EP1597432B1 - Dispersion de revetement utilisable de maniere multifonctionnelle pour des substrats d'impression - Google Patents

Dispersion de revetement utilisable de maniere multifonctionnelle pour des substrats d'impression Download PDF

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Publication number
EP1597432B1
EP1597432B1 EP03773607A EP03773607A EP1597432B1 EP 1597432 B1 EP1597432 B1 EP 1597432B1 EP 03773607 A EP03773607 A EP 03773607A EP 03773607 A EP03773607 A EP 03773607A EP 1597432 B1 EP1597432 B1 EP 1597432B1
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Prior art keywords
coating
coating dispersion
paper
previous
printing
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German (de)
English (en)
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EP1597432A1 (fr
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Josef Weigl
Christian Weigl
Konrad Goebel
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Weipatech GmbH
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Weipatech GmbH
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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
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/38—Coatings with pigments characterised by the pigments
    • D21H19/40—Coatings with pigments characterised by the pigments siliceous, e.g. clays
    • 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

Definitions

  • the invention relates to a coating color dispersion for coating print media, in particular paper and cardboard.
  • the printers are looking for the so-called cold-set printing further capacity utilization for the daytime existing capacity, but make some demands on the coated papers to be processed.
  • multipurpose typefaces and printing papers are described, used for copying and / or printed by means of offset and new ink printing methods.
  • the porosity of the paper structure thus influences, to a greater or lesser extent, some individual properties which are important for printing paper.
  • the mineral oil of the printing ink preferably penetrates into the paper with some binder, while the pigment with the remaining binder remains on the surface.
  • the specific surface area decreases, the separation efficiency or the chromatographic effect decreases and this leads to corresponding problems.
  • DE-A-4038886 discloses hydrous organophilic bentonite-based phyllosilicates for coating paper.
  • From DE-A-3506278 is a method for improving the holdout of printing inks, paints and coating compositions containing organic solvents, known on paper, in which an organophilic complex of a swellable smectic layered silicate and an onium compound is introduced into the pulp or into the surface of the paper, the organophilic complex forming a barrier layer by reaction with the organic solvent.
  • EP-A-0542215 discloses similar aqueous fine suspensions of an organophilic phyllosilicate consisting of a swellable, cation-exchangeable phyllosilicate and a quaternary organic onium salt reacted therewith and containing from 3 to 30% by weight, based on the organophilic phyllosilicate, of polyvinyl alcohol.
  • a coating color for a print carrier by the ink jet printing method is known, which is essentially characterized in that a three-layer silicate is modified by acid activation of an alkali or Erdalkalismektits or by incorporation of metal oxide bridges in the layer structure and about 10 Contains -50 parts by weight, preferably 20 to 25 parts by weight of binder and other additives.
  • a coating ink for a printing substrate by the ink-jet printing method which consists essentially of a montmorillonite having a high swelling power and optionally a high surface area pigment such as synthetic silicic acid or calcium carbonate, and a water insoluble Contains binder.
  • DE 4438305.3 describes a pigment for coating printing paper, in particular a pigment for carbonless paper based on an acid-activated alkali and / or Erdalkalismektits, which is characterized in that the alkali and / or Erdalkalismektit with at least a Brönstedt and / or Lewis acid is partially activated and has a content of amorphous silica of not more than 15 wt .-%.
  • EP0755989A2 describes a coating pigment mixture with improved low-pressure suitability of calcium carbonate, small amounts of swellable phyllosilicate and an acid-activated phyllosilicate, as well as rotogravure binders such as dispersing agents, thickeners and defoamers.
  • application weights 4-12 g / m 2 preferably 6-10 g / m 2 are given per page.
  • Coating pigments based on swellable, smectitic clays are also known from EP-A-0283300.
  • these coating pigments may contain up to 30% secondary or extender pigments, such as kaolin or calcium carbonate.
  • the pigment application is not more than 5 g / m 2 , preferably not more than 1 g / m 2 .
  • As the smectitic clay naturally occurring sodium bentonite (Wyoming bentonite) can be used, for example. This has a swelling capacity of 50 ml (2g in 100 ml of water).
  • EP 0688376B1 describes a process for producing a thin printing paper at high production speeds, which is suitable for both the offset and gravure printing processes.
  • a coating pigment which is fixable on paper and cardboard substantially without binders and results in deep and offset printable areas.
  • This pigment consists of at least 30% by weight of a swellable phyllosilicate and has a swelling volume of from 5 to 30 ml (based on a suspension of 2 g in 100 ml of distilled water).
  • swellable layered silicates especially minerals of the smectite group, preferably bentonite or synthetic hectorite are used.
  • the remaining 70% by weight of the coating pigment may consist of conventional coating pigments, such as kaolin, CaCO 3 , etc.
  • EP-A-0 785 307 a process for the production of coated web printing papers is known, which should lead to good printing results when printed with cold offset printing process.
  • the aim here is a certain water absorption or a surface printability, a Farbwegscher and a Bekk smoothness. This is to be achieved by a specific mixing ratio of conventional coating pigments, binders and other additives in the coating process.
  • a coating color dispersion for coating printing media in particular paper and cardboard, at least one of the predetermined proportions of water, a predetermined proportion of at least one swellable layered silicate and a predetermined proportion of a stabilized by adding at least one water-soluble polymer crosslinking agent, which is a chemical Binding both with at least one silanol group of the layered silicate, as well as at least one functional group of the base paper received.
  • water-soluble polymer crosslinking agent which is a chemical Binding both with at least one silanol group of the layered silicate, as well as at least one functional group of the base paper received.
  • chemical bonding is understood to mean at least one bond from the group of bonds having covalent bonds, hydrogen bonds, Vander-Waal bonds, ionic bonds, and the like.
  • the coating color dispersion is according to a particularly preferred embodiment on the print substrate of a surface-related, oven-dried mass (otro) between 0.5 and 6 g / m 2 , preferably between 0.6 and 5 g / m 2 , more preferably between 0.8 and 4 g / m 2 and according to a preferred embodiment, in particular ⁇ 4 g / m 2 applied.
  • otro surface-related, oven-dried mass
  • phyllosilicates such as bentonites, Alkali bentonites, such as Wyoming bentonite, montmorillonite, hectorite, saponite, nontronite, alkali phyllosilicates, Alkaline earth phyllosilicates, calcium bentonite and the like understood.
  • Bentonites are three-layer aluminosilicates in which the central AlO 6 octahedral layers are chemically linked to two SiO 4 tetrahedral layers. Isomorphous replacement of Al 3+ by, for example, Mg 2+ in the middle lamella produces negative layer charges, which are compensated by cations on interstitial sites. These cations are hydratable and thus mobile. Depending on the charge density, the exchange capacity is between 60 and 120 meq per 100 g. The high swelling volume causes a simple delamination of the bentonite into the individual lamellae, which leads to high viscosity and thixotropic flow behavior.
  • the aspect ratio of bentonite in the dry state is between 20 and 50 and theoretically increases to about 1000 after complete delamination. So here we are dealing with extremely thin, flexible platelets with a specific surface area of up to 750 have m 2 / g in suspension.
  • the main cause of the adhesion effect of strongly delaminated bentonites to fibrous materials is believed to be the formation of hydrogen bonds and, possibly, binding via van der Waals forces.
  • the delaminated bentonite and the fiber must be brought to each other during the dewatering process to this small distance.
  • a further aspect of the invention is thus the use of chemical aids that develop crosslinking reactions highly stable binding forces even when moistened with water.
  • alkaline activated bentonites show increasing crosslinking results with high strength values with increasing swelling or delamination and specific surface area.
  • Smectic phyllosilicates are e.g. Bentonite, montmorillonite, hectorite, saponite or nontronite. Bentonite and montmorillonite are preferably used from this series.
  • the swellability of the phyllosilicates is greater in the alkali-layer silicates than in the alkaline-earth layer silicates.
  • the natural alkali bentonites e.g., Wyoming bentonite
  • the natural alkali bentonites may be used as the swellable.
  • the required swelling capability can also be achieved by alkaline activation of alkaline earth metal silicates (eg.
  • Calcium bentonite are generated. Excessively high swelling power, however, gives high viscosity coating colors, so that the highly swellable phyllosilicates are generally added in minor proportions. The less swellable alkaline earth metal phyllosilicates can be added in higher proportions.
  • These layered silicates can be dispersed in aqueous suspension with shearing action largely in the individual lamellae and have a high proportion of SiOH groups or a high surface area.
  • a high swelling capacity with a high specific surface area ensures a good crosslinking reaction but with the production and manufacturing problems already described.
  • high-quality coated functional grades can also be produced with these layer silicates.
  • the phyllosilicates or alkaline-activated bentonites used for the purposes according to the invention are, for example, commercially available products such as Printosil, Lightcoat, Optigel 800 and Optigel 805.
  • Opigel 805 as a highly purified modified layered silicate (100% Na-montmorillonite) after extensive swelling or delamination exhibits swelling capacities of 70 ml / g, a specific surface area of approximately 700 m 2 / g and a Brookfield viscosity (100 rpm) of approximately 800 mPa ⁇ s at a dye content of 5%. Due to the low solids content, this product can only be used with so-called extenders or on slow-running production lines with appropriate base paper.
  • alkaline activated bentonites with solids contents between 5 to 30%, especially products between 12 to 27% at a Brookfield viscosity of about 100-700 mPa ⁇ s and a specific surface area after swelling of 100-700 m 2 / g , preferably used 200-500 m 2 / g.
  • the proportion of the layered silicate in the coating color dispersion is greater than 70% by weight of otro.
  • the solids content of the swellable phyllosilicate on the coating color dispersion is preferably from 5 to 35% by weight of otro, preferably from 8 to 20% by weight of otro. Furthermore, such a dispersion has a Brookfield viscosity which, at a speed of 100 rpm, is between 50 and 2000 mPa.s, and preferably between 250 and 1200 mPa.s. Furthermore, silicates with a high surface area also have a certain crosslinking reaction.
  • the crosslinking agent is understood to be at least one component from a group of components comprising wet strength agents such as formaldehyde, melamine-formaldehyde resins, aliphatic epoxy resins, epichlorohydrin resins, polyamide-polyamine-epichlorohydrin resins, zirconium compounds, glyoxal compounds, polyisocyanates, alkyl ketone dimers (AKD ), Alkyl succinic anhydrides (ASA) and polyvinylamines and the like.
  • wet strength agents such as formaldehyde, melamine-formaldehyde resins, aliphatic epoxy resins, epichlorohydrin resins, polyamide-polyamine-epichlorohydrin resins, zirconium compounds, glyoxal compounds, polyisocyanates, alkyl ketone dimers (AKD ), Alkyl succinic anhydrides (ASA) and polyvinylamines and the like.
  • zirconium salts e.g. Ammonium zirconium carbonate (AZC) predominantly with -COOH groups and only weakly react with -OH groups.
  • AZC Ammonium zirconium carbonate
  • HF resins MF resins
  • epichlorohydrin resins The effect of HF resins, MF resins and epichlorohydrin resins is mainly due to the fact that the products predominantly crosslink with themselves and thus protect the already existing fiber-fiber bonds from destruction by water.
  • UF resin As an example of the self-condensation reaction, UF resin can be shown. This is a three-dimensional network, which is also referred to in English usage as a cross-linked network (see Fig. 1).
  • this wet strength agent also reacts additionally with carboxyl, aldehyde or hydroxyl groups.
  • modified and stabilized glyoxal resins reactive polyhydroxylate compounds
  • glyoxal-polyacrylamide derivatives and polyisocyanates preference is given to reactions with OH groups which obviously can also react with SiOH groups (see FIG. 1).
  • the crosslinking agent used is glyoxal, in particular a modified glyoxal compound.
  • polyisocyanate is used.
  • crosslinking agent can be stabilized by the addition of at least one water-soluble polymer and / or changed in its charge character and / or in its interface properties or adapted to the required property criteria.
  • water-soluble polymers for example, polyvinyl alcohols, polyethylene glycols, polyvinylpyrrolidone and the like are used.
  • otro Based on the proportion of crosslinking agent, according to a particularly preferred embodiment, from 2 to 10% by weight of otro, preferably from 4 to 7% by weight, of otro are added to polyvinyl alcohol.
  • the crosslinking agent a proportion of from 2 to 6 wt .-% otro, preferably between 3 to 5 wt .-% otro of polyethylene glycol, based on the crosslinking agent, admixed.
  • the crosslinking agent can be admixed with further additives or additives which, according to a particularly preferred embodiment, are selected from the group of additives which include optical brighteners, thickeners, biocides, preservatives, buffer solutions, catalysts, inhibitors, Dispersants, complexing agents and the like.
  • the crosslinking agent 0.1 to 1 wt .-% commercial goods (HW), preferably added between 0.2 and 0.4 wt .-% commercial goods of optical brightener.
  • a proportion of crosslinking agent is between 0.1 to 6 wt .-% otro, based on the pigment, preferably between 0.6 and 7.4 wt .-% otro, based on the pigment, and particularly preferably between 0.8 and 3 wt .-%, based on the pigment admixed.
  • the coating color dispersion is admixed with at least one extender pigment selected from a group of pigments comprising precipitated silicate, acid-activated bentonites, hydrothermally-produced silicates, aluminum hydroxides and the like.
  • the coating color dispersion is admixed with at least one further pigment selected from a group of pigments comprising kaolin, ground calcium carbonate, precipitated calcium carbonate, talc, zeolite, titanium dioxide and the like.
  • alkaline activated bentonites can be interspersed with these coating pigments, depending on the desired paper properties 5 and 20 parts preferably between 8 and 15 parts without addition of binder with 0.8 to 3 parts of modified crosslinker at application weights between 0.8 to 4 g / m 2 produce a functional line that provides good printing results in all printing processes.
  • the solids content of the coating composition to be processed is between 12 and 35 wt .-% otro.
  • the area-related application weight is in any case below 4 g / m 2 and paper side.
  • An application weight of between 0.8 and 4 g / m 2 and side is preferred.
  • the order amount may be less than 0.8 g / m 2 .
  • the above-described coating color dispersion may additionally be admixed with a binder selected from a group of binders containing synthetic binders, natural binders, polyvinyl alcohol, starch, carboxymethyl cellulose, latex and the like.
  • a binder selected from a group of binders containing synthetic binders, natural binders, polyvinyl alcohol, starch, carboxymethyl cellulose, latex and the like.
  • a binder content between 0.5 and 10 wt .-% otro, preferably between 1 and 7 wt .-% otro and particularly preferably between 1, Used 5 and 5 wt .-% otro.
  • a binder content between 0.5 and 10 wt .-% otro, preferably between 1 and 7 wt .-% otro and particularly preferably between 1.5 and 5 wt .-% otro used.
  • the fraction of the binder fraction used in the coating color dispersion tends to be lower than the required binder amount when using another pigment, as described above.
  • bonding takes place both with the phyllosilicate and with fibrous materials or hydrocolloids, such as starch, guar, carboxymethylcellulose (CMC), polyvinyl alcohol and the like.
  • fibrous materials or hydrocolloids such as starch, guar, carboxymethylcellulose (CMC), polyvinyl alcohol and the like.
  • the functional groups of the crosslinking agent react with the functional groups of the swellable phyllosilicates, in particular the silanol groups. Furthermore, the functional groups of the crosslinking agent react with the functional groups of the print carrier such as the pulp, in particular with its free hydroxyl groups.
  • the functional groups of the crosslinking agent are free hydroxyl groups.
  • Free hydroxyl groups are understood as meaning, in particular, binding-active groups (see FIG. 2).
  • the functional groups of the crosslinking agent are free aldehyde groups.
  • Fig. 2 shows the reaction of glyoxal compounds with OH groups.
  • Glyoxal-polyarcylamide derivatives are obtained by a reaction of glyoxal with low molecular weight polyacrylamide (PAM) to give a network (matrix) structure and with a relatively high aldehyde group content (see FIG. 3).
  • PAM low molecular weight polyacrylamide
  • crosslinking agent can also be used for bonding the phyllosilicates or the pulp and / or hydrocolloids.
  • the crosslinking agent causes a temporary solidification of the print carrier and / or the bar, which in particular already occurs in the manufacturing process in the paper machine and / or the coating machine.
  • the pH of the coating color dispersion is between pH 6 and pH 9.5, preferably between pH 6.8 and pH 9.2, and particularly preferably between pH 8.1 and pH 9.0.
  • the print carrier used is a paper or board produced from wood-free fibrous material, the use of further components, such as, for example, fillers, brand, etc., also being within the meaning of the present invention.
  • the print carrier can also be made essentially of wood-containing fibrous material.
  • the print carrier is made of a freely selectable fraction of waste paper between 0 and 100%. produced.
  • the fibrous materials described above it is also within the meaning of the present invention to use combinations of the fibrous materials described above.
  • the print carrier has, according to a particularly preferred embodiment, a basis weight between 30 g / m 2 otro and 250 g / m 2 otro, preferably between 32 g / m 2 otro and 130 g / m 2 otro and more preferably between 35 g / m 2 otro and 100 g / m 2 otro.
  • base paper wood-free wood-containing and up to 100% waste paper contained base paper is also suitable with low surface masses.
  • the unsuitable base paper is very hydrophobic paper, i. highly sized mass and surface glued base papers.
  • highly sized mass and / or surface-coated base papers are understood papers which are referred to in the prior art as vollgeleimte papers.
  • the coated paper made with various layered silicates, as well as blends with other coating pigments and 0.8 to 3.0 parts of the crosslinker compound without binder on a base paper with 100% waste paper shows good printing results and further processing properties in all printing processes. Furthermore, the crosslinkers give in particular an increase in the strength of the base paper
  • Matt coated papers are most commonly used in offset printing because this printing process is able to even out the rough surface with the help of a rubber elastic blanket. Lately matte coated papers have also been gaining increasing market share in gravure printing. The gravure requires a very smooth surface and good compressibility of the papers. For a good printability, therefore, a high smoothness of the paper is of central importance, which stands in contradiction - due to the strong calendering conditions - to the demand for low gloss.
  • micro-roughness of the surface achieved by the layered silicates which is retained even with very strong calendering, which in turn ensures high surface smoothness and good rotogravure printability, promotes the desired diffuse reflection of the light and thus the matt effect.
  • Matt-coated paper with high surface smoothness makes it possible to brilliantly reproduce reproductions even with fine grids in offset printing and letterpress printing, which extends the field of application of such a paper from car, fashion and cosmetic brochures, school textbooks and catalogs.
  • Multi-purpose writing and printing papers are described, used for copying and printed by offset and inkjet printing methods.
  • Office papers must take this development into account, and in addition to the primary suitability for copiers, also have good offset, laser and color inkjet printability.
  • the paper manufacturer should therefore have a fully functional Deliver the product that meets all requirements, all printer types and all ink formulations.
  • the high microcapillarity or specific surface area of the functional bar results in excellent inkjet printability in color printouts with good color brilliance, optical density of the colors and dot sharpness.
  • These papers are also characterized by a fast color drying and higher water resistance. Since water-based flexographic printing is the same printing ink, i. anionic water-soluble dyes, the high specific surface area of the thin-line has a positive effect on the print quality of the flexo print as it does on the inkjet.
  • the acid anionic, water-soluble inks of inkjet and flexo inks are anchored to the surface by rapid adsorption.
  • the high capillarity of the pigments promotes the separation of dyes and liquid by the chromatographic effect.
  • the larger dye molecules remain on the pigment surface, while smaller molecules, especially water and additives, are drawn into the interior of the pigments by the capillary forces. This requires a high microcapillarity (specific surface area) with defined pore radius and / or improved water resistance.
  • the swollen sheet silicates and thus the coating applied to the outer layer of the print carrier absorb heat-related pollutant emissions of the print carrier, such as are released during the temperature treatment in the laser printing process for fixing the toner.
  • DIPN Diisopropylnaphthalene
  • bentonites have the special property of binding foreign substances, odors and flavorings, especially aromatics, and rendering them harmless.
  • the bilateral bentonite layer of the functional line according to the invention with the high specific surface acts as an adsorption barrier and thus leads to a strong relief of the pollutant concentration on laser printers and copiers.
  • coated paper requires high capillarity or an open structure.
  • the functional coating gives a fast immobilization of the subsequent coating with the known advantages, a good fiber coverage with barrier function with uniform stroke distribution of the top coat and cost savings due to the high specific surface area. With Linerkarton, this barrier function can be further improved by adding a small amount of sizing agent to the functional coating.
  • the functional line shows, especially at low basis weights, higher smoothness, lower missing dots, higher print gloss with low paper gloss, no gloss (friction) during further processing and cost advantages.
  • LWC offset matte papers have low paper gloss, high gloss, high smoothness, no gloss (gloss), better ink rub resistance and smudge resistance, lower carbonization, lower mottling, higher residual crush strength (avoid breakage in the seam), avoid blistering and lower line costs achieved.
  • Preference falz mecanic occurs with increasing coating order, with CaCO 3 as a coating pigment, high binder contents (especially starch) and high calendering conditions.
  • the invention further provides that the invention, thin, functional order quantities on a base paper not only high quality grades result in all printing processes, but also due to the low application rate, high production speeds and binder savings and economic benefits in all cases can be achieved.
  • a further aspect of the invention is that the coated paper according to the invention has an excellent recycling behavior, since it contains no synthetic binders and the crosslinkers used have a temporarily solidifying action and thus after brief exposure to water to the coated paper in contrast to other Verrietzern such as HF, MF, Epichlorhydrinharze is easily processed.
  • an aspect of the invention a method for producing a multifunctional coated paper by applying a low reactive coating layer based on alkaline activated bentonites between 0.8 to max. 4 g / m 2 per side, without binder with high binding capacity by crosslinking reactions with special crosslinkers on a base paper with up to 100% waste paper content with a film press, curtain coater or possibly spray application at production speeds up to 2000 m / min, both for Conventional printing processes as well as in the specialty paper sector comparable, if not better print quality and combines economic advantages with excellent recyclability.
  • the object of the invention is also achieved by a method for producing a coated print carrier according to claim 17.
  • Preferred embodiments are subject of the dependent claims.
  • a method of making a coated print carrier comprises the step of machine coating a spread color dispersion on the print carrier.
  • the coating color dispersion consists of at least a predetermined proportion of water, a predetermined proportion of at least one swellable layered silicate and a predetermined proportion of stabilized by adding at least one water-soluble polymer crosslinking agent, which is a chemical bond both with at least one silanol group of the layered silicate, as well as with at least a functional group of the base paper.
  • the process also includes the drying of coated coating color dispersion.
  • the print substrate after painting and printing satin.
  • the application of the coating color dispersion is carried out according to a particularly preferred method of the present invention Invention inside (online) and / or outside (offline) the paper machine.
  • the applicators used are those known from the prior art applicators, which includes, for example, film presses, curtain coater, spray application, roller coating, Rackelstreichvon, blade coater, speed coater, Massey method, Flooded-Nip and the like.
  • Suitable aggregates offered on the market are, for example, the film presses from Jagenberg, from Voith and BTG from Sweden and Metso.
  • the produced coating colors can be applied both online with a film press, but also with new application systems such as curtain coating and spray application (Opti-Spray) with application weights of 0.5 - 4 g / m 2 at high speed.
  • curtain coating and spray application Opti-Spray
  • the process represents an alternative to the conventional application process with forward-looking high-precision application technology, which promises high production speeds with low paper web load.
  • the Opti-Spray application system is a spray process that is also preferred for such thin coating jobs.
  • the coating speed of the coating color dispersion is carried out according to a further particularly preferred embodiment at a speed between 150 m / min and 2300 m / min, preferably between 200 m / min and 2100 m / min and more preferably between 500 m / min and 2000 m / min.
  • a coating color dispersion is applied to the print substrate whose basis weight is between 0.5 and 6 g / m 2 otro, more preferably between 0.8 and 4 g / m 2 otro and according to another particularly preferred embodiment is in particular less than 4 g / m 2 otro.
  • the print substrate prepared according to this method using the described coating colors and / or dispersion is suitable for processing in at least one, in particular a plurality of (multifunctional) printing processes, as known in the art.
  • These may be, for example, the offset printing method, the gravure printing method, inkjet method, flexo printing method, carbonless copying papers, heat set method, cold set method, laser printing method and the like.
  • the print carrier is multifunctional for various methods.
  • the invention is illustrated by the following examples in a non-limiting manner.
  • the base paper used was a 48 g / m 2 wood-containing, unsized LWC base paper and a 48 g / m 2 LWC base paper made with 100% waste paper.
  • the bentonite slurries were applied by means of a motorized hand doctor blade (Erichsen K Conrol Coater) to wood-containing or AP-containing base paper with an application rate of 1 g / m 2 .
  • the thus surface-treated paper is calendered in a laboratory calender under the following conditions.
  • Embodiment 2 relates to the production of a thin-layer paper with alkaline activated bentonite different delamination with small amounts of binder.
  • An automatic laboratory cooker was used to loosen the PVA and to digest starch.
  • the dispersion of the pigments was carried out in a high shear dispersing device (laboratory disperger with toothed disk).
  • a laboratory mixer with propeller stirrer was used, with the methods mentioned in Example 1 being used to measure the rheological properties.
  • the pigments used were Printosil and Lighcoat (manufacturer Süd-Chemie, Kunststoff). After dispersing or delamination of the bentonites (see Example 1), the respective binder amounts in parts by weight of otro were added. The pH values were between 8.0 and 9.0.
  • the produced coating colors were applied with a heliocoater to a base paper with 100% AP material and a basis weight of 48 g / m 2 .
  • This plant is the Helicoater 2000 of the company ECC (English China Clays), which is designed for the Schaberstheimvon.
  • a highly concentrated coating color is transferred to the paper web by means of a spatula-type metal blade which is pressed against a rubber-coated cylinder.
  • the carrier roll on which the paper to be spread is clamped, consists of a hollow cylinder made of steel, which is additionally supported on the inside by ribs.
  • the side parts are made of welded steel plates. On this cylinder a layer of hard rubber is applied.
  • the roller can be accelerated up to a peripheral speed of 2000 m / min.
  • the traversing pond serves as a paint container and paint application system, making it the heart of the system.
  • the rear helicoater flap contains the infrared drying unit. This consists of several rows of IR emitters, with which the paper is dried after brushing.
  • the coating colors were applied at a speed of 600 m / min.
  • the thus surface-treated paper is calendered in a laboratory calender under the following conditions: Roll surface temperature: 90 ° C Line force: 250 N / mm Speed: 10 m / min Number of passes: 4
  • a cationization of PVAl also has a detrimental effect on the development of strength.
  • the impact behavior slows down (over 1800), which possibly leads to deposition in sheetfed offset.
  • Embodiment 3 relates to the use of wet strength agent (crosslinker) for improving the offset ability of thin-layer papers
  • coated papers and cardboard often comes into contact with water.
  • offset papers in the printing press are exposed to the dampening water.
  • packaging papers are exposed to moisture or moisture during transport.
  • coated inkjet papers also a certain wet strength of the stroke is required.
  • wet strength agents are capable of undergoing crosslinking reactions with the SiOH groups of the alkaline activated bentonites, thus making an important contribution to setting the pigment particles together and the pigment particles to the base paper.
  • test results indicate that, surprisingly strong cross-linking reactions between the modified glyoxal, the SiOH groups of the bentonite and the OH - groups is of the fibers.
  • Embodiment 4 relates to modified glyoxal (Cartabond TSI) optimization works for developing a thin line without binder moieties.
  • Cartabond TSI Further optimization with Cartabond TSI showed that at pH values greater than pH 9 and / or increasing temperatures, especially at longer residence times, an increasing viscosity is observed, which in practice leads to processing problems. This effect was more pronounced when added to carriers of PVAl based optical brighteners.
  • the pigments used were Printosil and Lightcoat (manufacturer Süd-Chemie, Kunststoff).
  • the coating colors produced without dwell times were applied to a base paper with a helicoater (see Example 2) applied with 100% AP material and a basis weight of 48 g / m 2 .
  • the thus surface-treated paper is calendered in a laboratory calender according to Embodiment 1.
  • the embodiment 5 relates to the investigation of the offset ability of different silicates with different specific surface by crosslinking reactions with "glyoxal compound”.
  • kaolin (CamCoat 80 manufacturer Amberger Kaolinwerke E. Kick GmbH) with 12 m 2 / g, an acid-activated bentonite (Copisil N401 manufacturer Süd-Chemie, Kunststoff) with a surface area of about 340 m 2 / g and a precipitated Na alumium silicate (Zeocopy manufacturer JM Cooperation) with a surface area of about 200 m 2 / g used for the investigations.
  • Example 2 After dispersion (see Example 1) with 0.3 dispersant (polyacrylate-based) and pH adjustment with sodium hydroxide to 8.5, in each case 2% of crosslinker glyoxal compound were added.
  • the pigment slurry was applied as in Working Example 1 by means of a doctor blade to an AP-containing base paper (48 g / m 2 ) with an application rate of 3 g / m 2 .
  • the thus surface-treated paper is calendered in a laboratory calender according to Embodiment 1.
  • the embodiment 6 shows the suitability of various coating base papers for the production of multifunction papers.
  • base paper was a 48 g / m 2 wood-containing, unsized LWC-base paper, a weakly sized, wood-containing 54 g / m 2 base paper, a wood-free, unsized 70 g / m 2 base paper, a woodfree, weakly sized 80g / m 2 base paper and a wood-free, strongly sized (mass and surface sizing with a synthetic hydrophobing agent) used 82 g / m 2 base paper.
  • the suitability of coated base paper with 100% waste paper for a multi-function paper has already been provided in the embodiments 3 and 4.
  • Example 2 For the investigations, an alkaline activated bentonite (Lightcoat manufacturer Süd-Chemie München) was used, which was prepared as described in Example 1 and applied with a helicoater, as described in accordance with Example 2.
  • the crosslinkers used were 1.7% otro glyoxal compound.
  • the pH was adjusted to 8.8.
  • the solids content was 14.2% at a Brookfield viscosity (100) of 690 mPa ⁇ s.
  • the thus surface-treated paper is satinized as described in Example 1 and evaluated the offset ability.
  • the tested base papers are all suitable for the thin slab according to the invention except for the heavily sized h.f. Coating base. This causes wetting problems, i. it was not possible to apply the desired amount of application.
  • coated papers also achieved excellent inkjet printability with the HP CP 1160, HP 895CXI, Epson C 80 and Canon J 750 printers.
  • Embodiment 7 relates to the determination of the boundary regions of pigment mixtures with alkaline activated bentonite for the production of multifunction paper.
  • the following coating pigments were also used for the investigations: kaolin (Camcoat 80 manufacturer AKW-Kick), ground calcium carbonate GCC (Hydrocarb producer Omya, precipitated calcium carbonate PCC (Socal P2 manufacturer Solvay) precipitated Al silicate (Zeocopy manufacturer JMHuber Corporation) and a synthetic calcium hydrates (Circolit manufacturer Cirkel) produced by the hydrothermal process Lightcoat (manufacturer Süd-Chemie, Kunststoff) was used as the alkaline activated bentonite.
  • the delaminated and dispersed bentonite (see Example 1) is initially charged and the respective coating pigment is added slowly while stirring in the desired amount.
  • 1% of PVAl (Mowio13-83) as carrier and 0.5% optical brightener (Leukophor AL manufacturer Clariant) were added.
  • 2.5% of otro glyoxal compound crosslinker was added.
  • the pH was adjusted to 8.8 with sodium hydroxide solution.
  • the pH was adjusted with hydrochloric acid to pH 8.8.
  • the coating colors produced were applied with a helicoate as described in Example 2 to a base paper with 100% AP material and a basis weight of 48 g / m 2 . In each case 2g / m 2 were applied.
  • the thus surface-treated paper is satinized in a laboratory calender according to Embodiment 1 Table 7: Assessment of dry and wet pick resistance (offset) No. Pigment mixtures: Solids content [%] Viscosity Brookfield 100 [mPa.s] wet pick resistance dry pick 1 100T Lightcoat 14.6 880 + + 2 90T Lightcoat + 10T Kaolin Camcoat 80 17.2 920 + + 2a 80T Lightcoat + 20T Kaolin Camcoat 80 20.6 1100 (+) + 3 90T Lightcoat + 10T nat. CaCO 3 Hydrocarb 90 18.8 790 + + 3a 80T Lightcoat + 20T nat. CaCO 3 Hydrocarb 90 23.2 960 (+) + 4 90T Lightcoat + 10T Prec.
  • Table 8 shows the test results of the paper test and Table 9 shows the results of the offset suitability of the chopped papers. Further, evaluation of printability was carried out in gravure, flexo, inkjet, laser and carbonless (SD).
  • Table 8 Paper test (Example 7) Paper no.
  • Printing machine W + 4 Printing ink: Michael Huber, water-based
  • the evaluation of the papers examined showed good flexographic printability on all papers with somewhat lower print gloss and density values compared to a standard flexographic printing paper.
  • the coated papers 2a, 4a and 6 showed somewhat better print gloss and density values.
  • the results of the investigation showed that the "smear" of the thin-layer papers provides excellent inkjet printability on both HP CP 1160, HP 895 Cxi, HP 950, Epson C 80, and Canon J750, which is significantly superior to conventionally coated and surface-glued papers differ in terms of color brilliance, optical density of colors, dot sharpness, bleeding and mottling.
  • the thin-strip papers are also characterized by rapid color drying (increase in smudge resistance) and higher water resistance.
  • the inkjet printing results of the thin-strip papers are very much influenced by the inks, in addition to the type of printer used.
  • the Canon BJ2000 a good color brilliance is achieved due to an unpigmented ink, but this tends to cause the ink to bleed a lot, which leads to some bleeding and bleeding.
  • a glued paper With a glued paper, on the other hand, with the function bar, an excellent inkjet result could be achieved.
  • a significant improvement could be achieved by the addition of 0.2% AKD.
  • the painted patterns 4a, 5a and 6 showed the best results.
  • the pattern 5a comes very close to the standard quality.
  • Embodiment 8 relates to coating experiments which were carried out on a high-speed pilot coating unit on a 1: 1 scale.
  • a thickener (Sterocoll SL, manufacturer BASF Ludwigshafen) was additionally used.
  • the base papers used were a paper based on 100% paper pulp having a basis weight of 54 g / m 2 and a highly surface-sized wood-free base paper with a weight per unit area of 80 g / m 2 .
  • the production speed was not at the planned 1800 m / min at V1 and V2, because problems arose because of too high residual moisture or too low solids content of the coating colors (drying problem). Stable running was possible up to 1000 m / min.
  • V5 could not transfer more than 0.5 g / m 2 to the paper web.
  • coated papers V1-V6 were calendered on the supercalender under the following conditions: speed 600 m / min line load 180 kN / m temperature 90 ° C
  • Embodiment 7 Gravure printability was determined by M. Huber Maschinenwerke on a printing machine (Testacolor) with an S.W. (Illustrative gravure ink, toluolbasierend) performed. The LWC offset and rotogravure papers were each checked only for the intended printability.
  • Inkjet printability was performed on an HP CP1160, HP 895Cxi, Epson C80 and Canon J 750 printers.
  • an offset capability is achieved, for example, from an LWC offset paper with 12 parts binder and a coat application of 7 g / m 2 .
  • the binder-free coating layer with high specific surface area also ensures good gravure, flexo and inkjet printability.

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  • Paper (AREA)
  • Developing Agents For Electrophotography (AREA)
  • Fittings On The Vehicle Exterior For Carrying Loads, And Devices For Holding Or Mounting Articles (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Claims (20)

  1. Dispersion de couchage pour couchage de substrats d'impression en particulier de papier et carton avec au moins :
    - une part prédéterminée d'eau
    - une part prédéterminée d'au moins un phyllosilicate capable de gonflement ;
    - une part prédéterminée d'un agent de réticulation qui est stabilisé par l'ajout d'au moins un polymère soluble dans l'eau et qui forme une liaison chimique avec au moins un groupement fonctionnel de phyllosilicate et aussi avec au moins avec un groupement fonctionnel du substrat d'impression, particulièrement du papier de base.
  2. Dispersion de couchage selon la revendication 1 caractérisé en ce que
    le poids de couchage par page sur le substrat d'impression est entre 0,5 et 6 g/m2 sec absolu de préférence entre 0,8 et 4 g/m2 sec absolu et en particulier inférieur à 4 g/m2 sec absolu.
  3. Dispersion de couchage selon au moins une des revendications précédentes caractérisé en ce que
    le phyllosilicate capable de gonflement est au moins un phyllosilicate smectique d'un groupe de phyllosilicate qui comprend les bentonites, les bentonites alcalines, comme par exemple la bentonite Wyoming, la montmorillonite, l'hectorite, la saponite, la nontronite, le phyllosilicate alcalin, le phyllosilicate alcalino terreux, comme la bentonite de calcium etc.
  4. Dispersion de couchage selon au moins une des revendications précédentes caractérisé en ce que
    le phyllosilicate est activé où l'activation en particulier est atteinte par l'ajout d'une solution aqueuse de soude caustique et/ou par une dispersion mécanique à une viscosité prédéterminée.
  5. Dispersion de couchage selon au moins une des revendications précédentes caractérisé en ce que
    l'agent de réticulation comprend un composant issu d'un groupe de composants qui comprend des agents résistants à l'humidité comme le formaldéhyde (UF), les résines mélamine formaldéhyde, les résines époxy aliphatique, les résines épichlorhydrine, les résines épichlorydrine polyamide polyamine (PAMMAM-EPI), les composés de zirconium, les composés de glyoxal, les polyisocyanates, les dimères de cétone d'alkyle (AK), les anhydrides succincts d'alkyle, les polyvinylamines et identique.
  6. Dispersion de couchage selon au moins une des revendications précédentes caractérisé en ce que
    l'agent de réticulation est du glyoxal en particulier un composé de glyoxal modifié.
  7. Dispersion de couchage selon au moins une des revendications précédentes caractérisé en ce que
    à l'agent de réticulation est mélangé une part entre 2 et 10 pds. % sec absolu, de préférence entre 4 et 7 pds % sec absolu d'alcool polyvinylique (PVAL).
  8. Dispersion de couchage selon au moins une des revendications précédentes caractérisé en ce que à l'agent de réticulation est mélangé une part entre 2 et 6 pds. % sec absolu, de préférence entre 3 et 5 pds % de glycol polyéthylenique (PEG).
  9. Dispersion de couchage selon au moins une des revendications précédentes caractérisé en ce que
    à la dispersion de couchage est mélangé au moins un pigment diluant qui est choisi parmi un groupe de pigments qui comprend le silicate précipité, la bentonite activée à l'acide, le silicate produit à base d'un process hydrothermal, la zéolithe, l'hydroxyde d'aluminium et identique.
  10. Dispersion de couchage selon au moins une des revendications précédentes caractérisé en ce que
    à la dispersion de couchage est mélangé au moins un pigment diluant (autre pigment) qui est choisi parmi un groupe de pigments qui comprend le kaolin, le carbonate de calcium broyé (GCC), le carbonate de calcium précipité (PCC), le talc, le blanc de titane et identique.
  11. Dispersion de couchage selon au moins une des revendications précédentes caractérisé en ce que
    l'agent de réticulation produit une liaison en particulier une réticulation avec le phyllosilicate et/ou avec des matières fibreuses ou des hydrocolloides comme l'amidon, le glycolate de cellulose sodique (CMC), l'alcool polyvinylique et identique.
  12. Dispersion de couchage selon au moins une des revendications précédentes caractérisé en ce que
    la réaction de réticulation a lieu entre les groupements fonctionnels de l'agent de réticulation et les groupements fonctionnels du phyllosilicate capable de gonflement en particulier les groupements de silanole et les groupements fonctionnels de matières fibreuses en particulier les groupements hydroxyles libres.
  13. Dispersion de couchage selon au moins une des revendications précédentes caractérisé en ce que
    les groupements fonctionnels de l'agent de réticulation par entrée en action d'un produit mélangé de glyoxal avec du glycol polyéthylénique (PEG) et/ou de l'alcool polyvinylique sont des groupements hydroxyles libres.
  14. Dispersion de couchage selon au moins une des revendications précédentes caractérisé en ce que les groupements fonctionnels de l'agent de réticulation par entrée en action d'un produit mélangé de glyoxal et de polyacrylamide (PAM) sont des groupements aldéhydiques libres.
  15. Dispersion de couchage selon au moins une des revendications précédentes caractérisé en ce que
    le pH de la dispersion de couchage est mis entre 6 et 9,5 de préférence entre 6,8 et 9,2 et en particulier préféré entre 8,1 et 9,0.
  16. Dispersion de couchage selon au moins une des revendications précédentes caractérisé en ce que
    la liaison chimique est au moins une liaison issue d'un groupement de liaisons qui comprend les liaisons covalentes, les liaisons hydrogènes, les liaisons Van der Waals, les liaisons ioniques et/ou tout mélange quelconque.
  17. Procédé pour fabriquer un substrat d'impression couché en particulier un papier ou carton avec les étapes :
    - application mécanique d'une dispersion de couchage sur un substrat d'impression, où la dispersion de couchage a au moins un des composants suivants :
    • une part prédéterminée en eau
    • une part prédéterminée d'au moins une couche de silicate capable de gonflement
    • une part prédéterminée d'un agent de réticulation qui est stabilisé par l'ajout d'au moins un polymère soluble dans l'eau et qui forme une liaison chimique avec au moins un groupement fonctionnel de phyllosilicate et aussi avec au moins avec un groupement fonctionnel du substrat d'impression, particulièrement du papier de base
    - séchage de la dispersion de couchage appliquée
  18. Procédé pour fabriquer un substrat d'impression couché selon la revendication 17, caractérisé en ce que
    un couchage est appliqué selon au moins une des revendications 1 à 16 sur le substrat d'impression.
  19. Substrat d'impression couché dont le couchage résulte d'une dispersion de couchage selon au moins une des revendications 1 à 16, et/ou sous utilisation d'au moins un procédé selon les revendications 17 à 18.
  20. Utilisation d'un substrat d'impression couché selon au moins une des revendication 1 à 19 pour au moins un procédé d'impression qui est choisi parmi un groupe de procédés d'impression, qui comprend l'impression offset, en creux, à jet d'encre, flexo, laser, papier auto-encreur et identique.
EP03773607A 2003-02-21 2003-08-14 Dispersion de revetement utilisable de maniere multifonctionnelle pour des substrats d'impression Expired - Lifetime EP1597432B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10307494 2003-02-21
DE10307494A DE10307494A1 (de) 2003-02-21 2003-02-21 Multifunktional einsetzbare Streichfarbendispersion für Druckträger
PCT/EP2003/009038 WO2004074576A1 (fr) 2003-02-21 2003-08-14 Dispersion de revetement utilisable de maniere multifonctionnelle pour des substrats d'impression

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EP1597432A1 EP1597432A1 (fr) 2005-11-23
EP1597432B1 true EP1597432B1 (fr) 2006-07-19

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US (1) US20060235129A1 (fr)
EP (1) EP1597432B1 (fr)
AT (1) ATE333533T1 (fr)
AU (1) AU2003282001A1 (fr)
DE (2) DE10307494A1 (fr)
WO (1) WO2004074576A1 (fr)

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BRPI0708360A2 (pt) * 2006-02-28 2011-05-24 Evonik Degussa Corp substrato revestido para desempenho de impressão aperfeiçoado e processo de fabricação do mesmo
CN101512070A (zh) * 2006-09-26 2009-08-19 赢创德固赛公司 具有增强的印刷性能的多功能纸
US20080173420A1 (en) * 2006-12-11 2008-07-24 Jay Chen Song Paper surface sizing composition, sized paper, and method for sizing paper
US8758567B2 (en) * 2009-06-03 2014-06-24 Hercules Incorporated Cationic wet strength resin modified pigments in barrier coating applications
US9580866B2 (en) * 2009-06-03 2017-02-28 Solenis Technologies, L.P. Cationic wet strength resin modified pigments in water-based latex coating applications
DE102009035555A1 (de) 2009-07-31 2011-02-03 S & B Industrial Minerals Gmbh Verfahren und Vorrichtung zur Herstellung einer Dispersion
DE102009044430A1 (de) 2009-11-05 2011-05-12 Baumeister Chemicals & Consulting Gmbh & Co. Kg Streichfarbe zur Verbesserung der Qualitäts- und Laufeigenschaften von Druckträgern und Herstellungsverfahren der Streichfarbe
EP2474668A1 (fr) * 2011-01-11 2012-07-11 Steinbeis Papier GmbH Papier d'impression à jet d'encre à contraste riche
EP2474667A1 (fr) * 2011-01-11 2012-07-11 Steinbeis Papier GmbH Papier d'impression à jet d'encre à contraste riche
FI124411B (fi) * 2012-07-05 2014-08-15 Upm Kymmene Corp Elintarvikepakkaus
US9499944B2 (en) * 2013-07-16 2016-11-22 Georgia-Pacific Chemicals Llc Wet strength treated paper and paperboard
ES2617559T3 (es) 2014-05-26 2017-06-19 Omya International Ag Carbonato de calcio para medio de impresión en rotograbado
US10589210B2 (en) 2014-12-30 2020-03-17 Evonik Operations Gmbh Aluminosilicates and coatings made therefrom for VOC removal
JP2021028114A (ja) * 2017-11-17 2021-02-25 星光Pmc株式会社 インクジェット印刷用前処理剤、インクセット、画像形成方法及び画像形成物

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DE4400609A1 (de) * 1994-01-12 1995-07-13 Haindl Papier Gmbh Dünndruckpapier und Verfahren zu dessen Herstellung
US5885340A (en) * 1994-10-14 1999-03-23 Ecc International Ltd. Quality of multiple coated paper
DE19601245A1 (de) * 1996-01-16 1997-07-17 Haindl Papier Gmbh Rollendruckpapier mit Coldset-Eignung und Verfahren zu dessen Herstellung
ATE224304T1 (de) * 2000-05-30 2002-10-15 Ilford Imaging Ch Gmbh Farbstoffempfangsmaterial für den tintenstrahldruck
DE10108349A1 (de) * 2001-02-21 2002-08-29 Basf Ag Papierstreichmassen

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AU2003282001A1 (en) 2004-09-09
DE10307494A1 (de) 2004-09-02
ATE333533T1 (de) 2006-08-15
EP1597432A1 (fr) 2005-11-23
DE50304316D1 (de) 2006-08-31
US20060235129A1 (en) 2006-10-19
WO2004074576A1 (fr) 2004-09-02

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