code: GR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20010613 Ref country code: CH Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20010613 Ref country code: BE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20010613 Ref country code: AT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20010613 |
|
REF | Corresponds to: |
Ref document number: 202220 Country of ref document: AT Date of ref document: 20010615 Kind code of ref document: T |
|
REF | Corresponds to: |
Ref document number: 69033748 Country of ref document: DE Date of ref document: 20010719 |
|
ET | Fr: translation filed | ||
ITF | It: translation for a ep patent filed | ||
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20010913 Ref country code: DK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20010913 |
|
NLV1 | Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act | ||
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20011121 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20011220 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: IF02 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20020116 Year of fee payment: 12 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20020128 Year of fee payment: 12 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed | ||
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20021121 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20030603 |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee | ||
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20030731 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: RN |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20041109 Year of fee payment: 15 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: IC |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED. Effective date: 20051121 |