WO2018203343A1 - Surface ou support d'écriture polymère réutilisable et procédés associés - Google Patents

Surface ou support d'écriture polymère réutilisable et procédés associés Download PDF

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Publication number
WO2018203343A1
WO2018203343A1 PCT/IN2018/050227 IN2018050227W WO2018203343A1 WO 2018203343 A1 WO2018203343 A1 WO 2018203343A1 IN 2018050227 W IN2018050227 W IN 2018050227W WO 2018203343 A1 WO2018203343 A1 WO 2018203343A1
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WO
WIPO (PCT)
Prior art keywords
polymeric
paper
media
present
agarose gel
Prior art date
Application number
PCT/IN2018/050227
Other languages
English (en)
Inventor
Animangsu Ghatak
Nitish SINGH
Original Assignee
Indian Institute Of Technology Kanpur
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Indian Institute Of Technology Kanpur filed Critical Indian Institute Of Technology Kanpur
Publication of WO2018203343A1 publication Critical patent/WO2018203343A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
    • 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
    • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
    • D21H27/02—Patterned paper

Definitions

  • the present invention relates to writing surfaces, and particularly to a polymeric writing surface or media.
  • the embodiments of the present invention relates to a reusable paper material and method of fabricating the same.
  • Paper has been a crucial writing surface for recording and disseminating information. From its invention in China to diffusion to India and rest of the world, paper replaced almost all writing surfaces those existed prior to it, and made the writing and maintaining written records far easier than any of its predecessors. Despite their impact on advancing human intellect and progress, their negative impact on environment cannot be understated, given that all paper comes from cutti ng of trees. It is a common knowledge that it takes about 12 trees to make one ton of 100 percent non- recycled newsprint It would take more than half a tree to make 10 reams of 100 percent, non- recycled 20- lb. copier paper. One tree makes about 16 reams of copy paper, or about 8000 sheets.
  • one ream uses 6 percent of a tree.
  • a large number of trees are cut every day to make paper that satisfies the global demand for paper.
  • the manufacturing of paper is also an energy intensive process that requires large quantity of water.
  • the paper is recyclable but process of recycling involves disintegration, decolouration, de-inking of fibres in paper to make a new sheet of paper. This process involves cost that prohibits largescale recycling. Furthermore, the quality of recycled paper too fails to meet the required standard for many applications.
  • paper includes randomly oriented fibres that render such surfaces rough and porous. Such surfaces are also hydrophilic so that when a drop of ink is dispersed on them, it wets the surface of the paper completely so that the colloidal particles that form the ink go into the pores of the paper and accomplish the act of writi ng.
  • the topographi cal and chemi cal property of the paper is controlled in a manner such that the ink spreads more along the thick direction into the paper, than in the horizontal direction; and thus, leading to very high resolution of the writi ng or printing.
  • the disadvantage of such large extent of wetting is that the ink particles no longer remain accessible for removal or de- wetting by any simple process and the paper essentially forfeits its reusability.
  • US 8203583 discloses an ink-free rewritable media that is imaged via a UV produced image in combination with a uniform heat source. The combination produces photochromic change i n the paper.
  • CN 103434309 discloses a reusable water rewritable paper using water hydrochromic that change their molecular configuration or conformation causing change in colour in presence of water.
  • W 02015032327 discloses a reusable water writing paper using oxazoline water- induced colour changing dye as the chromogenic component which changes its colour upon contacting water so as to display characters and/or patterns, and the colour returns when the water dries so as to cause the displayed characters and/or patterns to disappear.
  • CN2628572 Y discloses a reusable water writing paper havi ng a paper base, a carbon black layer and a white spray i ng layer.
  • the primary object of the present invention is to provide a writing surface or media that enables deletion of ink without complicated processes and by simple action of wiping or washing, and thus enabling reuse of same paper with same quality.
  • Another object of the present invention is to provide a writing media or surface wherein an ink can be easily removed by simply wiping with a wet cloth.
  • Y et another object of the present invention is to provide a writing surface or media that is made up of polymeric porous surface.
  • Y et another object of the present invention is to provide a writing media or surface that is partially hydrophilic in nature with a unique roughness pattern comprising nanostructures and microstructures.
  • Y et another object of the present invention is to provide a method of fabrication or synthesizing the reusable writing surface or media or paper.
  • Y et another object of the present invention is to provide a process for generati ng roughness patterns having length scales varying from tens of nanometers to tens micrometers by casting against porous and/ or rough templates havi ng controlled pore dimensions and pore morphology.
  • Y et another object of the present invention is to provide a writi ng and / or printing media or surface having porous surface with optimum three-dimensional structure and dimension so that particles remain weakly adhered to it and can be easi ly removed when ri nsed with water, or wi ped with a wet cl oth.
  • the various embodiments of the present invention provide a reusable writing surface or media and a method of fabricating the same.
  • the writing or surface or media comprises a paper material having a plurality of randomly placed polymeric structures forming varied templates on the surface of the paper material.
  • the plurality of polymeric structures are nanostructures and microstructures varying in diameter from 15 nm to ⁇ 150 ⁇ m and height of 5 nm to 27i m
  • a method of fabricating a reusable writing surface or media comprises preparing a rough polymeric template (101).
  • the polymeric template is prepared by using a polymer, a cross-linking agent, a promoter, a redox initiator and optionally a precipitator.
  • a polymeric film is casted on the polymeric template (102).
  • a sheet of paper is placed on the polymeric film while a cross- linking of a polymeric materials takes place (103) in the polymeric film and polymeric template.
  • the sheet of paper is peeled off from the polymeric template ( 104) . T he peel ed sheet of paper i s dri ed ( 105) .
  • the step of preparing the polymeric template comprises preparing a pre-polymer solution by mixing the polymer, the cross-linking agent the promoter, the redox initiator and optionally the precipitator.
  • the pre-polymer solution is poured on a tray, and the pre- pol y mer sol uti on i s dri ed at a predetermi ned temperature of 35°-40° C .
  • the polymer is 2- hydroxyethyl methacryl ate ( H E M A ) .
  • the cross-linking agent is Ethylene glycol dimethacrylate (EG DMA).
  • the promoter is T etramethyl ethyl enediami ne (T E M E D).
  • the redox initiator is Ammonium Per Sulfate (A PS).
  • the precipitator is sodi um chl oh de or cal ci um chl oh de.
  • the step of preparing the polymeric template comprises dissolving an agarose gel in Tris/Borate/E DTA (T BE) buffer solution to form an agarose gel solution.
  • T BE Tris/Borate/E DTA
  • the agarose gel solution is kept at a predetermined temperature of 90eC-100°C for atleast 4 minutes.
  • the hot agarose gel is poured on a tray or dish and the agarose gel solution is cooled down for atleast 2 hours.
  • the step of casting the polymeric film on the polymeric template comprises pouring a film formi ng material on a polymeric template forming a layer of thickness of 100-500 ⁇ m
  • the film forming material may be silicone, polyurethane but not excluding others.
  • the peeled sheet of paper comprises a plurality of randomly placed polymeric structures formi ng varied templates on the surface of the paper.
  • the plurality of polymeric structures are nanostructures and mi crostructures varying in diameter from 15 nm to 150 1 m and a height of 5 nm to 50 ⁇ m It is worth mentioning here that these ranges are not restrictive.
  • FIG . 1 is a flow chart showing the various steps involved in the method of fabricating a reusable writing surface or media, according to an embodiment of the present invention.
  • FIG . 2 is an image of roughness pattern of typical polymeric papers, wherein (a-d) show the optical profilometer images of different random surfaces of the reusable polymeric writing surface or media, according to an embodi ment of the present i nventi on.
  • FIG . 3 shows the surface patterns of the li ne drawn using the ball point pen on the polymeric writing surface or media, according to an embodiment of the present invention.
  • F I G . 4 shows surface patterns of the I i ne drawn usi ng the bal I poi nt pen on the polymeric writing surface or media, wherein images (a) to (c) correspond to following different pens: Cello gripper 0.5, Cello pinpoint X S and Rorito L i qui fast respectively, accordi ng to an embodi ment of the present i nventi on.
  • FIG . 5 illustrates laser printing on conventional paper and reusable polymeric surface, according to an embodiment of the present invention.
  • FIG . 6 shows that root mean square (rms) roughness of surface remains nearly unaltered over several cycles of writing with a ball pen and wiping the ink off the paper using a wet cloth and drying in atmospheric condition, according to an embodiment of the present invention.
  • F I G . 7 shows the opti cal prof i I ometer i mages of surfaces correspond! ng to FIG. 6, according to an embodiment of the present invention.
  • FIG . 8 il lustrates inkjet printing on convention paper and reusable polymeric surface, according to an embodiment herein.
  • FIG . 9 il lustrates wettability of Ink-jet printer's ink on A4 size paper and polymeric paper, wherein (a-e) shows wettability on A4 size paper and (f-j) shows wettability on rough polymeric paper, according to an embodiment of the present invention.
  • FIG . 10 shows the equi librium advancing contact angle that a typical ink of inkjet printer forms on polymeric paper of different roughness, according to an embodi ment of the present i nventi on.
  • T he writing surface or media enables deletion of ink without any complicated processes and by simple action of wiping or washing, and thus enabling the reuse of same material with same quality.
  • T he writing media is a polymeric writing media or surface.
  • the writing media or surface allows ink of a commonly used ball pen or other such pens, and other commonly used inks, and that from laser jet printers to produce delible impressions, which can then be wiped off gently with a wet cloth or other such equipment.
  • T he polymeric surface of the present embodiment may be used for multi ple cycles of writing and wiping without any damage to the surface.
  • the polymer media or surface has control led topography enabling it to be easily washed, dried and reused.
  • the present invention provides a novel reusable writing surface or material or media on which it is possible to write using a ball pen and to print using a laser jet and an inkjet printer.
  • the paper disclosed in the present invention, allows the ink to be removed by simple process without the surface physical and chemical features getting altered to any measurable extent and the cleaned surface allows it be re- used for writi ng and pri nti ng over many cycl es.
  • the reusable writing surface or media comprises a paper material having a plurality of randomly placed polymeric structures forming varied templates on the surface of the paper material.
  • the plurality of polymeric structures are nanostructures and mi crostructures varying in diameter from 15 nm to -150 ⁇ m and height of 5 nm to 50i m.
  • FIG . 1 is a flow chart showing the various steps involved in the method of fabricating a reusable writing surface or media, according to an embodiment of the present invention.
  • the method comprises preparing a polymeric template (101).
  • the polymeric template is prepared by using a polymer, a cross-linking agent, a promoter, a redox initiator and optionally a precipitator.
  • a polymeric film is casted on the polymeric template (102).
  • a sheet of paper is placed on the polymeric film while a cross-linking of a polymeric materials takes place (103) in the polymeric film and polymeric template.
  • the sheet of paper is peeled off from the polymeric template (104). T he peeled sheet of paper is dried (105).
  • the step of preparing the polymeric template comprises preparing a pre-polymer solution by mixing the polymer, the cross-linking agent the promoter, the redox initiator and optionally the precipitator.
  • the pre-polymer solution is poured on a tray, and the pre-polymer solution is dried at a predetermined temperature of 35°-40° C.
  • the polymer is 2- hydroxyethyl methacryl ate ( H E M A ) .
  • the cross-linking agent is Ethylene glycol dimethacrylate (EG DMA).
  • the promoter is T etramethyl ethyl enediami ne (T E M E D).
  • the precipitator is sodi um chl oh de or cal ci um chl oh de.
  • the step of preparing the polymeric template comprises dissolving an agarose gel in Tris/Borate/E DTA (T BE) buffer solution to form an agarose gel solution.
  • T BE Tris/Borate/E DTA
  • the agarose gel solution is kept at a predetermined temperature of 90eC-100°C for at I east 4 mi nutes.
  • T he hot agarose gel is poured on a tray or dish and the agarose gel solution is cooled down for at least 2 hours.
  • the step of casting the polymeric film on the polymeric template comprises pouring a si I i cone/poly urethane material on the polymeric template forming a layer of thickness of 50-500 1 m.
  • the peeled sheet of paper comprises a plurality of randomly placed polymeric structures forming varied templates on the surface of the paper.
  • the plurality of polymeric structures are nanostructures and mi crostructures varying in diameter from 15 nm to 150 1 m and a height of 5 nm to 50 1 m.
  • the present invention makes use of an environmentally benign polymeric material that has not been used earlier for writi ng or printing because of small frictional resistance that it exerts to sliding of a ball pen and because of its limited wettability by the ink.
  • the present invention has made the use of this material suitable for writing and printing by roughening its surface which enhances both frictional characteristics of the surface and its wettability. So when a ball pen is slide past its surface, ink from the pen gets dispensed on ⁇ the ink from different sources, e.g. ball pen, laser-jet can spread on it albeit to a limited extent and the ink can be easily removed by simple rinsing or wiping it with a wet cloth.
  • the paper can be subjected to many such cycles of writing/printing - cleaning and rewriting without any loss of reusability.
  • the invention opens up the possibility of reducing the usage of conventional paper which is expected to di mi ni sh the envi ronmental i mpact of usi ng paper.
  • the monomer-to-water weight ratio was maintained such that the final product contains 70%-98% by weight of water.
  • the prepolymer solution mixed with al I the reagents at desi red weight rati o was poured on a tray ( made of glass/A I uminium/steel/acrylic sheet), placed horizontally and was allowed to crosslink.
  • the quantity of the pre-polymer solution was such that after crosslinking 5-10 mm gel thickness is achieved.
  • the excess water in gel was drained out and fresh water was added to it for dissolvi ng any crystallized salt from the pores of the gel. This process was repeated 2-3 times.
  • the gel layer was allowed to dry out in a hot atmosphere of 35°-40° C to the extent that 20%-90% of the initial water content of the gel was removed.
  • the pores on the gel surface opened up while also remaining visi bly wet This surface was used as template for making the polymeric paper.
  • the resulting solution was placed inside a microwave oven maintained at ⁇ 90eC-100°C for 4 minutes within which the solution turned transparent Makeup water was added to keep the volume of the sol ution constant. It was stirred for another 2 minutes at that temperature and the hot solution was then poured inside a petridish or a tray The sol uti on was al I owed to cool down and crossl i nk for 2 hours.
  • C uring of the precursor /cross linkable liquid The film of liquid B is then crossl inked at room temperature for 2-3 hours during which it cures partially.
  • a backing material which is usually a sheet of paper is then placed on the top surface of the partially cured layer which is then completely crossli nked in another 2-3 hours.
  • FIG . 2 is an image of roughness pattern of typical polymeric papers, wherein (a-d) show the optical profilometer images of different random surfaces of the reusable polymeric writing surface or media, according to an embodiment of the present invention. With respect to FIG . 2, different patterns or templates of randomly rough surfaces of the writing material can be seen. These are the polymeric microstructures and the nanostructures.
  • the polymeric surface is partially hydrophobic and with roughness patterns as shown in the FIG . 2.
  • FIG. 3 shows the surface patterns of the li ne drawn usi ng the ball point pen on the polymeric writing surface or media, according to an embodi ment of the present i nvention.
  • the line was fully disintegrated into tiny droplets on a smooth surface with rms roughness 10 nm but became less disintegrated as roughness was increased.
  • the sharpness of i mage was found to maximize at an intermediate roughness of 0.75-0.93 ⁇ m
  • FIG. 4 shows surface patterns of the line drawn using the ball point pen on the polymeric writing surface or media, wherein images (a) to (c) correspond to following different pens: Cello gripper 0.5, Cello pinpoint X S and Rorito Liquifast respectively, according to an embodiment of the present invention.
  • images (a) to (c) correspond to following different pens: Cello gripper 0.5, Cello pinpoint X S and Rorito Liquifast respectively, according to an embodiment of the present invention.
  • the images clearly show that ball pen C el I o gri pper 0.5 generates sharpest and conti nuous I i ne.
  • the polymeric paper or media can be used for laser pri nting over several cycles.
  • laser printing can be done only once
  • laser printing can be done multi pi e ti mes, i .e. the pri nted i mage on paper can be wi ped off with wet cloth and dried in atmospheric condition and reused again for printing.
  • FIG . 5 illustrates laser printing on conventional paper and reusable polymeric surface, according to an embodiment of the present invention. With respect to FIG . 5, the series of images show that the quality of the printed image does not diminish over repeated cycles.
  • a polymeric paper of rms roughness 0.15 ⁇ m was used for demonstrati ng the reusabil ity of the paper.
  • FIG. 6 shows that root mean square (rms) roughness of surface remains nearly unaltered over several cycles of writing with a ball pen and wiping the ink off the paper using a wet cloth and drying in atmospheric condition, according to an embodiment of the present invention.
  • rms root mean square
  • F I G . 7 shows the opti cal prof i I ometer i mages of surfaces correspondi ng to F I G . 6, accordi ng to an embodi ment of the present i nventi on.
  • FIG . 8 il lustrates inkjet printing on convention paper and reusable polymeric surface, according to an embodiment herein.
  • the rough polymeric paper can be used for inkjet printing over several cycles. In each cycle, the printed i mage on paper is cleaned with wet cloth and dried in atmospheric condition. A polymeric paper of rms roughness of 0.15 ⁇ m was used in these experiments.
  • FIG . 9 il lustrates wettabil ity of Ink-jet printer's ink on A4 size paper and polymeric paper, wherein (a-e) shows wettability on A4 size paper and (f-j) shows wettability on rough polymeric paper, according to an embodiment of the present invention.
  • FIG . 9(a-e) shows that ink completely spreads/absorbs on the fibrous network of A4 Size paper.
  • ink disintegrates into tiny drops on polymeric surface as shown in FIG . 9(f-j ).
  • the rms roughness of papers as shown in figure (e) and (i) are 5.67 1 m and 1.33 1 m respectively.
  • FIG . 10 shows the equi librium advancing contact angle that a typical ink of inkjet printer forms on polymeric paper of different roughness, according to an embodiment of the present invention.
  • the angle varies from 31 degrees to 51 degrees.
  • the present invention provides a reusable paper wherein the ink can be removed by simple wiping off with a wet cloth.
  • the paper is used for several cycles which reduces the cost of making the paper.
  • the paper is reusable without any loss of quality over several cycles.
  • the roughness patterns of the paper can be opti mized for drawing continuous yet sharp li ne of ink on the paper, very much similar to conventional paper.
  • the paper allows almost all types of conventional inks to be used for writing without requiring any specially prepared ink material.
  • the ink can be easily removed without any need of sophisticated equipment.
  • the reusable paper does not require any special skill/equi pment to be adopted for writi ng and rewriti ng.

Abstract

La présente invention concerne une surface ou un support polymère réutilisable pour l'écriture. Le support se présente sous la forme d'un papier comportant une pluralité de motifs nanostructurés et microstructurés, une encre provenant d'un stylo à bille ou de l'impression à jet d'encre peut être essuyée facilement au moyen d'un procédé simple d'essuyage à l'aide d'un tissu humide. La présente invention concerne en outre un procédé de fabrication de papier ou surface ou support d'écriture réutilisable. Le procédé pour améliorer la rugosité de la surface ou support polymère par formation de cadres hydrogel est également décrit.
PCT/IN2018/050227 2017-05-01 2018-04-18 Surface ou support d'écriture polymère réutilisable et procédés associés WO2018203343A1 (fr)

Applications Claiming Priority (2)

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IN201711015292 2017-05-01
IN201711015292 2017-05-01

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WO2018203343A1 true WO2018203343A1 (fr) 2018-11-08

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109693460A (zh) * 2018-11-26 2019-04-30 安徽同和包装制品有限公司 一种环保数字印刷工艺

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011094350A1 (fr) * 2010-01-26 2011-08-04 3M Innovative Properties Company Article a surface d'ecriture effacable et son utilisation
WO2013104168A1 (fr) * 2012-01-09 2013-07-18 东莞中世拓实业有限公司 Tableau blanc souple pouvant être facilement réutilisé
US20130280691A1 (en) * 2011-12-18 2013-10-24 Tim O'Connor Write erasable component system
CN103434309A (zh) * 2013-09-09 2013-12-11 吉林大学 一种新型的可重复使用水写纸
US9352607B1 (en) * 2013-01-23 2016-05-31 Abraham R. Albenda Wipeable writing surface

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011094350A1 (fr) * 2010-01-26 2011-08-04 3M Innovative Properties Company Article a surface d'ecriture effacable et son utilisation
US20130280691A1 (en) * 2011-12-18 2013-10-24 Tim O'Connor Write erasable component system
WO2013104168A1 (fr) * 2012-01-09 2013-07-18 东莞中世拓实业有限公司 Tableau blanc souple pouvant être facilement réutilisé
US9352607B1 (en) * 2013-01-23 2016-05-31 Abraham R. Albenda Wipeable writing surface
CN103434309A (zh) * 2013-09-09 2013-12-11 吉林大学 一种新型的可重复使用水写纸

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109693460A (zh) * 2018-11-26 2019-04-30 安徽同和包装制品有限公司 一种环保数字印刷工艺

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