EP1164220A1 - Surface treatment of coating base paper - Google Patents

Surface treatment of coating base paper Download PDF

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Publication number
EP1164220A1
EP1164220A1 EP01890185A EP01890185A EP1164220A1 EP 1164220 A1 EP1164220 A1 EP 1164220A1 EP 01890185 A EP01890185 A EP 01890185A EP 01890185 A EP01890185 A EP 01890185A EP 1164220 A1 EP1164220 A1 EP 1164220A1
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EP
European Patent Office
Prior art keywords
cmc
paper
base paper
coating base
starch
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.)
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Application number
EP01890185A
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German (de)
French (fr)
Inventor
Thoralf Dr. Gliese
Friedrich Kainz
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.)
M Real Hallein AG
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M Real Hallein AG
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Filing date
Publication date
Application filed by M Real Hallein AG filed Critical M Real Hallein AG
Publication of EP1164220A1 publication Critical patent/EP1164220A1/en
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Classifications

    • 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
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/24—Polysaccharides
    • D21H17/25—Cellulose
    • D21H17/26—Ethers thereof
    • 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
    • D21H19/10—Coatings without pigments
    • D21H19/12—Coatings without pigments applied as a solution using water as the only solvent, e.g. in the presence of acid or alkaline compounds
    • 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
    • D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
    • D21H23/02—Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
    • D21H23/22—Addition to the formed paper
    • D21H23/24—Addition to the formed paper during paper manufacture
    • D21H23/26—Addition to the formed paper during paper manufacture by selecting point of addition or moisture content of the paper
    • 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
    • D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
    • D21H23/02—Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
    • D21H23/22—Addition to the formed paper
    • D21H23/52—Addition to the formed paper by contacting paper with a device carrying the material
    • D21H23/56—Rolls

Definitions

  • the present invention relates to new methods for surface treatment of wood-free Coating base papers, especially in glue and / or film presses, for targeted reduction the surface and structural embrittlement with the aim of processing problems how to avoid line breaking in the fold.
  • printing papers When producing wood-free, matt or glossy, multi-coated printing papers for offset printing, in addition to the properties of printability and printability important processing properties such as folding behavior also play an important role.
  • Such printing papers are usually produced according to the prior art, by coating base paper made from wood-free fibrous material (e.g. a mixture of hardwood and softwood pulp) and fillers in size or film presses by treatment with starch liquors is surface modified to provide good surface strength and printability to ensure. After that, pigment is applied one or more times (“Dash”) to provide the printing surface.
  • film-forming polymers such as e.g. Starch, polyvinyl alcohol (PVA) carboxymethyl cellulose (CMC), both as a thickener (see e.g. EP 455.073 A1, where fatty acid solutions from CMC are described as thickeners) as also used to modify the surface properties of paper.
  • PVA polyvinyl alcohol
  • CMC carboxymethyl cellulose
  • DE 195 03 745 A1 discloses printing paper for film production, the surface (s) of the base paper with film formers, e.g. (possibly modified) starch, CMC, PVA and galactomannan.
  • film formers e.g. (possibly modified) starch, CMC, PVA and galactomannan.
  • the present invention aims to provide paper for offset printing, in addition to good printability and printability, also improved folding behavior, i.e. reduced Occurrence of line breaks in the fold, shows without the cost of papermaking to increase.
  • this aim is achieved by a method for the surface treatment of Coating base paper reached, in which a solution based on instead of the usual starch liquor used by CMC.
  • anionic CMC solutions are combined in one Concentration range from 1% to 5% with a defined viscosity directly on a coating base paper applied, whereby the tensile strength and elasticity properties of the Coating base paper can be adapted to that of the coating material, which reduces tensile stress, local overextensions or signs of breakage in the surface are contained or even completely prevented.
  • the coating base paper can be conventional, wood-free, unsized or sized coating base paper in a basis weight range of 60-300 g / m 2 , ie the invention is applicable to a very wide basis weight range of printing papers.
  • the application of the CMC solution in the method according to the invention can be carried out by conventional means Glue or film presses take place, so that no conversion of existing or separate construction Attachments is required.
  • the structure and surface brittleness of coating base papers reduced to the extent that phenomena such as line breaking in the fold at one or multiple coated offset papers avoided or at least significantly restricted can be.
  • the process for the surface treatment of coating base paper is based on conventional coating base paper made from wood-free fibrous material and fillers.
  • the base paper usually consists of a mixture of hardwood and softwood pulp, preferably with a freeness of approx. 18-25 ° SR (i.e. significantly lower than the freeness of the paper for film production disclosed in DE 195 03 745 A1; 38-65 ° SR), and can have a basis weight in the range of 60-300 g / m 2 .
  • the filler content can also vary within wide limits, for example between 10% and 20%. Thus practically all common coating base papers of printing paper for offset printing can be surface-treated according to the invention.
  • double-coated paper with a final weight of 170 g / m 2 , including 60 g / m 2 coating; consisting of wood-free pulp, deciduous and softwood pulp in a mixture: 30-80% long fiber pulp (spruce sulfite and pine sulfate pulp) and 70-20% short fiber pulp (e.g. birch, beech, eucalyptus) - with a grinding degree of 18-25 ° SR and a filler content of 10-20%.
  • the paper was used in a standard size press with a vertical web guide aqueous CMC solution or starch liquor surface-treated in 3 concentrations, to apply the respective film formers (CMC or strength).
  • the CMC solutions were highly dilute solutions of technical Na-CMC, such as those caused by slow Pouring CMC granules into water in standard stirred tanks is easy can be.
  • the temperature is not particularly limited and depending on Web temperature, dissolution conditions and glue liquor circulation rate e.g. Values in the range conditions of around 25-60 ° C are possible without any problems of room temperature and atmospheric pressure.
  • the application pressure in the nip (nip) the size press was based on the desired order quantity.
  • the paper machine speed is also not particularly restricted, can be in one area from 50 m / min (laboratory) to 650 m / min (practice), however, can also be easily changed to higher ones Values such as 1,000 m / min, to be increased by the throughput and thus the Improve productivity.
  • Graphic 1 shows a comparison of the dry absorption of film formers by the paper (in g / m 2 ).
  • the basis for this is the setting of the suitable viscosity of the treatment solution and the selection of the most suitable CMC type (in terms of chain length / molecular weight), as shown in graphic 2 and table 2 below.
  • the concentrations of the CMC solutions were 1-5% (Brookfield viscosity at 100 min -1 in the range of 15-100 mPa.s).
  • Film maker Concentration % by weight
  • Viscosity mPa.s) (Water 0 0) Strength 3rd 23 Strength 6 42 Strength 9 69 CMC 1 18th CMC 2 30th CMC 5 94
  • the CMC solutions used have significantly higher viscosities have the same concentration as starch liquors, which leads to the above reduction in amount of film-forming agent penetrating into the coating base paper and therefore reduced Dry absorption leads.
  • the higher viscosity means an increased one Concentration of the film former on the surface, which leads to a better holdout for the subsequent stroke application and brings better printability with it.
  • the strength parameters in particular the splitting strength, remain in the ordered level due to the CMC treatment, as can be seen from graphic 3 and table 3 below.
  • Film maker Concentration % by weight
  • Gap resistance N
  • Strength 3rd 144
  • Strength 6 145
  • Strength 9 143
  • CMC 1 145
  • CMC 2 147
  • the gap strength values of the treated with CMC are Paper within a range of ⁇ 3% of the mean value of the starch treated Paper, are therefore quite comparable. These are gap strength values important as z-strength parameter especially for paper for offset printing.
  • This decrease in bending stiffness means that of surface treatment outgoing resistance to bending or folding even before the stroke reduced.
  • the starch-free surface treatment before the first coat application the tensile strength and Elastic properties of the base paper adapted to those of the coating material so that tensile stresses, local overstretching of the base paper or breakage in the surface can be contained or ideally completely prevented.
  • Figure 5 shows the relationship between the total starch content in the paper and the distribution of starch in the z direction (microtome sections with iodine staining). Papers with different starch concentration in the size press or different short fiber content in the base paper (with the same starch concentration) compared to the CMC-treated paper are shown.
  • microtome section shown for the CMC treatment is clearly a more homogeneous one Distribution of the overall reduced proportion of starch can be seen. Because of the missing Starch film on the surface can affect the elasticity of the paper structure or the folding behavior measurably improved.
  • the following graphics 6 and 7 are SEM images before and after the optimization of the paper by means of CMC treatment, viewed in the longitudinal and transverse directions.
  • the fold assessment was made visually using the school grade system from 1 to 5. The improvement but becomes most clear through the expansion of the groovability tolerance range of 2 possible settings - according to the FOGRA test for EAG 170 with 6% Strength - reflected in 7 possible settings for CMC-treated paper in the size press.
  • the inventive method Process for the production of coating base paper by treating the paper with CMC solutions instead of starch fleets base paper with a greatly reduced appearance from line break in the fold, better printability (better holdout for line application) wider groovability tolerance range, reduced dust tendency and simplified Manufacturing conditions can be provided without increasing costs.
  • the method according to the invention is characterized by diverse industrial applicability.

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  • Paper (AREA)

Abstract

A process for the surface treatment of coated paper comprises use of a solution of carboxymethylcellulose (CMC) in water instead of the usual starch liquor.

Description

Die vorliegende Erfindung betrifft neue Verfahren zur Oberflächenbehandlung holzfreier Streichrohpapiere, insbesondere in Leim- und/oder Filmpressen, zur gezielten Reduzierung der Oberflächen- und Gefügesprödigkeit mit dem Ziel, Verarbeitungsprobleme wie das Strichbrechen im Falz zu vermeiden.The present invention relates to new methods for surface treatment of wood-free Coating base papers, especially in glue and / or film presses, for targeted reduction the surface and structural embrittlement with the aim of processing problems how to avoid line breaking in the fold.

Bei der Herstellung holzfreier, matter oder glänzender, mehrfach gestrichener Druckpapiere für den Offsetdruck spielen neben den Eigenschaften der Be- und Verdruckbarkeit auch wichtige Verarbeitungseigenschaften wie das Falzverhalten eine bedeutende Rolle. Derartige Druckpapiere werden nach dem Stand der Technik üblicherweise hergestellt, indem Streichrohpapier aus holzfreiem Faserstoff (z.B. ein Gemisch aus Laub- und Nadelholz-Zellstoff) und Füllstoffen in Leim- oder Filmpressen durch Behandlung mit Stärkeflotten oberflächenmodifiziert wird, um gute Oberflächenfestigkeit und Bedruckbarkeit zu gewährleisten. Danach erfolgt ein- oder mehrfaches Auftragen von Pigment ("Strich"), um die Druckoberfläche bereitzustellen.When producing wood-free, matt or glossy, multi-coated printing papers for offset printing, in addition to the properties of printability and printability important processing properties such as folding behavior also play an important role. Such printing papers are usually produced according to the prior art, by coating base paper made from wood-free fibrous material (e.g. a mixture of hardwood and softwood pulp) and fillers in size or film presses by treatment with starch liquors is surface modified to provide good surface strength and printability to ensure. After that, pigment is applied one or more times ("Dash") to provide the printing surface.

Der obige Stärkeauftrag führt jedoch stets auch zu einer Versprödung des Papiergefüges aufgrund des unflexiblen Stärkefilms, die zum Brechen beim Falzen nach dem Druck führt. Ein einwandfreies und ästhetisch anspruchsvolles Druckerzeugnis (z.B. Broschüren, Folder etc.) darf aber beim Falzen nach dem Druck keine Bruch- bzw. Versprödungserscheinungen in der Falzkante zeigen. Dies gilt insbesondere für einen vollflächigen Druck höhergewichtiger Papiere (150 - 300 g/m2), bei dem das durch die zerstörte Strich- bzw. Druckfarbenschicht verursachte sichtbar Werden des weißen Rohpapiers als Papierfehler reklamiert wird.However, the above application of starch always leads to embrittlement of the paper structure due to the inflexible starch film, which leads to breaking when folding after printing. A perfect and aesthetically demanding print product (e.g. brochures, folders etc.) must not show any signs of breakage or embrittlement in the folded edge when folding after printing. This applies in particular to full-surface printing of high-weight papers (150-300 g / m 2 ), in which the visible appearance of the white base paper caused by the destroyed coating or printing ink layer is claimed as a paper defect.

Nach dem Stand der Technik werden filmbildende Polymere, wie z.B. Stärke, Polyvinylalkohol (PVA) Carboxymethylcellulose (CMC), sowohl als Verdickungsmittel (siehe z.B. EP 455.073 A1, wo Fettsäure-Lösungen von CMC als Verdicker beschrieben werden) als auch dazu eingesetzt, um die Oberflächenbeschaffenheit von Papier zu modifizieren. In the prior art, film-forming polymers such as e.g. Starch, polyvinyl alcohol (PVA) carboxymethyl cellulose (CMC), both as a thickener (see e.g. EP 455.073 A1, where fatty acid solutions from CMC are described as thickeners) as also used to modify the surface properties of paper.

In letzterem Zusammenhang offenbart die DE 195 03 745 A1 Druckpapier zur Folienherstellung, wobei die Oberfläche(n) des Rohpapiers mit Filmbildnern, wie z.B. (gegebenenfalls modifizierter) Stärke, CMC, PVA und Galaktomannan, beschichtet ist/sind.In the latter context, DE 195 03 745 A1 discloses printing paper for film production, the surface (s) of the base paper with film formers, e.g. (possibly modified) starch, CMC, PVA and galactomannan.

Das Problem des Strichbrechens im Falz bei Druckpapieren für den Offsetdruck wird dadurch jedoch nicht gelöst, da es sich um eine völlig andere Zielrichtung als bei der vorliegenden Erfindung handelt, die in dieser Veröffentlichung folglich auch gar nicht angesprochen wird. Darüber hinaus ergeben sich durch den Einsatz wässriger Dispersionen von Stärke und CMC Probleme aufgrund der Tatsache, dass der Filmbildner in solchen Dispersionen (oder auch Suspensionen) sorgfältig und mit starken Scherkräften eingerührt werden muss, um nicht zu Aggregation und Verklumpung zu führen, sowie dass Suspensions- bzw. Dispersionsmittel vonnöten sind, was die zur Herstellung benötigte Zeit und Kosten erhöht.The problem of line breaking in the fold in printing papers for offset printing will However, this does not solve it, since it is a completely different direction than the the present invention, which is consequently not at all in this publication is addressed. In addition, the use of aqueous dispersions results in of strength and CMC problems due to the fact that the film maker in such Dispersions (or suspensions) carefully and with strong shear forces must be stirred in so as not to lead to aggregation and clumping, and that suspending or dispersing agents are required, required time and costs increased.

Die vorliegende Erfindung zielt darauf ab, Papier für den Offsetdruck bereitzustellen, das neben guter Be- und Verdruckbarkeit auch verbessertes Falzverhalten, d.h. verringertes Auftreten von Strichbrechen im Falz, zeigt, ohne die Kosten der Papierherstellung zu erhöhen.The present invention aims to provide paper for offset printing, in addition to good printability and printability, also improved folding behavior, i.e. reduced Occurrence of line breaks in the fold, shows without the cost of papermaking to increase.

Dieses Ziel wird erfindungsgemäß durch ein Verfahren zur Oberflächenbehandlung von Streichrohpapier erreicht, worin anstelle der üblichen Stärkeflotte eine Lösung auf Basis von CMC verwendet wird. Dadurch werden die bei Stärke auftretenden Probleme der Versprödung bzw. überproportionaler Erhöhung der Biegesteifigkeit des Papiers wirkungsvoll vermieden, was eine Reduktion des Strichbrechens im Falz ermöglicht. Zudem wird der Holdout für weitere Oberflächenformulierungen und/oder Streichfarben und somit die Bedruckbarkeit verbessert.According to the invention, this aim is achieved by a method for the surface treatment of Coating base paper reached, in which a solution based on instead of the usual starch liquor used by CMC. This eliminates the problems with starch Embrittlement or disproportionate increase in the bending stiffness of the paper is effective avoided, which enables a reduction in line breaking in the fold. In addition becomes the holdout for further surface formulations and / or coating colors and thus improves printability.

In einer bevorzugten Ausführungsform werden anionische CMC-Lösungen in einem Konzentrationsbereich von 1 % bis 5 % bei definierter Viskosität direkt auf ein Streichrohpapier aufgetragen, wodurch die Zugfestigkeits- und Elastizitätseigenschaften des Streichrohpapiers denen des Strichmaterials angepasst werden können, was Zugspannungen, lokale Überdehnungen oder Brucherscheinungen in der Oberfläche eindämmt oder sogar gänzlich verhindert.In a preferred embodiment, anionic CMC solutions are combined in one Concentration range from 1% to 5% with a defined viscosity directly on a coating base paper applied, whereby the tensile strength and elasticity properties of the Coating base paper can be adapted to that of the coating material, which reduces tensile stress, local overextensions or signs of breakage in the surface are contained or even completely prevented.

Das Streichrohpapier kann dabei herkömmliches, holzfreies, ungeleimtes oder geleimtes Streichrohpapier in einem Flächengewichtsbereich von 60 - 300 g/m2 sein, d.h. die Erfindung ist auf einen sehr breiten Flächengewichtsbereich von Druckpapieren anwendbar.The coating base paper can be conventional, wood-free, unsized or sized coating base paper in a basis weight range of 60-300 g / m 2 , ie the invention is applicable to a very wide basis weight range of printing papers.

Der Auftrag der CMC-Lösung im erfindungsgemäße Verfahren kann mittels herkömmlicher Leim- oder Filmpressen erfolgen, so dass kein Umbau bestehender oder Bau gesonderter Anlagen erforderlich ist.The application of the CMC solution in the method according to the invention can be carried out by conventional means Glue or film presses take place, so that no conversion of existing or separate construction Attachments is required.

Erfindungsgemäß werden die Gefüge- und Oberflächensprödigkeit von Streichrohpapieren dahingehend reduziert, dass Phänomene wie das Strichbrechen im Falz bei ein-oder mehrfach gestrichenen Offsetpapieren vermieden oder zumindest deutlich eingeschränkt werden können.According to the invention, the structure and surface brittleness of coating base papers reduced to the extent that phenomena such as line breaking in the fold at one or multiple coated offset papers avoided or at least significantly restricted can be.

Die vorliegende Erfindung wird nachstehend unter Bezugnahme auf die eingefügten Grafiken detaillierter beschrieben, worin

  • Grafik 1 eine Balkengrafik ist, die einen Vergleich zwischen der Trockenaufnahme im Falle der Beschichtung mit Stärke gegenüber jener bei der erfindungsgemäßen Beschichtung mit CMC zeigt;
  • Grafik 2 einen ähnlichen Vergleich zwischen den Viskositäten der Beschichtungsflotte zeigt;
  • Grafik 3 wiederum einen ähnlichen Vergleich zwischen den erzielten Spaltfestigkeiten des Streichrohpapiers zeigt;
  • Grafik 4 wiederum einen ähnlichen Vergleich zwischen den erzielten geometrischen Steifigkeiten des Streichrohpapiers zeigt;
  • Grafik 5 einen Vergleich verschiedener Streichrohpapiere mit unterschiedlichem Stärkegehalt zusammen mit Mikrotomschnitten zeigt;
  • Grafik 6 rasterelektronenmikroskopische Aufnahmen eines Falzes vor der Optimierung des Papiers mittels CMC-Behandlung in Längs- und Querrichtung gesehen zeigt; und
  • Grafik 7 rasterelektronenmikroskopische Aufnahmen eines Falzes nach der Optimierung des Papiers mittels CMC-Behandlung in Längs- und Querrichtung gesehen zeigt.
    • The present invention is described in more detail below with reference to the inserted graphics, in which
  • Graph 1 is a bar graph showing a comparison between the dry absorption in the case of the coating with starch compared to that in the coating with CMC according to the invention;
  • Graph 2 shows a similar comparison between the viscosities of the coating liquor;
  • Figure 3 again shows a similar comparison between the achieved splitting strengths of the base paper;
  • Figure 4 again shows a similar comparison between the geometric stiffness of the base paper;
  • Figure 5 shows a comparison of different coating base papers with different starch content together with microtome sections;
  • Figure 6 shows scanning electron micrographs of a fold before optimization of the paper by means of CMC treatment seen in the longitudinal and transverse directions; and
  • Figure 7 shows scanning electron micrographs of a fold after optimization of the paper using CMC treatment seen in the longitudinal and transverse directions.

    • Das Verfahren zur Oberflächenbehandlung von Streichrohpapier geht von herkömmlichem Streichrohpapier aus holzfreiem Faserstoff und Füllstoffen aus. Üblicherweise besteht das Rohpapier aus einem Gemisch aus Laub- und Nadelholz-Zellstoff, vorzugsweise mit einem Mahlgrad von ca. 18-25° SR (also deutlich niedriger als die in der DE 195 03 745 A1 geoffenbarten Mahlgrade des Papiers zur Folienherstellung; 38-65° SR), und kann ein Flächengewicht im Bereich von 60-300 g/m2 aufweisen. Der Füllstoffgehalt kann ebenso in weiten Grenzen, z.B. zwischen 10% und 20%, schwanken. Somit können praktisch alle gängigen Streichrohpapiere von Druckpapier für den Offsetdruck erfindungsgemäß oberflächenbehandelt werden.The process for the surface treatment of coating base paper is based on conventional coating base paper made from wood-free fibrous material and fillers. The base paper usually consists of a mixture of hardwood and softwood pulp, preferably with a freeness of approx. 18-25 ° SR (i.e. significantly lower than the freeness of the paper for film production disclosed in DE 195 03 745 A1; 38-65 ° SR), and can have a basis weight in the range of 60-300 g / m 2 . The filler content can also vary within wide limits, for example between 10% and 20%. Thus practically all common coating base papers of printing paper for offset printing can be surface-treated according to the invention.

    Zur Veranschaulichung der Vorteile der Erfindung wurden die nachstehenden Versuche mit folgendem Papier durchgeführt: doppelt gestrichenes Papier mit einem Endgewicht von 170 g/m2, einschließlich von 60 g/m2 Strich; bestehend aus holzfreiem Faserstoff-Laub- und Nadelholzzellstoff im Gemisch: 30-80% Langfaserzellstoff (Fichtensulfit- und Kiefernsulfat-Zellstoff) und 70-20% Kurzfaserzellstoff (z.B. Birke, Buche, Eukalyptus)-mit einem Mahlgrad von 18-25° SR und einem Füllstoffgehalt von 10-20%. To illustrate the advantages of the invention, the following experiments were carried out on the following paper: double-coated paper with a final weight of 170 g / m 2 , including 60 g / m 2 coating; consisting of wood-free pulp, deciduous and softwood pulp in a mixture: 30-80% long fiber pulp (spruce sulfite and pine sulfate pulp) and 70-20% short fiber pulp (e.g. birch, beech, eucalyptus) - with a grinding degree of 18-25 ° SR and a filler content of 10-20%.

    Das Papier wurde jeweils in einer Standard-Leimpresse mit vertikaler Bahnführung mit wässriger CMC-Lösung bzw. Stärkeflotte in jeweils 3 Konzentrationen oberflächenbehandelt, um den jeweiligen Filmbildner (CMC bzw. Stärke) aufzubringen. Die CMC-Lösungen waren stark verdünnte Lösungen technischer Na-CMC, wie sie durch langsames Einbringen von CMC-Granulat in Wasser in Standardrührbehältern problemlos hergestellt werden können.The paper was used in a standard size press with a vertical web guide aqueous CMC solution or starch liquor surface-treated in 3 concentrations, to apply the respective film formers (CMC or strength). The CMC solutions were highly dilute solutions of technical Na-CMC, such as those caused by slow Pouring CMC granules into water in standard stirred tanks is easy can be.

    Obwohl die Temperatur nicht speziell eingeschränkt ist und in Abhängigkeit von Bahntemperatur, Auflösebedingungen und Leimflottenumwälzrate z.B. Werte im Bereich von etwa 25-60°C problemlos möglich sind, herrschten jeweils die Bedingungen von Raumtemperatur und Atmosphärendruck. Der Auftragsdruck im Nip (Walzenspalt) der Leimpresse richtete sich nach der gewünschten Auftragsmenge. Die Papiermaschinen-Geschwindigkeit ist ebenfalls nicht speziell eingeschränkt, kann in einem Bereich von 50 m/min (Labor) bis 650 m/min (Praxis) variieren aber auch problemlos auf höhere Werte, wie z.B. 1.000 m/min, angehoben werden, um den Durchsatz und somit die Produktivität zu verbessern.Although the temperature is not particularly limited and depending on Web temperature, dissolution conditions and glue liquor circulation rate e.g. Values in the range conditions of around 25-60 ° C are possible without any problems of room temperature and atmospheric pressure. The application pressure in the nip (nip) the size press was based on the desired order quantity. The paper machine speed is also not particularly restricted, can be in one area from 50 m / min (laboratory) to 650 m / min (practice), however, can also be easily changed to higher ones Values such as 1,000 m / min, to be increased by the throughput and thus the Improve productivity.

    Grafik 1 zeigt einen Vergleich der Trockenaufnahme an Filmbildner durch das Papier (in g/m2).

    Figure 00060001
    Graphic 1 shows a comparison of the dry absorption of film formers by the paper (in g / m 2 ).
    Figure 00060001

    Die Messwerte sind zur Übersicht erneut in folgender Tabelle 1 angeführt. Filmbildner Konzentration (Gew.-%) Trockenaufnahme (g/m2) (Wasser 0 0) Stärke 3 1,15 Stärke 6 2,05 Stärke 9 2,85 CMC 1 0,41 CMC 2 0,77 CMC 5 1,65 The measured values are listed again in Table 1 below for an overview. Film maker Concentration (% by weight) Dry absorption (g / m 2 ) (Water 0 0) Strength 3rd 1.15 Strength 6 2.05 Strength 9 2.85 CMC 1 0.41 CMC 2 0.77 CMC 5 1.65

    Die Daten aus Grafik 1 und Tabelle 1 zeigen, dass die Trockenaufnahme an Filmbildner durch das Papier unter Einsatz der unterschiedlich konzentrierten CMC-Lösungen gesenkt werden kann.The data from graphic 1 and table 1 show that the dry absorption on film formers lowered through the paper using the differently concentrated CMC solutions can be.

    Die Grundlage dafür ist die Einstellung der geeigneten Viskosität der Behandlungslösung und die Wahl der am besten geeigneten CMC-Type (hinsichtlich Kettenlänge/Molekulargewicht), wie folgender Grafik 2 und Tabelle 2 zu entnehmen. Die Konzentrationen der CMC-Lösungen lagen bei 1-5% (Brookfield-Viskosität bei 100 min-1 im Bereich von 15-100 mPa.s).

    Figure 00070001
    Filmbildner Konzentration (Gew.-%) Viskosität (mPa.s) (Wasser 0 0) Stärke 3 23 Stärke 6 42 Stärke 9 69 CMC 1 18 CMC 2 30 CMC 5 94 The basis for this is the setting of the suitable viscosity of the treatment solution and the selection of the most suitable CMC type (in terms of chain length / molecular weight), as shown in graphic 2 and table 2 below. The concentrations of the CMC solutions were 1-5% (Brookfield viscosity at 100 min -1 in the range of 15-100 mPa.s).
    Figure 00070001
    Film maker Concentration (% by weight) Viscosity (mPa.s) (Water 0 0) Strength 3rd 23 Strength 6 42 Strength 9 69 CMC 1 18th CMC 2 30th CMC 5 94

    Es ist zu erkennen, dass die verwendeten CMC-Lösungen deutlich höhere Viskositäten besitzen als Stärkeflotten der gleichen Konzentration, was zu der obigen Reduktion der in das Streichrohpapier eindringenden Menge an Filmbildner und daher zur verringerten Trockenaufnahme führt. Die höhere Viskosität bedeutet jedoch gleichzeitig eine erhöhte Konzentration des Filmbildners an der Oberfläche, was zu besserem Holdout für den nachfolgenden Strichauftrag führt und bessere Bedruckbarkeit mit sich bringt. It can be seen that the CMC solutions used have significantly higher viscosities have the same concentration as starch liquors, which leads to the above reduction in amount of film-forming agent penetrating into the coating base paper and therefore reduced Dry absorption leads. However, the higher viscosity means an increased one Concentration of the film former on the surface, which leads to a better holdout for the subsequent stroke application and brings better printability with it.

    Die Festigkeitsparameter, insbesondere die Spaltfestigkeit, bleiben durch die CMC-Behandlung im gerorderten Niveau, wie aus nachstehender Grafik 3 und Tabelle 3 ersichtlich.

    Figure 00080001
    Filmbildner Konzentration (Gew.-%) Spaltfestigkeit (N) (Wasser 0 144) Stärke 3 144 Stärke 6 145 Stärke 9 143 CMC 1 145 CMC 2 147 CMC 5 140 The strength parameters, in particular the splitting strength, remain in the ordered level due to the CMC treatment, as can be seen from graphic 3 and table 3 below.
    Figure 00080001
    Film maker Concentration (% by weight) Gap resistance (N) (Water 0 144) Strength 3rd 144 Strength 6 145 Strength 9 143 CMC 1 145 CMC 2 147 CMC 5 140

    Wie aus obigen Daten zu erkennen liegen die Spaltfestigkeitswerte des mit CMC behandelten Papiers innerhalb eines Bereichs von ± 3% vom Mittelwert des mit Stärke behandelten Papiers, sind also durchaus damit vergleichbar. Diese Spaltfestigkeitswerte sind als z-Festigkeitsparameter insbesondere für Papier für den Offsetdruck von Bedeutung.As can be seen from the above data, the gap strength values of the treated with CMC are Paper within a range of ± 3% of the mean value of the starch treated Paper, are therefore quite comparable. These are gap strength values important as z-strength parameter especially for paper for offset printing.

    Die Biegesteifigkeit nimmt aber durch die CMC-Behandlung im Mittel um rund 17% gegenüber der Stärkebehandlung ab, wie aus folgenden Daten der geometrischen Steifigkeit (Grafik 4 und Tabelle 4) ersichtlich.

    Figure 00090001
    Filmbildner Konzentration (Gew.-%) geometr. Steifigkeit (mN) (Wasser 0 520) Stärke 3 641 Stärke 6 649 Stärke 9 687 CMC 1 543 CMC 2 559 CMC 5 622 However, the CMC treatment reduces the bending stiffness on average by around 17% compared to the starch treatment, as can be seen from the following data on the geometric stiffness (Figure 4 and Table 4).
    Figure 00090001
    Film maker Concentration (% by weight) geometr. Stiffness (mN) (Water 0 520) Strength 3rd 641 Strength 6 649 Strength 9 687 CMC 1 543 CMC 2 559 CMC 5 622

    Durch diese Abnahme der Biegesteifigkeit werden die von der Oberflächenbehandlung ausgehenden Widerstandskräfte gegen Biegung bzw. Falzung bereits vor dem Strichauftrag herabgesetzt. This decrease in bending stiffness means that of surface treatment outgoing resistance to bending or folding even before the stroke reduced.

    Durch Verwendung von CMC-Lösungen wird zusätzlich die Staubneigung des Streichrohpapiers reduziert, da ansonsten auftretende "lose" Bestandteile der Stärkeflotte besser in das Rohpapier eingebunden werden.By using CMC solutions the tendency of the coating base paper to dust is additionally reduced reduced, since otherwise occurring "loose" components of the starch fleet are better be incorporated into the base paper.

    Insbesondere können aber durch den reduzierten Stärkegesamtanteil im Papier durch die stärkefreie Oberflächenbehandlung vor dem ersten Strichauftrag die Zugfestigkeitsund Elastizitätseigenschaften des Streichrohpapiers jenen des Strichmaterials angepasst werden, so dass Zugspannungen, lokale Überdehnungen des Rohpapiers oder Bruch in der Oberfläche eingedämmt oder im Idealfall gänzlich verhindert werden können.In particular, however, due to the reduced total amount of starch in the paper the starch-free surface treatment before the first coat application the tensile strength and Elastic properties of the base paper adapted to those of the coating material so that tensile stresses, local overstretching of the base paper or breakage in the surface can be contained or ideally completely prevented.

    Grafik 5 zeigt nachstehend den Zusammenhang zwischen dem Gesamtstärkegehalt im Papier und der Verteilung der Stärke in z-Richtung (Mikrotomschnitte mit lodanfärbung). Gezeigt werden Papiere mit unterschiedlicher Stärkekonzentration in der Leimpresse bzw. unterschiedlichem Kurzfaseranteil im Rohpapier (bei gleicher Stärkekonzentration) im Vergleich zum CMC-behandelten Papier.

    Figure 00100001
    Figure 5 below shows the relationship between the total starch content in the paper and the distribution of starch in the z direction (microtome sections with iodine staining). Papers with different starch concentration in the size press or different short fiber content in the base paper (with the same starch concentration) compared to the CMC-treated paper are shown.
    Figure 00100001

    In dem für die CMC-Behandlung gezeigten Mikrotomschnitt ist deutlich eine homogenere Verteilung des insgesamt reduzierten Stärkeanteils zu erkennen. Durch den fehlenden Stärkefilm an der Oberfläche kann die Elastizität des Papiergefüges bzw. das Falzverhalten messbar verbessert werden.The microtome section shown for the CMC treatment is clearly a more homogeneous one Distribution of the overall reduced proportion of starch can be seen. Because of the missing Starch film on the surface can affect the elasticity of the paper structure or the folding behavior measurably improved.

    Die folgenden Grafiken 6 und 7 sind REM-Aufnahmen vor bzw. nach der Optimierung des Papiers mittels CMC-Behandlung, jeweils in Längs- und Querrichtung gesehen.

    Figure 00110001
    Figure 00110002
    The following graphics 6 and 7 are SEM images before and after the optimization of the paper by means of CMC treatment, viewed in the longitudinal and transverse directions.
    Figure 00110001
    Figure 00110002

    Aus diesen Ansichten geht deutlich das wesentlich verbesserte Falzverhalten der Papiere nach der CMC-Behandlung hervor. Das Auftreten von Bruch im Falz kann durch die erfindungsgemäße Behandlung im Wesentlichen verhindert werden.These views clearly show the significantly improved folding behavior of the papers after the CMC treatment. The occurrence of breakage in the fold can be caused by the invention Treatment can essentially be prevented.

    Das Verarbeitungsverhalten der erfindungsgemäß behandelten Papiere ist gegenüber dem Stand der Technik ebenfalls verbessert, was durch nachstehende Tabelle 5 mit Prüfwerten des FOGRA-Tests für Standard- (d.h. mit Stärke behandeltes) und CMC-behandeltes Papier belegt wird. Nr. Sorte FLG |g/m2| Bemerkung Falz- Beurteilung Optimales Werkzeug Optimales Werkzeug Toleranz- Bereich Beurteilung FOGRA Längsnut Quernut 0 - 16 Nut Wulst Breite Tiefe Breite Tiefe L/Q L/Q 1 EAG 170 Standard 4 - 5 1,2 0,1 1,4 0,2 2 3/3 2/3 2 EAG 170 Neu (CMC) 3 1,0-1,2 0,1 1,1 - 1.3 0.2 7 2/2 2/3 The processing behavior of the papers treated according to the invention is also improved compared to the prior art, which is confirmed by the following table 5 with test values of the FOGRA test for standard (ie treated with starch) and CMC-treated paper. No. variety FLG | g / m 2 | comment Folding assessment Optimal tool Optimal tool Tolerance range Assessment FOGRA Longitudinal groove Cross groove 0-16 Groove bead width depth width depth L / Q L / Q 1 EAEC 170 default 4 - 5 1.2 0.1 1.4 0.2 2 3/3 2/3 2 EAEC 170 New (CMC) 3rd 1.0-1.2 0.1 1.1 - 1.3 0.2 7 2/2 2/3

    Die Falzbeurteilung erfolgte visuell mittels des Schulnotensystems von 1 bis 5. Die Verbesserung wird aber am deutlichsten durch die Erweiterung des Rillbarkeitstoleranzbereichs von 2 möglichen Einstellungen - gemäß dem FOGRA-Test für EAG 170 mit 6% Stärke - auf 7 mögliche Einstellungen für CMC-behandeltes Papier in der Leimpresse widergespiegelt.The fold assessment was made visually using the school grade system from 1 to 5. The improvement but becomes most clear through the expansion of the groovability tolerance range of 2 possible settings - according to the FOGRA test for EAG 170 with 6% Strength - reflected in 7 possible settings for CMC-treated paper in the size press.

    Zur Frage der Kosten wird abschließend festgestellt, dass die etwas höheren Kosten für die CMC im Vergleich zur herkömmlichen Stärkeflotte durch den geringeren Trockenauftrag bzw. die verringerte Penetration in das ungeleimte Rohpapier ausgeglichen werden, so dass hinsichtlich der Materialien Kostenneutralität gegeben ist. Aus den Vorteilen der einfacheren und rascheren Herstellung und Handhabung der CMC-Lösungen resultiert in Summe eine Kosten-Ersparnis gegenüber dem Stand der Technik. On the question of costs, it is concluded that the somewhat higher costs for the CMC compared to conventional starch fleets due to the lower dry application or compensate for the reduced penetration into the unsized raw paper, so that the materials are cost neutral. From the advantages the easier and faster production and handling of the CMC solutions overall, this results in cost savings compared to the prior art.

    Zusammenfassend kann somit festgestellt werden, dass durch das erfindungsgemäße Verfahren zur Herstellung von Streichrohpapier unter Behandlung des Papiers mit CMC-Lösungen anstelle von Stärkeflotten Streichrohpapier mit stark reduziertem Auftreten von Strichbruch im Falz, besserer Bedruckbarkeit (besserem Holdout für den Strichauftrag) weiterem Rillbarkeitstoleranzbereich, verringerter Staubneigung und vereinfachten Herstellungsbedingungen ohne Kostenerhöhung bereitgestellt werden kann. Nicht zuletzt, weil Papier in einem weiten Bereich von Flächengewichten erzeugt werden kann, ist das erfindungsgemäße Verfahren durch vielfältige gewerbliche Anwendbarkeit gekennzeichnet.In summary, it can thus be stated that the inventive method Process for the production of coating base paper by treating the paper with CMC solutions instead of starch fleets, base paper with a greatly reduced appearance from line break in the fold, better printability (better holdout for line application) wider groovability tolerance range, reduced dust tendency and simplified Manufacturing conditions can be provided without increasing costs. Not least, because paper can be made in a wide range of basis weights, the method according to the invention is characterized by diverse industrial applicability.

    Claims (4)

    Verfahren zur Oberflächenbehandlung von Streichrohpapier, dadurch gekennzeichnet, dass anstelle der üblichen Stärkeflotte eine Lösung von Carboxymethylcellulose (CMC) in Wasser verwendet wird.Process for the surface treatment of coating base paper, characterized in that a solution of carboxymethyl cellulose (CMC) in water is used instead of the usual starch liquor. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass wässrige anionische CMC-Lösungen in einem Konzentrationsbereich von 1 bis 5 % bei definierter Viskosität direkt auf ein Streichrohpapier aufgetragen werden.A method according to claim 1, characterized in that aqueous anionic CMC solutions in a concentration range of 1 to 5% at a defined viscosity are applied directly to a base paper. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass das Streichrohpapier holzfreies, ungeleimtes oder geleimtes Streichrohpapier in einem Flächengewichtsbereich von 60 - 300 g/m2 ist.Method according to claim 1 or 2, characterized in that the coating base paper is wood-free, unsized or sized coating base paper in a basis weight range of 60-300 g / m 2 . Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass der Auftrag der CMC-Lösung mittels Leim- oder Filmpresse erfolgt.Method according to one of claims 1 to 3, characterized in that the CMC solution is applied by means of a glue or film press.
    EP01890185A 2000-06-16 2001-06-13 Surface treatment of coating base paper Withdrawn EP1164220A1 (en)

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