EP1817455B1 - Cellulose-containing filling material for paper, tissue, or cardboard products, method for the production thereof, paper, tissue, or cardboard product containing such a filling material, or dry mixture used therefor - Google Patents

Cellulose-containing filling material for paper, tissue, or cardboard products, method for the production thereof, paper, tissue, or cardboard product containing such a filling material, or dry mixture used therefor Download PDF

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EP1817455B1
EP1817455B1 EP05824751.1A EP05824751A EP1817455B1 EP 1817455 B1 EP1817455 B1 EP 1817455B1 EP 05824751 A EP05824751 A EP 05824751A EP 1817455 B1 EP1817455 B1 EP 1817455B1
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Prior art keywords
starch
paper
filler
mill
cellulose
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German (de)
French (fr)
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EP1817455A1 (en
Inventor
Alex Ozersky
Ralf Recknagel
Hans-Georg Brendle
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J Rettenmaier and Soehne GmbH and Co KG
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J Rettenmaier and Soehne GmbH and Co KG
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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/24—Polysaccharides
    • D21H17/25—Cellulose
    • 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
    • D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
    • D21H11/16—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only modified by a particular after-treatment
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/63—Inorganic compounds
    • D21H17/67—Water-insoluble compounds, e.g. fillers, 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
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/63—Inorganic compounds
    • D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
    • D21H17/69—Water-insoluble compounds, e.g. fillers, pigments modified, e.g. by association with other compositions prior to incorporation in the pulp or paper

Definitions

  • the invention relates to a cellulose-containing filler for paper, tissue or paperboard products and to manufacturing processes therefor, and to a paper, tissue or paperboard product or dry mix used for such a filler according to the preambles of claims 1, 39, 52 and 38, respectively.
  • cellulosic fibers made of various vegetable raw materials have been used as the raw material for the production of paper and cardboard.
  • These long-fiber products are the basis of paper and board production; Without them, no paper or cardboard can be produced. Their bond leads to the necessary sheet formation. They can differ in the degree of purity as well as in the fiber structure (freeness ° SR). Highly purified, lignin-free celluloses are known as well as lignin-containing fibers (groundwood, CTMP) and recycled fibers, which are obtained from waste paper and are accordingly still contaminated with various impurities.
  • Finely divided products such as native starch, calcium carbonate, kaolin or titanium dioxide are used in the production process of board and paper mills for various reasons. Due to their small particle size, these products are easily washed out of the paper web. Additional measures are needed to achieve retention in the paper web, at least to some extent. But this involves higher costs and other technological disadvantages. According to the literature, on polymer paper machines running at high speed (> 1500 m / min), the retention rate of fillers and pigments is currently often below 40% despite polymeric retention agents.
  • the EP 0930 345 A2 discloses a filler for the production of papers, in order to be able to increase the content of filler in the paperboard, while maintaining sufficient tear resistance.
  • a pigment very specifically an inorganic pigment, is mixed with fibrillated cellulose in a liquid state. This is intended to solve the problem of producing a high-quality paper despite reduced consumption of raw material, the desired opacity, which requires a higher filler content in the paper, to be achieved without reducing other paper properties, such as its strength.
  • GB 1 287 576 discloses a process for producing inorganic white pigments containing optical brighteners and corresponding pigment preparations as well as their use in colored plastics.
  • GB 1 25960 The task is to increase the retention of titanium dioxide during the production process of paper. For this purpose, she proposes to coat titanium dioxide particles with aminated polysekerides.
  • GB 1 363 016 relates to a process for producing filled paper containing agglomerates of mineral particles in the presence of water and a swellable organic material of synthetic ceramics, starch or alginate.
  • EP 1 172 478 A1 relates to a process for loading fibers contained in a pulp suspension with calcium carbonate
  • WO 97/01 670 discloses a papermaking filler consisting essentially of calcium carbonate deposited on the surface of "Noil-fibrils”.
  • the invention binds additives for paper, tissue or paperboard production to the cellulosic component of the filler, so that they remain adhering to the fibers to a considerable extent even in aqueous suspensions.
  • liquid substrates such as wet strength agents or optical brighteners, which are used in the paper formulations anyway. Since these fibers are coarse enough to remain in the paper web without additional effort, the finely divided components adhering to the surface are also held in the paper web.
  • the novel development of the invention provides better retention on the sheet former.
  • the fixation reduces the amount of expensive additives and reduces the wastewater load.
  • complex processes such as starch cooking or size press are replaced by simpler processes in the paper mill.
  • the filler according to the invention comprises cellulose, lignocellulose or microcrystalline cellulose (i.e., a cellulosic component), it also means cellulose-containing precursors or intermediates which comprise other vegetable ingredients such as protein, protein, starch and / or mineral components and others. It is therefore not absolutely necessary to drive too far a chemical treatment of the vegetable raw material. Rather, vegetable ingredients may be included in the cellulosic component, the proportion of which should not exceed 25% of the total cellulosic component.
  • the particle sizes of the cellulosic component will preferably be limited to not more than 1 mm particle size, preferably not more than 0.5 mm particle size, with no restriction being required for smaller particle sizes, since nanoscale particle sizes can also be used successfully.
  • the particle sizes are preferably not more than 0.1 mm, preferably not more than 0.05 mm. Again, a limitation of the particle size down is not required. Rather, it is important to ensure that the particle size of the additives used is generally lower, preferably significantly lower than the particle size of the cellulosic component.
  • the mass ratio between the cellulosic component and the additive component is preferably not less than 1 to 10, and more preferably not less than 2 to 10. In the direction of larger mass ratios, no restriction is required because very small amounts of additive may be sufficient to achieve the desired effect paper, tissue or board production. Otherwise, it is also possible to apply the additives in several layers to the particles of the cellulosic component. This allows the achievement of very small mass ratios of cellulosic component to additive component.
  • additives are not only additives in pure form into consideration. Rather, the raw materials contained in the additive can also be introduced into the production process of the filler according to the invention, so that the raw material preparation and the fixing or coating of the additives on the particles of the cellulosic component takes place in one working process.
  • starch-containing raw materials such as soft wheat semolina, oat bran fractions, and extruded or cooked pregelatinized starches are used, on the one hand to increase the strength of the paper or cardboard or on the other hand to improve the internal bond between fiber and coating substrate and the "dusting" to decrease from the paper.
  • nanodisperse celluloses e.g. based on a microcrystalline cellulose, to provide a carrier, e.g. for optical brighteners to at least partially replace additives such as polyvinyl alcohol, spray starch and CMC and to improve printability.
  • Laboratory sheets were prepared at 6.00 g at 35 ° SR and a concentration of 6 g / 4 liters.
  • the handsheets were dried in a drying oven at 125 ° C for 2 hours and conditioned at room temperature for 4 hours.
  • the drop test was carried out as a rapid test with 75% formic acid. Especially when tested with the Emtec Penetration Tester and the Cobb 300 value, the result is an improved sizing result.
  • Headbox was OCC Fumish 60 °, gray fiber, grammage 200 g / m 2 , freeness 31 ° SR. Laboratory sheets were made with 6 g per 4 liters on Rapid Köthen Blattressner and tested after drying and conditioning to Mullen burst index.
  • the dewatering performance in milliliters [ml] with the Dynamic Drainage Jar (Mytec) shows that the starch compounds can increase the drainage of the paper web and at the same time increase the strength after drying.
  • the titanium dioxide pigment used was a rutile pigment from Kronos called "Kronos 2050". 20 grams of compounds were stirred in a Waring Blender with 200 ml of water for 1 minute, then diluted to 2 L of water and stirred with magnetic stirrers for 5 minutes, then filtered through a 45 ⁇ m PP Tissue fabric (air flow 440 L / m 2 min). The ash values were determined in a muffle furnace at 850 ° C.
  • Optical brighteners from Ciba Pfersee were used to increase the whiteness of the ARBOCEL BER 40 cellulose fibers. These components are in turn suitable in the mixture for the color lightening of celluloses and MCC, in particular for the reduction of the b * value.
  • the brightness values achieved allow a reformulation of the paper pulp with regard to "light fastness" and formulation costs.
  • the freeness was determined according to Schopper Riegler according to ISO 5267/1. In each case, the freeness was counter checked at 35-750 ml drainage with the DDJ drainage meter, with 1000 ml for 60 seconds at 3.0% TS and 20 ° C on 60 mesh ° SR sieve. The amount of filtrate [ml] after 60 seconds corresponds to the CSF value [ml].
  • the whiteness [% ISO] was measured as a reflection at 460 nm using the Minolta CM 3600 colorimeter, CIE or Hunter color values.
  • the ash content was determined in a muffle furnace at 450 ° C. (after 5 hours) or 850 ° C. (after 8 hours).
  • the starch content was determined by an iodometric titration according to Tappi T 419 om-91.
  • the fiber suspension is dewatered on a sieve with constant stirring - without the formation of a filter layer.
  • the total and filler retention can be calculated.
  • Fiber structure Fiber length particle size freeness White [460 nm] microns ° SR % ISO LIGNOCEL C 120 lignocellulose 120 11-12 54 - 57 LIGNOCEL CB 120 lignocellulose 120 50 - 55 ARBOCEL B 600 cellulose 60 86 - 90 ARBOCEL C 100 lignocellulose 100 10-11 55 - 56 ARBOCEL C 750 lignocellulose 80 14-16 58 - 60 VIVAPUR 101 Microcrystalline cellulose 50 85-91 ARBOCEL C 750 BRIGHT Bleached lignocellulose 80 16-18 70 - 73 ARBOCEL CW 630 PU 40 60 - 61 ARBOCEL E 140 lignocellulose 120 57 - 58
  • micro-composites are particles smaller than 500 ⁇ m, which consist of several phases - for example cellulose, lignin and starch].
  • Wood pulp is a TMP wood fiber that has been produced by a wood grinder and is generally a softwood long fiber.
  • CTMP is a bleached chemo-thermo-mechanical pulp, a bleached, high-temperature, chemical-treated pulp containing many wood constituents unlike pulp].
  • Retention agents provide a high molecular weight via bridging or via cationic charge together with inorganic fines and prevent the leaching of very fine particles during the formation of the leaves, so they retain these particles].
  • ["Fiber Loading” is a special coating process that, for example, provides a coating layer of calcium carbonate on the fiber from aqueous calcium hydroxide solution and carbon dioxide gas].
  • ["Mullen Burst" provides the bursting pressure [kPa] and the bursting index [kPa m 2 / g] in the dry state, according to Tappi Method T 80-7; is therefore a measure of the mechanical strength of paper or cardboard].
  • ["Ply Bond” provides the internal ply strength [kPa] measured in the tensile direction in the vertical direction according to Tappi Method UM 808].
  • the "breaking length” is a measure of the static tensile strength [km] below the dead weight of the blade, similar to the maximum breaking load, but with constant deflection according to Tappi Method T 494 (DIN 53112)].
  • enzymes such as ligninases or cellubiohydrolases are useful.
  • Basis of the wet-strength agent may be polyamidoamine-epichlorohydrin, melamine-formaldehyde or urea-formaldehyde].
  • Optical fluorescent brighteners are all organic molecules that can absorb UV light and emit blue visible light].
  • NMC microcrystalline cellulose
  • Water repellents in the paper industry are in particular the chemicals Alkylketendimer (AKD), Alkenylketendimer, alkyl succinic acid and its derivatives (A-SA), hydrocarbon resins and rosins, fluorocarboxylic acids, polycarboxylic acids, fluoroorgans, acid amides, fluorine-containing silanes, fluorosiloxanes, and acidic papers also alums and aluminum sulphate].
  • ALD Alkylketendimer
  • A-SA alkenylketendimer
  • A-SA alkyl succinic acid and its derivatives
  • hydrocarbon resins and rosins hydrocarbon resins and rosins
  • fluorocarboxylic acids polycarboxylic acids
  • fluoroorgans fluoroorgans
  • acid amides fluorine-containing silanes
  • fluorosiloxanes fluorosiloxanes
  • acidic papers also alums and aluminum sulphate
  • Nara Hybridizer is a pilot plant from the company Nara for dry comminution, process similar to an impeller mill].
  • SAE polymers are styrene-acrylate copolymers as used for paper sizing].
  • SC Paper Supercalendered Paper
  • SC Paper is a type of paper that has been given a very homogeneous smooth surface via calender
  • tissue is a nonwoven with a grammage of about 8 - 35 g / m 2 ].
  • Coupled value 300 determines the amount of water taken up by a sized paper in a specific time span (here: 300 seconds) under standard conditions, according to Tappi Method T 441 and EN ISO 20535].
  • the “drop test” is carried out by means of a micropipette and determines the time until the absorption of a certain amount of liquid water or water-isopropanol mixture].
  • the iodometric quantitative starch detection is carried out by titration with an iodine titre solution.
  • the "Rapid Köthen Sheet Former” is a pilot plant for the production of standardized laboratory sheets with a diameter of 200 mm].
  • the "Waring Blender” is a machine with a fast-running rotor for mixing liquids].
  • ["AP substance" is a waste paper pulp of the European variety A 12 or comparable quality].
  • the SR sieve is a mesh sieve as used for the Schopper-Riegler measurement.

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Description

TECHNISCHES GEBIETTECHNICAL AREA

Die Erfindung betrifft einen cellulosehaltigen Füllstoff für Papier-, Tissue- oder Kartonprodukte sowie Herstellungsverfahren hierfür sowie einen solchen Füllstoff enthaltendes Papier-, Tissue- oder Kartonprodukt oder hierfür verwendete Trockenmischung gemäß den Oberbegriffen der Patentansprüche 1, 39, 52 bzw. 38.The invention relates to a cellulose-containing filler for paper, tissue or paperboard products and to manufacturing processes therefor, and to a paper, tissue or paperboard product or dry mix used for such a filler according to the preambles of claims 1, 39, 52 and 38, respectively.

TECHNISCHER HINTERGRUNDTECHNICAL BACKGROUND

Grundstoff für die Herstellung von Papier und Karton sind seit Jahrtausenden cellulosische Fasern, die aus verschiedenen pflanzlichen Rohstoffen hergestellt wurden. Heutzutage werden praktisch ausschließlich Cellulosefasern verwendet, die aus Holz gewonnen werden. Allen gemeinsam ist, dass es sich um langfasrige, in einem Nassmahlverfahren hergestellte Produkte handelt. Durch die große Faserlänge wird ein guter Verbund im Papier und Karton erreicht, der zur Blattbildung führt und der für die mechanische Festigkeit von höchster Bedeutung ist. Diese langfasrigen Produkte sind die Basis der Papier- und Kartonherstellung; ohne sie kann kein Papier oder Karton hergestellt werden. Ihr Verbund führt zur notwendigen Blattbildung. Sie können sich im Reinheitsgrad sowie in der Faserstruktur (Mahlgrad °SR) unterscheiden. Man kennt hoch aufgereinigte, ligninfreie Cellulosen ebenso wie ligninhaltige Fasern (Holzschliff, CTMP) sowie Recyclingfasern, die aus Altpapier gewonnen werden und dementsprechend noch mit diversen Verunreinigungen behaftet sind.For millennia, cellulosic fibers made of various vegetable raw materials have been used as the raw material for the production of paper and cardboard. Today, almost exclusively cellulose fibers are used, which are obtained from wood. They all have in common that they are long-fiber products produced in a wet grinding process. Due to the large fiber length is a good Composite in the paper and cardboard is achieved, which leads to sheet formation and which is of the highest importance for the mechanical strength. These long-fiber products are the basis of paper and board production; Without them, no paper or cardboard can be produced. Their bond leads to the necessary sheet formation. They can differ in the degree of purity as well as in the fiber structure (freeness ° SR). Highly purified, lignin-free celluloses are known as well as lignin-containing fibers (groundwood, CTMP) and recycled fibers, which are obtained from waste paper and are accordingly still contaminated with various impurities.

Feinteilige Produkte wie native Stärke, Calciumcarbonat, Kaolin oder Titandioxid werden aus verschiedenen Gründen im Produktionsprozess von Karton- und Papierfabriken eingesetzt. Aufgrund ihrer geringen Partikelgröße werden diese Produkte sehr leicht aus der Papierbahn ausgewaschen. Es bedarf zusätzlicher Maßnahmen, um die Retention in der Papierbahn wenigstens zu einem gewissen Grad zu erreichen. Damit sind aber höhere Kosten sowie andere technologische Nachteile verbunden. Nach Literaturangaben findet man auf schnell laufenden Papiermaschinen (> 1500 m/min) derzeit trotz polymerer Retentionsmittel oftmals unter 40 % Retentionsgrad der Füllstoffe und Pigmente.Finely divided products such as native starch, calcium carbonate, kaolin or titanium dioxide are used in the production process of board and paper mills for various reasons. Due to their small particle size, these products are easily washed out of the paper web. Additional measures are needed to achieve retention in the paper web, at least to some extent. But this involves higher costs and other technological disadvantages. According to the literature, on polymer paper machines running at high speed (> 1500 m / min), the retention rate of fillers and pigments is currently often below 40% despite polymeric retention agents.

Zusätzlich zu den oben genannten cellulosischen, verhältnismäßig langen Fasern werden spezielle, meist durch trockene oder feuchte Mahltechnologien zerkleinerte cellulosische Fasern als Additiv zur Herstellung von Kartonagen und Papieren der Faserpulpe zugesetzt, um höheres Volumen oder niedrigere Grammaturen, eine bessere Formation sowie eine schnellere Entwässerung zu erzielen. Diese Fasern weisen eine deutlich kürzere Faserlänge als oben beschriebenen blattbildenden Cellulosefasern auf. Ihre Einsatzmenge liegt unter 10%. Ihre Aufgabe besteht darin, die Blattbildung der langen Cellulosefasern so zu beeinflussen, dass die vorstehende genannten Effekte erzielt werden. Nachteilig sind hierbei die negative Beeinflussung der mechanischen Festigkeitswerte sowie im Fall von ligninhaltigen Additiven eine Verschlechterung des Weißgrads beim Fertigprodukt.In addition to the above-mentioned cellulosic, relatively long fibers, special cellulosic fibers, usually crushed by dry or wet milling technologies, are added as an additive to the production of cardboard and paper pulp to achieve higher volume or lower grammages, better formation, and faster dewatering , These fibers have a significantly shorter fiber length than the above-described cellulosic cellulosic fibers. Their amount used is less than 10%. Their task is to influence the sheet formation of the long cellulose fibers so that the above-mentioned effects are achieved. The disadvantage here is the negative influence on the mechanical strength values and in the case of lignin-containing additives, a deterioration of the whiteness of the finished product.

Die EP 0930 345 A2 , von der die Erfindung ausgeht, offenbart einen Füller zur Herstellung von Papleren, um den Gehalt an Füller im Papler, unter Beibehaltung ausreichender Reißfestigkeit erhöhen zu können. Dazu wird In einem Nassprozess ein Pigment, ganz konkret ein anorganisches Pigment, mit fibrillierter Cellulose in flüssigen Zustand verrührt. Hierdurch soll das Problem gelöst werden, ein hochwertiges Papier trotz reduziertem Verbrauch an Rohmaterial herzustellen, wobei die gewünschte Opazität, die einen höheren Fülleranteil im Papier erfordert, erreicht werden soll, ohne andere Papiereigenschaften, wie dessen Festigkeit, zu vermindern. Zur besseren Retention der Füllstoffe, die aber nicht im Fokus steht, wird in dieser Druckschrift vorgeschlagen, Calciumcarbonat mit kleinen Cellulosefasern aus der Reinigung von Cellulosefasern in einem nassen Prozess in jedem bekannten Mischer zu vermischen, denn es wird immer von einer Pulpe, einer breiigen Masse gesprochen. Als weitere Pigmente kommen gemäß dieser Druckschrift Kaolin, Talkum, Titanoxid, gemahlenes Calciumcarbonat, niedergeschlagenes Calciumcarbonat, Kalk, synthetische Silikate, Bariumsulfat und oder Aluminiumhydroxid in Betracht. Insgesamt verfolgt die EP 0 930 345 A2 das Ziel, ein "Netz" aus sorgsam und sehr fein aufbereiteten Fasern zu bilden, das die Additive zurückhalten soll, und Pigment mit den so aufbereiteten Fasern physikalisch so zu mischen, dass beide Partikelarten in gute Gleichverteilung vorliegen.The EP 0930 345 A2 , from which the invention proceeds, discloses a filler for the production of papers, in order to be able to increase the content of filler in the paperboard, while maintaining sufficient tear resistance. For this purpose, in a wet process, a pigment, very specifically an inorganic pigment, is mixed with fibrillated cellulose in a liquid state. This is intended to solve the problem of producing a high-quality paper despite reduced consumption of raw material, the desired opacity, which requires a higher filler content in the paper, to be achieved without reducing other paper properties, such as its strength. For better retention of the fillers, which is not the focus, it is proposed in this document to mix calcium carbonate with small cellulose fibers from the purification of cellulose fibers in a wet process in any known mixer, because it is always a pulp, a pulpy mass spoken. Kaolin, talc, titanium oxide, ground calcium carbonate, precipitated calcium carbonate, lime, synthetic silicates, barium sulfate and / or aluminum hydroxide come into consideration as further pigments according to this publication. Overall, the EP 0 930 345 A2 the goal is to form a "net" of carefully and very finely prepared fibers, which is to retain the additives, and to physically mix pigment with the thus processed fibers in such a way that both types of particles are in good uniform distribution.

GB 1 287 576 offenbart ein Verfahren zur Herstellung anorganischer weißer Pigmente enthaltend optische Aufheller sowie entsprechende Pigmentepräparationen als auch ihre Verwendung in eingefärbten Kunststoffen. GB 1 287 576 discloses a process for producing inorganic white pigments containing optical brighteners and corresponding pigment preparations as well as their use in colored plastics.

GB 1 25960 stellt sich die Aufgabe, die Retention von Titandioxid während des Herstellprozesses von Papier zu erhöhen. Dazu schlägt sie vor, Titandioxidpartikel mit aminierten Polysecheriden zu coaten. GB 1 25960 The task is to increase the retention of titanium dioxide during the production process of paper. For this purpose, she proposes to coat titanium dioxide particles with aminated polysekerides.

GB 1 363 016 betrifft ein Verfahren zur Herstellung von gefüllten Papier, enthaltend Agglomerate von mineralischen Partikeln in Gegenwart von Wasser und einem quellbaren organischen Material synthetischer Kunatstoffe, Stärke oder Alginat. GB 1 363 016 relates to a process for producing filled paper containing agglomerates of mineral particles in the presence of water and a swellable organic material of synthetic ceramics, starch or alginate.

EP 1 172 478 A1 betrifft ein Verfahren zum Beladen von In einer Faserstoffsuspension enthaltene Fasern mit Calciumcarbonat EP 1 172 478 A1 relates to a process for loading fibers contained in a pulp suspension with calcium carbonate

WO 97/01 670 offenbart einen Füller für die Papierherstellung, der im Wesentlichen aus Calciumcarbonat besteht, dass auf die Oberfläche von "Noil-fibrils" niedergeschlagen wird. WO 97/01 670 discloses a papermaking filler consisting essentially of calcium carbonate deposited on the surface of "Noil-fibrils".

DIE ERFINDUNGTHE INVENTION

Um den Additiv-Verbrauch zu vermindern und gegebenenfalls den Additiv-bedingten Behandlungsbedarf des bei der Herstellung von Papier- , Tissue- oder Kartonprodukten anfallenden Wassers zu reduzieren wird ein Füllstoff mit den Merkmalen des Anspruchs 1, ein Verfahren zu dessen Herstellung mit den Merkmalen des Anspruchs 39, ein entsprechendes Papier, Tissue- oder Kartonagenprodukt nach Anspruch 52 sowie eine Trockenmischung nach Anspruch 38 vorgeschlagen. Bevorzugte Ausführungen und Anwendungen ergeben sich aus den Unteransprüchen.In order to reduce the additive consumption and optionally to reduce the additive-related treatment requirement of the resulting in the production of paper, tissue or paperboard products water is a filler with the features of claim 1, a process for its preparation with the features of the claim 39, a corresponding paper, tissue or Kartonagenprodukt according to claim 52 and a dry mix according to claim 38 proposed. Preferred embodiments and applications emerge from the subclaims.

Durch die Erfindung werden Additive für die Papier, Tissue- oder Kartonherstellung an die cellulosische Komponente des Füllstoffs gebunden, so dass sie auch in wässrigen Suspensionen zu einem erheblichen Anteil auf den Fasern haften bleiben. Hierbei können auch flüssige Substrate, wie Nassfestmittel oder optische Aufheller, zum Einsatz kommen, welche ohnehin in den Papierrezepturen eingesetzt werden. Da diese Fasern grob genug sind, um ohne Zusatzaufwand in der Papierbahn zu verbleiben, werden auch die auf der Oberfläche haftenden feinteiligen Komponenten in der Papierbahn gehalten.The invention binds additives for paper, tissue or paperboard production to the cellulosic component of the filler, so that they remain adhering to the fibers to a considerable extent even in aqueous suspensions. In this case, it is also possible to use liquid substrates, such as wet strength agents or optical brighteners, which are used in the paper formulations anyway. Since these fibers are coarse enough to remain in the paper web without additional effort, the finely divided components adhering to the surface are also held in the paper web.

Gegenüber der Dosage von pulverförmigem Pigment und Füllstoff liefert die erfindungsgemäße Neuentwicklung eine bessere Retention auf dem Blattbildner. Durch die Fixierung wird die Einsatzmenge an kostspieligen Additiven reduziert und weiterhin die Abwasserfracht verringert. Darüber hinaus werden aufwendige Verfahren wie Stärkekochung oder Leimpresse durch einfachere Verfahren in der Papierfabrik ersetzt.Compared to the dosage of powdered pigment and filler, the novel development of the invention provides better retention on the sheet former. The fixation reduces the amount of expensive additives and reduces the wastewater load. In addition, complex processes such as starch cooking or size press are replaced by simpler processes in the paper mill.

Während "Fiber loading"-Verfahren eine Vorbehandlung mit flüssigem Calciumhydroxid sowie eine Umsetzung mit gasförmigem Kohlendioxid voraussetzt, liefert die erfindungsgemäße Neuentwicklung stabile Coatings mit einfachen mechanischen Verfahren.While "fiber loading" process requires a pretreatment with liquid calcium hydroxide and a reaction with gaseous carbon dioxide, the new development according to the invention provides stable coatings with simple mechanical processes.

Es wird also ein multifunktioneller mindestens ein Additiv aufweisender Füllstoff vorgeschlagen, welcher u. a. folgende Vorteile bieten kann:

  1. 1. Erhöhung der Drainage und Produktivität
  2. 2. Verbesserung der rheologischen Eigenschaften (im Vergleich zu Holzstoffen)
  3. 3. Verbesserung der Formation
  4. 4. Verringerung der Trocknungskosten
  5. 5. Erhöhte Dimensionsstabilität
  6. 6. Höheres Volumen
  7. 7. Erhöhte Füllstoff-Retention, im Einzelfall geringerer Retensionsmittel-Verbrauch
  8. 8. Verbessertes Sizing für Hydrophobie und Oleophobie
  9. 9. Erhöhter Weißgrad und bessere Bedruckbarkeit (im Vergleich zu Holzstoffen)
  10. 10. Höhere Opazität
  11. 11. Höhere Festigkeiten
  12. 12. Bessere Wirkung der Optischen Aufheller im Strich und bessere Bedruckbarkeit
  13. 13. Biozid-Ausrüstung
  14. 14. Flammwidrigkeit
  15. 15. Antistatische Eigenschaften
  16. 16. Kationisierung und Anpassung des Zeta-Potentials
  17. 17. Höhere Affinität zu Farbstoffen
  18. 18. Höherer Feststoffgehalt
  19. 19. Reduzierung der qualitativen Schwankungen bei Recyclingpapieren
Thus, a multifunctional filler having at least one additive is proposed, which can offer, inter alia, the following advantages:
  1. 1. Increase of drainage and productivity
  2. 2. improvement of rheological properties (compared to wood pulp)
  3. 3. Improvement of the formation
  4. 4. Reduction of drying costs
  5. 5. Increased dimensional stability
  6. 6. Higher volume
  7. 7. Increased filler retention, in individual cases lower Retensionsmittel consumption
  8. 8. Improved sizing for hydrophobicity and oleophobicity
  9. 9. Increased whiteness and better printability (compared to wood pulp)
  10. 10. Higher opacity
  11. 11. Higher strengths
  12. 12. Better effect of the optical brightener in the line and better printability
  13. 13. Biocide equipment
  14. 14. Flame retardancy
  15. 15. Antistatic properties
  16. 16. Cationization and adaptation of the zeta potential
  17. 17. Higher affinity to dyes
  18. 18. Higher solids content
  19. 19. Reduction of qualitative variations in recycled paper

Soweit der erfindungsgemäße Füllstoff Cellulose, Lignocellulose oder mikrokristalline Cellulose (d.h. eine cellulosische Komponente) aufweist, werden hierunter auch cellulosehaltige Vor- oder Zwischenprodukte verstanden, die noch andere pflanzliche Inhaltstoffe umfassen, wie Eiweiß, Protein, Stärke und/oder mineralische Bestandteile und andere. Es ist also nicht zwingend erforderlich, eine chemische Aufbereitung des pflanzlichen Rohstoffes allzu weit zu treiben. Es können vielmehr pflanzliche Inhaltsstoffe in der cellulosischen Komponente enthalten sein, wobei deren Anteil nicht mehr als insgesamt 25% der cellulosischen Komponente betragen sollte.As far as the filler according to the invention comprises cellulose, lignocellulose or microcrystalline cellulose (i.e., a cellulosic component), it also means cellulose-containing precursors or intermediates which comprise other vegetable ingredients such as protein, protein, starch and / or mineral components and others. It is therefore not absolutely necessary to drive too far a chemical treatment of the vegetable raw material. Rather, vegetable ingredients may be included in the cellulosic component, the proportion of which should not exceed 25% of the total cellulosic component.

Die Partikelgrößen der cellulosischen Komponente wird bevorzugt auf nicht mehr als 1 mm Partikelgröße, vorzugsweise nicht mehr als 0,5 mm Partikelgröße beschränkt werden, wobei zu kleineren Partikelgrößen hin keine Beschränkung erforderlich ist, da auch Partikelgrößen um Nanobereich erfolgreich einsetzbar sind.The particle sizes of the cellulosic component will preferably be limited to not more than 1 mm particle size, preferably not more than 0.5 mm particle size, with no restriction being required for smaller particle sizes, since nanoscale particle sizes can also be used successfully.

Sofern die Additive in Teilchenform eingesetzt wird, betragen die Partikelgrößen vorzugsweise nicht mehr als 0,1 mm, vorzugsweise nicht mehr als 0,05 mm. Auch hier ist eine Begrenzung der Partikelgröße nach unten nicht erforderlich. Vielmehr ist darauf zu achten, dass die Partikelgröße der eingesetzten Additive in der Regel geringer, vorzugsweise deutlich geringer als die Partikelgröße der cellulosischen Komponente ist.If the additives are used in particulate form, the particle sizes are preferably not more than 0.1 mm, preferably not more than 0.05 mm. Again, a limitation of the particle size down is not required. Rather, it is important to ensure that the particle size of the additives used is generally lower, preferably significantly lower than the particle size of the cellulosic component.

Das Massenverhältnis zwischen der cellulosischen Komponente und der Additivkomponente ist vorzugsweise nicht kleiner als 1 zu 10 und besonders bevorzugt nicht kleiner als 2 zu 10. In Richtung größerer Massenverhältnisse ist keine Beschränkung erforderlich, da unter Umständen sehr geringe Additivmengen ausreichen können, um den erwünschten Effekt bei der Papier-, Tissue- oder Kartonherstellung zu erreichen. Ansonsten ist es auch möglich, die Additive in mehreren Schichten auf die Partikel der cellulosischen Komponente aufzubringen. Dies ermöglicht die Erreichung sehr kleiner Massenverhältnisse von cellulosischer Komponente zu Additivkomponente.The mass ratio between the cellulosic component and the additive component is preferably not less than 1 to 10, and more preferably not less than 2 to 10. In the direction of larger mass ratios, no restriction is required because very small amounts of additive may be sufficient to achieve the desired effect paper, tissue or board production. Otherwise, it is also possible to apply the additives in several layers to the particles of the cellulosic component. This allows the achievement of very small mass ratios of cellulosic component to additive component.

Als Additive, wie sie im Einzelnen noch weiter unten erwähnt werden, kommen nicht nur Additive in reiner Form in Betracht. Vielmehr können auch das Additiv enthaltene Rohstoffe in den Herstellungsprozess des erfindungsgemäßen Füllstoffs eingebracht werden, so dass die Rohstoffaufbereitung und das Fixieren oder Coaten der Additive auf den Partikeln der cellulosischen Komponente in einem Arbeitsprozess abläuft. So können z.B. stärkehaltige Rohstoffe, wie zum Beispiel Weichweizengriess, Haferkleie-Fraktionen, sowie extrudierte oder gekochte pregelatinierte Stärken zum Einsatz kommen, um einerseits die Festigkeit des Papiers oder Kartons zu erhöhen oder andererseits den internen Verbund zwischen Faser und Coating-Substrat zu verbessern sowie das "Ausstauben" aus dem Papier zu verringern. Weiterhin können nanodisperse Cellulosen, z.B. auf Basis einer mikrokristallinen Cellulose, eingesetzt werden, um bei Streichmassen einen Trägerstoff, z.B. für optische Aufheller bereitzustellen, um Additive wie Polyvinylalkohol, Sprühstärke und CMC zumindest teilweise zu ersetzen und die Bedruckbarkeit zu verbessern.As additives, as mentioned in more detail below, are not only additives in pure form into consideration. Rather, the raw materials contained in the additive can also be introduced into the production process of the filler according to the invention, so that the raw material preparation and the fixing or coating of the additives on the particles of the cellulosic component takes place in one working process. Thus, e.g. starch-containing raw materials, such as soft wheat semolina, oat bran fractions, and extruded or cooked pregelatinized starches are used, on the one hand to increase the strength of the paper or cardboard or on the other hand to improve the internal bond between fiber and coating substrate and the "dusting" to decrease from the paper. Furthermore, nanodisperse celluloses, e.g. based on a microcrystalline cellulose, to provide a carrier, e.g. for optical brighteners to at least partially replace additives such as polyvinyl alcohol, spray starch and CMC and to improve printability.

Mit der Erfindung kann eine Vielzahl von verschieden wirkenden Füllstoffen für die Papier-, Tissue- oder Kartonproduktion verwirklicht werden. Die bevorzugten Ausführungsformen werden nachfolgend beschrieben:With the invention, a variety of different acting fillers for paper, tissue or cardboard production can be realized. The preferred embodiments are described below:

Die nachfolgenden Füllstoffe haben das gemeinsame Konzept, Cellulosefasern insbesondere solchen von der Anmelderin, als Trägerstoff für traditionelle Papiermacher-Additive einzusetzen, um die Effektivität der Additive zu erhöhen, ihren Verbrauch zu verringern und die CSB-Abwasserfrachten zu verringern:

  1. 1) Ein neuartiges Sizing-Compound, welches aus Fasern und einem Sizing-Komplex besteht, der die Hydrophobie und / oder die Oleophobie der Papiere und Kartonagen, die Dauerhaftigkeit und Gleichförmigkeit der Leimung sowie die Retension des Leimungsmittels bei der Blattbildung verbessert. Ein weitere Gegenstand der Erfindung ist ein Herstellverfahren für Sizing-Compounds. Der Einsatz des Sizing-Compounds liefert ein verbessertes Preis-Leistungs-Verhältnis bei der Leimung.
  2. 2) Ein neuartiges Mineral-Compound, welches aus Fasern und Mineralien (Füllstoffe, Pigmente) besteht. Weißgrad und Lichtechtheit der eingesetzten Fasern wird durch die Oberflächenmodifizierung deutlich verbessert, wodurch der Einsatz auch in sehr hellen Kartonagen und Papieren möglich wird.
    Gegenstand der Erfindung ist ein Leichtfüllstoff, der aus Fasern und Mineral besteht, für die Fertigung von Papier und Kartonage. Der Leichtfüllstoff kann das Volumen der Papieres, die Maschinengeschwindigkeit und die FüllstoffRetension erhöhen.
  3. 3) Ein neuartiges Stärke-Compound, welches aus Fasern und nativer oder kationischer Stärke besteht und die Festigkeitswerte (Mullen Berstfestigkeit, Ply Bond Lagenfestigkeit, Tear Index, Tensile Index, Reißlänge, ..) bei identischer Grammatur erhöhen kann oder eine Verringerung der Grammatur ohne Festigkeitsverluste zulässt. Der Einsatz soll bevorzugt, aber nicht ausschließlich, im Wet End Bereich erfolgen. Die Stärke auf der Faser kann teilweise pregelatiniert oder mit der Faser homogenisiert sein oder wiederum aus Stärkemischungen bestehen. Die Modifizierung der Faser mit Stärke führt zu einer Verbesserung der mechanischen Festigkeiten des Faserverbunds im Endprodukt. Gegenstand der Erfindung ist eine bessere Retension der Stärke in Papier und Kartonage, speziell bei Recycling-Papierstoff mit hoher anionischer Fracht und hohem Mineralstoff Anteil, um Papier und Karton mit einer höheren Festigkeit auszustatten. Ein weiterer Gegenstand der Erfindung ist die Fertigung einer neuen Type von festigkeitssteigenden Zusatzmitteln, wobei Fasern im Hochkonsistenz-Bereich oder trocken mit Stärke umgesetzt oder pregelatiniert werden.
  4. 4) Ein neuartiges Biozid-Compound, welches aus Fasern und einem Biozid-Komplex besteht. Das Biozid kann auf der Oberfläche der Faser immobilisiert sein. Das Biozid-Compound kann zum Beispiel für Wellpappen-Rohpapiere und für Gipsfaserplatten im Wet-End Bereich eingesetzt werden.
  5. 5) Ein neuartiges Aufheller-Compound, welches aus Fasern oder mikrokristalliner kolloidaler Cellulose besteht und einen Optischen Aufheller enthalten kann. Der Aufheller kann auf der Oberfläche der Faser oder in einem Cellulose-Gel immobilisiert sein. Die Faser kann in Gegenwart von üblichen Bleichungsmitteln wie Wasserstoffperoxid, Sauerstoff oder Ozon gebleicht sein. Die Zubereitung kann weiterhin pulverförmige oder flüssige Aufheller enthalten, wie sie als optischer Aufheller für Lignocellulosen beschrieben sind.
  6. 6) Ein neuartiges Antistatik-Compound, welches aus Fasern und einem elektrisch ableitfähigem, antistatischem Zusatz besteht. Der antistatische Zusatz kann auf der Oberfläche der Faser immobilisiert sein.
  7. 7) Ein neuartiges kationionisches Faser-Compound, welches aus Fasern und einem Kationisierungsmittel besteht und zur Einstellung des Zeta-Potentials bei Kartonagen und Papieren dient.
  8. 8) Ein neuartiges flammwidriges Faser-Compound, welches aus Fasern und einem Flammschutzmittelmittel besteht und zur Einstellung der Schwerentflammbarkeit bei Kartonagen und Papieren dient.
  9. 9) Ein neuartiges Flüssigharz-Faser-Compound, welches aus Fasern und einem Flüssigharz oder einem Gel besteht und zur Einstellung der Festigkeit bei Kartonagen und Papieren dient.
The following fillers have the common concept of using cellulose fibers, in particular those of the Applicant, as a carrier for traditional papermaking additives in order to increase the effectiveness of the additives, to reduce their consumption and to reduce COD wastewater loads:
  1. 1) A novel sizing compound consisting of fibers and a sizing complex that enhances the hydrophobicity and / or oleophobicity of the papers and cardboards, the durability and uniformity of sizing and the retention of sizing agent in sheet formation. Another object of the invention is a production process for sizing compounds. The use The sizing compound provides an improved price / performance ratio for sizing.
  2. 2) A novel mineral compound consisting of fibers and minerals (fillers, pigments). The degree of whiteness and light fastness of the fibers used is significantly improved by the surface modification, which makes it possible to use even in very light cardboard and paper.
    The invention relates to a lightweight filler, which consists of fibers and mineral, for the production of paper and cardboard. The lightweight filler can increase the volume of the paper, the machine speed and the filler retention.
  3. 3) A novel starch compound consisting of fibers and native or cationic starch which can increase strength values (Mullen Bursting Strength, Ply Bond Ply Strength, Tear Index, Tensile Index, Tear Length, etc.) at identical grammages or a reduction in grammage without Loss of strength allows. The use should preferably, but not exclusively, take place in the wet end area. The starch on the fiber may be partially pregelatinised or homogenized with the fiber or in turn consist of starch mixtures. The modification of the fiber with starch leads to an improvement of the mechanical strength of the fiber composite in the final product. The invention relates to a better retention of the starch in paper and cardboard, especially in recycled pulp with high anionic cargo and high mineral content to equip paper and cardboard with a higher strength. Another object of the invention is the production of a new type of strength-increasing additives, wherein fibers in the high-consistency range or dry reacted with starch or pregelatiniert.
  4. 4) A novel biocide compound consisting of fibers and a biocide complex. The biocide may be immobilized on the surface of the fiber. The biocide compound can be used, for example, for corrugated base papers and for gypsum fiber boards in the wet-end area.
  5. 5) A novel brightener compound , which consists of fibers or microcrystalline colloidal cellulose and may contain an optical brightener. The brightener may be immobilized on the surface of the fiber or in a cellulose gel. The fiber may be bleached in the presence of common bleaching agents such as hydrogen peroxide, oxygen or ozone. The preparation may further contain powdery or liquid brighteners, as described as an optical brightener for lignocelluloses.
  6. 6) A novel antistatic compound , which consists of fibers and an electrically dissipative, antistatic additive. The antistatic additive may be immobilized on the surface of the fiber.
  7. 7) A novel cationic fiber compound , which consists of fibers and a cationizing agent and serves to adjust the zeta potential in cardboard and paper.
  8. 8) A novel flame retardant fiber compound , which consists of fibers and a flame retardant agent and is used to adjust the flame retardancy of cardboard and paper.
  9. 9) A novel liquid resin-fiber compound composed of fibers and a liquid resin or gel for adjusting the strength of cardboard and paper.

Ausführungsbeispiel 1 - Sizing CompoundEmbodiment 1 - Sizing compound

Es wurden Laborblätter zu 6.00 g bei 35° SR und einer Konzentration von 6 g / 4 Liter hergestellt. Die Laborblätter wurden in einen Trockenschrank bei 125°C über 2 Stunden getrocknet und bei Raumtemperatur über 4 Stunden konditioniert. Der Tropfentest wurde als Schnelltest mit 75% Ameisensäure durchgeführt. Speziell bei Prüfung mit dem Emtec- Penetrationstestgerät und beim Cobb 300 Wert zeigt sich deutlich ein verbessertes Leimungsergebnis. Probe AKD-Harz Vergleich C100-33 AKD J C 100-46 AKD J C 100-67 AKD WM Einsatzmenge AKD % 3 3 3 3 Massezunahme g/12 g 0.36 1.20 0.93 0.57 Tropfentest Vorderseite sec 244 126 1593 Tropfentest Rückseite sec 285 175 2308 Cobb 300 sec g 52.2 39.8 42.7 37.1 Laboratory sheets were prepared at 6.00 g at 35 ° SR and a concentration of 6 g / 4 liters. The handsheets were dried in a drying oven at 125 ° C for 2 hours and conditioned at room temperature for 4 hours. The drop test was carried out as a rapid test with 75% formic acid. Especially when tested with the Emtec Penetration Tester and the Cobb 300 value, the result is an improved sizing result. sample AKD resin comparison C100-33 AKD J C 100-46 AKD J C 100-67 AKD World Cup Amount used AKD % 3 3 3 3 mass increase g / 12 g 12:36 1.20 0.93 12:57 Drop test front sec 244 126 1593 Drop test backside sec 285 175 2308 Cobb 300 sec G 52.2 39.8 42.7 37.1

Ausführungsbeispiel 2 - Stärke CompoundEmbodiment 2 - Starch Compound

Es wurden aus 50 % Holzfaser ARBOCEL C 100 und 50 % nativer Kartoffelstärke von Fa. Aroostook mittels Verreibung gecoatete Faserstoffe hergestellt, die zur Herstellung von Laborblättern (157-158 g/m2 bei 40°SR) eingesetzt wurden, bei zwei Einsatzmengen. Der iodometrische Stärkenachweis in den Faserstoffen belegt die gute Retension der Stärke in der Papierbahn; zusätzliche Retensionsmittel waren nicht notwendig. Eine Trockenmischung C 100 mit nativer Kartoffelstärke liefert auf dem Blattbildner keine nennenswerte Stärkeretension. Compound Absorption 580 nm Gemessener Stärkegehalt im Papier Stärke-Retension Grammatur Feuchte [% ISO] [%] [%] [g/m2] [%] C100 - 50 NPS 41.87 0.87 87 158 7.3 C100 - 50 NPS 62.83 1.60 78 157 8.1 From 50% wood fiber ARBOCEL C 100 and 50% native potato starch from the company. Aroostook were prepared by trituration coated fibers, which were used for the production of laboratory sheets (157-158 g / m 2 at 40 ° SR), for two amounts. The iodometric determination of starch in the fibers confirms the good retention of the starch in the paper web; additional retention funds were not necessary. A dry mix C 100 with native potato starch does not provide any significant starch retention on the sheet former. compound Absorption 580 nm Measured starch content in paper Strength Retension grammage humidity [% ISO] [%] [%] [g / m 2 ] [%] C100 - 50 NPS 41.87 0.87 87 158 7.3 C100 - 50 NPS 62.83 1.60 78 157 8.1

Ausführungsbeispiel 3 - Stärke CompoundEmbodiment 3 - Starch Compound

Stoffauflauf war OCC Fumish 60°, graue Faser, Grammatur 200 g/m2, Mahlgrad 31 °SR. Es wurden Laborblätter mit 6 g pro 4 Liter auf Rapid Köthen Blattbildner hergestellt und nach Trocknung und Konditionierung auf Mullen Berstindex geprüft.Headbox was OCC Fumish 60 °, gray fiber, grammage 200 g / m 2 , freeness 31 ° SR. Laboratory sheets were made with 6 g per 4 liters on Rapid Köthen Blattbildner and tested after drying and conditioning to Mullen burst index.

Es zeigt sich, daß das Faser-Stärke-Compound qualitativ ähnlich gut abschneidet wie pregelatinierte Stärke. Rezeptur Grammatur Mullen Berst-Index g/Blatt kPa / g Basis Stoffauflauf OCC - 60° 5.88 2.08 6.21 2.03 +5 % ARBOCEL C 100 6.69 2.00 6.85 1.93 + 5 % ARBOCEL C 100 6.77 1.84 + 5 % EmCat C-FF (kat. Kartoffelstärke) 6.55 2.07 + 5 % ARBOCEL C 100 6.41 2.69 + 5 % Pregel CPS Roquette CWS 45 6.54 2.68 + 10 % C 100 - 50 CPS C (Compound mit 50% kat. Kartoffelstärke) 6.86 2.52 6.71 2.56 It turns out that the fiber-starch compound performs qualitatively as well as pregelatinized starch. recipe grammage Mullen Burst Index g / sheet kPa / g Base headbox OCC - 60 ° 5.88 2:08 6.21 2:03 + 5% ARBOCEL C 100 6.69 2:00 6.85 1.93 + 5% ARBOCEL C 100 6.77 1.84 + 5% EmCat C-FF (cat. Potato starch) 6:55 2:07 + 5% ARBOCEL C 100 6:41 2.69 + 5% Pregel CPS Roquette CWS 45 6:54 2.68 + 10% C 100 - 50 CPS C (Compound with 50% cater potato starch) 6.86 2:52 6.71 2:56

Ausführungsbeispiel 4 - Stärke CompoundEmbodiment 4 - Starch Compound

Die Entwässerungsleistung im Millilitern [ml] mit dem Dynamic Drainage Jar (Mytec) zeigt, daß die Stärke-Compounds die Drainage der Papierbahn erhöhen und gleichzeitig nach Trocknung die Festigkeit erhöhen können.The dewatering performance in milliliters [ml] with the Dynamic Drainage Jar (Mytec) shows that the starch compounds can increase the drainage of the paper web and at the same time increase the strength after drying.

Es wurde ein AP-Stoff (30° SR, Asche 15 %) bei 2.00 % Trockenstoff eingesetzt, der wiederum 3 - 7 % Stärke-Compound enthält. Das Stärke-Compound C 100-15 CS enthält 15 % kationische Maisstärke. Die Rührergeschwindigkeit war 300 Umdrehungen pro Minute auf SR-Sieb. 2% AP-Slurry + Zusatz C 100 - 15 CS ohne Zusatz Dosage % 3 5 7 10 0 5 sec g 166 168 175 148 30 sec g 390 396 400 350 60 sec g 519 524 530 463 An AP material (30 ° SR, ash 15%) at 2.00% dry weight was used, which in turn contains 3-7% starch compound. Starch Compound C 100-15 CS contains 15% cationic cornstarch. The stirrer speed was 300 revolutions per minute on SR sieve. 2% AP slurry + Addition C 100 - 15 CS without addition Dosage % 3 5 7 10 0 5 sec G 166 168 175 148 30 sec G 390 396 400 350 60 sec G 519 524 530 463

Ausführungsbeispiel 5.1 - Mineral CompoundExemplary embodiment 5.1 - mineral compound

Compound-Proben wurden mittels Retsch Vibrationssieb über 5 Minuten bei 10 mm Amplitude fraktioniert. Die Asche wurde in einem Muffelofen über 4 Stunden bei 850°C bestimmt, wobei sich Calciumcarbonat zu Calciumoxid umwandelt; Titandioxid bleibt bei dieser Veraschung unverändert. Physikalische Trocken- Mischung # 1.1 Compound # 1.2 Physikalische Trocken- Mischung # 1.3 Compound # 1.4 Zusammensetzung LlGNOCEL C 120 LIGNOCEL C 120 ARBOCEL C 750 ARBOCEL C 750 +40% CaCO3 +40% CaCO3 +50% CaCO3 +50% CaCO3 Mineral / Pigment Hydrocarb 10160 Hydrocarb 10160 Omyacarb 2GU Omyacarb 2GU Schüttgewicht g/L 180 193 164 202 Feuchte % 9.5 9.4 3.6 3.6 Aschegehalt der Siebfraktionen Vibrationssieb : < 32 µm % TS 32.3 20.2 21.3 4.9 32 - 50 µm % TS 19.4 31.2 50 - 90 µm % TS 23.3 48.0 90 - 150 µm % TS 26.4 11.2 150 - 200 µm % TS 36.6 4.0 Compound samples were fractionated by Retsch vibrating sieve for 5 minutes at 10 mm amplitude. The ash was determined in a muffle furnace for 4 hours at 850 ° C, wherein calcium carbonate converts to calcium oxide; Titanium dioxide remains unchanged during this ashing. Physical dry mix # 1.1 Compound # 1.2 Physical dry mix # 1.3 Compound # 1.4 composition LlGNOCEL C 120 LIGNOCEL C 120 ARBOCEL C 750 ARBOCEL C 750 + 40% CaCO 3 + 40% CaCO 3 + 50% CaCO 3 + 50% CaCO 3 Mineral / pigment Hydrocarb 10160 Hydrocarb 10160 Omyacarb 2GU Omyacarb 2GU bulk weight g / L 180 193 164 202 humidity % 9.5 9.4 3.6 3.6 Ash content of the sieve fractions Vibration sieve: <32 μm % TS 32.3 20.2 21.3 4.9 32-50 μm % TS 19.4 31.2 50-90 μm % TS 23.3 48.0 90-150 μm % TS 26.4 11.2 150-200 μm % TS 36.6 4.0

Die hohen Ascheanteile in allen Fraktionen zeigen, dass die mineralischen Komponenten in hohem Maße auf der Oberfläche der Faserpartikeln gebunden sind. Im Falle einer rein physikalischen Mischung sind Mineralpartikel überwiegend im Feinanteil < 32 µm zu finden.The high levels of ash in all fractions indicate that the mineral components are highly bound to the surface of the fiber particles. In the case of a purely physical mixture, mineral particles are predominantly found in the fines content of <32 μm.

Ausführungsbeispiel 5.2 - Mineral CompoundExemplary embodiment 5.2 - mineral compound

Mittels Mullen-Mischer (MM) und mittels Nara Hybridizer (NH) wurden verschiedene Compounds mit anorganischen Füllstoffen und Pigmenten hergestellt.Mullen mixers (MM) and Nara Hybridizers (NH) were used to make various compounds with inorganic fillers and pigments.

Das eingesetzte Titandioxid-Pigment war ein Rutil-Pigment von Kronos mit der Bezeichnung "Kronos 2050". 20 Gramm Compounds wurden in einem Waring Blender mit 200 ml Wasser für 1 Minute gerührt, dann auf 2 L Wasser verdünnt und mit Magnetrührer 5 minuten gerührt, dann über ein 45 µm PP Tressengewebe (Luftdurchsatz 440 L / m2 min) filtriert. Die Aschewerte wurden im Muffelofen bei 850°C bestimmt. Verfahren Compound Asche vor Wäsche [%] Asche nach der Wäsche [%] Füllstoff-Retension [%] NH BE 600/10 TG - 30 TiO2 25.67 21.93 85.4 NH BE 600/30 PU - 30 TiO2 27.78 18.02 64.9 NH BWW 40 - 25 TiO2 18.58 12.33 66.4 MM BWW 40 - 50 TiO2 49.56 36.05 72.7 The titanium dioxide pigment used was a rutile pigment from Kronos called "Kronos 2050". 20 grams of compounds were stirred in a Waring Blender with 200 ml of water for 1 minute, then diluted to 2 L of water and stirred with magnetic stirrers for 5 minutes, then filtered through a 45 μm PP Tissue fabric (air flow 440 L / m 2 min). The ash values were determined in a muffle furnace at 850 ° C. method compound Ash before washing [%] Ash after washing [%] Filler Retention [%] NH BE 600/10 TG - 30 TiO2 25.67 21.93 85.4 NH BE 600/30 PU - 30 TiO2 27.78 2.18 64.9 NH BWW 40 - 25 TiO2 18:58 12:33 66.4 MM BWW 40 - 50 TiO2 49.56 36.05 72.7

Ausführungsbeispiel 6 - Aufheller CompoundEmbodiment 6 - Brightener Compound

Es wurden Optische Aufheller von Ciba Pfersee eingesetzt, um die Weiße der Cellulosefasern ARBOCEL BER 40 zu erhöhen. Diese Komponenten eignen sich wiederum in der Mischung für die Farbaufhellung von Cellulosen und MCC, insbesondere zur Verringerung des b* Wertes. Die erzielten Helligkeitswerte ermöglichen eine Umformulierung der Papiermasse unter Hinsicht auf "Light Fastness" und Rezepturkosten. Mischung Reflexion bei 440 nm [% ISO] Weiße bei 460 nm [% ISO] BER 40 86,2 BER 40 + 0,1% UVITEX BHT 105,4 101,2 BER 40 + 0,3% UVITEX BHT 110,4 102,8 Optical brighteners from Ciba Pfersee were used to increase the whiteness of the ARBOCEL BER 40 cellulose fibers. These components are in turn suitable in the mixture for the color lightening of celluloses and MCC, in particular for the reduction of the b * value. The brightness values achieved allow a reformulation of the paper pulp with regard to "light fastness" and formulation costs. mixture Reflection at 440 nm [% ISO] White at 460 nm [% ISO] BER 40 86.2 BER 40 + 0.1% UVITEX BHT 105.4 101.2 BER 40 + 0.3% UVITEX BHT 110.4 102.8

Arbeitsmethodenworking methods

Der Mahlgrad wurde nach Schopper Riegler gemäß ISO 5267/1 bestimmt. Im Einzelfall wurde der Mahlgrad bei 35-750 ml Drainage mit dem DDJ Drainagemeßgerät gegengeprüft, mit 1000 ml über 60 Sekunden bei 3.0 % TS und 20°C auf 60 mesh °SR Sieb. Die Filtratmenge [ml] nach 60 Sekunden entspricht dem CSF-Wert [ml].The freeness was determined according to Schopper Riegler according to ISO 5267/1. In each case, the freeness was counter checked at 35-750 ml drainage with the DDJ drainage meter, with 1000 ml for 60 seconds at 3.0% TS and 20 ° C on 60 mesh ° SR sieve. The amount of filtrate [ml] after 60 seconds corresponds to the CSF value [ml].

Laborblätter mit 100 cm2 wurden auf einem Rapid-Köthen-Blattbilder nach DIN 54358 /ISO 5269/2 hergestellt. Bei Laborblättern mit gleicher Grammatur wurde der Berstdruck als Mullen Burst Index bestimmt.100 cm 2 handsheets were made on a Rapid-Köthen sheet according to DIN 54358 / ISO 5269/2. For laboratory papers of the same grammage, the bursting pressure was determined to be the Mullen Burst Index.

Die Weiße [% ISO] wurde als Reflexion bei 460 nm mittels Minolta Farbmeßgerät CM 3600 gemessen, Farbwerte gemäß CIE oder Hunter.The whiteness [% ISO] was measured as a reflection at 460 nm using the Minolta CM 3600 colorimeter, CIE or Hunter color values.

Der Aschegehalt wurde im Muffelofen bei 450°C (nach 5 Std.) beziehungsweise 850°C (nach 8 Std.) bestimmt. Der Stärkegehalt wurde durch eine iodometrische Titration nach Tappi T 419 om - 91 bestimmt.The ash content was determined in a muffle furnace at 450 ° C. (after 5 hours) or 850 ° C. (after 8 hours). The starch content was determined by an iodometric titration according to Tappi T 419 om-91.

Cobb Wert wurde gemäß ISO 535, EN 20535 sowie Tappi T441 bestimmt, sowie mit dem Emtec Penetrationstestgerät.Cobb value was determined according to ISO 535, EN 20535 and Tappi T441, as well as with the Emtec Penetration Tester.

Drainage und Retension wurden mit Mytek Drainage-Meßgerät bestimmt. Bei der Entwässerungsmessung wird die Fasersuspension in die Rührkammer gefüllt und nach Additiv-Zugabe einer Scherung unterzogen. Beim Meßvorgang wird die Suspension auf einem Sieb filtriert und die Filtratmenge gravimetrisch über die Entwässerungszeit. Rührgeschwindigkeit 300 Upm bei 2 % TS entsprechen den Prüfungen im Kartonbereich (Graubereich).Drainage and retention were determined with Mytek drainage meter. During the dewatering measurement, the fiber suspension is filled into the stirred chamber and subjected to shear after addition of additive. During the measurement process, the suspension is filtered on a sieve and the amount of filtrate gravimetrically over the dewatering time. Stirring speed 300 rpm at 2% TS correspond to the tests in the carton area (gray area).

Bei der Retensionsmessung wird die Fasersuspension unter ständigem Rühren - ohne Aufbau einer Filterschicht - auf einem Sieb entwässert. Durch Bestimmung des Feststoffgehaltes im Filtrat bzw. nach Trocknung und Veraschung läßt sich die Gesamt- und Füllstoffretension berechnen.In the retention measurement, the fiber suspension is dewatered on a sieve with constant stirring - without the formation of a filter layer. By determining the solids content in the filtrate or after drying and ashing, the total and filler retention can be calculated.

Verschiedene Holzfaserstoffe wurden mit sehr feinteiligen mineralischen Additiven wie Titandioxid oder Calciumcarbonat durch reibende mechanische Kräfte gecoatet (durchschnittliche Partikelgröße der Mineralien: < 10 µm). Die eingesetzten Faserstoffe waren unter anderem. Faserstoff Struktur Faserlänge Partikelgröße Mahlgrad Weiße [460 nm] µm °SR % ISO LIGNOCEL C 120 Lignocellulose 120 11-12 54 - 57 LIGNOCEL CB 120 Lignocellulose 120 50 - 55 ARBOCEL B 600 Cellulose 60 86 - 90 ARBOCEL C 100 Lignocellulose 100 10-11 55 - 56 ARBOCEL C 750 Lignocellulose 80 14-16 58 - 60 VIVAPUR 101 Microkristalline Cellulose 50 85-91 ARBOCEL C 750 BRIGHT Gebleichte Lignocellulose 80 16-18 70 - 73 ARBOCEL CW 630 PU 40 60 - 61 ARBOCEL E 140 Lignocellulose 120 57 - 58 Various wood fiber materials were coated with very finely divided mineral additives such as titanium dioxide or calcium carbonate by rubbing mechanical forces (average particle size of the minerals: <10 μm). The fibers used were among others. fiber structure Fiber length particle size freeness White [460 nm] microns ° SR % ISO LIGNOCEL C 120 lignocellulose 120 11-12 54 - 57 LIGNOCEL CB 120 lignocellulose 120 50 - 55 ARBOCEL B 600 cellulose 60 86 - 90 ARBOCEL C 100 lignocellulose 100 10-11 55 - 56 ARBOCEL C 750 lignocellulose 80 14-16 58 - 60 VIVAPUR 101 Microcrystalline cellulose 50 85-91 ARBOCEL C 750 BRIGHT Bleached lignocellulose 80 16-18 70 - 73 ARBOCEL CW 630 PU 40 60 - 61 ARBOCEL E 140 lignocellulose 120 57 - 58

Es wurden folgende Komponenten eingesetzt :

  • Kationische Kartoffelstärke Hi-CAT® CWS 42 (Roquette Deutschland)
  • Partikelgröße bis 500 µm, Feuchte 8 %, Stickstoffgehalt unter 2 %
  • Kationische Maisstärke C* Bond HR 05946 und C* Bond HR 05947 (Cerestar Niederlande)
  • Partikelgröße 8 - 25 µm, Feuchte 10%, Stickstoffgehalt unter
  • Native Kartoffelstärke (Roquette Frankreich / Beinheim)
  • Partikelgröße 15-60 µm, Feuchte 12 %
  • Polyvinylamin-Harzlösung (BASF Deutschland)
  • Lupamin- und Basocoll-Marken, mit max. 9 % Stickstoffgehalt
  • Calciumcarbonat Hydrocarb "Grade 10160" (Omya Deutschland)
  • Partikelgröße 2-3 µm
  • Calciumcarbonat Omyacarb 2 GU (Omya Österreich / Gummern)
  • Partikelgröße 2 µm, PCC-Qualität, Feuchte 0.28 %, Weiße 90.2 %
  • Titandioxid "KRONOS 2050" (99% TiO2, Rutil-Type, Kronos Deutschland)
  • Partikelgröße 1.1 - 2.5 µm, Weiße > 99.8 % gegenüber Bariumsulfat Standard
  • Titandioxid "TiPure 938" (99% TiO2, Rutil-Type, DuPont Deutschland)
  • Partikelgröße 1.2 - 2.5 µm, Weiße > 99.6 % gegenüber Bariumsulfat Standard
  • Aquapel D 310 Alkyl Keten Dimer (Hercules)
  • Leimungsmittel für Papier auf Basis von Alkylketen-Dimer-Harz und Emulgator, Trockenstoffgehalt etwa 13 %
  • Alkylbernsteinsäureanhydrid ASA (Hercules)
  • Mittelviskoses Harz mit 100 % Wirksubstanz
  • Lodyne 2000 Fluorkohlenwasserstoff FDA (Ciba)
  • Ölige Flüssigkeit, 100 % Wirksubstanz, FDA Approval, für Lebensmittelkontakt geeignet
  • Oleophobol CO Fluorkohlenwasserstoff (Ciba)
  • Technischer Fluorkohlenwasserstoff, ohne FDA Approval
  • Tinofix AP Liquid Kationisierungsharz (Ciba England)
  • Additiv für Farbstoff-Fixierung und Bedruckbarkeit
The following components were used:
  • Cationic potato starch Hi-CAT® CWS 42 (Roquette Germany)
  • Particle size up to 500 μm, humidity 8%, nitrogen content below 2%
  • Cationic Corn Starch C * Bond HR 05946 and C * Bond HR 05947 (Cerestar Netherlands)
  • Particle size 8 - 25 μm, humidity 10%, nitrogen content below
  • Native potato starch (Roquette France / Beinheim)
  • Particle size 15-60 μm, humidity 12%
  • Polyvinylamine resin solution (BASF Germany)
  • Lupamin and Basocoll brands, with max. 9% nitrogen content
  • Calcium carbonate Hydrocarb "Grade 10160" (Omya Germany)
  • Particle size 2-3 μm
  • Calcium carbonate Omyacarb 2 GU (Omya Austria / Gummern)
  • Particle size 2 μm, PCC quality, humidity 0.28%, whiteness 90.2%
  • Titanium dioxide "KRONOS 2050" (99% TiO 2 , rutile type, Kronos Germany)
  • Particle size 1.1 - 2.5 μm, whiteness> 99.8% compared to barium sulfate standard
  • Titanium dioxide "TiPure 938" (99% TiO 2 , rutile type, DuPont Germany)
  • Particle size 1.2 - 2.5 μm, whiteness> 99.6% compared to barium sulfate standard
  • Aquapel D 310 Alkyl Keten Dimer (Hercules)
  • Sizing agent for paper based on alkyl ketene dimer resin and emulsifier, dry matter content about 13%
  • Alkyl succinic anhydride ASA (Hercules)
  • Medium viscosity resin with 100% active substance
  • Lodyne 2000 fluorocarbon FDA (Ciba)
  • Oily liquid, 100% active substance, FDA Approval, suitable for food contact
  • Oleophobol CO fluorocarbon (Ciba)
  • Hydrogen fluorocarbon, without FDA approval
  • Tinofix AP Liquid Cationizing Resin (Ciba England)
  • Additive for dye fixation and printability

Bedeutung der bzw. Erläuterungen zu den verwendeten Fachausdrücken und Abkürzungen:Meaning or explanation of the terms and abbreviations used: in der Zusammenfassungin the summary

[Micro-Composite sind in diesem Zusammenhang Partikel kleiner 500 µm, die aus mehreren Phasen bestehen - zum Beispiel aus Cellulose, Lignin und Stärke].[In this context, micro-composites are particles smaller than 500 μm, which consist of several phases - for example cellulose, lignin and starch].

in der Beschreibung der Erfindungin the description of the invention

[Schopper-Riegler-Mahlgrad (°SR) ist die Drainagemessung von 1 Liter Stoffauflauf (Fasersuspension) mit 0.2 % Trockenstoff, gemäß EN ISO 5267-1].[Schopper-Riegler-Mahlgrad (° SR) is the drainage measurement of 1 liter headbox (fiber suspension) with 0.2% dry matter, according to EN ISO 5267-1].

[Holzschliff ist eine TMP-Holzfaser, die über einen Holzschleifer hergestellt wurde und im allgemeinen eine Weichholz-Langfaser ist].[Wood pulp is a TMP wood fiber that has been produced by a wood grinder and is generally a softwood long fiber].

[CTMP ist gebleichter chemo-thermomechanischer Pulp, also ein gebleichter, bei hoher Temperatur mit Chemikalien behandelter Faserstoff, der im Gegensatz zum Zellstoff noch viele Holzinhaltsstoffe enthält].[CTMP is a bleached chemo-thermo-mechanical pulp, a bleached, high-temperature, chemical-treated pulp containing many wood constituents unlike pulp].

[Grammatur ist das Gramm-Gewicht des Papiers oder der Kartonage, gemessen in g /m2].[Grammage is the gram weight of the paper or cardboard, measured in g / m 2 ].

[Retensionsmittel liefern über Brückenbildung oder über kationische Ladung zusammen mit anorganischen Feinstoffen eine hohe Molmasse und verhindern die Auswaschung sehr feiner Partikel bei der Blattbildung, retendeieren also diese Partikel].[Retention agents provide a high molecular weight via bridging or via cationic charge together with inorganic fines and prevent the leaching of very fine particles during the formation of the leaves, so they retain these particles].

["Fiber Loading" ist ein spezielles Coating-Verfahren, das zum Beispiel aus wässriger Calciumhydroxid-Lösung und Kohlendioxid-Gas eine Coating-Schicht von Calciumcarbonat auf der Faser liefert].["Fiber Loading" is a special coating process that, for example, provides a coating layer of calcium carbonate on the fiber from aqueous calcium hydroxide solution and carbon dioxide gas].

["Mullen Burst" liefert den Berstdruck [kPa] sowie den Berst-Index [kPa m2 / g] im trockenen Zustand, gemäß Tappi Methode T 80-7; ist also ein Maß für die mechanische Festigkeit von Papier oder Karton].["Mullen Burst" provides the bursting pressure [kPa] and the bursting index [kPa m 2 / g] in the dry state, according to Tappi Method T 80-7; is therefore a measure of the mechanical strength of paper or cardboard].

["Ply Bond" liefert die interne Lagenfestigkeit [kPa], gemessen bei Zugbeanspruchung in vertikaler Richtung, gemäß Tappi Methode UM 808].["Ply Bond" provides the internal ply strength [kPa] measured in the tensile direction in the vertical direction according to Tappi Method UM 808].

["Tensile Index" und "Tensile Breaking Strength" sind die normierten Zugfestigkeiten, gemessen in prozentualer Auslenkung mittels Kraft-Weg-Aufnehmer pro Flächeneinheit].["Tensile Index" and "Tensile Breaking Strength" are the normalized tensile strengths, measured in percent deflection by force-displacement transducer per unit area].

[Die "Reißlänge" ist ein Maß für die statische Zugfestigkeit [km] unter dem Eigengewicht des Blattes, ähnlich der maximalen Bruchlast, allerdings bei konstanter Auslenkung nach Tappi Methode T 494 (DIN 53112)].[The "breaking length" is a measure of the static tensile strength [km] below the dead weight of the blade, similar to the maximum breaking load, but with constant deflection according to Tappi Method T 494 (DIN 53112)].

[Sauerstoff wirkt im elektronisch angeregten Singulett-Zustand als Bleichmittel in einer Peroxid-Bleichsequenz deutlich besser als Luft-Sauerstoff im Triplett-Grundzustand].[Oxygen in the electronically excited singlet state as a bleaching agent in a peroxide bleaching sequence is significantly better than air-oxygen in the triplet ground state].

[Als Verbehandlung vor der Bleiche von Lignocellulosen sind Enzyme wie Ligninasen oder Cellubiohydrolasen sinnvoll].[As a pretreatment before the bleaching of lignocelluloses, enzymes such as ligninases or cellubiohydrolases are useful].

["Nassfestmittel" sind für Papiersorten wie zum Beispiel Tissue, Filterpapiere, Etikettenpapiere, Geld- und Wertpapiere und Teebeutelpapiere erforderlich; Basis der Naßfestmittel kann Polyamidoamin-Epichlorhydrin, Melamin-Formaldehyd oder Harnstoff-Formaldehyd sein].["Wet strength agents" are required for paper types such as tissue, filter papers, label papers, money and securities and teabag papers; Basis of the wet-strength agent may be polyamidoamine-epichlorohydrin, melamine-formaldehyde or urea-formaldehyde].

["Optische Fluoreszenz-Aufheller" sind alle organischen Moleküle, die UV-Licht absorbieren und blaues sichtbares Licht emittieren können].["Optical fluorescent brighteners" are all organic molecules that can absorb UV light and emit blue visible light].

[Die "Formation" ist eine ästhetische Beurteilung der Gleichförmigkeit des Blattes].[The "formation" is an aesthetic assessment of the uniformity of the leaf].

["Nanodisperse Cellulose" ist eine scherkraft-empfindliche mikrokristalline Cellulose (MCC) mit entsprechender Partikelstruktur].["Nanodisperse cellulose" is a shear-sensitive microcrystalline cellulose (MCC) with appropriate particle structure].

[Hohe "Opazität" bedeutet geringes Durchscheinen des Druckbildes bei graphischem Papier; die Messung erfolgt wiederum als Reflexionsmessung bei 457 nm mittels Farbmessgerät].[High "opacity" means low show through of printed image on graphic paper; the measurement is again carried out as a reflection measurement at 457 nm by means of a colorimeter].

[CSB ist der chemische Sauerstoff-Bedarf [ml / kg] im Abwasser].[COD is the chemical oxygen demand [ml / kg] in the wastewater].

[Flockungsmittel, Störstoffbinder, Antislip-Additive und Zusätze zur Farbstoff-Fixierung können jeweils unterschiedlichen Stoffgruppen zugeordnet sein].[Flocculants, contaminant binders, anti-slip additives and dye-fixing additives can each be assigned to different substance groups].

[Hydrophobierungsmittel in der Papierindustrie sind insbesondere die Chemikalien Alkylketendimer (AKD), Alkenylketendimer, Alkylbernsteinsäure und deren Derivate (A-SA), Kohlenwasserstoffharze und Collophoniumharze (Rosin), Fluorcarbonsäuren, Polycarbon-säuren, Fluororganyle, Säureamide, fluorhaltige Silane, Fluorsiloxane, sowie für saure Papiere auch Alaune und Aluminiumsulfat].[Water repellents in the paper industry are in particular the chemicals Alkylketendimer (AKD), Alkenylketendimer, alkyl succinic acid and its derivatives (A-SA), hydrocarbon resins and rosins, fluorocarboxylic acids, polycarboxylic acids, fluoroorgans, acid amides, fluorine-containing silanes, fluorosiloxanes, and acidic papers also alums and aluminum sulphate].

in den Patentansprüchenin the claims

["Mullen Mischer" ist eine diskontinierliche Impellermühle, die das Mahlgut einer Friktion unterwirft und gleichzeitig zerkleinert.]["Mullen Mixer" is a discontinuous impeller mill that subjects the regrind to friction and crushes it at the same time.]

["Nara Hybridizer" ist ein Technikumsgerät von Fa. Nara zur trockenen Zerkleinerung, Verfahren ähnlich einer Impellermühle].["Nara Hybridizer" is a pilot plant from the company Nara for dry comminution, process similar to an impeller mill].

["SAE-Polymere" sind Styrol-Acrylat-Copolymere, wie sie für die Papierleimung eingesetzt werden].["SAE polymers" are styrene-acrylate copolymers as used for paper sizing].

[LWC-Papier ist ein leichtgewichtiges gestrichenes Papier; Grammatur unter 26 pounds pro 1000 square feet].[LWC paper is a lightweight coated paper; Grammage below 26 pounds per 1000 square feet].

[Mattpapier ist ein relativ scheuerfestes gestrichenes oder maschinengestrichenes mattes Druckpapier].[Matt paper is a relatively abrasion-resistant coated or machine coated matte printing paper].

[Satinierte Papiere sind mit einem Finish seidenmatt bis hochglänzend ausgerüstete Papiere].[Satin papers are semi-gloss to high gloss finished papers].

[SC-Papier (Supercalendered Paper) ist eine Papiersorte, die über Kalander eine sehr homogene glatte Oberfläche erhalten hat][SC Paper (Supercalendered Paper) is a type of paper that has been given a very homogeneous smooth surface via calender]

[Zeitungsdruckpapier ist ein opakes dünnes Druckpapier auf Basis Deinkingstoff, Weichholz-TMP und Recyclingfaser, mit etwa 2 - 28 % Asche].[Newsprint is an opaque thin printing paper based on deinked pulp, softwood TMP and recycled fiber, with about 2 - 28% ash].

[Tissue ist ein Vliesstoff mit einer Grammatur von etwa 8 - 35 g/m2].[Tissue is a nonwoven with a grammage of about 8 - 35 g / m 2 ].

[Testliner für Wellenkarton und dergleichen wird aus Recyclingfaser hergestellt und hat meist eine Grammatur von 115 - 150 g/m2; wird überwiegend für Verpackung eingesetzt][Testliner for wave carton and the like is made of recycled fiber and usually has a grammage of 115 - 150 g / m 2 ; is mainly used for packaging]

[Fluting ist ebenfalls überwiegend aus Recyclingfaser hergestellt, mit spezieller Oberflächen-behandlung].[Fluting is also mostly made from recycled fiber, with special surface treatment].

[Size Press bezeichnet das Verfahren Leimung nach der Blattbildung].[Size Press refers to the method of sizing after sheet formation].

Im Ausführungsbeispiel 1 - Sizing CompoundIn Example 1 - Sizing compound

[Der "Cobb Wert 300" bestimmt die Menge an Wasser, die von einem geleimten Papier in einer spezifischen Zeitspanne (hier: 300 Sekunden) unter Standardbedingungen aufgenommen wird, gemäß Tappi Methode T 441 und EN ISO 20535].[The "Cobb value 300" determines the amount of water taken up by a sized paper in a specific time span (here: 300 seconds) under standard conditions, according to Tappi Method T 441 and EN ISO 20535].

[Der "Tropfentest" wird mittel Mikropipette durchgeführt und ermittelt die Zeit bis zur Absortion einer bestimmten Flüssigkeitsmenge Wasser oder Wasser-Isopropanol-Mischung].[The "drop test" is carried out by means of a micropipette and determines the time until the absorption of a certain amount of liquid water or water-isopropanol mixture].

[Penetrationstests gemäß Tappi T 530 oder Tappi 433 bestimmen die Zeitspanne bis zum Durchschlagen einer Wasserschicht durch ein geleimtes Papier].[Tappi T 530 or Tappi 433 penetration tests determine the time it takes for a layer of water to pass through a sized paper].

Im Ausführungsbeispiel 2 - Stärke CompoundIn the embodiment 2 - starch compound

[Der iodometrische quantitiative Stärke-Nachweis erfolgt über eine Titration mit einer Iod-Titerlösung].[The iodometric quantitative starch detection is carried out by titration with an iodine titre solution].

Im Ausführungsbeispiel 3 - Stärke CompoundIn the embodiment 3 - starch compound

["OCC Furnish" ist ein spezieller brauner oder grauer Stoffauflauf aus Recycling-Faltschachtel-Kartonage (old corrugated containers), der Faserlängen 3-4 mm aufweisen kann]["OCC Furnish" is a special brown or gray headbox made from recycled corrugated cardboard boxes with a fiber length of 3-4 mm]

[Der "Rapid Köthen Blattbildner" ist ein Technikumsgerät zur Herstellung standardisierter Laborblätter mit Durchmesser 200 mm].[The "Rapid Köthen Sheet Former" is a pilot plant for the production of standardized laboratory sheets with a diameter of 200 mm].

[Der "Waring Blender" ist eine Maschine mit schnell-laufendem Rotor zur Mischung von Flüssigkeiten].[The "Waring Blender" is a machine with a fast-running rotor for mixing liquids].

Im Ausführungsbeispiel 4 - Stärke CompoundIn the embodiment 4 - starch compound

["Dynamic Drainage Meßgerät" von Fa. Mytec ist ein Präzessions-Meßgerät zur Erfassung der Entwässerungsleistung von Faserstoffen, ohne die Bildung eienr Anschwemmschicht].["Dynamic Drainage Meter" by Fa. Mytec is a precession meter to measure the dewatering performance of pulp without the formation of a precoat layer].

["AP-Stoff" ist ein Altpapierstoff der europäischen Sorte A 12 oder vergleichbare Qualität].["AP substance" is a waste paper pulp of the European variety A 12 or comparable quality].

[Das SR-Sieb ist ein Maschensieb, wie es für die Schopper-Riegler-Messung eingesetzt wird].[The SR sieve is a mesh sieve as used for the Schopper-Riegler measurement].

Im Ausführungsbeispiel 5 - Mineral CompoundIn the embodiment 5 - mineral compound Im Ausführungsbeispiel 6 - Aufheller CompoundIn the embodiment 6 - brightener compound

["Light Fastness" bschreibt die Prüfung auf Lichtechtheit nach Tappi].["Light Fastness" writes the test for light fastness after Tappi].

Claims (52)

  1. Fibre-like or particle-like filler for paper, cardboard and tissue products, in which the filler has an elevated retention, at least consisting of cellulose, lignocellulose, or microcrystalline cellulose (MCC) which is intact or fragmented to small particle size and at least one additive, in which the additive is applied to the surface of the cellulose component in solid, liquid, amorphous or microdispersed form by input of energy and is thereby coated or fixed on the fibre surface, wherein the additive is selected from the group
    - particulate or granular starch, modified starch, cationic starch or starch ethers,
    - sizing agent (sizing additive),
    - optical brighteners,
    - flame retardants,
    - biocides,
    - wet strength agents or
    - hydrophobizing agents.
  2. Filler according to claim 1, characterised in that the additive component(s) is/are substantially coated or fixed to the surface of the cellulose fibres of the filler by thermo-mechanical forces, cross-linking, or drying.
  3. Filler according to claim 1 or 2, characterised in that the cellulose component comes from a raw material based on wood, cellulose (such as wood, straw, bamboo), microcrystalline cellulose (MCC), cotton, papermaking stock, reject stock, old paper, deinking paper, ground wood pulp, TMP, (B) CTMP or annual and perennial plants (such as chopped straw, soybean pods, oat husks, spelt, rice husks, ramie, sisal, bamboo, kenaf, flax, hemp, jute, prairie grass, kapok fibre, sugar beet pulp, Miscanthus).
  4. Filler according to any one of claims 1 to 3, characterised in that the additive component(s), for their part, are already coated, surface-modified, compounded or microstructurized.
  5. Filler according to any one of claims 1 to 4, characterised in that the particle sizes of the filler lie below 5 mm, preferably below 2000 µm and especially preferably below 400 µm.
  6. Filler according to any one of claims 1 to 5, characterised in that the mass ratio of cellulose component to additive is at least 1/10, preferably at least 2/10.
  7. Filler according to any one of claims 1 to 6, characterised in that the additives comprise minerals, fillers and/or pigments typical of the paper industry.
  8. Filler according to any one of claims 1 to 7, characterised in that the additives comprise minerals and/or pigments in the form of kaolin, talc, titanium dioxide, fractured calcium carbonate (GCC), precipitated calcium carbonate (PCC), chalk, marble meal, silicate, silicic acid, barium sulfate, aluminium hydroxide, barium sulfide, barium titanate, corundum and/or zinc sulfide, which are also used as a water slurry in the presence of pregelatinized starch.
  9. Filler according to any one of claims 1 to 6, characterised in that the additive comprises particulate or granular starch, modified starch, cationic starch or starch ethers, possibly in the form of a raw material or intermediate product containing the starch (fibre-starch microcompound), preferably making use of soft wheats (semolina, wood splitter dust, shredded wheat, Graham wheat, coarse-grained wheat flour, wheat feed meal, wheat leaf bran, feed wheat scraps) hard wheats (durum fine-ground meal, durum whole grain meal), oats (oat husk bran, rolled oat grain, oatmeal), rye (coarse rye meal, whole grain rye, rye bran, rolled rye grains, rye feed meal), barley (crushed barley grain, barley meal, feed barley), sprouted cereal meal, corn (cornmeal, corn scraps, corn semolina) or other starch-containing byproducts (such as potato pulp, rice flakes, soy meal, rice bran, dinkel meal, buckwheat groats), as the raw material.
  10. Filler according to claim 9, wherein the particulate or granular starch is native or modified starch, based on potato, corn, waxy corn, wheat, triticale, barley, oats, rye, dinkel, buckwheat, rice, tapioca, sago and sorghum.
  11. Filler according to any one of claims 1 to 6, characterised in that the additive comprises sizing agent (sizing additive).
  12. Filler with a sizing additive according to claim 11, wherein the sizing agent comprises components such as alkyl ketene dimer (AKD), alkylsuccinic acid and its derivatives (ASA), colophony resin (rosin), fluorohydrocarbons, fluorinated carboxylic acids, polycarboxylic acids and acid amides, fluorine-containing silanes, and/or fluorosiloxanes, as well as optionally additives such as sodium oleate, betulinol, tripalmitin, polyaluminium chloride, papermaking alum or resin dispersions (such as styrene-acrylate, polyurethane dispersions), or also components for surface sizing, such as SAE polymers or polyurethane polymers.
  13. Filler according to any one of claims 1 to 6, characterised in that it further comprises an optical brightener and is optionally present as a homogeneous cellulose or MCC microcompound or as nanodispersed filler for paper coating.
  14. Filler according to claim 13, characterised in that it further comprises a liquid or powder-like brightener with aromatic and/or partially unsaturated aliphatic structure, for example, on the chemical basis of stilbene, azo-compounds, nitrogen heterocyclic compounds, sulfur compounds and the like; wherein the fibres used are possibly bleached in the presence of hydrogen peroxide, oxygen or ozone.
  15. Filler according to any one of claims 1 to 6, characterised in that it further comprises a flame retardant.
  16. Filler according to claim 15, characterised in that the flame retardant comprises borate, boric acid, phosphate, phosphonate, triphenylphosphinoxide, polyoxazolidinone, bromoorganyls with antimony trioxide, polyunsaturated carbon resins, cashew nut shell liquid CNSL, and/or arachidonic acid.
  17. Filler according to any one of claims 1 to 6, characterised in that it comprises a biocide, wherein the biocide can be present in powder or liquid form, optionally together with thickeners, plant gums, carboxymethyl starch.
  18. Filler according to claim 17, characterised in that the biocide is an inorganic or organic boron compound, a nitrogen or sulfur compound.
  19. Filler according to any one of claims 1 to 7, as a fibre light filler for paper, cardboard and tissue products, in which the filler has an elevated retention.
  20. Filler according to any one of claims 1 to 7, as a fibre light filler for paper, cardboard and tissue products, for volume enhancement.
  21. Filler according to any one of claims 1 to 6, to increase the starch retention.
  22. Filler according to any one of claims 1 to 6 to increase the strength.
  23. Filler according to any one of claims 1 to 6 to increase the sizing retention.
  24. Filler according to any one of claims 1 to 6 to improve the hydrophobicity and/or oleophobicity.
  25. Filler according to any one of claims 1 to 6, to increase the stability during the sizing.
  26. Filler according to any one of claims 1 to 6, characterised in that it comprises an antistatic additive, especially an electrically conductive substrate.
  27. Filler according to claim 26 to improve the conductivity of paper and cardboard products, also in the form of a laminate.
  28. Filler according to any one of claims 1 to 6, characterised by further additive components such as binders, wet strength agents, cationized guar, xanthane derivatives, polyimines, polyvinylamines, flocculating agents, nanoparticle systems, impurity binders, polymers, antislip additives, additives for pigment fixation, brighteners, defoamers or preservatives.
  29. Filler according to claim 28, characterised in that it is present in the form of a granulate, microgranulate, pelletized granulate, pellet, compactate, molded body, press bar or press ball, which can also be redispersable.
  30. Filler according to any one of claims 1 to 6, for use in the field of pulp cardboard, recycling cardboard, packaging papers, food cardboard, eating trays, packing trays, LWC paper, coated base paper, LWC roller offset, graphic papers, mat paper, calendered and satinized papers, SC papers, corrugated cardboard base paper, newspaper print papers, nonwovens and tissue, testliner and fluting.
  31. Filler according to any one of claims 1 to 6, also as a granulate, for use in paper coating, for coating of paper or cardboard with the usual coating method.
  32. Filler according to any one of claims 1 to 6, also as a low-dust granulate, further comprising fillers such as natural calcium carbonate (GCC), precipitated calcium carbonate (PCC), kaolin (aluminium silicate), calcined kaolins, talc (magnesium silicate), marble meal, limestone meal, chalk, as well as pigments like titanium dioxide, barium sulfate, barium titanate, zinc sulfide, corundum, as well as starch-containing products (native starch, cooking starch, cold watersoluble starch, extruded or pregelatinized starch, cationized starch) based on wheat, corn, potato, tapioca, rice or amaranth, as well as aluminium salts, alums and binders like latex, or sizing agents such as caseinates, as additive.
  33. Filler according to any one of claims 1 to 6, characterised in that the cellulose component or the filler is cationized or contains additives (such as cationized starch, cationized regenerate fibres, cationized lignocellulose, polyimine, urea-glyoxal reaction products), which change the zeta potential.
  34. Filler according to any one of claims 1 to 6, characterised in that the mixture further comprises wet strength agents such as urea-formaldehyde resin or polyamidamine-epichlorohydrin resins, ketene derivatives, or diketenes.
  35. Filler according to any one of claims 1 to 6, characterised in that the mixture comprises hydrophobicizing agents (such as calcium stearate, magnesium stearate, zinc stearate, silicone-vinyl resins, Montan wax or carnauba wax, fluoroorganic components) or ultrafine colloids.
  36. Filler according to any one of claims 1 to 6, characterised in that the additive is flame-retardant, such as phosphate salts, borate salts, micro-encapsulated phosphonates, carboxymethyl cellulose, starch (also modified starch and derivatives), preservatives.
  37. Filler according to any one of claims 1 to 6, characterised in that the cellulose fibre used comprises primarily cellulose derivatives or regenerated celluloses.
  38. Dry mixture of paper additives characterised in that it comprises a filler according to any one of claims 1 to 6.
  39. Method for making a fibre-like or particle-like filler for paper, cardboard and tissue products, according to any one of claims 1 to 37, at least consisting of cellulose, lignocellulose, or microcrystalline cellulose (MCC) which is intact or fragmented to small particle size and at least one additive, in which the additive is applied to the surface of the cellulose component in solid, liquid, amorphous or microdispersed form, wherein mechanical, especially thermomechanical energy is introduced into a mixture of the cellulose component with the additive component in order to fix or to coat the at least one additive on the surface of the cellulose component taking into account an adequately long treatment time.
  40. The method according to claim 39, characterised in that the mechanical or thermo-mechanical energy is introduced in such a way that the mixture is subjected to pressure and internal friction within the mixture.
  41. The method according to claim 39 or 40, characterised in that to produce fibre compounds with mineral and/or pigment additives, a device from the group of roller mill, roll compactor, cylinder mill, Kahl press, RIM (rotor inertia mill), hybridizer, gyratory mill, impeller mill, Mullen mixer, disk vibration mill, extruder, extrusion press, vertical kneader, co-kneader is used.
  42. The method according to claim 39 or 40 to produce fibre compounds with starch, modified starch, cationic starch or starch ether, in particular according to claim 9, wherein the starch is preferably partially pre-gelatinized by introducing thermo-mechanical energy.
  43. The method according to claim 39 or 40, characterised in that to produce fibre compounds with starch, modified starch, cationic starch or starch ether, in particular according to claim 9, a device from the group of roll mill, roll compactor, cylinder mill, Kahl press, RIM (rotor inertia mill), hybridizer, gyratory mill, impeller mill, Mullen mixer, disk vibration mill, extruder, extrusion press, vertical kneader, co-kneader, or the like is used.
  44. The method according to claim 39 or 40, characterised in that to produce fibre compounds with sizing additive according to claim 11 or 12, dry cellulose fibres are treated with at least one liquid sizing additive in a mixer, an intensive mixer, a rotor mill, a sifter mill, in order to fix or to coat the sizing agent on the surface.
  45. The method according to claim 39 or 40, for producing fibre compounds with optical brightener according to claim 13, characterised in that the cellulose or microcrystalline cellulose (MCC) is reacted with a liquid optical brightener by means of mixer, rotor mill, turbo-mill, impact crusher, pinned disk mill or sifter mill.
  46. The method according to claim 39 or 40, for producing of fibre compounds with flame retardants according to claim 15 or 16, characterised in that the cellulose component is reacted with a liquid, water-dilutable or emulsifiable flame retardant by means of a baker's paddle mixer, ploughshare mixer, rotor mill, turbo-mill, impact crusher, pinned disk mill or sifter mill.
  47. The method according to claim 39 or 40, for producing fibre compounds with biocidal coating according to claim 18, characterised in that the cellulose component is reacted with a liquid, water-dilutable or emulsifiable biocide by means of a baker's paddle mixer, ploughshare mixer, rotor mill, turbo-mill, impact crusher, pinned disk mill or sifter mill.
  48. The method according to claim 39 or 40, for producing fibre compounds with antistatic additive according to claim 26 or 27, characterised in that dry fibres are reacted with at least one liquid conductive resin or one conductive substrate or one conductive pigment paste.
  49. The method according to claim 39 or 40, characterised by a processing of the fibre substance through granulating rolls (with and without friction, with and without fluting, with and without cam crusher), roll compactor (with and without friction), briquetting system, bar press, flat-die or round-die pelleting press, calendering layout, tabletting machine, double and multiple-roll granulator, fluidized bed granulator, granulating mill, beater screen machine, granulate grater (grater shredder) machines, press table, transfer press, extruder, co-kneader, traveling screen press or extrusion press.
  50. The method according to claim 39 or 40, characterised in that the components of the mixture for the paper coating are processed on a size press as pumpable formulation, especially in the presence of calcium carbonate, kaolin, binder, brightener, pigment, carboxymethyl cellulose (CMC), casein, low-molecular polyvinyl alcohols or soluble starch or other components as are typical of coating formulas.
  51. The method according to claim 39 or 40, characterised in that the components of the mixture, especially for roll application with doctor blade or Mayer bar, comprises thickening and/or rheological adjuvants, such as carboxymethyl cellulose (CMC), xanthane, cellulose gel.
  52. Paper, tissue or cardboard product, characterised in that it comprises a filler according to one of claims 1 to 37.
EP05824751.1A 2004-11-03 2005-11-03 Cellulose-containing filling material for paper, tissue, or cardboard products, method for the production thereof, paper, tissue, or cardboard product containing such a filling material, or dry mixture used therefor Revoked EP1817455B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL05824751T PL1817455T3 (en) 2004-11-03 2005-11-03 Cellulose-containing filling material for paper, tissue, or cardboard products, method for the production thereof, paper, tissue, or cardboard product containing such a filling material, or dry mixture used therefor

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102004053654 2004-11-03
PCT/EP2005/011758 WO2006048280A1 (en) 2004-11-03 2005-11-03 Cellulose-containing filling material for paper, tissue, or cardboard products, method for the production thereof, paper, tissue, or cardboard product containing such a filling material, or dry mixture used therefor

Publications (2)

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EP1817455A1 EP1817455A1 (en) 2007-08-15
EP1817455B1 true EP1817455B1 (en) 2013-04-10

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US (1) US20080265222A1 (en)
EP (1) EP1817455B1 (en)
ES (1) ES2424293T3 (en)
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WO (1) WO2006048280A1 (en)

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US20080265222A1 (en) 2008-10-30
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EP1817455A1 (en) 2007-08-15

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