WO1996022244A1 - Novel temperature-activated polysilicic acids and their use in paper production processes - Google Patents
Novel temperature-activated polysilicic acids and their use in paper production processes Download PDFInfo
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- WO1996022244A1 WO1996022244A1 PCT/US1996/000788 US9600788W WO9622244A1 WO 1996022244 A1 WO1996022244 A1 WO 1996022244A1 US 9600788 W US9600788 W US 9600788W WO 9622244 A1 WO9622244 A1 WO 9622244A1
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- WO
- WIPO (PCT)
- Prior art keywords
- alkali metal
- metal silicate
- acid
- temperature
- aqueous alkali
- Prior art date
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Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/06—Paper forming aids
- D21H21/10—Retention agents or drainage improvers
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
- C01B33/141—Preparation of hydrosols or aqueous dispersions
- C01B33/142—Preparation of hydrosols or aqueous dispersions by acidic treatment of silicates
- C01B33/143—Preparation of hydrosols or aqueous dispersions by acidic treatment of silicates of aqueous solutions of silicates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
- C01B33/141—Preparation of hydrosols or aqueous dispersions
- C01B33/142—Preparation of hydrosols or aqueous dispersions by acidic treatment of silicates
- C01B33/143—Preparation of hydrosols or aqueous dispersions by acidic treatment of silicates of aqueous solutions of silicates
- C01B33/1435—Preparation of hydrosols or aqueous dispersions by acidic treatment of silicates of aqueous solutions of silicates using ion exchangers
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/63—Inorganic compounds
- D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
- D21H17/68—Water-insoluble compounds, e.g. fillers, pigments siliceous, e.g. clays
Definitions
- the present invention relates to a temperature- activated polysilicic acid prepared by heating ⁇ an acidified aqueous alkali metal silicate.
- the present invention also relates to a process for the production of paper utilizing the temperature-activated polysilicic acid for improvement of retention and water removal .
- U.S. Patent No. 4,954,220 to Rushmere relates to the use of anionic polysilicate microgels in combination with an organic polymer to flocculate pulp and papers fines in a papermaking operation.
- the polysilicate microgels are formed by the partial gelation of an alkali metal silicate or a polysilicate such as sodium polysilicate.
- the microgels are referred to as active silica in contrast to commercial colloidal silica and consist of aggregates of very small particles, e.g., 1 nanometer, and form three-dimensional networks.
- microgels are described as having very high surface areas and are used in the papermaking process in conjunction with cationic polymers.
- section of the patent under "Detailed Description of the Invention” reference is made to the description of active silicas in the book “The Chemistry of Silica” published in 1979 by R.K. Her as providing a disclosure of active silica microgels which can be used in the patented invention.
- polysilicate microgels may be prepared, including: 1) aqueous solutions of alkali metal silicates which have been acidified by acid exchange resins; 2) inorganic and organic acid aqueous solutions of alkali metal silicates which have been acidified by acids, salts and gases; 3) aqueous solutions of alkali metal silicates to which alkali metal salts of amphoteric metal acids have been added; and 4) alkali metal silicates to which certain organic compounds have been added.
- EKA Nobel PCT Published Application WO-91/07543 discloses a process for the production of paper in which three components are added to the paper suspension, a cationic starch, a cationic polyacrylamide, and a polymeric silicic acid, to improve retention and water removal in paper production.
- This PCT application discloses that the polymeric silicic acid is the same product as disclosed in Swedish Patent Application No. 8801951-8, which product has a very high specific surface area in the range of 1100 to 1700 m 2 /g, and can be prepared by acidification of an alkali metal silicate such as sodium waterglass, the acidification being conducted by use of a mineral acid such as sulfuric acid or acid ion exchangers.
- Example 1 on page 7 the polymeric silicic acid was prepared from waterglass which was diluted with water to an Si0 2 content of 5% by weight, after which the aqueous solution was ion exchanged with ion exchange resin Amberlite IR-120 to a pH of 2.3.
- EKA European Patent Application No. 041056, directed to a paper making process is disclosed in column 1 of the EKA Nobel published PCT application.
- This published application discloses a papermaking process which uses a binder of colloidal silicic acid and cationic starch added to the stock for improving the paper or retention of the stock components.
- Colloidal silicic acid is described, for example at page 7, as being a known material made by reacting waterglass with sulfuric acid by known procedures to provide a silica having molecular weights up to about 100,000.
- Example IV there is a specific description for producing a colloidal silicic acid component wherein 100 ml of waterglass were diluted with 160 milliliters of water and slowly fed into 130 milliliters of 10% sulfuric acid under vigorous agitation. When all the waterglass had been added, the pH was 2.7 and the Si0 2 content was 8% by weight. This acid sol was diluted to 2% Si0 2 by weight, added to an English China Clay grade C followed by addition of 2% cationic starch solution. These mixtures were then added to the paper.
- Finnish Application No. 68283 discloses a two- component system used in the paper making process.
- the system comprises a cationic starch and a colloidal silica sol. This system is intended for improving retention and strength properties of the paper product.
- this two-component system is not commercially attractive due to the high price of the colloidal silica sol.
- Finnish Application No. 894362 proposes a two component system in which colloidal silica sol is replaced with a certain anionic polysilicate microgel, which is prepared by a partial gelation of an alkali metal silicate by adding certain initiators to an aqueous solution of the alkali metal silicate.
- a temperature-activated polysilicic acid prepared by heating an acidified aqueous alkali metal silicate has improved properties as a retention agent in paper production.
- none of these publications disclose a process for the production of paper utilizing a temperature-activated silicate for improvement of retention and water removal.
- the present invention provides a novel temperature- activated polysilicic acid prepared by heating an acidified aqueous alkali metal silicate.
- Use of the novel temperature-activated silicate in the paper production process represents a significant improvement over the prior art for the following reasons: 1. They improve the mechanical properties of the finished paper; 2. They improve the recovery of fines and colloids from the water cycle; 3. They improve filterability; 4. They improve grammage and ash retention, i.e., filler retention; and 5. They are economical and easy to use.
- the present invention provides a novel temperature- activated polysilicic acid agent prepared by heating an acidified aqueous alkali metal silicate.
- Another aspect of the present invention relates to a process for the production of paper comprising the steps of: adding components comprising a temperature-activated polysilicic acid and a cationic polymer to an aqueous fiber pulp suspension; and, carrying out sheet forming and water removal.
- the present invention further provides a method for improving' retention in a papermaking process wherein a temperature-activated polysilicic acid is added to an aqueous fiber pulp suspension.
- the present invention relates to a temperature- activated polysilicic acid prepared by heating an acidified aqueous alkali metal silicate.
- Use of this novel temperature-activated polysilicic acid in a papermaking process results in the production of paper having superior properties.
- the present invention is based, in part, on the inventor's unexpected discovery of a temperature-activated polysilicic acid prepared by heating an acidified aqueous alkali metal silicate.
- the alkali metal silicate can be acidified to a broad pH range, from about 0 to 5, and more preferably to a pH range from about 0 to 2.
- the alkali metal silicate when the alkali metal silicate is acidified to a pH near or below the isoelectric point of the alkali metal silicate, i.e., about 2.0, the polysilicic acid no longer functions well as a retention aid in the paper production process. It should therefore be appreciated that the present invention is also based on the inventor's surprising discovery that when an aqueous alkali metal silicate is acidified to a pH near or below the isoelectric point of the alkali metal silicate and is then heated for varying time periods to produce a temperature-activated polysilicic acid, the temperature-activated polysilicic acid greatly improves the papermaking process by producing paper with superior fiber and ash retention levels.
- the temperature-activated polysilicic acid of the present invention has increased adherence efficiency over prior art agents.
- the temperature- activated polysilicic acids of the present invention combine and adhere strongly with only one cationic polymer. This eliminates the need to use two or more cationic polymers as in many of the prior art systems.
- the temperature-activated polysilicic acid used in the present invention has a very high surface area of approximately 1350-1600 m 2 /g. The given specific surface area is measured by the titration method cf G. W. Sears, Anal. Chem. 28, (1956) , p. 1981.
- the temperature- activated polysilicic acid of the present invention is prepared by acidification of an alkali metal silicate, such as potassium or sodium silicate, preferably sodium silicate, followed by heating.
- Potassium and sodium silicate are available with varying molar ratios of Si0 2 to Na 2 0 or K 2 0 and the molar ratio is usually within the range of from 1.5:1 to 4.5:1, preferably 3.3:1, and the alkali metal silicate usually has an original pH around 13. Waterglass is especially preferred. Mineral acids, such as sulfuric acid, hydrochloric acid and phosphoric acid are used to acidify the aqueous alkali metal silicate. The acidification is carried out to a pH within the range of from about 0 to 5 and more preferably to a pH within the range of from about 0 to 2.
- the aqueous alkali metal silicate may be acidified by slow addition of a diluted alkali metal silicate solution into a mineral acid.
- Acidification with an ion exchange agent or organic acids, such as acetic acid may also be used.
- the Si0 2 concentration in the aqueous alkali metal silicate solution to be heated is preferably about 1-20 weight percent.
- the temperature- activated polysilicic acid agent obtained after heating is diluted with water to a desired concentration.
- the aqueous alkali metal silicate solution is heated to a temperature of about 30-250°C and more preferably to a temperature of about 60-90°C, for a period of about 1- 120 hours, more preferably about 1-20 hours.
- the heating may be done by using the secondary temperature of a paper mill in a tank adjacent the papermaking machinery.
- the heating may also be done under pressure necessary to achieve the desired temperature.
- the resulting temperature-activated polysilicic acid may be mixed at room temperature and diluted, more preferably mixed at room temperature for 72 hours and diluted to 0.15% Si0 2 .
- Another aspect of the present invention relates to a process for the production of paper comprising the steps of: adding components comprising a temperature-activated polysilicic acid and a cationic polymer to an aqueous fiber pulp suspension; and, carrying out sheet formation and water removal.
- the fiber pulp used in the suspensions of the present invention may be derived from any fibrous raw materials including hardwood, softwood, nonwood, straw, bamboo, hemp or recycled paper, board, or mixtures from different fibrous raw materials.
- the fibers may be obtained by any process known to those skilled in the papermaking art including mechanical or chemical pulping such as refiner groundwood, kraft pulping, sulfite pulping or mixtures of pulp obtained from different methods.
- Cationic polymers useful in the present invention include cationic starches, cationic guars and cationic polyacrylamides. Cationic starches are particularly useful in that they are inexpensive and impart dry strength to the paper.
- the amount of cationic polymer to be added to the fiber pulp suspension is preferably about 0.005 to about 5 wt . % calculated from dry fiber.
- the amount of temperature-activated polysilicic acid and cationic polymer used in the process for paper production according to the present invention can vary within wide limits depending among other things on the type of stock, the presence of fillers and other conditions.
- the amount of temperature-activated polysilicic acid, calculated as Si0 2 , that may be added to the fiber pulp suspension is about 0.005-10 weight percent, more preferably about 0.05-5 weight %, calculated from dry fiber.
- Additional materials may be added to the pulp to improve the properties of paper for particular uses.
- additional materials include dyes which may be added to produce colored paper; fillers such as kaolin or other clays, calcium carbonate, silicon dioxide, synthetic silicates or titanium dioxide may be added to increase the density of the sheet, to decrease its porosity, and to increase its opacity.
- Wax may be impregnated into the paper, or a polyethylene or other polymer film may be applied to the surface, for water proofing. Bentonite may be added to the fiber pulp suspension before the water removal stage to further improve retention in the system.
- a temperature-activated polysilicic acid according to the present invention is prepared.
- 3.3 MR (molar ratio) sodium silicate solution 60 ml was diluted with 290 ml of deionized water.
- the 3.3 MR sodium silicate was Zeopol * 33, sold by Zeofinn Oy of Finland. This solution, which had a concentration of about 6% Si0 2 , was added slowly into a solution of 248.5 ml of deionized water and 48.5 ml of 10% sulfuric acid under strong agitation. The final silica concentration was 1.5% Si0 2 .
- This solution was heated at 60°C for 20 hours and then diluted to a silica concentration of about 0.15%.
- the pH of the final solution was 1.4.
- EXAMPLE 2 In this example, a temperature-activated polysilicic acid agent of the present invention is prepared.
- EXAMPLE 3 In this example, a temperature-activated polysilicic acid according to the present invention is prepared.
- 3.3 MR (molar ratio) sodium silicate solution 60 ml was diluted with 290 ml of deionized water.
- the 3.3 MR sodium silicate was Zeopol" 33, sold by Zeofinn Oy of Finland. This solution, which had a concentration of about 6% Si0 2 , was added slowly into a solution of 248.5 ml of deionized water and 48.5 ml of 10% sulfuric acid under strong agitation. The final silica concentration was 1.5% Si0 2 .
- This solution was heated at 60°C for 20 hours and then mixed at room temperature (23°C) for 72 hours before it was diluted to a silica concentration of about 0.15%.
- the pH of the final solution was 1.4.
- Fine Paper Trial - Comparative Tests This example compares the performance of the temperature-activated polysilicic acid agent prepared in Example 1 and Example 2 (with starch or polyacrylamide) with that of Compozil (colloidal silica and cationic starch) and Hydrocol (bentonite and polyacrylamide) .
- Bleached softwood pulp was used with calcium carbonate as a filler.
- the calcium carbonate was Snowcal 75, sold by Omya Ltd.
- the pulp was received from a pulp mill in Finland as a bale and was free of chlorine (TCF- pulp) .
- the pulp was ground in a Valley-hollander to SR- number 35 according to method SCAN-C 25:76.
- Laboratory handsheets were prepared as following standard SCAN methods. Filled sheets were produced to achieve a grammage of 90 g/m 2 at a filler level of 25%.
- Fine paper machines normally use either alkyl succinic acid (ASA) or alkyl ketone dimer (AKD) to make paper hydrophobic.
- ASA alkyl succinic acid
- the cationic starch was added into the pulp slurry first and mixed well for 30 seconds at 600 rpm with pulp fibers and calcium carbonate in a Britt Dynamic Drainage Jar (DDJ) . At 600 rpm, the effect of shear forces are minimal.
- the pH was adjusted to 8 with IN sodium hydroxide before the filler and cationic retention aids were added into the pulp. Then, the rotation speed was increased to 2500 rpm for 2 minutes in order to simulate shear forces encountered in commercial papermaking.
- the cationic substance is normally added before the mixing or machine chest in the backwater system of a paper machine. Just before the headbox strong shear forces caused by screens and pumps, break the polymer loops between the anionic substances of the pulp slurry. The second component is then added before the headbox in order to increase retention level.
- pulp slurry was poured into a Noble & Woods sheet former and the pH of the water was adjusted to 8 before slurry addition.
- the temperature-activated polysilicic acid agent prepared in Example 1 or Example 2, Compozil, or Hydrocol was added into the sheet former. One minute mixing with air bubbles in the sheet former was applied before the sheet was filtered.
- the cationic starch was Hi-Cat 142, sold by Roquette Ltd.
- the cationic polyacrylamide was Hydrocol 847, sold by Allied Colloids Ltd.
- the bentonite was Hydrocol O, and the colloidal silica was BMA 590, sold by EKA Nobel Ltd. See Table 1 for results.
- the temperature-activated polysilicic acid of Example 1 showed a significant improvement over Compozil and Hydrocol.
- the temperature-activated polysilicic acid of Example 2 showed comparable performance to Compozil and Hydrocol .
- This example describes the effects of heating on the temperature-activated polysilicic acid of the present invention and compares the temperature-activated polysilicic acid with polysilicic acid.
- the temperature-activated polysilicic acid was prepared according to Example 1.
- the non-temperature-activated polysilicic acid was prepared by diluting 60 ml of 3.3 MR sodium silicate solution with 290 ml of deionized water. This solution, which had a silica concentration of about 6% was added slowly into a solution of 248.5 ml of deionized water and 48.5 ml of 10% sulfuric acid under strong agitation. The final silica concentration was 1.5%. The solution was not heated, but was stirred at room temperature for 20 244 PC17US96/00788
- the polysilicic acid was prepared by adding a thin stream of sodium silicate solution with a Si0 2 :Na 2 0 ratio of 3.25:1.0 into the vortex of a violently stirred solution of H 2 S0 4 kept at 0-5°C, stopping the addition when the pH rose to about 1.7.
- a 6% solution was made by bringing together solutions of sodium silicate and acid in a zone of intense turbulence and in such proportions that the mixture had a pH about 1.5-2.0. This solution was immediately diluted after preparation to obtain a 0.15% Si0 2 concentration.
- Handsheets were produced using the laboratory sheet making procedure is as described in Example 3. See Table 2 for results.
- the temperature-activated polysilicic acid which was prepared by heating at 60°C for 20 hours showed a significant improvement in grammage and ash retention over both the unheated product and polysilicic acid.
- Example 2 This example compares the performance of the temperature-activated polysilicic acid prepared in Example 1 (with starch) with that of a polysilicate microgel and Compozil (colloidal silica and cationic starch) .
- the polysilicate microgel was prepared in accordance with the description in Moffett, R.H., On-site Production of a Silica Based Microparticulate Retention and Drainage Aid. Papermakers Conference, Book 1, San Francisco, California, Marriott, 1994, pp. 243-255.
- the polysilicate microgel was prepared by adding diluted sulfuric acid to diluted 3.3 MR sodium silicate with vigorous mixing to obtain a final silica concentration of 2% and a pH of 9. The solution was then mixed for ten minutes at room temperature. Then, the solution was diluted to a 0.15% silica concentration with deionized water.
- Handsheets were produced using the laboratory sheet making procedure was as described in Example 3. See Table 3 for results.
- the temperature-activated polysilicic acid of Example 1 showed comparable performance to the polysilicate microgel and Compozil.
- This example compares the performance of four products: the temperature-activated polysilicic acid of Example 1, the temperature-activated polysilicic acid of Example 3, Compozil (colloidal silica and cationic starch) and Hydrocol (bentonite and polyacrylamide) .
- Unbleached groundwood pulp was used with kaolin.
- the kaolin was C kaolin, sold by ECC International.
- the pulp was received from a Finnish pulp mill as a bale.
- the groundwood pulp was hot-disintegrated to eliminate the latency of pulp, according to method SCAN-M 10:77.
- Laboratory handsheets were prepared as follows, to achieve a 90 g/m 2 sheet containing 25% kaolin filler.
- Wood containing paper machines typically may not use hydrophobic agents. Accordingly, AKD and ASA glues were not used in this example.
- the cationic substance starch or polyacrylamide
- the pH was adjusted to 5 with IN sulfuric acid before the filler and cationic retention aids were added to the pulp. Then, the rotation speed was increased to 2500 rpm for 2 minutes in order to simulate shear forces encountered in commercial papermaking.
- the cationic substance is normally added before the mixing or machine chest in the backwater system of a paper machine. Just before the headbox, strong shear forces caused by screens and pumps break the polymer loops between the anionic substances of the pulp slurry. The second component is then added before the headbox in order to increase retention level.
- pulp slurry was poured into a Noble & Woods sheet former and the pH of the water was adjusted to 5 before slurry addition. Then, the temperature-activated polysilicic acid agent prepared in
- Example 1 or Example 2 Compozil, or Hydrocol was added into the sheet former before filtration took place after
- Example 3 In this groundwood paper trial the temperature- activated polysilicic acid of Example 3 showed a significant improvement in grammage and ash retention levels over the temperature-activated polysilicic acid agent of Example 1, in which the solution was not mixed at room temperature before dilution, Compozil (colloidal silica and cationic starch) and Hydrocol (bentonite and polyacrylamide) .
- Compozil colloidal silica and cationic starch
- Hydrocol bentonite and polyacrylamide
- This example compares the performance of a temperature-activated polysilicic acid of the present invention with a colloidal silica.
- the temperature- activated polysilicic acid agent of the present invention showed activity at least as good as the colloidal silica and a somewhat enhanced activity at dosages of 0.13, 0.22, and 0.43% Si0 2 .
Abstract
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Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE69602169T DE69602169T2 (en) | 1995-01-20 | 1996-01-19 | TEMPERATURE-ACTIVATED POLYESILIC ACIDS AND THEIR USE IN PAPER PRODUCTION PROCESSES |
AU47034/96A AU4703496A (en) | 1995-01-20 | 1996-01-19 | Novel temperature-activated polysilicic acids and their use in paper production processes |
EP96902742A EP0804382B1 (en) | 1995-01-20 | 1996-01-19 | Novel temperature-activated polysilicic acids and their use in paper production processes |
FI973053A FI116285B (en) | 1995-01-20 | 1997-07-18 | Novel heat-activated polysilicon acids and their use in papermaking processes |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US08/375,886 | 1995-01-20 | ||
US08/375,886 US5571494A (en) | 1995-01-20 | 1995-01-20 | Temperature-activated polysilicic acids |
Publications (2)
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WO1996022244A1 true WO1996022244A1 (en) | 1996-07-25 |
WO1996022244B1 WO1996022244B1 (en) | 1996-09-12 |
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PCT/US1996/000788 WO1996022244A1 (en) | 1995-01-20 | 1996-01-19 | Novel temperature-activated polysilicic acids and their use in paper production processes |
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US (3) | US5571494A (en) |
EP (1) | EP0804382B1 (en) |
AR (1) | AR000745A1 (en) |
AT (1) | ATE179150T1 (en) |
AU (1) | AU4703496A (en) |
DE (1) | DE69602169T2 (en) |
ES (1) | ES2132884T3 (en) |
FI (1) | FI116285B (en) |
TW (1) | TW349138B (en) |
WO (1) | WO1996022244A1 (en) |
ZA (1) | ZA96441B (en) |
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-
1996
- 1996-01-18 TW TW085100592A patent/TW349138B/en active
- 1996-01-18 AR ARP960101063A patent/AR000745A1/en unknown
- 1996-01-19 EP EP96902742A patent/EP0804382B1/en not_active Revoked
- 1996-01-19 AU AU47034/96A patent/AU4703496A/en not_active Abandoned
- 1996-01-19 ES ES96902742T patent/ES2132884T3/en not_active Expired - Lifetime
- 1996-01-19 ZA ZA96441A patent/ZA96441B/en unknown
- 1996-01-19 AT AT96902742T patent/ATE179150T1/en not_active IP Right Cessation
- 1996-01-19 WO PCT/US1996/000788 patent/WO1996022244A1/en active IP Right Grant
- 1996-01-19 DE DE69602169T patent/DE69602169T2/en not_active Expired - Fee Related
- 1996-01-29 US US08/592,950 patent/US5707493A/en not_active Expired - Fee Related
- 1996-07-17 US US08/682,465 patent/US5688482A/en not_active Expired - Fee Related
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1997
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Also Published As
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US5688482A (en) | 1997-11-18 |
FI973053A0 (en) | 1997-07-18 |
EP0804382B1 (en) | 1999-04-21 |
AU4703496A (en) | 1996-08-07 |
ZA96441B (en) | 1996-07-23 |
ES2132884T3 (en) | 1999-08-16 |
AR000745A1 (en) | 1997-08-06 |
FI973053A (en) | 1997-09-17 |
EP0804382A1 (en) | 1997-11-05 |
TW349138B (en) | 1999-01-01 |
US5707493A (en) | 1998-01-13 |
DE69602169T2 (en) | 1999-10-14 |
US5571494A (en) | 1996-11-05 |
ATE179150T1 (en) | 1999-05-15 |
FI116285B (en) | 2005-10-31 |
DE69602169D1 (en) | 1999-05-27 |
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