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EP2758249B1 - Recording material for offset printing - Google Patents

Recording material for offset printing Download PDF

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Publication number
EP2758249B1
EP2758249B1 EP12745873.5A EP12745873A EP2758249B1 EP 2758249 B1 EP2758249 B1 EP 2758249B1 EP 12745873 A EP12745873 A EP 12745873A EP 2758249 B1 EP2758249 B1 EP 2758249B1
Authority
EP
European Patent Office
Prior art keywords
recording layer
layer
coating
recording
coating composition
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.)
Active
Application number
EP12745873.5A
Other languages
German (de)
French (fr)
Other versions
EP2758249A1 (en
Inventor
Gerhard Stork
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsubishi HiTec Paper Europe GmbH
Original Assignee
Mitsubishi HiTec Paper Europe GmbH
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 Mitsubishi HiTec Paper Europe GmbH filed Critical Mitsubishi HiTec Paper Europe GmbH
Publication of EP2758249A1 publication Critical patent/EP2758249A1/en
Application granted granted Critical
Publication of EP2758249B1 publication Critical patent/EP2758249B1/en
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Classifications

    • 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
    • B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
    • B41M2205/04—Direct thermal recording [DTR]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
    • B41M2205/38—Intermediate layers; Layers between substrate and imaging layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
    • B41M2205/40—Cover layers; Layers separated from substrate by imaging layer; Protective layers; Layers applied before imaging
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
    • B41M2205/42—Multiple imaging layers
    • 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
    • B41M5/52—Macromolecular coatings
    • B41M5/5227—Macromolecular coatings characterised by organic non-macromolecular additives, e.g. UV-absorbers, plasticisers, surfactants
    • 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
    • B41M5/52—Macromolecular coatings
    • B41M5/5254—Macromolecular coatings characterised by the use of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers

Definitions

  • the invention relates to a recording material suitable for offset printing, even at higher printing speeds, which in particular does not have process- and raw-material-cost-intensive protective layers on at least one recording layer formed thereunder.
  • the present invention is directed to recording materials having at least one heat and / or pressure sensitive recording layer and / or having an ink jet receiving layer as the respective recording layer.
  • the invention also aims to the same extent to a method for producing such a recording material, suitable for offset printing, even at higher printing speeds
  • the present invention now provides a first task aspect in providing the public with a recording material which is suitable for offset printing, even at relatively high printing speeds, in which the guarantee of chemical resistance of a protective layer to be formed is less important and which nevertheless results from convincing layer sealing in the sense of of the second bullet point of the previous paragraph.
  • the new recording material should ideally and preferably have improved scratch resistance as a second task aspect.
  • Such scratch resistance implies that mutual displacement of the recording material to be proposed here in the stack does not result in visible scratch marks on the surface of the recording material and / or visible color reaction in the heat and / or pressure sensitive recording layer of the recording material to be proposed here.
  • the recording material to be proposed here has to be as particularly favorable in production as possible, in order to be still competitively priced with superior product characteristics in the current market situation.
  • the inventors are interested in the fact that the recording material to be proposed should have a good stampability, which means for the purposes of the present invention that a stamp imprint, as it is preferably used for devaluation in public transport, after 10 seconds exposure time can not be wiped dry or damp without residue.
  • the coating composition for forming a coating layer covering the recording layer and also the coating layer itself mainly comprises binder preferably selected from the list comprising ethylene-vinyl alcohol copolymer (EVOH), carboxyl group-, silanol- or diacetone-modified polyvinyl alcohol as well as unmodified polyvinyl alcohol, wherein the previously enumerated as preferred binders in a first particularly preferred embodiment alone, in a second particularly preferred embodiment in admixture with each other or in a third embodiment in admixture with other binders in the coating layer to be involved.
  • binder preferably selected from the list comprising ethylene-vinyl alcohol copolymer (EVOH), carboxyl group-, silanol- or diacetone-modified polyvinyl alcohol as well as unmodified polyvinyl alcohol, wherein the previously enumerated as preferred binders in a first particularly preferred embodiment alone, in a second particularly preferred embodiment in admixture with each other or in a third embodiment in admi
  • the binders enumerated above as preferred always contain from 50% by weight to 100% by weight, very particularly preferably from 75% by weight to 98% by weight, in each case on the total weight of the coating composition to form a coating layer covering the recording layer over its entire area.
  • the coating composition for forming a coating layer covering the recording layer and also the coating layer itself preferably contains at least one crosslinking aid selected from the list comprising boric acid, polyamine, epoxy resin, dialdehyde, formaldehyde oligomers, epiochlorohydrin resin, adipic dihydrazide, dimethylurea, melamine formaldehyde enumerated crosslinking aids should preferably be incorporated in the coating layer alone or in admixture with one another. Also, a mixture of enumerated crosslinking aids with other crosslinking aids not mentioned here is conceivable. In total, the crosslinking aids preferably constitute from 3% to 20% by weight, based on the total weight of the coating composition, of a coating layer which covers the entire surface of the recording layer.
  • pigments in particular inorganic pigments
  • the coating composition for forming a coating layer covering the recording layer over its entire surface and likewise in the coating layer itself but it represents a clearly favored embodiment if these Coating layer remains pigment-free.
  • possible further ingredients of the coating composition for forming a coating layer covering the recording layer over its entire area and also the coating layer itself are optical brighteners, optionally defoamers and flow improvers in the case of a possible application of the coating layer by means of a curtain coater.
  • a coating layer as proposed in the previous paragraphs [0004] to [0008] is capable of significantly increasing the pick resistance of the proposed recording material on the side on which the coating layer is at least applied, at a low or even justifiable economic cost and thus to improve the offset printability.
  • the scratch resistance of the proposed recording material is significantly improved on the side on which the coating layer is at least applied.
  • the recording material for offset printing proposed here initially has few limiting obstacles, but the invention is directed to a recording material having at least one recording layer on at least one side of the substrate, the recording layer preferably being selected from the list comprising: heat-sensitive recording layer , pressure-sensitive recording layer, inkjet-receiving layer.
  • the proposed method initially provides the formation of the web-like substrate, for example, and in a preferred embodiment on a paper machine, in which at least one upstream Mischbütte a paper pulp of different pulps, optionally groundwood, fillers and water is applied and where to this paper pulp before your Feeding to the paper machine prefers other ingredients such as resin glue for engine sizing and other conventional additives such as pigments, Nuancierfarbstoffe and / or optical brighteners are added.
  • the proposed method further provides for preparing a coating composition for forming a recording layer on at least one side of the substrate, wherein said recording layer is preferably selected from the list comprising: heat-sensitive recording layer, pressure-sensitive recording layer, inkjet-receiving layer.
  • the coating composition to be prepared for this purpose comprises at least one dye precursor and at least one color acceptor, the dye precursor and color acceptor reacting with one another under the action of heat.
  • N- (p-toluenesulphonyl) -N'-3- (p-toluenesulphonyl-oxyphenyl) -urea which is very particularly preferred because of its resistance to organic solvents is also known as Pergafast® 201 from BASF Corporation and can be represented as the following formula ( 1), although in some representations the CH3 groups are also omitted.
  • N- (p-toluenesulphonyl) -N'-3- (p-toluenesulphonyl-oxy-phenyl) urea possibly used as a color acceptor in the coating composition
  • a urea-urethane compound according to the following formula (2):
  • 4,4'-Dihydroxydiphenylsulfon is also often referred to as 4,4'-sulfonyldiphenol and is also known under the trade name 4.4 bisphenol S.
  • 4,4'-Dihydroxydiphenylsulfone has the chemical formula C12H10O4S and can be represented as the following formula (3):
  • the coating composition for forming the thermosensitive recording layer has more than one dye precursor, then preferably each selected from the dye precursors listed in the above paragraph.
  • the coating composition for forming the heat-sensitive recording layer most preferably contains at least one sensitizer selected from the list including stearic acid amide, dimethylsulfone and 2- (2H-benzotriazol-2-yl) -p-cresol for the purpose of enhancing thermal responsiveness , which according to a first preferred embodiment alone, that is, not used in combination with another sensitizer, in particular not with one of the three mentioned sensitizers of the above list. According to a second, almost preferred embodiment, two sensitizers selected from the list comprising stearic acid amide, dimethylsulfone and 2- (2H-benzotriazol-2-yl) -p-cresol may also be used in the coating composition for forming the thermosensitive recording layer involved. Of the three sensitizers mentioned, dimethylsulfone is considered to be very particularly preferred.
  • Suitable binders for incorporation in the coating composition for forming the heat-sensitive recording layer are, for example, water-soluble binders such as starch, hydroxyethylcellulose, methylcellulose, carboxymethylcellulose, gelatin, casein, polyvinyl alcohols, modified polyvinyl alcohols, ethylene-vinyl alcohol copolymers, sodium polyacrylates, acrylamide-acrylate copolymers, acrylamide Acrylate-methacrylate terpolymers and alkali metal salts of styrene-maleic anhydride copolymer or ethylene-maleic anhydride copolymer, which binders can be used alone or in combination with one another; Water-insoluble latex binders such as styrene-butadiene copolymers, acrylonitrile-butadiene copolymers and methyl acrylate-butadiene copolymers are also suitable as binders for incorporation into the heat-sensitive recording layer.
  • water-soluble binders
  • polyvinyl alcohol, ethylene-vinyl alcohol copolymers or polyvinyl alcohol in combination with ethylene-vinyl alcohol copolymers are particularly preferred binders which together in a range from 10 to 20% by weight, based on the total weight of the heat-sensitive recording layer. are incorporated in the heat-sensitive recording layer.
  • the coating composition for forming the thermosensitive recording layer may further contain slip and release agents such as metal salts of higher fatty acids, for example, zinc stearate, calcium stearate and waxes such as paraffin, oxidized paraffin, Polyethylene, polyethylene oxide, stearamides and castor wax.
  • slip and release agents such as metal salts of higher fatty acids, for example, zinc stearate, calcium stearate and waxes such as paraffin, oxidized paraffin, Polyethylene, polyethylene oxide, stearamides and castor wax.
  • pigments preferably inorganic pigments such as, for example, aluminum (hydr) oxide, silica and calcium carbonate, in particular calcium carbonate, which should preferably be incorporated into the recording layer in an amount of from 0 to 45% by weight, very particularly preferably in an amount of from 10 to 40% by weight, based in each case on the total weight of the recording layer, as preferably applies.
  • inorganic pigments such as, for example, aluminum (hydr) oxide, silica and calcium carbonate, in particular calcium carbonate, which should preferably be incorporated into the recording layer in an amount of from 0 to 45% by weight, very particularly preferably in an amount of from 10 to 40% by weight, based in each case on the total weight of the recording layer, as preferably applies.
  • the coating composition for forming a coating layer covering the recording layer over the entire area is most preferably applied by means of a coating unit selected from the list, comprising: roller coater, curtain coater (in the embodiment as slot coater or slip surface coater) and air brush. Subsequently, this applied coating composition is crosslinked depending on the given component entry and / or dried by means of heat.
  • a coating unit selected from the list, comprising: roller coater, curtain coater (in the embodiment as slot coater or slip surface coater) and air brush.
  • the coating units preferably used for the formation of the pigmented intermediate layer are, in particular, leveling coating units selected from the list, comprising: roller coater, doctor blade coater or doctor blade coater. Especially in a method using one of these mentioned coating method, such a pigmented intermediate layer can make a positive contribution to equalize the substrate surface, which reduces the amount of applied mass of a usually expensive coating composition for forming the recording layer.
  • the subsequent drying of the coating composition to form the pigmented intermediate layer is done again and here usually by a method in which heat is supplied, as is done by hot-air floating dryer or contact dryer. Proven is also a combination of the listed dry processes. For the basis weight of the pigmented intermediate layer, a preferred range between 5 and 20 g / m 2 and even better between 7 and 12 g / m 2 has proven.
  • This coating composition for forming the pigmented intermediate layer contains binders and preferably a mixture of organic pigments and inorganic pigments.
  • the inorganic pigments are thereby preferred, individually or in combination with one another, selected from the list, comprising: silicon (di) oxide, bentonite, talc, calcined kaolin, calcium carbonate and aluminum oxide and here in particular boehmite.
  • the above inorganic pigments, individually or in combination with one another, selected from the list above, are quoted as one of the list comprising: calcined kaolin, calcium carbonate and aluminum oxide, and here especially boehmite.
  • the coating composition for forming the pigmented intermediate layer contains at least one binder, preferably based on a synthetic polymer, wherein, for example, styrene-butadiene latex gives particularly good results.
  • a synthetic binder with the admixture of at least one natural polymer, such as particularly preferred starch, represents a particularly suitable embodiment.
  • the surface mass,% by weight (% by weight) and parts by weight (parts by weight) given in the specification and claims refer to the "atro" weight, respectively. absolutely dry parts by weight.
  • the relevant figures are calculated from the "lutro" weight, i. air-dry parts by weight, minus the proportion by weight of water around and inside the pigments in their form of delivery.

Landscapes

  • Heat Sensitive Colour Forming Recording (AREA)

Description

Die Erfindung betrifft ein Aufzeichnungsmaterial, geeignet zur Offset-Bedruckung auch mit höheren Druckgeschwindigkeiten, das insbesondere nicht über Prozess- wie Rohstoffkostenintensive Schutzschichten auf mindestens einer darunter ausgebildeten Aufzeichnungsschicht verfügt. Insbesondere zielt die vorliegende Erfindung auf Aufzeichnungsmaterialien mit mindestens einer wärme- und/oder druckempfindlichen Aufzeichnungsschicht und/oder mit einer Tintenstrahlempfangsschicht als jeweilige Aufzeichnungsschicht. Die Erfindung zielt im gleichen Maße auch auf ein Verfahren zur Herstellung eines solchen Aufzeichnungsmaterials, geeignet zur Offset-Bedruckung auch mit höheren DruckgeschwindigkeitenThe invention relates to a recording material suitable for offset printing, even at higher printing speeds, which in particular does not have process- and raw-material-cost-intensive protective layers on at least one recording layer formed thereunder. In particular, the present invention is directed to recording materials having at least one heat and / or pressure sensitive recording layer and / or having an ink jet receiving layer as the respective recording layer. The invention also aims to the same extent to a method for producing such a recording material, suitable for offset printing, even at higher printing speeds

Aufzeichnungsmaterialien, insbesondere wärmeempfindliche Aufzeichnungsmaterialien, welche geeignet sein sollen zur Offset-Bedruckung auch mit höheren Druckgeschwindigkeiten, weisen in aller Regel eine die wärmeempfindliche Aufzeichnungsschicht vollflächig abdeckende Schutzschicht auf.

  • □ Eine solche Schutzschicht gewährleistet zum einen höhere Beständigkeiten gegenüber organischen Lösungsmitteln, Weichmachern, gegebenenfalls Photoinitiatoren, wie sie bei der Bedruckung mit UV-vernetzenden Druckfarben zum Einsatz kommen, Ölen und Fetten: wärmeempfindliche Aufzeichnungsmaterialien mit derartigen Schutzschichten gelten teilweise als ausgesprochen bewährt und sind Gegenstand unter anderem der EP 1 333 991 , der EP 1 663 662 , der DE 199 58 095 und auch weiterer Patentschriften, bei denen die Schutzschicht nicht zentraler Gegenstand der Erfindungsidee zu sein hat. Die Gewährleistung hervorzuhebender Chemikalienbeständigkeiten von auszubildenden Schutzschichten auf einer gegebenen wärme- und/oder druckempfindlichen Aufzeichnungsschicht ist jedoch nicht Gegenstand der hier vorliegenden Erfindung. Eine derartige Beständigkeit muss bei den hier zum Tragen kommenden Aufzeichnungsmaterialien entweder nicht notwendig oder aus der gegebenen Aufzeichnungsschicht heraus gegeben sein.
  • □ Eine solche Schutzschicht gewährleistet zum anderen auch die notwendige Schichtversiegelung, damit die bei einer möglichen Bedruckung mittels Offset zu nutzenden Aufzeichnungsmaterialien den beim Druckvorgang auftretenden Zug- und Rupfkräfte, die ein Herausreißen einzelner Partikel, insbesondere einzelner Pigmentteilchen bewirken können, standhalten können.
Recording materials, in particular heat-sensitive recording materials, which should be suitable for offset printing, even at higher printing speeds, generally have a protective layer which covers the heat-sensitive recording layer over its entire area.
  • □ Such a protective layer ensures, on the one hand, greater resistance to organic solvents, plasticizers, if appropriate photoinitiators, as used in printing with UV-crosslinking printing inks, oils and fats: heat-sensitive recording materials with such protective layers are sometimes considered to be extremely well-tried and are the subject of other the EP 1 333 991 who EP 1 663 662 , of the DE 199 58 095 and also other patents in which the protective layer does not have to be a central subject of the inventive idea. However, the provision of chemical resistance to be emphasized by protective layers to be formed on a given heat- and / or pressure-sensitive recording layer is not the subject matter of the present invention. Such resistance may not be necessary or absent from the given recording layer in the recording materials used herein.
  • On the other hand, such a protective layer also ensures the necessary layer sealing, so that the recording materials to be used in the event of possible printing by means of offset can withstand the tensile and plucking forces which occur during printing and which can cause individual particles, in particular individual pigment particles, to tear out.

Die vorliegende Erfindung sieht nun einen ersten Aufgabenaspekt darin, der Öffentlichkeit ein zur Offset-Bedruckung auch mit höheren Druckgeschwindigkeiten geeignetes Aufzeichnungsmaterial zur Verfügung zu stellen, bei dem es auf die Gewährleistung von Chemikalienbeständigkeiten einer auszubildenden Schutzschicht weniger ankommt und das dennoch über eine überzeugende Schichtversiegelung im Sinne des zweiten Aufzählungspunktes des vorherigen Absatzes verfügt. Damit einhergehend soll das neue Aufzeichnungsmaterial idealerweise und bevorzugt über eine verbesserte Kratzbeständigkeit als zweiten Aufgabenaspekt verfügen. Eine solche Kratzbeständigkeit beinhaltet, dass ein gegenseitiges Verschieben des hier vorzuschlagenden Aufzeichnungsmaterials im Stapel nicht schon zu sichtbaren Kratzspuren auf der Oberfläche des Aufzeichnungsmaterials und/oder zu einer sichtbaren Farbreaktion in der wärme- und/oder druckempfindlichen Aufzeichnungsschicht des hier vorzuschlagenden Aufzeichnungsmaterials führt. Entscheidenderweise muss aber das hier vorzuschlagende Aufzeichnungsmaterial möglichst besonders günstig in der Herstellung sein, um bei der derzeitigen Marktsituation noch preislich konkurrenzfähig bei überlegenen Produktmerkmalen zu sein. In einem weiteren, vierten Aufgabenaspekt ist die Erfinderschaft daran interessiert, dass das vorzuschlagende Aufzeichnungsmaterial über eine gute Bestempelbarkeit verfügen soll, was im Sinne der vorliegenden Erfindung bedeutet, dass ein Stempelaufdruck, wie er zur Entwertung im öffentlichen Nahverkehr bevorzugt eingesetzt wird, nach 10 Sekunden Einwirkzeit weder trocken noch feucht rückstandlos weggewischt werden kann.The present invention now provides a first task aspect in providing the public with a recording material which is suitable for offset printing, even at relatively high printing speeds, in which the guarantee of chemical resistance of a protective layer to be formed is less important and which nevertheless results from convincing layer sealing in the sense of of the second bullet point of the previous paragraph. Along with this, the new recording material should ideally and preferably have improved scratch resistance as a second task aspect. Such scratch resistance implies that mutual displacement of the recording material to be proposed here in the stack does not result in visible scratch marks on the surface of the recording material and / or visible color reaction in the heat and / or pressure sensitive recording layer of the recording material to be proposed here. Crucially, however, the recording material to be proposed here has to be as particularly favorable in production as possible, in order to be still competitively priced with superior product characteristics in the current market situation. In a further, fourth task aspect, the inventors are interested in the fact that the recording material to be proposed should have a good stampability, which means for the purposes of the present invention that a stamp imprint, as it is preferably used for devaluation in public transport, after 10 seconds exposure time can not be wiped dry or damp without residue.

Zur Lösung dieser anstehenden Aufgaben wird ein Aufzeichnungsmaterial zur Offset-Bedruckung vorgeschlagen,

  • mit einem bahnförmigen Substrat, aufweisend eine Vorderseite und eine der Vorderseite gegenüberliegende Rückseite,
  • mit mindestens einer Aufzeichnungsschicht auf mindestens einer Seite des Substrats,
  • mit mindestens einer die Aufzeichnungsschicht vollflächig abdeckenden Streichschicht,
wobei das neue Aufzeichnungsmaterial dadurch gekennzeichnet wird, dass die mindestens eine die Aufzeichnungsschicht vollflächig abdeckenden Streichschicht eine flächenbezogene Masse zwischen 0,05 und 0,8 g/m2 aufweist. Bevorzugt liegt die flächenbezogene Masse sogar nur innerhalb eines Bereichs von 0,08 und 0,5 g/m2 bzw. noch weiter begrenzt innerhalb eines Bereichs von 0,15 und 0,35 g/m2.To solve these pending problems, a recording material for offset printing is proposed,
  • with a web-shaped substrate, having a front side and a rear side opposite the front side,
  • with at least one recording layer on at least one side of the substrate,
  • with at least one coating layer covering the entire surface of the recording layer,
wherein the novel recording material is characterized in that the at least one coating layer covering the entire recording layer has a weight per unit area of between 0.05 and 0.8 g / m 2 . Preferably, the area-related Mass even within a range of 0.08 and 0.5 g / m 2 or even further limited within a range of 0.15 and 0.35 g / m 2 .

Die Beschichtungszusammensetzung zur Ausbildung einer die Aufzeichnungsschicht vollflächig abdeckenden Streichschicht und genauso die Streichschicht selbst umfasst hauptsächlich Bindemittel, das bevorzugt ausgesucht ist aus der Liste, umfassend Ethylen-Vinyl-Alkohol-Copolymer (EVOH), Carboxylgruppen-, Silanol-, oder Diaceton-modifizierter Polyvinylalkohol sowie nicht modifizierter Polyvinylalkohol, wobei die zuvor als bevorzugt aufgezählten Bindemittel im Rahmen einer ersten besonders bevorzugten Ausführungsvariante allein, im Rahmen einer zweiten besonders bevorzugten Ausführungsvariante in Abmischung untereinander oder im Rahmen einer dritten Ausführungsvariante in Abmischung mit anderen Bindemitteln in der Streichschicht eingebunden sein sollen.The coating composition for forming a coating layer covering the recording layer and also the coating layer itself mainly comprises binder preferably selected from the list comprising ethylene-vinyl alcohol copolymer (EVOH), carboxyl group-, silanol- or diacetone-modified polyvinyl alcohol as well as unmodified polyvinyl alcohol, wherein the previously enumerated as preferred binders in a first particularly preferred embodiment alone, in a second particularly preferred embodiment in admixture with each other or in a third embodiment in admixture with other binders in the coating layer to be involved.

Es gilt als bevorzugt, wenn allemal die zuvor als bevorzugt aufgezählten Bindemittel einen Anteil von 50 Gew.-% bis hin zu 100 Gew.-%, ganz besonders bevorzugt einen Anteil von 75 Gew.-% bis 98 Gew.-%, jeweils bezogen auf das Gesamtgewicht der Beschichtungszusammensetzung zur Ausbildung einer die Aufzeichnungsschicht vollflächig abdeckenden Streichschicht, ausmachen.It is preferred that the binders enumerated above as preferred always contain from 50% by weight to 100% by weight, very particularly preferably from 75% by weight to 98% by weight, in each case on the total weight of the coating composition to form a coating layer covering the recording layer over its entire area.

Optional enthält die Beschichtungszusammensetzung zur Ausbildung einer die Aufzeichnungsschicht vollflächig abdeckenden Streichschicht und genauso die Streichschicht selbst bevorzugt mindestens ein Vernetzungshilfsmittel, ausgesucht aus der Liste, umfassend: Borsäure, Polyamin, Epoxyharz, Dialdehyd, Formaldehydoligomere, Epiochlorhydrinharz, Adipinsäuredihydrazid, Dimethylharnstoff, Melaminformaldehyd, wobei die zuvor aufgezählten Vernetzungshilfsmittel bevorzugt allein oder in Abmischung untereinander in der Streichschicht eingebunden sein sollen. Auch ist eine Abmischung der aufgezählten Vernetzungshilfsmittel mit weiteren hier nicht genannten Vernetzungshilfsmitteln vorstellbar. Insgesamt machen die Vernetzungshilfsmittel bevorzugt einen Anteil von 3 Gew.-% bis 20 Gew.-%, bezogen auf das Gesamtgewicht der Beschichtungszusammensetzung zur Ausbildung einer die Aufzeichnungsschicht vollflächig abdeckenden Streichschicht, aus.Optionally, the coating composition for forming a coating layer covering the recording layer and also the coating layer itself preferably contains at least one crosslinking aid selected from the list comprising boric acid, polyamine, epoxy resin, dialdehyde, formaldehyde oligomers, epiochlorohydrin resin, adipic dihydrazide, dimethylurea, melamine formaldehyde enumerated crosslinking aids should preferably be incorporated in the coating layer alone or in admixture with one another. Also, a mixture of enumerated crosslinking aids with other crosslinking aids not mentioned here is conceivable. In total, the crosslinking aids preferably constitute from 3% to 20% by weight, based on the total weight of the coating composition, of a coating layer which covers the entire surface of the recording layer.

Grundsätzlich ist es möglich, in die Beschichtungszusammensetzung zur Ausbildung einer die Aufzeichnungsschicht vollflächig abdeckenden Streichschicht und genauso in die Streichschicht selbst Pigmente, insbesondere anorganische Pigmente einzubinden, doch stellt es eine eindeutig favorisierte Ausführungsform dar, wenn diese Streichschicht pigmentfrei bleibt. Hingegen sind mögliche weitere Inhaltsstoffe der Beschichtungszusammensetzung zur Ausbildung einer die Aufzeichnungsschicht vollflächig abdeckenden Streichschicht und genauso der Streichschicht selbst: optische Aufheller, gegebenenfalls Entschäumer und Fließverbesserer bei einer möglichen Aufbringung der Streichschicht mittels Vorhangbeschichter.In principle, it is possible to incorporate pigments, in particular inorganic pigments, in the coating composition for forming a coating layer covering the recording layer over its entire surface and likewise in the coating layer itself, but it represents a clearly favored embodiment if these Coating layer remains pigment-free. On the other hand, possible further ingredients of the coating composition for forming a coating layer covering the recording layer over its entire area and also the coating layer itself are optical brighteners, optionally defoamers and flow improvers in the case of a possible application of the coating layer by means of a curtain coater.

Eine wie in den vorherigen Absätzen [0004] bis [0008] vorgeschlagene Streichschicht ist bei geringem bzw. noch vertretbarem wirtschaftlichem Aufwand in der Lage, die Rupffestigkeit des vorgeschlagenen Aufzeichnungsmaterials auf der Seite, auf der die Streichschicht mindestens aufgetragen ist, in entscheidender Weise zu erhöhen und somit die Offset-Bedruckbarkeit zu verbessern. Gleichzeitig wird die Kratzbeständigkeit des vorgeschlagenen Aufzeichnungsmaterials auf der Seite, auf der die Streichschicht mindestens aufgetragen ist, signifikant verbessert.A coating layer as proposed in the previous paragraphs [0004] to [0008] is capable of significantly increasing the pick resistance of the proposed recording material on the side on which the coating layer is at least applied, at a low or even justifiable economic cost and thus to improve the offset printability. At the same time, the scratch resistance of the proposed recording material is significantly improved on the side on which the coating layer is at least applied.

Bei dem hier vorgeschlagenen Aufzeichnungsmaterial zur Offset-Bedruckung gibt es zunächst wenig einschränkende Hemmnisse, die Erfindung ist jedoch ausgerichtet hinsichtlich eines Aufzeichnungsmaterials mit mindestens einer Aufzeichnungsschicht auf mindestens einer Seite des Substrats, wobei die Aufzeichnungsschicht bevorzugt ausgesucht sein soll aus der Liste, umfassend: wärmeempfindliche Aufzeichnungsschicht, druckempfindliche Aufzeichnungsschicht, Tintenstrahlempfangsschicht.The recording material for offset printing proposed here initially has few limiting obstacles, but the invention is directed to a recording material having at least one recording layer on at least one side of the substrate, the recording layer preferably being selected from the list comprising: heat-sensitive recording layer , pressure-sensitive recording layer, inkjet-receiving layer.

Als bahnförmiges Substrat gilt Papier als bevorzugt, dass insbesondere

  • ▪ als nicht oberflächenbehandeltes, idealerweise in der Masse geleimtes Papier,
  • ▪ als ungeleimtes, aber zumindest einseitig präpariertes Papier,
  • ▪ als zumindest einseitig mit einer Polyolefinbeschichtung versehenes Papier zum Einsatz kommt.
As a web-shaped substrate paper is preferred as that particular
  • ▪ as non-surface treated, ideally sized paper,
  • ▪ as unsized but at least unilaterally prepared paper,
  • ▪ is used as at least one side provided with a polyolefin coating paper.

Die Erfindung betrifft ferner im gleichen Maße auch ein Verfahren zur Herstellung eines Aufzeichnungsmaterials zur Offset-Bedruckung in all den hier bereits vorgeschlagenen Ausführungsformen und -varianten. Ein derartiges Verfahren umfasst dabei mindestens die folgenden Verfahrensschritte:

  • ▪ Ausbilden eines bahnförmigen Substrats, aufweisend eine Vorderseite und eine der Vorderseite gegenüberliegende Rückseite,
  • ▪ Aufbringen einer vorbereiteten Beschichtungszusammensetzung zur Ausbildung einer Aufzeichnungsschicht auf mindestens einer Seite des Substrats,
  • ▪ Trocknen der Beschichtungszusammensetzung zur Ausbildung einer Aufzeichnungsschicht,
  • ▪ Aufbringen einer vorbereiteten Beschichtungszusammensetzung zur Ausbildung einer die Aufzeichnungsschicht vollflächig abdeckenden Streichschicht,
  • ▪ Trocknen und/oder Vernetzen der die Aufzeichnungsschicht vollflächig abdeckenden Streichschicht,
wobei das neue Verfahren zur Herstellung eines Aufzeichnungsmaterials zur Offset-Bedruckung dadurch gekennzeichnet wird, dass die mindestens eine die Aufzeichnungsschicht vollflächig abdeckenden Streichschicht eine flächenbezogene Masse zwischen 0,05 und 0,8 g/m2, ganz besonders bevorzugt zwischen 0,15 und 0,35 g/m2 aufweist.The invention also relates, to the same extent, to a method for producing a recording material for offset printing in all the embodiments and variants already proposed here. Such a method comprises at least the following method steps:
  • Forming a web-shaped substrate comprising a front side and a rear side opposite the front side,
  • Applying a prepared coating composition to form a recording layer on at least one side of the substrate,
  • Drying the coating composition to form a recording layer,
  • Application of a prepared coating composition to form a coating layer covering the recording layer over its entire area,
  • Drying and / or crosslinking of the coating layer covering the entire surface of the recording layer,
wherein the new method for producing a recording material for offset printing is characterized in that the at least one coating layer covering the entire recording layer has a basis weight of between 0.05 and 0.8 g / m 2 , very particularly preferably between 0.15 and 0 , 35 g / m 2 .

Das vorgeschlagene Verfahren sieht zunächst das Ausbilden des bahnförmigen Substrates beispielsweise und im Rahmen einer bevorzugten Ausführungsform auf einer Papiermaschine vor, bei der in mindestens einer vorgeschalteten Mischbütte eine Papierpulpe aus verschiedenen Zellstoffen, gegebenenfalls Holzschliff, Füllstoffen und Wasser angesetzt wird und wo zu dieser Papierpulpe vor Ihrer Zuführung zur Papiermaschine bevorzugt weitere Bestandteile wie beispielsweise Harzleim zur Masseleimung sowie weitere übliche Zuschlagstoffe, wie Pigmente, Nuancierfarbstoffe und/oder optische Aufheller zugegeben werden.The proposed method initially provides the formation of the web-like substrate, for example, and in a preferred embodiment on a paper machine, in which at least one upstream Mischbütte a paper pulp of different pulps, optionally groundwood, fillers and water is applied and where to this paper pulp before your Feeding to the paper machine prefers other ingredients such as resin glue for engine sizing and other conventional additives such as pigments, Nuancierfarbstoffe and / or optical brighteners are added.

Das vorgeschlagene Verfahren sieht ferner das Vorbereiten einer Beschichtungszusammensetzung zur Ausbildung einer Aufzeichnungsschicht auf mindestens einer Seite des Substrats vor, bei dem diese Aufzeichnungsschicht bevorzugt ausgesucht sein soll aus der Liste, umfassend: wärmeempfindliche Aufzeichnungsschicht, druckempfindliche Aufzeichnungsschicht, Tintenstrahlempfangsschicht.The proposed method further provides for preparing a coating composition for forming a recording layer on at least one side of the substrate, wherein said recording layer is preferably selected from the list comprising: heat-sensitive recording layer, pressure-sensitive recording layer, inkjet-receiving layer.

Sofern im Rahmen einer möglichen Ausführungsvariante eine wärmeempfindliche Aufzeichnungsschicht auf mindestens einer Seite des Substrats aufgetragen werden soll, umfasst die zu diesem Zweck vorzubereitende Beschichtungszusammensetzung mindestens einem Farbstoffvorläufer und mindestens einem Farbakzeptor, wobei Farbstoffvorläufer und Farbakzeptor unter Einwirkung von Wärme farbbildend miteinander reagieren.If a heat-sensitive recording layer is to be applied to at least one side of the substrate in the context of a possible embodiment variant, the coating composition to be prepared for this purpose comprises at least one dye precursor and at least one color acceptor, the dye precursor and color acceptor reacting with one another under the action of heat.

Allgemein ist als möglicher Farbakzeptor insbesondere mindestens eine der Substanzen bevorzugt, ausgesucht aus der Liste, umfassend:

  • ▪ 2,2 bis (4-hydroxyphenyl)-propan - auch bekannt als Bisphenol A,
  • ▪ 4-[(4-(1-methylethoxy)phenyl)sulfonyl]phenol - auch bekannt als D8,
  • ▪ N-(p-toluensulphonyl)-N'-(3-p-toluensulphonyl-oxy-phenyl)-harnstoff,
  • ▪ 2,4'-dihydroxy-diphenylsulfon,
  • ▪ 4,4'-Dihydroxydiphenylsulfon,
  • ▪ N-(2-hydroxyphenyl)-2-[(4-hydroxyphenyl)thio]acetamid,
ohne auf die oberen Farbakzeptoren in irgendeiner Art und Weise beschränkt zu sein.In general, as a possible color acceptor, in particular at least one of the substances selected from the list is preferred, comprising:
  • ▪ 2,2 bis (4-hydroxyphenyl) -propane - also known as bisphenol A,
  • ▪ 4 - [(4- (1-methylethoxy) phenyl) sulfonyl] phenol - also known as D8,
  • ▪ N- (p-toluenesulphonyl) -N '- (3-p-toluenesulphonyl-oxy-phenyl) -urea,
  • ▪ 2,4'-dihydroxydiphenyl sulfone,
  • ▪ 4,4'-dihydroxydiphenyl sulfone,
  • ▪ N- (2-hydroxyphenyl) -2 - [(4-hydroxyphenyl) thio] acetamide,
without being limited to the upper color acceptors in any way.

Das wegen seiner Beständigkeiten gegenüber organischen Lösungsmitteln ganz besonders bevorzugte N-(p-toluensulphonyl)-N'-3-(p-toluensulphonyl-Oxyphenyl)-harnstoff ist auch bekannt als Pergafast® 201 der Firma BASF Corporation und ist darstellbar als folgende Formel (1), wobei in manchen Darstellungen die CH3-Gruppen auch weggelassen werden.

Figure imgb0001
The N- (p-toluenesulphonyl) -N'-3- (p-toluenesulphonyl-oxyphenyl) -urea which is very particularly preferred because of its resistance to organic solvents is also known as Pergafast® 201 from BASF Corporation and can be represented as the following formula ( 1), although in some representations the CH3 groups are also omitted.
Figure imgb0001

Insbesondere wegen seines hohen Preises gilt es als ganz besonders bevorzugt im Rahmen der vorliegenden Erfindung, den möglicherweise als Farbakzeptor eingesetzten N-(p-toluensulphonyl)-N'-3-(p-toluensulphonyl-Oxy-phenyl)-harnstoff in der Beschichtungszusammensetzung zur Ausbildung der wärmeempfindlichen Aufzeichnungsschicht zu kombinieren mit einer Harnstoff-Urethan-Verbindung gemäß der folgenden Formel (2):

Figure imgb0002
In particular, because of its high price, it is considered very particularly within the scope of the present invention, the N- (p-toluenesulphonyl) -N'-3- (p-toluenesulphonyl-oxy-phenyl) urea possibly used as a color acceptor in the coating composition Forming the heat-sensitive recording layer to be combined with a urea-urethane compound according to the following formula (2):
Figure imgb0002

Das ebenfalls ganz besonders bevorzugte 4,4'-Dihydroxydiphenylsulfon wird auch häufig als 4,4'-Sulfonyldiphenol bezeichnet und ist genauso unter der Handelsbezeichnung 4,4 Bisphenol S bekannt. 4,4'-Dihydroxydiphenylsulfon weist die chemische Summenformel C12H10O4S auf und ist darstellbar als folgende Formel (3):

Figure imgb0003
The also most preferred 4,4'-Dihydroxydiphenylsulfon is also often referred to as 4,4'-sulfonyldiphenol and is also known under the trade name 4.4 bisphenol S. 4,4'-Dihydroxydiphenylsulfone has the chemical formula C12H10O4S and can be represented as the following formula (3):
Figure imgb0003

Die Beschichtungszusammensetzung zur Ausbildung der wärmeempfindlichen Aufzeichnungsschicht umfasst als Farbstoffvorläufer bevorzugt solche, die ausgesucht sind aus der Liste, umfassend:

  • 3-diethylamino-6-methyl-7-Anilinofluoran, 3-dibutylamino-6-methyl-7-Anilinofluoran, 3-(N-methyl-N-propyl)amino-6-methyl-7-Anilinofluoran, 3-(N-ethyl-N-isoamyl)amino-6-methyl-7-Anilinofluoran, 3-(N-methyl-N-cyclohexyl)amino-6-methyl-7-Anilinofluoran, 3-(N-ethyl-N-tolyl)amino-6-methyl-7-Anilinofluoran und 3-(N-ethyl-N-tetrahydrofuryl)amino-6-methyl-7-Anilinofluoran. Ganz besonders bevorzugt ist dabei 3-dibutylamino-6-methyl-7-Anilinofluoran - auch bekannt als ODB-2.
The coating composition for forming the thermosensitive recording layer preferably comprises as a dye precursor those selected from the list, comprising:
  • 3-diethylamino-6-methyl-7-anilinofluoran, 3-dibutylamino-6-methyl-7-anilinofluoran, 3- (N-methyl-N-propyl) amino-6-methyl-7-anilinofluoran, 3- (N- ethyl-N-isoamyl) amino-6-methyl-7-anilinofluoran, 3- (N-methyl-N-cyclohexyl) amino-6-methyl-7-anilinofluoran, 3- (N-ethyl-N-tolyl) amino 6-methyl-7-anilinofluoran and 3- (N-ethyl-N-tetrahydrofuryl) amino-6-methyl-7-anilinofluoran. Very particular preference is given to 3-dibutylamino-6-methyl-7-anilinofluoran - also known as ODB-2.

Es ist möglich, dass die Beschichtungszusammensetzung zur Ausbildung der wärmeempfindlichen Aufzeichnungsschicht mehr als einen Farbstoffvorläufer aufweist, dann bevorzugt jeweils ausgesucht aus den im obigen Absatz aufgelisteten Farbstoffvorläufern.It is possible that the coating composition for forming the thermosensitive recording layer has more than one dye precursor, then preferably each selected from the dye precursors listed in the above paragraph.

Die Beschichtungszusammensetzung zur Ausbildung der wärmeempfindlichen Aufzeichnungsschicht enthält ganz besonders bevorzugt und mit dem Ziel einer Erhöhung der thermischen Ansprechempfindlichkeit mindestens einen Sensibilisator, insbesondere ausgesucht aus der Liste, umfassend Stearinsäureamid, Dimethylsulfon und 2-(2H-benzotriazol-2-yl)-p-cresol, die entsprechend einer ersten bevorzugten Ausführungsvariante allein, das bedeutet, nicht in Kombination mit einem anderen Sensibilisator, insbesondere nicht mit einem solchen aus den drei genannten Sensibilisatoren der vorstehenden Liste, eingesetzt sind. Entsprechend einer zweiten, gleichsam bevorzugten Ausführungsvariante können auch zwei Sensibilisatoren, ausgesucht aus der Liste umfassend Stearinsäureamid, Dimethylsulfon und 2-(2H-benzotriazol-2-yl)-p-cresol, in der Beschichtungszusammensetzung zur Ausbildung der wärmeempfindlichen Aufzeichnungsschicht eingebunden. Von den drei genannten Sensibilisatoren gilt Dimethylsulfon als ganz besonders bevorzugt.The coating composition for forming the heat-sensitive recording layer most preferably contains at least one sensitizer selected from the list including stearic acid amide, dimethylsulfone and 2- (2H-benzotriazol-2-yl) -p-cresol for the purpose of enhancing thermal responsiveness , which according to a first preferred embodiment alone, that is, not used in combination with another sensitizer, in particular not with one of the three mentioned sensitizers of the above list. According to a second, almost preferred embodiment, two sensitizers selected from the list comprising stearic acid amide, dimethylsulfone and 2- (2H-benzotriazol-2-yl) -p-cresol may also be used in the coating composition for forming the thermosensitive recording layer involved. Of the three sensitizers mentioned, dimethylsulfone is considered to be very particularly preferred.

2-(2H-benzotriazol-2-yl)-p-cresol ist dabei erhältlich als Tinuvin® der Firma BASF Corporation und lässt sich darstellen gemäß der folgenden Formel (4):

Figure imgb0004
2- (2H-benzotriazol-2-yl) -p-cresol is available as Tinuvin® from BASF Corporation and can be prepared according to the following formula (4):
Figure imgb0004

Geeignete Bindemittel zur Einbindung in die Beschichtungszusammensetzung zur Ausbildung der wärmeempfindlichen Aufzeichnungsschicht sind beispielsweise wasserlösliche Bindemittel wie Stärke, Hydroxyethylzellulose, Methylzellulose, Carboxymethylzellulose, Gelatine, Kasein, Polyvinylalkohole, modifizierte Polyvinylalkohole, Ethylen-Vinylalkohol-Coplymere, Natriumpolyacrylate, Acrylamid-Acrylat-Copolymere, Acrylamid-Acrylat-Methacrylat-Terpolymere sowie Alkalisalze von Styrol-Maleinsäureanhydrid-Copolymer oder Ethylen-Maleinsäureanhydrid-Copolymer, wobei die Bindemittel allein oder in Kombination untereinander eingesetzt werden können; auch wasserunlösliche Latexbinder wie Styrol-Butadiene-Copolymere, Acrylnitril-Butadien-Copolymere und Methyl-Acrylat-Butadien-Copolymere bieten sich als Bindemittel zur Einbindung in die wärmeempfindliche Aufzeichnungsschicht an. Im Sinne der vorliegenden Erfindung gelten Polyvinylalkohol, Ethylen-Vinylalkohol-Coplymere oder Polyvinylalkohol in Verbindung mit Ethylen-Vinylalkohol-Coplymeren als besonders bevorzugte Bindemittel, die zusammen, bezogen auf das Gesamtgewicht der wärmeempfindlichen Aufzeichnungsschicht, in einem Bereich von 10 bis 20 Gew.-% in die wärmeempfindliche Aufzeichnungsschicht eingebunden sind.Suitable binders for incorporation in the coating composition for forming the heat-sensitive recording layer are, for example, water-soluble binders such as starch, hydroxyethylcellulose, methylcellulose, carboxymethylcellulose, gelatin, casein, polyvinyl alcohols, modified polyvinyl alcohols, ethylene-vinyl alcohol copolymers, sodium polyacrylates, acrylamide-acrylate copolymers, acrylamide Acrylate-methacrylate terpolymers and alkali metal salts of styrene-maleic anhydride copolymer or ethylene-maleic anhydride copolymer, which binders can be used alone or in combination with one another; Water-insoluble latex binders such as styrene-butadiene copolymers, acrylonitrile-butadiene copolymers and methyl acrylate-butadiene copolymers are also suitable as binders for incorporation into the heat-sensitive recording layer. For the purposes of the present invention, polyvinyl alcohol, ethylene-vinyl alcohol copolymers or polyvinyl alcohol in combination with ethylene-vinyl alcohol copolymers are particularly preferred binders which together in a range from 10 to 20% by weight, based on the total weight of the heat-sensitive recording layer. are incorporated in the heat-sensitive recording layer.

Zur Verbesserung der Gleiteigenschaften an einem Thermokopf und zur Vermeidung einer übermäßigen Abnutzung des Thermokopfes kann die Beschichtungsmasse zur Ausbildung der wärmeempfindlichen Aufzeichnungsschicht weiterhin Gleit- und Trennmittel enthalten wie Metallsalze höherer Fettsäuren, zum Beispiel Zinkstearat, Kalziumstearat sowie Wachse, wie zum Beispiel Paraffin, oxidiertes Paraffin, Polyethylen, Polyethylenoxid, Stearamide und Kastorwachs. Weitere Bestandteile der Aufzeichnungsschicht sind gegebenenfalls beispielsweise Pigmente, bevorzugt anorganische Pigmente wie beispielsweise Aluminium(hydr)oxid, Kieselsäure und Kalziumkarbonat, wobei hier insbesondere Kalziumkarbonat, das bevorzugt in einer Menge von 0 bis 45 Gew.-%, ganz besonders bevorzugt in einer Menge von 10 bis 40 Gew.-%, jeweils bezogen auf das Gesamtgewicht der Aufzeichnungsschicht, in die Aufzeichnungsschicht eingebunden sein soll, als bevorzugt gilt.In order to improve the sliding properties on a thermal head and to prevent excessive wear of the thermal head, the coating composition for forming the thermosensitive recording layer may further contain slip and release agents such as metal salts of higher fatty acids, for example, zinc stearate, calcium stearate and waxes such as paraffin, oxidized paraffin, Polyethylene, polyethylene oxide, stearamides and castor wax. Further constituents of the recording layer are optionally, for example, pigments, preferably inorganic pigments such as, for example, aluminum (hydr) oxide, silica and calcium carbonate, in particular calcium carbonate, which should preferably be incorporated into the recording layer in an amount of from 0 to 45% by weight, very particularly preferably in an amount of from 10 to 40% by weight, based in each case on the total weight of the recording layer, as preferably applies.

Bevorzugt wird die Beschichtungszusammensetzung zur Ausbildung der Aufzeichnungsschicht, insbesondere ausgesucht aus der Liste, umfassend:

  • wärmeempfindliche Aufzeichnungsschicht,
  • druckempfindliche Aufzeichnungsschicht,
  • Tintenstrahlempfangsschicht
mittels eines Streichaggregats aufgebracht wird, ausgesucht aus der Liste, umfassend: Rollrakelstreichwerk, Messerstreichwerk, Vorhangbeschichter (in der Ausführung als Schlitzgießer oder Gleitflächengießer) und Luftbürste. Dabei ist die zur Ausbildung der Aufzeichnungsschicht genutzte Beschichtungszusammensetzung bevorzugt wässerig. Die anschließende Trocknung der Beschichtungsmasse geschieht üblicherweise durch ein Verfahren, bei dem Wärme zugeführt wird, wie es durch Heißluft-Schwebetrockner oder auch Kontakttrockner geschieht. Bewährt ist auch eine Kombination aus den aufgeführten Trockenverfahren. Die flächenbezogene Masse der Aufzeichnungsschicht liegt bei dem hier vorgeschlagenen Aufzeichnungsmaterial bevorzugt zwischen 2 und 6 g/m2.Preferably, the coating composition for forming the recording layer, in particular selected from the list, comprises:
  • heat-sensitive recording layer,
  • pressure-sensitive recording layer,
  • Ink-receiving layer
is applied by means of a coating unit selected from the list, comprising: roller blade coater, knife coater, curtain coater (in the embodiment as slit caster or sliding surface caster) and air brush. In this case, the coating composition used to form the recording layer is preferably aqueous. The subsequent drying of the coating composition is usually done by a method in which heat is supplied, as is done by hot-air floating dryer or contact dryer. Proven is also a combination of the listed dry processes. The basis weight of the recording layer is preferably between 2 and 6 g / m 2 in the case of the recording material proposed here.

Die Beschichtungszusammensetzung zur Ausbildung einer die Aufzeichnungsschicht vollflächig abdeckenden Streichschicht wird ganz besonders bevorzugt mittels eines Streichaggregats aufgebracht, ausgesucht aus der Liste, umfassend: Walzenstreichwerk, Vorhangbeschichter (in der Ausführung als Schlitzgießer oder Gleitflächengießer) und Luftbürste. Anschließend wird diese aufgetragene Beschichtungszusammensetzung je nach gegebenem Komponenteneintrag vernetzt und/oder mittels Wärmezufuhr getrocknet.The coating composition for forming a coating layer covering the recording layer over the entire area is most preferably applied by means of a coating unit selected from the list, comprising: roller coater, curtain coater (in the embodiment as slot coater or slip surface coater) and air brush. Subsequently, this applied coating composition is crosslinked depending on the given component entry and / or dried by means of heat.

Gerade mit Blick auf den zugrunde liegenden Aufgabenaspekt einer wirtschaftlich möglichst günstigen Herstellung sieht das vorgeschlagene Verfahren bevorzugt vor, dass

  1. (a.) das Aufbringen einer vorbereiteten Beschichtungszusammensetzung zur Ausbildung einer Aufzeichnungsschicht auf mindestens einer Seite des Substrats und
  2. (b.) das Aufbringen einer vorbereiteten Beschichtungszusammensetzung zur Ausbildung einer die Aufzeichnungsschicht vollflächig abdeckenden Streichschicht
im Rahmen genau eines Maschinendurchlaufs geschieht. Dieses kann im Rahmen einer ersten bevorzugten Ausführungsvariante derart geschehen, dass auf einer Papier- oder Streichmaschine zunächst die Beschichtungszusammensetzung zur Ausbildung der Aufzeichnungsschicht aufgetragen und getrocknet wird und anschließend die Beschichtungszusammensetzung zur Ausbildung jener die Aufzeichnungsschicht vollflächig abdeckenden Streichschicht aufgetragen und getrocknet wird. Im Rahmen einer zweiten bevorzugten Ausführungsvariante wird zunächst die Beschichtungszusammensetzung zur Ausbildung der Aufzeichnungsschicht und direkt anschließend (nassin-nass) die Beschichtungszusammensetzung zur Ausbildung jener die Aufzeichnungsschicht vollflächig abdeckenden Streichschicht aufgetragen. Die gemeinsame Trocknung der beiden aufgetragenen Schichten schließt sich daran an. In einer Abart der zweiten bevorzugten Ausführungsvariante werden die Beschichtungszusammensetzung zur Ausbildung der Aufzeichnungsschicht und die Beschichtungszusammensetzung zur Ausbildung jener die Aufzeichnungsschicht vollflächig abdeckenden Streichschicht gemeinsam aufgebracht, wozu ein Vorhangbeschichter in Ausführung eines Gleitflächengießers zum Einsatz kommt.Especially with regard to the underlying task aspect of economically most economical production, the proposed method preferably provides that
  1. (a.) applying a prepared coating composition to form a recording layer on at least one side of the substrate and
  2. (b.) applying a prepared coating composition to form a coating layer covering the recording layer over the entire area
in the context of exactly one machine run happens. This can be done in the context of a first preferred embodiment such that on a paper or coater first the coating composition for forming the recording layer is applied and dried and then the coating composition for forming those of the recording layer over the entire area covering coating layer is applied and dried. In the context of a second preferred embodiment variant, the coating composition for forming the recording layer and immediately thereafter (wet-wet) the coating composition is applied to form the coating layer which covers the recording layer over its entire area. The joint drying of the two applied layers follows it. In a variant of the second preferred embodiment, the coating composition for forming the recording layer and the coating composition for forming the coating layer covering the recording layer over the entire area are co-applied, using a curtain coater in the form of a slip surface caster.

Es stellt eine weiterhin bevorzugte Ausführungsform des vorgeschlagenen Verfahrens dar, wenn das Verfahren die mindestens zwei zusätzlichen Verfahrensschritte umfasst:

  • ▪ Aufbringen einer vorbereiteten Beschichtungszusammensetzung zur Ausbildung einer zwischen Substrat und Aufzeichnungsschicht angeordneten pigmentierten Zwischenschicht,
  • ▪ Trocknen der pigmentierten Zwischenschicht,
wobei diese mindestens zwei zusätzlichen Verfahrensschritte vor den Verfahrensschritt "Aufbringen einer vorbereiteten Beschichtungszusammensetzung zur Ausbildung einer Aufzeichnungsschicht auf mindestens einer Seite des Substrats" einzuschieben sind.It represents a further preferred embodiment of the proposed method, if the method comprises the at least two additional method steps:
  • Applying a prepared coating composition to form a pigmented intermediate layer disposed between the substrate and the recording layer,
  • ▪ drying the pigmented intermediate layer,
these being at least two additional process steps prior to the step of "applying a prepared coating composition to form a recording layer on at least one side of the substrate".

Die zur Ausbildung der pigmentierten Zwischenschicht bevorzugt eingesetzten Streichaggregate sind insbesondere egalisierende Streichaggregate, ausgesucht aus der Liste, umfassend: Walzenstreichwerk, Streichmesser- oder (Roll-)Rakelstreichwerk. Gerade bei einem Verfahren unter Verwendung eines dieser genannten Streichverfahren kann eine solche pigmentierte Zwischenschicht einen positiven Beitrag zur Egalisierung der Substratoberfläche leisten, womit sich die Menge an aufzubringender Masse einer meist teuren Beschichtungszusammensetzung zur Ausbildung der Aufzeichnungsschicht reduziert. Die anschließende Trocknung der Beschichtungsmasse zur Ausbildung der pigmentierten Zwischenschicht geschieht erneut und hier üblicherweise durch ein Verfahren, bei dem Wärme zugeführt wird, wie es durch Heißluft-Schwebetrockner oder auch Kontakttrockner geschieht. Bewährt ist auch eine Kombination aus den aufgeführten Trockenverfahren. Für die flächenbezogene Masse der pigmentierten Zwischenschicht hat sich ein bevorzugter Bereich zwischen 5 und 20 g/m2 und noch besser zwischen 7 und 12 g/m2 bewährt.The coating units preferably used for the formation of the pigmented intermediate layer are, in particular, leveling coating units selected from the list, comprising: roller coater, doctor blade coater or doctor blade coater. Especially in a method using one of these mentioned coating method, such a pigmented intermediate layer can make a positive contribution to equalize the substrate surface, which reduces the amount of applied mass of a usually expensive coating composition for forming the recording layer. The subsequent drying of the coating composition to form the pigmented intermediate layer is done again and here usually by a method in which heat is supplied, as is done by hot-air floating dryer or contact dryer. Proven is also a combination of the listed dry processes. For the basis weight of the pigmented intermediate layer, a preferred range between 5 and 20 g / m 2 and even better between 7 and 12 g / m 2 has proven.

Diese Beschichtungsmasse zur Ausbildung der pigmentierten Zwischenschicht enthält Bindemittel sowie bevorzugt eine Mischung aus organischen Pigmenten und anorganischen Pigmenten. Die anorganischen Pigmente sind dabei bevorzugt, einzeln oder in Kombination untereinander, ausgesucht aus der Liste, umfassend: Silizium(di)oxid, Bentonit, Talkum, kalziniertes Kaolin, Kalziumkarbonat sowie Aluminiumoxid und hier besonders Böhmit. Aus dieser vorstehenden Liste gelten gleichsam als ganz besonders bevorzugt die folgenden anorganischen Pigmente, einzeln oder in Kombination untereinander, ausgesucht aus der Liste, umfassend: kalziniertes Kaolin, Kalziumkarbonat sowie Aluminiumoxid und hier besonders Böhmit.This coating composition for forming the pigmented intermediate layer contains binders and preferably a mixture of organic pigments and inorganic pigments. The inorganic pigments are thereby preferred, individually or in combination with one another, selected from the list, comprising: silicon (di) oxide, bentonite, talc, calcined kaolin, calcium carbonate and aluminum oxide and here in particular boehmite. The above inorganic pigments, individually or in combination with one another, selected from the list above, are quoted as one of the list comprising: calcined kaolin, calcium carbonate and aluminum oxide, and here especially boehmite.

Neben den anorganischen und gegebenenfalls auch organischen Pigmenten enthält die Beschichtungsmasse zur Ausbildung der pigmentierten Zwischenschicht mindestens ein Bindemittel bevorzugt auf Basis eines synthetischen Polymers, wobei beispielsweise Styrol-Butadien-Latex besonders gute Ergebnisse liefert. Die Verwendung eines synthetischen Bindemittels unter Beimischung mindestens eines natürlichen Polymers, wie besonders bevorzugt Stärke, stellt eine besonders geeignete Ausführungsform dar.In addition to the inorganic and optionally also organic pigments, the coating composition for forming the pigmented intermediate layer contains at least one binder, preferably based on a synthetic polymer, wherein, for example, styrene-butadiene latex gives particularly good results. The use of a synthetic binder with the admixture of at least one natural polymer, such as particularly preferred starch, represents a particularly suitable embodiment.

Die in Beschreibung und Patentansprüchen gemachten Angaben zur flächenbezogenen Masse, zu Gew.-% (Gewichts-%) und zu Gew.-Teilen (Gewichts-Teilen) beziehen sich jeweils auf das "atro"-Gewicht, d.h. absolut trockene Gewichtsteile. In den Ausführungen zu den organischen Pigmenten der pigmenthaltigen Zwischenschicht sind die diesbezüglichen Zahlenangaben berechnet aus dem "lutro"-Gewicht, d.h. lufttrockene Gewichtsteile, abzüglich des Gewichtsanteils von Wasser um und im Inneren der Pigmente in ihrer Lieferform.The surface mass,% by weight (% by weight) and parts by weight (parts by weight) given in the specification and claims refer to the "atro" weight, respectively. absolutely dry parts by weight. In the comments on the organic pigments of the pigment-containing interlayer, the relevant figures are calculated from the "lutro" weight, i. air-dry parts by weight, minus the proportion by weight of water around and inside the pigments in their form of delivery.

Claims (12)

  1. Recording material for offset printing
    - with a web-form substrate, having a front side and a rear side opposite the front side,
    - with at least one recording layer on at least one side of the substrate,
    - with at least one coating layer that covers the entire surface of the recording layer,
    characterised in that
    the at least one coating layer that covers the entire surface of the recording layer has a mass per unit area between 0.15 and 0.35 g/m2 and the at least one coating layer that covers the entire surface of the recording layer is pigment-free.
  2. Recording material according to claim 1,
    characterised in that the at least one coating layer that covers the entire surface of the recording layer contains at least one binder, selected from the list comprising:
    - ethylene vinyl alcohol copolymer (EVOH),
    - polyvinyl alcohol modified with carboxy groups, with silanol or with diacetone,
    - non-modified polyvinyl alcohol,
    alone or in admixture with one another.
  3. Recording material according to either one of claims 1 and 2, characterised in that
    the at least one coating layer that covers the entire surface of the recording layer contains at least one crosslinking auxiliary, selected from the list comprising:
    boric acid, polyamine, epoxy resin, dialdehyde, formaldehyde oligomers, epichlorohydrin resin, adipic acid dihydrazide, dimethylurea, melamine formaldehyde,
    alone or in admixture with one another.
  4. Recording material according to either one of claims 1 and 2, characterised in that the at least one recording layer on at least one side of the substrate is a recording layer selected from the list comprising:
    heat-sensitive recording layer,
    pressure-sensitive recording layer,
    inkjet receiving layer.
  5. Method of producing a recording material for offset printing, the method having at least the method steps:
    - forming a web-form substrate, having a front side and a rear side opposite the front side,
    - applying a prepared coating composition to form a recording layer on at least one side of the substrate,
    - drying the coating composition to form a recording layer,
    - applying a prepared coating composition to form a coating layer that covers the entire surface of the recording layer,
    - drying and/or crosslinking the coating layer that covers the entire surface of the recording layer,
    characterised in that
    the at least one coating layer that covers the entire surface of the recording layer has a mass per unit area between 0.15 and 0.35 g/m2 and the at least one coating layer that covers the entire surface of the recording layer is pigment-free.
  6. Method of producing a recording material according to patent claim 5, characterised in that the method comprises the at least two additional method steps:
    - applying a prepared coating composition to form a pigmented intermediate layer arranged between the substrate and the recording layer,
    - drying the pigmented intermediate layer,
    wherein those at least two additional method steps are to be inserted before the method step "applying a prepared coating composition to form a recording layer on at least one side of the substrate".
  7. Method of producing a recording material according to either one of patent claims 5 and 6, characterised in that the at least one recording layer on at least one side of the substrate is a recording layer selected from the list comprising:
    - heat-sensitive recording layer,
    - pressure-sensitive recording layer,
    - inkjet receiving layer.
  8. Method of producing a recording material according to any one of patent claims 5 to 7, characterised in that the coating composition for forming the recording layer is applied by means of a coating unit, selected from the list comprising: doctor roller coating device, blade coating device, curtain coater and airbrush.
  9. Method of producing a recording material according to any one of patent claims 5 to 8, characterised in that the coating composition for forming a coating layer that covers the entire surface of the recording layer is applied by means of a coating unit, selected from the list comprising: roller coating device, curtain coater and airbrush.
  10. Method of producing a recording material according to any one of patent claims 5 to 9, characterised in that
    (a.) the application of a prepared coating composition to form a recording layer on at least one side of the substrate
    and
    (b.) the application of a prepared coating composition to form a coating layer that covers the entire surface of the recording layer takes place in the course of just one pass through the machine.
  11. Method of producing a heat-sensitive recording material according to any one of patent claims 5 to 10, characterised in that the web-form substrate is paper.
  12. Use of a recording material according to any one of claims 1 to 4 in offset printing.
EP12745873.5A 2011-09-23 2012-08-12 Recording material for offset printing Active EP2758249B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE201110114129 DE102011114129A1 (en) 2011-09-23 2011-09-23 Recording material for offset printing
PCT/EP2012/065775 WO2013041302A1 (en) 2011-09-23 2012-08-12 Recording material for offset printing

Publications (2)

Publication Number Publication Date
EP2758249A1 EP2758249A1 (en) 2014-07-30
EP2758249B1 true EP2758249B1 (en) 2016-04-13

Family

ID=46642556

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Application Number Title Priority Date Filing Date
EP12745873.5A Active EP2758249B1 (en) 2011-09-23 2012-08-12 Recording material for offset printing

Country Status (3)

Country Link
EP (1) EP2758249B1 (en)
DE (1) DE102011114129A1 (en)
WO (1) WO2013041302A1 (en)

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000318319A (en) * 1998-12-02 2000-11-21 Mitsubishi Paper Mills Ltd Information recording material
DE10051294C1 (en) 2000-10-16 2002-04-18 Mitsubishi Hitec Paper Flensbu Thermographic material useful for ticket, especially lottery ticket, has protective coating of water-insoluble, self-crosslinking acrylic polymer and crosslinker pigmented (mainly) with highly purified, alkali-treated bentonite
DE10341168A1 (en) 2003-09-06 2005-04-07 Mitsubishi Hitec Paper Flensburg Gmbh Heat-sensitive recording material and its use
EP2033801B1 (en) * 2007-09-10 2010-02-24 Mitsubishi HiTec Paper Flensburg GmbH Heat sensitive recording material

Also Published As

Publication number Publication date
DE102011114129A1 (en) 2013-03-28
WO2013041302A1 (en) 2013-03-28
EP2758249A1 (en) 2014-07-30

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