Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B43—WRITING OR DRAWING IMPLEMENTS; BUREAU ACCESSORIES
  • B43L—ARTICLES FOR WRITING OR DRAWING UPON; WRITING OR DRAWING AIDS; ACCESSORIES FOR WRITING OR DRAWING
  • B43L1/00—Repeatedly-usable boards or tablets for writing or drawing

Definitions

• This invention relates to articles having an erasable writing surface, e.g., dry erase articles, labels, sheets of writing media, etc., and methods of making and using such articles.
• an erasable writing surface e.g., dry erase articles, labels, sheets of writing media, etc.
• Writing material refers to materials that provide surfaces on which people use appropriate writing instruments, e.g., pencils, pens, markers, etc., to inscribe writing or written matter through deposit of marking material, e.g., pencil led, ink, etc. on the writing surface.
• marking material e.g., pencil led, ink, etc.
• Illustrative examples include sheets of paper, sometimes in multilayer form such as adhesive-backed labels, as well as dry erase articles, folders with tabs, etc.
• a typical concern with writing materials is that they exhibit effective writability with compatible writing instruments and can be used neatly, including, if desired, exhibiting resistance to smudging, erasability, and reusability.
• dry erase boards typically have hard and smooth surfaces. Smooth dry erase boards are easier to erase than rough dry erase boards.
• smooth dry erase boards have several drawbacks. Such boards are typically glossy or shiny and thus do not work well as a projection screen as is desired in some embodiments. Dry erase writing can be easily smeared or erased unintentionally by a hand or clothing rubbing against the board.
• a dry erase board with low gloss It is desirable to have a dry erase board with low gloss. It is also desired to have a dry erase board with projection capability equal to a commercially available projection screen. In some cases, a dry erase board with smear resistant capability is desired to avoid accidental erasure of the writing or to avoid getting dry erase ink on hands or clothing.
• Paper in sheet and pad form, has been used for many decades as a writing material, either as stand alone media or incorporated into, e.g., adhesive-backed label form. For some applications, however, improved writability, erasability, smudge resistance, etc. are desired.
• the present invention provides novel erasable articles having writing surfaces with novel characteristics, methods for making such articles, and methods of using such articles.
• the surface structures of the writing surface are characterized by an Rz value as measured by a WYKO optical interferometer.
• Rz is the average of the 10 highest peak-to- valley values within the measurement area.
• the article of the invention is a dry erase article.
• Rz is greater than about 1 um
• the gloss of the dry erase article is reduced.
• Rz is greater than about 10 um
• the dry erase article can be used as a projection screen.
• Rz is greater than about 15 um
• the dry erase article is resistant to smear of dry erase ink by casual contact.
• the dry erase article is preferably erased with a synthetic fiber dry eraser or a 3MTM Whiteboard Eraser as conventional felt erasers may not perform as well as desired.
• dry erase articles of the invention typically exhibit an Ra of about 0.25, sometimes at least about 0.70, and sometimes at least about 1.0, where Ra is the average roughness value within the measurement area.
• the present invention provides writing surfaces having surface structures or features on erasable articles that solve one or more of the problems with dry erase boards, paper, films, labels, tabs, folders, pockets, and the like.
• Writing surfaces having surface structures can be generated over a range of roughness from low roughness to high roughness can be fabricated for desired applications in accordance with the invention. For instance, at a low value of roughness, the gloss of the board is reduced. At a higher value of roughness, the dry erase article can effectively double as a projection screen. At a still higher value of roughness, the dry erase article provides resistance of dry erase ink writing to smearing by casual contact while continuing to perform effectively as a projection screen.
• the article of the invention is erasable with a pencil eraser.
• the erasable article provides resistance of most writing to smearing by casual and deliberate contact.
• this invention comprises surface structures on a dry erase article and a method for making the surface structures.
• the surface structures are defined by an Rz value as measured by a WYKO optical interferometer.
• Rz is the average of the 10 highest peak-to-valley values within the measurement.
• Rz is greater than about 1 um
• the gloss of the dry erase article is reduced.
• Rz is greater than about 10 um
• the dry erase article typically also exhibits optical properties suitable for use as a projection screen.
• Rz is greater than about 15 um, the dry erase article is resistant to smear of dry erase ink by casual contact.
• the dry erase article is preferably erased with a synthetic fiber dry eraser or a 3MTM Whiteboard Eraser as conventional felt erasers may no perform as well as desired.
• dry erase articles of the invention typically exhibit an Ra of about 0.25, sometimes at least about 0.70, and sometimes at least about 1.0.
• the invention provides a method for making such dry erase articles which includes providing a coated substrate, the coated substrate comprising a first coatable material applied to a substrate, the coatable material forming a first major surface of the coated substrate; means for changing the viscosity of the first coatable material from a first viscosity to a second viscosity; a face-side roller having an outer surface positioned to contact the first major surface of the coated substrate to impart a matte finish thereon; means for hardening the first coatable material; and optionally additives to the coatable material that reduce the surface energy of the coated and cured substrate.
• a method of the invention comprises the steps of (1) providing a coated substrate comprising a curable coatable material disposed on a substrate, the curable coatable material providing a first major surface of the coated substrate; (2) changing the viscosity of the curable coatable material from the initial viscosity to a second viscosity; (3) contacting the first major surface of the coated substrate with at least one face-side roller to impart a matte finish; and (4) hardening or curing the curable coatable material to provide the film.
• Dry erase articles can provide many advantageous benefits. In many instances it is desirable to resist accidentally erasing portions of the content as you write (e.g., writer's sleeve or palm smears existing writing), interact with (e.g., gesture or point at the board), walk past (e.g., accidentally brush by), or purposely edit content on the dry erase surface. In the editing situation, a smear resistant board affords more control to erase only the desired portions. Also, due to the robust nature of the hardcoat, dry erase articles of the invention are more abrasion and scuff resistant than are many previously available alternative dry erase materials.
• the method of using such articles comprises: (1) providing a writing member of the invention; (2) writing first written matter on the writing surface using a writing instrument; and (3) erasing at least a portion of the first written matter.
• Conventional writing surfaces include paper, film, labels, folders, pockets and the like. In many cases it is desirable that these surfaces be writable with most markers, pens, and pencils and also be erasable with a pencil eraser. An erasable writing surface can be erased and reused rather than being discarded after a single use. As an added benefit, the invention provides a conventional writing surface with smear resistance to accidental or deliberate contact with hands.
• FIG. 1 is a cross-sectional schematic of an illustrative embodiment of the invention
• Fig. 2 is a schematic view of a system for making a writing member according to an embodiment of the invention.
• Fig. 3 is a schematic view of a portion of a system for making a writing member according to an embodiment of the invention.
• polymer will be understood to include polymers, copolymers (e.g., polymers formed using two or more different monomers), oligomers and combinations thereof, as well as polymers, oligomers, or copolymers that can be formed in a miscible blend by, for example, coextrusion or reaction, including transesterification. Both block and random copolymers are included, unless indicated otherwise.
• Weight percent, percent by weight, % by weight, and the like are synonyms that refer to the concentration of a substance as the weight of that substance divided by the weight of the composition and multiplied by 100.
• Ra refers to a measure of average surface roughness
• Rz refers to a measure of the average of the 10 highest peak-to-valley distances within an area of about 0.5 mm x 0.6 mm unit measurement with an optical interferometer. Ra is discussed in ASME B46.1-1995, ISO 4287-1997, and ISO 4287/1-1997. Rz is discussed in ASME B46.1-1995 and ISO 4287-1997.
• FIG. 1 An erasable article of the invention is shown in Fig. 1 wherein article 10 comprising writing member 12 and optional backing member 14 is shown.
• front face 16 of writing member 12, i.e., the writing surface has structured features in accordance with the invention.
• writing surface 16 is characterized by such properties as good writing receptivity, erasability, and resistance to smudging.
• backing member 14 comprises structural member 18 and optional primer layer 20 to achieve desired interply adhesion to writing member 12.
• article 10 may further comprise optional adhesive 22 on its back side, e.g., shown here on the back side of backing member 14, adhesive 22 providing means to adhere article 10 to an adherend as desired.
• article 10 may further comprise frame member 24 on one or more edge portions to secure the component members of article 10 together, facilitate handling of article 10, provide means of attaching article 10 to a supporting surface, etc.
• writability Acceptance of an inscribing with a compatible writing instrument is referred to as writability. For instance, use of a pencil to write on paper.
• An advantage of articles of the invention is that they exhibit superior erasability to compatible writing instruments, i.e., they can be inscribed with writing, and then the writing or a portion thereof can be easily and cleanly removed when desired, perhaps replaced by alternative writing if desired.
• Articles of the invention can be made in a variety of embodiments as desired, illustrative examples including, individual or padded sheets, e.g., similar to paper, films, adhesive-back labels, incorporated into folders, notebook covers, dry erase articles, etc. Dry Erase Article
• articles of the invention are used as dry erase articles.
• Acceptance of ink on writing surface 16 as written indicia without beading of the ink can be defined as the "wettability" of the dry erase writing surface. Wettability refers to a writing line that can retain its shape and continuity as the solvent dries. Dewetting of the solvent causes the line to move in or break at certain points, causing voids in the writing. Acceptable wettability (or writing without dewetting) is typically accomplished if the surface energy of the writing surface is greater than the surface tension of the solvents in the marker inks. On some matte dry erase films, dewetting of dry erase markers can be hard to detect by the naked eye. Sometimes the dewetting occurs between the peaks or high roughness areas on the film. This "microscopic" dewetting can be observed under a microscope.
• the writing surface additionally provides a level of "erasability" which allows the user to wipe away (e.g. with a dry cloth or dry eraser) indicia written with a dry erase marker once it is no longer desired.
• Low surface energy components may be added to the writing surface in order to improve the erasability as long as the writing surface accepts dry erase writing without macroscopic or microscopic dewetting. Reducing the surface energy is thought to prevent tenacious adhesive of the binders and other solids in the marker inks to the writing surface.
• the present invention provides a dry erase article with reduced gloss, ability to project on the surface, resistance to smear of dry erase writing, and convenient erase on demand performance.
• the dry erase article accepts ink from all dry erase markers and in some embodiments is erasable by standard dry erasers, a 3M SCOTCH-BRITETM High Performance Cleaning Cloth, or by the 3MTM Whiteboard Eraser. In the case of embodiments with higher Rz, it has been found that a higher performance eraser such as a 3M SCOTCH-BRITETM High Performance Cleaning Cloth or 3MTM Whiteboard Eraser should be used. Dry erase articles of the invention can also be cleaned with commercially available dry erase cleaners if desired.
• Optional backing 14 is selected to impart desired performance, e.g., color background to the writing surface, reflective properties in the case of dry erase articles with improved projection capability, transmission properties in the case of a dry erase overlay, etc.
• the dry erase article comprises a coating 12 on a substrate 14 with an adhesive coated on the second side of 14 and a release liner on the back of the adhesive.
• the dry erase article is a substrate with a coating on one side and an adhesive on the other side, in which the article is laminated to a second substrate which is then framed to make a dry erase board.
• the writing surface of articles of the invention will have an Rz value of at least 1 micron. In some embodiments it is preferable to have an Rz value of around 10 um. In other embodiments, it is preferable to have an Rz value of 15 um or greater.
• Rz is preferably greater than about 10 microns.
• Projection screens generally have a 60° gloss value of less than 30.
• a projection screen has a 60° gloss value of less than 20.
• the present invention provides for a dry erase article with a 60° gloss value of less than 20. Reduction of gloss value is desirable for reduction of so-called hot spots, improving the legibility of information written or, in the case of projection embodiments, projected on the dry erase article.
• the dry erase article When Rz is greater than about 15 microns, the dry erase article is resistant to smear of dry erase ink by casual contact. Information can be easily lost from a conventional dry erase article when the writing is accidentally erased by contact with a hand or with clothing.
• the present invention provides for surface structures on the dry erase article that are large enough to protect the writing from accidental erasing. With such embodiments it is typically preferred to use high performance erasing devices, e.g., a 3M SCOTCH-
• BRITETM High Performance Cleaning Cloth or by the 3MTM Whiteboard Eraser, rather than conventional felt erasers.
• Such embodiments can also be cleaned with commercially available dry erase cleaners or window cleaners.
• dry erase articles of the invention typically exhibit an Ra of about 0.25, sometimes at least about 0.70, and sometimes at least about 1.0.
• the coatable material of the instant invention is a mixture of one or more monomers, oligomers and/or polymers and radiation cure initiators.
• the coatable material includes the foregoing oligomer(s), monomer(s) and/or polymer(s) along with a volume of nanoparticles.
• the coatable material includes the foregoing oligomer(s), monomer(s) and/or polymer(s) along with the optional ingredients of nanoparticles, solvents, and a monomer, oligomer, or polymer capable of reducing the surface energy of the coated and cured article.
• the coating formulation may include one or more monomers, oligomers, or polymers capable of reducing the surface energy of the cured formulation. It is understood that the term low surface energy monomer refers to one or more monomers, oligomers, or polymers capable of reducing the surface energy of the cured formulation.
• the low surface energy monomer may be chosen from the group of fluorocarbon, silicone, or hydrocarbon containing monomers, oligomers, or polymers.
• the amount of the monomer, oligomer, or polymer is chosen to reduce the surface energy of the cured coating without causing dewetting or beading up of any dry erase marker on the dry erase article. In one embodiment, the amount of monomer, oligomer, or polymer is chosen to reduce the surface energy of the cured coating without causing dewetting of alcohol or ketone based dry erase markers.
• reduction of surface energy of the writing surface is achieved by the addition of monomers, oligomers, or polymers that tend to migrate to the surface of the coating formulation.
• monomers, oligomers, or polymers that tend to migrate to the surface of the coating formulation.
• the dry erase article also can exhibit reduced ghosting of dry erase markers and resistance to staining, e.g., by permanent markers.
• the low surface energy monomer, oligomer, or polymer may be chosen from the group of fluorocarbon, silicone, or hydrocarbon monomers.
• Fluorocarbon monomers suitable for the invention include but are not limited to per fluoro acrylates or
• Perfiuoroacrylates suitable for the invention include Ci to C 6 perfluoroalkyl acrylates or the type
• n is an integer in a range of from 1 to 6, inclusive, O R O
• X is S— NC m H 2m - , CNC m H 2m - ,
• R is H or an alkyl group having 1 to 4 carbon atoms
• m is an integer in a range of from 2 to 8, inclusive
• R f is C n F2 n+1
• y is an integer in a range of from 0 to 6, inclusive
• q is an integer in a range of from 1 to 8, inclusive
• A is a hydrocarbylene group
• p is an integer in a range of from 2 to 30, inclusive
• R' is H, CH 3 , or F.
• A is selected from the group consisting of -C 6 H 12 -,
• fluorochemical additives suitable for the invention include perfluoropolyether urethane acrylates described in US Patent No. 7,173,778 (Jing et al).
• Fluorochemical oligomers suitable for the invention include FC-4430 and FC-4432 from 3M Company, St. Paul, MN.
• Fluorochemical polymers suitable for the invention include perfluoropolyether polymers with poly(alkylene oxide) repeat units described in PCT Application No. WO2009/076389 (Yang et al).
• Silicone monomers suitable for the invention include but are not limited to silicone acrylate monomers.
• Exemplary silicone acrylate monomers include BYK-371 Reactive Silicone Surface Additive, BYK-373 Reactive Silicone Surface Additive. BYK-377 Reactive Silicone Surface Additive, BYK-UV 3500 Surface Additives for Radiation Curable Systems, BYK-UV 3530 Surface Additives for Radiation Curable Systems, BYK- UV 3570 Surface Additives for Radiation Curable Systems.
• Other suitable silicone monomers include TEGORADTM 2100, TEGORADTM 2200N, TEGORADTM 2250, and TEGORADTM 2300 silicone acrylate monomers from Evonik Goldschmidt Corporation, Hopewell, VA.
• Hydrocarbon monomers can be used to reduce the surface energy of a coating.
• hydrocarbon monomers are typically characterized by a long side chain that can form a crystalline structure on a surface.
• Suitable hydrocarbon monomers include but are not limited to octadecyl acrylate.
• the radiation curable material includes the foregoing oligomer(s), monomer(s) and/or polymer(s) in one or more solvents along with a volume of optional particles or nanoparticles, e.g., to impart increased hardness and durability to the writing member.
• Nanoparticles can be surface modified which refers to the fact that the
• stable dispersion refers to a dispersion in which the colloidal nanoparticles do not agglomerate after standing for a period of time, such as about 24 hours, under ambient conditions, e.g., room temperature (about 20 to about 22°C), and atmospheric pressure, without extreme electromagnetic forces.
• Surface-modified colloidal nanoparticles can optionally be present in a polymer coating used as a coatable composition herein with nanoparticles present in an amount effective to enhance the durability of the finished element.
• the surface-modified colloidal nanoparticles described herein can have a variety of desirable attributes, including, for example, nanoparticle compatibility with a coatable composition such that the
• nanoparticles form stable dispersions within the coatable composition, reactivity of the nanoparticle with the coatable composition making the composite more durable, and a low impact or uncured composition viscosity.
• a combination of surface modifications can be used to manipulate the uncured and cured properties of the composition.
• Surface-modified nanoparticles can improve optical and physical properties of the coatable composition such as, for example, improved resin mechanical strength, minimized viscosity changes while increasing solids volume loading in the coatable composition and maintain optical clarity while increasing solid volume loading in the coatable composition.
• the nanoparticles are surface-modified nanoparticles.
• Suitable surface-modified colloidal nanoparticles can comprise oxide particles.
• Nanoparticles may comprise a range of particle sizes over a known particle size
• the average particle size may be within a range from about 1 nm to about 100 nm.
• Particle sizes and particle size distributions may be determined in a known manner including, for example, by
• Suitable nanoparticles can comprise any of a variety of materials such as metal oxides selected from alumina, tin oxide, antimony oxide, silica, zirconia, titania and combinations of two or more of the foregoing.
• Surface- modified colloidal nanoparticles can be substantially fully condensed.
• silica nanoparticles can have a particle size ranging from about 5 to about 100 nm. In some embodiments, silica nanoparticles can have a particle size ranging from about 10 to about 30 nm. Silica nanoparticles can be present in the coatable composition in an amount from about 10 to about 100 phr. In some embodiments, silica nanoparticles can be present in the coatable composition in an amount from about 25 to about 90 phr. Silica nanoparticles suitable for use in the coatable compositions of the present invention are commercially available from Nalco Chemical Co. (Naperville, IL) under the product designation NALCOTM Colloidal Silicas.
• Suitable silica products include NALCOTM products 1040, 1042, 1050, 1060, 2327 and 2329.
• Suitable fumed silica products include for example, products sold under the trade name AEROSIL series OX-50, -130, -150, and -200 from DeGussa AG, (Hanau, Germany), and CAB-O-
• Surface-treating the nanosized particles can provide a stable dispersion in the coatable composition (e.g., a polymeric resin).
• the surface- treatment stabilizes the nanoparticles so that the particles will be well dispersed in the coatable composition and results in a substantially homogeneous composition.
• the nanoparticles can be modified over at least a portion of its surface with a surface treatment agent so that the stabilized particle can copolymerize or react with the coatable composition during curing.
• dimethoxysilane 3-(acryloyloxypropyl) methyldimethoxysilane, 3-(methacryloyloxy) propyldimethylethoxysilane, 3-(methacryloyloxy) propyldimethylethoxysilane, vinyldimethyl ethoxysilane, phenyltrimethoxysilane, n-octyltrimethoxysilane,
• the average particle sizes may be within the range from about 1 nm to about 1000 nm .
• the average particle sizes use of smaller and larger average particle sizes are also contemplated.
• at least a portion of the foregoing particles may be surface modified in the manner described above. In other embodiments, all of the particles are surface modified. In still other embodiments, none of the particles are surface modified.
• Suitable substrates for this coating include but are no limited to glass, , , paper, coated paper, paper film laminates, polymeric films, polymeric sheets, metallic foils, metallic sheets, porcelain sheets, etc.
• Polymeric films and sheets may include but are not limited to polyester, polypropylene, polyethylene, polystyrene, cellulose acetate, cellulose triacetate, polycarbonate, and polyvinyl chloride.
• Polymeric films and sheets may include copolymers, blends, or coextruded multilayer films of the aforementioned polymers or other polymers.
• the backing member may include or even consist of an adhesive on the rear surface thereof to facilitate bonding of the resultant dry erase article to a substrate or surface.
• the writing member can be preferably be substantially clear and the backing member will have reflective characteristics.
• the projection member disclosed in U.S. Patent Appln. No. 12/684,565, filed December 15, 2009 could be used in dry erase articles of the invention.
• a backing member An important attribute of a backing member is a good bond between the backing member and the writing member.
• the substrate may have to be primed or surface treated before application of the coating formulation.
• Suitable primers include with one or more chemicals known in the art such as acrylic polymers, melamine polymers, urethane polymers, and vinyl chloride containing polymers.
• Surface treatments include but are not limited to corona, plasma, flame, or flash lamp treatment.
• the radiation curable coatable material has a first or initial viscosity and is in contact with the surface of the substrate, the opposite surface of the coatable material forming a first major surface of the coated substrate.
• Means are provided for changing the viscosity of the coatable material from the first or initial viscosity to a second viscosity.
• the means for changing the viscosity comprises a means for increasing the viscosity of the coatable material from a first lower viscosity (e.g., as a liquid, paste or gel-like material) to a second higher viscosity (e.g., a partially cured, thickened, somewhat hardened solid).
• a first lower viscosity e.g., as a liquid, paste or gel-like material
• second higher viscosity e.g., a partially cured, thickened, somewhat hardened solid.
• means for changing the viscosity of the coatable material comprises means for decreasing the viscosity of the coatable material from a first higher viscosity to a second lower viscosity.
• means for decreasing the viscosity of the coatable material typically include evaporation of a solvent and chilling the substrate to increase viscosity and heating the substrate to reduce viscosity.
• the coated substrate is conveyed over idler rollers to a second station, where the coated substrate is subjected to conditions to change the viscosity by increasing the viscosity of the coatable material from an initial or first viscosity to a second viscosity, the second viscosity being greater than the initial viscosity.
• the coatable material when first applied to the substrate, is typically liquid or gel-like and is flowable or spreadable so as to form a liquid or gel- like film of material on a major surface of the substrate.
• the invention also encompasses a method of using writing articles as disclosed herein comprising: (1) providing a writing member of the invention; (2) writing first written matter on the writing surface using a writing instrument; and (3) erasing at least a portion of the first written matter.
• Gloss Gloss is measured at 60 degrees according to ASTM D 2467, Standard Test
• Two colors of marker from each brand were chosen, one black and the other red, green, or blue.
• a horizontal space about 2.5 cm high on the sample surface was reserved for that marker brand.
• the first marker was used to write the marker brand name on the left hand side of the 2.5 cm high space and the second marker was used to write the same marker brand name on the right hand side of the 2.5 cm high space. In this manner, all the writing from each marker brand is lined up in one erasable horizontal line.
• a standard 2.54 x 7.62 cm glass microscope slide was used to scrape the writing along the surface. The slide was held at an angle of 135° away from the line. The edge of the slide was then moved across the line without adding additional hand pressure. The percent of the dry erase ink remaining on the film after scraping with the microscope slide was visually estimated. After each test, the edge of the microscope slide was cleaned with a paper towel. The average percent maker ink remaining was calculated after all markers were tested on the film.
• Example 2 Protectable dry erase article: 3M 906 hardcoat was diluted to 25% solids with ethyl acetate. In addition, hexafluoro propylene oxide urethane acrylate monomer (HFPO-UA) was added to the formulation at a concentration of 0.18% to solids. The final formulation was coated on 3 mil (76 micron) white polyester film, dried, and cured on a coater by the method in Example 1. The dry coating thickness of the formulation on the film was 2.0 ⁇ .
• HFPO-UA hexafluoro propylene oxide urethane acrylate monomer
• Comparative Example C4 This comparative example is an AVERYTM Durable Write-On Plastic Divider (product number #16170). The product is described as write, erase and reuse.
• Table 4 Smear testing at various dry times.
• Values in the table are the percent of the original writing remaining after rubbing the surface with a paper sheet.
• Values in the table are the ercent of the writin removed b the eraser.
• Table 6 Erasability testing with and a pencil eraser.
• Values in the table are the number of rubs with a encil eraser re gnad to remove all of the writin .

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• 2011
  • 2011-01-26 CN CN201180016288.6A patent/CN102821973B/zh not_active Expired - Fee Related
  • 2011-01-26 EP EP11703773A patent/EP2528750A1/en not_active Withdrawn
  • 2011-01-26 WO PCT/US2011/022628 patent/WO2011094350A1/en active Application Filing
  • 2011-01-26 BR BR112012019442A patent/BR112012019442A2/pt not_active IP Right Cessation
  • 2011-01-26 KR KR1020127021925A patent/KR20120125633A/ko active IP Right Grant

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