EP2325389B1 - Coating material for fibrous compounds - Google Patents

Coating material for fibrous compounds Download PDF

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Publication number
EP2325389B1
EP2325389B1 EP10190836.6A EP10190836A EP2325389B1 EP 2325389 B1 EP2325389 B1 EP 2325389B1 EP 10190836 A EP10190836 A EP 10190836A EP 2325389 B1 EP2325389 B1 EP 2325389B1
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EP
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Prior art keywords
solid
paper
mass
coating
amorphous
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EP10190836.6A
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German (de)
French (fr)
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EP2325389A1 (en
Inventor
Reinhard Kräuter
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Bene_fit Systems & Co KG GmbH
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Bene_fit Systems & Co KG 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
    • D21H19/38—Coatings with pigments characterised by the pigments
    • D21H19/40—Coatings with pigments characterised by the pigments siliceous, e.g. clays

Definitions

  • the present invention relates to the use of an SiO 2 -containing solid or a composition containing this solid as a coating color for coating paper surfaces, wherein the solid is present as an amorphous, non-crystalline solid and the solid or composition is produced at low calender pressure or without calendering paper with high gloss, high smoothness, high porosity, high opacity and high paper volume.
  • Another essential aspect of the invention is a process for producing paper of high gloss, high smoothness, high porosity, high opacity and high paper volume, wherein an amorphous, non-crystalline solid or composition containing such a solid is applied to the paper and the paper is processed at low calender or without calendering.
  • the invention relates to a paper with high gloss, high smoothness, high porosity, high opacity and high paper volume, which was prepared using such a solid or a composition containing this solid as a pigment or coating color.
  • Paper is a mostly vegetable fiber material that is mainly used for writing and printing.
  • Important additives are fillers, pigments and additives.
  • stroke By applying a so-called stroke, one or both surfaces of the paper can be finished.
  • This surface treatment gives the paper an at least partially closed, smooth and stable surface, which is necessary for the modern requirements of the printing industry.
  • Other important paper properties are eg the opacity, the porosity, the volume, the smoothness, the Printability as well as the haptic properties. In particular, it is often desirable to provide high opacity and high gloss with high paper volume and tactile properties.
  • High-gloss paper surfaces are called “cast coated” and produced by pressing the paper web, which always appears to be matt, onto highly polished heated surfaces. This is usually done in calenders by chrome-plated casting or drying cylinders, which dry the paper webs at about 90-95 ° C.
  • the coating color used for coating is generally a suspension of water, one or more adhesives and binders, dispersants and any other additives and, as a rule, mineral constituents, the so-called pigments.
  • the most important pigments used so far are:
  • Kaolin has been the preferred pigment used in papermaking in the past. It remains chemically inert over a wide pH range and can therefore be used in both acidic and alkaline production processes. Despite the universal applicability of kaolin, its proportion of pigments used is currently declining.
  • Titanium dioxide has the highest covering power of all previously known white pigments and is therefore also used in wall paints and varnishes. Due to the high price, however, titanium dioxide is generally used in the paper industry only for high-quality specialty papers, where particularly high demands are required on opacity, light scattering and gloss.
  • Satin White is a very high quality white pigment used in the paper industry. It is produced industrially by the precipitation of aluminum sulfate with calcium hydroxide from aqueous solutions. Due to its high whiteness, high gloss, and pleasant feel, it is being used for the production of very high quality grades of paper, such as the pH and tackiness. Art prints and brochures used.
  • GCC Ground calcium carbonate
  • GCC Ground calcium carbonate
  • Precipitated calcium carbonate is produced industrially by introducing carbon dioxide into calcium-containing solutions.
  • the properties of the PCC z. B. in terms of particle size, particle size distribution and surface properties of the respective requirements of the paper industry in light transmission, whiteness u. ⁇ . be adapted.
  • New pigments or the improvement of the properties of known pigments and optimization of the methods for applying and drying the applied pigment dispersions are the subject of various publications.
  • DE 101 15 570 relates, for example, to a titanium dioxide-based white pigment with particularly high opacity as a coating material for decorative base papers. This is achieved by adding aluminum and silicon to the titanium dioxide, which is preferably present in rutile structure.
  • US 2007/0289499 discloses a kaolin based white pigment.
  • the improved properties described in this patent over other kaolin based pigments are achieved by the preference for small size platelet kaolin crystals.
  • Suitable pigments mentioned include clay, eg, high brightness clay, ground calcium carbonate, precipitated calcium carbonate (PCC), titanium dioxide, aluminum trihydrate, satin white, plastic pigment, silica, and mixtures thereof one. Those skilled in the art know how to choose the appropriate pigment (s) to achieve their desired end properties.
  • the coating preferably includes at least 60 parts pigment, more preferably at least 80 parts pigment.
  • DE 603 20 423 T2 relates to the technical field of mineral fillers, in particular the paper sector and in particular paper coatings and pulp fillers for paper or even areas such as painting, water treatment, in particular the field of sewage sludge, cleaning agents, ceramics, cement or hydraulic binders, public works, inks and lacquers, gluing of textiles or even any type of industry which requires the use of concentrated pigment suspensions, in particular in the areas of paper, water treatment, painting and ceramics.
  • the mineral is selected from natural calcium carbonate, synthetic (precipitated) calcium carbonate, anatase or rutile titanium dioxide, kaolin, aluminum hydroxide, clays or their mixtures.
  • gloss after 75 ° C TAPPI of the previously coated sheet of paper is determined prior to calendering by passing the coated paper through a Lehmann TM Lab glossmeter. It is used for the paper made by means of the aqueous calcium carbonate suspension from the in DE 603 20 423 T2 Example 4 coated coating composition, a gloss after 75 ° C TAPPI of 63.5 was obtained.
  • the coated paper is also calendered by means of a 9-zone supercalender between two rolls sold by Kleinewefers.
  • the gloss after 75 ° C TAPPI is then 69.3.
  • the material according to a in DE 199 83 417 T1 said aspect may be the coarse product fraction separated by the particle size classifier in the process according to the first aspect of the invention. It may be mixed with other coating pigment products comprising kaolin and / or one or more coating pigments known in the art, for example selected from ground or precipitated carbonates such as calcium carbonate, calcined kaolin, talc, satin white, titanium dioxide, aluminum trihydrate, amorphous silica and silicates. Zinc oxide, barium sulfate and so-called plastic pigments to obtain a coating pigment mixture or composition.
  • coating pigment products comprising kaolin and / or one or more coating pigments known in the art, for example selected from ground or precipitated carbonates such as calcium carbonate, calcined kaolin, talc, satin white, titanium dioxide, aluminum trihydrate, amorphous silica and silicates.
  • Zinc oxide, barium sulfate and so-called plastic pigments to obtain a coating pigment mixture or composition
  • DE 699 08 353 T2 relates to pigment products and their preparation and use in coating compositions. Described is the preparation of improved inorganic pigments for paper coating compositions, and in particular pigments for use in compositions for the production of glossy coated paper, in particular lightly coated and ultralight coated paper, eg a pigment product for use in a coating composition for the production of a glossy layer on a paper the pigment product contains processed particulate kaolin whose particles have a particle size distribution such that at least 80% by weight of the particles have a sphere equivalent diameter of less than 2 microns and not less than 8% by weight have a sphere equivalent diameter less than 0.25 microns; Particles have a form factor of at least 45.
  • a transparent or powder-white pigment which could deliver the desired requirements for paper gloss, smoothness and opacity even in thinner layers, would create the possibility of being able to adapt paper volume and haptics while reducing the residence time in the calender.
  • Particularly preferred would be a transparent pigment that can ensure high paper gloss and high smoothness of the coating layer even at reduced calendering pressure, or even without being treated in the calender.
  • paper volume, haptics and opacity during calendering would not be adversely affected or, in the case of unnecessary calendering, would not be adversely affected. This is not possible with the hitherto used pigments and additives and the coating colors resulting therefrom, as well as the available and used machine technology, the available and used processes and processes.
  • Amorphous SiO 2 especially precipitated or fumed silica, becomes matting agent in the paper coating due to the high porosity or the high specific surface area or for rapid ink absorption, eg used as a pigment in the coating of inkjet paper.
  • Disadvantage of these amorphous silicas is that they can be dispersed in water only with a very low solids content and here show a very high viscosity, which is at the high speeds of the paper coating of extreme disadvantage.
  • a further object of the invention is to provide a paper with high gloss, high smoothness, high porosity, high opacity and high paper volume, which is produced by this method and therefore meets the required quality standards despite the low calendering pressure or even without calendering.
  • An essential aspect of the invention is therefore the use of a SiO 2 -containing solid or a composition containing this solid as
  • a coating color for coating paper surfaces wherein the solid is present as an amorphous, non-crystalline solid and the solid or composition is suitable for producing high gloss, high smoothness, high porosity, high opacity and high paper volume at low calendering or calendering.
  • the solid used is transparent and / or white as a powder.
  • the particularly frequently used paper color white is particularly easy to realize and discoloration is avoided.
  • other pigment colors and opacities are possible, e.g. to achieve colorations of the paper or certain color effects.
  • a SiO 2 -containing solid or of a composition containing this solid as a pigment or coating color for coating paper surfaces wherein the solid or the composition has a SiO 2 content of 40-100 M%, particularly preferably 60-100 Has m%.
  • the solid in the form of solid particles having a particle size (equivalent diameter) of at least 99% by mass ⁇ 100 .mu.m, preferably at least 99% by mass ⁇ 50 .mu.m, preferably at least 80% by mass ⁇ 5 .mu.m, preferably 20 - 50 Ma% ⁇ 2 microns, more preferably at least 20 Ma% of 1 - 2 microns.
  • the equivalent diameter is determined by the rate of descent of the particles in viscous medium. The measurement is carried out with suitable equipment, e.g. the Sedigraph of the company Micromeritics.
  • the solids used are characterized by a high reflectivity. Therefore, they preferably have smooth surfaces with no or only a few bumps. As a result, the specific surface area is comparatively small.
  • the solid has a specific surface area BET ⁇ 100 m 2 / g, preferably ⁇ 50 m 2 / g.
  • a SiO 2 -containing solid or a composition containing this solid as a pigment or coating color for coating paper surfaces, wherein the solid or the composition has a dry weight fraction of 20-85% by mass, preferably 30-80% by mass, particularly preferably 35-75% by mass.
  • An essential aspect of the invention is a process for the production of paper of high gloss, high smoothness, high porosity, high opacity and high paper volume, wherein on the paper an amorphous, non-crystalline solid or a composition containing such a solid is applied as a coating color and the Paper is processed at low calendering or without calendering.
  • the amorphous, non-crystalline solid or composition containing such a solid is obtained by dry and / or wet treatment of suitable materials, e.g. Glass, by process steps, which pre-sorting, breaking, screening, milling, classifying, preferably air classification, or a selection of these and optionally a subsequent drying and / or dispersion with the addition of inorganic or organic additives such. Dispersants or pigments prepared.
  • suitable materials e.g. Glass
  • the amorphous, non-crystalline solid powders or suspensions according to the invention are prepared by selecting suitable materials, for example glass and, if appropriate, processing, for example by presorting, breaking, sieving, milling, classifying (eg air classification) as a possible process sequence in the context of dry processing optionally with a downstream dispersion with the addition of dispersants, additives or other organic or inorganic constituents such as other pigments to a pigment dispersion. This can possibly be used directly as a coating color.
  • amorphous, non-crystalline solid powders or suspensions of this invention e.g. by presorting, crushing, screening, possibly pre-grading, classifying, wet-milling, fractionating, e.g. by means of hydrocyclone or other suitable methods, as a possible process sequence in the context of a dry treatment or wet treatment or a combined dry and wet processing, optionally combined with a dispersion with the addition of additives such.
  • a suspension prepared by wet processing may also be converted to the dry form, e.g. by spray-drying, in order to then possibly return this powder to a suspension in a later step.
  • a coating color using the amorphous non-crystalline solid powders or suspension according to the invention by adding water and additives such as e.g. Rheology additives, dispersants, thickeners, bactericides, and optionally other coating pigments, e.g. Kaolin, satin white, talc, calcium carbonate (precipitated or ground), titanium dioxide, precipitated or fumed silica, aluminum hydroxide, dolomite, barium sulfate, zinc oxide, bentonite.
  • water and additives such as e.g. Rheology additives, dispersants, thickeners, bactericides, and optionally other coating pigments, e.g. Kaolin, satin white, talc, calcium carbonate (precipitated or ground), titanium dioxide, precipitated or fumed silica, aluminum hydroxide, dolomite, barium sulfate, zinc oxide, bentonite.
  • the amorphous, non-crystalline solid or the composition containing such a solid is applied by blade coating, curtain coating, cast coat, film press, size press or other suitable method, wherein after drying, the paper already has a sufficiently homogeneous surface structure and a Smoothing with calender is not necessary, or can be done at low pressure.
  • the coating of paper surfaces with the described suspensions or coating colors can consequently be carried out by conventional methods such as blade coating, curtain coating, cast coating, film press, size press or other suitable method, followed by drying the coated paper web and smoothing with low pressure by means of calender or other suitable method. It is (depending on the requirement of the Paper and depending on the customer's wishes) also a complete elimination of the process step of smoothing possible.
  • Another essential aspect of the invention is a paper having high gloss, high smoothness, high porosity, high opacity and high paper volume which comprises a surface coating, the surface coating comprising a solid or a composition containing this solid, the solid being an amorphous, non-crystalline Solid is present and the solid or composition is suitable at low calendering or calendering to produce paper with high gloss, high smoothness, high porosity, high opacity and high paper volume.
  • Such paper in contrast to the prior art, has improved properties, e.g. in terms of opacity and paper volume. Furthermore, it is characterized by high gloss, high smoothness, high porosity and optionally also other positive properties.
  • the paper has a gloss which at a measurement angle of 60 °> 2.0, preferably> 2.5, more preferably> 5.0 and most preferably> 7.5 and at a measurement angle of 85 °> 2.5, preferably> 3.5, more preferably> 10 and most preferably> 15.
  • the measurement of the gloss takes place, unless otherwise stated, according to standard EN ISO 2813.
  • the paper preferably has a picking strength with multiple printing of> 4, preferably> 6, particularly preferably> 8, preferably> 10, preferably> 12.
  • such papers can be particularly white.
  • the paper has a brightness measured as L * in the L * a * b * color space of> 95, preferably ⁇ 95.5. This makes it suitable for a variety of applications covering a broad spectrum.
  • such a coated paper is suitable for example as a carrier medium, for example of color.
  • the information storage is possible.
  • the powder materials were each used as indicated in Table 1. Unless otherwise stated, a 40% suspension in each case of water was prepared without further additives. With a semi-automatic squeegee (Erichsen) with a smooth rod (ie without winding), the homogeneous suspensions at a rate of 10 mm / sec. on an uncoated carrier paper (80 g / m 2 ), dried at room temperature overnight and the gloss measured at two different angles (Byk Gardner, handheld device) without further treatment. The values measured at angles of 60 ° and 85 ° are shown in Table 2.
  • the product of the present invention was tested against a standard coating color formulation containing calcium carbonate and kaolin (75 and 25 parts by mass).
  • a standard coating color formulation containing calcium carbonate and kaolin (75 and 25 parts by mass).
  • calcium carbonate (90, 80 and 70 parts) with 10, 20 and 30 parts instead of the kaolin was added under otherwise identical conditions and painted on paper.
  • the coated paper was then measured for brightness.
  • the pick resistance is essentially dependent on the type and amount of binder contained in the coating color. A high amount of binder goes along with an improved pick resistance, but also means considerable additional costs. As can now be seen, the picking strength can also be significantly improved with the product according to the invention or, conversely, the proportion of binder can be significantly reduced.

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Description

Die vorliegende Erfindung bezieht sich auf die Verwendung eines SiO2-enthaltenden Feststoffs oder einer diesen Feststoff enthaltenden Zusammensetzung als Streichfarbe zur Beschichtung von Papieroberflächen, wobei der Feststoff als amorpher, nichtkristalliner Feststoff vorliegt und der Feststoff oder die Zusammensetzung bei geringem Kalanderdruck oder ohne Kalandrierung zur Erzeugung von Papier mit hohem Glanz, hoher Glätte, hoher Porosität, hoher Opazität und hohem Papiervolumen geeignet ist. Ein weiterer wesentlicher Aspekt der Erfindung ist ein Verfahren zur Herstellung von Papier mit hohem Glanz, hoher Glätte, hoher Porosität, hoher Opazität und hohem Papiervolumen, wobei auf das Papier ein amorpher, nichtkristalliner Feststoff oder eine einen solchen Feststoff enthaltende Zusammensetzung aufgebracht wird und das Papier bei geringem Kalanderdruck oder ohne Kalandrierung weiterverarbeitet wird. Weiterhin bezieht sich die Erfindung auf ein Papier mit hohem Glanz, hoher Glätte, hoher Porosität, hoher Opazität und hohem Papiervolumen, das unter Verwendung eines derartigen Feststoffes oder einer diesen Feststoff als Pigment oder Streichfarbe enthaltenden Zusammensetzung hergestellt wurde.The present invention relates to the use of an SiO 2 -containing solid or a composition containing this solid as a coating color for coating paper surfaces, wherein the solid is present as an amorphous, non-crystalline solid and the solid or composition is produced at low calender pressure or without calendering paper with high gloss, high smoothness, high porosity, high opacity and high paper volume. Another essential aspect of the invention is a process for producing paper of high gloss, high smoothness, high porosity, high opacity and high paper volume, wherein an amorphous, non-crystalline solid or composition containing such a solid is applied to the paper and the paper is processed at low calender or without calendering. Furthermore, the invention relates to a paper with high gloss, high smoothness, high porosity, high opacity and high paper volume, which was prepared using such a solid or a composition containing this solid as a pigment or coating color.

Papier ist ein größtenteils aus pflanzlichen Fasern bestehendes Material, das vorwiegend zum Beschreiben und Bedrucken verwendet wird. Wichtige Zusatzstoffe sind Füllstoffe, Pigmente und Additive. Durch das Aufbringen eines sogenannten Striches können eine oder beide Oberflächen des Papieres veredelt werden. Durch diese Oberflächenbehandlung bekommt das Papier eine mindestens teilweise geschlossene, glatte und stabile Oberfläche, wie es für moderne Anforderungen der Druckindustrie notwendig ist. Weitere wichtige Papiereigenschaften sind z.B. die Opazität, die Porosität, das Volumen, die Glätte, die Bedruckbarkeit sowie die haptischen Eigenschaften. Insbesondere ist es häufig wünschenswert eine hohe Opazität und einen hohen Glanz bei gleichzeitig hohem Papiervolumen und vorteilhaften haptischen Eigenschaften zur Verfügung zu stellen.Paper is a mostly vegetable fiber material that is mainly used for writing and printing. Important additives are fillers, pigments and additives. By applying a so-called stroke, one or both surfaces of the paper can be finished. This surface treatment gives the paper an at least partially closed, smooth and stable surface, which is necessary for the modern requirements of the printing industry. Other important paper properties are eg the opacity, the porosity, the volume, the smoothness, the Printability as well as the haptic properties. In particular, it is often desirable to provide high opacity and high gloss with high paper volume and tactile properties.

Für die Beschichtung werden verschiedenen Verfahren eingesetzt, z.B. Blade Coating, Curtain Coating, Fimpresse, Leimpresse oder Gussstrich. Hochglänzende Papieroberflächen werden als "gussgestrichen" ("cast coated") bezeichnet und durch Anpressen der auch mit Strich zunächst immer matt erscheinenden Papierbahnen an hochpolierte erhitzte Oberflächen hergestellt. Dies erfolgt in der Regel in Kalandern durch verchromte Guss- oder Trockenzylinder, die die Papierbahnen bei etwa 90-95°C trocknen.Various methods are used for the coating, e.g. Blade Coating, Curtain Coating, Fimpresse, size press or cast. High-gloss paper surfaces are called "cast coated" and produced by pressing the paper web, which always appears to be matt, onto highly polished heated surfaces. This is usually done in calenders by chrome-plated casting or drying cylinders, which dry the paper webs at about 90-95 ° C.

Die zur Beschichtung eingesetzte Streichfarbe ist im Allgemeinen eine Suspension aus Wasser, einem oder mehreren Klebe- und Bindemitteln, Dispersionsmitteln und eventuellen weiteren Additiven sowie in der Regel mineralischen Bestandteilen, den sogenannten Pigmenten. Die wichtigsten bisher eingesetzten Pigmente sind:The coating color used for coating is generally a suspension of water, one or more adhesives and binders, dispersants and any other additives and, as a rule, mineral constituents, the so-called pigments. The most important pigments used so far are:

Kaolinkaolin

Kaolin war in der Vergangenheit das bei der Papierherstellung bevorzugt verwendete Pigment. Es bleibt über ein weites pH-Spektrum chemisch inert und kann deshalb sowohl in sauren als auch alkalischen Produktionsverfahren verwendet werden. Trotz der universellen Einsetzbarkeit von Kaolin ist zurzeit dessen Anteil an eingesetzten Pigmenten rückläufig.Kaolin has been the preferred pigment used in papermaking in the past. It remains chemically inert over a wide pH range and can therefore be used in both acidic and alkaline production processes. Despite the universal applicability of kaolin, its proportion of pigments used is currently declining.

TitandioxidTitanium dioxide

Titandioxid hat das höchste Deckungsvermögen aller bisher bekannten Weißpigmente und wird daher auch in Wandfarben und Lacken verwendet. Aufgrund des hohen Preises wird Titandioxid jedoch in der Papierindustrie in der Regel nur für hochwertige Spezialpapiere verwendet, wo besonders hohe Anforderungen an Opazität, Lichtstreuung und Glanz gefordert werden.Titanium dioxide has the highest covering power of all previously known white pigments and is therefore also used in wall paints and varnishes. Due to the high price, however, titanium dioxide is generally used in the paper industry only for high-quality specialty papers, where particularly high demands are required on opacity, light scattering and gloss.

SatinweißSatin White

Satinweiß ist ein sehr hochwertiges in der Papierindustrie verwendetes Weißpigment. Es wird industriell durch die Fällung von Aluminiumsulfat mit Calciumhydroxid aus wässrigen Lösungen hergestellt. Aufgrund seines hohen Weißgrads, dem hohen Glanz und der angenehmen Haptik wird es trotz der pH-Empfindlichkeit und der Klebrigkeit für die Produktion von sehr hochwertigen Papiersorten wie z.B. Kunstdrucken und Broschüren verwendet.Satin White is a very high quality white pigment used in the paper industry. It is produced industrially by the precipitation of aluminum sulfate with calcium hydroxide from aqueous solutions. Due to its high whiteness, high gloss, and pleasant feel, it is being used for the production of very high quality grades of paper, such as the pH and tackiness. Art prints and brochures used.

Gemahlenes Calciumcarbonat (GCC):Ground calcium carbonate (GCC):

Gemahlenes Calciumcarbonat (GCC) ist das zurzeit am meisten verwendete Pigment in der Papierindustrie. Mit Körnungen von weniger als 2 µm ist das günstige GCC sowohl ein wichtiger Papierfüllstoff als auch das in Europa verbreiteteste Papierstreichpigment.Ground calcium carbonate (GCC) is currently the most widely used pigment in the paper industry. With grain sizes of less than 2 microns, the cheap GCC is both an important paper filler and the most widely used paper coating pigment in Europe.

Gefälltes Calciumcarbonat (PCC):Precipitated calcium carbonate (PCC):

Gefälltes Calciumcarbonat (PCC) wird industriell durch einleiten von Kohlendioxid in calciumhaltige Lösungen hergestellt. Durch Variation der Reaktionsbedingungen können die Eigenschaften des PCC z. B. in puncto Korngröße, Korngrößenverteilung und Oberflächeneigenschaften den jeweiligen Anforderungen der Papierindustrie an Lichtdurchlässigkeit, Weißgrad u. ä. angepasst werden.Precipitated calcium carbonate (PCC) is produced industrially by introducing carbon dioxide into calcium-containing solutions. By varying the reaction conditions, the properties of the PCC z. B. in terms of particle size, particle size distribution and surface properties of the respective requirements of the paper industry in light transmission, whiteness u. Ä. be adapted.

Neue Pigmente oder die Verbesserung der Eigenschaften bekannter Pigmente sowie Optimierung der Verfahren zum Aufbringen und trocknen der aufgebrachten Pigmentdispersionen sind Gegenstand diverser Druckschriften.New pigments or the improvement of the properties of known pigments and optimization of the methods for applying and drying the applied pigment dispersions are the subject of various publications.

DE 101 15 570 betrifft beispielsweise ein auf Titandioxid basierendes Weißpigment mit besonders hoher Opazität als Streichmasse für Dekorrohpapiere. Erreicht wird dies durch Zusätze von Aluminium und Silicium zu dem bevorzugt in Rutilstruktur vorliegenden Titandioxid. DE 101 15 570 relates, for example, to a titanium dioxide-based white pigment with particularly high opacity as a coating material for decorative base papers. This is achieved by adding aluminum and silicon to the titanium dioxide, which is preferably present in rutile structure.

US 2007/0289499 offenbart ein auf Kaolin basierendes Weißpigment. Die in dieser Patentschrift beschriebenen verbesserten Eigenschaften gegenüber anderen kaolinbasierenden Pigmenten werden durch die Bevorzugung von plättchenförmigen Kaolinkristallen geringer Größe erreicht. US 2007/0289499 discloses a kaolin based white pigment. The improved properties described in this patent over other kaolin based pigments are achieved by the preference for small size platelet kaolin crystals.

In Druckschrift DE 600 06 991 T2 genannte geeignete Pigmente schließen Ton, z.B. Ton von hoher Helligkeit, gemahlenes Calciumcarbonat, präzipitiertes Calciumcarbonat (PCC), Titandioxid, Aluminiumtrihydrat, Satinweiß, Kunststoffpigment, Siliziumdioxid und Gemische davon ein. Fachleute wissen, wie man das geeignete Pigment/die geeigneten Pigmente wählt, um sie gewünschten Endeigenschaften zu erlangen. Die Beschichtung schließt bevorzugt mindestens 60 Teile Pigment, bevorzugter mindestens 80 Teile Pigment ein.In publication DE 600 06 991 T2 Suitable pigments mentioned include clay, eg, high brightness clay, ground calcium carbonate, precipitated calcium carbonate (PCC), titanium dioxide, aluminum trihydrate, satin white, plastic pigment, silica, and mixtures thereof one. Those skilled in the art know how to choose the appropriate pigment (s) to achieve their desired end properties. The coating preferably includes at least 60 parts pigment, more preferably at least 80 parts pigment.

DE 603 20 423 T2 betrifft das technische Gebiet der mineralischen Füllstoffe, wie insbesondere das Papiergebiet und insbesondere Papierbeschichtungen und Massefüllstoffe für Papier oder auch Gebiete wie Anstreichen, Wasserbehandlung wie insbesondere das Gebiet der Klärschlämme, Reinigungsmittel, Keramiken, Zement oder Hydraulische Bindemittel, öffentliche Bauarbeiten, Tinten und Lacke, Verleimen von Textilien oder auch jeder Art von Industrie, bei der die Anwendung von konzentrierten Pigmentsuspensionen erforderlich ist, und betrifft insbesondere die Gebiete Papier, Wasserbehandlung, Anstreichen und Keramik. DE 603 20 423 T2 relates to the technical field of mineral fillers, in particular the paper sector and in particular paper coatings and pulp fillers for paper or even areas such as painting, water treatment, in particular the field of sewage sludge, cleaning agents, ceramics, cement or hydraulic binders, public works, inks and lacquers, gluing of textiles or even any type of industry which requires the use of concentrated pigment suspensions, in particular in the areas of paper, water treatment, painting and ceramics.

Das dort genannte Verfahren zur Herstellung von wässrigen Suspensionen aus Mineralstoffen ist dadurch gekennzeichnet, dass der Mineralstoff ausgewählt werden kann aus

  • natürlichen Calciumcarbonaten wie insbesondere verschiedenen Kreidearten, Kalkspaten, Marmoren oder
  • aus synthetischen Calciumcarbonaten wie gefällten Calciumcarbonaten in verschiedenen Stadien der Kristallisierung oder
  • aus Magnesium-Calcium-Mischcarbonaten wie z.B. Dolomiten ausgewählt oder
  • aus Magnesiumcarbonat, Zinkcarbonat, Kalk, Magnesia, Bariumsulfat wie z.B. Baryt, Calciumsulfat, Siliziumdioxid, aus Magnesiumsilikaten wie z.B. Talk, Wollastonit, aus Tonarten und Alumosilikaten wie z.B. Kaolinen, Glimmer, Metall- oder Erdalkalimetalloxiden oder-hydroxiden wie z.B. Magnesiumhydroxid, Eisenoxiden, Zinkoxid, Titanoxid, Titandioxiden in Anatas- oder Rutilform und deren Mischungen, und insbesondere aus Mischungen von Talk und Calciumcarbonat.
The process mentioned therein for the preparation of aqueous suspensions of minerals is characterized in that the mineral can be selected from
  • natural calcium carbonates such as in particular various types of chalk, calcareous, marble or
  • from synthetic calcium carbonates such as precipitated calcium carbonates in various stages of crystallization or
  • selected from magnesium-calcium mixed carbonates such as Dolomites or
  • from magnesium carbonate, zinc carbonate, lime, magnesia, barium sulfate such as barite, calcium sulfate, silicon dioxide, from magnesium silicates such as talc, wollastonite, from clays and aluminosilicates such as kaolins, mica, metal or alkaline earth metal oxides or hydroxides such as magnesium hydroxide, iron oxides, zinc oxide , Titanium oxide, anatase or rutile titanium dioxide and mixtures thereof, and in particular mixtures of talc and calcium carbonate.

Vorzugsweise wird der Mineralstoff aus natürlichem Calciumcarbonat, synthetischem (gefälltem) Calciumcarbonat, Titandioxid in Anatas- oder Rutilform, Kaolin, Aluminiumhydroxid, den Tonerden oder ihren Mischungen ausgewählt.Preferably, the mineral is selected from natural calcium carbonate, synthetic (precipitated) calcium carbonate, anatase or rutile titanium dioxide, kaolin, aluminum hydroxide, clays or their mixtures.

Ferner wird Glanz nach 75°C TAPPI des vorher beschichteten Blatt Papiers vor dem Kalandrieren bestimmt, indem das beschichtete Papier durch ein Glanzmessgerät des Labors Lehmann™ geschickt wurde. Es wird für das Papier, das mittels der die wässrige Calciumcarbonat-Suspension aus dem in DE 603 20 423 T2 genannten Beispiel 4 enthaltenden Streichmasse beschichtet wurde, ein Glanz nach 75°C TAPPI von 63,5 erhalten.Further, gloss after 75 ° C TAPPI of the previously coated sheet of paper is determined prior to calendering by passing the coated paper through a Lehmann ™ Lab glossmeter. It is used for the paper made by means of the aqueous calcium carbonate suspension from the in DE 603 20 423 T2 Example 4 coated coating composition, a gloss after 75 ° C TAPPI of 63.5 was obtained.

Das beschichtete Papier wird auch mittels eines Superkalanders mit 9 Kontaktzonen zwischen zwei Walzen, vertrieben von Kleinewefers, kalandriert. Der Glanz nach 75°C TAPPI beträgt dann 69,3.The coated paper is also calendered by means of a 9-zone supercalender between two rolls sold by Kleinewefers. The gloss after 75 ° C TAPPI is then 69.3.

DE 199 83 417 T1 beschreibt die Bereitstellung eines kaolinhaltigen anorganischen Teilchenmaterials, welches als Pigment oder Pigment-Inhaltsstoff in einer Zusammensetzung zum Streichen von Papier oder einem ähnlichen Material eine bessere Kombination von Aufstricheigenschaften, einschließlich Weißgrad, bspw. Weißgrad zusammen mit Druckfähigkeit und Lauffähigkeit, ergibt. Wird ein mit einer kaolinhaltigen Zusammensetzung gestrichenes Druckpapier kalandriert, orientieren sich die plättchenartigen Kristalle in der Papierebene und Glätte und Glanz des Papiers werden erhöht. DE 199 83 417 T1 describes the provision of a kaolin-containing inorganic particulate material which, as a pigment or pigment ingredient in a composition for painting paper or similar material, results in a better combination of spread properties, including whiteness, e.g., whiteness, together with printability and runnability. When a printing paper coated with a kaolin-containing composition is calendered, the plate-like crystals orient in the plane of the paper and smoothness and gloss of the paper are increased.

Das Material gemäß eines in DE 199 83 417 T1 genannten Aspektes kann die grobe Produktfraktion sein, die durch den Teilchengrößenklassierer im Verfahren gemäß dem ersten Aspekt der Erfindung abgetrennt wird. Sie kann mit anderen Streichpigmentprodukten gemischt sein, die Kaolin und/oder ein oder mehrere im Fachgebiet bekannte Streichpigmente umfassen, bspw. ausgewählt aus gemahlenen oder gefällten Carbonaten, wie Calciumcarbonat, kalziniertem Kaolin, Talk, Satinweiß, Titandioxid, Aluminiumtrihydrat, amorphen Siliziumdioxiden und Silikaten, Zinkoxid, Bariumsulfat und sogenannten Kunststoffpigmenten, so dass eine Streichpigmentmischung oder -zusammensetzung erhalten wird.The material according to a in DE 199 83 417 T1 said aspect may be the coarse product fraction separated by the particle size classifier in the process according to the first aspect of the invention. It may be mixed with other coating pigment products comprising kaolin and / or one or more coating pigments known in the art, for example selected from ground or precipitated carbonates such as calcium carbonate, calcined kaolin, talc, satin white, titanium dioxide, aluminum trihydrate, amorphous silica and silicates. Zinc oxide, barium sulfate and so-called plastic pigments to obtain a coating pigment mixture or composition.

DE 699 08 353 T2 betrifft Pigmenterzeugnisse sowie ihre Herstellung und Verwendung in Beschichtungszusammensetzungen. Beschrieben ist die Herstellung verbesserter anorganischer Pigmente für Papierbeschichtungszusammensetzungen, und insbesondere Pigmente zur Verwendung in Zusammensetzungen für die Herstellung von glanzbeschichtetem Papier, insbesondere leicht gestrichenem und ultraleicht gestrichenem Papier, z.B. ein Pigmenterzeugnis zur Verwendung in einer Beschichtungszusammensetzung für die Herstellung einer Glanzschicht auf einem Papier, wobei das Pigmenterzeugnis prozessiertes teilchenförmiges Kaolin enthält, dessen Teilchen eine solche Teilchengrößenverteilung besitzen, dass mindestens 80 Gew.% der Teilchen einen Kugeläquivalentdurchmesser von weniger als 2 Mikrometer haben und nicht weniger als 8 Gew.% einen Kugeläquivalentdurchmesser von weniger al 0,25 Mikrometer, wobei die Teilchen einen Formfaktor von mindestens 45 besitzen. DE 699 08 353 T2 relates to pigment products and their preparation and use in coating compositions. Described is the preparation of improved inorganic pigments for paper coating compositions, and in particular pigments for use in compositions for the production of glossy coated paper, in particular lightly coated and ultralight coated paper, eg a pigment product for use in a coating composition for the production of a glossy layer on a paper the pigment product contains processed particulate kaolin whose particles have a particle size distribution such that at least 80% by weight of the particles have a sphere equivalent diameter of less than 2 microns and not less than 8% by weight have a sphere equivalent diameter less than 0.25 microns; Particles have a form factor of at least 45.

Bislang gehen die genannten Produkte, Verfahren und Prozesse von der Verwendung verschiedener, in der Regel anorganischer Pigmente oder Pigmentmischungen aus, welche als Streichfarbe mittels verschiedener Auftragstechnik auf das Papier gebracht werden. Diese Schicht wird anschließend getrocknet und thermomechanisch bei hohem Druck und erhöhter Temperatur geglättet (kalandriert oder satiniert).So far, the above products, processes and processes are based on the use of various, usually inorganic pigments or pigment mixtures, which as Coating color can be applied to the paper by means of various application techniques. This layer is then dried and smoothed thermomechanically at high pressure and elevated temperature (calendered or satined).

Nach dem derzeitigen Stand der Technik werden Papierglanz und Papierglätte durch Behandlungen mit Pigmentdispersionen und anschließendes Kalandrieren erhöht. Um mit den bekannten Pigmenten die gewünschten Papiereigenschaften zu erhalten ist teilweise das Aufbringen einer sehr dicken Strichschicht notwendig und anschließendes Kalandrieren unvermeidlich. Dieser Kalandriervorgang erfolgt bei hohem Druck und Temperaturen um bis zu ca. 100°C und hat zur Folge, dass z.B. das Papiervolumen durch den Druck reduziert wird. Das sinkende Papiervolumen verschlechtert die Haptik und senkt die Opazität dadurch, dass Lufteinschlüsse, die als Reflexionsflächen dienen und somit die Opazität steigern könnten, herausgedrückt werden. Das Kalandrieren reduziert die Porosität was wiederum die Fähigkeit des Papiers verringert, Wasserdampf an die Umgebung abzugeben. Die einfache Möglichkeit der Abgabe von Wasserdampf ist wichtig, da es sonst zu Blasenbildung Ablösung des Striches oder sogar zum Reißen des Papiers kommen kann. Daher sind bei der Herstellung von Spezialpapieren mit dickem Strich lange Verweildauern im in der Regel sehr teuren Kalander notwendig, was das Papier zusätzlich zu den zusätzlichen Kosten der dick aufgetragenen Strichdispersion weiter verteuert.In the current state of the art, paper gloss and paper smoothness are increased by treatments with pigment dispersions and subsequent calendering. In order to obtain the desired paper properties with the known pigments, the application of a very thick coating layer is necessary in some cases, and subsequent calendering is unavoidable. This calendering process is carried out at high pressure and temperatures up to about 100 ° C and has the consequence that e.g. the paper volume is reduced by the pressure. The decreasing paper volume degrades the haptic and lowers the opacity by forcing out air inclusions, which serve as reflection surfaces and thus increase the opacity. Calendering reduces porosity which in turn reduces the paper's ability to deliver water vapor to the environment. The simple way of dispensing water vapor is important, otherwise it may cause blistering, separation of the line or even tearing of the paper. Therefore, in the production of special papers with a thick line long residence times in the usually very expensive calender are necessary, which further increases the cost of paper in addition to the additional cost of thickly applied line dispersion.

Ein transparentes bzw. ein als Pulver weiß erscheinendes Pigment, dass die gewünschten Anforderungen an Papierglanz, -glätte und Opazität auch schon in dünneren Schichten liefern könnten, würde die Möglichkeit schaffen, Papiervolumen und Haptik anpassen zu können und gleichzeitig die Verweilzeit im Kalander zu reduzieren. Besonders bevorzugt wäre ein transparentes Pigment, das hohen Papierglanz und hohe Glätte der Strichschicht bereits bei reduziertem Kalanderdruck, oder sogar ohne im Kalander behandelt zu werden, gewährleisten kann. So würden Papiervolumen, Haptik und Opazität während des Kalandrierens weniger oder, im Fall eines nicht notwendigen Kalandrierens, gar nicht negativ beeinflusst. Dies ist mit den bislang eingesetzten Pigmenten und Additiven und den daraus resultierenden Streichfarben sowie der verfügbaren und eingesetzten Maschinentechnik, den verfügbaren und eingesetzten Verfahren und Prozessen nicht möglich.A transparent or powder-white pigment, which could deliver the desired requirements for paper gloss, smoothness and opacity even in thinner layers, would create the possibility of being able to adapt paper volume and haptics while reducing the residence time in the calender. Particularly preferred would be a transparent pigment that can ensure high paper gloss and high smoothness of the coating layer even at reduced calendering pressure, or even without being treated in the calender. Thus, paper volume, haptics and opacity during calendering would not be adversely affected or, in the case of unnecessary calendering, would not be adversely affected. This is not possible with the hitherto used pigments and additives and the coating colors resulting therefrom, as well as the available and used machine technology, the available and used processes and processes.

Bisher werden in der Papierveredelung überwiegend kristalline Pigmente verwendet. Amorphes SiO2, speziell gefällte oder pyrogene Kieselsäure wird aufgrund der hohen Porosität bzw. der hohen spezifischen Oberfläche als Mattierungsmittel in der Papierbeschichtung oder zur schnellen Farbaufnahme, z.B. als Pigment in der Beschichtung von Inkjetpapier eingesetzt. Nachteil dieser amorphen Kieselsäuren ist, dass diese nur mit einem sehr geringen Feststoffgehalt in Wasser dispergiert werden können und hier eine sehr hohe Viskosität zeigen, was bei den hohen Geschwindigkeiten der Papierbeschichtung von extremen Nachteil ist.So far, predominantly crystalline pigments have been used in paper finishing. Amorphous SiO 2 , especially precipitated or fumed silica, becomes matting agent in the paper coating due to the high porosity or the high specific surface area or for rapid ink absorption, eg used as a pigment in the coating of inkjet paper. Disadvantage of these amorphous silicas is that they can be dispersed in water only with a very low solids content and here show a very high viscosity, which is at the high speeds of the paper coating of extreme disadvantage.

Aufgabe der Erfindung ist es daher, Möglichkeiten zur Verwendung eines SiO2-enthaltenden amorphen, nichtkristallinen Feststoffs oder einer diesen Feststoff enthaltenden Zusammensetzung als Streichfarbe zur Beschichtung von Papieroberflächen bereitzustellen um bei geringem Kalanderdruck oder ohne Kalandrierung die Herstellung von Papier mit hohem Glanz, hoher Glätte, hoher Porosität, hoher Opazität und hohem Papiervolumen zu ermöglichen.It is therefore an object of the invention to provide possibilities for using a SiO 2 -containing amorphous, noncrystalline solid or a composition containing this solid as a coating color for coating paper surfaces in order to produce paper of high gloss, high smoothness, with low calendering pressure or without calendering. high porosity, high opacity and high paper volume.

Weiterhin ist es Aufgabe der Erfindung, ein Verfahren zur Herstellung von Papier mit hohem Glanz, hoher Glätte, hoher Porosität, hoher Opazität und hohem Papiervolumen bereitzustellen, durch welches auf das Papier ein amorpher, nichtkristalliner Feststoff oder eine einen solchen Feststoff enthaltende Zusammensetzung aufgebracht wird und das Papier bei geringem Kalanderdruck oder ohne Kalandrierung weiterverarbeitet wird.It is another object of the invention to provide a process for the production of paper with high gloss, high smoothness, high porosity, high opacity and high paper volume, by which on the paper an amorphous, non-crystalline solid or a composition containing such a solid is applied and the paper is processed at low calendering or without calendering.

Eine weitere Aufgabe der Erfindung ist es, ein Papier mit hohem Glanz, hoher Glätte, hoher Porosität, hoher Opazität und hohem Papiervolumen bereitzustellen, welches nach diesem Verfahren hergestellt wird und daher die erforderlichen Qualitätsansprüche trotz des geringem Kalanderdrucks oder sogar ohne Kalandrierung erfüllt.A further object of the invention is to provide a paper with high gloss, high smoothness, high porosity, high opacity and high paper volume, which is produced by this method and therefore meets the required quality standards despite the low calendering pressure or even without calendering.

Diese Aufgaben werden durch die Gegenstände der unabhängigen Ansprüche 1, 7 und 10 gelöst.These objects are achieved by the subject-matter of independent claims 1, 7 and 10.

Überraschender Weise hat sich gezeigt, dass die Verwendung von neuartigen amorphen, nichtkristallinen Feststoffpulvern als Teil einer Streichfarbe zur Beschichtung von Papieroberflächen besonders vorteilhaft zur Erzeugung ganz besonders glatter und glänzender Oberflächen geeignet ist und zudem mit sehr niedriger Viskosität bei sehr hohem Feststoffgehalt zur Verfügung gestellt werden können. Derartige Pigmente zeigen also entgegengesetzte Eigenschaft und Wirkung zu den bisher bekannten amorphen gefällten und pyrogenen Kieselsäuren und übertreffen auch die bisher eingesetzten kristallinen Pigmente in den von der Papierindustrie geforderten Eigenschaften deutlich. Derartige amorphe, nichtkristalline Feststoffe als Pigmente wurden bislang noch nicht beschrieben und sind daher eine vollkommen neue Pigmentgruppe.Surprisingly, it has been found that the use of novel amorphous, non-crystalline solid powders as part of a coating color for coating paper surfaces is particularly advantageous for producing very particularly smooth and shiny surfaces and can also be provided with very low viscosity at very high solids content , Thus, such pigments show opposite property and effect to the hitherto known amorphous precipitated and fumed silicas and also clearly exceed the previously used crystalline pigments in the properties required by the paper industry. such Amorphous, non-crystalline solids as pigments have not been described so far and are therefore a completely new pigment group.

Ein wesentlicher Aspekt der Erfindung ist daher die Verwendung eines SiO2-enthaltenden Feststoffs oder einer diesen Feststoff enthaltenden Zusammensetzung alsAn essential aspect of the invention is therefore the use of a SiO 2 -containing solid or a composition containing this solid as

Streichfarbe zur Beschichtung von Papieroberflächen, wobei der Feststoff als amorpher, nichtkristalliner Feststoff vorliegt und der Feststoff oder die Zusammensetzung bei geringem Kalanderdruck oder ohne Kalandrierung zur Erzeugung von Papier mit hohem Glanz, hoher Glätte, hoher Porosität, hoher Opazität und hohem Papiervolumen geeignet ist.A coating color for coating paper surfaces, wherein the solid is present as an amorphous, non-crystalline solid and the solid or composition is suitable for producing high gloss, high smoothness, high porosity, high opacity and high paper volume at low calendering or calendering.

Die amorphen, nichtkristallinen Feststoffe bzw. Feststoffpulver oder Suspensionen dieser zeichnen sich aus durch:

  • bevorzugt sehr hohe Transparenz der Partikel (glasklar), optional auch trüb,
  • bevorzugt farblos, als Pulver weiß erscheinend, optional auch farbig,
  • bevorzugt frei von Einschlüssen und Poren in den Pulverpartikeln, optional auch mit,
  • hohe Stabilität gegenüber Wasser, Hydrolytische Klasse < 4 nach ISO 719 / DIN 12111,
  • bevorzugt eine Hydrolytische Klasse < 3 nach ISO 719 / DIN 12111,
  • einen Anteil von mindestens: 20-100 Ma-% SiO2 in der Zusammensetzung,
  • bevorzugt mindestens enthaltend SiO2 von 40-60 Ma-%, weiter bevorzugt von 60-100 Ma-%,
  • optional zusätzlich enthaltend: Al, Zn, Ca, B, Ba, Mg, Ti, Na, K, P, O, H von 0,1-80 Ma-%,
  • optional zusätzlich enthaltend färbende Elemente wie z.B. Fe, Co, Cu, Ni, Cr, ZrO2, F von 0,01-40 Ma-%,
  • Partikel in einer Korngröße von 100 Ma-% <100 µm, bevorzugt 100 Ma-% < 50 µm,
  • bevorzugt in einer Korngröße von mindestens 80 Ma-% < 5 µm,
  • in einer Korngröße mindestens 20 Ma-% < 2 bis > 50 Ma-% < 2,
  • weiter bevorzugt mit mindestens 20 Ma-% von 1 nm bis 2 µm,
  • vergleichsweise niedrige spezifischen Oberfläche BET < 100 m2/g,
  • weiter bevorzugt mit einer BET < 50 m2/g,
  • mit einem Feststoffgehalt > 20 Ma-% in der Suspension,
  • optional weitere in der Suspension enthaltene Additive wie z.B. Dispergiermittel, Verdicker oder andere anorganische oder organische Pigmente,
  • alternative Bereitstellung als Pulver mit einer Feuchtigkeit < 20 Ma-%, bevorzugt < 10 Ma-%.
The amorphous, non-crystalline solids or solid powders or suspensions thereof are characterized by:
  • prefers very high transparency of the particles (crystal clear), optionally turbid,
  • preferably colorless, appearing white as powder, optionally also colored,
  • preferably free of inclusions and pores in the powder particles, optionally also with,
  • high stability against water, hydrolytic class <4 according to ISO 719 / DIN 12111,
  • preferably a hydrolytic class <3 according to ISO 719 / DIN 12111,
  • a proportion of at least: 20-100% by mass SiO 2 in the composition,
  • preferably at least containing SiO 2 of 40-60% by mass, more preferably of 60-100% by mass,
  • optionally additionally containing: Al, Zn, Ca, B, Ba, Mg, Ti, Na, K, P, O, H of 0.1-80% by mass,
  • optionally additionally containing coloring elements such as Fe, Co, Cu, Ni, Cr, ZrO 2 , F of 0.01-40% by mass,
  • Particles in a particle size of 100% by mass <100 μm, preferably 100% by mass <50 μm,
  • preferably in a particle size of at least 80% by mass <5 μm,
  • in a particle size at least 20% by mass <2 to> 50% by mass <2,
  • more preferably at least 20% by mass from 1 nm to 2 μm,
  • comparatively low specific surface area BET <100 m 2 / g,
  • more preferably with a BET <50 m 2 / g,
  • with a solids content> 20% by mass in the suspension,
  • optionally further additives contained in the suspension, for example dispersants, thickeners or other inorganic or organic pigments,
  • alternative provision as a powder with a humidity of <20% by mass, preferably <10% by mass.

In einer bevorzugten Variante ist der verwendete Feststoff transparent und/oder als Pulver weiß erscheinend. Dadurch ist die besonders häufig verwendete Papierfarbe weiß besonders einfach zu realisieren und Verfärbungen werden vermieden. Wie jedoch in obiger Auflistung bereits erwähnt wurde, sind auch andere Pigmentfarben und Trübungen möglich, z.B. um Färbungen des Papiers oder bestimmte Farbeffekte zu erreichen.In a preferred variant, the solid used is transparent and / or white as a powder. As a result, the particularly frequently used paper color white is particularly easy to realize and discoloration is avoided. However, as already mentioned in the above list, other pigment colors and opacities are possible, e.g. to achieve colorations of the paper or certain color effects.

Weiter bevorzugt ist eine Verwendung eines SiO2-enthaltenden Feststoffs oder einer diesen Feststoff enthaltenden Zusammensetzung als Pigment oder Streichfarbe zur Beschichtung von Papieroberflächen wobei der Feststoff oder die Zusammensetzung einen SiO2-Anteil von 40-100 Ma-%, besonders bevorzugt von 60-100 Ma-% aufweist.Further preferred is a use of a SiO 2 -containing solid or of a composition containing this solid as a pigment or coating color for coating paper surfaces wherein the solid or the composition has a SiO 2 content of 40-100 M%, particularly preferably 60-100 Has m%.

Bevorzugt ist weiterhin eine Verwendung bei der der Feststoff in Form von Feststoffpartikeln einer Korngröße (Äquivalentdurchmesser) von mindestens 99 Ma-% < 100 µm, bevorzugt mindestens 99 Ma-% < 50 µm, bevorzugt mindestens 80 Ma-% < 5 µm, bevorzugt 20 - 50 Ma% < 2 µm, besonders bevorzugt mindestens 20 Ma% von 1 - 2 µm aufweist. Der Äquivalentdurchmesser wird soweit nicht anders angegeben durch die Sinkgeschwindigkeit der Partikel in viskosem Medium bestimmt. Die Messung erfolgt mit geeigneten Geräten wie z.B. dem Sedigraph der Firma Micromeritics.Also preferred is a use in which the solid in the form of solid particles having a particle size (equivalent diameter) of at least 99% by mass <100 .mu.m, preferably at least 99% by mass <50 .mu.m, preferably at least 80% by mass <5 .mu.m, preferably 20 - 50 Ma% <2 microns, more preferably at least 20 Ma% of 1 - 2 microns. Unless otherwise specified, the equivalent diameter is determined by the rate of descent of the particles in viscous medium. The measurement is carried out with suitable equipment, e.g. the Sedigraph of the company Micromeritics.

Die verwendeten Feststoffe zeichnen sich durch ein hohes Reflektionsvermögen aus. Bevorzugt weisen sie daher glatte Oberflächen ohne oder mit lediglich wenigen Unebenheiten auf. Dadurch ist die spezifische Oberfläche vergleichsweise klein.The solids used are characterized by a high reflectivity. Therefore, they preferably have smooth surfaces with no or only a few bumps. As a result, the specific surface area is comparatively small.

Der Feststoff weist eine spezifische Oberfläche BET < 100 m2/g, bevorzugt < 50 m2/g auf.The solid has a specific surface area BET <100 m 2 / g, preferably <50 m 2 / g.

Selbstverständlich sind auch (in Abhängigkeit von der Korngröße) noch geringere spezifische Oberflächen möglich.Of course, even smaller specific surface areas are possible (depending on the grain size).

Weiterhin ist eine Verwendung eines SiO2-enthaltenden Feststoffs oder einer diesen Feststoff enthaltenden Zusammensetzung als Pigment oder Streichfarbe zur Beschichtung von Papieroberflächen bevorzugt, wobei der der Feststoff oder die Zusammensetzung einen Trockenmasseanteil von 20-85 Ma-%, bevorzugt 30-80 Ma-%, besonders bevorzugt von 35-75 Ma-% aufweist.Furthermore, it is preferable to use a SiO 2 -containing solid or a composition containing this solid as a pigment or coating color for coating paper surfaces, wherein the solid or the composition has a dry weight fraction of 20-85% by mass, preferably 30-80% by mass, particularly preferably 35-75% by mass.

Ein wesentlicher Aspekt der Erfindung ist ein Verfahren zur Herstellung von Papier mit hohem Glanz, hoher Glätte, hoher Porosität, hoher Opazität und hohem Papiervolumen, wobei auf das Papier ein amorpher, nichtkristalliner Feststoff oder eine einen solchen Feststoff enthaltende Zusammensetzung als Streichfarbe aufgebracht wird und das Papier bei geringem Kalanderdruck oder ohne Kalandrierung weiterverarbeitet wird.An essential aspect of the invention is a process for the production of paper of high gloss, high smoothness, high porosity, high opacity and high paper volume, wherein on the paper an amorphous, non-crystalline solid or a composition containing such a solid is applied as a coating color and the Paper is processed at low calendering or without calendering.

Dadurch ist es möglich, die gewünschten Anforderungen an Papierglanz, -glätte und Opazität auch durch dünne Strichschichten bereitstellen zu können und gleichzeitig Papiervolumen und Haptik positiv beeinflussen zu können. Durch die geringer Verweilzeit im Kalander und den geringeren Kalanderdruck wird das Papier während der Herstellung weniger stark komprimiert, was sich positiv auf das Papiervolumen, Opazität und Haptik auswirkt. Im Fall der vollständigen Vermeidung des Kalandrierens würden Papiervolumen, Haptik und Opazität noch weniger negativ bzw. gar nicht negativ beeinflusst. Dies war mit den bislang eingesetzten Pigmenten und Additiven und den daraus hergestellten Streichfarben sowie den verfügbaren und eingesetzten Verfahren und Prozessen nicht möglich.This makes it possible to provide the desired requirements for paper gloss, smoothness and opacity even through thin coating layers and at the same time be able to positively influence paper volume and feel. The shorter dwell time in the calender and the lower calendering pressure mean that the paper is less compressed during production, which has a positive effect on paper volume, opacity and feel. In the case of complete avoidance of calendering paper volume, haptics and opacity would be even less negative or not negatively affected. This was not possible with the hitherto used pigments and additives and the coating colors produced therefrom, as well as the available and used processes and processes.

In einer bevorzugten Variante des Verfahrens wird der amorphe, nichtkristalline Feststoff oder die einen solchen Feststoff enthaltende Zusammensetzung mittels Trocken- und/oder Nassaufbereitung geeigneter Materialien, wie z.B. Glas, durch Prozessschritte, welche Vorsortierung, Brechen, Sieben, Mahlen, Klassieren, bevorzugt Windsichtung, oder eine Auswahl dieser umfassen und optional einer anschließenden Trocknung und/oder Dispergierung unter Zusatz von anorganischen oder organischen Additiven wie z.B. Dispergiermittel oder Pigmenten, vorbereitet.In a preferred variant of the process, the amorphous, non-crystalline solid or composition containing such a solid is obtained by dry and / or wet treatment of suitable materials, e.g. Glass, by process steps, which pre-sorting, breaking, screening, milling, classifying, preferably air classification, or a selection of these and optionally a subsequent drying and / or dispersion with the addition of inorganic or organic additives such. Dispersants or pigments prepared.

Die Herstellung der erfindungsgemäßen amorphen, nichtkristallinen Feststoffpulver oder Suspensionen dieser erfolgt demnach durch Auswahl geeigneter Materialien, z.B. Glas und ggf. deren Aufbereitung, beispielsweise durch z.B. Vorsortierung, brechen, sieben, mahlen, klassieren (z.B. Windsichtung) als eine mögliche Prozessfolge im Rahmen einer Trockenaufbereitung, gegebenenfalls mit einer nachgeschalteten Dispergierung unter Zusatz von Dispergiermitteln, Additiven oder anderen organischen oder anorganischen Bestandteilen wie z.B. anderen Pigmenten zu einer Pigmentdispersion. Diese kann ggf. direkt als Streichfarbe eingesetzt werden.Accordingly, the amorphous, non-crystalline solid powders or suspensions according to the invention are prepared by selecting suitable materials, for example glass and, if appropriate, processing, for example by presorting, breaking, sieving, milling, classifying (eg air classification) as a possible process sequence in the context of dry processing optionally with a downstream dispersion with the addition of dispersants, additives or other organic or inorganic constituents such as other pigments to a pigment dispersion. This can possibly be used directly as a coating color.

Alternativ und bevorzugt die Herstellung der erfindungsgemäßen amorphen, nichtkristallinen Feststoffpulver oder Suspensionen dieser z.B. mittels Vorsortierung, brechen, sieben, ggf. vormahlen, klassieren, nassmahlen, fraktionieren, z.B. mittels Hydrozyklon oder anderen geeigneten Verfahren, als eine mögliche Prozessfolge im Rahmen einer Trockenaufbereitung oder Nassaufbereitung oder einer kombinierten Trocken- und Nassaufbereitung, ggf. kombiniert mit einer Dispergierung unter Zusatz von Additiven wie z.B. Dispergiermittel und optional anderen organischen oder anorganischen Bestandteilen wie z.B. anderen Pigmenten zu einer Pigmentdispersion. Diese kann ggf. direkt als Streichfarbe eingesetzt werden.Alternatively, and preferred is the preparation of the amorphous, non-crystalline solid powders or suspensions of this invention, e.g. by presorting, crushing, screening, possibly pre-grading, classifying, wet-milling, fractionating, e.g. by means of hydrocyclone or other suitable methods, as a possible process sequence in the context of a dry treatment or wet treatment or a combined dry and wet processing, optionally combined with a dispersion with the addition of additives such. Dispersants and optionally other organic or inorganic ingredients, e.g. other pigments to a pigment dispersion. This can possibly be used directly as a coating color.

Alternativ kann auch eine durch Nassaufbereitung hergestellt Suspension in die trockene Form überführt werden, z.B. mittels Sprühtrocknung, um dieses Pulver in einem späteren Schritt dann gegebenenfalls wieder in eine Suspension zurückzuführen.Alternatively, a suspension prepared by wet processing may also be converted to the dry form, e.g. by spray-drying, in order to then possibly return this powder to a suspension in a later step.

Aus dem Pigmentpulver oder der -dispersion kann dann optional in einem (oder mehreren) weiteren Schritt eine Streichfarbe unter Verwendung der erfindungsgemäßen amorphen nichtkristallinen Feststoffpulver oder Suspension durch Zusatz von Wasser und Additiven wie z.B. Rheologieadditive, Dispergiermittel, Verdicker, Bakteriziden, sowie gegebenenfalls anderer Streichpigmente wie z.B. Kaolin, Satinweiß, Talkum, Calciumcarbonat (gefällt oder gemahlen) Titandioxid, gefällter oder pyrogener Kieselsäure, Aluminiumhydroxid, Dolomit, Bariumsulfat, Zinkoxid, Bentonit hergestellt werden.From the pigment powder or dispersion it is then optionally possible in one (or more) further step to apply a coating color using the amorphous non-crystalline solid powders or suspension according to the invention by adding water and additives such as e.g. Rheology additives, dispersants, thickeners, bactericides, and optionally other coating pigments, e.g. Kaolin, satin white, talc, calcium carbonate (precipitated or ground), titanium dioxide, precipitated or fumed silica, aluminum hydroxide, dolomite, barium sulfate, zinc oxide, bentonite.

In einer weiteren bevorzugten Variante des Verfahrens wird der amorphe, nichtkristalline Feststoff oder die einen solchen Feststoff enthaltende Zusammensetzung mittels Bladecoating, Curtaincoating, Gussstrich, Filmpresse, Leimpresse oder anderer geeigneter Verfahren aufgebracht, wobei nach einer Trocknung das Papier bereits eine ausreichend homogene Oberflächenstruktur aufweist und ein Glätten mittels Kalander nicht nötig ist, oder bei geringem Druck erfolgen kann.In a further preferred variant of the method, the amorphous, non-crystalline solid or the composition containing such a solid is applied by blade coating, curtain coating, cast coat, film press, size press or other suitable method, wherein after drying, the paper already has a sufficiently homogeneous surface structure and a Smoothing with calender is not necessary, or can be done at low pressure.

Das Beschichten von Papieroberflächen mit den beschriebenen Suspensionen bzw. Streichfarben kann folglich mit den gängigen Verfahren wie z.B. Bladecoating, Curtaincoating, Gussstrich, Filmpresse, Leimpresse oder anderer geeigneten Verfahren durchgeführt werden, gefolgt von der Trocknung der gestrichenen Papierbahn und dem Glätten mit geringem Druck mittels Kalander oder anderen geeigneten Verfahren. Es ist (je nach Anspruch an das Papier und abhängig von den Kundenwünschen) auch ein vollkommener Wegfall des Prozessschrittes der Glättung möglich.The coating of paper surfaces with the described suspensions or coating colors can consequently be carried out by conventional methods such as blade coating, curtain coating, cast coating, film press, size press or other suitable method, followed by drying the coated paper web and smoothing with low pressure by means of calender or other suitable method. It is (depending on the requirement of the Paper and depending on the customer's wishes) also a complete elimination of the process step of smoothing possible.

Ein weiterer wesentlicher Aspekt der Erfindung ist ein Papier mit hohem Glanz, hoher Glätte, hoher Porosität, hoher Opazität und hohem Papiervolumen, welches eine Oberflächenbeschichtung umfasst, wobei die Oberflächenbeschichtung einen Feststoff oder eine diesen Feststoff enthaltende Zusammensetzung umfasst, wobei der Feststoff als amorpher, nichtkristalliner Feststoff vorliegt und der Feststoff oder die Zusammensetzung bei geringem Kalanderdruck oder ohne Kalandrierung zur Erzeugung von Papier mit hohem Glanz, hoher Glätte, hoher Porosität, hoher Opazität und hohem Papiervolumen geeignet ist.Another essential aspect of the invention is a paper having high gloss, high smoothness, high porosity, high opacity and high paper volume which comprises a surface coating, the surface coating comprising a solid or a composition containing this solid, the solid being an amorphous, non-crystalline Solid is present and the solid or composition is suitable at low calendering or calendering to produce paper with high gloss, high smoothness, high porosity, high opacity and high paper volume.

Ein derartiges Papier weist gegenüber dem Stand der Technik trotz vereinfachter Herstellung verbesserte Eigenschaften z.B. in Bezug auf die Opazität und das Papiervolumen auf. Weiterhin zeichnet es sich durch hohen Glanz, hohe Glätte, hohe Porosität und optional auch weitere positive Eigenschaften aus.Such paper, in contrast to the prior art, has improved properties, e.g. in terms of opacity and paper volume. Furthermore, it is characterized by high gloss, high smoothness, high porosity and optionally also other positive properties.

Das Papier weist einen Glanz auf, welcher bei einem Messwinkel von 60° > 2,0, bevorzugt > 2,5, besonders bevorzugt > 5,0 und meist bevorzugt > 7,5 und bei einem Messwinkel von 85° >2,5, bevorzugt > 3,5, besonders bevorzugt > 10 und meist bevorzugt > 15 beträgt. Die Messung des Glanzes erfolgt sofern nicht anders angegeben nach Norm EN ISO 2813.The paper has a gloss which at a measurement angle of 60 °> 2.0, preferably> 2.5, more preferably> 5.0 and most preferably> 7.5 and at a measurement angle of 85 °> 2.5, preferably> 3.5, more preferably> 10 and most preferably> 15. The measurement of the gloss takes place, unless otherwise stated, according to standard EN ISO 2813.

Bevorzugt weist das Papier eine Rupffestigkeit bei Mehrfachbedruckung von > 4, bevorzugt > 6, besonders bevorzugt > 8, bevorzugt > 10, bevorzugt > 12 aufweist.The paper preferably has a picking strength with multiple printing of> 4, preferably> 6, particularly preferably> 8, preferably> 10, preferably> 12.

Weiterhin können derartige Papiere besonders weiß sein. In einer bevorzugten Ausführungsform weist das Papier eine Helligkeit gemessen als L* im L*a*b*-Farbraum von > 95, bevorzugt ≥ 95,5 auf. Damit ist es für eine Vielzahl von Anwendungen geeignet, welche ein breites Spektrum abdecken. Insbesondere eignet sich ein derartiges gestrichenes Papier z.B. als Trägermedium, z.B. von Farbe. Somit ist beispielsweise die Informationsspeicherung möglich. Tabelle 1 Material Korngröße, d50* Papier, unbeschichtet -- Papier, nur mit Wasser beschichtet -- Äquimolare Mischung: Ca(OH)2+Mg(OH)2, Slurry, TS** 30 Ma-% 0,3 Kaolin 1: 80 Ma-% < 2 µm, Primärlagerstätte, nass gemahlen 1,3 Kaolin 2: 55 Ma-% < 2 µm, Primärlagerstätte, ungemahlen 1,8 Kaolin 3: 90 Ma-% < 2 µm, Sekundärlagerstätte, ungemahlen 0,5 CaCO3 1: GCC, Glanzpigment 0,9 Al2O3 1: nass gemahlen 0,15 Kalziniertes Kaolin, trocken gemahlen 1,5 Ca-Na-Silikat, trocken gemahlen, amorph 4 Amorphes SiO2 (gefällte Kieselsäure)*** 11 Amorphes SiO2 (pyrogene Kieselsäure), Aggregatgröße, REM, µm 0,05-0,3 Amorphes SiO2 (pyrogene Kieselsäure), Primärpartikelgröße, REM, nm 5-15 Erfindungsgemäße Zusammensetzung, trocken gemahlen, grob 3,0 Erfindungsgemäße Zusammensetzung, trocken gemahlen, fein 2,0 Erfindungsgemäße Zusammensetzung, nass gemahlen, sehr fein 0,3 * gemessen mit Sedigraph, Fa. Micromeritics
** TS: Trockensubstanz
***: gemessen mit Laserbeugung Furthermore, such papers can be particularly white. In a preferred embodiment, the paper has a brightness measured as L * in the L * a * b * color space of> 95, preferably ≥ 95.5. This makes it suitable for a variety of applications covering a broad spectrum. In particular, such a coated paper is suitable for example as a carrier medium, for example of color. Thus, for example, the information storage is possible. Table 1 material Grain size, d 50 * Paper, uncoated - Paper, only coated with water - Equimolar mixture: Ca (OH) 2 + Mg (OH) 2 , slurry, TS ** 30% by mass 0.3 Kaolin 1: 80% by mass <2 μm, primary deposit, wet-ground 1.3 Kaolin 2: 55% by mass <2 μm, primary deposit, unground 1.8 Kaolin 3: 90% by mass <2 μm, secondary deposit, unground 0.5 CaCO 3 1: GCC, luster pigment 0.9 Al 2 O 3 1: wet milled 0.15 Calcined kaolin, ground dry 1.5 Ca-Na silicate, dry-ground, amorphous 4 Amorphous SiO 2 (precipitated silica) *** 11 Amorphous SiO 2 (fumed silica), aggregate size, REM, μm 0.05-0.3 Amorphous SiO 2 (pyrogenic silica), primary particle size, REM, nm 5-15 Composition according to the invention, dry-ground, coarse 3.0 Composition according to the invention, dry-ground, fine 2.0 Composition according to the invention, wet-ground, very fine 0.3 * measured with Sedigraph, Fa. Micromeritics
** TS: dry substance
***: measured with laser diffraction

Beispiel 1:Example 1:

Die Pulvermaterialien wurden jeweils wie in Tabelle 1 angegeben verwendet. Wenn nicht anders beschrieben wurde von diesen jeweils eine 40%-ige Suspension in Wasser ohne weitere Zusätze hergestellt. Mit einem halbautomatischen Rakelgerät (Fa. Erichsen) wurden mit einem Glattstab (d.h. ohne Wicklung) die homogenen Suspensionen mit einer Geschwindigkeit von 10 mm/sek. auf ein ungestrichenes Trägerpapier (80 g/m2) aufgetragen, bei Raumtemperatur über Nacht getrocknet und der Glanz bei zwei verschiedenen Winkeln (Byk Gardner, Handgerät) ohne weitere Behandlung gemessen. Die bei Winkeln von 60° und 85° gemessenen Werte sind in Tabelle 2 dargestellt. Tabelle 2 Probe Glanz 85° Glanz 60° Papier, unbeschichtet 3,9 3,6 Papier, nur mit Wasser beschichtet 2,0 3,4 Äquimolare Mischung: Ca(OH)2+Mg(OH)2, Slurry, TS 30 Ma-% 8,1 4,6 Kaolin 1: 80 Ma-% < 2 µm, Primärlagerstätte, nass gemahlen 3,3 4,3 Kaolin 2: 55 Ma-% < 2 µm, Primärlagerstätte, ungemahlen 2,7 4,2 Kaolin 3: 90 Ma-% < 2 µm, Sekundärlagerstätte ungemahlen 8,0 4,4 CaCO3 1: GCC, Glanzpigment 4,2 2,3 Al2O3 1: nass gemahlen 4,3 4,6 Kalziniertes Kaolin, trocken gemahlen 2,7 2,5 Ca-Na-Silikat, trocken gemahlen, amorph 1,3 2,5 Amorphes SiO2 (gefällte Kieselsäure), Surry, TS 10 Ma-% 0,8 2,6 Amorphes SiO2 (pyrogene Kieselsäure), TS 5 Ma-% 1,4 2,8 Erfindungsgemäße Zusammensetzung, trocken gemahlen, grob 2,7 2,6 Erfindungsgemäße Zusammensetzung, trocken gemahlen, fein 4,9 2,5 Erfindungsgemäße Zusammensetzung, nass gemahlen, sehr fein 17,4 8,4 The powder materials were each used as indicated in Table 1. Unless otherwise stated, a 40% suspension in each case of water was prepared without further additives. With a semi-automatic squeegee (Erichsen) with a smooth rod (ie without winding), the homogeneous suspensions at a rate of 10 mm / sec. on an uncoated carrier paper (80 g / m 2 ), dried at room temperature overnight and the gloss measured at two different angles (Byk Gardner, handheld device) without further treatment. The values measured at angles of 60 ° and 85 ° are shown in Table 2. Table 2 sample Gloss 85 ° Gloss 60 ° Paper, uncoated 3.9 3.6 Paper, only coated with water 2.0 3.4 Equimolar mixture: Ca (OH) 2 + Mg (OH) 2 , slurry, TS 30% by mass 8.1 4.6 Kaolin 1: 80% by mass <2 μm, primary deposit, wet-ground 3.3 4.3 Kaolin 2: 55% by mass <2 μm, primary deposit, unground 2.7 4.2 Kaolin 3: 90% by mass <2 μm, secondary deposit unground 8.0 4.4 CaCO 3 1: GCC, luster pigment 4.2 2.3 Al 2 O 3 1: wet ground 4.3 4.6 Calcined kaolin, ground dry 2.7 2.5 Ca-Na silicate, dry-ground, amorphous 1.3 2.5 Amorphous SiO 2 (precipitated silica), Surry, TS 10 Ma-% 0.8 2.6 Amorphous SiO 2 (Fumed Silica), TS 5 Ma-% 1.4 2.8 Composition according to the invention, dry-ground, coarse 2.7 2.6 Composition according to the invention, dry-ground, fine 4.9 2.5 Composition according to the invention, wet-ground, very fine 17.4 8.4

Die in Tabelle 2 gezeigten Messwerte zeigen, dass das erfindungsgemäße Produkt bei entsprechender Feinheit sowohl bei 85° als auch bei 60° eine deutliche Glanzsteigerung des gestrichenen Papiers bewirkt, und in beiden Fällen erheblich über den Glanzwerten vergleichbarer Pigmente nach dem Stand der Technik liegt. Die Aufgabenstellung wurde somit erfüllt.The measured values shown in Table 2 show that the product according to the invention, with a corresponding degree of fineness, produces a marked gloss increase of the coated paper both at 85 ° and 60 °, and in both cases is considerably higher than the gloss values of comparable prior art pigments. The task was thus fulfilled.

Beispiel 2Example 2

Das erfindungsgemäße Produkt wurde im Vergleich zu einer Calciumcarbonat und Kaolin (75 und 25 Massenteile) enthaltenden Standard-Streichfarbenrezeptur geprüft. Dazu wurde dieses neben Calciumcarbonat (90, 80 und 70 Teile) mit 10, 20 und 30 Teilen anstatt dem Kaolin bei ansonst gleichen Bedingungen zugegeben und auf Papier gestrichen. Vom gestrichenen Papier wurde danach die Helligkeit gemessen. Zusätzlich wurde die Rupffestigkeit bei Mehrfachbedruckung (Offsettest) geprüft. Dazu wurden Teststreifen wiederholt bedruckt. Die Rupffestigkeit ist umso besser je höher die Anzahl von Druckvorgängen bis zum ersten Rupfen ist. Tabelle 3 Nr. Calciumcarbonat Kaolin Erfindungsgemäßes Produkt Helligkeit L* Rupffestigkeit Durchgänge 1 75 25 95,0 8 2 90 10 95,5 >12 3 80 20 95,5 >12 4 70 30 95,5 >12 The product of the present invention was tested against a standard coating color formulation containing calcium carbonate and kaolin (75 and 25 parts by mass). For this purpose, in addition to calcium carbonate (90, 80 and 70 parts) with 10, 20 and 30 parts instead of the kaolin was added under otherwise identical conditions and painted on paper. The coated paper was then measured for brightness. In addition, the pick resistance tested for multiple printing (offsetting test). For this purpose, test strips were printed repeatedly. The picking resistance is the better the higher the number of printing operations up to the first picking. Table 3 No. calcium carbonate kaolin Inventive product Brightness L * Pick resistance passes 1 75 25 95.0 8th 2 90 10 95.5 > 12 3 80 20 95.5 > 12 4 70 30 95.5 > 12

Aus den Ergebnissen geht hervor, dass neben der in Beispiel 1 beschriebenen Glanzsteigerung zusätzlich auch die Helligkeit erhöht und die Rupffestigkeit sogar deutlich verbessert werden kann.It can be seen from the results that in addition to the gloss increase described in Example 1, the brightness can also be increased and the pick resistance can even be significantly improved.

Die Rupffestigkeit ist wesentlich von der Art und der Menge des in der Streichfarbe enthaltenen Bindemittels abhängig. Eine hohe Bindemittelmenge geht einher mit einer verbesserten Rupffestigkeit, bedeutet aber auch erhebliche Mehrkosten. Wie sich nun zeigt, kann mit dem erfindungsgemäßen Produkt auch die Rupffestigkeit deutlich verbessert oder umgekehrt der Anteil an Bindemittel deutlich reduziert werden.The pick resistance is essentially dependent on the type and amount of binder contained in the coating color. A high amount of binder goes along with an improved pick resistance, but also means considerable additional costs. As can now be seen, the picking strength can also be significantly improved with the product according to the invention or, conversely, the proportion of binder can be significantly reduced.

Claims (11)

  1. Use of a solid containing SiO2 or a composition containing this solid in a proportion of at least 20 % by mass, as a coating paint for coating paper surfaces, characterised in that the solid is present as an amorphous, noncrystalline solid of a hydrolytic class < 4 according to ISO 719 / DIN 12111 having a particle size (hydrodynamic equivalent diameter) of 20 - 50 % by mass < 2 µm and a specific surface area according to BET < 100 m2/g, and the solid or the composition is suitable, at a low calendar pressure or without calendaring, for producing paper having a gloss > 2.0 at a measurement angle of 60° and >2.5 at a measurement angle of 85°.
  2. Use according to claim 1, characterised in that the solid is transparent and/or appears white as a powder.
  3. Use according to either claim 1 or claim 2, characterised in that the solid or the composition comprises a SiO2 proportion of 40-100 % by mass, preferably of 60-100 % by mass.
  4. Use according to any of claims 1-3, characterised in that the solid in the form of solid particles has a particle size (hydrodynamic equivalent diameter) of at least 99 % by mass < 100 µm, preferably at least 99 % by mass < 50 µm, preferably at least 80 % by mass < 5 µm, particularly preferably at least 20 % by mass of 1-2 µm.
  5. Use according to any of claims 1-4, characterised in that the solid has a specific surface area BET < 50 m2/g.
  6. Use according to any of claims 1 to 5, characterised in that the solid or the composition has a dry mass proportion of 20-85 % by mass, preferably 30-80 % by mass, particularly preferably 35-75 % by mass.
  7. Method for manufacturing paper having a gloss > 2.0 at a measurement angle of 60° and > 2.5 at a measurement angle of 85°, characterised in that an amorphous, noncrystalline, SiO2-containing solid of a hydrolytic class < 4 according to ISO 719 / DIN 12111 having a particle size (hydrodynamic equivalent diameter) of 20-50 % by mass < 2 µm and a specific surface area according to BET < 100 m2/g, or a composition containing such a solid in a proportion of at least 20 % by mass, is applied to the paper as a coating paint and the paper is further processed at a low calendar pressure or without calendaring.
  8. Method according to claim 7, characterised in that the amorphous, noncrystalline solid or the composition containing such a solid is prepared by dry and/or wet processing of suitable materials, such as for example glass, by process steps which include presorting, breaking, sieving, grinding, sizing, preferably by air classification, or a selection thereof, and optionally subsequent drying and/or dispersing with the addition of inorganic or organic additives such as for example dispersants or pigments.
  9. Method according to claim 8, characterised in that the amorphous, noncrystalline solid or the composition containing such a solid is applied by means of blade coating, curtain coating, cast coating, film pressing, size pressing or another suitable method and, after drying, the paper already has a sufficiently homogenous surface structure and smoothing by calendar is not required, or can occur at low pressure.
  10. Paper having a gloss > 2.0 at a measurement angle of 60° and > 2.5 at a measurement angle of 85°, which comprises a surface coating, characterised in that the surface coating comprises a SiO2-containing solid of a hydrolytic class < 4 according to ISO 719 / DIN 12111 or a composition containing this solid in a proportion of at least 20 % by mass, the solid being present as an amorphous, noncrystalline solid having a particle size (hydrodynamic equivalent diameter) of 20-50 % by mass < 2 µm and a specific surface area according to BET < 100 m2/g, and the solid or the composition is suitable, at a low calendar pressure or without calendaring, for producing paper having a gloss > 2.0 at a measurement angle of 60° and > 2.5 at a measurement angle of 85°.
  11. Paper according to claim 10, characterised in that the surface coating comprises a SiO2-containing solid having a specific surface area according to BET < 50 m2/g.
EP10190836.6A 2009-11-12 2010-11-11 Coating material for fibrous compounds Not-in-force EP2325389B1 (en)

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JPS5922794A (en) * 1982-07-30 1984-02-06 Mizusawa Ind Chem Ltd Filler for heat sensitive recording paper
NZ232170A (en) * 1989-03-23 1993-01-27 Tasman Pulp & Paper Co Ltd Precipitation of amorphous silica from geothermal fluid; use of silica in coating paper sheet
DE69406599T2 (en) * 1993-06-15 1998-04-02 Canon K.K., Tokio/Tokyo Cast coated paper for ink jet recording, its manufacturing process and ink jet printing process therewith
GB9807180D0 (en) * 1998-04-04 1998-06-03 Ecc Int Ltd Pigment products
GB9816578D0 (en) 1998-07-31 1998-09-30 Ecc Int Ltd Inorganic particulate materials and their production
US6582821B1 (en) 1999-10-29 2003-06-24 S. D. Warren Services Company Cast coated sheet and method of manufacture
DE10115570B4 (en) 2001-03-28 2005-09-08 Technocell Dekor Gmbh & Co. Kg Decorative paper with improved opacity
FR2842436B1 (en) 2002-07-17 2005-05-06 Omya Sa PROCESS FOR THE PREPARATION OF AQUEOUS SUSPENSIONS OF MINERAL. AQUEOUS SUSPENSIONS OF MINERAL CHARGES OBTAINED AND USES THEREOF
DE102006042167B4 (en) * 2005-09-06 2010-10-28 Gebrüder Dorfner GmbH & Co. Kaolin- und Kristallquarzsand-Werke KG Pigment composition for the coating of carrier media, ink jet printing medium and use of a pigment composition
US20070289499A1 (en) 2006-05-05 2007-12-20 Valadares Maria C A High performance kaolin pigment, paper coating paint and method for producing such paint

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