Classifications

• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
  • D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
  • D21C9/001—Modification of pulp properties
  • D21C9/002—Modification of pulp properties by chemical means; preparation of dewatered pulp, e.g. in sheet or bulk form, containing special additives
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
  • D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
  • D21C9/10—Bleaching ; Apparatus therefor
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
  • D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
  • D21C9/10—Bleaching ; Apparatus therefor
  • D21C9/1026—Other features in bleaching processes
  • D21C9/1036—Use of compounds accelerating or improving the efficiency of the processes
• • 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
  • D21H21/14—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 characterised by function or properties in or on the paper
  • D21H21/30—Luminescent or fluorescent substances, e.g. for optical bleaching

Definitions

• the present invention relates to a method of increasing the brightness of pulp, pulp made from such methods and methods of using such pulp.
• Bleaching is a common method for increasing the whiteness of pulp. Industry practice for improving appearance of fluff pulp is to bleach the pulp to ever-higher levels of brightness (the Technical Association of the Pulp & Paper Industry (“TAPPI”) or the International Organization for Standardization (“ISO”)). However, bleaching is expensive, environmentally harsh and often is a source of manufacturing bottleneck. Widespread consumer preference for a brighter, whiter pulp drives manufacturers to pursue ever more aggressive bleaching strategies. While highly bleached pulps are "whiter” than their less-bleached cousins, they are still yellow-white in color. A yellow-white product is undesirable. Countless studies suggest that consumers clearly favor a blue-white over a yellow-white color. The former is perceived to be whiter, i.e., "fresh”, “new” and “clean”, while the latter is judged to be “old”, “faded”, and "dirty”.
• any optical enhancement is usually accomplished by addition of tinting colorants, fillers, and/or fluorescent dye during the papermaking stage.
• a process for enhancing the whiteness, brightness, and chromaticity of papermaking fibers has been described in U.S. Pat. No. 5,482,514. The process relates to adding photoactivators, particularly water-soluble phthalocyanines, to papermaking fibers to enhance their optical properties by a catalytic photosensitizer bleaching process. The resulting bleached papermaking fibers can be advantageously incorporated into paper sheets.
• TAPPI brightness serves as the de facto standard in lieu of an industry-specific whiteness specification such as CIE Whiteness (Commission Internationale d'Eclairage). Because of this, brightness serves two key roles. First, brightness is a manufacturing parameter. Second, brightness is a specification for classifying finished product grades. The implicit, but dubious, assumption to this day has been that brightness is equivalent to whiteness. Common papermaking practice is to either add blue tinting dyes or tinting pigments and/or different types of blue-violet fluorescent dyes to boost whiteness properties. Tinting colorants are either finely ground colored pigments suspended in a dispersant or synthetically produced direct dyes. Tinting dyes have some affinity to cellulose while tinting pigments have little to none.
• Fluorescent whitening agents FWA or optical brightening agents (OBA) are used in the pulp and paper industry are of three types: di-, tetra-, or hexasulphonated stilbene compounds, for example. These chemicals require ultraviolet (UV) light to excite fluorescence. While there is strong UV content in daylight, even common office lights produce enough UV light to permit some excitation.
• UV ultraviolet
• OBAs are added at the wet end of papermaking processes, which include for example, the machine chest and/or the fan pump, where the fiber solution is at low consistencies that are less than about 3% solids.
• the fiber solution is at low consistencies that are less than about 3% solids.
• the OBA must be added at high concentrations (lbs/ton of fiber or pulp) in order to achieve high quality fibers having high brightness and high brightness improvements.
• FIGURE 1 Graphs of ISO Brightness v.s OBA Level of Handsheets made from pulp treated with OBA, full data set.
• FIGURE 2 Graphs of ISO Brightness v.s OBA Level of Handsheets made from pulp treated with OBA, dose data set.
• FIGURE 3 Graphs of ISO Brightness v.s OBA Level of Handsheets made from pulp treated with OBA, effect of OBA dose in the presence of 10 and 20% filler.
• FIGURE 4 Graphs of ISO Brightness v.s OBA Level of Handsheets made from pulp treated with OBA effect of OBA dose in the presence of 10 and 20% filler, regression lines added.
• FIGURE 5 Raman spectra of OBA only and pulp with different levels of OBA added conventionally.
• FIGURE 6 Raman spectra of pulp with different levels of OBA added according to one aspect of the present invention.
• FIGURE 7 Raman spectra of pulp with different levels of OBA added conventionally and added according to one aspect of the present invention.
• FIGURE 8 Graph of the peak ratio (1604/900Cm "1 ) within Raman spectra of pulp with different levels of OBA added conventionally and added according to one aspect of the present invention (Hardwood and Softwood) as depicted in Table 10.
• FIGURE 9 UV/VIS absorbance at 350 nm of water estract vs. Actual Amount of OBA on fibers, lbs/ton.
• FIGURE 10 OBA peak height vs. OBA added (lbs/ton) via the conventional addition method and added according to one aspect of the present invention (Hardwood and Softwood).
• FIGURE 11 OBA peak height vs. OBA added (lbs/ton) via the conventional addition method and added according to one aspect of the present invention (Hardwood and Softwood).
• the present inventor has surprisingly found an method of efficiently increasing the brightness and whiteness of pulp and paper while using less OBA applied thereto, thereby providing for a much more efficient manner of providing a fiber-OBA complex containing greater fiber-OBA interaction on the whole than conventional methodologies of creating a fiber- OBA complex.
• Such a fiber-OBA complex made by the method according to the present invention has greater increases in brightness and whiteness than the fiber alone as compared to traditional methodologies as described below.
• the present invention relates, in part, to a method of making pulp.
• the pulp may be fluff or papermakmg pulp.
• the method may be used and added to any traditional methods of making papermaking or fluff pulp.
• the pulp may be used in any conventional uses of pulp, including any conventional papermaking processes of making paper and/or paperboard substrates.
• Such conventional pulp and papermaking processes in the pulp, paper and paperboard art may be found, for example, in "Handbook For Pulp & Paper Technologies", 2 nd Edition, G.A. Smook, Angus Wilde Publications (1992) and references cited therein, which are hereby incorporated, in their entirety, herein by reference.
• a typical pulp/paper making process may include, but is not limited to, the following stages:
• D. High Density Storage Stage where the bleached/washed pulp is stored at relatively high density as for example more than about 7%, preferably from about 7.5 to about 15%, and preferably from about 10 to about 12%;
• Blend Chest/Machine Chest Stages where the pulp having a consistency preferably from about 3 to about 4% is mixed with wet end chemicals used in paper making such as fillers, retention aids, dyes and optical brighteners and the like.
• wet end chemicals used in paper making such as fillers, retention aids, dyes and optical brighteners and the like.
• Such a traditional processes may include repeats of any one or more of the above-mentioned steps.
• the present invention may be combined with traditional methods of adding OBA to fibers, such as the conventional wet-end addition points as well as size press addition points and coating addition points, when making paper and/or paperboard.
• the present invention relates, in part, to a method of adding OBA to fibers at any point after the last bleaching/extraction stage and up to and prior to the Blend Chest/Machine Chest
• the source of the fibers may be from any fibrous plant.
• the paper substrate of the present invention may contain recycled fibers, deinked fibers and/or virgin fibers. Examples of such fibrous plants are trees, including hardwood and softwood fibrous trees, including mixtures thereof.
• at least a portion of the pulp fibers may be provided from non- woody herbaceous plants including, but not limited to, kenaf, hemp, jute, flax, sisal, or abaca although legal restrictions and other considerations may make the utilization of hemp and other fiber sources impractical or impossible.
• Either bleached or unbleached pulp fiber may be utilized in the process of this invention. Recycled pulp fibers are also suitable for use.
• the pulp of the present invention may contain from 1 to 99 wt%, preferably from 5 to 95 wt%, cellulose fibers originating from hardwood species and/or softwood species based upon the total amount of cellulose fibers. This range includes 1, 2, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, and 100wt%, including any and all ranges and subranges therein, based upon the total amount of cellulose fibers.
• the hardwood/softwood ratio be from 0.001 to 1000.
• This range may include 0.001, 0.002, 0.005, 0.01, 0.02, 0.05, 0.1, 0.2, 0.5, 1, 2, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 200, 300, 400, 500, 600, 700, 800, 900, and 1000 including any and all ranges and subranges therein and well as any ranges and subranges therein the inverse of such ratios.
• Optical brighteners are dye-like fluorescent compounds which absorb the short-wave ultraviolet light not visible to the human eye and emit it as longer- wave blue light, with the result that the human eye perceives a higher degree of whiteness and the degree of whiteness is thus increased.
• the optical brighteners used in the paper industry are generally 1,3,5-triazinyl derivatives of 4,4'-diaminostilbene-2,2'-disulfonic acid, which may carry additional sulfo groups, for example altogether 2, 4 or 6.
• An overview of such brighteners is to be found, for example, in Ullmann's Encyclopedia of Industrial Chemistry, Sixth Edition, 2000 Electronic Release, OPTICAL BRIGHTENERS-Chemistry of Technical Products.
• the present invention relates in part, to a fiber.OBA complex in which the affinity of the OBA added to the fiber according to present invention is preferably greater than that when the OBA is added to the fiber conventionally.
• the increased affinity of the OBA to the fiber may be measured by extraction methods using any solvent, preferably water, at any temperature. Because the OBA has increased affinity to the fiber overall in the present inventive pulps and paper substrates made therefrom compared to conventional pulp, it will take a longer period of time for the OBA to be extracted from the pulp: OBA complex of the present invention (pulp and/or paper) at a given time period and temperature for a given solvent.
• the present invention preferably relates to a method of increasing the penetration of OBA into the cell wall of a fiber.
• the amount of OBA present within the cell wall of the fiber is increased by at least 1% than the amount of OBA present within the cell wall of fiber that was treated in conventional methods.
• the amount of OBA present within the cell wall of the fiber is increased by at least 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 100, 200, 300, 500, and 1000% than the amount of OBA present within the cell wall of fiber that was treated in conventional methods, including any and all ranges and subranges therein.
• the amount of OBA present within the cell wall of fiber may be measured, for example, by microscopy, more specifically fluorescent microscopy. While any amount of OBA may be added to the fiber so long as it is added at any point after the last bleaching/extraction stage and up to and prior to the Blend Chest/Machine Chest Stages, it is preferable that from 1 to 60 lbs of OBA per ton of fiber, more preferably not more then 30 lbs/ton, most preferably, not more than 15 lbs/ton OB A/fiber.
• This range includes 60, 55, 50, 45, 40, 30, 35, 30, 25, 20, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2, and 1 lbs of OBA per ton of fiber (lbs/ton) including any and all ranges and subranges therein.
• the fiber may be in solution, or added to solution at the same time, as the OBA.
• the fiber is in solution prior to contacting the OBA thereto, hi one embodiment of the present invention, the fiber may have any consistency.
• it is preferably to have a consistency that is equal to or greater than 4% solids, more preferably, not less than about 5 % solids, most preferably, not less than about 10% solids, hi addition, it is preferable that the fibers have a consistency that is not more than about 35% solids, preferably not more than 20% solids, more preferably not more than about 15% solids.
• These ranges include 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, and 20% solids as the fiber consistency at the time the OBA is added thereto, including any and all ranges and subranges therein.
• the pH may be any pH.
• the pH may range from 2.5 to 8.0, more preferably from 3.5 to 5.5. This range includes 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5, and 8.0, including any and all ranges and subranges therein.
• the temperature may be any temperature. However, it is preferable that means be applied, such as heating, so as to generate a temperature that is from 35 to 95 0 C, preferably from 50 to 9O 0 C, more preferably from 60 to 8O 0 C.
• This range includes 35, 40, 45, 50, 55, 60, 61, 62, 63, 64, 65, 66, 61, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 85, 90 and 95 0 C, including any and all ranges and subranges therein.
• the time in which the OBA is contacted with the fiber may be for any duration of time.
• the OBA and fiber may be contacted from 30 minutes to 12 hours, more preferably from 45 minutes to 8 hours, most preferably from lhour to 6 hours.
• This range includes 0.5, 0.75, 1, 1.25, 1.5, 1.75, 2, 2.25, 2.5, 2.75, 3, 3.25, 3.5, 3.75, 4, 4.25, 4.5, 4.75, 5, 5.25, 5.5, 5.75, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, 11, and 12 hrs, including any and all ranges and subranges therein.
• retention aids may optionally be present or added therewith.
• Alum and/or cationic retention aids are examples of such retention aids. Examples of retention aids is found in United State Provisional Patent Application 60/660703, filed March 11, 2005, and United States Patent Number 6,379,497, which are hereby incorporated, in their entirety, herein by reference.
• any retention aid commonly used with OBAs may be used. While the retention aid may be present in any amount, or not at all, preferably, the amount of retention aid present is less than that required during conventional processes and addition points used to contact OBA with fibers. Most preferably, no retention aids are used.
• retention aids it is preferable that there is at least a 1% reduction in the amount of retention aid present as compared to that of conventional methods and addition points for contacting OBA with fiber.
• the preferred reduction is at least 2, 3, 4, 5, 10, 15, 20, 25, 30, 35, 40, 50, 60, 75, 100, 200, 300, 500, and 1000% reduction in the amount of retention aid present in the present invention as compared to conventional methods and addition points for contacting OBA with fiber, including any and all ranges and sub-ranges therein.
• the fiber may be refined at any time, preferably, the fiber is refined after the OBA is contacted with the fiber. Therefore, the fibe ⁇ OBA complex of the present invention is refined. Accordingly, any conventional refining may occur, including but not limited the chemical refining, mechanical refining, thermochemical refining, thermomechanical refining, chemithermomechanical refining, etc may occur. Therefore the pulp produced may include TMP, CTMP, MP, BCTMP, etc.
• the pulp of the present invention and method of making the same may be incorporated into any traditional papermaking process.
• the pulp and/or paper substrate may also include other conventional additives such as, for example, starch, mineral and polymeric fillers, sizing agents, retention aids, and strengthening polymers.
• the fillers that may be used are organic and inorganic pigments such as, by way of example, minerals such as calcium carbonate, kaolin, and talc and expanded and expandable microspheres.
• Other conventional additives include, but are not restricted to, wet strength resins, internal sizes, dry strength resins, alum, fillers, pigments and dyes.
• Dyes that are especially preferably are those of the blue dye type which are capable of increasing the CIE Whiteness of the pulp and/or paper substrate.
• pulp and paper substrate of the present invention made according to the present invention is capable of achieving CIE Whiteness that is much higher than conventional pulps and substrates made by conventional methods, even at CIE Whiteness levels that usually result in decreased ISO brightness levels.
• the pulp and/or paper substrate of the present invention may have any CIE whiteness, but preferably has a CIE whiteness of greater than 70, more preferably greater than 100, most preferably greater than 125 or even greater than 150.
• the CIE whiteness may be in the range of from 125 to 200, preferably from 130 to 200, most preferably from 150 to 200.
• the CIE whiteness range may be greater than or equal to 70, 80, 90, 100, 110, 120, 125, 130, 135, 140, 145, 150, 155, 160, 65, 170, 175, 180, 185, 190, 195, and 200 CIE whiteness points, including any and all ranges and subranges therein. Examples of measuring CIE whiteness and obtaining such whiteness in a fiber and paper made therefrom can be found, for example, in United States Patent 6,893,473, which is hereby incorporated, in its entirety, herein by reference.
• the pulp and/or paper substrate of the present invention has a CIE whiteness that is increased over conventional pulp and/or paper substrates made by conventional methods.
• the preferred increase is at least 2, 3, 4, 5, 10, 15, 20, 25, 30, 35, 40, 50, 60, 75, 100, 200, 300, 500, and 1000% increase in CIE whiteness as compared to that of conventional pulps, paper substrates made by conventional methods and addition points for contacting OBA with fiber, including any and all ranges and sub-ranges therein.
• the pulp and paper substrate of the present invention may have any ISO brightness, but preferably greater than 80, more preferably greater than 90, most preferably greater than 95 ISO brightness points.
• the ISO brightness may be preferably from 80 to 100, more preferably from 90 to 100, most preferably from 95 to 100 ISO brightness points. This range include greater than or equal to 80, 85, 90, 91, 92, 93, 94, 95, 96, 91, 98, 99, and 100 ISO brightness points, including any and all ranges and subranges therein. Examples of measuring ISO brightness and obtaining such brightness in a papermaking fiber and paper made therefrom can be found, for example, in United States Patent 6,893,473, which is hereby incorporated, in its entirety, herein by reference.
• the pulp and/or paper substrate of the present invention has an ISO brightness that is increased over conventional pulp and/or paper substrates made by conventional methods.
• the preferred increase is at least 2, 3, 4, 5, 10, 15, 20, 25, 30, 35, 40, 50, 60, 75, 100, 200, 300, 500, and 1000% increase in an ISO brightness as compared to that of conventional pulps, paper substrates made by conventional methods and addition points for contacting OBA with fiber, including any and all ranges and sub-ranges therein.
• Brightness loss as a result of pulp refining operation is well recognized in papermaking. Under refining condition used in example 6, it was 1.6 points for the original softwood and 0.8 points for the original hardwood. Brightness losses were very similar for the case where pulps were fixed with OBA, suggesting that the created bonding between OBA and fiber was very strong and was not affected by the mechanical shear action of the refiner. The net brightness gain, obtained from OBA fixation, remained essentially unchanged and were not affected by the pulp refining process.
• OBA Clariant Leucophor ANO optical brightening agent
• the new addition point resulted in a brightness increase of about 1.9 units of ISO brightness.
• Pulp used for this study was unrefined hardwood and softwood taken from the washer of the last bleaching stage.
• the hardwood and softwood pulps separately with two levels of OBA, 3.3 and 10 pounds /ton of OBA.
• the OBA used was Leucophor ANO (Clariant), which is a di-sulfonated OBA.
• the conditions were 10% consistency, mixed for 2 hours at 7O 0 C.
• the pulps Prior to refining, the pulps were combined into a 70:30 HWD: SWD ratio. Refining was performed in the LRl, a laboratory disk refiner. Two energies were used, 35 kW/T and 45 kW/T. The freeness of the resulting pulps were -580 and ⁇ 320 csf, respectively.
• Sheets were made on the dynamic sheet former with the following procedure: The pulp was diluted to 1% consistency and mixed vigorously. SMFs Albacar LO PCC was added first and allowed to mix for 1 minute. Then a predetermined and accurate amount of OBA was added and mixed for 15 minutes. The sheet was then formed. After forming, the sheets were pressed to
• the handsheets were tested for various optical properties using the DataColor Elrepho Spectrophotometer.
• Samples of softwood and hardwood pulp with OBA added during the conventional and new processes were hot plate digested with hydrogen peroxide and nitric acid.
• a sample of OBA used in the process was dried and digested under the same conditions.
• the digested samples were analyzed for sulfur content by ICP. The results are presented in the table below.
• Untreated pulp was also analyzed under the same conditions and determined sulfur concentrations were subtracted from the concentrations in the treated pulp in order to establish the amount of OBA present in the pulp, which is reported on the dry weight of the OBA.
• the sulfur concentrations in the pulp indicate that the amount of OBA present in the pulp treated in the new process at 10 lb/ton OBA is comparable to the amount of the pulp from the conventional process at 20 lb/ton loading.
• the water extracts were filtered through a 0.45 ⁇ m filter, reduced to approximately 2 ml volume in a LABCONCO Rapidvap Nitrogen Evaporation System using air as the purge gas.
• the Evaporator was run at 24% vortex speed at a temperature of 30 0 C. After evaporation to
• HPLC instrumental conditions are below:
• PIC-A 50% methanol 50% PIC-A buffer solution at 0.7 ml minute.
• PIC-A is sold by the Waters Corporation and is a reverse phase ion pairing buffer solution composed of 0.005 m tetrabutyl ammonium phosphate buffered to a pH of 7.5.
• Detector Waters 400 photo diode array detector (PDA) over the range of 200 -800 nm. The peak at 254 nm was selected for the analysis.
• PDA photo diode array detector
• UV/VIS instrumental conditions are below:
• ranges are used as a short hand for describing each and every value that is within the range, including all subranges therein.

Landscapes

• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Wood Science & Technology (AREA)
• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Paper (AREA)
• Polishing Bodies And Polishing Tools (AREA)

Applications Claiming Priority (2)

Publications (1)

Family

ID=36617346

Family Applications (1)

Country Status (9)

Families Citing this family (29)

Family Cites Families (12)

• 2006
  • 2006-02-21 RU RU2007134269/12A patent/RU2386738C2/ru not_active IP Right Cessation
  • 2006-02-21 NZ NZ561652A patent/NZ561652A/en not_active IP Right Cessation
  • 2006-02-21 CN CNA2006800052300A patent/CN101128630A/zh active Pending
  • 2006-02-21 WO PCT/US2006/006011 patent/WO2006089274A1/en active Application Filing
  • 2006-02-21 US US11/358,543 patent/US20060185808A1/en not_active Abandoned
  • 2006-02-21 AU AU2006213983A patent/AU2006213983B2/en not_active Ceased
  • 2006-02-21 CA CA2601926A patent/CA2601926C/en not_active Expired - Fee Related
  • 2006-02-21 EP EP06735601A patent/EP1848856A1/de not_active Withdrawn
  • 2006-02-21 BR BRPI0607171-6A patent/BRPI0607171A2/pt not_active IP Right Cessation
• 2010
  • 2010-01-20 RU RU2010101656/12A patent/RU2010101656A/ru not_active Application Discontinuation

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events