EP3655575B1 - Papiervliese mit asymmetrischer silica-imprägnierung und verfahren zur herstellung der vliese sowie deren verwendung - Google Patents

Papiervliese mit asymmetrischer silica-imprägnierung und verfahren zur herstellung der vliese sowie deren verwendung Download PDF

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Publication number
EP3655575B1
EP3655575B1 EP19778972.0A EP19778972A EP3655575B1 EP 3655575 B1 EP3655575 B1 EP 3655575B1 EP 19778972 A EP19778972 A EP 19778972A EP 3655575 B1 EP3655575 B1 EP 3655575B1
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Prior art keywords
weight
sio
paper
fleece
main surfaces
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EP19778972.0A
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German (de)
English (en)
French (fr)
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EP3655575A1 (de
Inventor
Maximilian Nau
Markus BIESALSKI
Nicole Herzog
Annette ANDRIEU-BRUNSEN
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Technische Universitaet Darmstadt
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Technische Universitaet Darmstadt
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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
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/13—Silicon-containing compounds
    • 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
    • D21H25/00—After-treatment of paper not provided for in groups D21H17/00 - D21H23/00
    • D21H25/04—Physical treatment, e.g. heating, irradiating
    • D21H25/06—Physical treatment, e.g. heating, irradiating of impregnated or coated paper
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/04—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres having existing or potential cohesive properties, e.g. natural fibres, prestretched or fibrillated artificial fibres
    • D04H1/26—Wood pulp
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/58—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives
    • D04H1/587—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives characterised by the bonding agents used
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/58—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives
    • D04H1/64—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives the bonding agent being applied in wet state, e.g. chemical agents in dispersions or solutions
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/77—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof
    • D06M11/79—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof with silicon dioxide, silicic acids or their salts
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
    • D06M23/16—Processes for the non-uniform application of treating agents, e.g. one-sided treatment; Differential treatment
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/63—Inorganic compounds
    • D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
    • 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
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/38—Coatings with pigments characterised by the pigments
    • D21H19/40—Coatings with pigments characterised by the pigments siliceous, e.g. clays
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/46—Non-macromolecular organic compounds
    • 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
    • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
    • D21H27/10—Packing paper
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/02—Natural fibres, other than mineral fibres
    • D06M2101/04—Vegetal fibres
    • D06M2101/06—Vegetal fibres cellulosic
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10—Repellency against liquids
    • D06M2200/12—Hydrophobic properties

Definitions

  • the present invention relates to paper webs with asymmetrical silica impregnation and processes for their production and uses of the webs, in particular in the field of packaging materials.
  • composite materials are provided in which a modifying layer is located on the surface of the paper fleece.
  • composite materials made of paper and polyethylene are known. These composite materials are obtained by lamination of the paper surface with polyethylene films. Layer composites are created that have hydrophobic surface properties on one side or on both sides. An anisotropic distribution of the chemical impregnation within the paper fleece cannot be achieved with these techniques. In addition, such composite materials are difficult or impossible to recycle (keyword: microplastics). The relatively large amounts of material required for a coating, for example, are also particularly disadvantageous.
  • Papers can also be made hydrophobic with so-called sizing agents (for example alkylated ketene dimers (AKD)).
  • sizing agents for example alkylated ketene dimers (AKD)
  • WO 2016/133328 A1 relates to a non-woven fabric in which the non-woven fabric is uniformly impregnated with a fine powder, in particular non-woven fabric in which the non-woven fabric is impregnated with a fine powder is uniformly impregnated with a silica component, and manufacturing method thereof.
  • EP 1 944 351 A1 relates to fire-retardant compositions, in particular fire-retardant compositions for the impregnation of lignocellulosic-based materials, such as honeycomb structures made of (recycled) paper, which are often used in doors, walls, furniture and the like.
  • EP 1 262 586 A1 relates to fabrics consisting of heat-resistant fibers, characterized in that the contacts between the fibers are bound by means of an inorganic binder.
  • US 2018/233121 A1 relates to sound-absorbing fabrics with improved thermal insulation and a process for their production, in which an inorganic airgel powder and a thermoset binder resin are used.
  • An anisotropic distribution of the chemical impregnation which can also be referred to as an asymmetrical distribution, would, however, have many advantages. Functional coatings could thus be applied in much lower application weights with the same effect.
  • the targeted adjustment of the material concentration would enable the creation of more complex structures (e.g. sandwich-like channels in the paper) in one process step with minimal use of material.
  • the anisotropic chemical structure would result in advantageous property profiles in the nonwovens, for example barrier effects.
  • a fleece could be obtained that is not wetted with fluids (for example water) on the outside, but could absorb (and release, pass on, and so on ...) the same fluid on the inside, as also described further below.
  • paper fleeces are to be provided which are functionalized in such a way that they have chemically anisotropic properties in cross-section. It should be possible to produce the nonwovens using a process which allows the paper fibers to be given localized hydrophobic or hydrophilic properties. The process should be simple and also allow uncomplicated upscaling.
  • biocompatible materials are to be obtained. The distribution of SiO 2 in the form of a gradient makes it possible that one side of the fleece, in particular the paper, absorbs water and the other side repels water, or that both surfaces repel water and only water can be absorbed inside the material, analogous to a chemical sandwich structure. In addition, the water absorption behavior can be adjusted by adjusting the amount of SiO 2.
  • the method developed by the inventors uses preferably only one silane component (in particular tetraethylorthosilicate (TEOS), preferably prepolymerized) and a paper fleece to build up the anisotropic (asymmetric) impregnation.
  • the silane component can be introduced into the paper in a simple dipping step.
  • Other impregnation methods are also possible.
  • the nonwoven is preferably impregnated with the impregnation solution according to step c) of the method using an impregnation method selected from the group consisting of dip coating, spray coating (optionally also on both sides), size press, roller coating, blade coating and curtain coating. Dip coating and spray coating are particularly preferred. Dip coating is very particularly preferred.
  • the impregnation solution is preferably distributed uniformly over the surface and the interior of the fleece.
  • the silane component becomes a silica impregnation in the form of polymeric SiO 2 , which is also referred to as a silicate component can be.
  • a silicate component can be.
  • the distribution of the amount of polymeric silicate component is preferably controlled by the drying process, which particularly preferably includes the control of the condensation reaction of the silane component (in particular TEOS) that takes place parallel to the drying.
  • the localization of the impregnation is preferably controlled by the intrinsic diffusion and reactivity of the silane component, which in turn can be easily adjusted via the drying conditions (humidity, temperature, pressure). There is therefore no need to produce a laminate in multiple steps with many additives.
  • the method enables the saving of process steps and the amount of material introduced and thus of energy and materials based on fossil raw materials.
  • the new materials obtainable with the method can be used in a variety of ways, for example for hydrophobization in the packaging and food sector.
  • the present invention relates to a paper fleece with asymmetrical silica impregnation, the fleece having two main surfaces, the weight fraction of SiO 2 decreasing towards the interior of the fleece starting from at least one of the two main surfaces.
  • the web of the present invention is a paper web.
  • the impregnated paper fleece preferably comprises SiO 2 in a proportion of 0.1 to 10% by weight, more preferably 0.2 to 7.5% by weight, more preferably 0.5 to 5% by weight.
  • the impregnated paper fleece preferably consists of the fiber component and the impregnation component (SiO 2 ).
  • the impregnated paper fleece preferably comprises the fiber component in a proportion of 90 to 99.9% by weight, more preferably from 92.5 to 99.8% by weight, more preferably from 95% by weight to 99.5% by weight. -%.
  • the impregnated paper fleece of the invention preferably consists of the fiber component and the impregnation component (SiO 2 ).
  • the fleece can contain further components, but preferably in a proportion of at most up to 50% by weight, for example 0 to 30% by weight, more preferably up to 25% by weight, more preferably up to 10% by weight , more preferably up to 5% by weight, more preferably up to 2% by weight, more preferably up to 1% by weight, more preferably less than 0.5% by weight.
  • These further components can in particular be inorganic and / or organic fillers.
  • the proportion of the fiber component and impregnation component in the fleece of the present invention is preferably at least 50% by weight, more preferably at least 75% by weight, more preferably at least 90% by weight, more preferably at least 95% by weight, more preferably at least 98% by weight, more preferably at least 99% by weight.
  • the impregnated paper web of the invention preferably consists of the fiber component and the impregnation component.
  • the web of the present invention has an asymmetric (anisotropic) silica impregnation.
  • asymmetrical and “anisotropic” are used synonymously in the present description.
  • the silica impregnation is in the form of polymeric SiO 2 , which can also be referred to as a silicate component.
  • the silica impregnation is asymmetrical, i.e. anisotropic. This means that the proportion of SiO 2 is not distributed homogeneously over the fleece, as explained in more detail below.
  • the web of the invention has two major surfaces.
  • the length and width of the fleece, or in the case of fleeces with a round base area, the diameter of the fleece are many times greater than the thickness of the fleece.
  • the ratio of length and width or diameter of the fleece to the thickness of the fleece is preferably at least 5, more preferably at least 10, more preferably at least 20.
  • the shape of the fleece can therefore also be described as sheet-like, film-like, plate-like or disc-like.
  • the two main surfaces can also be referred to as the top and bottom or the front and back of the fleece.
  • the weight fraction of SiO 2 decreases starting from at least one of the two main surfaces towards the interior of the fleece.
  • the proportion by weight of SiO 2 is therefore higher on at least one of the two main surfaces than the proportion by weight of SiO 2 below the corresponding main surface.
  • the formation of such an SiO 2 gradient has a number of advantages compared to materials with SiO 2 that is essentially uniformly distributed over the thickness of the fleece. For example, inner channels and / or different wetting properties of the surfaces can be obtained. In addition, a lower use of materials is made possible.
  • the proportion by weight of SiO 2 on at least one of the two main surfaces is preferably at least 1.1 times as high, further preferably at least twice as high, further preferably at least three times as high, further preferably at least four times as high, further preferably at least five times as high, further preferably at least six times as high, further preferably at least seven times as high, further preferably at least eight times as high, further preferably at least nine times as high, further preferably at least ten times as high as the weight fraction of SiO 2 in the middle of the fleece.
  • the middle of the fleece denotes the Positions in the interior of the fleece which are in the shortest possible distance from both main surfaces in each case the same distance, which is based on the thickness of the fleece in the middle of the fleece.
  • the SiO 2 is not only present in a gradient distribution with respect to one main surface, but also with respect to the other main surface.
  • the gradient does not have to be formed in the same way from both main surfaces to the interior of the fleece.
  • the weight fraction of SiO 2 decreases starting from one of the two main surfaces towards the interior of the fleece, while the weight fraction of SiO 2 increases starting from the other of the two main surfaces towards the interior of the fleece.
  • Such fleeces preferably differ with regard to their properties on the two main surfaces.
  • a fleece with a hydrophobic main surface and a hydrophilic main surface is particularly preferred.
  • the proportion by weight of SiO 2 on one of the two main surfaces is preferably at least 1.1 times as high, more preferably at least twice as high, further preferably at least three times as high, further preferably at least four times as high, further preferably at least five times as high, further preferably at least six times as high, further preferably at least seven times as high, further preferably at least eight times as high, further preferably at least nine times as high, further preferably at least ten times as high as the weight fraction of SiO 2 in the center of the fleece.
  • the weight fraction of SiO 2 on the other of the two main surfaces is preferably at most 0.9 times, more preferably at most half, further preferably at most a third, further preferably at most a quarter, further preferably at most one fifth, further preferably at most one sixth , more preferably at most one seventh, further preferably at most one eighth, further preferably at most one ninth, further preferably at most one tenth of the weight fraction of SiO 2 in the center of the fleece.
  • the proportion by weight of SiO 2 on one of the two main surfaces is preferably at least 1.2 times, more preferably at least 4 times, more preferably at least 10 times, more preferably at least 20 times, more preferably at least 50 times. Times, more preferably at least 100 times, the proportion by weight of SiO 2 on the other of the two main surfaces.
  • the weight fraction of SiO 2 decreases starting from both main surfaces towards the interior of the fleece.
  • Such nonwovens preferably do not differ or do not differ significantly with regard to their properties on the two main surfaces.
  • both main surfaces are hydrophobic.
  • a fleece with two hydrophobic main surfaces is particularly preferred. Less material is required compared to a uniform impregnation over the entire thickness of the fleece.
  • the weight fraction of SiO 2 on both main surfaces is preferably at least 1.1 times as high, more preferably at least 1.2 times as high, more preferably at least 1.5 times as high as the weight fraction of SiO 2 in the middle of the Fleece.
  • the ratio of the weight fraction of SiO 2 on one main surface to the weight fraction of SiO 2 on the other main surface is preferably in a range from 0.95: 1 to 1.05: 1, more preferably from 0.98: 1 to 1.02 : 1, more preferably from 0.99: 1 to 1.01: 1.
  • the relative SiO 2 distribution in the webs is preferably confocal with the aid of laser scanning microscopy (CLSM, English: "confocal scanning laser microscopy”) analyzes on cross sections of embedded samples.
  • CLSM laser scanning microscopy
  • absolute SiO 2 amounts per fleece which are preferably determined with the help of thermogravimetric analysis (TGA), this enables a quantitative statement to be made about the material amounts per volume increment.
  • the nonwovens of the invention preferably have a high degree of flexibility.
  • a paper fleece is provided.
  • the paper web provided has a grammage of 65 to 120 g / m 2 , more preferably from 70 to 100 g / m 2 , more preferably from 75 to 90 g / m 2 .
  • the paper fleece can be a commercially available paper fleece.
  • the step of providing the paper fleece can also include the step of producing the paper fleece.
  • a paper web is preferably produced using the Rapid-Köthen process, particularly preferably in a Rapid-Köthen sheet-forming system, very particularly preferably in accordance with DIN 54358 and / or ISO 5269/2 (ISO5269-2: 2004 (E), "Pulps - Preparation of Laboratory Sheets for Physical Testing - Part 2: Rapid Koethen Method, 2004 ").
  • no further additives or fillers are used in the production of the paper fleece.
  • an impregnation solution which contains a silane component.
  • the terms "impregnation solution” and “impregnation solution” are used synonymously.
  • the impregnation solution can be one-component, that is to say consist of a single component.
  • the impregnation solution can in particular also be referred to as “impregnation fluid” or “impregnation fluid”.
  • the impregnation solution consists of the silane component.
  • the proportion of the silane component in the impregnation solution is 100% by weight.
  • the impregnation solution can thus be pure silane.
  • the impregnation solution contains, in addition to the silane component, at least one further component, for example a solvent component and / or an acid component.
  • the proportion of the silane component in the impregnation solution is preferably in a range from 5% by weight to 100% by weight, more preferably 10% by weight to 99% by weight, more preferably 20% by weight to 98% % By weight, more preferably 40% by weight to 97% by weight, more preferably 60% by weight to 96% by weight, more preferably 80% by weight to 95% by weight.
  • the extent of the water-repellent surface properties of the nonwovens can be specifically adjusted via the proportion of the silane component. Higher proportions of silane components are associated with more hydrophobic surface properties.
  • the silane component is preferably selected from the group consisting of tetraethyl orthosilicate (TEOS), tetramethyl orthosilicate, polydimethoxysiloxane, 1,2-bis (triethoxysilyt) ethane, Tetramethylorthosilicate (TMOS), silicon tetraacetate, and mixtures of two or more thereof.
  • TEOS tetraethyl orthosilicate
  • TMOS Tetramethylorthosilicate
  • silicon tetraacetate silicon tetraacetate
  • the silane component TEOS is particularly preferred.
  • TEOS is a common base chemical that is cheap and readily available.
  • the silane component is preferably prepolymerized.
  • prepolymerized means that only oligomers have already been formed and the material has not yet been fully polymerized.
  • the impregnation solution preferably contains solvent in a proportion which is in a range from 0 to 98% by weight, more preferably from 0.1 to 50% by weight, more preferably from 0.2 to 20% by weight, more preferably from 0.5 to 10% by weight, even more preferably from 1 to 5% by weight.
  • the solvent is preferably selected from the group consisting of water, ethanol and mixtures of two or more thereof. The solvent water is particularly preferred.
  • the impregnation solution preferably contains water in a proportion which is in a range from 0 to 20% by weight, more preferably from 0.5 to 10% by weight, more preferably from 1 to 5% by weight.
  • the impregnation solution preferably contains HCl in a proportion of from 0.001 to 0.2% by weight, more preferably from 0.005 to 0.1% by weight, more preferably from 0.01 to 0.05% by weight.
  • the impregnation solution according to the invention is preferably at least 95% by weight, more preferably at least 98% by weight, more preferably at least 99% by weight, more preferably at least 99.9% by weight, more preferably at least 99.99% by weight. -% from ethanol, water, silane component and HCl. It is a particular advantage of the method according to the invention that no further components are required in the impregnation solution.
  • the impregnation solution is particularly preferably at least 95% by weight, more preferably at least 98% by weight, more preferably at least 99% by weight, more preferably at least 99.9% by weight, more preferably at least 99.99% by weight .-% of water, silane component and HCl.
  • the impregnation solution is preferably stirred for a period of 6 to 48 hours, more preferably from 12 to 36 hours, more preferably from 18 to 30 hours, before the impregnation of the paper fleece with the impregnation solution according to step c) of the method according to the invention he follows.
  • the impregnation solution consists of a silane component (in particular TEOS)
  • such stirring preferably does not take place.
  • Step c) of impregnating the paper fleece with the impregnation solution is preferably carried out at a relative humidity in the range of 10% to 95%, more preferably from 30% to 70%, more preferably 40% to 60%, more preferably 45% to 55% and / or at a temperature in a range from 15 ° C to 30 ° C, more preferably 20 ° C to 25 ° C.
  • the paper fleece is preferably impregnated with the impregnation solution by exposing the fleece to the impregnation solution, in other words by bringing the fleece into contact with the impregnation solution.
  • the paper web is preferably impregnated with the impregnation solution according to step c) of the process using an impregnation process selected from the group consisting of dip coating, spray coating (optionally also on both sides), size press, roller coating, blade coating and curtain coating. Dip coating and spray coating are particularly preferred. Dip coating is very particularly preferred.
  • the impregnation solution is preferably distributed uniformly over the surface and the interior of the fleece.
  • the impregnation in step c) of the invention takes place by immersing the fleece in the impregnation solution.
  • the paper fleece is preferably completely immersed in the impregnation solution.
  • the immersion is preferably carried out in such a way that the paper fleece is oriented essentially vertically.
  • a perpendicular orientation means that the two main surfaces of the fleece are arranged in such a way that area vectors perpendicular to the main surfaces are oriented essentially horizontally.
  • the area vectors of the two main surfaces preferably each form an angle of at least 70 ° and at most 110 °, more preferably of at least 80 ° and at most 100 °, more preferably of at least 85 ° and at most 95 °, with the vector of the immersion direction.
  • the fleece is preferably removed from the impregnation solution at a point in time which is one to ten seconds, more preferably two to five seconds after the end of the immersion of the fleece in the impregnation solution.
  • the fleece is preferably removed from the impregnation solution in such a way that the fleece is oriented essentially vertically.
  • a perpendicular orientation means that the two main surfaces of the fleece are arranged in such a way that area vectors perpendicular to the main surfaces are oriented essentially horizontally.
  • the area vectors of the two main surfaces preferably each form an angle of at least 70 ° and at most 110 ° with the vector of the distance direction, more preferably of at least 80 ° and at most 100 °, more preferably at least 85 ° and at most 95 °.
  • the drying of the fleece takes place at temperatures in a range from 70.degree. C. to 190.degree.
  • the nonwoven is preferably dried at temperatures in a range from 80 ° C to 180 ° C, more preferably from 90 ° C to 170 ° C, more preferably from 100 ° C to 160 ° C, more preferably from 110 ° C to 150 ° C, more preferably from 120 ° C to 140 ° C, more preferably from 125 ° C to 135 ° C.
  • the nonwoven is preferably dried in accordance with step d) until the residual moisture content of the nonwoven is in a range from 3% by weight to 7% by weight.
  • the residual moisture is preferably determined by means of gravimetric analysis, in particular according to DIN EN 20287.
  • the drying according to step d) of the method according to the invention takes place immediately, in other words immediately after the impregnation of the fleece with the impregnation solution according to step c) of the method.
  • the impregnation according to step c) is preferably completed when the paper fleece is no longer exposed to the impregnation solution, or in other words when the paper fleece is no longer brought into contact with the impregnation solution.
  • the impregnation according to step c) is, for example, preferably completed when the paper fleece has been completely removed from the impregnation solution, for example pulled out.
  • the impregnation according to step c) is, for example, preferably completed when the nonwoven is no longer sprayed with the impregnation solution.
  • the drying according to step d) preferably begins when the fleece comes into an environment which is intended to remove moisture and / or condensation products, for example in an oven.
  • the migration of the silane component through the fleece at the elevated drying temperatures can be influenced, in particular, by adjusting the ambient pressures during drying.
  • the migration of the silane component can in particular also be influenced by the evaporation of the silane component and / or the solvent at the elevated drying temperatures, since the silane component migrates with the solvent through the fleece .
  • the method of the present invention provides that there is a period of at most 60 seconds between the completion of the impregnation in accordance with step c) and the start of the drying in accordance with step d). Extensive polymerization has therefore not yet taken place at the start of drying, so that the silane component present in the impregnation solution migrates through the fleece and the distribution of the silica impregnation can therefore be influenced in a targeted manner via the migration.
  • paper webs with an asymmetrical silica impregnation is designed such that the SiO 2 weight fraction on one main surface is higher than in the center of the fleece, while the SiO 2 weight fraction on the other main surface is less than in the middle of the fleece.
  • fiber nonwovens can be obtained with an asymmetrical silica impregnation, which is designed in such a way that the SiO 2 weight fraction is approximately the same on both main surfaces, namely higher than in the middle of the nonwoven, since the silane component migrates from the center in the direction of the main surfaces and there is then an increased formation of the polymeric silica impregnation.
  • the drying is preferably carried out with the aid of a dryer.
  • the dryer is preferably selected from the group consisting of hot air dryers, ovens, drum dryers and IR dryers.
  • drying can be carried out in an oven, preferably in a vacuum oven or in a muffle oven.
  • the oven is preferably preheated, in particular to the drying temperature, so that after the impregnation in accordance with step c), the drying in accordance with step d) can be started particularly quickly.
  • the dryer is particularly preferably a hot air dryer. Hot air drying is particularly preferred.
  • the properties of the nonwovens obtained can be influenced not only via the method steps described above, but in particular also via the ambient pressure prevailing during drying. It has surprisingly been found that the distribution of the SiO 2 content in the nonwovens can be controlled in a targeted manner via the pressure conditions during drying. Nonwovens with comparatively high SiO 2 contents on both main surfaces can be obtained in particular at low pressures. In contrast, higher pressures promote differences between the SiO 2 contents of the two main surfaces, so that nonwovens are obtained in which one of the main surfaces is significantly more hydrophobic than the other main surface.
  • the pressure during the drying in step d) is preferably in a range from 0.1 kPa to 500 kPa, more preferably from 0.2 kPa to 200 kPa.
  • the pressure during drying according to step d) is in a range from 0.1 kPa to 30 kPa, more preferably from 0.2 kPa to 20 kPa, more preferably from 0.5 kPa to 10 kPa, more preferably from 1 kPa to 5 kPa.
  • Such embodiments are particularly suitable for producing such fleeces in which the SiO 2 content is comparatively high on both main surfaces, but comparatively low in the middle of the fleece (so-called sandwich structure).
  • the pressure during drying according to step d) is in a range from> 30 kPa to 500 kPa, more preferably from 50 kPa to 200 kPa, more preferably from 60 kPa to 150 kPa, more preferably from 70 kPa to 130 kPa, more preferably from 80 kPa to 120 kPa, more preferably from 90 kPa to 110 kPa.
  • Such embodiments are particularly suitable for producing such fleeces in which the SiO 2 content on one of the two main surfaces is significantly higher than on the other of the two main surfaces, while the SiO 2 content is in the middle of the fleece is less than one of the two main surfaces, but higher than the other of the two main surfaces.
  • the fleeces are preferably arranged essentially horizontally or oriented horizontally during drying.
  • a horizontal orientation means that the two main surfaces of the fleece are arranged in such a way that area vectors perpendicular to the main surfaces are oriented essentially vertically.
  • the nonwovens are preferably cooled to a temperature of 15 ° C to 30 ° C, more preferably 20 ° C to 25 ° C.
  • the method preferably consists of the steps indicated. It is a particular advantage of the method according to the invention that the method manages with very few steps.
  • the present invention also relates to the use of a nonwoven fabric of the present invention, in particular as a packaging material.
  • Preferred uses as packaging material include use as frozen paper, use for products that come into contact with food, such as in particular (paper) cups and / or (paper) straws, and use as packaging for materials that come into contact with food Liquid should be protected, but should still exchange moisture.
  • the nonwovens of the present invention can be used for plastic-free straws and / or paper cups. Against the background of possible regulations to reduce plastic waste, it can be assumed that there will be an increased demand for plastic-free products. Nonwovens for the uses mentioned, in particular for use in drinking straws and cups, are often also referred to as special papers.
  • Embodiments in which the SiO 2 content on one of the two main surfaces is significantly higher than on the other of the two main surfaces are particularly suitable for use as paper cups.
  • the main surface with the higher SiO 2 content is suitable as the inside of the cup because of its hydrophobicity, since the hydrophobic properties of the surface prevent excessive penetration of the liquid in the cup into the interior of the fleece.
  • the more hydrophilic surface works well as the outer surface of the mug as it promotes printability.
  • those embodiments are particularly suitable in which the SiO 2 content is comparatively high on both main surfaces, but comparatively low in the middle of the fleece (so-called sandwich structure).
  • the high SiO 2 content on the two main surfaces prevents excessive ingress of liquid into the interior of the fleece.
  • the fact that the SiO 2 content in the middle of the fleece is comparatively low enables material to be saved.
  • the present invention also relates to the use of a fleece of the present invention as a membrane, in particular as a membrane for water / oil separation.
  • a membrane can in particular be used for the spatial separation of mixtures consisting of a liquid, hydrophobic component (in particular oil) and water.
  • the present invention also relates to the use of a nonwoven fabric of the present invention as special paper for use at elevated temperatures, in particular the use of a nonwoven fabric of the present invention as baking paper.
  • Eucalyptus sulfate fiber (“curl”: 16.2%; degree of fibrillation: 1.3%; fines: 15.2%) was used to produce a paper fleece.
  • the pulp was ground in a Voith LR 40 laboratory refiner. It was ground with an effective specific energy of 16 kWh / t (750,000 revolutions).
  • the eucalyptus sulfate pulp was made into paper webs with a grammage of 80 ⁇ 0.9 g / m 2 using a Rapid-Koethen sheet-forming system in accordance with DIN 54358 and ISO 5269/2 (ISO5269-2: 2004 (E), "Pulps - Preparation of Laboratory Sheets for Physical Testing - Part 2: Rapid Köthen Method, 2004 "). No additives or fillers were used.
  • TEOS TEOS
  • EtOH ethanol
  • H 2 O water
  • HCl HCl
  • Thermogravimetric analysis was carried out with a TGA 1 (Mettler-Toledo). The samples were moved from 25 ° C to 600 ° C at a rate of 10 ° C / min under a constant flow of air heated by 30 ml / min. With these measurements it is possible to determine the SiO 2 content, since SiO 2 is stable up to temperatures of 1700 ° C.
  • thermogravimetric analysis results are summarized in Table 2 below.
  • Table 1 ⁇ /b> sample Weight loss (TGA) Proportion of SiO 2 Paper fleece from Example 1 95.6% - Fleece from example 2 (low-concentration solution) 95.0% 0.60% Fleece from example 2 (medium-concentrated solution) 93.67% 1.93% Fleece from example 2 (highly concentrated solution) 91.57% 4.03%
  • the proportion of SiO 2 in the SiO 2 -paper hybrid materials is therefore approximately 0.6% by weight for the nonwovens obtained by treatment with the low-concentration TEOS solution, and approximately 4% by weight for the Nonwovens obtained by treatment with the highly concentrated TEOS solution.
  • Each sample was embedded in a mixture of 49.9875% by weight Desmodur 3200, 49.9875% by weight Albodur 956 VP and 0.025% by weight TIB-KAT 318.
  • the mixture is a commercial polyurethane system.
  • the freshly embedded samples were subjected to several vacuum cycles at room temperature in order to remove remaining air bubbles.
  • the resin was then cured at 80 ° C. for 18 hours.
  • specimens with a thickness of 120 ⁇ m were cut. The cutting plane was chosen so that it is oriented orthogonally to both main surfaces.
  • the samples were placed between two 25 mm round microscope coverslips using Leica Type F immersion fluid.
  • the recordings were made on a Leica TCS SP8.
  • the image data of the various confocal planes were combined and a gray value analysis was carried out for each row of image points, that is, the gray values of each row were added for each individual column. From this, the distribution through the fleece from one of the main sides to the other main side was determined.
  • CFW serves as a reference value.
  • CFW has a high affinity for cellulose and is therefore evenly distributed over the entire thickness of the fleece. If the CFW fluorescence value fluctuates significantly across the paper cross-section, this can indicate problems in the beam path (such as air inclusions), since CFW is physically homogeneously distributed on the paper.
  • amino groups of CFW can react with the polyurethane resin, which deactivates the fluorescence of CFW.
  • CFW is protected by SiO 2 , it does not occur Reacts with the resin so that the fluorescence is maintained. Therefore, in addition to the reference, the extent of the CFW fluorescence is a measure of the content of SiO 2 at a certain depth position within the fleece.
  • Rhodamine B serves as a ratiometric marker for the proportion of SiO 2 .
  • RhoB fluorescence the higher the proportion of SiO 2 .
EP19778972.0A 2018-10-01 2019-09-25 Papiervliese mit asymmetrischer silica-imprägnierung und verfahren zur herstellung der vliese sowie deren verwendung Active EP3655575B1 (de)

Applications Claiming Priority (2)

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DE102018124255.7A DE102018124255A1 (de) 2018-10-01 2018-10-01 Faservliese mit asymmetrischer Silica-Imprägnierung und Verfahren zur Herstellung der Vliese sowie deren Verwendungen
PCT/EP2019/075927 WO2020069943A1 (de) 2018-10-01 2019-09-25 Faservliese mit asymmetrischer silica-imprägnierung und verfahren zur herstellung der vliese sowie deren verwendung

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EP4311872A1 (en) * 2022-07-27 2024-01-31 Technische Universität Darmstadt Wet strength improved fibrous non-woven fabrics, in particular paper, uses of these wet strength fabrics as well as production methods of the same
EP4311875A1 (en) * 2022-07-27 2024-01-31 Technische Universität Darmstadt Non-woven fabric coated with silica, method for manufacturing it and its use

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US20220034041A1 (en) 2022-02-03
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