EP2314765A1 - Fabrication d'un composite en fibre, son utilisation et composite en fibre - Google Patents

Fabrication d'un composite en fibre, son utilisation et composite en fibre Download PDF

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Publication number
EP2314765A1
EP2314765A1 EP10185955A EP10185955A EP2314765A1 EP 2314765 A1 EP2314765 A1 EP 2314765A1 EP 10185955 A EP10185955 A EP 10185955A EP 10185955 A EP10185955 A EP 10185955A EP 2314765 A1 EP2314765 A1 EP 2314765A1
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EP
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Prior art keywords
fiber composite
pulp
fiber
composite
formation
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EP10185955A
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German (de)
English (en)
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EP2314765B1 (fr
Inventor
Reinhard Kräuter
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Bene_fit Systems & Co KG GmbH
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Bene_fit Systems & Co KG GmbH
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    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • 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
    • D21H17/675—Oxides, hydroxides or carbonates
    • 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
    • D21H17/68—Water-insoluble compounds, e.g. fillers, pigments siliceous, e.g. clays
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • 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
    • 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
    • D21H17/70—Inorganic compounds forming new compounds in situ, e.g. within the pulp or paper, by chemical reaction with other substances added separately

Definitions

  • the invention relates to a process for the production of a fiber composite, which comprises at least one additive and at least one organic fiber, wherein the fiber is selected from a group of wood pulp, half-pulp, pulp, wool, silk, linen, cotton, synthetic polymer fibers and / or comprises other fibrous materials with fiber thicknesses of less than 0.5 mm, with at least one additive being added which comprises Ca and / or Mg compounds and which changes its structure in the fiber composite and / or forms a structure and after the structural change and / or or structuring a network-like pulp structure, which is formed by the pulp, interspersed to stabilize the fiber composite as a three-dimensional composite of Ca and / or Mg compounds.
  • the invention relates to a fiber composite, which comprises at least one additive and at least one organic pulp, wherein the pulp is selected from a group comprising wood pulp, half-pulp, pulp, wool, silk, linen, cotton, synthetic polymer fibers and / or other fibers Fiber thicknesses of less than 0.5 mm and at least one of the additives comprises a Ca and / or Mg compound, which is present in a three-dimensional composite of Ca and / or Mg compounds, which is a net-like Fiber structure, which is formed or formed by the pulp, has interspersed structure for stabilizing the fiber composite.
  • the pulp is selected from a group comprising wood pulp, half-pulp, pulp, wool, silk, linen, cotton, synthetic polymer fibers and / or other fibers Fiber thicknesses of less than 0.5 mm and at least one of the additives comprises a Ca and / or Mg compound, which is present in a three-dimensional composite of Ca and / or Mg compounds, which is a net-like Fiber structure, which is formed or
  • the invention relates to the use of such a fiber composite as a medium for information storage, packaging material, decorating means (e.g., wallpaper), sanitary articles, insulating material, gas, water or vapor barrier, flame retardant material, sound insulation material, material, insulation means or the like.
  • decorating means e.g., wallpaper
  • sanitary articles e.g., insulating material, gas, water or vapor barrier, flame retardant material, sound insulation material, material, insulation means or the like.
  • a fiber composite is to be understood as meaning any fiber composites, as preferred in the form of paper, paperboard, corrugated board or boards, or else in another form, e.g. as packaging material, decorative material (e.g., wallpaper), sanitary articles, insulating material, gas, water or vapor barrier, flame retardant material, soundproofing material, material, insulation means may be used.
  • a fiber composite according to the invention is, for example, paper. Paper is predominantly used for writing and printing and so far consists mostly of vegetable fibers. In addition, fillers, pigments and additives are used. Important areas of application are packaging (cardboard, cardboard), sanitary papers such as toilet paper and special papers such as wallpapers. Paper is usually made of pulp or wood pulp (recycled wood pulp), as well as fibers made of recycled paper.
  • the paper is produced from wood in the form of wood pulp, semichemical pulp or pulp. Often, conifers such as spruce, fir, pine and larch are used. Due to the longer fibers compared to deciduous trees, softwood fibers are felted more easily, resulting in a higher strength of the paper.
  • the fibrous material used in the paper is one of the largest cost factors for paper raw materials because it is expensive compared to other fillers used and is also used in large proportions. Increasingly paper demand is expected globally, combined with further rising fiber prices. Furthermore, due to the anticipated increased competition of different uses for renewable raw materials (for example for energy use, bio-based polymers), a further significant shortage of pulp is expected, which could lead to further price increases.
  • fillers are already added to the prior art stock. These may be e.g. kaolin, talc, titanium dioxide, ground calcium carbonate (GCC) and precipitated calcium carbonate (PCC).
  • GCC ground calcium carbonate
  • PCC precipitated calcium carbonate
  • Kaolin is added both as fillers and as a coating pigment.
  • Kaolin remains chemically inert over a wide pH range and can therefore be used not only in acidic but also in alkaline production processes.
  • Talc is added to paper to reduce the porosity of the paper and thus to improve the printability of uncoated papers.
  • the use of high-quality talcum to influence the wood fiber grain improves the running properties of the paper.
  • Titanium Dioxide is a particularly effective white pigment that can be added to a paper to provide very high opacity, good light diffusion and excellent gloss. Since this material is many times more expensive than calcium carbonate, it is not used in standard filling or coating applications, but only in very high quality papers.
  • Calcium carbonate can be added to papers in two different modifications, namely as ground or precipitated calcium carbonate.
  • GCC Ground calcium carbonate
  • CaC0 3 -containing materials used for the production of GCC are sedimentary rocks (limestone or chalk) and the metamorphic marble rock.
  • Precipitated calcium carbonate is a synthetic industrial mineral made from quick lime or its raw material, limestone.
  • the paper industry where it is used as a filler and as a coating pigment, is the largest consumer of PCC.
  • Additives from PCC have a positive effect on a variety of properties of the paper.
  • PCC-containing papers have greater brightness, opacity and thickness than GCC-containing papers.
  • PCC can not be used indefinitely as a filler because it reduces fiber strength.
  • the fillers soften and soften the paper, giving it a smooth surface.
  • the proportion of fillers in the basis weight is expressed in the so-called ash number.
  • the composition and crystal structure of the fillers determines transparency and opacity of a paper as well as the ink acceptance when printing with weg knownden colors.
  • One of the key objectives in papermaking is to provide high tensile strength, such as As in the manufacture of kraft paper to achieve.
  • the tensile strength of a paper is given in N / m. Since the tensile strength mainly depends on the basis weight, the tensile index is often given in units of Nm / g.
  • pulp is one of the largest cost factors in papermaking. He is currently many times more expensive than the fillers used. For this reason in particular, the paper industry has great interest in having the means to be able to provide a paper product with the same or better properties and functionality, in particular high strength, at a reasonable price in the future.
  • Possibilities for this are to change the fibers and / or the fillers, for example by means of physical, chemical or mechanical processes (or combinations thereof) so that they give the paper higher strength and at the same time less fiber quantity.
  • the relative filler content can be increased thereby.
  • a positive side effect here is that the optical properties and processing properties thus produced Papers are also improved due to the higher filler content.
  • the grammage could also be reduced without significantly affecting other parameters.
  • PCC calcium carbonate
  • the strength of bleached pulp or waste paper pulp from mixed waste paper can also be increased by addition of carboxy-methyl cellulose (ERHARD K. and K. FROHBERG, Improvement of the Splitting Strength of Paper by CMC-Modified Fibers, PTS Research Report on the Research Project BMWA 408 / 03 and ERHARD K. and T. G ⁇ TZE, Improvement of the Usage Characteristics of Recycled Paper for the Production of Corrugated Paper by Chemical Reactivation of the Fiber Surface, PTS Research Report on Research Project AiF 12110B).
  • carboxy-methyl cellulose ERHARD K. and K. FROHBERG, Improvement of the Splitting Strength of Paper by CMC-Modified Fibers, PTS Research Report on the Research Project BMWA 408 / 03 and ERHARD K. and T. G ⁇ TZE, Improvement of the Usage Characteristics of Recycled Paper for the Production of Corrugated Paper by Chemical Reactivation of the Fiber Surface, PTS Research Report on Research Project AiF 12110B).
  • the aim of the invention is therefore methods for producing a fiber composite such. Paper, paperboard or cardboard to provide, wherein the fiber composite comprises at least one additive and at least one organic pulp and this at least one additive is added, which includes Ca and / or Mg compounds and which changes its structure in the fiber composite and / or a structure is formed and present after the structural change and / or structure formation as a three-dimensional composite for stabilizing the fiber composite.
  • the proportion of organic fibers in the production of a fiber composite should be reduced and at the same time its strength reduced only slightly, kept constant or increased, and the cost of production can be reduced.
  • the aim of the invention is also to provide a fiber composite, which comprises at least one additive and at least one organic fiber, wherein at least one of the additives comprises a Ca and / or Mg compound, which is convertible into a three-dimensional composite for stabilizing the fiber composite.
  • the optical properties such as opacity, whiteness, brightness, yellowness value and / or the physical properties such as air permeability or porosity are only marginally deteriorated, maintained or even improved.
  • the processing properties of the fiber composite at the e.g. Printing, cutting, folding, laminating, dyeing, bonding, etc. are also only marginally deteriorated, maintained or even improved.
  • the manufacture of the fiber composite should be only slightly affected, maintained or even simplified or accelerated, for example, in terms of sheet formation, drainage, drying or paper finishing.
  • should Energy can be saved or reduced by the invention in the dewatering and drying.
  • the amount of exhaust air and waste water should be increased only slightly, maintained or even reduced and the CO 2 balance in the production of a fiber composite deteriorated only slightly, maintained or even improved.
  • An essential aspect of the invention is a process for producing a fiber composite comprising at least one additive and at least one organic pulp, wherein the pulp is selected from a group consisting of groundwood, half-pulp, pulp, wool, silk, linen, cotton, synthetic polymer fibers and / or other fibrous materials having fiber thicknesses of less than 0.5 mm, wherein at least one additive is added which comprises Ca and / or Mg compounds and which changes its structure in the fiber composite and / or forms a structure and after Structure change and / or structure formation a reticulated fiber structure, which is formed by the pulp, interspersed to stabilize the fiber composite as a three-dimensional composite of Ca and / or Mg compounds.
  • a three-dimensional composite or three-dimensional network-like structure is understood as meaning a spatial connection of individual crystals or other solid particles of these Ca and / or Mg compounds.
  • the individual crystals or particles are interconnected and / or in a physical interaction with each other, which leads to the net-like (or framework-like) arrangement of the individual crystals or particles.
  • the three-dimensional composite thus formed has free spaces between the crystals and / or other solid particles, through which gases can diffuse, or in which individual fibers of the fibrous material or other additives can be arranged.
  • this (over) structure is referred to in this context as a crystal structure.
  • crystal structure In connection with certain forms of individual crystals such as rod-shaped, platelet-shaped, fibrous, star-shaped or tuft-shaped crystals, the term crystal structure for used the homogeneous three-dimensional arrangement of individual atoms within a crystalline particle.
  • a further reticulated (or skeletal) fiber braid is formed.
  • there are two reticulated fiber braids in the fiber composite which support each other in their capacity as a framework of the fiber composite. It is therefore possible to form two nested net-like structures, each of which has a positive influence on the stability of the fiber composite.
  • one of the structure-forming substances - ie either the Ca and / or Mg compound or the fibers of the pulp - is significantly smaller than the respective other structure-forming substance. This makes it possible for each of these to have a significantly different framework or network structure with e.g.
  • the smaller of the structure-forming substances interacts with pores, cracks, furrows, elevations, edges or other surface features of the larger structure-forming substances and thus integrates this larger structure into its own network-like structure. This is particularly the case when comparatively small Ca and / or Mg compounds interact with larger fibers of the pulp and are firmly attached to its surface. This placement on the surface is usually done only sporadically to increase the material properties of the fibers of the pulp and e.g. not excessively negatively affecting the binding of the fibers to each other.
  • the Ca and / or Mg compounds within the fiber composite do not completely enclose the fibers of the pulp, but cover the surface of the fibers only in sections.
  • the proportion of these covered by the Ca and / or Mg compounds sections is less than 95%, preferably less than 90%, more preferably less than 80%, but may also be less than 70% or less than 50%.
  • the Ca and / or Mg compound is used as sulfate, hydroxide, silicate, aluminate, ferrite and / or mixtures thereof in a proportion of 1-50% by mass, preferably 2-40 Ma-% and these by a reaction with water, CO 2 , carbonate ions, sulfate ions, oxygen, other additives and / or combinations thereof or by elimination of water or gases, such as CO 2 , O 2 or others, optionally under energy supply or discharge, to the three-dimensional Composite of Ca and / or Mg compounds implemented.
  • the Ca and / or Mg compounds may be, for example, cement or gypsum precursors such as CaSO 4 ("anhydrite") or CaSO 4 .1 ⁇ 2H 2 O ("bassanite", also "hemihydrate” or “hemihydrate”), however, as described above, any other Ca and / or Mg compound which forms reticulate, three-dimensional superstructures or composites.
  • the Ca and / or Mg compound can be used as a solution, suspension or solid. Preferably, they are soluble salts.
  • the formation of the structures or of the crosslinked crystal structures can be initiated, for example, by a reaction with water, CO 2 , oxygen, further additives and / or combinations thereof or by removal of water or gases, such as CO 2 , O 2 or others.
  • an energy supply or removal may be necessary.
  • air lime can harden and solidify by absorbing CO 2 .
  • Cement for example, reacts with water to form insoluble, stable calcium silicate hydrates, which form fine needle-shaped crystals which interlock with one another and thus lead to the high strength of the resulting fiber composite.
  • oxidation processes are also conceivable which lead to the formation of the crosslinked crystal structures.
  • Other possible reactions occur with elimination of smaller molecules such as water, CO 2 , O 2 , other gases or similar. as is the case for example in condensation reactions or polymerization reactions.
  • rod-forming, star-forming, tuft-forming or similar structures-forming materials or blends of these with each other or with other materials are preferred.
  • a structure-forming material such as a crystal structure-forming material or mixtures of these with each other or with others is dependent on the circumstances and the desired product properties. Depending on these, a specific selection can be made.
  • Crystal structure forming material example Structure formation eg Crystal structure formation Plaster, or dehydrated CaSO 4 * 0.5H 2 O, By reaction with water or partially dewatered gypsum precursors CaSO 4 with or other additives under certain conditions Mg compounds Mg (OH) 2 By reaction with CO 2 in water with or without other additives under certain conditions Ca and / or Al silicates Tricalcium silicate, C3S By reaction with water (3 CaO x SiO 2 with or without sulfate or Dicalcium silicate, C2S other additives (2 CaO x SiO 2 certain conditions Tricalcium aluminate, C3A (3 CaO x Al 2 O 3 ) Tetracalcium aluminate ferrite C4AF (4 CaO ⁇ Al 2 O 3 ⁇ Fe 2 O 3 ) Ca and / or Al silicates with Tricalcium silicate, C3S By reaction with water a low Fe 2 O 3 - (3 CaO x SiO 2 ) with or without sulfate or Content ⁇ 5%
  • Ca 3 Al 2 (OH) 12 tricalcium aluminate hydrate or [3CaO * A1 2 O 3 * 6 H 2 O] With or without sulfate or other additives in water under certain conditions
  • Ca 4 Al 2 (OH) 14 tetracalcium aluminate hydrate or [4CaO * Al 2 O 3 * 7H 2 O]
  • Table 2 shows an overview of chemical-physical parameters for further description of the properties of the structure-forming materials, such as the crystal structure-forming materials, which can be used by the invention:
  • the aggregates used for dry or wet grinding can be, for example: ball mills, pin mills, jet mill or bead mills, stirred ball mills, high-performance dispersers or high-pressure homogenizers.
  • the structure-forming materials may be other, especially organic or inorganic fiber materials of any origin and purity (natural, synthetic, recycled) and fiber length (long fiber, short fiber, nanofiber, microfibrillated fiber and mixtures thereof), fillers and / or pigments, and additives singly or in mixtures be added.
  • the structures formed by the respective reaction from the Ca and / or Mg compounds usually have the properties listed in Table 3.
  • Table 3 parameter unit Area prefers Mostly preferred refractive index 1-3 1.2-2.9 1.4 to 2.7 Whiteness R457, ISO 2470 % 1-100 5-100 10-100 Particle size *) microns .001-10000 0.01 to 7500 0.05 to 5000 Particle size **) microns .001-10000 0.01 to 7500 0.05 to 5000 Abrasion after Einlehne mg ⁇ 5000 ⁇ 4000 ⁇ 3000 Spec.
  • the Ca and / or Mg compound is present in the form of contiguous Ca and / or Mg-containing particles which a particle size, measured as d 50 (volume) between 0.001 and 10,000 microns, preferably between 0.01 and 7500 microns, more preferably between 0.05 and 5000 microns have.
  • a Ca and / or Mg compound is used which, after the structural change and / or structure formation in the fiber composite, has a refractive index n D of 1-3, preferably 1.2. 2.9, particularly preferably from 1.4 to 2.7 and has a whiteness R457 according to ISO 2470 of 1 to 100, preferably 5 to 100, particularly preferably 10 to 100.
  • a suitable structure-forming material e.g., paper, paperboard, cardboard
  • the requirements placed on a fiber composite can be very different. Due to the large number of possible choices of structure-forming materials and the properties of the forming structures or crystal structures, the requirements placed on a fiber composite can be met within a wide range.
  • the production of the fiber composite takes place. There are several ways to do this:
  • the structure-forming material, or the Ca and / or Mg compound can be brought in a suitable form (for example after preparation, as described above) in a first step to form the structures, such as the crystal structure ( eg also mixed with other materials) and brought in a second step on an already existing first fiber composite in order to then solidify this near the surface, for example.
  • a suitable form for example after preparation, as described above
  • the structures such as the crystal structure ( eg also mixed with other materials)
  • a second step on an already existing first fiber composite in order to then solidify this near the surface, for example.
  • This can also be done several times, with equipment and conditions for this purpose to those skilled in the art known (eg Blad Huawei, curtain coating, film press, size press, etc.).
  • Any pretreatment of the uncoated fiber composite or a post-treatment of the fiber composite with known suitable technical methods is possible.
  • the above fiber composite may be a known material in the art, e.g. Paper, cardboard, cardboard, fleece or a similar material. But it can also be a structure-containing fiber composite.
  • the structure-forming material, or the Ca and / or Mg compound can also be applied to an already existing first fiber composite in a suitable form (eg after preparation, as explained above) and there in a subsequent process step the structures , such as the crystal structures are brought to training.
  • the structure-forming material such as e.g. the crystal structure-forming material, thereby mixed together with other materials and applied in this form on a fiber composite. This may also be done several times, equipment and conditions of which may be varied and known to those skilled in the art (e.g., blading, curtain coating, film press, size press, etc.).
  • any pretreatment of the uncoated fiber composite or a post-treatment of the fiber composite after the formation of the three-dimensional composite of Ca and / or Mg compound, on or in this according to the known suitable technical methods is possible.
  • Forming the structures, e.g. the crystal structures can also be interrupted, e.g. by removal of the reactive component (such as water) and may e.g. B. temporally and later by the addition of a reactive component (such as water) in time and possibly also be separated spatially.
  • the structural change and / or structure formation of the Ca and / or Mg compounds is interrupted before the complete formation of the three-dimensional composite by a change of ambient conditions and the structural change and / or the structure formation up to complete formation of the three-dimensional composite at a later date, optionally after the fiber composite has been brought into a predetermined shape, continued by changing the environmental conditions again.
  • the structuring material may be added before, during, or after patterning, such as, e.g. crystal structure formation, with other materials (such as fillers, additives).
  • the fiber for this variant can also be mixed before, during or after the mixing with the formed structures of the Ca and / or Mg compounds and with other materials (for example fillers, additives).
  • the structure-forming material before, during, or after patterning e.g. crystal structure formation
  • the fiber may also be mixed with other materials and / or fibers before, during or after the mixing with the structure-forming material.
  • a pulp with a structure-forming material e.g. To bring a crystal structure-forming material, and other additives to a fiber composite and bring the structures until later in the training.
  • This can e.g. done by the fiber composite after training still a reactive component, e.g. Contains water and the structure-forming component, e.g. the crystal structure-forming component, together with this water forms the structures within this fiber composite. Thereafter, the fiber composite can be dried or further processed.
  • a fiber composite for example, a targeted shaping and then this form by forming structures, for example. Retains crystal structures, or is fixed by the fiber composite, a reactive component, e.g. Water is added.
  • a reactive component e.g. Water
  • the structures in the fiber composite can also be made such that they are very finely divided, whereby a flame-resistant and / or heat-insulating material is produced.
  • a pulp with a structure-forming material and other additives to a fiber composite and bring the structures of Ca and / or Mg compounds until later in the training.
  • This can be done, for example, by providing the fiber composite with a reactive, for forming the structures, such. the crystal structures, necessary component (such as water) is removed or this is not added and thus the structure formation, or the crystal structure formation, is interrupted in time.
  • the formation of structures such as e.g. crystal structures, and further crosslinking may then be initiated at a later time for the same or a different application by adding to the fiber composite the reactive component, e.g. Water is added.
  • the formation of the three-dimensional composite of the Ca and / or Mg compounds takes place before, during or after crosslinking of the organic fibrous materials.
  • the above-mentioned methods for producing a fiber composite can take place temporally and spatially next to one another or offset from one another. In addition, they can run continuously or in batch mode or in the form of intermediates of these methods.
  • Another essential aspect of the invention is a fiber composite comprising at least one additive and at least one organic pulp, wherein the pulp is selected from a group consisting of groundwood, half-pulp, pulp, wool, silk, linen, cotton, synthetic polymer fibers and / or comprising other fibrous materials having a fiber thickness of less than 0.5 mm, at least one of the additives comprising a Ca and / or Mg compound present in or translatable into a three-dimensional composite of the Ca and / or Mg compounds; which has a network-like fibrous structure, which is formed or formed by the fibrous material, passing through structure for stabilizing the fiber composite.
  • Such fiber composites can be cheaper in the material costs by the substitution of comparatively expensive organic fiber materials than comparable fiber composites in which the three-dimensional crosslinking is based exclusively on the crosslinking of the organic fiber materials.
  • these fiber composites due to the three-dimensionally crosslinked bond of the Ca and / or Mg compounds, these fiber composites can have a similar, or even improved Have strength as comparable fiber composites based on exclusively organic fibers.
  • Such a fiber composite preferably comprises the Ca and / or Mg compound in a proportion of 1-50% by mass, preferably 2-40% by mass, and the Ca and / or Mg compound is selected from a group which comprises sulfates , Hydroxides, silicates, aluminates, ferrites and / or mixtures thereof, in particular cements, gypsum and / or precursors thereof and by reaction with water, gases, in particular CO 2 or oxygen, carbonate ions, sulfate ions, further additives and / or combinations thereof or by elimination of water or gases such as CO 2 , O 2 or others, optionally with Energyzu- or -abssel, is a three-dimensional composite of Ca and / or Mg compounds in the fiber composite before or can be formed.
  • the Ca and / or Mg compound is selected from a group which comprises sulfates , Hydroxides, silicates, aluminates, ferrites and / or mixtures thereof, in particular cements, gypsum
  • the Ca and / or Mg compounds are present within the three-dimensional composite in substantially homogeneous crystal structures, which are preferably predominantly rod-shaped, platelet-shaped, fibrous, star-shaped or tuft-shaped.
  • These crystal structures are particularly suitable because of their geometry, as they are e.g. by interactions of their ends, corners or edges with adjacent crystals can form a three-dimensional net-like structure or a three-dimensional composite.
  • This three-dimensional structure can be referred to as reticulate or skeletal, since due to the geometry of the crystals cavities can be formed, which are comparable to the mesh of a network or the free spaces within a scaffold.
  • the interactions between the individual crystals can be physical or chemical in nature. For example, it may be a hooking or projections or the like. act. Likewise, however, electronic or electrostatic interactions between the ends as well as sticking (e.g., by a binder) of ends to each other are possible.
  • a fiber composite preferably comprises organic fibers which comprise individual fibers which have a substantially circular diameter of a size of less than 0.5 mm, preferably less than 0.25 mm, particularly preferably less than 0 , 01 mm.
  • These fibers may be, for example, groundwood, semi-pulp, cellulose, wool, silk, linen, cotton and other natural products, but also synthetic polymer fibers of organic origin such as (polyamides, polyesters, polyethers, polyolefins such as PE, PP, etc., polyurethanes and other organic polymers Substances).
  • the average length of the individual fibers is preferably less than 10 mm. But it can also be larger depending on the type and material of the fiber.
  • the Ca and / or Mg compound after the change and / or formation of the three-dimensional composite has a whiteness R457 according to ISO 2470 from 1 to 100, preferably from 5 to 100, more preferably from 10 to 100.
  • additives that positively affect the whiteness. These are known in the art and may be, for example, TiO 2 , kaolin, CaCO 3 , etc.
  • a surface coating can be applied to the fiber composite, can be printed, sprayed on, laminated on, rolled up, adhesively bonded or applied in another suitable manner. This makes it possible to further refine the fiber composite.
  • This surface coating can serve, for example, in the form of writing as an information medium.
  • other surface coatings are conceivable, the fiber composite only for subsequent applications (such as information storage, as packaging material, as decoration (eg wallpaper), as hygiene articles, as insulating material, as a gas, water or steam barrier, as a flame retardant, as Sound insulation material, as a material, as an insulating agent or the like) prepare.
  • These surface coatings can change the surface properties and, for example, adjust porosity, color, gloss, opacity, haptics, transparency, water resistance, wettability, and many others according to requirements.
  • the fiber composites described above also by several layers of these respective fiber composites or mixed with each other or with each other Materials (eg polymer films, metal foils) to merge into a multilayer fiber composite material.
  • Materials eg polymer films, metal foils
  • the fiber composites may be further processed according to the requirement and intended use or application, e.g. coated, printed, sprayed, rolled, laminated, folded, cut, pasted, coated, etc.
  • the abovementioned processes for producing a fiber composite can take place temporally and spatially next to one another or offset from one another. In addition, they can run continuously or in batch mode or in the form of intermediates of these methods.
  • the composite structures are each shown by scanning electron micrographs (SEM).
  • SEM scanning electron micrographs
  • Fig. 1a the fiber composite is shown, in which no structure-forming material, such as crystal structure-forming material, is included. Only the fibers are visible here. These form a loose, irregular network, with comparatively large pores in between. The strength of this network is based solely on the interactions of these fibers to each other and is therefore low.
  • Fig. 1b shows an enlarged view.
  • Fig. 2a shows a fiber composite with formed structures, such as crystal structures.
  • Fig. 2b shows an enlargement.
  • Fig. 2a and Fig. 2b show a fiber composite resulting from the use of a structure-forming material, here a rod and crystal structure-forming material in admixture with organic fibers, wherein the rod and crystal structures are formed before the fiber composite production.
  • the formation of the fiber composite together with the structure-forming material takes place first by adding a structure-forming material, such as e.g. a crystal structure forming material, selected and then mixed together with pulp in aqueous suspension, the structures such as e.g. Crystal structures, brought to training and finally the fiber composite is formed.
  • a structure-forming material such as e.g. a crystal structure forming material
  • a structure-forming material such as, for example, crystal structure-forming material, having a high degree of whiteness is selected, in this case a low-iron Ca-Al silicate.
  • a structure-forming material such as, for example, crystal structure-forming material, having a high degree of whiteness
  • a structure-forming material such as, for example, crystal structure-forming material, having a high degree of whiteness
  • a structure-forming material such as, for example, crystal structure-forming material, having a high degree of whiteness
  • d 50 laser diffraction
  • Quantachrome Quantachrome
  • a pulp is used as in Example 1 and this a structure-forming material, such as crystal structure-forming material (low iron Ca-Al-silicate), with a proportion> 0.1% by mass, preferably 1-50% by mass on the pulp, added and made an aqueous suspension.
  • this composite consisting of pulp and formed structures, here for example crystal structures, produced by filtration, this composite is then dried and examined the composite structure by scanning electron microscope (SEM).
  • the resulting fiber composite ( Fig. 2a and Fig. 2b ) shows both the fibers and the structures, here rod or crystal structures. These are intimately connected and form a felt.
  • the structures, here rod or crystal structures form networks and are connected to each other as well as to the pulp, so that the pores are also largely bridged.
  • the strength of such a paper is also based on interactions of the constituents contained. Due to the high degree of crosslinking, the interaction is also very high, combined with a significant increase in strength.
  • a pattern-forming material such as e.g. a crystal structure-forming material, are selected and then transferred separately from the pulp in an aqueous suspension and therein the structures, here rod or crystal structures are formed and only then combined with the pulp and finally formed the fiber composite.
  • a structure-forming material such as a crystal structure-forming material: Since a high degree of whiteness is required of the paper to be produced, a structuring, eg crystal structure-forming material is selected with a high degree of whiteness, in this case a low-iron Ca-Al-silicate ..
  • pulp is again used as unrefined hardwood pulp (Eucalyptus grandis) and a first suspension 1 is produced therefrom.
  • a first suspension 1 is produced therefrom.
  • a second suspension 2 is prepared and therein the structures, here rod and crystal structures, brought to training.
  • the two suspension mixed, so that structure-forming material, such as crystal structure-forming material, with a proportion of> 0.1% by mass, preferably 1-50% by mass based on pulp, is included.
  • the fiber composite consisting of pulp and formed structures, here rod or crystal structures, produced by filtration, then dried and examined the composite structure by scanning electron microscope (SEM).
  • the resulting fiber composite ( Fig. 3a and Fig. 3b ) shows both the fibers and the structures, here rod or crystal structures. These are intimately connected and form a felt.
  • the structures, here rod and crystal structures form networks and are connected with each other as well as with the pulp, so that the pores are also largely bridged.
  • the strength of such a paper is also based on interactions of the constituents contained. Due to the high degree of crosslinking, the interaction is very high, combined with a significant increase in strength.
  • Example 2 Compared with the REM images of the fiber composite Fig. 2a and Fig 2b , this shows a similar picture.
  • Example 2 two ways of producing the fiber composite could be demonstrated, the two having in common that the structures, here rod or crystal structures are formed to a large extent, before it comes to fiber composite formation, ie sheet formation.
  • the interaction and thus the paper strength in the composite is greater in both methods, compared with the method which is mentioned in Example 1.
  • Fig. 4a and Fig. 4b show a fiber composite produced by using a structure-forming material, such as a crystal structure-forming material, and the formation of this fiber composite, wherein the structures, here rod or crystal structures, are formed only after the fiber composite production.
  • a structure-forming material such as a crystal structure-forming material
  • a structure-forming material such as a crystal structure-forming material
  • this then mixed together with fiber in aqueous suspension and the fiber composite is formed.
  • Much of the structures, here chopsticks or crystal structures, is then brought to training and the fiber composite thereby further crosslinked.
  • a pulp is used as in Example 1 and this is a structure-forming material, such as. Crystal structure-forming material (low iron Ca-Al-silicate), with a proportion> 0.1 Ma-% preferably 1-50 Ma-% based on pulp added and an aqueous suspension prepared.
  • the fiber composite consisting of pulp and the structure-forming material, such as. the crystal structure-forming material in which the structures, here rod or crystal structures are largely not yet formed, produced by filtration.
  • the structures, here rod or crystal structures are formed in the composite. Thereafter, this composite is dried and the composite structure examined by scanning electron microscope (SEM).
  • the resulting fiber composite ( Fig. 4a and Fig. 4b ) shows both the fibers and the structures, here rod or crystal structures. These are intimately connected and form a felt.
  • the structures, here rod or crystal structures form networks and are connected with each other as well as with the pulp, so that the pores are also largely bridged.
  • the strength of such a manufactured paper is also based on interactions of the constituents contained. Due to the high degree of crosslinking, the interaction is also very high, combined with a significant increase in strength.
  • Fig. 5a shows Ca-Al-silicate as an example of a structure-forming eg crystal structure-forming material
  • Fig. 5b shows wollastonite as an example of a non-structuring but rod-shaped material. Therefore, wollastonite is not suitable for forming the three-dimensional composite structure under the selected conditions, even though the individual wollastonite particles are in the form of crystals having a regular crystal structure.
  • the fiber composite is produced by using a structure-forming material, such as a crystal structure-forming material, with increasing concentration and subsequent formation of this fiber composite.
  • the structures here are rod and crystal structures ( Fig. 5a ), are formed only after the fiber composite production - in contrast to a fiber composite, which is made with pulp and a non-structuring mineral but rod-shaped mineral (wollastonite) ( Fig. 5b ).
  • a structure-forming material such as e.g. a crystal structure-forming material, selected and this then mixed together with pulp in aqueous suspension and formed the fiber composite.
  • a structure-forming material such as e.g. a crystal structure-forming material
  • the selection of the structure-forming material such as. of the crystal structure-forming material. Since the paper to be produced requires a high degree of whiteness, a pattern-forming material, e.g. a crystal structure-forming material selected with a high degree of whiteness, in this case a low-iron Ca-Al silicate. A pretreatment of the low-iron Ca-Al silicate does not take place in this case.
  • a pulp is used as in Example 1 and this a structure-forming material, such as a crystal structure-forming material (low iron Ca-Al-silicate), was added and prepared an aqueous suspension.
  • a structure-forming material such as a crystal structure-forming material (low iron Ca-Al-silicate)
  • the fiber composite consisting of pulp and the structure-forming material, such as the crystal structure-forming material, but which has the structures (here rod or crystal structures) largely not yet formed, produced by filtration. Only then are the structures, here rod or crystal structures, formed in the composite. Thereafter, this composite is dried and the composite structure examined by scanning electron microscope (SEM).
  • the fiber composites produced using low-iron Ca-Al silicate and wollastonite also differ significantly.
  • the fiber composites based on low-iron Ca-Al silicate ( Fig. 6a . 7a, 8a .) Show both the fibers and the structures, here rod and crystal structures. These are intimately connected and form a felt.
  • the structures, here rod and crystal structures form networks and are connected with each other as well as with the pulp, so that the pores are also largely bridged.
  • the strength of such a paper is also based on interactions of the constituents contained. Due to the high degree of crosslinking, the interaction is also very high, combined with a significant increase in strength.
  • the fiber composites based on wollastonite ( Fig. 6b . 7b, 8b ) Only a loose, loose assembly of the respective components, without that they are recognizable connected.
  • Example 4 shows the difference in the use of a structure-forming material, such as a crystal structure-forming material, as compared to a non-structural but rod-shaped material.
  • a structure-forming material such as a crystal structure-forming material
  • the interactions in the composite and thus also the paper strength are much more pronounced in the first case.
  • a particular advantage of the structure formation (here rod and crystal structure formation) after fiber composite formation is that a part of the residual water contained by the structure formation (here rod and crystal structure formation reaction) is chemically bonded and does not have to be removed by drying, creating an additional benefit Energy saving is given.
  • a fiber composite is formed by the use of a structure-forming material, such as e.g. of a crystal structure-forming material, wherein the structure-forming material, such as e.g. Crystal structure-forming material, only subsequently applied to an already formed first fiber composite and the structures, here rod or crystal structures, are then formed.
  • a structure-forming material such as e.g. of a crystal structure-forming material
  • the structure-forming material such as e.g. Crystal structure-forming material
  • a structure-forming material such as a crystal structure-forming material is selected, and this is then applied in an aqueous suspension to a first fiber composite.
  • a structure-forming material such as a crystal structure-forming material is selected, and this is then applied in an aqueous suspension to a first fiber composite.
  • the majority of the structures, here rod and crystal structures, are only brought to the training after the order on the fiber composite and the fiber composite thus networked near the surface.
  • the selection of the structure-forming material such as the crystal structure-forming material. Since the paper to be produced requires a high degree of whiteness, a structure-forming material, such as a crystal structure-forming material, with a high degree of whiteness is selected, in this case a low-iron Ca-Al silicate.
  • Example 2 To form the first fiber composite, a pulp is used as in Example 1, and an aqueous suspension is produced therefrom. From this, the first fiber composite, consisting only of pulp produced by filtration. This first fiber composite can then be processed dry or wet. In this example, processing was continued in dry form.
  • an aqueous suspension of low-iron Ca-Al silicate is prepared and applied by means of a doctor blade on the first fiber composite.
  • the fiber composite is dried and the structure examined by scanning electron microscope (SEM).
  • SEM scanning electron microscope
  • the resulting fiber composite shows both the fibers and the structures, here rods and crystal structures. These are intimately connected and form a felt.
  • the Sticks form networks and are connected with each other as well as with the pulp, so that the pores are also largely bridged.
  • the strength of such a paper is also based on interactions of the constituents contained. Due to the high degree of crosslinking, the interaction is also very high, combined with a significant increase in strength.
  • the structure-forming e.g. Crystal structure-forming material applied to a fiber composite, wherein the structures, here rod or crystal structures, the fiber composite network near the surface.
  • the interaction in the formed fiber composite and thus also the paper strength increases in this case too.
  • a particular advantage in the subsequent coating of a fiber composite with a structure-forming material, such. a crystal structure-forming material is that a part of the contained residual water is chemically bound by the pattern-forming reaction, here, a sticking or crystal-forming reaction, and need not be removed by drying, thereby providing an additional benefit through energy saving.
  • the structure-forming material e.g. a crystal structure-forming material
  • the structure-forming material e.g. a crystal structure-forming material
  • the structure formation in this case rod and crystal structure formation, can then be continued by addition of a reactive component (for example water here).
  • Example 6 a paper prepared by using a pattern-forming material, such as e.g. a crystal structure forming material together with a filler and fibers.
  • a pattern-forming material such as e.g. a crystal structure forming material
  • the selection of the structure-forming material such as crystal structure-forming material. Since a high degree of whiteness is required of the paper to be produced, a structuring material such as a crystal structure-forming material having a high whiteness is selected, in this case a low-iron Ca-Al silicate.
  • other materials used in papermaking such as those mentioned by way of example at the various points of paper, paperboard or paperboard (fiber composite) production, such as fillers, dispersants, pigments or additives, which at different times during the process with the structure-forming materials, such as with crystal structure forming materials as well as with the fibers, can be combined.
  • the properties can be influenced, modified or optimized, for example, by physical and / or chemical and / or mechanical methods. For example, such property changes by addition of accelerator or retarder, Dispersants, surface coating, mixtures with organic and / or inorganic components and fillers, additives, fibers, thickeners or polymers, etc. can be achieved.
  • the properties of the materials used and thus of the fiber composite produced therefrom for example by dry milling, (for example by means of ball mills, jet mills, roller mills, pin mills, hammer mills, Attritiormühlen, rod mills, etc.), separation of fine and / or coarse fraction (for example, by screening and optionally Grobgut Vietnameselauf arrangement or electrostatic treatment and optionally magnetic separation, screening, etc.) or by wet comminution (for example by means of stirred ball mill, bead mill, ball mill or high pressure homogenizer, etc.) and optionally separated according to particle size and adapted according to the respective requirements.
  • dry milling for example by means of ball mills, jet mills, roller mills, pin mills, hammer mills, Attritiormühlen, rod mills, etc.
  • separation of fine and / or coarse fraction for example, by screening and optionally Grobgut Vietnameselauf arrangement and optionally magnetic separation, screening, etc.
  • wet comminution for example by means of stirred ball mill,
  • the structure-forming materials thus available can be used during the production process of a fiber composite during various process steps (eg fiber preparation, sheet formation, coating, finishing, spraying, coating) or as a separate process step and in different dosage forms (eg dry, wet, alone, with others) Be used.
  • the structures can be brought to the respective requirements (fast, slow) in different places (at the place of manufacture, the finishing or the place of processing) or afterwards by different methods at different times for training.
  • a variety of properties can be variably set or influence.
  • Possible material properties that can be influenced in the production of a fiber composite according to the invention are, for example, the strength, wet strength, elongation, optical properties, whiteness, brightness, yellowness, opacity, refraction, scattering, reflection, chromaticity, gloss, paper volume, pore size, number and distribution, vapor-tightness, water-tightness, gas-tightness, smoothness, wettability, absorbency, copiability, sealability, adhesion, non-sticky effect, flammability, corrosion-inhibiting effect, fungicidal, bactericidal, insecticidal action, resistance to aging, dust-free, high resistance to wet and alkali, good embossability, Coatability, coatability, printability, uniformity, calendering behavior, dimensional stability (eg flatness, plates, cockling, edge waviness), waviness and curl, ink
  • fiber composites according to the invention are suitable for a large number of uses.
  • An essential aspect of the invention is therefore the use of a fibrous composite as described above as a medium for information storage, packaging material, decorating means (e.g., wallpaper), sanitary articles, insulating material, gas, water or vapor barrier, flame retardant material, sound insulation material, material, insulation means or the like.
  • the fiber composite of the fiber composite is used in the form of paper as a medium for information storage.
  • structure-forming materials such as e.g. crystal structure-forming materials
  • structure-forming materials such as e.g. crystal structure-forming materials
  • the optical properties such as opacity, whiteness, brightness, yellowness value or physical properties, e.g. Air permeability or porosity, only marginally deteriorated, maintained or even improved.
  • the structure-forming materials e.g. crystal structure-forming materials
  • the processing properties of a fiber composite at e.g. Printing, cutting, folding, laminating, dyeing, bonding, etc. only marginally deteriorated, maintained or even improved.
  • the fiber composite eg paper or cardboard

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Paper (AREA)
EP10185955.1A 2009-10-01 2010-10-01 Fabrication d'un composite en fibre, son utilisation et composite en fibre Not-in-force EP2314765B1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0692456A1 (fr) * 1994-07-15 1996-01-17 Compania General Yesera, S.A. Procédé d'obtention d'une charge radiale, destinée en particulier à l'industrie papétière, charge obtenue formée de sulfate de calcium anhydre et hémihydrate et composition utile pour préparer cette charge
US6494991B1 (en) * 1998-07-17 2002-12-17 Boise Cascade Corporation Paper products comprising filler materials preflocculated using starch granules and/or polymerized mineral networks
DE102006029642B3 (de) 2006-06-28 2008-02-28 Voith Patent Gmbh Verfahren zum Beladen einer Faserstoffsuspension mit Füllstoff
EP2180095A1 (fr) * 2008-10-23 2010-04-28 Bene_fit Systems GmbH & Co. KG Procédé de fabrication pour matériaux fibreux organiques blanchis, utilisation d'un agent blanchissant pour matériaux fibreux organiques blanchis et matériaux fibreux blanchis

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0692456A1 (fr) * 1994-07-15 1996-01-17 Compania General Yesera, S.A. Procédé d'obtention d'une charge radiale, destinée en particulier à l'industrie papétière, charge obtenue formée de sulfate de calcium anhydre et hémihydrate et composition utile pour préparer cette charge
US6494991B1 (en) * 1998-07-17 2002-12-17 Boise Cascade Corporation Paper products comprising filler materials preflocculated using starch granules and/or polymerized mineral networks
DE102006029642B3 (de) 2006-06-28 2008-02-28 Voith Patent Gmbh Verfahren zum Beladen einer Faserstoffsuspension mit Füllstoff
EP2180095A1 (fr) * 2008-10-23 2010-04-28 Bene_fit Systems GmbH & Co. KG Procédé de fabrication pour matériaux fibreux organiques blanchis, utilisation d'un agent blanchissant pour matériaux fibreux organiques blanchis et matériaux fibreux blanchis

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
ERIKSSON M.: "The Influence of Molecular Adhesion on Paper strength", DISSERTATION KTH STOCKHOLM, 2006
LINGSTRÖM R.: "Formation and Properties of Polyelectrolyte Multilayers on Wood fibres: Influence on Paper Strength and fibre Wettability", DISSERTATION KTH STOCKHOLM, 2006

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