EP2314765B1 - Production of a fibre compound, use of same and fibre compound - Google Patents

Description

The invention relates to a method for producing a fiber composite according to claim 1.

Furthermore, the invention relates to a fiber composite according to claim 6.

Moreover, 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.

A fiber composite is to be understood in the following as any fiber composites, as preferred in the form of paper, cardboard, corrugated board or plates or in another form, for example as packaging material, decorative material (eg wallpaper), hygiene articles, insulating material, gas, water or steam barrier, flame retardant material, sound insulation material, material, insulation means can be used. An inventive fiber composite 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.

• Faserstoffe (Holzschliff, Halbzellstoffe, Zellstoffe, andere Fasern)
• Leimung und Imprägnierung (tierische Leime, Harze, Paraffine, Wachse)
• Füllstoffe (Kaolin, Talkum, Gips, Bariumsulfat, Calciumcarbonat, Titanweiß)
• Hilfsstoffe (Wasser, Farbstoffe, Entschäumer, Dispergiermittel, Retentionsmittel, Flockungsmittel, Netzmittel).

The starting materials necessary for the paper can be divided into four groups:

• Fibers (groundwood, semi-pulps, pulps, other fibers)
• Sizing and impregnation (animal glues, resins, paraffins, waxes)
• Fillers (kaolin, talc, gypsum, barium sulfate, calcium carbonate, titanium white)
• Auxiliaries (water, dyes, defoamers, dispersants, retention aids, flocculants, wetting agents).

• Primärfaserstoffe, nämlich Rohstoffe, die erstmals in der Produktion eingesetzt werden, und
• Sekundärfaserstoffe, nämlich Recyclingstoffe, die nach dem Gebrauch noch einmal dem Produktionsprozess zugeführt werden.

The fibers, in turn, can be divided into two groups:

• Primary fibers, namely raw materials used for the first time in production, and
• Secondary fiber materials, namely recycled materials, which are reused in the production process after use.

According to the state of the art, about 95% of 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.

In addition to the fibers, more than 30% of 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).

One of the materials traditionally often used in papermaking is kaolin, which is added both as fillers and as a coating pigment. Kaolin stays over chemically inert 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.

Ground calcium carbonate (GCC) with a proportion of 40-75% particles with a size of less than 2 μm is used predominantly as a filler. In addition to this application, GCC is also used as a paper coating pigment, especially in Europe. The most important CaCO ₃ -containing materials used for the production of GCC are sedimentary rocks (limestone or chalk) and the metamorphic marble rock.

Precipitated calcium carbonate (PCC) 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. In particular, PCC-containing papers have greater brightness, opacity and thickness than GCC-containing papers. However, PCC can not be used indefinitely as a filler because it reduces fiber strength.

By filling in the gaps between the fibers, 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 wegschlagenden 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.

As already described, 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 of papers produced in this way are also improved due to the higher filler content. The grammage could also be reduced without significantly affecting other parameters.

DE 10 2006 029 642 B3 describes for example a method for loading a pulp suspension with fillers, in particular calcium carbonate (PCC) wherein calcium hydroxide is introduced in liquid or dry form into the fiber suspension and the filler is precipitated by a chemical reaction in the pulp suspension. The PCC is rhombohedral, scalenohedral or spherical and the crystals have dimensions of 0.05-5 microns, especially 0.3-2.5 microns.

Furthermore, it is possible by multiple, alternating deposition of cationic and anionic polyelectrolytes on the charged surface of cellulosic fibers to coat them so that - without prior grinding - considerable paper strengths can be generated ( ERIKSSON M., The Influence of Molecular Adhesion on Paper Strength, Dissertation KTH Stockholm, Department of Fiber and Polymer Technology, Stockholm 2006 and LINGSTRÖM R., Formation and Properties of Polyelectrolytes Multilayers on Wood Fibers: Influence on Paper Strength and Fiber Wettability, Dissertation KTH Stockholm, Department of Fiber and Polymer Technology, Stockholm, 2006 ).

In addition, 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. GÖTZE, 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 prior art attempts by physical and / or mechanical and / or chemical modification of the fibers and / or the fillers or a combination of these methods z. In combination with other methods or materials, e.g. Fillers, a way to reduce the relative amount of fiber in the paper and to maintain the paper strength or to reduce the sheet weight and at the same time the paper properties such. to maintain the optical properties and processing characteristics.

These measures are intended to reduce the manufacturing costs with the same or better paper quality as possible with long-term assured production by raw materials that are also secured in the long term. The manufacturing processes should be as easy to adapt to new methods as possible. These goals are not satisfactorily solved in view of the described future requirements, the expected fiber shortage and the resulting increasing fiber costs in accordance with the prior art.

The aim of the invention is therefore to provide methods for producing a fiber composite such as paper, paperboard or cardboard, wherein the fiber composite comprises at least one additive and at least one organic pulp and this is added at least one additive which comprises Ca and / or Mg compounds and which changes its structure in the fiber composite and / or forms a structure and is present after the structural change and / or the structure formation as a three-dimensional composite for stabilizing the fiber composite. By such a method, the proportion of organic fibers in the Reduced production of a fiber composite while its strength is only slightly reduced, 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.

At the same time, other properties of the fiber composite, such as 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. Furthermore, 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.

If possible, 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. In particular, should be saved or reduced by the invention of energy in the drainage and drying. In addition, if possible, 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.

These objects are achieved by the subject-matter of independent claims 1 and 6 and dependent claim 13.

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 strengths of less than 0.5 mm, wherein at least one additive is added, which comprises Ca and / or Mg compounds and which in the fiber composite changes its structure and / or forms a structure and after the structural change and / or structure formation, a reticulated fibrous structure, which is formed by the fibrous material, to stabilize the fiber composite as a three-dimensional composite of Ca and / or Mg compounds interspersed.

In these added Ca and / or Mg compounds, the use of a large variety of compounds is possible, provided that they form a three-dimensional composite, or three-dimensional reticular structure in the fiber composite. In this context, 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. If this composite is formed of predominantly crystalline Ca and / or Mg compounds, this (over) structure is referred to in this context as a crystal structure. In connection with certain forms of individual crystals, e.g. rod-shaped, platelet-shaped, fibrous, star-shaped or tuft-shaped crystals, the term crystal structure is used for the homogeneous three-dimensional arrangement of individual atoms within a crystalline particle.

By means of the fibers of the pulp in the free spaces of the three-dimensional composite formed by the Ca and / or Mg compounds, a further reticulated (or skeletal) fiber braid is formed. As a result, 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. In particular, it is possible that 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 that they each form a significantly different framework or network structure with eg other geometry, mesh size, degree of crosslinking, size, bond strength or other physical properties. It is also possible that the smaller of the structure-forming substances interacts with pores, cracks, furrows, elevations, edges or other surface peculiarities of the larger of the 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 selectively, so as not to excessively adversely affect the material properties of the fibers of the pulp and, for example, the bonding of the fibers with one another. Preferably, 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%.

In the process for producing a fiber composite, 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% by mass 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 with Energiezu- or -Discharge, converted to the three-dimensional composite of Ca and / or Mg compounds. The Ca and / or Mg compounds may be, for example, cement or gypsum precursors such as CaSO ₄ ("anhydrite") or CaSO ₄ .½H ₂ O ("bassanite", also "hemihydrate" or "hemihydrate"), but as described above also any other Ca and / or Mg compound, which forms net-like, 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.

• entweder getrennt von anderen oder zusammen mit anderen Materialien (z.B. organischen oder anorganischen Fasern, Additiven oder Füllstoffen) gemischt wird, danach die Strukturen, wie z.B. die Kristallstrukturen, zur Ausbildung gebracht werden und anschließend der Faserverbund, z.B. aus einer Mischung der separat hergestellten Strukturen, wie z.B. Kristallstrukturen, und anderer Komponenten (Fasern, Additiven oder Füllstoffen) gebildet wird, und/oder
• getrennt von anderen oder zusammen mit anderen Materialien (z.B. organischen oder anorganischen Fasern, Additiven oder Füllstoffen) gemischt wird, danach der Faserverbund z. B. aus einer Mischung der getrennt hergestellten Komponente und anderer Komponenten (Fasern, Additiven oder Füllstoffen) gebildet wird und die Strukturen, wie z.B. die Kristallstrukturen, erst dann zur Ausbildung gebracht werden, und/oder
• alleine oder zusammen mit anderen auf einen ersten Faserverbund aufgetragen wird und die Strukturen, wie z.B. die Kristallstrukturen, auf diesem oberflächennah zur Ausbildung gebracht werden, wobei der erste Faserverbund wie z. B. Papier, Pappe, Karton oder ein anderer Faserverbund oder ein Faserverbund wie unter a) oder b) beschrieben sein kann

wobei jeweils der resultierende Faserverbund Papier, Pappe oder Karton oder vergleichbare Materialien und Folgeprodukte dieser, z. B. in Kombination mit anderen Materialien, sein kann.The production and use of a fiber composite can be carried out by using the mentioned structure-forming Ca and / or Mg compounds in addition to the fibrous materials. These are also referred to as structure-forming materials or as crystal structure-forming materials, to illustrate that they form three-dimensionally networked structures in which individual crystals or crystal composites of these compounds and / or resulting products resulting from these compounds form a three-dimensional composite. According to the invention, this is done by a structure-forming in a first step Material, such as a crystal structure-forming material, selected and this is optionally further refined and then the structure-forming material:

• either separately from other or together with other materials (eg organic or inorganic fibers, additives or fillers) is mixed, then the structures, such as the crystal structures are brought to training and then the fiber composite, for example from a mixture of separately prepared structures, such as crystal structures, and other components (fibers, additives or fillers) is formed, and / or
• separated from others or together with other materials (eg organic or inorganic fibers, additives or fillers) is mixed, then the fiber composite z. B. from a mixture of separately prepared component and other components (fibers, additives or fillers) is formed and the structures, such as the crystal structures, only then brought to training, and / or
• applied alone or together with others on a first fiber composite and the structures, such as the crystal structures, are brought to this close to the surface for training, wherein the first fiber composite such. As paper, cardboard, cardboard or another fiber composite or a fiber composite as under a) or b) may be described

wherein in each case the resulting fiber composite paper, cardboard or cardboard or comparable materials and derivatives thereof, z. B. in combination with other materials may be.

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. Optionally, an energy supply or removal may be necessary. For example, 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. Likewise, 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.

Among the suitable structure-forming materials, rod-forming, star-forming, tuft-forming or similar structures-forming materials or blends of these with each other or with other materials are preferred.

The selection of 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. An overview of suitable structure-forming materials, from a chemical-mineralogical point of view, is shown in Table 1: Table 1 Structure-forming material, such as crystal structure-forming material example Structure formation eg crystal structure formation Gypsum, or dewatered or partially dewatered gypsum precursors CaSO ₄ .5H ₂ O, CaSO ₄ By reaction with water with or other additives in 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 (3 CaO x SiO ₂ ) By reaction with water with or without sulfate or other additives under certain conditions Dicalcium silicate, C2S (2 CaO x SiO ₂ ) Tricalcium aluminate, C3A (3 CaO x Al ₂ O ₃ ) Tetracalcium aluminate ferrite C4AF (4 CaO x Al ₂ O ₃ x Fe ₂ O ₃ ) Ca and / or Al silicates with Tricalcium silicate, C3S By reaction with water a low Fe ₂ O ₃ content <5% by mass, preferably <3% by mass, most preferably <1% by mass (3 CaO x SiO ₂ ), with or without sulphate or other additives under certain conditions Dicalcium silicate, C2S (2 CaO x SiO ₂ ) Tricalcium aluminate, C3A (3 CaO x Al ₂ O ₃ ) Tetracalcium aluminate ferrite, C4AF (4 CaO x Al ₂ O ₃ x Fe ₂ O ₃ ). Precipitated calcium aluminates Ca ₃ Al ₂ (OH) ₁₂ = tricalcium aluminate hydrate or [3CaO * Al ₂ O ₃ * 6H 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] Precipitated calcium aluminates having a low Fe ₂ O ₃ content <5% by mass, preferably <3% by mass, most preferably <1% by mass Ca ₃ Al ₂ (OH) ₁₂ = tricalcium aluminate hydrate or [3CaO * Al ₂ O ₃ * 6H 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] Burnt calcium aluminates CaO * Al ₂ O ₃ , [CA] By reaction with water with or without sulfate or other additives under certain conditions 3CaO * Al ₂ O _3, [C3A] CaO * 2Al ₂ O ₃ , [CA 2] 12CaO * 7Al ₂ O ₃ , [C12A7] Calcined calcium aluminates having a Fe ₂ O ₃ content <5% by mass, preferably <3% by mass, most preferably <1% by mass CaO * Al ₂ O ₃ , [CA] By reaction with water with or without sulfate or other additives under certain conditions 3CaO * Al ₂ O ₃ , [C3A] CaO * 2Al ₂ O ₃ , [CA 2] 12CaO * 7Al ₂ O ₃ , [C12A7] calcium sulfoaluminate C4A3S By reaction with water with or without sulfate or other additives under certain conditions Calciumsulfoaluminat with a Fe ₂ O ₃ content <5% by mass, preferably <3% by mass, most preferably <1% by mass C4A3S By reaction with water with or without sulfate or other additives under certain conditions Katoite having an Fe ₂ O ₃ content of <5% by mass, preferably <3% by mass, most preferably <1% by mass Tricalcium aluminate hydrate With or without sulfate or other additives in water under certain conditions

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: Table 2 parameter unit Area prefers Mostly preferred Purity****) ma% 1-100 5-100 10-100 Heavy metals ***) ma% <1 <0.5 <0.1 Moisture when used as a powder ma% <10 <7.5 <5 Moisture when used as a slurry ma% <99 <95 <90 BET m ² / g 0.001 to 1000 0.01-500 0.01-100 refractive index 1.0-3.0 1.2-2.9 1.4 to 2.7 Whiteness R457, according to ISO 2470 % 1-100 5-100 10-100 Particle size *) microns 0.001 to 1000 0.001-500 0.001 to 250 Particle size **) microns 0.001 to 1000 0.001-500 0.001 to 250 Abrasion, after Einlehner mg <5000 <4000 <3000 Spec. Weight g / cm ³ <8 <7 <6 grain distribution Uni- to multimodal Uni- to multimodal Uni- to multimodal particle structure irregular irregular irregular *) measured as d ₅₀ (volume) by sedimentation, eg Sedigraph
**) measured as d ₅₀ (volume) by laser diffraction, eg cilas
***) Sum of: Cu, Pb, Hg, Zn, Ni, Cd, Cr
****) purity as a single substance or as a mixture of substances

Chemically similar synthetic or natural compounds, which also form three-dimensional crosslinked structures or composites with comparable properties, but are not explicitly mentioned in Table 1, are also part of the invention. Likewise, mixtures of the structure-forming compounds with one another or with other materials in any mixing ratio are the subject of the invention.

• Trockenmahlung und/oder z.B. Sichtung, Magnetscheidung, Beschichtung, Homogenisierung oder Aktivierung mittels aller dafür geeigneter Aggregate oder z.B.
• Nassmahlung und/oder z. B. Feinstofftrennung mittels Zyklon oder Zentrifuge und/oder Kreislaufführung, Magnetscheidung, chemischer oder physikalischer Bleiche, optional mit Additivierung, Homogenisierung, Beschichtung oder Abtrennung von Bestandteilen mittels aller dafür geeigneten Aggregate.

The structure-forming materials, such as, for example, the crystal structure-forming materials, may additionally be additionally treated chemically and / or physically and / or mechanically or by combinations of these processes prior to use. These methods can be, for example:

• Dry grinding and / or eg screening, magnetic separation, coating, homogenization or activation by means of all suitable aggregates or eg
• Wet grinding and / or z. B. fines separation by means of cyclone or centrifuge and / or recycling, magnetic separation, chemical or physical bleaching, optionally with additives, homogenization, coating or separation of components by means of all suitable aggregates.

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. Weight g / cm ³ <8 <7 <6 Structure diameter ****) microns .001-10000 0.001 to 7500 0.001 to 5000 Structure length ****) microns 0.01-10000 0.01 to 7500 0.02-5000 Aspect ratio ***) 1-10000 2-7500 2-5000 crystal structure rod, platelet, fibrous, star, tufted or otherwise shaped rod, platelet, fibrous, star, tufted or otherwise shaped rod, platelet, fibrous, star, tufted or otherwise shaped Structure shape and location Crystal structures to other particles / fibers Each, eg single, twin, bundle, star, tuft, with and without embedded and attached particles / fibers Each, eg single, twin, bundle, star, tuft, with and without embedded and attached particles / fibers Each, eg single, twin, bundle, star, tufts, with and without in and feeder particles / fibers Description Composite material Network of structures with eg other anorg. and / or org. Fibers or fillers / pigments Network of structures with eg other anorg. and / or org. Fibers or fillers / pigments Network of structures with eg other anorg. and / or org. Fibers or fillers / pigments *) measured as d ₅₀ (volume) by sedimentation, eg Sedigraph
**) measured as d ₅₀ (volume) by laser diffraction, eg cilas
***) Particle length / particle diameter, area
****) Scanning electron microscope, SEM

In a preferred variant of the method for producing a fiber composite, after the formation of the three-dimensional composite of the Ca and / or Mg compounds, 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.

In a preferred variant of the method for producing a fiber composite, therefore, 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.

Preferably, depending on the properties required by the fiber composite, e.g. Whiteness and price or strength selected a suitable structure-forming material and used for the production of fiber composite. The requirements placed on a fiber composite (e.g., paper, paperboard, cardboard) 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.

• Beispielsweise kann das strukturbildende Material, bzw. die Ca- und/oder Mg-Verbindung, in geeigneter Form (z. B. nach Aufbereitung, wie oben ausgeführt) in einem ersten Schritt zur Ausbildung der Strukturen, wie z.B. der Kristallstruktur, gebracht werden (z.B. auch vermischt mit anderen Materialien) und in einem zweiten Schritt auf einen bereits bestehenden ersten Faserverbund gebracht werden, um diesen dann oberflächennah z.B. zu verfestigen. Dies kann auch mehrmals erfolgen, wobei Geräte und Bedingungen hierzu dem Fachmann aus dem Stand der Technik bekannt sind (z.B. Bladeauftrag, Curtaincoating, Filmpresse, Leimpresse usw.). Auch jegliche Vorbehandlung des unbeschichteten Faserverbundes oder auch eine Nachbehandlung des Faserverbundes mit bekannten geeigneten technischen Verfahren ist möglich.

After selecting the suitable structure-forming material, the production of the fiber composite takes place. There are several ways to do this:

• For example, 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. This can also be done several times, with equipment and conditions for this purpose to those skilled in the art known (eg Bladauftrag, 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.

Furthermore, 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. In a variant thereof, 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 for which may be varied and known to those skilled in the art (e.g., blading, curtain coating, film press, size press, etc.). Also, 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.

In a preferred variant of the method for producing a fiber composite, 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.

• Einerseits besteht die Möglichkeit, die Strukturen alleine zur Ausbildung zu bringen, danach mit anderen Fasern zu mischen und erst in einem folgenden Prozessschritt den Faserverbund auszubilden.

As an alternative to coating an existing first fiber composite, structures such as crystal structures can also be formed directly in the fiber composite. There are several ways to do this:

• On the one hand, it is possible to bring the structures alone to training, then mix with other fibers and only in a subsequent process step to form the fiber composite.

In a further variant, 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). Furthermore, 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).

Furthermore, it is possible to add the structure-forming material before, during, or after patterning, e.g. crystal structure formation, be mixed with the fibers and / or other materials. As already described above, the fiber may also be mixed with other materials and / or fibers before, during or after the mixing with the structure-forming material.

In a further variant, it is possible to use 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.

As a result, novel design-technical applications are possible by exposed in a variant, 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.

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.

Furthermore, it is also possible to convert 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.

In a preferred variant of the process for the preparation, therefore, 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. At the same time, 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 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 sulphates, Hydroxides, silicates, aluminates, ferrites and / or mixtures of these, in particular cements, gypsum and / or precursors thereof and by reaction with water, gases, in particular CO ₂ or oxygen, carbonate ions, sulfate ions, other additives and / or combinations thereof or by elimination of water or gases such as CO ₂ , O ₂ or others, optionally with energy supply or removal, is a three-dimensional composite of Ca and / or Mg compounds in the fiber composite or can be formed.

Preferably, in a fiber composite, 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.

In addition to the structure-forming Ca and / or Mg compound, 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.

In a preferred embodiment of the fiber composite, after the change and / or formation of the three-dimensional composite, the Ca and / or Mg compound has a refractive index n _D of 1 to 3, preferably 1.2 to 2.9, particularly preferably 1, 4 - 2,7 on. Due to the large difference in the refractive index in the particularly preferred range of n _D = 1.4 to 2.7 to the refractive index of the air (n _D ≈ 1), these substances have particularly good optical properties, such as high opacity, high whiteness, etc.

Since particularly white paper is required in large quantities in particular in applications of fiber composites as paper, in a further preferred embodiment of the fiber composite, 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, particularly preferably from 10 to 100. In order to further increase the whiteness of the fiber composite, it is possible to further add additives that positively affect the whiteness. These are known in the art and may be, for example, TiO ₂ , kaolin, CaCO ₃ , etc.

In a preferred embodiment of the fiber composite, 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. In addition, however, 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.

It is also possible, 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. For the respective processes, all suitable technical processes and materials known to the person skilled in the art can be used.

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.

According to the invention, 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 production of a laminar fiber composite according to the invention will be described below by way of concrete examples, here paper, of course without excluding other applications.

The composite structures are each shown by scanning electron micrographs (SEM). To form the fiber composite in the following examples unground hardwood pulp (Eucalyptus grandis) is used as pulp. From an aqueous suspension of this pulp and optionally further additives, a fiber composite (paper) is produced by filtration, this then dried and examined the composite structure by scanning electron microscope.

Fig. 1a und 1b

eine rasterelektronische Aufnahme eines Faserverbunds ohne Zusatz von strukturbildenden Materialien;

Fig. 2a und 2b

eine rasterelektronische Aufnahme eines Faserverbunds mit ausgebildeten netzartigen Strukturen, hier eines u.a. stäbchen- und nadelförmige Kristallstrukturen ausbildenden Materials, wobei die Stäbchen- und Kristallstrukturen bereits vor der Faserverbundherstellung ausgebildet worden sind;

Fig. 3a und 3b

eine weitere rasterelektronische Aufnahme eines Faserverbunds mit ausgebildeten netzartigen Strukturen, hier eines u.a. Stäbchen- und nadelförmige Kristallstrukturen ausbildenden Materials, wobei die Stäbchen- und Kristallstrukturen einen besonders engmaschigen, filzartigen Faserverbund ausbilden;

Fig. 4a und 4b

eine rasterelektronische Aufnahme eines Faserverbunds mit ausgebildeten netzartigen Strukturen, wobei Strukturen nach der Herstellung des Verbundes der organischen Fasern ausgebildet worden sind und wiederum einen filzartigen Faserverbund ausbilden;

Fig. 5a

eine rasterelektronische Aufnahme von Ca-Al-Silikat als Beispiel für ein strukturbildendes Material;

Fig. 5b

eine rasterelektronische Aufnahme von Wollastonit als weiteres Beispiel für ein Material, welches keine dreidimensionale Verbundstruktur ausbildet;

Fig. 6a, 7a und 8a

eine rasterelektronische Aufnahme eines Faserverbunds mit ausgebildeten netzartigen Strukturen unter Verwendung von Ca-Al-Silikat als Strukturbildendes Material;

Fig. 6b, 7b und 8b

eine rasterelektronische Aufnahme eines Faserverbunds ohne ausgebildeten netzartigen Strukturen der den organischen Fasern zugesetzten Ca- und/oder Mg-Verbindung Wollastonit (Ca₃[Si₃O₉]) und

Fig. 9a und 9b

eine rasterelektronische Aufnahme eines Faserverbunds mit ausgebildeten netzartigen Strukturen, wobei das Strukturbildende Ca-Al-Silikat nach Ausbildung eines ersten Faserverbundes aus organischen Fasern mittels Rakel auf diesen aufgetragen wurde und anschließend zur Ausbildung der dreidimensional vernetzen Struktur gebracht wurde.

Show:

Fig. 1a and 1b

a grid-electronic recording of a fiber composite without the addition of structure-forming materials;

Fig. 2a and 2b

a grid-electronic recording of a fiber composite with trained net-like structures, here a rod-like and needle-shaped crystal structures forming material, the rod and crystal structures have been formed before the fiber composite production;

Fig. 3a and 3b

a further grid-electronic recording of a fiber composite with formed net-like structures, here a rod-like and needle-shaped crystal structures forming material, wherein the rod and crystal structures form a particularly close-meshed, felt-like fiber composite;

Fig. 4a and 4b

a grid-electronic recording of a fiber composite with formed net-like structures, wherein structures have been formed after the production of the composite of organic fibers and in turn form a felt-like fiber composite;

Fig. 5a

a scanning electron micrograph of Ca-Al silicate as an example of a structure-forming material;

Fig. 5b

a scanning electronic image of wollastonite as another example of a material which does not form a three-dimensional composite structure;

Fig. 6a, 7a and 8a

a scanning electron micrograph of a fiber composite with formed net-like structures using Ca-Al-silicate as structure-forming material;

Fig. 6b, 7b and 8b

a grid-electronic recording of a fiber composite without trained net-like structures of the organic fibers added Ca and / or Mg compound wollastonite (Ca ₃ [Si ₃ O ₉ ]) and

Fig. 9a and 9b

a grid-electronic recording of a fiber composite with formed net-like structures, wherein the structure-forming Ca-Al-silicate was applied to form a first fiber composite of organic fibers by means of a doctor blade on this and then brought to form the three-dimensionally networked structure.

These figures and some exemplary and non-limiting examples of the formation of a fiber composite according to the invention are described in more detail below:

Example 1:

Production of a fiber composite without the addition of structure-forming materials, such as, for example, crystal structure-forming materials (US Pat. Fig. 1a and 1b ).

In 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.

Example 2:

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, e.g. Crystal structure-forming material, in this example a low-iron Ca-Al silicate with a certain fineness, 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.

Since a high degree of whiteness is required of the paper to be produced, 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. In the case of using cardboard would z. As well as low-iron Ca-Al silicate with lower whiteness suitable. A pretreatment of the low-iron Ca-Al silicate in this case takes place in that the fineness (measured as d ₅₀ , laser diffraction ("Cilas", Quantachrome, in volume / passage) by dry grinding (eg with a ball mill) starting from d ₅₀ = 20 μm is reduced by 50%.

To form the fiber composite 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. From this, the fiber 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.

Alternatively, 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.

For this purpose, the selection of 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 .. A Pretreatment of the low-iron Ca-Al silicate in this case takes place in such a way that the fineness (measured as d ₅₀ , laser diffraction ("Cilas", Quantachrome, in volume / passage) by dry grinding (eg with a ball mill) from d ₅₀ = 20 μm is reduced by 50%.

To form the fiber composite, pulp is again used as unrefined hardwood pulp (Eucalyptus grandis) and a first suspension 1 is produced therefrom. From the structure-forming material, such as crystal structure-forming material (low-iron Ca-Al silicate), a second suspension 2 is prepared and therein the structures, here rod and crystal structures, brought to training. After that, 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.

From this mixture of the two suspensions, finally, 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.

Compared with the REM images of the fiber composite Fig. 2a and Fig 2b , this shows a similar picture. Thus, in 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.

Example 3:

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.

This is done by selecting a structure-forming material, such as a crystal structure-forming material, and 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.

For this purpose, in the first step, 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. Pretreatment of the low-iron Ca-Al silicate in this case takes place in that the fineness (measured as d ₅₀ , laser diffraction ("Cilas", Quantachrome, in volume / passage) by dry grinding (eg with a ball mill) by 50 % is reduced starting from d ₅₀ = 20 μm.

To form the fiber composite, 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. From this, 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. Subsequently, 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).

Also, 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.

Thus, a further way of producing a fiber composite is shown, wherein in this fiber composite, the majority of the structures, here rod or crystal structures, only then forms when the fiber composite, so the sheet formation has already happened. The Interactions in the composite and thus also paper strength increases in this case too. A particular advantage in the structure formation, here rod or crystal structure formation, after the fiber composite formation is that a part of the residual water contained by the structure formation reaction, here the rod or crystal structure formation reaction, chemically bonded and must not be removed by drying, which gives an additional benefit through energy saving.

Example 4:

Fig. 5a shows Ca-Al-silicate as an example of a structure-forming eg crystal structure-forming material and 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 ).

In this example, 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. Most of the structures, here rod and crystal structures are only then brought to training and the fiber composite thus further crosslinked.

For this purpose, in the first step, 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.

To form the fiber composite, 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. Out of this will 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).

In the same way, a fiber composite of pulp and a non-structure, but a rod-shaped material is produced, wherein the ratio of pulp and rod-shaped material is the same. After drying, this fiber composite is also examined by means of SEM.

Wollastonite (d ₅₀ = 10 μm, ("Cilas", Quantachrome, in volume / passage) is used here as nonstructural, but rod-shaped material.) Wollastonite has the property that it is already present as a rod-shaped material Advantage of structure formation, here rod or crystal structure formation compared to the use of a non-structure, but it rod-shaped material show.

• Einwiegen von Faserstoff und eisenarmes Ca-Al-Silikat (bzw. Wollastonit)
• Dispergieren der Komponenten in 50 ml Wasser
• Verdünnen der Suspension auf 1 Liter mit Wasser
• Entwässern der Suspensionen über einem Sieb
• Lagerung der feuchten Blätter unter Luftabschluss
• Trocknung der Blätter, nachdem die Ausbildung der Strukturen, hier Stäbchen- und Kristallstrukturen vollzogen ist. Wollastonit wurde analog dazu behandelt.

The following procedures were used in the experiments:

• Weighing fiber and low-iron Ca-Al silicate (or wollastonite)
• Disperse the components in 50 ml of water
• Dilute the suspension to 1 liter with water
• Dewatering the suspensions over a sieve
• Storage of moist leaves under exclusion of air
• Drying of the leaves, after the formation of structures, here rod and crystal structures completed. Wollastonite was treated analogously.

In the experiments, a material composition was selected according to Table 4: Table 4 unit 10 % 25% 50% original water ml 50 50 50 cellulose G 3.6 3.0 2.0 low iron Ca-Al silicate G 0.4 1.0 2.0 Mineral fiber (wollastonite) G 0.4 1.0 2.0 dilution water ml 950 950 950

The morphological differences between the two feedstocks low-iron Ca-Al silicate ( Fig. 5a ) and wollastonite ( Fig. 5b ) can be clearly recognized in the SEM images.

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. In contrast, 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. 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.

Example 5:

In Example 5, 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.

This is done by using 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.

For this purpose, in the first step, 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. A pretreatment of the low-iron Ca-Al silicate takes place in In this case, the fineness (measured as d ₅₀ , laser diffraction, ("Cilas", Quantachrome, in volume / passage) is reduced by 50% by dry milling (eg with a ball mill) starting from d ₅₀ = 20 μm ,

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.

In parallel, 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 majority of the structures, here rod and crystal structures, form on the surface of the first fiber composite and crosslink it. Thereafter, the fiber composite is dried and the structure examined by scanning electron microscope (SEM). Also, the resulting fiber composite ( Fig. 9a and Fig. 9b ) shows both the fibers and the structures, here rod 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.

In the production according to the invention of a fiber composite according to Example 5, 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.

In an alternative method according to the invention, it is also possible, after being combined with the structure-forming material, e.g. a crystal structure-forming material, has been coated to dry, so as to withdraw a structural component necessary for the reactive component and so disrupt the structure formation, here a rod or crystal structure formation. In a further step, spatially and spatially separated from this, 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

In 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.

For this purpose, in the first step, 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. A pretreatment of the low-iron Ca-Al silicate in this case takes place in such a way that the fineness (Measured as d ₅₀ , laser diffraction ("Cilas", Quantachrome, in volume / passage) is reduced by dry milling (eg with a ball mill) by 75% starting from d ₅₀ = 20 μm.

To form the fiber composite, 300 ml of pulp suspension (2% by mass, ground pulp) are mixed with 110 ml of TiO ₂ suspension (4% by mass, filler), and made up to 1000 ml with drinking water. Then wet strength agent and structure-forming material, here crystal structure-forming material according to the table is added and the mixture is homogenized. For the sheet formation, in each case 300 ml of this suspension are used and the sheet formed at 90 ° C for 10 min dried (= paper). For lamination, this sheet is then dipped in melamine resin for 30 seconds, completely wetted, excess resin is removed and then dried at 100 ° C. for 30 seconds. Thereafter, the paper is again completely wetted by immersion in resin, excess resin is removed and finally the paper is dried at 100 ° C. for 120 seconds. Finally, the thus impregnated paper is pressed at 100 bar, 160 ° C., 120 seconds, followed by cooling by means of cooling plates (= laminate). Table 5 No. TiO ₂ WZ * WZ * sheet weight ash TI *** paper laminate g / batch % TiO ₂ ** g / batch G % N **** **** 1 4.4 0 0 2.9 35.0 31.0 0 nb 2 4.4 5 0.22 3.2 37.6 40.0 + 0 3 4.4 15 0.66 3.5 38.8 32.2 - nb 4 4.4 5 0.22 3.3 37.3 38.0 + + 5 4.4 15 0.66 3.5 38.7 31.5 - nb 6 4.4 0 0 2.9 35.0 30.0 0 0 7 4.4 5 0.22 3.1 37.1 39.0 + + 8th 4.4 15 0.66 3.2 39.3 33.0 - nb *: WZ = short name for structure-forming material, here crystal-structure-forming material
**: share of weight in relation to mass of total filler, rounded
***: Tensile index
****: Visual evaluation of optical properties: + = better; - = poor evaluation criteria Paper: Whiteness, Formation, Uniformity Evaluation criteria Laminate: Opacity, whiteness, uniformity
nb: not determined

From the results, it is clear that the ash content increases as a measure of the degree of filling, at the same time the strength increases, in part, significantly. Both the paper and laminate properties can be kept constant or even improved. It is thus - as shown in the examples given - possible to meet by the inventive method and the fiber composite according to the invention the above-mentioned objects and requirements in terms of function and effect of a new fiber composite.

According to the invention, 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.

Below is a selection of the advantages of fiber composites of the invention made using structure-forming, e.g. crystal structure-forming materials, according to the present invention shown.

Due to the multitude of choices in the properties of structure-forming materials, a great variety is offered, whereby the properties can be adapted to later application. Possible properties that can be used as a selection criterion are, for. The nature of the structure-forming material, grain size, topcut, grain size distribution, morphology, chemical composition, mineralogical composition, purity, abrasion, solubility, dispersibility, binder requirement, rheology, optical properties such as whiteness and yellowness, opacity, Blaine value, reactivity, crystal structure, specific Surface, surface charge, density, bulk density, aspect ratio, structure of structures to be formed, etc.

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. Furthermore, 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 Grobgutkreislaufführung 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.

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.

In a fiber composite with the structure-forming materials described 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 receptivity, ink adsorption capacity, thermal stability, heat conduction, abrasion resistance, splittability, Lightfastness, wipe resistance, low tendency to curl, glossy printing, ink-repellent behavior, pick resistance, binder requirement, Fiber coverage, immobilization, breaking strength, elongation at break, fold strength, flexural strength, roughness and others.

Therefore, 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.

In a preferred use of the fiber composite of the fiber composite is used in the form of paper as a medium for information storage.

By the use according to the invention of structure-forming materials, such as e.g. crystal structure-forming materials, to produce a fiber composite is achieved that in particular the proportion of organic fibers and thus the cost of producing a fiber composite, such. Paper or cardboard reduced while the strength is only marginally reduced, maintained or even increased.

Furthermore, through the use of structuring materials, e.g. crystal structure-forming materials, for the production of a fiber composite at the same time other properties of the fiber composite (for example, paper or cardboard), such. 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.

Advantageously, by using the structure-forming materials, e.g. crystal structure-forming materials, for the production of a fiber composite at the same time the processing properties of a fiber composite (e.g., paper or cardboard) at e.g. Printing, cutting, folding, laminating, dyeing, bonding, etc. only marginally deteriorated, maintained or even improved.

In addition, by the inventive use of the structure-forming materials, such as the crystal structure-forming materials, for producing a fiber composite at the same time the production of the fiber composite (eg paper or cardboard) only insignificant impaired, maintained or even improved, eg by sheet formation, by dewatering and drying or paper finishing. In particular, it is additionally possible to reduce the energy costs during the drying of a fiber composite.

Due to the particularly high strength of the fiber composites, it is even possible to produce objects that have particular stability requirements from such fiber composites. In a variant of the use of fiber composite this is used as furniture.

By the use of structure-forming materials in the manufacture of a fiber composite, such. As paper or cardboard, some production processes can be optimized in terms of modern environmental requirements. Thus, in the production of a fiber composite as described above, it is possible to only slightly increase, maintain or even reduce the amount of waste air and waste water. Also, the CO ₂ emissions can only negligibly degraded, are maintained or even improved.

All disclosed in the application documents features are claimed as essential to the invention, provided they are new individually or in combination over the prior art.

Claims (14)

1. Method for producing a fibre compound that comprises at least one additive and at least one organic fibrous material, the fibrous material being selected from a group comprising mechanical wood pulp, semi-chemical pulp, chemical pulp, wool, silk, linen, cotton, synthetic polymer fibres and/or other fibrous materials having fibre thicknesses of less than 0.5 mm, at least one additive being added that comprises Ca and/or Mg compounds as a sulfate, hydroxide, silicate, aluminate, ferrite and/or mixtures thereof,
   characterised in that
   the Ca and/or Mg compounds are used in an amount of from 1 to 50 wt.%, and said compounds are transformed into the three-dimensional compound of the Ca and/or Mg compounds by a reaction with water, CO2, carbonate ions, sulfate ions, oxygen, further additives and/or combinations thereof or by separating water or gases, such as CO2, O2 or others, optionally while supplying or discharging energy, and the structure of said compounds changes in the fibre compound and/or said compounds form a structure in the fibre compound, and after the structural change and/or the structure formation, individual crystals or particles are interconnected and/or physically interact so as to achieve a cross-linked fibrous material structure, formed by the fibrous material, in order to stabilise the fibre compound as a three-dimensional compound of the Ca and/or Mg compounds, the three-dimensional compound of the Ca and/or Mg compounds being formed after the organic fibrous materials have been cross-linked.
2. Method for producing a fibre compound according to claim 1,
   characterised in that
   the Ca and/or Mg compound is used in an amount of from 2 to 40 wt.%.
3. Method for producing a fibre compound according to any of the preceding claims,
   characterised in that
   a Ca and/or Mg compound is used which, after the structural change and/or the structure formation in the fibre compound, has a refractive index nD of from 1 to 3, preferably from 1.2 to 2.9, particularly preferably from 1.4 to 2.7, and a brightness R457 according to ISO 2470 of from 1 to 100, preferably from 5 to 100, particularly preferably from 10 to 100.
4. Method for producing a fibre compound according to any of the preceding claims,
   characterised in that,
   after the three-dimensional compound of the Ca and/or Mg compounds has been formed, the Ca and/or Mg compound is the form of connected, Ca-containing and/or Mg-containing particles that have a particle size, measured as d50 (volume), of between 0.001 and 10,000 µm, preferably between 0.01 and 7,500 µm, particularly preferably between 0.05 and 5,000 µm.
5. Method for producing a fibre compound according to any of the preceding claims,
   characterised in that
   the structural change and/or the structure formation of the Ca and/or Mg compounds is interrupted by a change in ambient conditions before the three-dimensional compound has been completely formed, and at a later time once the fibre compound has been made into a predetermined shape, the structural change and/or the structure formation can be continued until the three-dimensional compound has been completely formed by another change in the ambient conditions.
6. Fibre compound that comprises at least one additive and at least one organic fibrous material, the fibrous material being selected from a group comprising mechanical wood pulp, semi-chemical pulp, chemical pulp, wool, silk, linen, cotton, synthetic polymer fibres and/or fibrous materials having fibre thicknesses of less than 0.5 mm, at least one of the additives comprising a Ca and/or Mg compound as a sulfate, hydroxide, aluminate, ferrite and/or mixtures thereof,
   characterised in that
   the fibre compound comprises the Ca and/or Mg compound in an amount of from 1 to 50 wt.%, and the Ca and/or Mg compound is in the form of a three-dimensional compound of the Ca and/or Mg compounds in the fibre compound as a result of a reaction with water, gases, in particular CO2 or oxygen, carbonate ions, sulfate ions, further additives and/or combinations thereof or as a result of separating water or gases, such as CO2, O2 or others, optionally while supplying or discharging energy, or such a fibre compound can be formed, it being possible for the additive to be converted into a three-dimensional compound of the Ca and/or Mg compounds, in which individual crystals or particles are interconnected and/or physically interact so as to form a structure that achieves a cross-linked fibrous material structure, formed by the fibrous material, in order to stabilise the fibre compound.
7. Fibre compound according to claim 6,
   characterised in that
   the fibre compound comprises the Ca and/or Mg compound in an amount of from 2 to 40 wt.%.
8. Fibre compound according to either claim 6 or claim 7,
   characterised in that
   the Ca and/or Mg compound within the three-dimensional compound is in the form of largely homogeneous crystal structures which are preferably predominantly rod-shaped, platelet-shaped, fibrous, star-shaped or fascicular.
9. Fibre compound according to any of claims 6 to 8,
   characterised in that
   the organic fibrous materials comprise individual fibres that have a largely circular diameter of a size of less than 0.5 mm, preferably less than 0.25 mm, particularly preferably less than 0.01 mm.
10. Fibre compound according to any of claims 6 to 9,
    characterised in that,
    after the change and/or the formation of the three-dimensional compound, the Ca and/or Mg compound has a refractive index nD of from 1 to 3, preferably from 1.2 to 2.9, particularly preferably from 1.4 to 2.7.
11. Fibre compound according to any of claims 6 to 10,
    characterised in that,
    after the change and/or the formation of the three-dimensional compound, the Ca and/or Mg compound has a brightness R457 according to ISO 2470 of from 1 to 100, preferably from 5 to 100, particularly preferably 10 to 100.
12. Fibre compound according to any of claims 6 to 11,
    characterised in that
    a surface coating can be painted, printed, sprayed, laminated, rolled, adhesively bonded or applied in another suitable manner to the fibre compound.
13. Use of a fibre compound according to any of claims 6 to 12,
    characterised in that
    the fibre compound is used as a medium for storing information, packaging material, decoration means, sanitary article, insulation material, a gas, water or moisture barrier, flame-retardant material, sound-proofing material, material, insulant or the like.
14. Use of a fibre compound according to claim 13,
    characterised in that
    the fibre compound is used in the form of paper as a medium for storing information.

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