EP1180173B1 - Printed and printable substrates - Google Patents

Printed and printable substrates Download PDF

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Publication number
EP1180173B1
EP1180173B1 EP00915089A EP00915089A EP1180173B1 EP 1180173 B1 EP1180173 B1 EP 1180173B1 EP 00915089 A EP00915089 A EP 00915089A EP 00915089 A EP00915089 A EP 00915089A EP 1180173 B1 EP1180173 B1 EP 1180173B1
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EP
European Patent Office
Prior art keywords
filmable
fixing layer
coating
layer
especially preferably
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP00915089A
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German (de)
French (fr)
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EP1180173A1 (en
Inventor
Jakob Grob
Thomas Leu
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Landqart AG
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Landqart AG
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Publication of EP1180173A1 publication Critical patent/EP1180173A1/en
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    • 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
    • D21H19/00—Coated paper; Coating material
    • D21H19/80—Paper comprising more than one coating
    • D21H19/82—Paper comprising more than one coating superposed
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/502—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording characterised by structural details, e.g. multilayer materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/502—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording characterised by structural details, e.g. multilayer materials
    • B41M5/506—Intermediate layers
    • 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
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/38—Coatings with pigments characterised by the pigments
    • D21H19/42—Coatings with pigments characterised by the pigments at least partly organic

Definitions

  • the present invention relates to printable and printed substrates, in particular Specialty papers, processes for making them and their uses.
  • WO 97/18090 (Kimberly-Clark) describes a printable special paper which has a filmable layer arranged on a carrier material, and which is provided after printing using heat and / or Print to be filmed on a large scale. The print is then behind the filmed Layer essentially irreversibly bound and protected.
  • the specialty papers described above have a number of disadvantages. So the special papers need to be fully filmed for a period of 20-60s kept at temperatures of 140 ° C to 180 ° C. Such conditions can but only with very special heating presses or with laminators of the highest price range can be set. Furthermore, there is the problem that in particular a one-sided filmable coating (and this is often preferred for cost reasons) after the filming the special papers are no longer flat or a curvature the papers already appear during filming in the laminator and the papers therefore occasionally have a tendency to get stuck in the laminator.
  • the object of the invention is to specify how prints, in particular inkjet prints, are more abrasion-resistant, smudge-proof, water-resistant, brilliant, light-resistant and finally also be made more resistant in the sense of increased security against counterfeiting can.
  • the substrate should also be inexpensive and using conventional machines can be manufactured.
  • the invention relates to a printable substrate according to claim 1 and a method for producing such a substrate according to claim 7.
  • the invention further relates to a printed substrate according to claim 10 and a method for producing such a substrate according to claim 12.
  • Claims 17-19 relate to special uses of the substrates according to the invention.
  • the essence of the present invention is therefore to apply to a substrate e.g. out First apply a pressure-fixing layer to paper on at least one side, and on this pressure-fixing layer an organic pigments (plastic pigments) and binders Applying filmable coating containing.
  • This filmable coating is intended, after printing by feeding at least of Heat, but preferably heat and pressure, to be filmed.
  • the ink penetrates into the porous filmable coating during printing, penetrates this and becomes when reaching between the carrier material and filmable Layer arranged pressure fixing layer bound on or in the fixing layer. In front in other words, part of the ink is in the filmable part Layer, and the other, usually larger part of the ink is in resp. on the pressure fixing layer bound.
  • Other printing inks, such as those used in offset processes are used, and which due to their physico-chemical properties cannot penetrate into the filmable coating, remain after the printing process essentially on the surface of the filmable coating.
  • the filming of the filmable layer has the effect that the print is subsequently behind or in the filmed layer more abrasion-resistant, smudge-proof, water-resistant, brilliant, and is more lightfast.
  • the use of the pressure fixing layer leads to the fact that if there is residual porosity after filming or if it is microscopic If the film is torn, the print is still water-resistant because the pressure-fixing layer the ink binds under the film. The printed image appears Viewer with increased brilliance. It has also been shown that according to the invention Print images produced are much more lightfast than conventional inkjet prints. Additional and expensive laminations, such as those made with inkjet papers are superfluous. After printing essentially on the Other printing inks remaining on the surface are also removed by filming partially welded in and tied more tightly.
  • Such a formulation of the filmable layer allows filming temperatures below or in the range of 100 ° C. These are conditions with cheap laminators can be easily adjusted.
  • the wording allows despite the low film forming temperature is still a coating process for that Substrate for which none of the filmable layer is dry when the application is dried early filming of the coating takes place, and also the substrate before printing, do not store under special conditions such as cooling become.
  • the low filming temperature also results in The advantage is that the film does not dry out as much as it does when filming Temperatures above 100 ° C is the case. So the substrates remain after filming still flat and the risk of a jam in the laminator is reduced. It shows that especially when using the above, low-melting organic pigments the use of the pressure fixing layer a pinpoint and waterproof print results.
  • Another embodiment is characterized in that the pressure fixing layer cationic and absorbent, particularly preferably water-resistant is.
  • the ink becomes active from the print fixing layer during printing sucked down and, since inks are usually anionic in character, precipitated from the cationic portions of the pressure fixing layer and fixed.
  • the print image appears both with a high resolution and also results from the use an already waterproof pressure-fixing layer an increase in water resistance.
  • Figure 1 shows a section through the layered structure of the proposed substrate 13.
  • a carrier material 12 which is usually a paper, but optionally can also be a pretreated or semi-synthetic paper or a film here on one of the surfaces preferably all over with a pressure fixing layer 11 coated. Over the pressure fixing layer 11 and covering the substrate superficially there is a filmable coating 10. Depending on the application, this can Substrate 13 also made of a carrier material coated on both sides with layers 11 and 10 12 exist. It can then be printed and filmed on both sides.
  • the substrate 13 should in particular be used with conventional if possible, cheap film laminators in particular.
  • conventional low-cost laminators for the continuous process usually have at least a pair of counter-rotating rollers between which the laminate to be led. Either one or both are used to heat the laminate the rollers are heated, or a heating element is connected directly upstream of the rollers, which the paper or film to be laminated between penetrates the rollers warmed.
  • the cheap laminators mostly only allow the setting of a single predetermined temperature, usually in the range from 120 ° C to 130 ° C, as cooling or special materials for higher temperatures for rollers and housing are necessary.
  • the pressure between the rollers can be in usually not changed, and the transport speed, if any, often only be set between a few discrete values.
  • conventional filmable and printable substrates according to the prior art can be found in film such laminators mostly unsatisfactorily, because higher filming temperatures and / or higher pressure are necessary, and the papers also tend after the filming to bulge.
  • the three-layer laminate shown in FIG. 1 now solves this problem area by the ink after at least partial penetration into the porous filmable layer 10 is bound by a pressure fixing layer 11.
  • the inks, or corresponding colors which are due to their physico-chemical properties are able to form into the filmable layer 10 penetrate, are sucked down and localized on the fixing layer 11 bound.
  • the water resistance remains so high, there is no blurring of the ink on.
  • Other printing inks, such as those used in offset processes, and which, due to their physico-chemical properties, cannot be filmed Coating can penetrate, can also be applied, remain but after the printing process essentially on the surface of the filmable Coating.
  • carrier material 12 With regard to the type of carrier material 12 and its basis weight, there are no special requirements. Normal cellulose or cotton papers or combinations thereof with typical basis weights in the range between 80 g / m 2 and 300 g / m 2 are suitable. For prints of photographic representations it is preferred to use papers with a higher basis weight in the upper part of the specified range.
  • the structure is the same for applications in the security field, but papers with additional security elements (such as watermarks, chemical security agents or paint applications containing iridescent pigments) in the weight range of 70-150 g / m 2 are preferably used here.
  • the pressure fixing layer 11 is advantageously already in one in the paper production process integrated step e.g. applied with a film press.
  • Layer 11 should be absorbent so that the ink from the layer 11 is active during the printing process from the filmable coating 10 is added to the pressure fixing layer 11.
  • layer 11 should fix the ink and bind it waterproof.
  • conventional Inks are mostly anionic in character, and fixing is easiest with achieved cationic substances to which the ink components in a precipitation be bound locally.
  • absorbent components be present (e.g. silicas), a cationic binder (e.g. cationic Polyvinylamine) and preferably a binder around the dried layer to anchor the paper better.
  • Other components such as plasticizers or substances to maintain lightfastness and / or UV resistance can be optional be attached.
  • composition of the pressure fixing layer 11 formulated for application as an aqueous dispersion has proven to be suitable, for example: 50 g Aerosil K315 (15% dispersion, weight of the dispersion) 70 g water 26.5g Catiofast * PR 8106 (22% dispersion, weight of the dispersion) 6 g Plextol E220 (60% dispersion, weight of the dispersion) 10 g Syloid 244 (Powder weight)
  • Aerosil K315 (Degussa AG, DE) is a brilliant, white, absorbent finely divided fumed silica. It is a 15% aqueous dispersion of Silica powder before. Catiofast * PR 8106 (BASF, Ludwigshafen, DE) is actually a AOX-free wet strength agent for the production of wet strength paper grades in the neutral range. It is a light to dark yellow aqueous, 22% solution of one Polymer based on vinylamine and N-vinyl formamide and acts as a cationic, water-soluble, high molecular resin for fixing anionic inks. It works also as a binder.
  • Plextol E220 Polymer Latex GmbH & Co KG, Dormagen, DE is a 60% dispersion of a self-adhesive acrylic polymer and acts as Binder.
  • Syloid 244 W.R. Grace & Co, USA is a powdered matting agent made of silica, it also reduces the viscosity of the dispersion for the Line.
  • the grain size can be set to ⁇ 120 ⁇ m or smaller if required.
  • the dispersion has a pH in the range of 7.5.
  • the layer should be in the range of 6-10 g / m 2 , with the above-mentioned formulation ideally 8-8.5 g / m 2 are applied.
  • the filmable coating 10 should have a minimum film-forming temperature which on the one hand enables filming at the lowest possible temperatures, but still an efficient drying process, i.e. reasonable drying temperatures allowed for drying the filmable coating 10.
  • composition of the filmable layer 10 formulated for application as an aqueous dispersion has proven to be suitable, for example: 60 g Baystal S21C (50% dispersion, weight of the dispersion) 15 g Gohsenol GL-03 (10% solution, weight of the solution) 5 g Mowiol 28-99 (10% solution, weight of the solution) 4 g Litex PS 5020 (50% dispersion, weight of the dispersion) 4 g Plextol E 220 (60% dispersion, weight of the dispersion) 0.5 g Tinuvin 213 30 g water
  • Baystal Polymer Latex GmbH & Co KG, Dormagen, DE is a 50% colloidal Dispersion of a copolymer of butadiene, styrene and acrylic acid and a low one Emulsifier. The styrene content is approximately 78%. Baystal is the essential Proportion of filmable organic polymer with a glass transition temperature in the Range from 50 ° C-60 ° C. These are pigment spheres, such as those in the Emulsion polymerization occurs with a size in the range of 0.5 - 1 ⁇ m.
  • Gohsenol (Nippon Gohsei, Osaka, JP) and Mowiol (Clariant, Muttenz, CH) are aqueous Solutions of polyvinyl alcohol serve as binders and have a water-absorbing effect.
  • the binder content increase by 50% if necessary.
  • For possible microscopic cracking in the Avoid filmable layer 10 can advantageously particularly long-chain Polyvinyl alcohols can be used.
  • Litex (Polymer Latex GmbH & Co KG, Dormagen, DE) is an aqueous anionic 50% dispersion of a carboxylated styrene-butadiene copolymer (Copolymer of butadiene, styrene and acrylic acid), which is used as a binder for coating colors in the paper industry.
  • Litex has one Glass transition temperature of about -6 ° C and serves here as a film-forming aid as well to increase the shine.
  • Plextol Polymer Latex GmbH & Co KG, Dormagen, DE
  • Plextol® is a 60% dispersion of a self-adhesive acrylic polymer.
  • Tinuvin (Ciba SC, Basel, CH) is an optional UV stabilizer. Among other things, he supports the light fastness of the in the underlying pressure fixing layer 11 fixed colors. Optionally, you can also Plasticizers, inorganic pigments or other additives can be added.
  • the coating formulation can be applied offline or inline by means of a doctor blade application, a screen engraving roller, an air brush or in a casting process onto the substrate material 12 which has been pre-coated with the pressure-fixing layer 11.
  • the layer thickness should be chosen with the above formulation in the range of 9-12 g / m 2 . If you choose thicker layers, a higher temperature must usually be selected for filming; with a thinner coating, the protective function of the layer is reduced.
  • the finished non-filmed substrate can be printed using a classic printing process be, but it is particularly suitable for printing with an inkjet process.
  • the ink penetrates into or through the porous filmable layer 10 and is sucked by the pressure fixing layer 11 and on this due to the cationic character of layer 11 localized fixed.
  • Those types of inks, which cannot penetrate into the filmable coating remain, as they already do mentioned above, after the printing process essentially on the surface of the filmable Coating.
  • the paper can be used without any further Processing by a laminator at a local lamination temperature in the area of 100 ° C.
  • the local lamination temperature can be unadjustable Temperature of the laminator through the transport speed through the Laminator can be customized.
  • a pressure in the range between 0.5-5 bar in a static press or a corresponding line print in a continuous laminator has proven to be sufficient and inexpensive. It is also conceivable to film it to be carried out at low temperature but very high pressure, usually must then the period of time during which the pressure is applied is also essential increase.
  • Covers for the lamination process are siliconized papers, and it shows that especially not too thick papers with a thick siliconization too contribute to a good and even film adaptation.
  • a so-called carrier in which the substrate to be filmed can be inserted, and whose inner surface has the desired surface structure. The substrate is inserted into the carrier for the lamination process, and after lamination, the carrier is removed from the filmed paper again.
  • Such a carrier can ideally can be used several times.
  • the invention is therefore particularly suitable for use in the security field such as. for the production of ID cards, passports, certificates or the like.
  • the security paper can initially be made using a classic printing process such as. printed in an offset process and then individualized for the end user with a simple inkjet print and then in be filmed in a laminator.
  • the offset printing ink remains essentially on the surface, but is also partially welded in during filming and fixed. It is also conceivable for outdoor applications or similar applications, where an extremely pronounced protection of the printed image is necessary, the substrate with the use of conventional foil bags in which the paper is embedded and laminated.

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Abstract

In a printable substrate, particularly a paper-based substrate, improved printing quality, good print protection from water and frictional wear is achieved in that a support layer (12) has one print fixing layer (11) on at least one side and a film-forming organic pigment and a filmable coating (10) containing a binding agent are placed on the print fixing layer (11). The structure makes it possible to especially use low melting point organic pigments and enables simpler filming while preserving the flatness of the substrate.

Description

TECHNISCHES GEBIETTECHNICAL AREA

Die vorliegende Erfindung betrifft bedruckbare sowie bedruckte Substrate, insbesondere Spezialpapiere, Verfahren zu deren Herstellung, und ihre Verwendungen.The present invention relates to printable and printed substrates, in particular Specialty papers, processes for making them and their uses.

STAND DER TECHNIKSTATE OF THE ART

Die Mehrzahl der modernen bedruckbaren Papiere, sei es für klassische Druckverfahren oder für den Inkjet-Druck, weisen eine oberflächliche Beschichtung oder Imprägnierung auf, welche in unterschiedlichem Masse für eine optimale Haftung der Druckfarbe bzw. Tinte auf dem Papierträger, deren möglichst punktgenaue, nicht verschwimmende Lokalisierung nach der Auftragung, sowie für Lichtechtheit und andere Eigenschaften sorgen. Insbesondere im Bereich des Inkjet-Drucks werden Spezialpapiere eingesetzt, welche beispielsweise mit einer anorganische Pigmente enthaltenden Beschichtung unter anderem zur Erhöhung der Farbbrillanz versehen sind. Trotz derartiger Beschichtung weisen aber wässrige Inkjet-Drucke vielfach eine geringe Wisch- und/oder Wasserfestigkeit auf. Auch ihre Lichtbeständigkeit lässt zu wünschen übrig.The majority of modern printable papers, be it for classic printing processes or for inkjet printing, have a superficial coating or impregnation on which to varying degrees for optimal adhesion of the printing ink or ink on the paper carrier, the most precise, non-blurring Localization after application, as well as for lightfastness and other properties to care. Special papers are used especially in the field of inkjet printing, which, for example, with a coating containing inorganic pigments are provided, among other things, to increase the color brilliance. Despite such a coating however, aqueous inkjet prints often have a low wiping and / or Water resistance. Their lightfastness also leaves something to be desired.

Zum Schutze von Inkjet-Drucken, insbesondere gegen Feuchtigkeit und Verwischen, sowie in gewissem Masse auch zur Erhöhung des Glanzes, werden diese häufig mit einer Folie laminiert, wozu spezielle Laminatoren erhältlich sind. Derartige Applikationen finden sich auch im Ausweis- oder Sicherheitsbereich, wobei zusätzlich oft noch ein Foto, Passbild oder dergleichen in die Folie mit "eingeschweisst" wird. Dieses Einschweissen stellt für geschickte Fälscher jedoch kaum ein Fälschungshindernis dar.To protect inkjet prints, especially against moisture and smudging, and to a certain extent also to increase the gloss, these are often included laminated in a foil, for which special laminators are available. Such applications can also be found in the ID or security area, often in addition a photo, passport photo or the like is "welded" into the film. This welding in is hardly an obstacle to counterfeiting for skillful counterfeiters.

Die WO 97/18090 (Kimberly-Clark) beschreibt ein bedruckbares Spezialpapier welches eine auf einem Trägermaterial angeordnete, verfilmbare Schicht aufweist, und welches dazu vorgesehen ist, nach dem Bedrucken unter Anwendung von Wärme und/oder Druck grossflächig verfilmt zu werden. Der Druck ist anschliessend hinter der verfilmten Schicht im wesentlichen irreversibel gebunden und geschützt.WO 97/18090 (Kimberly-Clark) describes a printable special paper which has a filmable layer arranged on a carrier material, and which is provided after printing using heat and / or Print to be filmed on a large scale. The print is then behind the filmed Layer essentially irreversibly bound and protected.

Ein auf der im wesentlichen gleichen Idee beruhendes Spezialpapier beschreiben auch die DE 196 28 342 (Sihl GmbH, Düren) und die EP 0 826 823 der Anmelderin. Das Trägermaterial sowie die Formulierung der verfilmbaren Schicht werden in der ersten Schrift so gewählt, dass das verfilmte Papier gegenüber dem Einfluss von Wasser besonders widerstandsfähig ist.Also describe a special paper based on the essentially same idea DE 196 28 342 (Sihl GmbH, Düren) and EP 0 826 823 from the applicant. The Backing material and the formulation of the filmable layer are in the first Font chosen so that the filmed paper is special against the influence of water is resistant.

Die oben beschriebenen Spezialpapiere weisen eine Reihe von Nachteilen auf. So müssen die Spezialpapiere zur vollständigen Verfilmung während einer Zeit von 20-60s auf Temperaturen von 140°C bis 180°C gehalten werden. Derartige Bedingungen können aber nur mit sehr speziellen Heizpressen oder mit Laminatoren der obersten Preisklasse eingestellt werden. Des weiteren ergibt sich das Problem, dass insbesondere bei einer einseitigen verfilmbaren Beschichtung (und diese ist aus Kostengründen oft bevorzugt) nach der Verfilmung die Spezialpapiere nicht mehr plan sind oder eine Krümmung der Papiere bereits während des Verfilmens im Laminator auftritt und die Papiere deswegen gelegentlich die Tendenz haben, im Laminator stecken zu bleiben.The specialty papers described above have a number of disadvantages. So the special papers need to be fully filmed for a period of 20-60s kept at temperatures of 140 ° C to 180 ° C. Such conditions can but only with very special heating presses or with laminators of the highest price range can be set. Furthermore, there is the problem that in particular a one-sided filmable coating (and this is often preferred for cost reasons) after the filming the special papers are no longer flat or a curvature the papers already appear during filming in the laminator and the papers therefore occasionally have a tendency to get stuck in the laminator.

DARSTELLUNG DER ERFINDUNGPRESENTATION OF THE INVENTION

Aufgabe der Erfindung ist es anzugeben, wie Drucke, insbesondere Inkjet-Drucke, abriebfester, wischfester, wasserbeständiger, brillanter, lichtbeständiger und schliesslich auch noch beständiger im Sinne einer erhöhten Fälschungssicherheit gemacht werden können. Das Substrat soll ausserdem in kostengünstiger Weise und unter Verwendung konventioneller Maschinen herstellbar sein.The object of the invention is to specify how prints, in particular inkjet prints, are more abrasion-resistant, smudge-proof, water-resistant, brilliant, light-resistant and finally also be made more resistant in the sense of increased security against counterfeiting can. The substrate should also be inexpensive and using conventional machines can be manufactured.

Im Hinblick auf diese Aufgabe sind Gegenstand der Erfindung ein bedruckbares Substrat gemäss Anspruch 1 sowie ein Verfahren zur Herstellung eines solchen Substrats gemäss Anspruch 7. In view of this object, the invention relates to a printable substrate according to claim 1 and a method for producing such a substrate according to claim 7.

Gegenstand der Erfindung ist weiter ein bedrucktes Substrat gemäss Anspruch 10 sowie ein Verfahren zur Herstellung eines solchen Substrats nach Anspruch 12.The invention further relates to a printed substrate according to claim 10 and a method for producing such a substrate according to claim 12.

Die Ansprüche 17-19 etreffen spezielle Verwendungen der erfindungsgemässen Substrate.Claims 17-19 relate to special uses of the substrates according to the invention.

Der Kern der vorliegenden Erfindung besteht demnach darin, auf ein Substrat z.B. aus Papier mindestens einseitig zunächst eine Druckfixierschicht aufzustreichen, und auf diese Druckfixierschicht eine organische Pigmente (Kunststoff-Pigmente) und Bindemittel enthaltende verfilmbare Beschichtung aufzubringen. Diese verfilmbare Beschichtung ist dazu vorgesehen, nach dem Bedrucken durch Zuführung zumindest von Wärme, vorzugsweise jedoch von Wärme und Druck, verfilmt zu werden. Die Tinte dringt dabei beim Bedrucken in die porös ausgebildete verfilmbare Beschichtung ein, durchdringt diese und wird beim Erreichen der zwischen Trägermaterial und verfilmbarer Schicht angeordneten Druckfixierschicht auf bzw. in der Fixierschicht gebunden. Vor dem Verfilmen befindet sich mit anderen Worten ein Teil der Tinte, in der verfilmbaren Schicht, und der andere, in der Regel grössere Teil der Tinte ist in resp. auf der Druckfixierschicht gebunden. Andere Druckfarben, wie sie beispielsweise in Offset-Verfahren verwendet werden, und welche aufgrund ihrer physikalisch-chemischen Eigenschaften nicht in die verfilmbare Beschichtung eindringen können, verbleiben nach dem Druckvorgang im wesentlichen auf der Oberfläche der verfilmbaren Beschichtung.The essence of the present invention is therefore to apply to a substrate e.g. out First apply a pressure-fixing layer to paper on at least one side, and on this pressure-fixing layer an organic pigments (plastic pigments) and binders Applying filmable coating containing. This filmable coating is intended, after printing by feeding at least of Heat, but preferably heat and pressure, to be filmed. The ink penetrates into the porous filmable coating during printing, penetrates this and becomes when reaching between the carrier material and filmable Layer arranged pressure fixing layer bound on or in the fixing layer. In front in other words, part of the ink is in the filmable part Layer, and the other, usually larger part of the ink is in resp. on the pressure fixing layer bound. Other printing inks, such as those used in offset processes are used, and which due to their physico-chemical properties cannot penetrate into the filmable coating, remain after the printing process essentially on the surface of the filmable coating.

Das Verfilmen der verfilmbaren Schicht führt dazu, dass der Druck anschliessend hinter bzw. in der verfilmten Schicht abriebfester, wischfester, wasserbeständiger, brillanter, und lichtbeständiger ist. Die Verwendung der Druckfixierschicht führt dabei dazu, dass bei nach dem Verfilmen häufig vorhandener Restporosität oder bei mikroskopischen Rissen der verfilmten Schicht der Druck trotzdem wasserbeständig ist da die Druckfixierschicht die Tinte unter dem Film bindet. Das aufgebrachte Druckbild erscheint dem Betrachter mit erhöhter Brillanz. Es hat sich zudem gezeigt, dass nach der Erfindung hergestellte Druckbilder wesentlich lichtbeständiger sind als herkömmliche Inkjet-Drucke. Zusätzliche und teure Laminierungen, wie sie bei Inkjet-Papieren teilweise gemacht werden, sind überflüssig. Nach dem Druckvorgang im wesentlichen auf der Oberfläche verbleibende andere Druckfarben werden durch das Verfilmen ebenfalls teilweise mit eingeschweisst und stärker gebunden. The filming of the filmable layer has the effect that the print is subsequently behind or in the filmed layer more abrasion-resistant, smudge-proof, water-resistant, brilliant, and is more lightfast. The use of the pressure fixing layer leads to the fact that if there is residual porosity after filming or if it is microscopic If the film is torn, the print is still water-resistant because the pressure-fixing layer the ink binds under the film. The printed image appears Viewer with increased brilliance. It has also been shown that according to the invention Print images produced are much more lightfast than conventional inkjet prints. Additional and expensive laminations, such as those made with inkjet papers are superfluous. After printing essentially on the Other printing inks remaining on the surface are also removed by filming partially welded in and tied more tightly.

Eine erste bevorzugte Ausführungsform zeichnet sich dadurch aus, dass die verfilmbare Beschichtung folgende Komponenten enthält:

  • 20-90 Gew.%, insbesondere bevorzugt 70-90 Gew.% organische Pigmente,
  • 1-30 Gew.%, insbesondere bevorzugt 2-10 Gew.% Bindemittel
  • 0- 20 Gew.%, insbesondere bevorzugt 7-15 Gew.% Filmbildehilfsmittel
  • 0- 5 Gew.% UV-Stabilisatoren
  • 0 - 5 Gew. % Oxidationsstabilisatoren
wobei als organische Pigmente einer Partikelgrösse vorzugsweise im Bereich von 0.1-10µm, weiter vorzugsweise im Bereich zwischen 0.5 und 10µm, insbesondere bevorzugt im Bereich von 0.5 bis 2µm, vorzugsweise Styrole, Butadiene, Acrylate sowie deren Copolymere bzw. Kombinationen davon mit Glasübergangstemperaturen im Bereich zwischen 40°C und 90°C, insbesondere jedoch zwischen 50°C-70°C, als Filmbildehilfsmittel Styrole, Butadiene, Acrylate sowie deren Copolymere bzw. Kombinationen davon mit Glasübergangstemperaturen unterhalb der Raumtemperatur, insbesondere jedoch zwischen (-50°C)-(+20°C), und als Bindemittel vorzugsweise Stärke, Polyvinylalkohol, Polyvinylpyrrolidon oder eine Acrylat, Styrol oder PVAC enthaltende Kunststoff-Dispersion verwendet sind.A first preferred embodiment is characterized in that the filmable coating contains the following components:
  • 20-90% by weight, particularly preferably 70-90% by weight, organic pigments,
  • 1-30% by weight, particularly preferably 2-10% by weight, of binder
  • 0- 20% by weight, particularly preferably 7-15% by weight, film-forming aid
  • 0- 5% by weight UV stabilizers
  • 0 - 5 wt.% Oxidation stabilizers
the organic pigments having a particle size preferably in the range from 0.1-10 μm, more preferably in the range between 0.5 and 10 μm, particularly preferably in the range from 0.5 to 2 μm, preferably styrenes, butadienes, acrylates and their copolymers or combinations thereof with glass transition temperatures in the range between 40 ° C and 90 ° C, but especially between 50 ° C-70 ° C, as film-forming aids styrenes, butadienes, acrylates and their copolymers or combinations thereof with glass transition temperatures below room temperature, but especially between (-50 ° C) - ( + 20 ° C), and the binder used is preferably starch, polyvinyl alcohol, polyvinylpyrrolidone or a plastic dispersion containing acrylate, styrene or PVAC.

Eine derartige Formulierung der verfilmbaren Schicht erlaubt Verfilmungstemperaturen unterhalb oder im Bereich von 100°C. Dies sind Bedingungen, welche mit billigen Laminatoren problemlos eingestellt werden können. Die Formulierung erlaubt aber trotz der niedrigen Filmbildetemperatur immer noch einen Beschichtungsprozess für das Substrat, bei welchem beim Trocknen der Auftragung der verfilmbaren Schicht keine frühzeitige Verfilmung der Beschichtung stattfindet, und ausserdem muss das Substrat vor dem Bedrucken nicht unter speziellen Bedingungen wie unter Kühlung aufbewahrt werden. Des weiteren ergibt sich aus der niedrigen Verfilmungstemperatur auch der Vorteil, dass das Trägermaterial beim Verfilmen nicht so stark austrocknet, wie das bei Temperaturen oberhalb von 100°C der Fall ist. So bleiben die Substrate nach dem Verfilmen weiterhin plan und es reduziert sich die Gefahr eines Staus im Laminator. Es zeigt sich, dass insbesondere bei der Verwendung von den obigen, tiefschmelzenden organischen Pigmenten die Verwendung der Druckfixierschicht ein punktgenaues und wasserfestes Druckbild ergibt.Such a formulation of the filmable layer allows filming temperatures below or in the range of 100 ° C. These are conditions with cheap laminators can be easily adjusted. The wording allows despite the low film forming temperature is still a coating process for that Substrate for which none of the filmable layer is dry when the application is dried early filming of the coating takes place, and also the substrate before printing, do not store under special conditions such as cooling become. Furthermore, the low filming temperature also results in The advantage is that the film does not dry out as much as it does when filming Temperatures above 100 ° C is the case. So the substrates remain after filming still flat and the risk of a jam in the laminator is reduced. It shows that especially when using the above, low-melting organic pigments the use of the pressure fixing layer a pinpoint and waterproof print results.

Eine weitere Ausführungsform ist dadurch gekennzeichnet, dass die Druckfixierschicht kationisch und die Tinte saugend, insbesondere bevorzugt wasserfest bindend ausgebildet ist. Auf diese Weise wird die Tinte beim Bedrucken aktiv von der Druckfixierschicht nach unten gesaugt und, da Tinten in der Regel anionischen Charakters sind, von den kationischen Anteilen der Druckfixierschicht ausgefällt und fixiert. Das Druckbild erscheint so sowohl mit einer hohen Auflösung, als auch ergibt sich durch die Verwendung einer bereits wasserfesten Druckfixierschicht eine Erhöhung der Wasserfestigkeit.Another embodiment is characterized in that the pressure fixing layer cationic and absorbent, particularly preferably water-resistant is. In this way, the ink becomes active from the print fixing layer during printing sucked down and, since inks are usually anionic in character, precipitated from the cationic portions of the pressure fixing layer and fixed. The print image appears both with a high resolution and also results from the use an already waterproof pressure-fixing layer an increase in water resistance.

Eine andere Ausführungsform der Erfindung ist dadurch charakterisiert, dass insbesondere bevorzugt die Druckfixierschicht folgende Komponenten enthält:

  • 40-80 Gew.%, insbesondere bevorzugt 60-70 Gew.% anorganische Pigmente,
  • 5-40 Gew.%, insbesondere bevorzugt 15-25 Gew.% kationische Polymere, und
  • 1-20 Gew.%, Bindemittel,
wobei als anorganisches Pigment vorzugsweise Kieselsäuren oder Aluminiumoxidhydrate, als kationisches Polymer vorzugsweise ein Vinylamin-Polymeres, N-Vinylamin-Formamid-Polymeres, eine Kombination oder Copolymere davon und als Bindemittel vorzugsweise ein Polyacrylat oder Polyvinylalkohol verwendet wird. Die Verwendung von anorganischen Pigmenten führt zu der erwünschten Saugkraft der Druckfixierschicht, und die Verwendung eines kationischen Harzes erlaubt die dauerhafte, wasserfeste Fällung und lokale Fixierung von anionischen Tinten in der Schicht.Another embodiment of the invention is characterized in that the pressure-fixing layer particularly preferably contains the following components:
  • 40-80% by weight, particularly preferably 60-70% by weight, of inorganic pigments,
  • 5-40% by weight, particularly preferably 15-25% by weight, of cationic polymers, and
  • 1-20% by weight, binder,
preferably silica or aluminum oxide hydrates being used as the inorganic pigment, preferably a vinylamine polymer, N-vinylamine-formamide polymer, a combination or copolymers thereof as the cationic polymer and preferably a polyacrylate or polyvinyl alcohol as binder. The use of inorganic pigments leads to the desired absorbency of the pressure-fixing layer, and the use of a cationic resin allows the permanent, water-resistant precipitation and local fixing of anionic inks in the layer.

Weitere Ausführungsformen der Erfindung und der erfindungsgemässen Verfahren sowie Verwendungen sind in den abhangigen Ansprüchen beschrieben.Further embodiments of the invention and the method according to the invention as well Uses are described in the dependent claims.

WEGE ZUR AUSFÜHRUNG DER ERFINDUNGWAYS OF CARRYING OUT THE INVENTION

Figur 1 zeigt einen Schnitt durch den geschichteten Aufbau des vorgeschlagenen Substrates 13. Ein Trägermaterial 12, welches in der Regel ein Papier, gegebenenfalls aber auch ein vorbehandeltes oder teilsynthetisches Papier oder eine Folie sein kann, ist hier auf einer der Oberflächen bevorzugt ganzflächig mit einer Druckfixierschicht 11 beschichtet. Über der Druckfixierschicht 11 und das Substrat oberflächlich abdeckend befindet sich eine verfilmbare Beschichtung 10. Je nach Anwendungsbereich kann das Substrat 13 auch aus einem beidseitig mit den Schichten 11 und 10 beschichteten Trägermaterial 12 bestehen. Es ist dann beidseitig bedruck- und verfilmbar.Figure 1 shows a section through the layered structure of the proposed substrate 13. A carrier material 12, which is usually a paper, but optionally can also be a pretreated or semi-synthetic paper or a film here on one of the surfaces preferably all over with a pressure fixing layer 11 coated. Over the pressure fixing layer 11 and covering the substrate superficially there is a filmable coating 10. Depending on the application, this can Substrate 13 also made of a carrier material coated on both sides with layers 11 and 10 12 exist. It can then be printed and filmed on both sides.

Das Substrat 13 soll neben der Verfilmung in Laminierpressen insbesondere mit herkömmlichen, wenn möglich insbesondere billigen Laminatoren verfilmbar sein. Zur Zeit erhältliche kostengünstige Laminatoren zum Durchlaufverfahren weisen meist wenigstens ein Paar von gegenläufig rotierenden Walzen auf, zwischen welchen das Laminiergut geführt wird. Zur Erwärmung des Laminierguts werden entweder eine oder beide der Walzen beheizt, oder es wird den Walzen unmittelbar ein Heizelement vorgeschaltet, welches das zu laminierende Papier oder die Folie vor dem Eindringen zwischen die Walzen erwärmt. Insbesondere die billigen Laminatoren erlauben meist nur die Einstellung einer einzigen vorgegebenen Temperatur, normalerweise im Bereich von 120°C-130°C, da für höhere Temperaturen eine Kühlung oder besondere Materialien für Walzen und Gehäuse notwendig sind. Der Druck zwischen den Walzen kann in der Regel nicht verändert werden, und die Transportgeschwindigkeit kann, wenn überhaupt, oft nur zwischen wenigen diskreten Werten eingestellt werden. Herkömmliche verfilmbare und bedruckbare Substrate nach dem Stand der Technik lassen sich in derartigen Laminatoren meist nur unbefriedigend verfilmen, da höhere Verfilmungstemperaturen und/oder höherer Druck notwendig sind, und ausserdem neigen die Papiere nach dem Verfilmen dazu, sich aufzuwölben.In addition to filming in laminating presses, the substrate 13 should in particular be used with conventional if possible, cheap film laminators in particular. For now Available low-cost laminators for the continuous process usually have at least a pair of counter-rotating rollers between which the laminate to be led. Either one or both are used to heat the laminate the rollers are heated, or a heating element is connected directly upstream of the rollers, which the paper or film to be laminated between penetrates the rollers warmed. In particular, the cheap laminators mostly only allow the setting of a single predetermined temperature, usually in the range from 120 ° C to 130 ° C, as cooling or special materials for higher temperatures for rollers and housing are necessary. The pressure between the rollers can be in usually not changed, and the transport speed, if any, often only be set between a few discrete values. conventional filmable and printable substrates according to the prior art can be found in film such laminators mostly unsatisfactorily, because higher filming temperatures and / or higher pressure are necessary, and the papers also tend after the filming to bulge.

Werden nun, um die obigen Nachteile zu vermeiden, einfach bei verfilmbaren Papieren nach dem Stand der Technik Pigmente verwendet, die niedrigere Glasübergangstemperaturen aufweisen, so stellt man fest, dass die Druckbilder schlecht aufgelöst erscheinen, die Abrieb- und Wasserfestigkeit abnimmt, und dass ein Verfliessen der Druckfarbe bereits beim Bedrucken auftritt. Eine Beimischung von anorganischen Pigmenten in die verfilmbare Schicht 10 kann zwar die Druckqualität erhöhen, die Wasserfestigkeit bleibt aber trotzdem unbefriedigend schlecht.In order to avoid the above disadvantages, they are now easy for filmable papers According to the state of the art, pigments are used that have lower glass transition temperatures it is found that the printed images appear poorly resolved, the abrasion and water resistance decreases, and that a flowing of the Ink already occurs during printing. An admixture of inorganic pigments in the filmable layer 10 can increase the print quality, the water resistance but remains unsatisfactorily bad.

Eine übermässige Erniedrigung der Glasübergangstemperatur der organischen Pigmente führt ausserdem zu Problemen im Beschichtungsprozess bei der Herstellung der Papiere. Diese müssen nach der Beschichtung mit der verfilmbaren Schicht 10 getrocknet werden, wobei sich die Schicht noch nicht verfilmen darf. Da normalerweise zwecks Beschleunigung des Herstellungsprozesses die Trocknungstemperaturen im Bereich wenigstens von 30°C gewählt werden, muss bei der Wahl der Pigmente ein sinnvoller Kompromiss gefunden werden.An excessive decrease in the glass transition temperature of the organic pigments also leads to problems in the coating process in the manufacture of the Papers. These have to be dried after coating with the filmable layer 10 be, whereby the layer must not yet film. Because usually To accelerate the manufacturing process, the drying temperatures in the A range of at least 30 ° C must be selected when choosing the pigments reasonable compromise can be found.

Das in Figur 1 dargestellte, dreischichtige Laminat löst nun diesen Problemkreis, indem die Tinte nach dem wenigstens teilweisen Eindringen in die poröse verfilmbare Schicht 10 von einer Druckfixierschicht 11 gebunden wird. Auf diese Weise können die bei der Verwendung von tiefschmelzenden organischen Polymeren auftretenden Probleme einfach beseitigt werden. Die Tinten, oder entsprechende Farben, welche aufgrund ihrer physikalisch-chemischen Eigenschaften in der Lage sind, in die verfilmbare Schicht 10 einzudringen, werden nach unten gesaugt und auf der Fixierschicht 11 lokalisiert gebunden. Die Wasserfestigkeit bleibt so hoch, es tritt kein Verschwimmen der Tinte auf. Andere Druckfarben, wie sie beispielsweise in Offset-Verfahren verwendet werden, und welche aufgrund ihrer physikalisch-chemischen Eigenschaften nicht in die verfilmbare Beschichtung eindringen können, können ebenfalls aufgetragen werden, verbleiben aber nach dem Druckvorgang im wesentlichen auf der Oberfläche der verfilmbaren Beschichtung.The three-layer laminate shown in FIG. 1 now solves this problem area by the ink after at least partial penetration into the porous filmable layer 10 is bound by a pressure fixing layer 11. In this way, at Problems encountered using low melting organic polymers just be eliminated. The inks, or corresponding colors, which are due to their physico-chemical properties are able to form into the filmable layer 10 penetrate, are sucked down and localized on the fixing layer 11 bound. The water resistance remains so high, there is no blurring of the ink on. Other printing inks, such as those used in offset processes, and which, due to their physico-chemical properties, cannot be filmed Coating can penetrate, can also be applied, remain but after the printing process essentially on the surface of the filmable Coating.

Der dadurch mögliche Einsatz von tieferschmelzenden organischen Pigmenten erlaubt es, die lokal auftretende Laminiertemperatur wesentlich zu senken, insbesondere in den Bereich von 100°C, was nicht nur die Verwendung von Billiglaminatoren erlaubt, sondern auch dazu führt, dass das Trägermaterial 12 während des Laminierprozesses nicht so stark austrocknet und ein Aufwölben der Papiere deshalb weniger auftritt.This enables the use of deep-melting organic pigments to significantly reduce the local laminating temperature, especially in the range of 100 ° C, which not only allows the use of cheap laminators, but also results in the backing material 12 during the lamination process does not dry out as much and therefore there is less bulging of the papers.

Hinsichtlich der Art des Trägermaterials 12 und dessen Flächengewicht ergeben sich keine besonderen Anforderungen. Normale Zellstoff- oder Baumwollpapiere bzw. Kombinationen davon mit typischen Flächengewichten im Bereich zwischen 80 g/m2 und 300 g/m2 sind geeignet. Für Drucke von photographischen Darstellungen wird man bevorzugt Papiere mit einem höheren Flächengewicht im oberen Teil des angegeben Bereichs verwenden. Für Anwendungen im Sicherheitsbereich ist der Aufbau gleich, doch werden hier bevorzugt Papiere mit zusätzlichen Sicherheitselementen (wie z.B. Wasserzeichen, chemischen Sicherungen oder irisierende Pigmente enthaltende Farbaufträge) im Gewichtsbereich von 70-150 g/m2 verwendet.With regard to the type of carrier material 12 and its basis weight, there are no special requirements. Normal cellulose or cotton papers or combinations thereof with typical basis weights in the range between 80 g / m 2 and 300 g / m 2 are suitable. For prints of photographic representations it is preferred to use papers with a higher basis weight in the upper part of the specified range. The structure is the same for applications in the security field, but papers with additional security elements (such as watermarks, chemical security agents or paint applications containing iridescent pigments) in the weight range of 70-150 g / m 2 are preferably used here.

Die Druckfixierschicht 11 wird vorteilhafterweise bereits in einem im Papierherstellungsprozess integrierten Schritt z.B. mit einer Filmpresse aufgetragen. Die Schicht 11 soll saugend sein, damit die Tinte von der Schicht 11 aktiv beim Druckvorgang aus der verfilmbaren Beschichtung 10 auf die Druckfixierschicht 11 aufgenommen wird. Ausserdem sollte die Schicht 11 die Tinte fixieren und wasserfest binden. Herkömmliche Tinten sind meist anionischen Charakters, und eine Fixierung wird am einfachsten mit kationischen Substanzen erreicht, an welche die Tintenbestandteile in einer Fällung lokal gebunden werden. Um dies zu erreichen müssen anorganische, saugende Bestandteile vorhanden sein (z.B. Kieselsäuren), ein kationisches Bindemittel (z.B. kationische Polyvinylamine) sowie bevorzugt ein Bindemittel um die getrocknete Schicht auf dem Papier besser zu verankern. Weitere Bestandteile wie Weichmacher oder Substanzen zur Erhaltung der Lichtechtheit und/oder der UV-Beständigkeit können optional beigefügt werden.The pressure fixing layer 11 is advantageously already in one in the paper production process integrated step e.g. applied with a film press. Layer 11 should be absorbent so that the ink from the layer 11 is active during the printing process from the filmable coating 10 is added to the pressure fixing layer 11. Furthermore layer 11 should fix the ink and bind it waterproof. conventional Inks are mostly anionic in character, and fixing is easiest with achieved cationic substances to which the ink components in a precipitation be bound locally. To achieve this you need inorganic, absorbent components be present (e.g. silicas), a cationic binder (e.g. cationic Polyvinylamine) and preferably a binder around the dried layer to anchor the paper better. Other components such as plasticizers or substances to maintain lightfastness and / or UV resistance can be optional be attached.

Folgende zur Auftragung als wässrige Dispersion formulierte Zusammensetzung der Druckfixierschicht 11 hat sich z.B. als geeignet erwiesen: 50 g Aerosil K315 (15% Dispersion, Gewicht der Dispersion) 70 g Wasser 26.5g Catiofast* PR 8106 (22% Dispersion, Gewicht der Dispersion) 6 g Plextol E220 (60% Dispersion, Gewicht der Dispersion) 10 g Syloid 244 (Pulvergewicht) The following composition of the pressure fixing layer 11 formulated for application as an aqueous dispersion has proven to be suitable, for example: 50 g Aerosil K315 (15% dispersion, weight of the dispersion) 70 g water 26.5g Catiofast * PR 8106 (22% dispersion, weight of the dispersion) 6 g Plextol E220 (60% dispersion, weight of the dispersion) 10 g Syloid 244 (Powder weight)

Aerosil K315 (Degussa AG, DE) ist ein Brillanz erzeugendes weisses, saugendes hochdisperses pyrogenes Siliciumdioxid. Es liegt als 15%-ige, wässrige Dispersion des Kieselsäurepulvers vor. Catiofast* PR 8106 (BASF, Ludwigshafen, DE) ist eigentlich ein AOX-freies Nassverfestigungsmittel für die Herstellung von nassfesten Papierqualitäten im Neutralbereich. Es ist eine hell- bis dunkelgelbe wässrige, 22%-ige Lösung eines Polymers auf Basis von Vinylamin und N-Vinyl-Formamid und wirkt als kationisches, wasserlösliches, hochmolekulares Harz zur Fixierung von anionischen Tinten. Es wirkt ausserdem als Bindemittel. Plextol E220 (Polymer Latex GmbH &Co KG, Dormagen, DE) ist eine 60%-ige Dispersion eines selbstklebenden Acrylpolymeren und wirkt als Bindemittel. Syloid 244 (W.R. Grace & Co, USA) ist ein pulverförmiges Mattierungsmittel aus Kieselsäure, es reduziert ausserdem die Viskosität der Dispersion für den Strich.Aerosil K315 (Degussa AG, DE) is a brilliant, white, absorbent finely divided fumed silica. It is a 15% aqueous dispersion of Silica powder before. Catiofast * PR 8106 (BASF, Ludwigshafen, DE) is actually a AOX-free wet strength agent for the production of wet strength paper grades in the neutral range. It is a light to dark yellow aqueous, 22% solution of one Polymer based on vinylamine and N-vinyl formamide and acts as a cationic, water-soluble, high molecular resin for fixing anionic inks. It works also as a binder. Plextol E220 (Polymer Latex GmbH & Co KG, Dormagen, DE) is a 60% dispersion of a self-adhesive acrylic polymer and acts as Binder. Syloid 244 (W.R. Grace & Co, USA) is a powdered matting agent made of silica, it also reduces the viscosity of the dispersion for the Line.

Alle Bestandteile ausser Catiofast werden vorgemischt und nach Zugabe von Catiofast in der Kugelmühle homogenisiert. Die Korngrösse kann so auf <120µm oder bei Bedarf auch kleiner eingestellt werden. Die Dispersion weist einen pH im Bereich von 7.5 auf. Die Schicht sollte im Bereich von 6-10 g/m2 liegen, bei der obenerwähnten Formulierung werden idealerweise 8-8.5 g/m2 aufgetragen.All ingredients except Catiofast are premixed and homogenized after adding Catiofast in a ball mill. The grain size can be set to <120µm or smaller if required. The dispersion has a pH in the range of 7.5. The layer should be in the range of 6-10 g / m 2 , with the above-mentioned formulation ideally 8-8.5 g / m 2 are applied.

Die verfilmbare Beschichtung 10 soll eine Mindestfilmbildetemperatur aufweisen, welche auf der einen Seite eine Verfilmung bei möglichst niedrigen Temperaturen ermöglicht, aber dennoch einen effizienten Trocknungsprozess, d.h. sinnvolle Trocknungstemperaturen für die Trocknung der verfilmbaren Beschichtung 10 erlaubt. The filmable coating 10 should have a minimum film-forming temperature which on the one hand enables filming at the lowest possible temperatures, but still an efficient drying process, i.e. reasonable drying temperatures allowed for drying the filmable coating 10.

Folgende zur Auftragung als wässrige Dispersion formulierte Zusammensetzung der verfilmbaren Schicht 10 hat sich z.B. als geeignet erwiesen: 60 g Baystal S21C (50% Dispersion, Gewicht der Dispersion) 15 g Gohsenol GL-03 (10% Lösung, Gewicht der Lösung) 5 g Mowiol 28-99 (10% Lösung, Gewicht der Lösung) 4 g Litex PS 5020 (50% Dispersion, Gewicht der Dispersion) 4 g Plextol E 220 (60% Dispersion, Gewicht der Dispersion) 0.5 g Tinuvin 213 30 g Wasser The following composition of the filmable layer 10 formulated for application as an aqueous dispersion has proven to be suitable, for example: 60 g Baystal S21C (50% dispersion, weight of the dispersion) 15 g Gohsenol GL-03 (10% solution, weight of the solution) 5 g Mowiol 28-99 (10% solution, weight of the solution) 4 g Litex PS 5020 (50% dispersion, weight of the dispersion) 4 g Plextol E 220 (60% dispersion, weight of the dispersion) 0.5 g Tinuvin 213 30 g water

Baystal (Polymer Latex GmbH &Co KG, Dormagen, DE) ist eine 50%-ige, kolloidale Dispersion aus einem Copolymer aus Butadien, Styrol und Acrylsäure und einem niedrigen Emulgatoranteil. Der Styrolanteil beträgt ca. 78%. Baystal bildet den wesentlichen Anteil an verfilmbarem organischem Polymer mit einer Glasübergangstemperatur im Bereich von 50°C-60°C. Es handelt sich dabei um Pigmentkügelchen, wie sie in der Emulsionspolymerisation entstehen, mit einer Grösse im Bereich von 0.5 - 1 µm. Gohsenol (Nippon Gohsei, Osaka, JP) und Mowiol (Clariant, Muttenz, CH) sind wässrige Lösungen von Polyvinylalkohol, dienen als Bindemittel und wirken wasserziehend. Für die Verwendung des Substrats im Offset-Druck empfiehlt es sich, den Bindemittelanteil gegebenenfalls um 50% zu erhöhen. Um mögliche mikroskopische Rissbildung in der verfilmbaren Schicht 10 zu vermeiden, können vorteilhafterweise besonders langkettige Polyvinylalkohole verwendet werden. Litex (Polymer Latex GmbH &Co KG, Dormagen, DE) ist eine wässrige anionische 50%ige Dispersion eines carboxylierten Styrol-Butadien-Copolymerisates (Copolymer aus Butadien, Styrol und Acrylsäure), welche als Binder für Streichfarben in der Papierindustrie eingesetzt wird. Litex weist eine Glasübergangstemperatur von ca. -6°C auf und dient hier als Filmbildehilfsmittel sowie zur Erhöhung des Glanzes. Gleichermassen dient Plextol (Polymer Latex GmbH &Co KG, Dormagen, DE) mit einer Glasübergangstemperatur im Bereich von -47°C. Plextol ist eine 60%-ige Dispersion eines selbstklebenden Acrylpolymeren. Tinuvin (Ciba SC, Basel, CH) ist ein optionaler UV-Stabilisator. Er unterstützt u.a. die Lichtechtheit der in der darunterliegenden Druckfixierschicht 11 fixierten Farben. Optional können des weiteren Weichmacher, anorganische Pigmente oder andere Additive beigefügt werden. Baystal (Polymer Latex GmbH & Co KG, Dormagen, DE) is a 50% colloidal Dispersion of a copolymer of butadiene, styrene and acrylic acid and a low one Emulsifier. The styrene content is approximately 78%. Baystal is the essential Proportion of filmable organic polymer with a glass transition temperature in the Range from 50 ° C-60 ° C. These are pigment spheres, such as those in the Emulsion polymerization occurs with a size in the range of 0.5 - 1 µm. Gohsenol (Nippon Gohsei, Osaka, JP) and Mowiol (Clariant, Muttenz, CH) are aqueous Solutions of polyvinyl alcohol serve as binders and have a water-absorbing effect. For the use of the substrate in offset printing, it is recommended the binder content increase by 50% if necessary. For possible microscopic cracking in the Avoid filmable layer 10 can advantageously particularly long-chain Polyvinyl alcohols can be used. Litex (Polymer Latex GmbH & Co KG, Dormagen, DE) is an aqueous anionic 50% dispersion of a carboxylated styrene-butadiene copolymer (Copolymer of butadiene, styrene and acrylic acid), which is used as a binder for coating colors in the paper industry. Litex has one Glass transition temperature of about -6 ° C and serves here as a film-forming aid as well to increase the shine. Plextol (Polymer Latex GmbH & Co KG, Dormagen, DE) with a glass transition temperature in the range of -47 ° C. Plextol® is a 60% dispersion of a self-adhesive acrylic polymer. Tinuvin (Ciba SC, Basel, CH) is an optional UV stabilizer. Among other things, he supports the light fastness of the in the underlying pressure fixing layer 11 fixed colors. Optionally, you can also Plasticizers, inorganic pigments or other additives can be added.

Werden die obigen Bestandteile der verfilmbaren Schicht 11 vermischt, so bilden sich Partikel einer Grösse im Bereich von 20µm und die Dispersion weist einen pH im Bereich von 8 auf. Die Streichformulierung kann mittels eines Rakelauftrags, einer Rastergravurwalze, einer Luftbürste oder in einem Giessverfahren auf das mit der Druckfixierschicht 11 vorgestrichene Trägermaterial 12 offline oder inline aufgetragen werden. Die Schichtdicke sollte mit obiger Formulierung im Bereich von 9-12 g/m2 gewählt werden. Wählt man dickere Schichten, so muss zur Verfilmung in der Regel eine höhere Temperatur gewählt werden, bei einer dünneren Beschichtung wird die Schutzfunktion der Schicht heruntergesetzt.If the above constituents of the filmable layer 11 are mixed, particles of a size in the range of 20 μm are formed and the dispersion has a pH in the range of 8. The coating formulation can be applied offline or inline by means of a doctor blade application, a screen engraving roller, an air brush or in a casting process onto the substrate material 12 which has been pre-coated with the pressure-fixing layer 11. The layer thickness should be chosen with the above formulation in the range of 9-12 g / m 2 . If you choose thicker layers, a higher temperature must usually be selected for filming; with a thinner coating, the protective function of the layer is reduced.

Das fertige unverfilmte Substrat kann in einem klassischen Druckverfahren bedruckt werden, insbesondere geeignet ist es aber für ein Bedrucken mit einem Inkjet-Verfahren. Die Tinte dringt dort in bzw. durch die poröse verfilmbare Schicht 10 hindurch und wird von der Druckfixierschicht 11 angesaugt und auf dieser aufgrund des kationischen Charakters der Schicht 11 lokalisiert fixiert. Jene Arten von Druckfarben, welche nicht in die verfilmbare Beschichtung eindringen können, verbleiben, wie schon oben erwähnt, nach dem Druckvorgang im wesentlichen auf der Oberfläche der verfilmbaren Beschichtung. Anschliessend an das Bedrucken kann das Papier ohne weitere Bearbeitung durch einen Laminator bei einer lokalen Laminiertemperatur im Bereich von 100°C hindurch gelassen werden. Die lokale Laminiertemperatur kann bei unverstellbarer Temperatur des Laminators durch die Transportgeschwindigkeit durch den Laminator angepasst werden. Wie erwähnt, wird zum Verfilmen ausser Wärme vorzugsweise gleichzeitig Druck angewendet. Ein Druck im Bereich zwischen 0,5-5 bar in einer statischen Presse oder ein entsprechender Liniendruck in einem Durchlauflaminator hat sich als ausreichend und günstig erwiesen. Es ist auch denkbar, das Verfilmen bei niedriger Temperatur aber dafür sehr hohem Druck durchzuführen, meist muss dann aber auch die Zeitspanne, während derer der Druck angewendet wird, wesentlich erhöht werden.The finished non-filmed substrate can be printed using a classic printing process be, but it is particularly suitable for printing with an inkjet process. The ink penetrates into or through the porous filmable layer 10 and is sucked by the pressure fixing layer 11 and on this due to the cationic character of layer 11 localized fixed. Those types of inks, which cannot penetrate into the filmable coating remain, as they already do mentioned above, after the printing process essentially on the surface of the filmable Coating. After printing, the paper can be used without any further Processing by a laminator at a local lamination temperature in the area of 100 ° C. The local lamination temperature can be unadjustable Temperature of the laminator through the transport speed through the Laminator can be customized. As mentioned, preference is given to filming other than heat pressure applied simultaneously. A pressure in the range between 0.5-5 bar in a static press or a corresponding line print in a continuous laminator has proven to be sufficient and inexpensive. It is also conceivable to film it to be carried out at low temperature but very high pressure, usually must then the period of time during which the pressure is applied is also essential increase.

Wasserfestigkeit und Wischbeständigkeit, vor allem jedoch hohe Brillanz sind typische Eigenschaften von Papierabzügen fotografischer Bilder. Mit der Erfindung lassen sich z.B. ausgehend von elektronisch gespeicherten Bildern "Papierabzüge" von praktisch gleicher Qualität von jedermann mit einem Standard-Inkjet-Farbdrucker und einem einfachen Laminator herstellen. Im Vergleich zu Fotopapier ist das beschichtete Substrat nach der Erfindung meist billiger. Water resistance and smudge resistance, but above all high brilliance are typical Properties of paper prints of photographic images. With the invention e.g. starting from electronically stored images "paper prints" of practical same quality from everyone with a standard inkjet color printer and one make simple laminator. Compared to photo paper, the coated substrate is mostly cheaper according to the invention.

Selbst die Oberflächenbeschaffenheit der Bilder im Sinne von "matt" oder "glänzend" kann in einfachster Weise gesteuert und bestimmt werden durch Wahl der Oberfläche, welche während des Verfilmens mit der Bildoberfläche unter Druck in Kontakt ist. So genügt es z.B., zusammen mit dem zu verfilmenden Bild bzw. Druck eine matte oder glänzende Folie durch einen Durchlauflaminator laufen zu lassen. Für "matte" Oberflächen sind Folien mit einer Rauhtiefe zwischen 0,01 - 5 µm geeignet und für "glänzende" solche mit einer Rauhtiefe kleiner als 0.01 µm. Die Folie muss sich nach dem Verfilmen natürlich wieder gut von der verfilmten Oberfläche ablösen lassen. Geeignet sind deshalb Polyester- oder auch Polyamidfolien (wie z.B. GRILON 6, 10, 12). Ebenfalls mögliche Abdeckungen für den Laminiervorgang sind silikonisierte Papiere, und es zeigt sich, dass insbesondere nicht allzu dicke Papiere mit einer dicken Silikonisierung zu einer guten und gleichmässigen Verfilmung beitragen. Vorteilhaft ist z.B. die Gestaltung eines sog. Carriers, in welchen das zu verfilmende Substrat eingelegt werden kann, und dessen innere Oberfläche die gewünschte Oberflächenstruktur aufweist. Das Substrat wird für den Laminiervorgang in den Carrier eingelegt, und nach dem Laminieren, wird der Carrier wieder vom verfilmten Papier entfernt. Ein solcher Carrier kann idealerweise mehrfach verwendet werden.Even the surface quality of the pictures in the sense of "matt" or "glossy" can be controlled and determined in the simplest way by choosing the surface, which is in contact with the image surface under pressure during filming. So For example, it is sufficient to use a matt or with the image or print to be filmed let glossy film run through a continuous laminator. For "matt" surfaces foils with a roughness depth between 0.01 - 5 µm are suitable and for "shiny" those with a roughness depth of less than 0.01 µm. The film must be after filming of course let it peel off the filmed surface again. Are therefore suitable Polyester or polyamide films (such as GRILON 6, 10, 12). Also possible Covers for the lamination process are siliconized papers, and it shows that especially not too thick papers with a thick siliconization too contribute to a good and even film adaptation. It is advantageous e.g. the design a so-called carrier, in which the substrate to be filmed can be inserted, and whose inner surface has the desired surface structure. The substrate is inserted into the carrier for the lamination process, and after lamination, the carrier is removed from the filmed paper again. Such a carrier can ideally can be used several times.

Es ist andererseits auch möglich, die Walzen des Laminators direkt auf geeignete Weise zu beschichten. Für Walzen von Durchlaufvorrichtungen zum Verfilmen dürften Teflon oder keramische Materialien im Hinblick auf eine gute Wiederablösbarkeit geeignet sein. Um in einem Laminator zwei verschiedene Oberflächenstrukturierungen ohne notwendigen Umbau des Laminators zu ermöglichen ist es vorteilhaft, die zwei Walzen mit unterschiedlicher Rauhtiefe zu gestalten, so dass das Papier je nach gewünschter Oberfläche mit der verfilmbaren Schicht nach oben oder nach unten durch den Laminator geschickt wird.On the other hand, it is also possible to directly roll the laminator in a suitable manner to coat. Teflon should be used for rolls of continuous filming devices or ceramic materials with a view to good removability his. To have two different surface structures in one laminator To enable necessary conversion of the laminator, it is advantageous to use the two rollers with different surface roughness, so that the paper depending on the desired Surface with the filmable layer up or down through the laminator is sent.

Durch die Einbettung der Tinte in den sich ausbildenden Kunststoffilm sind nachträgliche Veränderungen des Druckbildes, ohne dass dies erkennbar wäre, kaum noch möglich. Die Erfindung eignet sich daher insbesondere auch zur Anwendung im Sicherheitsbereich wie z.B. zur Herstellung von Ausweisen, Pässen, Urkunden oder dergleichen. Dabei kann das Sicherheitspapier zunächst in einem klassischen Druckverfahren wie z.B. einem Offset-Verfahren formularmässig bedruckt werden und anschliessend beim Endverbraucher mit einem einfachen Inkjet-Druck individualisiert und daraufhin in einem Laminator verfilmt werden. Die Offset-Druckfarbe verbleibt dabei im wesentlichen auf der Oberfläche, wird aber beim Verfilmen ebenfalls teilweise eingeschweisst und fixiert. Es ist auch denkbar, für Aussenanwendungen oder ähnliche Anwendungen, bei denen ein äusserst ausgeprägter Schutz des Druckbildes nötig ist, das Substrat mit der Verwendung von konventionellen Folientaschen, in welche das Papier eingebettet und einlaminiert wird, zu kombinieren.By embedding the ink in the plastic film being formed, subsequent Changes to the printed image without this being recognizable are hardly possible. The invention is therefore particularly suitable for use in the security field such as. for the production of ID cards, passports, certificates or the like. The security paper can initially be made using a classic printing process such as. printed in an offset process and then individualized for the end user with a simple inkjet print and then in be filmed in a laminator. The offset printing ink remains essentially on the surface, but is also partially welded in during filming and fixed. It is also conceivable for outdoor applications or similar applications, where an extremely pronounced protection of the printed image is necessary, the substrate with the use of conventional foil bags in which the paper is embedded and laminated.

Claims (18)

  1. A printable substrate with a backing layer (12), wherein a print fixing layer (11) is provided on at least one side of the backing layer, wherein a filmable coating (10) containing film-forming organic pigments and binders is provided on the print fixing layer (11), and wherein the print fixing layer (11) is cationic and is designed to be absorbing a printing ink.
  2. A substrate according to claim 1, characterized in that the filmable coating (10) contains the following components:
    20-90 wt%, especially preferably 70-90 wt% organic pigments,
    1-30 wt%, especially preferably 2-10 wt% binders,
    0-20 wt%, especially preferably 7-15 wt% film-forming aids,
    0-5 wt% UV stabilizers,
    0-5 wt% oxidation stabilizers,
    whereby:
    preferably styrenes, butadienes, acrylates and their copolymers or combinations thereof having glass transition temperatures in the range between 40 °C and 90 °C, but especially between 50 °C and 70 °C, are used as the organic pigments having a particle size preferably in the range of 0.1 to 10 mm, especially preferably in the range of 0.5 to 2 mm,
    styrenes, butadienes, acrylates and their copolymers and combinations thereof having glass transition temperatures below,room temperature, but especially between (-50 °C) and (+20 °C), are used as the film-forming aids, and
    starch, polyvinyl alcohol, polyvinylpyrrolidone or a plastic dispersion containing an acrylate, styrene or PVAC is preferably used as the binder.
  3. A substrate according to one of claims 1 or 2, characterized in that the print fixing layer is designed to be waterproof and binding.
  4. A substrate according to one of claims 1 through 3, characterized in that the print fixing layer (11) contains the following components:
    40-80 wt%, especially preferably 60-70 wt% inorganic pigments,
    5-40 wt%, especially preferably 15-25 wt% cationic polymers, and
    1-20 wt% binders,
    whereby
    silicic acids or aluminum oxide hydrates are preferably used as the inorganic pigment,
    a vinylamine polymer, an N-vinylamine-formamide polymer, a combination or copolymer thereof is preferably used as the cationic polymer, and
    a polyacrylate or a polyvinyl alcohol is preferably used as the binder.
  5. A substrate according to one of claims 1 through 4, characterized in that the filmable coating (10) is applied with a weight of 9-12 g/m2 and the print fixing layer (11) is applied with a weight of 6-10 g/m2, especially preferably 8-9 g/m2.
  6. A substrate according to one of claims 1 through 5, characterized in that a paper or film that is optionally pretreated or is partially synthetic is used as the backing layer (12).
  7. A method of producing a substrate according to one of claims 1 through 6, wherein a paper substrate is precoated or impregnated on at least one side with a first mixture which forms the print fixing layer (11), and wherein a second mixture which contains the filmable organic pigments and binders and forms the filmable coating (12) is applied over the print fixing layer (11).
  8. A method according to claim 7, characterized in that the first mixture and/or the second mixture is applied as an aqueous dispersion.
  9. A method according to one of claims 7 or 8, characterized in that the first mixture is applied with a film press, preferably in a step that is integrated into the papermaking process; the second mixture is applied with a doctor blade application, a raster gravure roller, an airbrush or by a casting method, and the subsequent drying of the filmable coating (10) is carried out at a surface temperature at which there is no filming of the filmable coating (10), especially preferably at a maximum temperature of 45 °C.
  10. A printed substrate, which has a print fixing layer (11) on at least one side, in and/or on which ink is fixed, and which has a filmed or sintered layer on the print fixing layer (11) to cover the print fixing layer (11) in a protective manner and in which filmed or sintered layer optionally another portion of the printing ink is embedded in filmed or sintered organic pigments and binders.
  11. A printed substrate according to claim 10, characterized in that a print fixing layer (11) has the following composition, apart from the printing ink and the paper fibers:
    40-80 wt%, especially preferably 60-70 wt% of inorganic pigments,
    5-40 wt%, especially preferably 15-25 wt% cationic polymers, and
    1-20 wt% binders,
    whereby
    silicic acids or aluminum oxide hydrates are preferably used as the inorganic pigment,
    a vinylamine polymer, an N-vinylamine-formamide polymer, a combination or copolymer thereof is preferably used as the cationic polymer, and
    a polyacrylate or polyvinyl alcohol is preferably used as the binder,
    and the filmed layer has the following composition, apart from the printing ink and paper fibers:
    20-90 wt%, especially preferably 70-90 wt% organic pigments,
    1-30 wt%, especially preferably 2-10 wt% binders,
    0-20 wt%, especially preferably 7-15 wt% film-forming aids,
    0-5 wt% UV stabilizers,
    0-5 wt% oxidation stabilizers,
    whereby:
    preferably styrenes, butadienes, acrylates and their copolymers or combinations thereof having a glass transition temperature in the range between 40 °C and 90 °C, but especially between 50 °C and 70 °C, are used as the organic pigments having a particle size preferably in the range of 0.1 to 10 mm, especially preferably in the range of 0.5 to 2 mm,
    styrenes, butadienes, acrylates and their copolymers and combinations thereof having glass transition temperatures below room temperature, but especially between (-50 °C) and (+20 °C), are used as the film-forming aids, and
    starch, polyvinyl alcohol, polyvinylpyrrolidone or a plastic dispersion containing acrylate, styrene or PVAC is preferably used as the binder.
  12. A method of producing a printed substrate according to one of claims 10 or 11, characterized by the following steps:
    printing a substrate according to one of claims 1 through 6,
    filming the filmable coating (10) by applying heat, namely at a temperature in the range between 70 °C and 140 °C, but especially in the range of 80 °C to 100 °C, optionally with simultaneously application of pressure, preferably between 0.5 and 5 bar.
  13. A method according to claim 12, characterized in that the filming is performed in a continuous process, especially preferably in a laminator through heated rollers or through rollers combined with heating elements.
  14. A method according to claim 13, characterized in that at least the roller facing the filmable coating has a coating of Teflon with a certain predetermined peak-to-valley height, which is determined by the surface characteristic of the substrate surface in the filmed state.
  15. A method according to one of claims 12 through 14, characterized in that the filming is performed immediately following printing, especially in an inkjet printer, while still in the printer or in a filming unit connected to it.
  16. A use of the method according to one of claims 12 through 15 for producing a print with an abrasion-resistant and/or water-resistant surface.
  17. A use of the method according to one of claims 12 through 16 to produce an identification or security document, some other document or the like.
  18. A use of the method according to one of claims 12 through 17 to produce copies of photographs.
EP00915089A 1999-05-05 2000-04-25 Printed and printable substrates Expired - Lifetime EP1180173B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
CH84099 1999-05-05
CH84099 1999-05-05
PCT/CH2000/000232 WO2000068501A1 (en) 1999-05-05 2000-04-25 Printed and printable substrates

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EP1180173A1 EP1180173A1 (en) 2002-02-20
EP1180173B1 true EP1180173B1 (en) 2004-06-16

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AT (1) ATE269440T1 (en)
AU (1) AU3653000A (en)
CA (1) CA2372770A1 (en)
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WO (1) WO2000068501A1 (en)

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Publication number Priority date Publication date Assignee Title
GB2352681A (en) 1999-08-04 2001-02-07 Ilford Imaging Uk Ltd Ink jet printing method
DE10055592A1 (en) 2000-11-09 2002-05-23 Basf Ag Paper coating composition, used for paper is used in printing, contains N-vinylformamide polymer or copolymer with water-soluble ionic monomer, e.g. (meth)acrylic acid or salt, as cobinder
DE10161158A1 (en) * 2001-02-23 2002-09-05 Basf Ag Composition for coating ink-jet recording materials, comprises nonionic or cationic polymer containing N-vinylformamide functioning as a binder, flow agent and fixative
ES2238895B1 (en) * 2003-02-11 2007-02-16 Industrias De Hijos De Antonio Fabregas, S.A. SECURITY ROLE.
MY196893A (en) 2017-03-01 2023-05-09 Avery Dennison Corp Print receptive topcoat
GB2573272A (en) 2018-04-04 2019-11-06 Innovation Tech Coatings Limited An image-receptive coating for high-speed printing applications

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JP2856285B2 (en) * 1989-11-27 1999-02-10 日本製紙株式会社 Printing coated paper and method for producing the same
CA2235385C (en) * 1995-11-13 2004-08-31 Kimberly-Clark Worldwide, Inc. Image-receptive coating
DE19628342C2 (en) * 1996-07-13 1999-03-04 Sihl Gmbh Recording material and its use for inkjet printing
EP0826823A1 (en) * 1996-08-29 1998-03-04 - Sihl - Zürcher Papierfabrik An Der Sihl Special paper
ATE228439T1 (en) * 1997-02-18 2002-12-15 Canon Kk RECORDING MATERIAL, METHOD OF PRODUCING THEREOF AND INKJET PRINTED IMAGES USING SUCH MATERIAL

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DE50006826D1 (en) 2004-07-22
AU3653000A (en) 2000-11-21

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