EP0456659A1 - Ladungssteuerungszusammensetzung - Google Patents
LadungssteuerungszusammensetzungInfo
- Publication number
- EP0456659A1 EP0456659A1 EP90902057A EP90902057A EP0456659A1 EP 0456659 A1 EP0456659 A1 EP 0456659A1 EP 90902057 A EP90902057 A EP 90902057A EP 90902057 A EP90902057 A EP 90902057A EP 0456659 A1 EP0456659 A1 EP 0456659A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- charge director
- solvent
- charge
- monomer species
- polar monomer
- 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
- 239000000203 mixture Substances 0.000 title claims abstract description 25
- 239000000178 monomer Substances 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 24
- 239000002904 solvent Substances 0.000 claims abstract description 20
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 10
- 230000000087 stabilizing effect Effects 0.000 claims abstract description 10
- IIZPXYDJLKNOIY-JXPKJXOSSA-N 1-palmitoyl-2-arachidonoyl-sn-glycero-3-phosphocholine Chemical group 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 claims description 18
- 239000000787 lecithin Substances 0.000 claims description 18
- 229940067606 lecithin Drugs 0.000 claims description 18
- 235000010445 lecithin Nutrition 0.000 claims description 18
- 229920000642 polymer Polymers 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- CNPVJWYWYZMPDS-UHFFFAOYSA-N 2-methyldecane Chemical group CCCCCCCCC(C)C CNPVJWYWYZMPDS-UHFFFAOYSA-N 0.000 claims description 7
- YCIGYTFKOXGYTA-UHFFFAOYSA-N 4-(3-cyanopropyldiazenyl)butanenitrile Chemical compound N#CCCCN=NCCCC#N YCIGYTFKOXGYTA-UHFFFAOYSA-N 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 2
- 229920006112 polar polymer Polymers 0.000 claims description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 2
- 230000000977 initiatory effect Effects 0.000 claims 2
- 150000002894 organic compounds Chemical class 0.000 claims 2
- 239000003960 organic solvent Substances 0.000 claims 2
- 229910052786 argon Inorganic materials 0.000 claims 1
- 239000011261 inert gas Substances 0.000 claims 1
- 229910052757 nitrogen Inorganic materials 0.000 claims 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 239000007788 liquid Substances 0.000 description 29
- 239000000243 solution Substances 0.000 description 29
- 239000000693 micelle Substances 0.000 description 24
- 230000015556 catabolic process Effects 0.000 description 16
- 238000006731 degradation reaction Methods 0.000 description 16
- 239000002245 particle Substances 0.000 description 8
- 230000007423 decrease Effects 0.000 description 7
- 230000005684 electric field Effects 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 7
- 238000003384 imaging method Methods 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000003999 initiator Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000012454 non-polar solvent Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 230000007928 solubilization Effects 0.000 description 2
- 238000005063 solubilization Methods 0.000 description 2
- YTZKOQUCBOVLHL-UHFFFAOYSA-N tert-butylbenzene Chemical compound CC(C)(C)C1=CC=CC=C1 YTZKOQUCBOVLHL-UHFFFAOYSA-N 0.000 description 2
- QQBUHYQVKJQAOB-UHFFFAOYSA-N 2-ethenylfuran Chemical compound C=CC1=CC=CO1 QQBUHYQVKJQAOB-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 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
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 239000013626 chemical specie Substances 0.000 description 1
- 230000001687 destabilization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- CRMMZOTYFUQOCW-UHFFFAOYSA-N phenyl-(2,3,4-triphenylphenyl)diazene Chemical compound C1=CC=CC=C1N=NC(C(=C1C=2C=CC=CC=2)C=2C=CC=CC=2)=CC=C1C1=CC=CC=C1 CRMMZOTYFUQOCW-UHFFFAOYSA-N 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film 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
- G03G9/13—Developers with toner particles in liquid developer mixtures characterised by polymer components
- G03G9/131—Developers with toner particles in liquid developer mixtures characterised by polymer components obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- 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
-
- 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
-
- 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
Definitions
- the present invention relates to liquid developer electrostatic photocopying and more particularly to a method of stabilizing charge director solutions and a new stabilized charge director composition.
- a photoconductive imaging surface is first provided with a uniform electrostatic charge, typically by moving the imaging surface past a charge corona at a uniform velocity.
- the imaging surface is then exposed to an optical image of an original to be copied.
- This optical image selectively discharges the imaging surface in a pattern to form a latent electrostatic image.
- this latent image consists of substantially undischarged print / portions corresponding to the graphic matter on the original, amidst a "background" portion that has been substantially discharged by exposure to light.
- the latent image is developed by exposure to oppositely charged, pigmented, toner particles, which deposit on the print portions of the latent image in a pattern corresponding to that of the original.
- these charged toner particles are suspended in a liquid developer comprising a carrier liquid, toner particles and charge directors.
- the entire latent electrostatic image is covered with a thin film of liquid developer from a liquid developer reservoir.
- the charged toner particles in the liquid developer migrate to the oppositely charged / print / portions of the latent image to form a pattern on the photoconductive surface. This pattern, and the corresponding toner particles, are then transferred to a sheet to produce a visible image. Any liquid developer remaining on the photoconductive surface after this process is recycled back into the liquid developer reservoir.
- Charge director plays an important role in the developing process described above.
- the charge director is a chemical species, either molecular or ionic, which acts to control the polarity and charge on the toner particles.
- the charge director creates charged species causing charging of the imaging material to ensure that the toner particles will be deposited and migrate in such a way as to form the desired image on the imaging surface.
- Counter ions are also created to keep the liquid developer substantially electrically neutral overall.
- the present invention may be practiced with any number of charge directors, of which lecithin and barium petronate are examples.
- the charge director molecules form inverse micelles.
- An example of these micelles is shown in Figure 1.
- the micelles are formed by aggregation such that the polar portions of the charge director molecules point inside, and the nonpolar portions point outside to decrease the overall surface energy of the system.
- These micelles may solubilize ions generated by the disassociation of the charge director molecules. It is believed that the solubilization of ions by the charge director micelles is due to the formation within and around the micelles, of a microenvironment having a higher dielectric constant.
- the solubilization of ions by the charge director micelles results in micelles containing a charged species in their center. Some of the micelles have a positive species in the center and others have a negative species in the center.
- one object of the present invention is a charge director composition which will resist degradation under the influence of an electric field.
- Another object of the present invention is a charge director composition which will resist degradation during the replenishment of carrier liquid in a liquid developer dispersion.
- a further object of the present invention is a charge director solution which will resist destabiliza- tion.
- Figure 1 is an idealized depiction of charge director micelles.
- Figure 2 is a graphic representation of the current in a lecithin solution for 4 successive electric pulses.
- Figure 3 is a graphic representation of the conductivity kinetics under dilution of lecithin and the material of the present invention.
- Figure 4 is a graphic representation of the stability of various charge director compositions of the present invention.
- Figure 5 shows the absolute change in conductivity during a long developing run for a 21% coverage target for lecithin and a charge director of the present invention.
- the present invention is directed to a method of stabilizing a charge director solution wherein a charge director, a solvent, and a polar monomer species are mixed, and subsequently the monomer molecules are polymerized.
- An initiator species is used to begin the polymerization and the reaction is allowed to proceed to substantial completion.
- the polar species stabilizes the core of the micelles and reduces the possibility of the micelle rupturing.
- charge director micelles are associated with insoluble polymer molecules so that the charged species are more stable and less susceptible to degradation. It will be appreciated that by reducing the degradation of the charged species of the liquid developer composition the images formed by the developer will be denser over a longer period of usage, since the presence of the charged species is essential to the electrophoretic imaging process.
- a charge director, a solvent, and a polar monomer species are mixed, and subsequently the monomer molecules are polymerized.
- An initiator species is used to begin the polymerization and the reaction is allowed to proceed to substantial completion.
- the polymer species which are formed are not soluble, the monomeric species of the present invention are soluble in the solvent containing the charge director.
- the charge director which is at least partially present as micelles, acts as a surfactant for the polymerization of the monomer species. It is believed the monomer species clings to the micelle and polymerizes in the core of the micelle.
- the selected solvent may be any.suitable solvent in which the necessary polymerization may occur. Many nonpolar solvents will work well in the present invention, including: Isopar (a trade arked product of the Exxon Corporation) , Isoparafine, hexane, cyclohexane, t-butylbenzene, 2,2, -trimethylpentane, and normal paraffins.
- the monomer species chosen may be any unsaturated monomer that is soluble in the selected solvent and polymerizes in the solvent in the presence of an appropriate initiator. It is believed a large number of unsaturated molecules will work well in the present invention as a monomer, but . certain species should work especially well, including l-vinyl-2- pyrrolidone, 2-vinyl pyridine, vinylfuran, and methylmethacrylate.
- the initiator may be any one of a large number of species which will initiate a polymerization reaction, including azobisbutyronitrile, benzoyl peroxide, triphenylazobenzene, cumene hydroperoxide, and t-butyl peracetate.
- Isopar is heated to approximately 50 degrees C in a reaction vessel fitted with a reflux condenser
- the reaction is run under a nitrogen atmosphere.
- Lecithin is slowly mixed into the Isopar.
- the solution is heated to about 80-90 degrees C and l-vinyl-2- pyrrolidone is added, followed by a polymerization initiator, e.g., azobisbutyronitrile.
- the temperature is kept constant, and the reaction is allowed to proceed for about 24 hours.
- the charge director composition formed by this process will be less subject to degradation of the charge-carrying species than a composition lacking the stabilizing polymer molecules. This superior resistance to degradation will be exhibited both when an electric current is applied to the composition, and when the composition is -diluted with solvent (Isopar) .
- a nonpolar solvent in which the-l-vinyl-2-pyrrolidone monomer is soluble, but the polymer is insoluble.
- the solvent should boil at a significantly higher temperature than 90 C, so that it will remain liquid under the reaction conditions. It is believed that, as the polymerization reaction progresses, the polymer molecules will reach a critical length above which they are insoluble in the solvent; a very fine dispersion of these polymer molecules in the solvent results, and the charge director micelles form around the polymer molecules. The micelles in turn are rigidized and stabilized by the polymer molecules.
- the critical percent of vinyl pyrrolidone polymer needed to obtain a large stabilization effect is between about 5- 9% on a weight-to-weight basis with respect to the charge director solids. With a polymer concentration of 9% or more, very little degradation of the charged species occurs upon dilution with solvent or the imposition of an electric field. Below a 5% polymer concentration, however, a significant amount of degradation will occur.
- the present invention is further illustrated by, but not limited to, the following examples.
- Isopar-H Under a nitrogen atmosphere, 1400 grams of Isopar-H was heated to 50 deg. C in a 4-necked, 2 liter, mechanically stirred glass reactor fitted with a reflux condenser. 600 grams of lecithin was dissolved in the Isopar-H by slow addition and stirring. The Isopar- H/Lecithin solution was then heated to 80 6 C and then 102 grams of l-vinyl-2-pyrrolidone was added to the solution. Three grams of azobisbutyronitrile suspended in 10-20 ml. of Isopar-H was then added, and the reaction allowed to proceed for 24 hours to completion.
- Table 1 and Figure 2 show the results of our experiment on the effect of an applied electric field to a common unstabilized charge director, lecithin, solution.
- Table 1 shows the charge transport in the solution for each pulse.
- Figure 2 is a graphic representation of the current in the Lantern solution during the time period of the pulse.
- Table 1 and Figure 2 the application of an electric pulse to a charge director solution changes the electrical properties of the solution.
- the applied electric pulse of the experiment is similar to the electric field created during the copying process.
- the effect of the electric pulse on the lecithin solution resembles the effect of the electric field created during the copying process of the liquid developer solution.
- Figure 3 show the conductivity of a composition comprising 17% monomer stabilized species by weight with respect to charge director solids, according to the present invention as compared to a lecithin control, in both cases after addition of a carrier liquid such as Isopar H.
- the conductivity of the stabilized composition in Isopar remains relatively constant with time, while that of the control decreases with time.
- the stabilized composition of the present invention is advantageous for use in a photocopier since the conductivity will not change appreciably with time.
- FIG 4 shows the results of a similar experiment on various stabilized charge director compositions according to the present invention.
- 800 V. DC pulses were sequentially applied to a cell containing a charge director solution and the total charge transport in the cell was measured for each pulse.
- the control charge director solution was an unstabilized lecithin solution as used in the above- mentioned experiment.
- Five stabilized charge director solutions made according to the present invention were also tested. Each charge director solution was made with a different percentage of the monomer stabilizing species. As shown in Figure 4, the charge director should comprise between 5% and 9% by weight with respect to charge director solids or more of the monomer stabilizing species to achieve a high degree of charge transport constancy.
- FIG. 4 shows the results of an experiment on the decrease in conductivity of a charge director solution during continuous electrophotocopier operation with no paper feed.
- the lecthin charge director solution shown on the chart is an unstabilized ordinary charge director solution.
- the other charge director is made according to example 1 of the present invention comprising 17% monomer stabilizing species by weight with respect to charge director solids.
- the unstabilized lecithin solution had a decrease of an 18picomho/cm in conductivity during the electyrophotocopier operation.
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Liquid Developers In Electrophotography (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US30615589A | 1989-02-06 | 1989-02-06 | |
| US306155 | 1989-02-06 | ||
| PCT/US1990/000155 WO1990008983A1 (en) | 1989-02-06 | 1990-01-16 | Charge director composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0456659A1 true EP0456659A1 (de) | 1991-11-21 |
| EP0456659B1 EP0456659B1 (de) | 2004-06-30 |
Family
ID=23184074
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP90902057A Expired - Lifetime EP0456659B1 (de) | 1989-02-06 | 1990-01-16 | Ladungssteuerungszusammensetzung |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP0456659B1 (de) |
| JP (1) | JP3076921B2 (de) |
| KR (1) | KR0180733B1 (de) |
| CN (1) | CN1041462C (de) |
| CA (1) | CA2026212C (de) |
| DE (1) | DE69034151T2 (de) |
| MX (1) | MX173774B (de) |
| WO (1) | WO1990008983A1 (de) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7118842B2 (en) | 2003-09-30 | 2006-10-10 | Samsung Electronics Company | Charge adjuvant delivery system and methods |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3542681A (en) * | 1968-07-10 | 1970-11-24 | Gaf Corp | Negative working electrostatic toners |
| CA967046A (en) * | 1968-08-19 | 1975-05-06 | Radio Corporation Of America | Liquid developers for electrostatic printing |
| DE2740870A1 (de) * | 1977-09-10 | 1979-03-22 | Hoechst Ag | Fluessigentwickler und hierzu geeignetnr ladungssteuerstoff |
| US4734352A (en) * | 1986-04-22 | 1988-03-29 | E. I. Du Pont De Nemours And Company | Polyhydroxy charging adjuvants for liquid electrostatic developers |
-
1990
- 1990-01-16 EP EP90902057A patent/EP0456659B1/de not_active Expired - Lifetime
- 1990-01-16 DE DE69034151T patent/DE69034151T2/de not_active Expired - Fee Related
- 1990-01-16 CA CA002026212A patent/CA2026212C/en not_active Expired - Fee Related
- 1990-01-16 JP JP02501977A patent/JP3076921B2/ja not_active Expired - Fee Related
- 1990-01-16 WO PCT/US1990/000155 patent/WO1990008983A1/en not_active Ceased
- 1990-01-16 KR KR1019910700908A patent/KR0180733B1/ko not_active Expired - Fee Related
- 1990-01-30 MX MX019312A patent/MX173774B/es unknown
- 1990-02-06 CN CN90101168A patent/CN1041462C/zh not_active Expired - Fee Related
Non-Patent Citations (1)
| Title |
|---|
| See references of WO9008983A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CA2026212C (en) | 1997-12-02 |
| KR920701871A (ko) | 1992-08-12 |
| HK1012439A1 (en) | 1999-07-30 |
| JP3076921B2 (ja) | 2000-08-14 |
| JPH04503262A (ja) | 1992-06-11 |
| DE69034151T2 (de) | 2005-06-30 |
| CA2026212A1 (en) | 1990-08-07 |
| CN1045304A (zh) | 1990-09-12 |
| MX173774B (es) | 1994-03-25 |
| WO1990008983A1 (en) | 1990-08-09 |
| EP0456659B1 (de) | 2004-06-30 |
| DE69034151D1 (de) | 2004-08-05 |
| CN1041462C (zh) | 1998-12-30 |
| KR0180733B1 (ko) | 1999-05-01 |
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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: 19910805 |
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| AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): CH DE FR GB IT LI |
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| RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: SPECTRUM SCIENCES B.V. |
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| RAP3 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: SPECTRUM SCIENCES B.V. |
|
| 17Q | First examination report despatched |
Effective date: 19950530 |
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| RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: INDIGO N.V. |
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| RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: HEWLETT-PACKARD INDIGO B.V. |
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| GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
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| GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
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