EP1817455A1 - 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 thereforInfo
- Publication number
- EP1817455A1 EP1817455A1 EP05824751A EP05824751A EP1817455A1 EP 1817455 A1 EP1817455 A1 EP 1817455A1 EP 05824751 A EP05824751 A EP 05824751A EP 05824751 A EP05824751 A EP 05824751A EP 1817455 A1 EP1817455 A1 EP 1817455A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- starch
- filler
- paper
- filler according
- mill
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- 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
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- 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 production processes therefor, and to a paper, tissue or paperboard product containing such a filler or dry mixture used therefor according to the preambles of claims 1, 39, 52 and 38, respectively.
- cellulosic fibers made from 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. What they all have in common is that they are long-fiber products produced in a wet process. Due to the large fiber length is a good Composite achieved in the paper and cardboard, which leads to sheet formation and which is of mechanical importance of the highest importance.
- 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 and in the fiber structure (freeness 0 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 were ⁇ used for various reasons in the production process of paperboard and Textilfabri ⁇ ken. 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 Lite ⁇ raturan composite can be found on high-speed paper machines (> 1500 m / min) currently despite polymeric retention agents often below 40% retention of fillers and pigments.
- the invention binds additives for paper, tissue or paperboard production to the cellulosic component of the filler, so that they also adhere to a considerable extent to the fibers in aqueous suspensions. 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.
- the new development according to the invention gives better retention on the sheet former.
- the fixation reduces the amount of expensive additives and reduces the wastewater load.
- complex processes such as starch coking or size press are replaced by simpler processes in the paper mill.
- the filler according to the invention comprises cellulose, lignoceilulose or microcrystalline cellulose (ie a cellulosic component), this also means cellulosic precursors or intermediates which also comprise other herbal ingredients, such as protein, protein, starch and / or mineral constituents and other. 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, care must be taken that the particle size of the additives used is generally lower, preferably considerably less 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 particularly preferably not less than 2 to 10. No limitation is required in the direction of relatively large mass ratios, since in some circumstances very small amounts of additive may suffice. to achieve the desired effect in 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 makes it possible to achieve very small mass ratios of cellulosic component to additive component. As additives, as mentioned in more detail below, not only additives in pure form come into consideration.
- raw materials containing 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 take place in one working process.
- starchy raw materials such as soft wheat semolina, oat bran fractions, and extruded or cooked pregelatinized starches can be used to increase the strength of the paper or board on the one hand or the internal bond between fiber and coating on the other hand
- nanodisperse celluloses for example based on a microcrystalline cellulose, can be used in order to provide a carrier for coating compositions, for example for optical brighteners, to additives such as polyvinyl alcohol, spray starch and CMC at least partially replace and improve the printability.
- 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:
- 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 the sizing agent in sheet formation.
- Another object of the invention is a production process for sizing compounds. The one Sizing compound provides an improved price-performance ratio for sizing.
- a novel mineral compound consisting of fibers and minerals (fillers, pigments).
- the degree of whiteness and light fastness of the fibers used is markedly improved by the surface modification, which makes the use even in very light cardboard and paper possible.
- the invention relates to a lightweight filler, which is made of fibers and mineral be ⁇ for the production of paper and cardboard.
- the lightweight filler can reduce the volume of the paper, the machine speed and the filler
- a novel starch compound which consists of fibers and native or cationic starch and can increase the strength values (mesh burst strength, PIy Bond ply strength, Tear Index, Tensile Index, tearing length,%) With identical grammage, or one Reduction of the grammage without strength losses zuiässt.
- 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 end product.
- the object of the invention is a better retention of the starch in paper and cardboard, especially in recycled pulp with high anionic freight and high mineral content, in order to provide paper and cardboard with a higher strength.
- Another object of the invention is the production of a new type of festig ⁇ keitsSWden additives, wherein fibers are reacted in the high-consistency range or dry with starch or pregelatiniert.
- 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.
- 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.
- 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.
- a novel cationic fiber compound which consists of fibers and a cationizing agent and serves to adjust the zeta potential in cardboard and paper.
- a novel flame-retardant fiber compound which consists of fibers and a flame retardant agent and serves to adjust the low flammability in cardboard and paper.
- a novel liquid resin-fiber compound which consists of fibers and a liquid resin or a gel and serves to adjust the strength in Karto ⁇ nagen and papers.
- Embodiment 1 - Sizing compound consists of fibers and a liquid resin or a gel and serves to adjust the strength in Karto ⁇ nagen and papers.
- 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, a significantly improved sizing result is clearly evident.
- Embodiment 2 Starch Compound
- Headbox was OCC Furnish 60 °, gray fiber, grammage 200 g / m 2, freeness 31 0 SR.
- Laboratory sheets were made with 6 g per 4 liters on Rapid Köthen Blattressner and tested after drying and conditioning to Müllen burst index. It turns out that the fiber-starch compound performs qualitatively as well as pregelatinized starch.
- 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.
- Mullen mixers MM
- Nara Hybridizers NH
- the titanium dioxide pigment used was a rutile pigment from Kronos with the designation "Kronos 2050".
- Embodiment 6 Brightener Compound
- Ciba Pfersee optical brighteners were used to increase the brightness of the ARBOCEL BER 40 cell phone. These components are in turn suitable in the mixture for the color lightening of celluloses and MCC, in particular for reducing the b * value.
- the brightness values achieved allow a reformulation of the pulp with regard to "light fastness" and formulation costs.
- the freeness was determined according to Schopper Riegler according to ISO 5267/1. In individual cases, the freeness at 35-750 ml drainage with the DDJ drainage meter was gegenge ⁇ checks, with 1000 ml for 60 seconds at 3.0% TS and 20 0 C on 60 mesh 0 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.
- Cobb value was determined according to ISO 535, EN 20535 and Tappi T441, as well as with the Emtec Penetration Tester.
- the fiber suspension is dewatered on a sieve with constant stirring - without the formation of a filter layer.
- Titanium dioxide "KRONOS 2050” (99% TiO 2 , rutile type, Kronos Germany) particle size 1.1 - 2.5 ⁇ m, 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 ⁇ m, whiteness> 99.6% compared to barium sulfate standard
- Oily liquid 100% active substance, FDA approval, suitable for contact with food
- Tinofix AP Liquid Cationizing Resin (Ciba England) Additive for dye fixation and printability
- micro-composites are particles smaller than 500 ⁇ m, which consist of several phases - for example of 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 bleached chemo-thermo-mechanical powder, which is a bleached, high-temperature, chemical-treated pulp that, unlike pulp, contains many wood constituents].
- [Retention agents provide a high molecular weight via bridge formation or via cationic charge together with inorganic fines and prevent the removal of very fine particles in the course of foliar formation, ie they retain these particles].
- ["Fiber Loading” is a special coating process which, for example, produces a coating layer of calcium carbonate on the fiber from aqueous calcium hydroxide solution and carbon dioxide gas].
- ["Müllen Burst” provides the bursting pressure [kPa] and the bursting index [kPa m 2 / g] in the dry state, according to Tappi Method T 807, ie is a measure of the mechanical strength of paper or board].
- ["PIy Bond” provides the internal ply strength [kPa], measured with tensile stress 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.
- wet strength agents are required for paper grades such as tissue, filter papers, label papers, cash and securities and teabag papers; the basis of the wet strength agents may be polyamidoamine-epichlorohydrin, melamine-formaldehyde or urea-formaldehyde].
- Optical fluorescence healers 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 alkyl ketene dimer (AKD), alkenyl ketene dimer, alkylsuccinic acid and its derivatives (A-SA), hydrocarbon resins and rosin resins, fluorocarboxylic acids, polycarboxylic acids, fluoroorganyls, acid amides, fluorine-containing silanes. Fluorosiloxanes, and for acidic papers also alums and aluminum sulphate].
- ALD alkyl ketene dimer
- A-SA alkenyl ketene dimer
- A-SA alkylsuccinic acid and its derivatives
- hydrocarbon resins and rosin resins hydrocarbon resins and rosin resins
- fluorocarboxylic acids polycarboxylic acids
- fluoroorganyls fluoroorganyls
- acid amides fluorine-containing silanes. Fluorosiloxanes, and for acid
- ["Müllen mixer” is a discontinuous impeller mill, which subjects the regrind to friction and crushes it at the same time.]
- ["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].
- Matt paper is a relatively abrasion-resistant, coated or machine-coated, matte printing paper.
- SC paper (supercalendered paper) is a type of paper that has been given a very homogeneous smooth surface by calenders]
- newsprint is an opaque thin printing paper based on deinked pulp
- tissue is a nonwoven with a grammage of about 8 - 35 g / m 2 ].
- 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]. [The “drop test” is carried out by means of a micropipette and determines the time until the absorption of a certain amount of water or water-isopropanol mixture].
- the "Waring Blender” is a machine with a fast-running rotor for mixing liquids].
- ["Dynamic Drainage Meter" from Fa. Mytec is a precession measuring device for detecting the dewatering performance of fibrous materials, without the formation of an antiperspirant layer].
- ["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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Abstract
Description
Cellulosehaltiger Füllstoff für Papier-, Tissue- oder Kartonprodukte sowie Herstel¬ lungsverfahren hierfür sowie einen solchen Füllstoff enthaltendes Papier-, Tis¬ sue- oder Kartonprodukt oder hierfür verwendete TrockenmischungCellulosic filler for paper, tissue or paperboard products and also manufac turing methods therefor and paper, tissue or paperboard product containing such a filler or dry mixture used therefor
TECHNISCHES GEBIETTECHNICAL AREA
Die Erfindung betrifft einen cellulosehaltigen Füllstoff für Papier-, Tissue- oder Karton¬ produkte 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 production processes therefor, and to a paper, tissue or paperboard product containing such a filler or dry mixture used therefor 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 cellulosi- sche Fasern, die aus verschiedenen pflanzlichen Rohstoffen hergestellt wurden. Heut¬ zutage werden praktisch ausschließlich Cellulosefasern verwendet, die aus Holz ge¬ wonnen werden. Allen gemeinsam ist, dass es sich um langfasrige, in einem Nass- mahiverfahren hergestellte Produkte handelt. Durch die große Faserlänge wird ein guter Verbund im Papier und Karton erreicht, der zur Blattbildung führt und der für die me¬ chanische Festigkeit von höchster Bedeutung ist. Diese langfasrigen Produkte sind die Basis der Papier- und Kartonherstellung; ohne sie kann kein Papier oder Karton herge¬ stellt werden. Ihr Verbund führt zur notwendigen Blattbildung. Sie können sich im Rein- heitsgrad sowie in der Faserstruktur (Mahlgrad 0SR) 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 from 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. What they all have in common is that they are long-fiber products produced in a wet process. Due to the large fiber length is a good Composite achieved in the paper and cardboard, which leads to sheet formation and which is of mechanical importance of the highest importance. 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 and in the fiber structure (freeness 0 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 wer¬ den aus verschiedenen Gründen im Produktionsprozess von Karton- und Papierfabri¬ ken 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 Lite¬ raturangaben 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 wer¬ used for various reasons in the production process of paperboard and Papierfabri¬ ken. 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 Lite¬ raturangaben can be found on high-speed paper machines (> 1500 m / min) currently despite polymeric retention agents often below 40% retention of fillers and pigments.
Zusätzlich zu den oben genannten cellulosischen, verhältnismäßig langen Fasern wer¬ den spezielle, meist durch trockene oder feuchte Mahltechnologien zerkleinerte cellulo- sische 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 Festig- keitswerte sowie im Fall von ligninhaltigen Additiven eine Verschlechterung des Wei߬ grads beim Fertigprodukt.In addition to the above-mentioned cellulosic, relatively long fibers, special cellulosic fibers, which are usually comminuted by dry or wet grinding technologies, are added as additive for producing cardboard and paper to the pulp, to obtain higher volume or lower grammages, better formation, and better results to achieve faster drainage. 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 In the case of lignin-containing additives, the degree of whiteness in the finished product deteriorates.
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 An¬ spruchs 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, if appropriate, to reduce the additive-related treatment requirement of the water produced during the production of paper, tissue or cardboard products, a filler with the features of claim 1, a process for its production with the features of claim 39, a corresponding paper, tissue or cardboard product 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 kön¬ nen 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 also adhere to a considerable extent to the fibers in aqueous suspensions. 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 erfin¬ dungsgemäße 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 Stärkeko- chung oder Leimpresse durch einfachere Verfahren in der Papierfabrik ersetzt. - A -Compared with the dosage of pulverulent pigment and filler, the new development according to the invention gives 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 coking or size press are replaced by simpler processes in the paper mill. - A -
Während „Fiber loading'-Verfahren eine Vorbehandlung mit flüssigem Calciumhydroxid sowie eine Umsetzung mit gasförmigem Kohlendioxid voraussetzt, liefert die erfin¬ dungsgemäße Neuentwicklung stabile Coatings mit einfachen mechanischen Verfah¬ ren.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 vorge¬ schlagen, welcher u. a. folgende Vorteile bieten kann:Thus, a multifunctional filler having at least one additive is proposed, which u. a. can offer the following benefits:
I . Erhöhung der Drainage und Produktivität 2. Verbesserung der Theologischen Eigenschaften ( im Vergleich zu Holzstoffen )I. Increased drainage and productivity 2. Improvement of theological properties (compared to wood pulp)
3. Verbesserung der Formation3. Improvement of the formation
4. Verringerung der Trocknungskosten4. Reduction of drying costs
5. Erhöhte Dimensionsstabilität5. Increased dimensional stability
6. Höheres Volumen 7. Erhöhte Füllstoff-Retention, im Einzelfall geringerer Retensionsmittel-Verbrauch6. Higher volume 7. Increased filler retention, in individual cases lower retention agent consumption
8. Verbessertes Sizing für Hydrophobie und Oleophobie8. Improved sizing for hydrophobicity and oleophobicity
9. Erhöhter Weißgrad und bessere Bedruckbarkeit ( im Vergleich zu Holzstoffen )9. Increased whiteness and better printability (compared to wood pulp)
10. Höhere Opazität10. Higher opacity
I 1. Höhere Festigkeiten 12. Bessere Wirkung der Optischen Aufheller im Strich und bessere BedruckbarkeitI 1. Higher strengths 12. Better effect of the optical brightener in the line and better printability
13. Biozid-Ausrüstung13. Biocide equipment
14. Flammwidrigkeit14. Flame retardancy
15. Antistatische Eigenschaften15. Antistatic properties
16. Kationisierung und Anpassung des Zeta-Potentials 17. Höhere Affinität zu Farbstoffen16. Cationization and adaptation of the zeta potential 17. Higher affinity to dyes
18. Höherer Feststoffgehalt18. Higher solids content
19. Reduzierung der qualitativen Schwankungen bei Recyclingpapieren Soweit der erfindungsgemäße Füllstoff Cellulose, Lignoceilulose oder mikrokristalline Cellulose (d.h. eine cellulosische Komponente) aufweist, werden hierunter auch cellulo- sehaltige Vor- oder Zwischenprodukte verstanden, die noch andere pflanzliche Inhalt¬ stoffe 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 Inhaltsstof¬ fe in der cellulosischen Komponente enthalten sein, wobei deren Anteil nicht mehr als insgesamt 25% der cellulosischen Komponente betragen sollte.19. Reduction of qualitative variations in recycled paper Insofar as the filler according to the invention comprises cellulose, lignoceilulose or microcrystalline cellulose (ie a cellulosic component), this also means cellulosic precursors or intermediates which also comprise other herbal ingredients, such as protein, protein, starch and / or mineral constituents and other. 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 vor¬ zugsweise 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, vor¬ zugsweise 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, care must be taken that the particle size of the additives used is generally lower, preferably considerably less than the particle size of the cellulosic component.
Das Massenverhältnis zwischen der cellulosischen Komponente und der Additivkompo¬ nente ist vorzugsweise nicht kleiner als 1 zu 10 und besonders bevorzugt nicht kleiner als 2 zu 10. In Richtung größerer Massen Verhältnisse ist keine Beschränkung erforder¬ lich, da unter Umständen sehr geringe Additivmengen ausreichen können, um den er- wünschten Effekt bei der Papier-, Tissue- oder Kartonherstellung zu erreichen. Ansons¬ ten ist es auch möglich, die Additive in mehreren Schichten auf die Partikel der cellulo¬ sischen Komponente aufzubringen. Dies ermöglicht die Erreichung sehr kleiner Mas¬ senverhältnisse von cellulosischer Komponente zu Additivkomponente. AIs 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 Roh¬ stoffe in den Herstellungsprozess des erfindungsgemäßen Füllstoffs eingebracht wer¬ den, so dass die Rohstoffaufbereitung und das Fixieren oder Coaten der Additive auf den Partikeln der cellulosischen Komponente in einem Arbeitsprozess abläuft. So kön¬ nen z.B. stärkehaltige Rohstoffe, wie zum Beispiel Weichweizengriess, Haferkleie- Fraktionen, sowie extrudierte oder gekochte pregelatinierte Stärken zum Einsatz kom¬ men, um einerseits die Festigkeit des Papiers oder Kartons zu erhöhen oder anderer¬ seits den internen Verbund zwischen Faser und Coating-Substrat zu verbessern sowie das „Ausstauben" aus dem Papier zu verringern. Weiterhin können nanodisperse CeIIu- losen, 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.The mass ratio between the cellulosic component and the additive component is preferably not less than 1 to 10 and particularly preferably not less than 2 to 10. No limitation is required in the direction of relatively large mass ratios, since in some circumstances very small amounts of additive may suffice. to achieve the desired effect in 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 makes it possible to achieve very small mass ratios of cellulosic component to additive component. As additives, as mentioned in more detail below, not only additives in pure form come into consideration. Rather, raw materials containing 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 take place in one working process. Thus, for example, starchy raw materials such as soft wheat semolina, oat bran fractions, and extruded or cooked pregelatinized starches can be used to increase the strength of the paper or board on the one hand or the internal bond between fiber and coating on the other hand Furthermore, nanodisperse celluloses, for example based on a microcrystalline cellulose, can be used in order to provide a carrier for coating compositions, for example for optical brighteners, to additives such as polyvinyl alcohol, spray starch and CMC at least partially replace and improve the printability.
Mit der Erfindung kann eine Vielzahl von verschieden wirkenden Füllstoffen für die Pa¬ pier-, Tissue- oder Kartonproduktion verwirklicht werden. Die bevorzugten Ausführungs¬ formen werden nachfolgend beschrieben:With the invention, a multiplicity of differently acting fillers for paper, tissue or board production can be realized. The preferred embodiments are described below:
Die nachfolgenden Füllstoffe haben das gemeinsame Konzept, Cellulosefasern insbe¬ sondere 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: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) 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 Ge¬ genstand der Erfindung ist ein Herstellverfahren für Sizing-Compounds. Der Ein- satz des Sizing-Compounds liefert ein verbessertes Preis-Leistungs-Verhältnis bei der Leimung.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 the sizing agent in sheet formation. Another object of the invention is a production process for sizing compounds. The one Sizing compound provides an improved price-performance ratio for sizing.
2) Ein neuartiges Mineral-Compound, welches aus Fasern und Mineralien (Füll- Stoffe, Pigmente) besteht. Weißgrad und Lichtechtheit der eingesetzten Fasern wird durch die Oberflächenmodifizierung deutlich verbessert, wodurch der Ein¬ satz auch in sehr hellen Kartonagen und Papieren möglich wird. Gegenstand der Erfindung ist ein Leichtfüllstoff, der aus Fasern und Mineral be¬ steht, für die Fertigung von Papier und Kartonage. Der Leichtfüllstoff kann das Volumen der Papieres, die Maschinengeschwindigkeit und die Füllstoff-2) A novel mineral compound consisting of fibers and minerals (fillers, pigments). The degree of whiteness and light fastness of the fibers used is markedly improved by the surface modification, which makes the use even in very light cardboard and paper possible. The invention relates to a lightweight filler, which is made of fibers and mineral be¬ for the production of paper and cardboard. The lightweight filler can reduce the volume of the paper, the machine speed and the filler
Retension erhöhen.Increase Retention.
3) Ein neuartiges Stärke-Compound, welches aus Fasern und nativer oder kationi¬ scher Stärke besteht und die Festigkeitswerte (Müllen Berstfestigkeit, PIy Bond Lagenfestigkeit, Tear Index, Tensile Index, Reißlänge, ..) bei identischer Gram- matur erhöhen kann oder eine Verringerung der Grammatur ohne Festigkeitsver¬ luste zuiässt. 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 mechani¬ schen Festigkeiten des Faserverbunds im Endprodukt. Gegenstand der Erfin¬ dung 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 wei- terer Gegenstand der Erfindung ist die Fertigung einer neuen Type von festig¬ keitssteigenden Zusatzmitteln, wobei Fasern im Hochkonsistenz-Bereich oder trocken mit Stärke umgesetzt oder pregelatiniert werden. 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.3) A novel starch compound which consists of fibers and native or cationic starch and can increase the strength values (mesh burst strength, PIy Bond ply strength, Tear Index, Tensile Index, tearing length,...) With identical grammage, or one Reduction of the grammage without strength losses zuiässt. 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 end product. The object of the invention is a better retention of the starch in paper and cardboard, especially in recycled pulp with high anionic freight and high mineral content, in order to provide paper and cardboard with a higher strength. Another object of the invention is the production of a new type of festig¬ keitssteigenden additives, wherein fibers are reacted in the high-consistency range or dry with starch or pregelatiniert. 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) 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 immobi¬ lisiert 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.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) 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.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) Ein neuartiges kationionisches Faser-Compound, welches aus Fasern und einem Kationisierungsmittel besteht und zur Einstellung des Zeta-Potentials bei Kartonagen und Papieren dient.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) Ein neuartiges flammwidriges Faser-Compound, welches aus Fasern und ei¬ nem Flammschutzmittelmittel besteht und zur Einstellung der Schwerentflamm¬ barkeit bei Kartonagen und Papieren dient.8) A novel flame-retardant fiber compound which consists of fibers and a flame retardant agent and serves to adjust the low flammability in cardboard and paper.
9) Ein neuartiges Flüssigharz-Faser-Compound, welches aus Fasern und einem Flüssigharz oder einem Gel besteht und zur Einstellung der Festigkeit bei Karto¬ nagen und Papieren dient. Ausführungsbeispiel 1 - Sizing Compound9) A novel liquid resin-fiber compound, which consists of fibers and a liquid resin or a gel and serves to adjust the strength in Karto¬ nagen and papers. Embodiment 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 1250C über 2 Stunden getrocknet und bei Raumtemperatur über 4 Stunden konditioniert. Der Tropfentest wur¬ de als Schnelltest mit 75% Ameisensäure durchgeführt. Speziell bei Prüfung mit dem Emtec- Penetrationstestgerät und beim Cobb 300 Wert zeigt sich deutlich ein verbes¬ sertes Leimungsergebnis.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, a significantly improved sizing result is clearly evident.
Probe AKD-Harz C100-33 C 100-46 C 100-67Sample AKD resin C100-33 C 100-46 C 100-67
Vergleich AKD J AKD J AKD WMComparison AKD J AKD J AKD WM
Einsatzmenge AKD % 3 3 3 3Amount used AKD% 3 3 3 3
Massezunahme g /12 g 0.36 1.20 0.93 0.57Mass increase g / 12 g 0.36 1.20 0.93 0.57
Tropfentest Vordersei¬ sec 244 126 1593 teDrip test Vordersei¬ sec 244 126 1593 te
Tropfentest Rückseite sec 285 175 2308Drop test on the back side sec 285 175 2308
Cobb 300 sec g 52.2 39.8 42.7 37.1Cobb 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 400SR) eingesetzt wurden, bei zwei Einsatzmen¬ gen. 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. From 50% wood fiber ARBOCEL C 100 and 50% native potato starch from the company. Aroostook produced by trituration coated fibers, which were used for the production of laboratory sheets (157-158 g / m 2 at 40 0 SR), with two Einsatzmen¬ conditions The iodometric determination of starch in the fibrous materials 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.
Ausführungsbeispiel 3 - Stärke CompoundEmbodiment 3 - Starch Compound
Stoffauflauf war OCC Furnish 60°, graue Faser, Grammatur 200 g/m2, Mahlgrad 31 0SR. Es wurden Laborblätter mit 6 g pro 4 Liter auf Rapid Köthen Blattbildner hergestellt und nach Trocknung und Konditionierung auf Müllen Berstindex geprüft. Es zeigt sich, daß das Faser-Stärke-Compound qualitativ ähnlich gut abschneidet wie pregelatinierte Stärke. Headbox was OCC Furnish 60 °, gray fiber, grammage 200 g / m 2, freeness 31 0 SR. Laboratory sheets were made with 6 g per 4 liters on Rapid Köthen Blattbildner and tested after drying and conditioning to Müllen burst index. It turns out that the fiber-starch compound performs qualitatively as well as pregelatinized starch.
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 gleichzei¬ tig 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 ent¬ hält 15 % kationische Maisstärke. Die Rührergeschwindigkeit war 300 Umdrehungen pro Minute auf SR-Sieb. + Zusatz C 100 - 15 CS ohne ZusatzAn AP material (30 ° SR, ash 15%) at 2.00% dry weight was used, which in turn contains 3-7% starch compound. The starch compound C 100-15 CS ent¬ holds 15% cationic corn starch. The stirrer speed was 300 revolutions per minute on SR sieve. + Additive C 100 - 15 CS without additive
2% AP-Slurry2% AP slurry
Dosage % 3 5 7 10 0Dosage% 3 5 7 10 0
5 sec g 166 168 175 1485 sec. G 166 168 175 148
30 sec g 390 396 400 35030 sec. G 390 396 400 350
60 sec g 519 524 530 46360 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 85O0C bestimmt, wobei sich Calciumcarbonat zu Calciumoxid umwandelt; Titandioxid bleibt bei dieser Veraschung unverändert. 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 85O 0 C, wherein calcium carbonate converts to calcium oxide; Titanium dioxide remains unchanged during this ashing.
Physikalische PhysikalischePhysical Physical
Trocken- Compound Trocken- CompoundDry compound dry compound
Mischung # 1.2 Mischung # 1.4Mixture # 1.2 Mixture # 1.4
# 1.1 # 1.3# 1.1 # 1.3
Zusammenset¬ LIGNOCEL C LIGNOCEL ARBOCEL C ARBOCEL C zung 120 C 120 750 750Composition LIGNOCEL C LIGNOCEL ARBOCEL C ARBOCEL C tion 120 C 120 750 750
+40% CaCO3 +40% +50% CaCO3 +50%+ 40% CaCO 3 + 40% + 50% CaCO 3 + 50%
CaCO3 CaCO3 CaCO 3 CaCO 3
Hydrocarb Hydrocarb Omyacarb OmyacarbHydrocarb Hydrocarb Omyacarb Omyacarb
Mineral /Mineral /
10160 10160 2GU 2GU Pigment g / L 180 193 164 20210160 10160 2GU 2GU Pigment g / L 180 193 164 202
Schüttgewichtbulk weight
Feuchte % 9.5 9.4 3.6 3.6Humidity% 9.5 9.4 3.6 3.6
Aschegehalt derAsh content of
Siebfraktionensieve fractions
Vibrationssieb :Vibrating sieve:
< 32 μm % TS 32.3 20.2 21.3 4.9<32 μm% TS 32.3 20.2 21.3 4.9
32 - 50 μm % TS 19.4 31.232 - 50 μm% TS 19.4 31.2
50 - 90 μm % TS 23.3 48.050 - 90 μm% TS 23.3 48.0
90 - 150 μm % TS 26.4 11.290 - 150 μm% TS 26.4 11.2
150 - 200 μm % TS 36.6 4.0150 - 200 μm% TS 36.6 4.0
Die hohen Ascheanteile in allen Fraktionen zeigen, dass die mineralischen Komponen¬ ten 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. Ausführungsbeispiel 5.2 - Mineral CompoundThe high proportions of ash in all fractions show that the mineral components are bound to a high degree on 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. Exemplary embodiment 5.2 - mineral compound
Mittels Mullen-Mischer (MM) und mittels Nara Hybridizer (NH) wurden verschiedene Compounds mit anorganischen Füllstoffen und Pigmenten hergestellt. Das eingesetzte Titandioxid-Pigment war ein Rutil-Pigment von Kronos mit der Be¬ zeichnung „Kronos 2050".Mullen mixers (MM) and Nara Hybridizers (NH) were used to make various compounds with inorganic fillers and pigments. The titanium dioxide pigment used was a rutile pigment from Kronos with the designation "Kronos 2050".
20 Gramm Compounds wurden in einem Waring Blender mit 200 ml Wasser für 1 Minu¬ te 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 Asche¬ werte wurden im Muffelofen bei 8500C bestimmt.20 g 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 stirrer for 5 minutes, then filtered through a 45 μm PP Tissue fabric (air flow 440 L / m 2 min). The Asche¬ values were determined in a muffle furnace at 850 0 C.
Ausführungsbeispiel 6 - Aufheller CompoundEmbodiment 6 - Brightener Compound
Es wurden Optische Aufheller von Ciba Pfersee eingesetzt, um die Weiße der CeIIuIo- sefasem ARBOCEL BER 40 zu erhöhen. Diese Komponenten eignen sich wiederum in der Mischung für die Farbaufhellung von Cellulosen und MCC, insbesondere zur Ver¬ ringerung des b* Wertes. Die erzielten Helligkeitswerte ermöglichen eine Umformulie- rung der Papiermasse unter Hinsicht auf „Light Fastness" und Rezepturkosten. Ciba Pfersee optical brighteners were used to increase the brightness of the ARBOCEL BER 40 cell phone. These components are in turn suitable in the mixture for the color lightening of celluloses and MCC, in particular for reducing the b * value. The brightness values achieved allow a reformulation of the pulp with regard to "light fastness" and formulation costs.
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 gegenge¬ prüft, mit 1000 ml über 60 Sekunden bei 3.0 % TS und 200C auf 60 mesh 0SR 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 individual cases, the freeness at 35-750 ml drainage with the DDJ drainage meter was gegenge¬ checks, with 1000 ml for 60 seconds at 3.0% TS and 20 0 C on 60 mesh 0 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 Müllen Burst Index bestimmt.100 cm 2 handsheets were made on a Rapid-Köthen sheet according to DIN 54358 / ISO 5269/2. For laboratory papers with the same grammage, the bursting pressure was determined as the Müllen 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 4500C (nach 5 Std.) beziehungsweise 8500C (nach 8 Std.) bestimmt. Der Stärkegehalt wurde durch eine iodometrische Titration nach Tappi T 419 om - 91 bestimmt. Cobb Wert wurde gemäß ISO 535, EN 20535 sowie Tappi T441 bestimmt, sowie mit dem Emtec Penetrationstestgerät.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 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 Ent¬ wässerungsmessung 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 Kartonbe- reich (Graubereich).Drainage and retention were determined with Mytek drainage meter. In the case of the water removal 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 corresponds 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 Fest¬ stoffgehaltes 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, it is possible to calculate the total and filler retention.
Verschiedene Holzfaserstoffe wurden mit sehr feinteiligen mineralischen Additiven wie Titandioxid oder Calciumcarbonat durch reibende mechanische Kräfte gecoatet (durch¬ schnittliche Partikelgröße der Mineralien: < 10 μm). Die eingesetzten Faserstoffe waren unter anderem. 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.
Es wurden folgende Komponenten eingesetzt :The following components were used:
Kationische Kartoffelstärke Hi-CAT® CWS 42 (Roquette Deutschland)Cationic potato starch Hi-CAT® CWS 42 (Roquette Germany)
Partikelgröße bis 500 μm, Feuchte 8 %, Stickstoffgehalt unter 2 %Particle size up to 500 μm, humidity 8%, nitrogen content below 2%
Kationische Maisstärke C* Bond HR 05946 und C* Bond HR 05947 (Cerestar Nie¬ derlande) Partikelgröße 8 - 25 μm, Feuchte 10%, Stickstoffgehalt unterCationic corn starch C * Bond HR 05946 and C * Bond HR 05947 (Cerestar Netherlands) Particle size 8 - 25 μm, moisture content 10%, nitrogen content below
Native Kartoffelstärke (Roquette Frankreich / Beinheim) Partikelgröße 15- 60 μm, Feuchte 12 %Native potato starch (Roquette France / Beinheim) Particle size 15- 60 μm, moisture 12%
Polyvinylamin-Harzlösung (BASF Deutschland) Lupamin- und Basocoll-Marken, mit max. 9 % StickstoffgehaltPolyvinylamine resin solution (BASF Germany) Lupamin and Basocoll brands, with max. 9% nitrogen content
Calciumcarbonat Hydrocarb "Grade 10160" (Omya Deutschland) Partikelgröße 2-3 μmCalcium carbonate Hydrocarb "grade 10160" (Omya Germany) particle size 2-3 μm
Calciumcarbonat Omyacarb 2 GU (Omya Österreich / Gummern) Partikelgröße 2 μm, PCC-Qualität, Feuchte 0.28 %, Weiße 90.2 %Calcium carbonate Omyacarb 2 GU (Omya Österreich / Gummern) particle size 2 μm, PCC-quality, humidity 0.28%, whiteness 90.2%
Titandioxid "KRONOS 2050" (99% TiO2, Rutil-Type, Kronos Deutschland) Partikelgröße 1.1 - 2.5 μm, Weiße > 99.8 % gegenüber Bariumsulfat StandardTitanium 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
Titandioxid „TiPure 938" (99% TiO2, Rutil-Type, DuPont Deutschland ) Partikelgröße 1.2 - 2.5 μm, Weiße > 99.6 % gegenüber Bariumsulfat StandardTitanium 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)Aquapel D 310 Alkyl Keten Dimer (Hercules)
Leimungsmittel für Papier auf Basis von Alkylketen-Dimer-Harz und Emulgator, Tro¬ ckenstoffgehalt etwa 13 %Sizing agent for paper based on alkyl ketene dimer resin and emulsifier, dry matter content about 13%
Alkylbernsteinsäureanhydrid ASA (Hercules) Mittelviskoses Harz mit 100 % WirksubstanzAlkyl succinic anhydride ASA (Hercules) Medium viscosity resin with 100% active substance
Lodyne 2000 Fluorkohlenwasserstoff FDA (Ciba)Lodyne 2000 fluorocarbon FDA (Ciba)
Ölige Flüssigkeit, 100 % Wirksubstanz, FDA Approval, für Lebensmittelkontakt ge¬ eignetOily liquid, 100% active substance, FDA approval, suitable for contact with food
Oleophobol CO Fluorkohlenwasserstoff (Ciba) Technischer Fluorkohlenwasserstoff, ohne FDA ApprovalOleophobol CO Fluorocarbon (Ciba) Technical grade fluorocarbon, without FDA approval
Tinofix AP Liquid Kationisierungsharz (Ciba England) Additiv für Farbstoff-Fixierung und BedruckbarkeitTinofix AP Liquid Cationizing Resin (Ciba England) Additive for dye fixation and printability
Bedeutung der bzw. Erläuterungen zu den verwendeten Fachausdrücken und Ab- kürzungen: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 meh¬ reren 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 of cellulose, lignin and starch].
in der Beschreibung der Erfindungin the description of the invention
[Schopper-Riegler-Mahlgrad (0SR) ist die Drainagemessung von 1 Liter Stoffauflauf[Schopper-Riegler-Mahlgrad ( 0 SR) is the drainage measurement of 1 liter headbox
(Fasersuspension) mit 0.2 % Trockenstoff, gemäß EN ISO 5267-1 ].(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 PuIp, also ein gebleichter, bei hoher Temperatur mit Chemikalien behandelter Faserstoff, der im Gegensatz zum Zellstoff noch viele Holzinhaltsstoffe enthält].[CTMP is bleached chemo-thermo-mechanical powder, which is a bleached, high-temperature, chemical-treated pulp that, unlike pulp, contains many wood constituents].
[ 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 zusam¬ men mit anorganischen Feinstoffen eine hohe Molmasse und verhindern die Auswa¬ schung sehr feiner Partikel bei der Blattbildung, retendeieren also diese Partikel ]. [„Fiber Loading" ist ein spezielles Coating-Verfahren, das zum Beispiel aus wässriger Calciumhydroxid-Lösung und Kohlendioxid-Gas eine Coating-Schicht von Calciumcar¬ bonat auf der Faser liefert].[Retention agents provide a high molecular weight via bridge formation or via cationic charge together with inorganic fines and prevent the removal of very fine particles in the course of foliar formation, ie they retain these particles]. ["Fiber Loading" is a special coating process which, for example, produces a coating layer of calcium carbonate on the fiber from aqueous calcium hydroxide solution and carbon dioxide gas].
[„Müllen Burst" liefert den Berstdruck [kPa] sowie den Berst-Index [ kPa m2 / g ] im tro¬ ckenen Zustand, gemäß Tappi Methode T 807; ist also ein Maß für die mechanische Festigkeit von Papier oder Karton].["Müllen Burst" provides the bursting pressure [kPa] and the bursting index [kPa m 2 / g] in the dry state, according to Tappi Method T 807, ie is a measure of the mechanical strength of paper or board].
[,,PIy Bond" liefert die interne Lagenfestigkeit [kPa], gemessen bei Zugbeanspruchung in vertikaler Richtung, gemäß Tappi Methode UM 808].["PIy Bond" provides the internal ply strength [kPa], measured with tensile stress 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 Flächenein¬ heit].["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, Etiketten¬ papiere, Geld- und Wertpapiere und Teebeutelpapiere erforderlich; Basis der Na߬ festmittel kann Polyamidoamin-Epichlorhydrin, Melamin-Formaldehyd oder Harnstoff- Formaldehyd sein ]. [ „Optische Fluoreszenz-Aufheiler" sind alle organischen Moleküle, die UV-Licht absor¬ bieren und blaues sichtbares Licht emittieren können ].["Wet strength agents" are required for paper grades such as tissue, filter papers, label papers, cash and securities and teabag papers; the basis of the wet strength agents may be polyamidoamine-epichlorohydrin, melamine-formaldehyde or urea-formaldehyde]. ["Optical fluorescence healers" 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-empfind liehe 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 Farb- messgerät ].[High "opacity" means low transparency of the printed image in graphic paper, the measurement is again made 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 Al- kylketendimer (AKD), Alkenylketendimer, Alkylbemsteinsäure und deren Derivate (A- SA), Kohlenwasserstoffharze und Collophoniumharze (Rosin), Fluorcarbonsäuren, Po- lycarbon-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 alkyl ketene dimer (AKD), alkenyl ketene dimer, alkylsuccinic acid and its derivatives (A-SA), hydrocarbon resins and rosin resins, fluorocarboxylic acids, polycarboxylic acids, fluoroorganyls, acid amides, fluorine-containing silanes. Fluorosiloxanes, and for acidic papers also alums and aluminum sulphate].
in den Patentansprüchenin the claims
[„Müllen Mischer" ist eine diskontinierliche Impellermühle, die das Mahlgut einer Friktion unterwirft und gleichzeitig zerkleinert. ] [ „Nara Hybridizer" ist ein Technikumsgerät von Fa. Nara zur trockenen Zerkleinerung, Verfahren ähnlich einer Impellermühle ].["Müllen mixer" is a discontinuous impeller mill, which subjects the regrind to friction and crushes it at the same time.] ["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 einge- setzt 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 mat- tes 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[Satin papers are finished with a satin finish to a high gloss finish
Papiere].Papers].
[ SC-Papier (Supercalendered Paper) ist eine Papiersorte, die über Kalander eine sehr homogene glatte Oberfläche erhalten hat ] [ Zeitungsdruckpapier ist ein opakes dünnes Druckpapier auf Basis Deinkingstoff,[SC paper (supercalendered paper) is a type of paper that has been given a very homogeneous smooth surface by calenders] [newsprint is an opaque thin printing paper based on deinked pulp,
Weichholz-TMP und Recyclingfaser, mit etwa 2 - 28 % Asche ].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 einge- setzt ][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 Ober- flächen-behandlung ].[Fluting is also mainly made from recycled fiber, with special surface treatment].
[ Size Press bezeichnet dasVerfahren Leimung nach der Blattbildung ].[Size Press refers to the process 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 auf¬ genommen wird, gemäß Tappi Methode T 441 und 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 "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]. [The "drop test" is carried out by means of a micropipette and determines the time until the absorption of a certain amount of 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 lod-Titerlösung ].[The iodometric quantitiative determination of starch 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 aufwei¬ sen kann ] [ Der „Rapid Köthen Blattbildner" ist ein Technikumsgerät zur Herstellung standardisier¬ ter Laborblätter mit Durchmesser 200 mm ].["OCC Furnish" is a special brown or gray headbox made of recycled corrugated cardboard boxes, which can have fiber lengths of 3-4 mm] ["The Rapid Köthen Sheet Former" is a pilot plant for the production of standardizers 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 Erfas¬ sung der Entwässerungsleistung von Faserstoffen, ohne die Bildung eienr An¬ schwemmschicht].["Dynamic Drainage Meter" from Fa. Mytec is a precession measuring device for detecting the dewatering performance of fibrous materials, without the formation of an antiperspirant layer].
[ „AP-Stoff" ist ein Altpapierstoff der europäischen Sorte A 12 oder vergleichbare Quali¬ tät ].["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 einge¬ setzt wird ]. Im Ausführungsbeispiel 5 - Mineral Compound[The SR sieve is a mesh sieve as used for the Schopper-Riegler measurement]. In 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
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 |
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| 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)
| Publication Number | Publication Date |
|---|---|
| EP1817455A1 true EP1817455A1 (en) | 2007-08-15 |
| EP1817455B1 EP1817455B1 (en) | 2013-04-10 |
Family
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|---|---|---|---|
| EP05824751.1A Revoked EP1817455B1 (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 |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US20080265222A1 (en) |
| EP (1) | EP1817455B1 (en) |
| ES (1) | ES2424293T3 (en) |
| PL (1) | PL1817455T3 (en) |
| WO (1) | WO2006048280A1 (en) |
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| CH533670A (en) | 1968-12-05 | 1973-02-15 | Ciba Geigy Ag | Inorganic white pigments containing optical brighteners |
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| US3892577A (en) * | 1971-11-23 | 1975-07-01 | Mizusawa Industrial Chem | White pigment excelling in resistance to flame and corrosion |
| SE432951B (en) * | 1980-05-28 | 1984-04-30 | Eka Ab | PAPER PRODUCT CONTAINING CELLULOSA FIBERS AND A BINDING SYSTEM CONTAINING COLOIDAL MILIC ACID AND COTIONIC STARCH AND PROCEDURE FOR PREPARING THE PAPER PRODUCT |
| US5270076A (en) * | 1991-04-11 | 1993-12-14 | E. I. Du Pont De Nemours And Company | Process for coating alkyl ketene dimer on titanium dioxide |
| WO1993012282A1 (en) * | 1991-12-17 | 1993-06-24 | Weyerhaeuser Company | Hopper blender system and method for coating fibers |
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| WO1998031730A1 (en) * | 1997-01-16 | 1998-07-23 | Sekisui Chemical Co., Ltd. | Fire-resistant sheetlike molding, fire-resistant laminate for covering steel, fire-resistant structure for wall, and method for constructing fire-resistant steel and fire-resistant wall |
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- 2005-11-03 WO PCT/EP2005/011758 patent/WO2006048280A1/en not_active Ceased
- 2005-11-03 US US11/666,934 patent/US20080265222A1/en not_active Abandoned
- 2005-11-03 EP EP05824751.1A patent/EP1817455B1/en not_active Revoked
- 2005-11-03 PL PL05824751T patent/PL1817455T3/en unknown
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9777143B2 (en) | 2014-04-11 | 2017-10-03 | Georgia-Pacific Consumer Products Lp | Polyvinyl alcohol fibers and films with mineral fillers and small cellulose particles |
| US9777129B2 (en) | 2014-04-11 | 2017-10-03 | Georgia-Pacific Consumer Products Lp | Fibers with filler |
| US10597501B2 (en) | 2014-04-11 | 2020-03-24 | Gpcp Ip Holdings Llc | Fibers with filler |
| US10696837B2 (en) | 2014-04-11 | 2020-06-30 | Gpcp Ip Holdings Llc | Polyvinyl alcohol fibers and films with mineral fillers and small cellulose particles |
| CN115147617A (en) * | 2022-09-06 | 2022-10-04 | 聊城集众环保科技有限公司 | Intelligent sewage treatment monitoring method based on computer vision |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2006048280A1 (en) | 2006-05-11 |
| EP1817455B1 (en) | 2013-04-10 |
| ES2424293T3 (en) | 2013-09-30 |
| US20080265222A1 (en) | 2008-10-30 |
| PL1817455T3 (en) | 2013-09-30 |
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