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EP0713548B1 - Paper or carboard with a coating applied by cast coating, process for producing the same and its use - Google Patents

Paper or carboard with a coating applied by cast coating, process for producing the same and its use Download PDF

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Publication number
EP0713548B1
EP0713548B1 EP94926127A EP94926127A EP0713548B1 EP 0713548 B1 EP0713548 B1 EP 0713548B1 EP 94926127 A EP94926127 A EP 94926127A EP 94926127 A EP94926127 A EP 94926127A EP 0713548 B1 EP0713548 B1 EP 0713548B1
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EP
European Patent Office
Prior art keywords
weight
coating
paper
parts
pigment
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EP94926127A
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German (de)
French (fr)
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EP0713548A1 (en
Inventor
Werner Bergmann
Paul-Heinz DÄHLING
Peter Pfeifer
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Stora Publication Paper AG
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Stora Publication Paper AG
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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
    • D21H19/36—Coatings with pigments
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/54—Starch
    • 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
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/62—Macromolecular organic compounds or oligomers thereof obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds

Definitions

  • the invention relates to a paper or a cardboard with a coating applied by means of the coating process, which is formed from a mineral pigment, latex, a starch derivative and an aqueous composition comprising casting coating aids known per se in the usual amount.
  • the invention also relates to a method for producing the specified paper or cardboard and its use.
  • JP-A-52 / 137,015 relates to a coating color which may contain casein and which, in order to improve the printability, contains a reaction product of an epihalohydrin with an aliphatic amine.
  • the use of the coating color described in a cast coating process and the use of kaolin as a pigment component are not disclosed.
  • US-A-3,607,331 discloses the use of crosslinking aids in coating compositions containing starch as binders, but without specifying the application of the coating compositions disclosed for the casting coating process.
  • DE-26 19 848 A1 discloses a non-proteinaceous binder composition for the cast coating of paper, in which the binder composition comprises modified starch and two carboxylated styrene-butadiene latices, which differ in their degree of carboxylation.
  • a pigment mixture given by way of example consists of 85 parts made of calcium carbonate and about 15 parts of a coating clay.
  • the known composition may contain a pentaerythritol ester resin and the dispersing and separating agents which are customary per se.
  • DE-26 19 848 A1 aims to replace casein as the main binder component for coating colors to be processed in the coating process and thus to avoid its disadvantages, in particular the high costs and the limited availability. At the same time, however, both a good release property of the dried coating color from the high-gloss cylinder and a high-quality paper sheet which has excellent printability, sheet gloss and water resistance should be achieved.
  • DE-23 02 044 C2 also refers to the disadvantages of using casein as a binder and therefore provides for a mixture of two latices as a binder, one latex not being alkali-soluble or swellable and the other latex being alkali-swellable or soluble.
  • the aqueous coating mass must be kept at a pH of ⁇ 7.0 and the coated paper web must be conveyed in cast-holding rollers with a chrome-plated surface which contain a bath of boiling water.
  • the coating composition applied to the paper web is first partially dried, but no gelation occurs and fed to the casting holding drum filled with boiling water while the paper web is pressed against the surface of the casting holding drum with a pressure roller. A water bath forms in the nip formed between the casting holding drum and the pressure roller.
  • casein as a natural product is subject to not inconsiderable quality fluctuations.
  • Another disadvantage of casein is its sensitivity to bacteria.
  • the qualitative requirements for cast-coated papers or cardboard types have become ever stricter; in particular, good wet scrub resistance and good gloss retention are required to an ever increasing extent. The demands made are to be seen from the point of view of changed printing techniques as well as modern warehousing and sales methods.
  • a cast-coated paper printed with aqueous or water-thinnable flexographic printing inks has a sufficiently high printing ink adhesion.
  • the binders made of latex to be used according to the invention with a glass transition temperature> 18 ° C. and a starch ether are excellently crosslinked by the addition of the crosslinking aids to be used according to the invention, so that in cooperation with the pigments provided according to the invention, a cast line is produced with excellent adhesion to the surface of paper or cardboard. who has excellent ink adhesion, especially of aqueous or water-thinnable inks.
  • the coating color is not impaired by heating the coating ink sump when the web enters the high-gloss cylinder.
  • a further advantage when using the crosslinking aids to be used according to the invention results from the fact that no harmful vapors escape, as z. B. in formaldehyde-releasing crosslinking agents during the Drying process is the case.
  • the pigment present in the coating contains up to 30 parts by weight of precipitated calcium carbonate, satin white, aluminum hydroxide, titanium dioxide or a mixture of these pigments, the mixture components adding up to a total of 100 parts by weight of pigment.
  • a hydroxypropyl starch ether has proven to be particularly suitable, in particular a hydroxypropyl starch ether with a degree of substitution ⁇ 0.2. However, a hydroxypropyl starch ether with a degree of substitution of 0.04 to 0.12 is very particularly preferred.
  • An aliphatic epoxy resin is particularly preferred as the crosslinking aid, in particular an epoxy resin based on bisphenol A and F and epichlorohydrin.
  • a butadiene-styrene latex containing carboxyl groups has proven to be a latex, furthermore a copolymer of acrylic acid esters with other vinyl compounds or a mixture of these two types of latex.
  • the glass transition temperature of the latex or the latex mixture is preferably in the range from 24 to 30 ° C. and the latex has a minimum film-forming temperature of 20 ° C.
  • a coating base paper or a coating base card that is only smoothed by satin coating can be used as the substrate for the application of the cast coating layer, but a coating base provided with a primer can also be used.
  • the minimum application weight of the cast coating layer is also 12 g / m 2 in the case of a pre-coated coating medium, if an uncoated coating medium is used, the coating can be applied up to a basis weight of 27 g / m 2 , application weights of 20 to are particularly preferred 25 g / m 2 .
  • the coatings according to the invention have a gloss (according to Gardener, angle 20 °) of 58 to 68%.
  • the coating according to the invention may also contain as coating additives, dispersing and wetting agents, release agents such as the stearates of sodium and calcium, oils, in particular Turkish red oil, optical brighteners, shading dyes, thickening aids, e.g. B. based on an alkali-soluble acrylate, defoamers and agents for regulating the pH, these G confusestreichilfsstoff in a total of 2 to 4 parts by weight, based on 100 parts by weight of pigment of the coating are present.
  • coating additives dispersing and wetting agents, release agents such as the stearates of sodium and calcium, oils, in particular Turkish red oil, optical brighteners, shading dyes, thickening aids, e.g. B. based on an alkali-soluble acrylate, defoamers and agents for regulating the pH, these G confusestreichilfsstoff in a total of 2 to 4 parts by weight, based on 100 parts by weight of pigment of the coating are present.
  • the process for producing the cast-coated paper according to the invention in which a composition is applied to a paper or cardboard web to form a coating, leveled and contacted with a heated high-gloss cylinder with simultaneous drying to form a high-gloss line, is characterized in that: the composition comprises a pigment consisting of 70 to 100 parts by weight of coating kaolin and / or talc; the composition as a binder - based on 100 parts by weight of pigment - 10 to 14 parts by weight of latex with a glass transition temperature> 18 ° C. 6 to 10% by weight of starch ether and 0.5 to 3.5 parts by weight of epoxy resin contains.
  • the invention is based on the so-called "direct method", i. H. the casting process, in which the material web provided with the leveled but still wet line is brought into contact with the heated surface of a high-gloss cylinder.
  • the so-called rewet method and the gelation method are not covered by the present invention.
  • the pigment present in the composition additionally contains up to 30% by weight of precipitated calcium carbonate, satin white, Contains aluminum hydroxide and titanium dioxide or a mixture of these pigments, with the mixture components adding up to a total of 100 parts by weight of pigment.
  • the temperature of the high-gloss cylinder is preferably kept in the range from 75 ° C. to ⁇ 100 ° C.
  • the coating colors for forming the coating according to the invention are adjusted to a pH> 8, preferably to ⁇ 12.
  • the viscosities range from 2,000 to 8,000 mPas, measured with a Brookfield viscometer at 100 rpm and spindles 4 to 6 depending on the degree of viscosity.
  • the paper or cardboard according to the invention can be used for printing with aqueous or water-dilutable printing inks, in particular the use for printing with aqueous or water-dilutable flexographic printing inks is preferred.
  • a butadiene styrene latex having a glass transition temperature of 24 ° C. and a minimum film-forming temperature of 20 ° C. is added in an amount of 12 parts by weight, calculated as parts by dry weight, based on the pigment.
  • 1.2 parts by weight of calcium stearate and 1 part by weight of a wetting agent are mixed in.
  • the coating color is adjusted to a pH of 8.6.
  • the finished coating color has a solids content of 57% by weight.
  • the dried paper can be easily detached from the high-gloss cylinder.
  • the gloss measurement (according to Gardener at an angle of 20 °) gave a value of 63%.
  • an aqueous flexographic printing ink was applied to a sample of the paper according to the invention using a hand-held applicator - as it is manufactured under the name Hand-Proofer by Pamarco Inc. Rosell NJ - and the "printed" samples immediately after application 10 Min. In a drying cabinet at 100 ° C.
  • the printed test paper is immersed in a water bath for a) 1 min., B) 10 min.
  • a white cotton cloth soaked in water for 1 minute is stretched around the weight of the scrubbing sled.
  • the 1 minute watered sample is loaded with 100 double strokes and the 10 minute watered sample with 25 double strokes of the scrubbing slide.
  • Fig. 1 shows almost completely intact samples of the paper according to the invention both after 1 and after 10 minutes of washing, with no discoloration of printing ink on the test report attached cotton rags can be seen. As a result, the cotton flaps are not visible on copies of the test report, see Fig. 1.
  • an examination of a cast-coated paper using casein shows a very low ink adhesion and consequently a strong staining of the cotton flap, see FIG. Fig. 2.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Paper (AREA)
  • Manufacture Of Alloys Or Alloy Compounds (AREA)
  • Valve Housings (AREA)
  • Glass Compositions (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

A coating applied by cast coating on paper or cardboard contains: as pigment, 70 to 100 parts by weight coating kaolin and/or talc; as binder, 10 to 14 parts by weight latex with a glass transition temperature above 18 DEG C, in relation to 100 parts by weight pigment; 6 to 10 parts by weight starch ether; 0.5 to 3.5 parts by weight of one or several cross-linking auxiliary agents from the group comprising polyamine epichlorhydrine resin, polyamide epichlorhydrine resin, epoxy resin and polyisocianate resin, as well as known cast coating auxiliary agents, added in the usual amounts.

Description

Die Erfindung betrifft ein Papier oder einen Karton mit einer im Gußstreichverfahren aufgebrachten Beschichtung, die aus einer mineralisches Pigment, Latex, ein Stärkederivat sowie in an sich üblicher Zugabemenge bekannte Gußstreichhilfsmittel umfassenden wäßrigen Zusammensetzung gebildet ist. Die Erfindung betrifft auch ein Verfahren zur Herstellung des angegebenen Papiers oder Kartons sowie seine Verwendung.The invention relates to a paper or a cardboard with a coating applied by means of the coating process, which is formed from a mineral pigment, latex, a starch derivative and an aqueous composition comprising casting coating aids known per se in the usual amount. The invention also relates to a method for producing the specified paper or cardboard and its use.

Die JP-A-52/137,015 betrifft eine ggf. Kasein enthaltende Streichfarbe, die zur Verbesserung der Bedruckbarkeit ein Reaktionsprodukt eines Epihalohydrins mit einem aliphatischen Amin enthält. Die Verwendung der beschriebenen Streichfarbe in einem Gußstreichverfahren und die Verwendung von Kaolin als Pigmentkomponente sind nicht offenbart.JP-A-52 / 137,015 relates to a coating color which may contain casein and which, in order to improve the printability, contains a reaction product of an epihalohydrin with an aliphatic amine. The use of the coating color described in a cast coating process and the use of kaolin as a pigment component are not disclosed.

Die US-A-3,607,331 offenbart den Einsatz von Vernetzungshilfsmitteln bei Stärke als Bindemittel enthaltenden Streichmassen, ohne daß jedoch die Anwendung der offenbarten Streichmassen für das Gußstreichverfahren angegeben wird.US-A-3,607,331 discloses the use of crosslinking aids in coating compositions containing starch as binders, but without specifying the application of the coating compositions disclosed for the casting coating process.

Aus der DE-26 19 848 Al ist eine nicht proteinartige Bindemittelzusammensetzung für die Gießbeschichtung von Papier bekannt, bei der die Bindemittelzusammensetzung modifizierte Stärke sowie zwei carboxylierte Styrol-Butadienlatices, die sich in ihrem Carboxylierungsgrad unterscheiden, umfaßt. Eine beispielhaft angegebene Pigmentmischung besteht zu 85 Teilen aus Calciumcarbonat und ungefähr 15 Teilen eines Beschichtungstons. Desweiteren kann die bekannte Zusammensetzung ein Pentaerythritesterharz sowie die an sich üblichen Dispergier- und Trennmittel enthalten. Die DE-26 19 848 A1 stellt darauf ab, Kasein als hauptsächlichen Bindemittelbestandteil für im Gußstreichverfahren zu verarbeitende Streichfarben zu ersetzen und damit dessen Nachteile, insbesondere die hohen Kosten und die begrenzte Verfügbarkeit zu umgehen. Gleichzeitig soll aber sowohl eine gute Ablöseeigenschaft der getrockneten Streichfarbe vom Hochglanzzylinder erzielt werden, als auch ein qualitativ hochwertiges Papierblatt, das über hervorragende Bedruckbarkeit, Blattglanz und Wasserbeständigkeit verfügt.DE-26 19 848 A1 discloses a non-proteinaceous binder composition for the cast coating of paper, in which the binder composition comprises modified starch and two carboxylated styrene-butadiene latices, which differ in their degree of carboxylation. A pigment mixture given by way of example consists of 85 parts made of calcium carbonate and about 15 parts of a coating clay. Furthermore, the known composition may contain a pentaerythritol ester resin and the dispersing and separating agents which are customary per se. DE-26 19 848 A1 aims to replace casein as the main binder component for coating colors to be processed in the coating process and thus to avoid its disadvantages, in particular the high costs and the limited availability. At the same time, however, both a good release property of the dried coating color from the high-gloss cylinder and a high-quality paper sheet which has excellent printability, sheet gloss and water resistance should be achieved.

Auch die DE-23 02 044 C2 verweist auf die Nachteile der Verwendung von Kasein als Bindemittel und sieht daher eine Mischung von zwei Latices als Bindemittel vor, wobei der eine Latex nicht alkalilöslich oder quellbar ist und der andere Latex alkaliquellbar oder löslich gemacht werden kann. Die wäßrige Überzugsmasse muß bei einem ph-Wert < 7,0 gehalten werden und die überzogene Papierbahn in Gußhaltewalzen mit verchromter Oberfläche befördert werden, die ein Bad aus siedendem Wasser enthalten. Bei diesem bekannten Verfahren wird die auf die Papierbahn aufgetragene Überzugsmasse zunächst teilweise getrocknet, wobei jedoch keine Gelierung eintritt und der mit siedendem Wasser gefüllten Gußhaltetrommel zugeführt, während die Papierbahn mit einer Druckwalze gegen die Oberfläche der Gußhaltetrommel gedrückt wird. In dem zwischen Gußhaltetrommel und Druckwalze gebildeten Walzenspalt bildet sich ein Wasserbad. Mit diesem bekannten Verfahren soll unter Verzicht auf den Einsatz von Kasein eine gute Strichoberfläche und eine gute Ablösbarkeit der getrockneten Strichoberfläche von der Gußhaltetrommel erzielt werden.DE-23 02 044 C2 also refers to the disadvantages of using casein as a binder and therefore provides for a mixture of two latices as a binder, one latex not being alkali-soluble or swellable and the other latex being alkali-swellable or soluble. The aqueous coating mass must be kept at a pH of <7.0 and the coated paper web must be conveyed in cast-holding rollers with a chrome-plated surface which contain a bath of boiling water. In this known method, the coating composition applied to the paper web is first partially dried, but no gelation occurs and fed to the casting holding drum filled with boiling water while the paper web is pressed against the surface of the casting holding drum with a pressure roller. A water bath forms in the nip formed between the casting holding drum and the pressure roller. With this known method, a good coat surface and good detachability of the dried coat surface from the casting holding drum are to be achieved without the use of casein.

Wenngleich die beschriebenen Nachteile von Kasein nach wie vor bestehen, wurden zwischenzeitlich weitere Rezepturvorschläge unter Einsatz von Kasein entwickelt, wozu auf die US 4,515,833 Al zu verweisen ist, die für die sogenannte rewet-Methode und das Gußstreichverfahren nach dem Gelierungsprinzip den Einsatz von 30 bis 80 Gew.% - bezogen auf Gesamtpigment - kubischen Calciumcarbonats vorsieht. Schließlich sieht auch die EP-0 331 143 A2 den Einsatz von Kasein zusätzlich zur Verwendung von zwei unterschiedlichen Latextypen vor. Auch hier wird wieder die sogenannte rewet-Variante des Gußstreichverfahrens beschrieben.Although the described disadvantages of casein still exist, other recipe proposals have been developed using casein, for which reference is made to US 4,515,833 A1, which use 30 to 80 for the so-called rewet method and the casting process based on the gelation principle % By weight - based on total pigment - provides cubic calcium carbonate. Finally, EP-0 331 143 A2 also provides for the use of casein in addition to the use of two different types of latex. Again, the so-called rewet variant of the casting process is described.

Die Verfügbarkeit von Kasein hat sich zwischenzeitlich nicht verbessert; die Kosten für dieses Produkt liegen nach wie vor auf einem hohen Niveau oder sind zumindest erheblichen Schwankungen unterworfen. Darüberhinaus besteht der Nachteil, daß Kasein als Naturprodukt nicht unerheblichen Qualitätsschwankungen unterliegt. Ein weiterer Nachteil von Kasein besteht in seiner Bakterienempfindlichkeit. Andererseits haben sich die qualitativen Anforderungen an gußgestrichene Papiere oder Kartonsorten ständig verschärft, insbesondere werden in ständig steigendem Umfang eine gute Naßscheuerbeständigkeit und ein guter Glanzerhalt gefordert. Dabei sind die erhobenen Forderungen unter dem Blickwinkel veränderter Drucktechniken sowie moderner Lagerhaltung und Verkaufsmethoden zu sehen. So besteht insbesondere die Forderung, daß ein mit wäßrigen oder wasserverdünnbaren Flexodruckfarben bedrucktes gußgestrichenes Papier über eine ausreichend hohe Druckfarbenhaftung verfügt. Diese Forderung begründet sich darin, daß gußgestrichene Papiere mit der vorstehend angegebenen Drucktechnik bedruckt, zu Etiketten verarbeitet und zur Kennzeichnung von gekühlten oder tiefgefrorenen Lebensmittelverpackungen eingesetzt werden. Nach Entnahme der tiefgefrorenen Packung, z. B. beim Einkauf, bildet sich auf der Verpackungsoberfäche Kondenswasser, das insbesondere bei gleichzeitiger Beanspruchung durch Stoßen oder Scheuern die Qualität des Druckbildes bis zur Unleserlichkeit beeinflussen kann.The availability of casein has not improved in the meantime; the costs for this product are still at a high level or are at least substantial Subject to fluctuations. In addition, there is the disadvantage that casein as a natural product is subject to not inconsiderable quality fluctuations. Another disadvantage of casein is its sensitivity to bacteria. On the other hand, the qualitative requirements for cast-coated papers or cardboard types have become ever stricter; in particular, good wet scrub resistance and good gloss retention are required to an ever increasing extent. The demands made are to be seen from the point of view of changed printing techniques as well as modern warehousing and sales methods. There is, in particular, the requirement that a cast-coated paper printed with aqueous or water-thinnable flexographic printing inks has a sufficiently high printing ink adhesion. This requirement is based on the fact that cast-coated papers are printed with the printing technique indicated above, processed into labels and used for labeling chilled or frozen food packaging. After removing the frozen pack, e.g. B. when shopping, condensation forms on the packaging surface, which can influence the quality of the printed image to the point of illegibility, especially when subjected to bumping or rubbing.

Ausgehend von diesen bekannten Problemen sieht die vorliegende Erfindung ihre Aufgabe in der Entwicklung eines gußgestrichenen Papiers oder Kartons,

  • bei dessen Herstellung die durch den Einsatz von Kasein als Bindemittel eintretenden Nachteile vermieden werden,
  • das Papier oder der Karton eine Beschichtung mit verbesserter Naßscheuerfestigkeit, insbesondere einer ausreichend hohen Flexodruckfarbenhaftung aufweisen,
  • die Beschichtung auf dem Papier oder Karton eine hohe Haftfestigkeit aufweist, so daß bei der Verwendung des Papiers als Etikett für Mehrwegflaschen bei der Reinigung der gebrauchten Flaschen die eingesetzten Spülflotten lange Standzeiten haben und nicht infolge einer ungenügenden Haftung des Striches auf dem Etikett vorzeitig erneuert werden müssen.
Based on these known problems, the present invention sees its task in Development of a cast coated paper or cardboard,
  • in the production of which the disadvantages arising from the use of casein as a binder are avoided,
  • the paper or the cardboard have a coating with improved wet abrasion resistance, in particular a sufficiently high flexographic printing ink adhesion,
  • the coating on the paper or cardboard has a high adhesive strength, so that when the paper is used as a label for reusable bottles when cleaning the used bottles, the washing liquors used have a long service life and do not have to be renewed prematurely due to insufficient adhesion of the line on the label .

Zur Lösung der gestellten Aufgabe sieht die Erfindung ein Papier oder einen Karton vor mit einer im Gußstreichverfahren aufgebrachten Beschichtung, die aus einer mineralisches Pigment, Latex, ein Stärkederivat sowie in an sich üblicher Zugabemenge bekannte Gußstreichhilfsmittel umfassenden wässrigen Zusammensetzung gebildet ist, wobei die Beschichtung durch die Kombination der folgenden Merkmale gekennzeichnet ist:

  • das Pigment besteht zu 70 bis 100 Gew.-Teilen aus Streichkaolin und/oder Talkum;
  • die Beschichtung enthält als Bindemittel, bezogen auf 100 Gew.-Teile Pigment: 10 bis 14 Gew.-Teile Latex mit einer Glasübergangstemperatur > 18 °C, 6 bis 10 Gew.-Teile Stärkeäther, 0,5 bis 3,5 Gew.-Teile eines oder mehrerer Vernetzungshilfsmittel aus der Gruppe: Polyaminepichlorhydrinharz, Polyamidepichlorhydrinharz, Epoxydharz, Polyisocyanatharz.
To achieve the object, the invention provides a paper or a cardboard with a coating applied by the coating method, which is formed from a mineral pigment, latex, a starch derivative and an aqueous composition comprising known coating additives, the coating being formed by the Combination of the following features is marked:
  • the pigment consists of 70 to 100 parts by weight of coating kaolin and / or talc;
  • the coating contains as a binder, based on 100 parts by weight of pigment: 10 to 14 parts by weight of latex with a glass transition temperature> 18 ° C., 6 to 10 parts by weight of starch ether, 0.5 to 3.5 parts by weight of one or more crosslinking aids of the group: polyamine epichlorohydrin resin, polyamide epichlorohydrin resin, epoxy resin, polyisocyanate resin.

Die erfindungsgemäß einzusetzenden Bindemittel aus Latex mit einer Glasübergangstemperatur > 18 °C und einem Stärkeäther werden durch den Zusatz der erfindungsgemäß einzusetzenden Vernetzungshilfsmittel hervorragend vernetzt, so daß im Zusammenwirken mit den erfindungsgemäß vorgesehenen Pigmenten ein Gußstrich mit ausgezeichneter Haftung auf der Oberfläche von Papier oder Karton entsteht, der über eine hervorragende Druckfarbenhaftung, insbesondere auch von wäßrigen oder wasserverdünnbaren Druckfarben verfügt. Zusätzlich entsteht noch der Vorteil, daß eine Beeinträchtigung der Streichfarbe durch Erhitzung des Streichfarbensumpfes beim Eintritt der Bahn auf den Hochglanzzylinder nicht erfolgt. Ein weiterer Vorteil beim Einsatz der erfindungsgemäß einzusetzenden Vernetzungshilfsmittel ergibt sich dadurch, daß keine gesundheitsschädlichen Dämpfe entweichen, wie dies z. B. bei Formaldehyd abspaltenden Vernetzungshilfsmitteln während des Trocknungsprozesses der Fall ist.The binders made of latex to be used according to the invention with a glass transition temperature> 18 ° C. and a starch ether are excellently crosslinked by the addition of the crosslinking aids to be used according to the invention, so that in cooperation with the pigments provided according to the invention, a cast line is produced with excellent adhesion to the surface of paper or cardboard. who has excellent ink adhesion, especially of aqueous or water-thinnable inks. In addition, there is the additional advantage that the coating color is not impaired by heating the coating ink sump when the web enters the high-gloss cylinder. A further advantage when using the crosslinking aids to be used according to the invention results from the fact that no harmful vapors escape, as z. B. in formaldehyde-releasing crosslinking agents during the Drying process is the case.

Gemäß einer vorzugsweisen Ausführungsform der Erfindung enthält das in der Beschichtung vorliegende Pigment bis zu 30 Gew.-Teile gefälltes Calciumcarbonat, Satinweiß, Aluminiumhydroxid, Titandioxid oder eine Mischung dieser Pigmente, wobei sich die Mischungsbestandteile zu insgesamt 100 Gew.-Teilen Pigment ergänzen.According to a preferred embodiment of the invention, the pigment present in the coating contains up to 30 parts by weight of precipitated calcium carbonate, satin white, aluminum hydroxide, titanium dioxide or a mixture of these pigments, the mixture components adding up to a total of 100 parts by weight of pigment.

Als besonders geeignet hat sich ein Hydroxypropylstärkeäther erwiesen, insbesondere ein Hydroxypropylstärkeäther mit einem Substitutionsgrad < 0,2. Ganz besonders bevorzugt ist jedoch ein Hydroxypropylstärkeäther mit einem Substitutionsgrad von 0,04 bis 0,12.A hydroxypropyl starch ether has proven to be particularly suitable, in particular a hydroxypropyl starch ether with a degree of substitution <0.2. However, a hydroxypropyl starch ether with a degree of substitution of 0.04 to 0.12 is very particularly preferred.

Als Vernetzungshilfsmittel wird insbesondere ein aliphatisches Epoxydharz bevorzugt, insbesondere ein Epoxydharz auf Basis von Bisphenol A und F und Epichlorhydrin.An aliphatic epoxy resin is particularly preferred as the crosslinking aid, in particular an epoxy resin based on bisphenol A and F and epichlorohydrin.

Als Latex hat sich insbesondere ein carboxylgruppenhaltiger Butadien-Styrol-Latex erwiesen, ferner ein Mischpolymerisat von Acrylsäureestern mit anderen Vinylverbindungen oder eine Mischung dieser beiden Latex-Typen. Vorzugsweise liegt die Glasübergangstemperatur des Latex bzw. der Latex-Mischung im Bereich von 24 bis 30 °C und der Latex weist eine Mindestfilmbildungstemperatur von 20 °C auf. Als Substrat für den Auftrag der Gußstreichschicht kann ein lediglich durch Satinage geglättetes Streichrohpapier bzw. ein Streichrohkarton eingesetzt werden, jedoch kann auch ein mit einem Vorstrich versehener Beschichtungsträger zum Einsatz kommen. Das Mindestauftragsgewicht der Gußstreichschicht liegt auch im Fall eines vorgestrichenen Beschichtungsträgers bei 12 g/m2, kommt ein nicht vorgestrichener Beschichtungsträger zum Einsatz, kann die Beschichtung bis zu einer Flächenmasse von 27 g/m2 aufgetragen werden, ganz besonders bevorzugt sind Auftragsgewichte von 20 bis 25 g/m2.In particular, a butadiene-styrene latex containing carboxyl groups has proven to be a latex, furthermore a copolymer of acrylic acid esters with other vinyl compounds or a mixture of these two types of latex. The glass transition temperature of the latex or the latex mixture is preferably in the range from 24 to 30 ° C. and the latex has a minimum film-forming temperature of 20 ° C. A coating base paper or a coating base card that is only smoothed by satin coating can be used as the substrate for the application of the cast coating layer, but a coating base provided with a primer can also be used. The minimum application weight of the cast coating layer is also 12 g / m 2 in the case of a pre-coated coating medium, if an uncoated coating medium is used, the coating can be applied up to a basis weight of 27 g / m 2 , application weights of 20 to are particularly preferred 25 g / m 2 .

Die erfindungsgemäßen Beschichtungen weisen einen Glanz (nach Gardener, Winkel 20 °) von 58 bis 68 % auf.The coatings according to the invention have a gloss (according to Gardener, angle 20 °) of 58 to 68%.

Als Gußstreichhilfsmittel kann die erfindungsgemäße Beschichtung außer den erfindungsgemäßen Pigmenten und Bindemittelkomponenten ferner noch enthalten: Dispergier- und Netzmittel, Ablösemittel, wie die Stearate von Natrium und Calcium, Öle, insbesondere Türkischrotöl, optische Aufheller, Nuancierungsfarbstoffe, Verdickungshilfsmittel, z. B. auf Basis eines alkalilöslichen Acrylates, Entschäumer und Mittel zur Regulierung des pH-Wertes, wobei diese Gußstreichilfsmittel in einer Menge von insgesamt 2 bis 4 Gew.-Teilen, bezogen auf 100 Gew.-Teile Pigment der Beschichtung vorliegen.In addition to the pigments and binder components according to the invention, the coating according to the invention may also contain as coating additives, dispersing and wetting agents, release agents such as the stearates of sodium and calcium, oils, in particular Turkish red oil, optical brighteners, shading dyes, thickening aids, e.g. B. based on an alkali-soluble acrylate, defoamers and agents for regulating the pH, these Gießstreichilfsmittel in a total of 2 to 4 parts by weight, based on 100 parts by weight of pigment of the coating are present.

Das Verfahren zur Herstellung des erfindungsgemäßen gußgestrichenen Papiers, bei dem zur Ausbildung einer Beschichtung eine Zusammensetzung auf eine Papier- oder Kartonbahn aufgebracht, egalisiert und mit einem beheizten Hochglanzzylinder unter gleichzeitiger Trocknung zur Ausbildung eines hochglänzenden Striches kontaktiert wird, ist dadurch gekennzeichnet, daß: die Zusammensetzung ein Pigment umfaßt, das zu 70 bis 100 Gew.-Teilen aus Streichkaolin und/oder Talkum besteht;
die Zusammensetzung als Bindemittel - bezogen auf 100 Gew.-Teile Pigment - 10 bis 14 Gew.-Teile Latex mit einer Glasübergangstemperatur > 18 °C 6 bis 10 Gew.-% Stärkeäther und 0,5 bis 3,5 Gew.-Teile Epoxydharz enthält.The process for producing the cast-coated paper according to the invention, in which a composition is applied to a paper or cardboard web to form a coating, leveled and contacted with a heated high-gloss cylinder with simultaneous drying to form a high-gloss line, is characterized in that: the composition comprises a pigment consisting of 70 to 100 parts by weight of coating kaolin and / or talc;
the composition as a binder - based on 100 parts by weight of pigment - 10 to 14 parts by weight of latex with a glass transition temperature> 18 ° C. 6 to 10% by weight of starch ether and 0.5 to 3.5 parts by weight of epoxy resin contains.

Aus der Beschreibung des erfindungsgemäßen Verfahrens wird ersichtlich, daß die Erfindung auf die sogenannte "direkte Methode" abstellt, d. h. das Gußstreichverfahren, bei dem die mit dem egalisierten, aber noch nassen Strich versehene Warenbahn mit der beheizten Oberfläche eines Hochglanzzylinders in Kontakt gebracht wird. Die sogenannte rewet-Methode und die Gelierungs-Methode werden von der vorliegenden Erfindung nicht umfaßt.From the description of the method according to the invention it can be seen that the invention is based on the so-called "direct method", i. H. the casting process, in which the material web provided with the leveled but still wet line is brought into contact with the heated surface of a high-gloss cylinder. The so-called rewet method and the gelation method are not covered by the present invention.

Es wird bevorzugt, daß das in der Zusammensetzung vorliegende Pigment zusätzlich bis zu 30 Gew.% gefälltes Calciumcarbonat, Satinweiß, Aluminiumhydroxid und Titandioxid oder eine Mischung dieser Pigmente enthält, wobei sich die Mischungsbestandteile zu insgesamt 100 Gew.-Teilen Pigment ergänzen.It is preferred that the pigment present in the composition additionally contains up to 30% by weight of precipitated calcium carbonate, satin white, Contains aluminum hydroxide and titanium dioxide or a mixture of these pigments, with the mixture components adding up to a total of 100 parts by weight of pigment.

Vorzugsweise wird die Temperatur des Hochglanzzylinders im Bereich von 75 °C bis < 100 °C gehalten.The temperature of the high-gloss cylinder is preferably kept in the range from 75 ° C. to <100 ° C.

Die Streichfarben zur Ausbildung der erfindungsgemäßen Beschichtung werden auf einen pH-Wert > 8 vorzugsweise bis < 12 eingestellt. Die Viskositäten liegen im Bereich von 2.000 bis 8.000 m Pa s, gemessen mit einem Brookfield-Viskosimeter bei 100 rpm und Spindel 4 bis 6 je nach Viskositätsgrad.The coating colors for forming the coating according to the invention are adjusted to a pH> 8, preferably to <12. The viscosities range from 2,000 to 8,000 mPas, measured with a Brookfield viscometer at 100 rpm and spindles 4 to 6 depending on the degree of viscosity.

Insbesondere kann das erfindungsgemäße Papier oder Karton zum Bedrucken mit wäßrigen oder wasserverdünnbaren Druckfarben verwendet werden, insbesondere wird die Verwendung zum Bedrucken mit wäßrigen oder wasserverdünnbaren Flexodruckfarben bevorzugt.In particular, the paper or cardboard according to the invention can be used for printing with aqueous or water-dilutable printing inks, in particular the use for printing with aqueous or water-dilutable flexographic printing inks is preferred.

Das nachfolgende Beispiel erläutert die Erfindung:The following example explains the invention:

Beispiel:Example:

Eine wäßrige Aufschlämmung aus 80 Gew.-Teilen Streichkaolin und 20 Gew.-Teilen gefälltem Calciumcarbonat wird unter Zusatz von 0,3 Gew.-Teilen, bezogen auf Pigment, eines polycarbonsauren Salzes als Dispergiermittel hergestellt und dieser Mischung 2 Gew.-Teile eines Reaktionsproduktes aus Bisphenol A und F mit Epichlorhydrin, wie es unter der Handelsbezeichnung XZ 95381.00 Epoxy Resin von der Fa. Dow hergestellt wird, zugesetzt und mit der Pigmentaufschlämmung homogen vermischt. Der gut durchgemischten Aufschlämmung wird eine Lösung eines Hydroxypropylstärkeäthers mit einem Substitutionsgrad von 0,07 in einer Menge von 8 Gew.-Teilen, bezogen auf Trockengewichtsteile des Pigmentes, zugegeben. Nach Durchmischung wird ein Butadienstyrollatex mit einer Glasübergangstemperatur von 24 °C und einer Mindestfilmbildungstemperatur von 20 °C in einer Menge von 12 Gew.-Teilen, gerechnet als Trockengewichtsteile, bezogen auf Pigment, zugegeben. Schließlich werden - bezogen auf Pigment - 1,2 Gew.-Teile Calciumstearat und 1 Gew.-Teil eines Netzmittels zugemischt. Die Streichfarbe wird auf einen pH-Wert von 8,6 eingestellt. Die fertige Streichfarbe hat einen Feststoffgehalt von 57 Gew.%.An aqueous slurry of 80 parts by weight of coating kaolin and 20 parts by weight of precipitated calcium carbonate becomes one with the addition of 0.3 part by weight, based on pigment polycarboxylic acid salt as a dispersant and 2 parts by weight of a reaction product of bisphenol A and F with epichlorohydrin, as it is manufactured under the trade name XZ 95381.00 Epoxy Resin from Dow, are added to this mixture and mixed homogeneously with the pigment slurry. A solution of a hydroxypropyl starch ether with a degree of substitution of 0.07 in an amount of 8 parts by weight, based on the dry parts by weight of the pigment, is added to the well-mixed slurry. After mixing, a butadiene styrene latex having a glass transition temperature of 24 ° C. and a minimum film-forming temperature of 20 ° C. is added in an amount of 12 parts by weight, calculated as parts by dry weight, based on the pigment. Finally, based on pigment, 1.2 parts by weight of calcium stearate and 1 part by weight of a wetting agent are mixed in. The coating color is adjusted to a pH of 8.6. The finished coating color has a solids content of 57% by weight.

Ein harzsauer geleimtes holzfreies Streichrohpapier mit einem Füllstoffgehalt von 7 Gew.%, das auf einer Leimpresse mit einer Stärkepräparation versehen wurde und eine Flächenmasse von 55 g/m2 aufweist, wird auf einer Gußstreicheinrichtung mit der vorstehend angegebenen Streichfarbe zur Ausbildung einer Gußstreichschicht versehen, wobei 24 g/m2-gerechnet als Trockengewichtsteile - aufgetragen werden. Die Ablösung des getrockneten Papiers vom Hochglanzzylinder erfolgt problemlos. Die Glanzmessung (nach Gardener bei einem Winkel von 20 °) ergab einen Wert von 63 %.A resin-acid-sized wood-free coating base paper with a filler content of 7% by weight, which was provided with a starch preparation on a size press and has a basis weight of 55 g / m 2 , is provided on a casting coating device with the coating color specified above to form a casting coating layer, whereby 24 g / m 2 - calculated as dry weight parts - to be applied. The dried paper can be easily detached from the high-gloss cylinder. The gloss measurement (according to Gardener at an angle of 20 °) gave a value of 63%.

Zur Prüfung der Flexodruckfarbenhaftung wurde eine wäßrige Flexodruckfarbe mit einem Handauftragsgerät - wie es unter der Bezeichnung Hand-Proofer von der Fa. Pamarco Inc. Rosell N. J. hergestellt wird - auf eine Probe des erfindungsgemäßen Papiers aufgetragen und die "bedruckten" Proben unmittelbar nach dem Auftrag 10 Min. bei 100 °C im Trockenschrank getrocknet.To test the flexographic printing ink adhesion, an aqueous flexographic printing ink was applied to a sample of the paper according to the invention using a hand-held applicator - as it is manufactured under the name Hand-Proofer by Pamarco Inc. Rosell NJ - and the "printed" samples immediately after application 10 Min. In a drying cabinet at 100 ° C.

Das bedruckte Prüfpapier wird a) 1 Min., b) 10 Min. in ein Wasserbad getaucht und ohne Abtropfen in die Prüfvorrichtung eines Scheuergerätes gelegt, das aus einem in Führungsschienen beweglichen Scheuerschlitten besteht, der manuell über die eingespannte Papierprobe geführt wird. Dabei ist ein weißer Baumwollappen, der 1 Min. in Wasser getränkt ist, um das Belastungsgewicht des Scheuerschlittens gespannt. Die 1 Min. gewässerte Probe wird mit 100 Doppelhüben und die 10 Min. gewässerte Probe mit 25 Doppelhüben des Scheuerschlittens beaufschlagt.The printed test paper is immersed in a water bath for a) 1 min., B) 10 min. A white cotton cloth soaked in water for 1 minute is stretched around the weight of the scrubbing sled. The 1 minute watered sample is loaded with 100 double strokes and the 10 minute watered sample with 25 double strokes of the scrubbing slide.

Fig. 1 zeigt nahezu völlig intakte Proben des erfindungsgemäßen Papiers sowohl nach 1 als auch nach 10 Min. Wässerung, wobei keine Abfärbung von Druckfarbe auf dem dem Untersuchungsbericht beigefügten Baumwollappen zu sehen ist. Infolgedessen wird auf Kopien des Untersuchungsberichtes der Baumwollappen nicht sichtbar, s. Fig. 1. Eine zum Vergleich durchgeführte Untersuchung eines unter Verwendung von Kasein gußgestrichenen Papiers zeigt demgegenüber eine sehr geringe Druckfarbenhaftung und demzufolge eine starke Anfärbung des Baumwollappens, s. Fig. 2.Fig. 1 shows almost completely intact samples of the paper according to the invention both after 1 and after 10 minutes of washing, with no discoloration of printing ink on the test report attached cotton rags can be seen. As a result, the cotton flaps are not visible on copies of the test report, see Fig. 1. By comparison, an examination of a cast-coated paper using casein shows a very low ink adhesion and consequently a strong staining of the cotton flap, see FIG. Fig. 2.

Claims (15)

  1. Paper or board having a coating applied in the cast-coating process, which coating is formed from a mineral pigment, latex, a starch derivative and an aqueous composition comprising known cast-coating auxiliaries in an addition amount which is usual per se, the coating being characterized by the combination of the following features:
    - the pigment comprises 70 to 100 parts by weight of coating kaolin and/or talc;
    - the coating contains as binder, based on 100 parts by weight of pigment:
    10 to 14 parts by weight of latex with a glass transition temperature > 18°C,
    6 to 10 parts by weight of starch ether,
    0.5 to 3.5 parts by weight of one or more crosslinking auxiliaries from the group consisting of:
    polyamine epichlorohydrin resin, polyamide epichlorohydrin resin, epoxy resin, polyisocyanate resin.
  2. Paper or board according to Claim 1, characterized in that the pigment additionally contains up to 30 parts by weight of precipitated calcium carbonate, satin white, aluminium hydroxide, titanium dioxide or a mixture of these pigments, the components of the mixture adding up to a total of 100 parts by weight of pigment.
  3. Paper or board according to one of Claims 1 and 2, characterized in that the starch ether is a hydroxypropyl starch ether.
  4. Paper or board according to one of Claims 1 to 3, characterized in that the hydroxypropyl starch ether has a degree of substitution < 0.2.
  5. Paper or board according to one of Claims 1 to 4, characterized in that the hydroxypropyl starch ether has a degree of substitution of 0.04 to 0.12.
  6. Paper or board according to one of Claims 1 to 5, characterized in that the epoxy resin is an aliphatic epoxy resin.
  7. Paper or board according to one of Claims 1 to 5, characterized in that the epoxy resin is a reaction product based on bisphenol A and F and epichlorohydrin.
  8. Paper or board according to one of Claims 1 to 7, characterized in that the latex is a butadiene styrene latex containing carboxyl groups, a copolymer of acrylic esters with other vinyl compounds or a mixture of these two types of latex.
  9. Paper or board according to one of Claims 1 to 8, characterized in that the latex has a glass transition temperature of 24 to 30°C and a minimum film-forming temperature of 20°C.
  10. Paper or board according to one of Claims 1 to 9, characterized in that the coating is applied to a paper or board web which is precoated and smoothed by calendering.
  11. Process for the production of a cast-coated paper or board according to one of Claims 1 to 10, in which to form a coating a composition is applied to a paper or board web, is equalized and is brought into contact with a heated high-gloss cylinder with simultaneous drying to form a high-gloss coating, characterized in that:
    the composition comprises a pigment which comprises 70 to 100 parts by weight of coating kaolin and/or talc;
    the composition contains as binder - based on 100 parts by weight of pigment -
    10 to 14 parts by weight of latex having a glass transition temperature > 18°C
    6 to 10 % by weight of starch ether and
    0.5 to 3.5 parts by weight of epoxy resin.
  12. Process according to Claim 11, characterized in that the pigment additionally contains up to 30 % by weight of precipitated calcium carbonate, satin white, aluminium hydroxide and titanium dioxide or a mixture of these pigments, the components of the mixture adding up to a total of 100 parts by weight of pigment.
  13. Process according to one of Claims 11 and 12, characterized in that the temperature of the high-gloss cylinder is kept in the range from 75°C to < 100°C.
  14. Use of a cast-coated paper or board according to one of Claims 1 to 10 for printing with aqueous or water-dilutable printing inks.
  15. Use of a cast-coated paper or board according to one of Claims 1 to 10 and 14 for printing with aqueous or water-dilutable flexographic printing inks.
EP94926127A 1993-08-14 1994-07-29 Paper or carboard with a coating applied by cast coating, process for producing the same and its use Expired - Lifetime EP0713548B1 (en)

Applications Claiming Priority (3)

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DE4327366A DE4327366C1 (en) 1993-08-14 1993-08-14 Paper or board having a coating applied by cast coating, process for the production and use
DE4327366 1993-08-14
PCT/EP1994/002509 WO1995005505A1 (en) 1993-08-14 1994-07-29 Paper or carboard with a coating applied by cast coating, process for producing the same and its use

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EP0713548A1 EP0713548A1 (en) 1996-05-29
EP0713548B1 true EP0713548B1 (en) 1997-04-16

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EP (1) EP0713548B1 (en)
JP (1) JPH09501745A (en)
AT (1) ATE151828T1 (en)
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WO (1) WO1995005505A1 (en)

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US7758690B2 (en) 2002-05-03 2010-07-20 Imerys Minerals, Ltd. Paper coating pigments

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DE19644014C2 (en) * 1996-10-31 1999-07-22 Stora Publication Paper Ag Paper with recording layer and process for its manufacture
DE19706574C2 (en) * 1997-02-20 1999-07-08 Stora Publication Paper Ag Paper coated with a coating method, process for its production and its use
DE19745935C2 (en) * 1997-10-17 2001-12-13 Mitsubishi Hitec Paper Bielefe Inkjet recording layer paper
DE19755724C1 (en) * 1997-12-15 1999-06-24 Zanders Feinpapiere Ag Matte cast-coated paper and process for its manufacture
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CA2531498C (en) * 2003-08-11 2013-09-03 Tokushu Paper Mfg. Co., Ltd. Oil-resistant sheet material
US11396199B2 (en) 2015-03-23 2022-07-26 Stora Enso Oyj Inkjet ink receptive coating comprising esterified or etherified starch and laponite
FR3065223B1 (en) * 2017-04-18 2019-07-05 Societe Bic DRY CLEANING INK WITH IMPROVED DRYING TIME

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US7758690B2 (en) 2002-05-03 2010-07-20 Imerys Minerals, Ltd. Paper coating pigments

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FI960603A (en) 1996-02-14
ATE151828T1 (en) 1997-05-15
WO1995005505A1 (en) 1995-02-23
EP0713548A1 (en) 1996-05-29
DE4327366C1 (en) 1995-01-05

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