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EP0786551B1 - Process for making a web of material - Google Patents

Process for making a web of material Download PDF

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Publication number
EP0786551B1
EP0786551B1 EP96101070A EP96101070A EP0786551B1 EP 0786551 B1 EP0786551 B1 EP 0786551B1 EP 96101070 A EP96101070 A EP 96101070A EP 96101070 A EP96101070 A EP 96101070A EP 0786551 B1 EP0786551 B1 EP 0786551B1
Authority
EP
European Patent Office
Prior art keywords
process according
soluble particles
backing
plastics
particles
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP96101070A
Other languages
German (de)
French (fr)
Other versions
EP0786551A1 (en
Inventor
Michael Dr.-Ing. Gass
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Munzinger Conrad and Cie AG
Original Assignee
Munzinger Conrad and Cie AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to EP96101070A priority Critical patent/EP0786551B1/en
Application filed by Munzinger Conrad and Cie AG filed Critical Munzinger Conrad and Cie AG
Priority to PT96101070T priority patent/PT786551E/en
Priority to ES96101070T priority patent/ES2144163T3/en
Priority to AT96101070T priority patent/ATE189017T1/en
Priority to DE59604228T priority patent/DE59604228D1/en
Priority to DK96101070T priority patent/DK0786551T3/en
Priority to TR97/01031T priority patent/TR199701031T1/en
Priority to KR1019970706657A priority patent/KR100257804B1/en
Priority to PCT/EP1997/000214 priority patent/WO1997027361A1/en
Priority to EP97901544A priority patent/EP0817887B1/en
Priority to SK1299-97A priority patent/SK279862B6/en
Priority to CZ19972998A priority patent/CZ287859B6/en
Priority to AU15422/97A priority patent/AU702029B2/en
Priority to BR9704640A priority patent/BR9704640A/en
Priority to CA002214003A priority patent/CA2214003C/en
Priority to SI9730088T priority patent/SI0817887T1/en
Priority to US08/913,809 priority patent/US6017583A/en
Priority to PL97322379A priority patent/PL182279B1/en
Priority to TW086100622A priority patent/TW339383B/en
Priority to MYPI97000234A priority patent/MY119139A/en
Priority to ZA9700597A priority patent/ZA97597B/en
Publication of EP0786551A1 publication Critical patent/EP0786551A1/en
Priority to MX9707251A priority patent/MX9707251A/en
Priority to NO19974422A priority patent/NO311809B1/en
Application granted granted Critical
Publication of EP0786551B1 publication Critical patent/EP0786551B1/en
Priority to GR20010400003T priority patent/GR3035184T3/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21FPAPER-MAKING MACHINES; METHODS OF PRODUCING PAPER THEREON
    • D21F7/00Other details of machines for making continuous webs of paper
    • D21F7/08Felts
    • D21F7/083Multi-layer felts
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21FPAPER-MAKING MACHINES; METHODS OF PRODUCING PAPER THEREON
    • D21F7/00Other details of machines for making continuous webs of paper
    • D21F7/08Felts
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21FPAPER-MAKING MACHINES; METHODS OF PRODUCING PAPER THEREON
    • D21F1/00Wet end of machines for making continuous webs of paper
    • D21F1/0027Screen-cloths
    • D21F1/0063Perforated sheets

Definitions

  • the invention relates to a method for producing a material web, on at least one side of a support a plastic layer made of a mixture of plastic material and particle-like soluble particles is generated, wherein the soluble particles can be removed by such a solvent are resistant to which the plastic material and that thereafter the soluble particles are at least partially from the plastic layer with the formation of through-channels be detached.
  • a material web of the type mentioned above for use in a paper machine is described in EP-B-0 196 045.
  • she has as a carrier a liquid-permeable fabric on which a 1.3 to 5 mm thick layer of an elastomeric polymer resin is applied.
  • the plastic layer has through channels on that of the otherwise smooth and flat outside go through to the support and in the paper machine as drainage channels serve.
  • the through channels are manufactured in such a way that textile fibers are homogeneously dispersed in the polymer resin, before the mixture of textile fibers and polymer resin on the carrier is applied.
  • a nonwoven can be used first applied to the carrier and then the coating with be made of the polymer resin.
  • the textile fibers are removed after application of the Polymer resin by applying the solvent so that channels arise that the shape and the course of the detached Correspond to textile fibers.
  • Textile fibers instead of Textile fibers suggested particulate particles that are homogeneous be distributed in the polymer resin. As material for this Particles become inorganic salts or their hydrates or oxides suggested. They can be made using appropriate solvents in the same way as the textile fibers made of the polymer resin are removed and leave pore cavities.
  • the soluble components - are there are fibers or particle-like particles - in the polymer resin distribute evenly and this distribution when applying maintain the mix.
  • the mixture it comes from polymer resin and soluble components to segregation, so that it is not guaranteed that by the detachment of the particles through passageways arise. Out for this reason, no different distributions can be made produce the soluble components across the cross-section.
  • polymer resins tend to harden after curing to form a closed surface, which is the detachment of the soluble textile fibers contained in the polymer resin or Particles hindered.
  • the surface of the plastic layer to grind so that a connection to the soluble Fibers produced and also creates a smooth surface becomes.
  • a grinding process is very time consuming.
  • it must be in an appropriate excess Plastic material can be applied and during the grinding process dust accumulates, which is vacuumed and either disposed of or returned must be processed.
  • a smooth surface arises, which detaches the paper web from the paper machine belt with special needs. Namely, paper webs tend to stick to themselves vacuum smooth surfaces.
  • paper machine belts are used This type has a number of advantages over known felts attributed according to the batt-on-base principle, namely enlarged Resistance to permanent deformation and therefore longer Operating times and consequently lower set-up costs, improved abrasion resistance and higher structural strength, lower Affinity for contaminating substances as well as more uniform Pressure distribution and thus improved drainage.
  • WO 86/05219 describes a method for producing a Paper machine belt disclosed in which a polymer material, mixed with soluble particles, in plasticized Form on a barbed tape to form a plastic layer is applied. For curing this plastic layer and / or to remove the detachable particles the plastic layer is subjected to a post-treatment with heat become. Leave after peeling off the polymer tape the spines of the barbed conical through holes back.
  • the polymer material can also have a reinforcing structure provided in the form of fibers, threads or fabrics his.
  • WO 91/14558 proposes the through-channels by producing that on the not yet hardened Put on a shadow mask and then this is irradiated. This hardens due to this radiation Plastic material in the area of the holes of the mask. After removing the shadow mask, the not yet hardened is then Plastic material removed using compressed air. Also this process is complex and leaves relatively large free areas and therefore cannot be used universally become. In addition, waste to be disposed of or reprocessed also falls here Waste.
  • the material web initially consists exclusively of polymer particles is produced by exposure to heat at their contact points be connected to each other. If necessary can complete a reinforcement structure like a reinforcement be stored in the band thus formed. Here it can be a pure fiber product or a fabric.
  • the particles can also have different diameters have one increasing from one side to the other To create permeability.
  • a polymer coating is made using a peel film under the simultaneous exposure to heat and Pressure applied to a support, the polymer film due to the heat on the peel-off film Drops forming free spaces with the Consequence that the plastic layer applied to the carrier is porous. It is also difficult with this method Permeability of the plastic layer can be set reproducibly and adapt to the respective requirements. Also stand Foils in the width required here are not available and would also not be able to be produced with sufficient uniformity.
  • the invention has for its object a method for manufacturing to provide a material web of the type mentioned at the outset, with which a desired distribution of the soluble Can achieve particles within the plastic layer.
  • a another task is to design the process so that the soluble particles are easily removed from the Let out the plastic layer.
  • This object is achieved in that as Plastic material a plastic powder is provided that mixes with the soluble particles and applied to the carrier and that by heat and pressure treatment from the Mixture of plastic powder and soluble particles a plastic layer generated with the soluble particles contained therein is before the soluble particles at least partially be detached from the plastic layer.
  • the grain size of the particles of the plastic powder and also the the soluble particles and their mixing ratio can each can be set within wide limits as required so that a desired structure of the plastic layer results, in particular what about after the soluble particles have been extracted resulting cavities of the through channels.
  • the soluble particles should have an average diameter from 30 to 50 ⁇ m.
  • the average grain size of the plastic powder should be less than that of the soluble particles, expediently only half to a third of the soluble Particles are and in no case be more than 100 microns. In this way the soluble particles become a plurality or even a variety of particles of plastic powder practically encased, and there is a relatively tight package.
  • the volume ratio between plastic powder and soluble Particles should expediently be set so that that the soluble particles are not just in the cross-plane direction the plastic layer, but also in the plane of the plastic layer lie at least partially against each other, so that also in the Level of the plastic layer open pores and thus drainage volume provided and thus the water absorption capacity is improved.
  • the volume ratio between plastic powder and soluble Particles are expediently in the range between 1/4: 3/4 and 1/2: 1/2, preferably in the range 2/3: 1/3.
  • the plastic powder and the soluble particles can also applied in layers, with different layers Grain sizes, materials and mixing ratios can be provided to account for the respective requirements to wear. So the soluble particles can go to the carrier grow in layers or continuously. Alternatively or in combination can also the number of soluble particles increase from layer to layer towards the carrier. Both measures serve to increase the permeability to the wearer to let this be particularly so when using the web of material desirable in the forming and press area of a paper machine is.
  • Another advantage of this procedure is that by indenting the soluble particles where the soluble particles Particles are present on the outside near the surface, a connection to these is established. After detaching The solvent has access to the soluble particles soluble soluble initially enclosed in the plastic layer Particles and can therefore also completely dissolve them remove. The impressions then form the openings of the through channels. The procedure thus replaces the Grinding treatment according to EP-B-0 273 613.
  • the soluble particles in such a density are applied to the plastic layer, that at least the impressions remaining after removal partly with each other and with the through channels stay in contact. This design is particularly effective when used as a paper machine belt cheap for drainage out.
  • the soluble particles should preferably be at a temperature the plastic layer can be pressed into this the plastic layer compared to the condition at room temperature is softened. This can be done in that the soluble Particles following the creation of the plastic layer applied at an even higher temperature and pressed in.
  • the pressing can be done by a calender treatment become.
  • the soluble particles should be a medium one Have a diameter of 5 to 100 ⁇ m.
  • both should be made of the same material so that the removal can be done in one operation using the same solvent.
  • those substances should be selected which remain essentially dimensionally stable under the heat effect of the production of the plastic layer.
  • polymeric particles come into question which have a higher heat resistance than that of the plastic matrix in which the soluble particles are embedded. These conditions should expediently also apply to the soluble particles pressed into the outside of the plastic layer.
  • soluble particles or particles are not adversely affected by the heat treatment necessary for the formation of the plastic layer and are easy to pour and therefore scatterable.
  • Organic substances e.g. B. carbohydrates (sugar), or salts of organic acids, such as citric acid, ascirbic acid etc.
  • An additional antioxidant should be added to the plastic powder.
  • soluble particles of at least two substances are used, each one of the substances by a solvent is removable, against which the other substance (s) is or are stable.
  • This idea is basically that EP-A-0 303 798 and EP-A-0 320 559 in which the use of soluble fibers within a felt is suggested has been. It is understood that these soluble particles compared to the conditions of use for which the material web is intended is, must be constant, d. H. in case of use as Paper machine belt compared to those coming from the paper web Liquids or vapors. Alternatively, can be provided be that the soluble particles are only delayed and successive let out of the matrix.
  • a second plastic layer with through channels created in the same way as on one side becomes.
  • the number and / or size of the soluble particles should be considered facing away from the carrier in the second plastic layer increase, and it should be the number and / or size of soluble Particles in the areas of both plastic layers adjacent to the carrier be the same size. It is understood that others too Distributions are possible if this is for the intended Use is more appropriate.
  • the outside the second plastic layer also in the already be described above with impressions that be generated by pressing in soluble particles.
  • the carrier of the material web according to the invention has the task the material web essentially only has dimensional and structural strength to give and if necessary absorb longitudinal and transverse forces.
  • Suitable for this textile supports formed in particular from threads, such as, for example Threads, knitted fabrics, knitted fabrics, fabrics or combinations such textile carrier.
  • the carrier can have one or more layers of strength be constructed.
  • a base fabric all types of fabric come in question, especially those from the field of Paper machine tapes are known.
  • For the threads are both Monofilaments as well as multifilaments made of preferably thermoplastic Plastic materials can be used.
  • the carrier can alternatively or in combination, a spunbonded nonwoven and / or have a punched or extruded network structure. It can also be provided with a fleece, so that it has a felt character.
  • Plastics such as these are suitable as materials for the carrier especially known from the field of paper machine tapes and are mentioned in the documents mentioned above.
  • the selection The plastic can be used for the respective purpose and prevailing conditions there are adapted.
  • such plastics should be selected that are used in the production the plastic layer and the associated heat do not suffer any impairments.
  • Polyamides such as polyamide, are suitable for the plastic layer 4.6, 6, 6.6, 6.10, 6.12, 11 and 12 as well as thermoplastic aromatic Polyamides.
  • polyester, polyphenylene sulfide, Polyether ether ketone, polyurethane, polysyl phones, Polyphthalamides and polypropylenes are used.
  • other polymeric and elastomeric plastics in Question how they are, for example, EP-B-0 196 045 and Have EP-B-0 273 613 removed.
  • the plastic layer can also consist of layers made of plastics with different elastic assets. So far can the selection of plastics and their elastic properties can also be adapted to the respective application.
  • the invention is greatly enlarged on the basis of a illustrated embodiment illustrated in more detail. It shows a section of a section of a material web 1.
  • the material web 1 has a carrier 2, the longitudinal thread 3 and cross thread 4 is formed as a fabric.
  • On the upper and the underside of the carrier 2 is each a plastic layer 5, 6.
  • the first plastic layer 5 is in accordance with the invention Process prepared by using a mixture from a plastic powder and soluble particles on the carrier 2 sprinkled and both together a heat and pressure treatment has undergone. This is a homogeneous Plastic layer 5 with substantially evenly distributed therein soluble particles have been generated, due to the pressure treatment has resulted in a flat outer surface. On the still heated and therefore plastically easily deformable outside 7 of the plastic layer 5 are then further soluble particles sprinkled and then by means of pressure rollers or the like has been pressed into the plastic layer 5. In corresponding The procedure is with the lower plastic layer 6 , especially with regard to the treatment of their Outside 8.
  • the material web 1 is a treatment with a solvent subjected to the soluble particles and particles been.
  • these impressions 9 have at least sometimes not only with each other, but also connection to the soluble particles close to the outer sides 7, 8 the plastic layers 5, 6 created so that the solvent these particles are also reached and dissolved.
  • the resolution has the consequence that 5, 6 pore cavities in the plastic layers - exemplified with 10 - arise, which have the shape of the particle detached and communicate with each other.
  • the pore cavities 10 of the top plastic layer 5 are towards the carrier 2 larger than in the area of the outside 7. This can be prepared by first mixing Plastic powder and relatively large soluble particles and after another mixture of plastic powder and in contrast smaller soluble particles is applied. With the underside Plastic layer 6 is a plastic powder with even larger soluble particles have been used so that the Pore cavities 10 are larger than that of the plastic layer on the top 3rd

Landscapes

  • Laminated Bodies (AREA)
  • Preliminary Treatment Of Fibers (AREA)
  • Polishing Bodies And Polishing Tools (AREA)
  • Paper (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Continuous Casting (AREA)
  • Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
  • Glass Compositions (AREA)
  • Dry Formation Of Fiberboard And The Like (AREA)
  • Manufacturing Of Steel Electrode Plates (AREA)
  • Iron Core Of Rotating Electric Machines (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Nonwoven Fabrics (AREA)
  • Medicinal Preparation (AREA)
  • Absorbent Articles And Supports Therefor (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)

Abstract

A process for manufacture of a web of material (1) entails producing a plastic layer (5, 6) on at least one side of a carrier (2) from a mixture of plastic material and granular soluble pieces, and afterwards dissolving out at least some of the pieces by a solvent against which the plastic is resistant while forming permeable channels. Plastic powder is prepared, mixed with the small soluble pieces and applied to the carrier. The plastic layer (5, 6) is formed from the mixture by heat and pressure treatment before dissolving at least some of the pieces.

Description

Die Erfindung betrifft ein Verfahren zur Herstellung einer Materialbahn, bei dem auf wenigstens einer Seite eines Trägers eine Kunststoffschicht aus einer Mischung von Kunststoffmaterial und partikelartigen löslichen Teilchen erzeugt wird, wobei die löslichen Teilchen durch ein solches Lösungsmittel herauslösbar sind, gegenüber dem das Kunststoffmaterial beständig ist, und daß danach die löslichen Teilchen zumindest teilweise aus der Kunststoffschicht unter Bildung von Durchgangskanälen herausgelöst werden.The invention relates to a method for producing a material web, on at least one side of a support a plastic layer made of a mixture of plastic material and particle-like soluble particles is generated, wherein the soluble particles can be removed by such a solvent are resistant to which the plastic material and that thereafter the soluble particles are at least partially from the plastic layer with the formation of through-channels be detached.

Eine Materialbahn der oben genannten Art für den Einsatz in einer Papiermaschine ist in der EP-B-0 196 045 beschrieben. Sie hat als Träger ein flüssigkeitsdurchlässiges Gewebe, auf dem eine 1,3 bis 5 mm dicke Schicht aus einem elastomeren Polymerharz aufgebracht ist. Die Kunststoffschicht weist Durchgangskanäle auf, die von der ansonsten glatten und ebenen Außenseite bis zum Träger hindurchgehen und in der Papiermaschine als Entwässerungskanäle dienen.A material web of the type mentioned above for use in a paper machine is described in EP-B-0 196 045. she has as a carrier a liquid-permeable fabric on which a 1.3 to 5 mm thick layer of an elastomeric polymer resin is applied. The plastic layer has through channels on that of the otherwise smooth and flat outside go through to the support and in the paper machine as drainage channels serve.

Die Herstellung der Durchgangskanäle geschieht in der Weise, daß Textilfasern homogen in dem Polymerharz dispergiert werden, bevor die Mischung aus Textilfasern und Polymerharz auf dem Träger aufgebracht wird. Alternativ dazu kann zunächst ein Faservlies auf den Träger aufgebracht und dann die Beschichtung mit dem Polymerharz vorgenommen werden. In beiden Fällen bestehen die Textilfasern aus einem organischen Material, das durch Anwendung eines Lösungsmittels auflösbar ist, wobei die Kunststoffschicht gegenüber diesem Lösungsmittel beständig ist. Das Herauslösen der Textilfasern geschieht nach dem Auftragen des Polymerharzes durch Auftragen des Lösungsmittels, so daß Kanäle entstehen, die der Formgebung und dem Verlauf der herausgelösten Textilfasern entsprechen.The through channels are manufactured in such a way that textile fibers are homogeneously dispersed in the polymer resin, before the mixture of textile fibers and polymer resin on the carrier is applied. Alternatively, a nonwoven can be used first applied to the carrier and then the coating with be made of the polymer resin. In both cases exist the textile fibers made of an organic material that by application a solvent is dissolvable, the plastic layer is resistant to this solvent. The The textile fibers are removed after application of the Polymer resin by applying the solvent so that channels arise that the shape and the course of the detached Correspond to textile fibers.

In einer weniger bevorzugten Ausführungsform werden statt der Textilfasern partikelförmige Teilchen vorgeschlagen, die homogen in dem Polymerharz verteilt werden. Als Material für diese Teilchen werden anorganische Salze oder deren Hydrate oder Oxide vorgeschlagen. Durch entsprechende Lösungsmittel können sie in der gleichen Weise wie die Textilfasern aus dem Polymerharz herausgelöst werden und hinterlassen dabei Porenhohlräume.In a less preferred embodiment, instead of Textile fibers suggested particulate particles that are homogeneous be distributed in the polymer resin. As material for this Particles become inorganic salts or their hydrates or oxides suggested. They can be made using appropriate solvents in the same way as the textile fibers made of the polymer resin are removed and leave pore cavities.

Bei der Herstellung des vorbeschriebenen Papiermaschinenbands bereitet es Schwierigkeiten, die löslichen Komponenten - seien es Fasern oder partikelartige Teilchen - in dem Polymerharz gleichmäßig zu verteilen und diese Verteilung beim Aufbringen der Mischung aufrechtzuerhalten. Bei der Verarbeitung der Mischung aus Polymerharz und löslichen Komponenten kommt es nämlich zu Entmischungen, so daß nicht gesichert ist, daß durch das Herauslösen der Teilchen Durchgangskanäle entstehen. Aus diesem Grund lassen sich auch keine unterschiedlichen Verteilungen der löslichen Komponenten über den Querschnitt herstellen.In the manufacture of the paper machine belt described above it creates difficulties, the soluble components - are there are fibers or particle-like particles - in the polymer resin distribute evenly and this distribution when applying maintain the mix. When processing the mixture it comes from polymer resin and soluble components to segregation, so that it is not guaranteed that by the detachment of the particles through passageways arise. Out for this reason, no different distributions can be made produce the soluble components across the cross-section.

Davon abgesehen neigen Polymerharze dazu, nach dem Aushärten eine geschlossene Oberfläche zu bilden, die das Herauslösen der in dem Polymerharz enthaltenen, löslichen Textilfasern bzw. Teilchen behindert. Zur Lösung dieses Problems ist in der EP-B-0 273 613 vorgeschlagen, die Oberfläche der Kunststoffschicht derart zu schleifen, daß eine Verbindung zu den löslichen Fasern hergestellt und zudem eine glatte Oberfläche zu erzeugt wird. Ein solcher Schleifvorgang ist jedoch sehr zeitaufwendig. Außerdem muß zuvor in einem entsprechenden Übermaß Kunststoffmaterial aufgetragen werden, und beim Schleifvorgang fällt Staub an, der abgesaugt und entweder entsorgt oder wieder aufbereitet werden muß. Hinzu kommt, daß eine glatte Oberfläche entsteht, die eine Ablösung der Papierbahn von dem Papiermaschinenband behindert. Papierbahnen neigen nämlich dazu, sich an glatten Oberflächen festzusaugen.That being said, polymer resins tend to harden after curing to form a closed surface, which is the detachment of the soluble textile fibers contained in the polymer resin or Particles hindered. To solve this problem is in the EP-B-0 273 613 proposed the surface of the plastic layer to grind so that a connection to the soluble Fibers produced and also creates a smooth surface becomes. However, such a grinding process is very time consuming. In addition, it must be in an appropriate excess Plastic material can be applied and during the grinding process dust accumulates, which is vacuumed and either disposed of or returned must be processed. Add to that a smooth surface arises, which detaches the paper web from the paper machine belt with special needs. Namely, paper webs tend to stick to themselves vacuum smooth surfaces.

Abgesehen von diesen Nachteilen werden Papiermaschinenbändern dieser Gattung eine Reihe von Vorteile gegenüber bekannten Filzen nach dem batt-on-base-Prinzip zugeschrieben, nämlich vergrößerter Widerstand gegen bleibende Verformung und damit längere Betriebszeiten und daraus folgend geringere Rüstkosten, verbesserte Abriebfestigkeit und höhere Strukturfestigkeit, geringere Affinität für kontaminierende Substanzen sowie gleichmäßigere Druckverteilung und damit verbesserte Entwässerung.Apart from these disadvantages, paper machine belts are used This type has a number of advantages over known felts attributed according to the batt-on-base principle, namely enlarged Resistance to permanent deformation and therefore longer Operating times and consequently lower set-up costs, improved abrasion resistance and higher structural strength, lower Affinity for contaminating substances as well as more uniform Pressure distribution and thus improved drainage.

Der vorbeschriebenen Entwicklung voraus ging ein Vorschlag, in die Fasern eines Papiermaschinenfilzes Fasern oder Partikel einzulagern, die mit Hilfe eines Lösungsmittels herauslösbar sind, gegenüber dem die übrigen Fasern und der Träger des Papiermaschinenbands lösungsmittelresistent, d. h. beständig ist (DE-C-34 19 708). Die Herstellung erfolgt in der Weise, daß ein Faservlies aus nicht löslichen Fasern und löslichen Komponenten gebildet und auf den Träger aufgenadelt und daß dann das Papiermaschinenband unter Druck und Hitze verdichtet wird. Dabei können die löslichen Komponenten miteinander verschmelzen. Durch das Auflösen der löslichen Komponenten entstehen Porenhohlräume, die dem Papiermaschinenband trotz der vorherigen Kompression und der hierdurch erzeugten hohen Dichte das für die Entwässerung benötigte Hohlraumvolumen geben.A development preceded the development described above the fibers of a paper machine felt store fibers or particles, which can be removed with the help of a solvent, compared to the other fibers and the carrier of the paper machine belt solvent resistant, d. H. is stable (DE-C-34 19 708). The production takes place in such a way that a Nonwoven fiber made of insoluble fibers and soluble components formed and needled onto the carrier and that then the paper machine belt is compressed under pressure and heat. You can fuse the soluble components together. By the dissolving of the soluble components creates pore cavities, the paper machine belt despite the previous compression and the resulting high density that for drainage give the required void volume.

Nachteilig bei dieser Lösung ist, daß trotz der Kompression die Haltbarkeit wesentlich geringer ist als mit kunststoffbeschichteten Trägern. Außerdem ist man für die Herstellung nach wie vor auf die hierfür üblichen Maschinen, insbesondere Webstühle und Nadelmaschinen, angewiesen.The disadvantage of this solution is that despite the compression Durability is much lower than with plastic-coated Carriers. Furthermore, one is like for the manufacture before the usual machines, especially looms and needle machines.

Es hat nicht an Versuchen gefehlt, Papiermaschinenbänder mit einem Träger und einer Durchgangskanäle aufweisenden Kunststoffschicht auf andere Weise herzustellen. So wird in der EP-B-0 037 387 eine Materialbahn vorgeschlagen, bei dem die Durchgangskanäle durch Perforierung einer zuvor aufgebrachten Kunststoffolie mittels einer Lasereinrichtung erzeugt werden. Abgesehen davon, daß die Durchgangskanäle keine Verbindung untereinander haben, ein Gas- oder wasserdurchtritt also quer zur Ebene der Materialbahn nicht erfolgen kann, ist auch die Herstellung dieser Bahn außerordentlich aufwendig, insbesondere dann, wenn größere Flächen mittels der Lasereinrichtung bearbeitet werden müssen, wie dies bei Papiermaschinenbändern der Fall ist. Außerdem sind Folien in der erforderlichen Breite und mit ausreichender Gleichmäßigkeit nicht herstellbar.There has been no shortage of attempts to use paper machine belts a carrier and a plastic layer having through-channels to manufacture in a different way. So in the EP-B-0 037 387 proposed a material web in which the Through channels by perforating a previously applied one Plastic film generated by means of a laser device become. Apart from the fact that the through channels are none Have connection with each other, a gas or water passage thus not across the plane of the material web can, the production of this track is extraordinary complex, especially when larger areas by means of the laser device must be processed, as is the case with Paper machine belts is the case. There are also slides in the required width and with sufficient uniformity not produceable.

In der WO 86/05219 ist ein Verfahren zur Herstellung eines Papiermaschinenbandes offenbart, bei dem ein Polymermaterial, vermischt mit löslichen Teilchen, in plastifizierter Form auf ein Stachelband unter Bildung einer Kunststoffschicht aufgetragen wird. Zum Aushärten dieser Kunststoffschicht und/oder zum Herauslösen der lösbaren Teilchen kann die Kunststoffschicht einer Nachbehandlung mit Wärme unterzogen werden. Nach dem Abziehen des Polymerbandes lassen die Stacheln des Stachelbandes konische Durchgangslöcher zurück. Das Polymermaterial kann auch mit einer Verstärkungsstruktur in Form von Fasern, Fäden oder Geweben versehen sein.WO 86/05219 describes a method for producing a Paper machine belt disclosed in which a polymer material, mixed with soluble particles, in plasticized Form on a barbed tape to form a plastic layer is applied. For curing this plastic layer and / or to remove the detachable particles the plastic layer is subjected to a post-treatment with heat become. Leave after peeling off the polymer tape the spines of the barbed conical through holes back. The polymer material can also have a reinforcing structure provided in the form of fibers, threads or fabrics his.

In der WO 91/14558 wird vorgeschlagen, die Durchgangskanäle dadurch zu erzeugen, daß auf die noch nicht gehärtete Kunststoffschicht eine Lochmaske aufgelegt und diese dann bestrahlt wird. Aufgrund dieser Bestrahlung härtet das Kunststoffmaterial im Bereich der Löcher der Maske aus. Nach Wegnahme der Lochmaske wird dann das noch nicht ausgehärtete Kunststoffmaterial mittels Preßluft entfernt. Auch dieses Verfahren ist aufwendig und hinterläßt relativ große freie Bereiche und kann deshalb nicht universell angewendet werden. Außerdem fällt auch hier zu entsorgender oder aufzubereitender Abfall an.WO 91/14558 proposes the through-channels by producing that on the not yet hardened Put on a shadow mask and then this is irradiated. This hardens due to this radiation Plastic material in the area of the holes of the mask. After removing the shadow mask, the not yet hardened is then Plastic material removed using compressed air. Also this process is complex and leaves relatively large free areas and therefore cannot be used universally become. In addition, waste to be disposed of or reprocessed also falls here Waste.

Einen konzeptionell anderen Weg ist man bei dem Vorschlag gemäß der EP-B-0 187 967 gegangen. Hier wird bei einem Papiermaschinenband eine poröse Kunststoffschicht auf einem Träger dadurch erzeugt, daß lose Partikel eines synthetischen Polymerharzes in der Größenordnung von 0,15 bis 5 mm auf der Oberfläche eines Trägergewebes verteilt und dann einer Wärmebehandlung unterzogen werden, bei dem die Polymerharzpartikel über den Erweichungspunkt hinaus erhitzt werden, so daß sie an ihren Berührungsstellen untereinander und mit dem Trägergewebe verschmelzen. Stattdessen oder in Kombination damit kann auch die Aufbringung eines harzförmigen Bindemittels vorgesehen sein. Alternativ zu den Partikeln können auch lose Fasern auf dem Trägergewebe verteilt werden. Nach dem Anhaften der Partikel bzw. Fasern untereinander und an dem Trägergewebe verbleiben Freiräume, die die Kunststoffschicht flüssigkeitsdurchlässig machen.There is a conceptually different approach to the proposal according to EP-B-0 187 967. Here is a paper machine belt a porous plastic layer on one Carrier produced in that loose particles of a synthetic Polymer resin in the order of 0.15 to 5 mm spread on the surface of a base fabric and then undergo a heat treatment in which the polymer resin particles heated beyond the softening point be so that they touch each other at their points of contact and fuse with the base fabric. Instead or in Combination with this can also apply a resinous Binder may be provided. As an alternative to the particles can also have loose fibers on the base fabric be distributed. After the particles or fibers have adhered free spaces remain among one another and on the carrier fabric, that make the plastic layer permeable to liquids.

Ähnliches wird in der EP-A-0 653 512 vorgeschlagen, nur daß hierbei die Materialbahn zunächst ausschließlich aus Polymerpartikeln hergestellt wird, die durch Hitzeeinwirkung an ihren Kontaktstellen miteinander verbunden werden. Soweit erforderlich, kann eine Verstärkungsstruktur nach Art einer Armierung vollständig in das so gebildete Band eingelagert werden. Hierbei kann es sich um ein reines Faserprodukt oder um ein Gewebe handeln. Die Partikel können auch unterschiedlichen Durchmesser haben, um eine von der einen zur anderen Seite hin zunehmende Durchlässigkeit zu erzeugen.Similar things are proposed in EP-A-0 653 512, only that The material web initially consists exclusively of polymer particles is produced by exposure to heat at their contact points be connected to each other. If necessary can complete a reinforcement structure like a reinforcement be stored in the band thus formed. Here it can be a pure fiber product or a fabric. The particles can also have different diameters have one increasing from one side to the other To create permeability.

Der Nachteil der nach diesem Prinzip hergestellten Materialbahnen liegt darin, daß es sehr schwierig ist, sie reproduzierbar herzustellen, insbesondere was die Durchlässigkeit angeht. Außerdem ist ihre Oberfläche sehr uneben, weshalb die gleichzeitige Anwendung von Druck und Hitze - soweit die Partikel aus Fasern ausgebildet sind (EP-B-0 187 967) - oder ein Schleifvorgang (EP-A-0 653 512) zwecks Einebnung der Oberfläche vorgeschlagen werden.The disadvantage of the material webs produced according to this principle is that it is very difficult to reproduce them to manufacture, especially in terms of permeability. In addition, their surface is very uneven, which is why the simultaneous Application of pressure and heat - as far as the particles are made Fibers are formed (EP-B-0 187 967) - or a grinding process (EP-A-0 653 512) for the purpose of leveling the surface become.

Nach der WO 95/21285 wird eine Polymerbeschichtung mit Hilfe einer Abziehfolie unter gleichzeitiger Einwirkung von Hitze und Druck auf einen Träger aufgebracht, wobei sich der Polymerfilm aufgrund der Hitzeeinwirkung auf der Abziehfolie zu zusammenhängenden Tropfen unter Bildung von Freiräumen ausformt mit der Folge, daß die auf den Träger aufgebrachte Kunststoffschicht porös ist. Auch bei diesem Verfahren ist es schwierig, die Durchlässigkeit der Kunststoffschicht reproduzierbar einzustellen und den jeweiligen Erfordernissen anzupassen. Außerdem stehen Folien in der hier erforderlichen Breite nicht zur Verfügung und wären auch nicht mit ausreichender Gleichmäßigkeit herstellbar. According to WO 95/21285, a polymer coating is made using a peel film under the simultaneous exposure to heat and Pressure applied to a support, the polymer film due to the heat on the peel-off film Drops forming free spaces with the Consequence that the plastic layer applied to the carrier is porous. It is also difficult with this method Permeability of the plastic layer can be set reproducibly and adapt to the respective requirements. Also stand Foils in the width required here are not available and would also not be able to be produced with sufficient uniformity.

Der Erfindung liegt die Aufgabe zugrunde, ein Verfahren zur Herstellung einer Materialbahn der eingangs genannten Art bereitzustellen, mit dem sich eine gewünschte Verteilung der löslichen Teilchen innerhalb der Kunststoffschicht erzielen läßt. Eine weitere Aufgabe besteht darin, das Verfahren so zu gestalten, daß sich die löslichen Teilchen auf einfache Weise aus der Kunststoffschicht herauslösen lassen.The invention has for its object a method for manufacturing to provide a material web of the type mentioned at the outset, with which a desired distribution of the soluble Can achieve particles within the plastic layer. A another task is to design the process so that the soluble particles are easily removed from the Let out the plastic layer.

Diese Auffabe wird erfindungsgemäß dadurch gelöst, daß als Kunststoffmaterial ein Kunststoffpulver bereitgestellt wird, das mit den löslichen Teilchen vermischt und auf den Träger aufgetragen wird, und daß durch Wärme- und Druckbehandlung aus der Mischung aus Kunststoffpulver und löslichen Teilchen eine Kunststoffschicht mit den darin befindlichen löslichen Teilchen erzeugt wird, bevor die löslichen Teilchen zumindest teilweise aus der Kunststoffschicht herausgelöst werden.This object is achieved in that as Plastic material a plastic powder is provided that mixes with the soluble particles and applied to the carrier and that by heat and pressure treatment from the Mixture of plastic powder and soluble particles a plastic layer generated with the soluble particles contained therein is before the soluble particles at least partially be detached from the plastic layer.

Durch die Herstellung einer zunächst pulverförmigen Mischung kann eine außerordentlich gleichmäßige Verteilung der löslichen Teilchen innerhalb des Kunststoffmaterials erreicht werden. Diese Verteilung ändert sich auch nicht beim oder nach dem Auftrag des Pulvers. Das Kunststoffpulver lädt sich nämlich elektrostatisch derart auf, daß die vermischten Pulverteilchen aus Kunststoff und löslichen Teilchen aneinander haften und deshalb ihre Lage nicht verändern. Es kommt somit nicht zu Entmischungsproblemen. Die anschließende Wärmebehandlung (Sintern) läßt aus der Pulverschicht eine durchgehende Kunststoffschicht entstehen. Dabei wird das Kunststoffpulver soweit plastifiziert wird, daß eine homogene, d. h. bis auf die löslichen Teilchen im wesentlichen porenlose Kunststoffschicht entsteht, die an dem Träger haftet. Dies wird durch die Druckbehandlung, die zudem für eine außenseitig ebene Oberfläche sorgt, unterstützt. Die Wärmebehandlung kann dabei in einem Heizofen oder unter Infrarotstrahlern erfolgen. Die Druckbehandlung kann anschließend in einem Kalander oder dergleichen durchgeführt werden. By producing an initially powdery mixture can be an extremely even distribution of soluble Particles within the plastic material can be reached. This distribution does not change either during or after the order of the powder. The plastic powder is charged electrostatically such that the mixed powder particles Plastic and soluble particles stick together and therefore do not change their position. There are therefore no segregation problems. The subsequent heat treatment (sintering) leaves out a continuous plastic layer is created in the powder layer. The plastic powder is plasticized as far as that a homogeneous, d. H. except for the soluble particles essentially pore-free plastic layer that forms on the support is liable. This is due to the pressure treatment, which is also for a flat surface on the outside provides support. The heat treatment can be in a heating oven or under infrared radiators respectively. The pressure treatment can then in a calender or the like.

Die Korngröße der Teilchen des Kunststoffpulvers und auch die der löslichen Teilchen sowie deren Mischungsverhältnis kann je nach Anforderung in weiten Grenzen so eingestellt werden, daß sich eine gewünschte Struktur der Kunststoffschicht ergibt, insbesondere was die nach dem Herauslösen der löslichen Teilchen ergebenden Hohlräume der Durchgangskanäle betrifft. Vorzugsweise sollten die löslichen Teilchen einen mittleren Durchmesser von 30 bis 50 µm haben. Die mittlere Korngröße des Kunststoffpulvers sollte geringer sein als die der löslichen Teilchen, zweckmäßigerweise nur die Hälfte bis ein Drittel der der löslichen Teilchen betragen und keinesfalls mehr als 100 µm sein. Auf diese Weise werden die löslichen Teilchen von einer Mehrzahl oder sogar Vielzahl von Teilchen des Kunststoffpulvers praktisch ummantelt, und es entsteht eine relativ dichte Pakkung.The grain size of the particles of the plastic powder and also the the soluble particles and their mixing ratio can each can be set within wide limits as required so that a desired structure of the plastic layer results, in particular what about after the soluble particles have been extracted resulting cavities of the through channels. Preferably the soluble particles should have an average diameter from 30 to 50 µm. The average grain size of the plastic powder should be less than that of the soluble particles, expediently only half to a third of the soluble Particles are and in no case be more than 100 microns. In this way the soluble particles become a plurality or even a variety of particles of plastic powder practically encased, and there is a relatively tight package.

Das Volumenverhältnis zwischen Kunststoffpulver und löslichen Teilchen sollte dabei zweckmäßigerweise so eingestellt werden, daß die löslichen Teilchen nicht nur in Richtung quer zur Ebene der Kunststoffschicht, sondern auch in der Ebene der Kunststoffschicht zumindest teilweise aneinanderliegen, damit auch in der Ebene der Kunststoffschicht offene Poren und damit Entwässerungsvolumen zur Verfügung gestellt und damit das Wasseraufnahmevermögen verbessert wird.The volume ratio between plastic powder and soluble Particles should expediently be set so that that the soluble particles are not just in the cross-plane direction the plastic layer, but also in the plane of the plastic layer lie at least partially against each other, so that also in the Level of the plastic layer open pores and thus drainage volume provided and thus the water absorption capacity is improved.

Das Volumenverhältnis zwischen Kunststoffpulver und löslichen Teilchen liegt zweckmäßigerweise im Bereich zwischen 1/4:3/4 und 1/2:1/2, vorzugsweise im Bereich 2/3:1/3.The volume ratio between plastic powder and soluble Particles are expediently in the range between 1/4: 3/4 and 1/2: 1/2, preferably in the range 2/3: 1/3.

Das Kunststoffpulver und die löslichen Teilchen können auch schichtweise aufgetragen werden, wobei für die Schichten unterschiedliche Korngrößen, Materialien und Mischungsverhältnisse vorgesehen sein können, um den jeweiligen Anforderungen Rechnung zu tragen. So können die löslichen Teilchen zum Träger hin schichtweise oder kontinuierlich größer werden. Alternativ oder in Kombination dazu kann auch die Anzahl der löslichen Teilchen zum Träger hin von Schicht zu Schicht zunehmen. Beide Maßnahmen dienen dazu, die Durchlässigkeit zum Träger hin größer werden zu lassen, wie dies insbesondere bei der Verwendung der Materialbahn im Formier- und Pressenbereich einer Papiermaschine erwünscht ist.The plastic powder and the soluble particles can also applied in layers, with different layers Grain sizes, materials and mixing ratios can be provided to account for the respective requirements to wear. So the soluble particles can go to the carrier grow in layers or continuously. Alternatively or in combination can also the number of soluble particles increase from layer to layer towards the carrier. Both measures serve to increase the permeability to the wearer to let this be particularly so when using the web of material desirable in the forming and press area of a paper machine is.

Nach der Erfindung ist ferner vorgeschlagen, daß bei oder nach Erzeugung der Kunststoffschicht lösliche Partikel auf die Außenseite der Kunststoffschicht aufgebracht und dann in die Kunststoffschicht eingedrückt werden, wobei die löslichen Partikel durch ein solches Lösungsmittel herauslösbar sind, gegenüber dem das Kunststoffmaterial beständig ist, und daß danach diese löslichen Partikel herausgelöst werden. Durch dieses Verfahren werden auf der Außenseite der Kunststoffschicht deren Rauhigkeit erhöhende Einprägungen erzeugt, was insbesondere bei Verwendung der Materialbahn als Papiermaschinenband von Vorteil ist. Hierdurch wird nämlich der Neigung der Papierbahn, an dem Papiermaschinenband zu sehr haften zu bleiben, entgegengewirkt, ohne daß Markierungen hervorgerufen werden. Die Papierbahn löst sich wesentlich problemloser von dem Papiermaschinenband als bei vorbekannten Ausführungen gleicher Gattung, wie sie aus der EP-B-0 196 045 und EP-B-0 273 613 bekannt sind. Die Einprägungen haben dabei durch ihre Verteilung im Verhältnis zu den öffnungen der Durchgangskanäle eine solch geringe Größe, daß genügend Kontaktfläche zur Papierbahn verbleibt, um eine gleichmäßige Abstützung und Druckübertragung zu ermöglichen. Die Durchgangskanäle und die Einprägungen haben zudem zur Folge, daß die Rückbefeuchtung der Papierbahn gering ist.According to the invention it is further proposed that at or after Generation of the plastic layer of soluble particles on the outside applied the plastic layer and then into the plastic layer are pressed in, the soluble particles are removable by such a solvent which the plastic material is stable, and that after that soluble particles can be removed. Through this procedure are the roughness on the outside of the plastic layer Increasing embossing creates what especially when used the material web as a paper machine belt is an advantage is. This is because the inclination of the paper web on the Paper machine tape to stick too much, counteracted, without causing markings. The paper web loosens itself much more easily from the paper machine belt than in known versions of the same genus, as from the EP-B-0 196 045 and EP-B-0 273 613 are known. The impressions have by their distribution in relation to the openings the through channels are so small that sufficient Contact area to the paper web remains to be even Allow support and pressure transfer. The through channels and the impressions also have the consequence that the Remoistening of the paper web is low.

Die Vorzüge der erfindungsgemäß aufgerauhten Oberfläche der Kunststoffschicht ist jedoch auf den Einsatz in Papiermaschinen nicht beschränkt. Auch bei Filtermitteln kann eine zu glatte Oberfläche zu einer so starken Anhaftung des abgeschiedenen Materials führen, daß dessen Abreinigung erschwert wird. The advantages of the roughened surface of the invention Plastic layer, however, is for use in paper machines not limited. Filter media can also be too smooth Surface to such a strong adhesion of the deposited material cause its cleaning is difficult.

Ein weiterer Vorzug dieser Verfahrensweise besteht darin, daß durch das Eindrücken der löslichen Partikel dort, wo die löslichen Teilchen an der Außenseite oberflächennah vorhanden sind, eine Verbindung zu diesen hergestellt wird. Nach dem Herauslösen der löslichen Partikel hat das Lösungsmittel Zugang zu den in der Kunststoffschicht zunächst eingeschlossenen löslichen Teilchen und kann deshalb auch diese vollständig auflösen und entfernen. Die Einprägungen bilden danach insoweit die öffnungen der Durchgangskanäle. Das Verfahren ersetzt damit die Schleifbehandlung gemäß der EP-B-0 273 613.Another advantage of this procedure is that by indenting the soluble particles where the soluble particles Particles are present on the outside near the surface, a connection to these is established. After detaching The solvent has access to the soluble particles soluble soluble initially enclosed in the plastic layer Particles and can therefore also completely dissolve them remove. The impressions then form the openings of the through channels. The procedure thus replaces the Grinding treatment according to EP-B-0 273 613.

Besonders vorteilhaft ist es, wenn die löslichen Partikel in einer solche Dichte auf die Kunststoffschicht aufgetragen werden, daß die nach dem Herauslösen verbleibenden Einprägungen zumindest teilweise untereinander und mit den Durchgangskanälen in Verbindung stehen. Diese Gestaltung wirkt sich besonders beim Einsatz als Papiermaschinenband günstig für die Entwässerung aus.It is particularly advantageous if the soluble particles in such a density are applied to the plastic layer, that at least the impressions remaining after removal partly with each other and with the through channels stay in contact. This design is particularly effective when used as a paper machine belt cheap for drainage out.

Die löslichen Partikel sollten vorzugsweise bei einer Temperatur der Kunststoffschicht in diese eingedrückt werden, bei der die Kunststoffschicht gegenüber dem Zustand per Raumtemperatur erweicht ist. Dies kann dadurch geschehen, daß die löslichen Partikel im Anschluß an die Erzeugung der Kunststoffschicht bei noch erhöhter Temperatur aufgebracht und eingedrückt werden. Das Eindrücken kann durch eine Kalanderbehandlung durchgeführt werden. Vorzugsweise sollten die löslichen Partikel einen mittleren Durchmesser von 5 bis 100 µm haben.The soluble particles should preferably be at a temperature the plastic layer can be pressed into this the plastic layer compared to the condition at room temperature is softened. This can be done in that the soluble Particles following the creation of the plastic layer applied at an even higher temperature and pressed in. The pressing can be done by a calender treatment become. Preferably the soluble particles should be a medium one Have a diameter of 5 to 100 µm.

Um den Vorzug des Herauslösens der löslichen Teilchen und der löslichen Partikel zu vereinfachen, sollten beide aus demselben Material bestehen, so daß das Herauslösen in einem Arbeitsgang unter Verwendung desselben Lösungsmittels erfolgen kann. Für die in der Kunststoffschicht enthaltenen löslichen Teilchen sollten solche Substanzen gewählt werden, die unter der Hitzeeinwirkung der Erzeugung der Kunststoffschicht im wesentlichen formbeständig bleiben. Hierfür kommen polymere Teilchen in Frage, die eine höhere Hitzebeständigkeit haben als die der Kunststoffmatrix, in die die löslichen Teilchen eingelagert sind. Zweckmäßigerweise sollten diese Bedingungen auch hinsichtlich der in die Außenseite der Kunststoffschicht eingedrückten löslichen Partikel gegeben sein. Für die Anwendung besonders günstig sind jedoch anorganische Substanzen und hier insbesondere wasserlösliche Salze wie NaCl, KCl und/oder CaCO3 sowie Chloride, Carbonate und/oder lösliche Sulfate der Alkali- oder Erdalkalielemente oder der Metalle sowie auch solche Salze, die sich zusätzlich noch aus der DE-C-34 19 708 ergeben. Solche löslichen Partikel bzw. Teilchen werden durch die für die Bildung der Kunststoffschicht notwendige Wärmebehandlung nicht beeinträchtigt und sind gut riesel- und damit streufähig. In Frage kommen aber auch organische Substanzen, z. B. Kohlehydrate (Zucker), oder Salze organischer Säuren, wie Zitronensäure, Ascirbinsäure etc. Dem Kunststoffpulver sollte zusätzlich ein Antioxidanz zugesetzt werden.In order to simplify the preference of removing the soluble particles and the soluble particles, both should be made of the same material so that the removal can be done in one operation using the same solvent. For the soluble particles contained in the plastic layer, those substances should be selected which remain essentially dimensionally stable under the heat effect of the production of the plastic layer. For this purpose polymeric particles come into question which have a higher heat resistance than that of the plastic matrix in which the soluble particles are embedded. These conditions should expediently also apply to the soluble particles pressed into the outside of the plastic layer. However, inorganic substances and in particular water-soluble salts such as NaCl, KCl and / or CaCO 3, as well as chlorides, carbonates and / or soluble sulfates of the alkali or alkaline earth elements or of the metals, and also such salts, which are additionally advantageous, are particularly favorable for use the DE-C-34 19 708 result. Such soluble particles or particles are not adversely affected by the heat treatment necessary for the formation of the plastic layer and are easy to pour and therefore scatterable. Organic substances, e.g. B. carbohydrates (sugar), or salts of organic acids, such as citric acid, ascirbic acid etc. An additional antioxidant should be added to the plastic powder.

In weiterer Ausgestaltung der Erfindung ist vorgesehen, daß lösliche Teilchen aus wenigstens zwei Substanzen verwendet werden, wobei jeweils eine der Substanzen durch ein Lösungsmittel herauslösbar ist, gegenüber dem die jeweils andere(n) Substanz(en) beständig ist bzw. sind. Dies eröffnet die Möglichkeit, zunächst nur einen Teil der löslichen Komponenten herauszulösen und dann nach Installation der Materialbahn und einer gewissen Betriebszeit einmal oder mehrmals eine Gruppe weiterer löslicher Teilchen herauszulösen und damit die anfängliche Durchlässigkeit der Materialbahn wiederherzustellen, wenn die Durchlässigkeit im Betrieb durch Verschmutzung etc. nachgelassen hat. Dieser Gedanke ist grundsätzlich schon der EP-A-0 303 798 und der EP-A-0 320 559 zu entnehmen, in denen der Einsatz löslicher Fasern innerhalb eines Filzes vorgeschlagen worden ist. Es versteht sich, daß diese löslichen Teilchen gegenüber den Einsatzbedingungen, für die die Materialbahn bestimmt ist, beständig sein muß, d. h. im Fall des Einsatzes als Papiermaschinenband gegenüber den aus der Papierbahn kommenden Flüssigkeiten oder Dämpfen. Alternativ dazu kann vorgesehen sein, daß sich die löslichen Teilchen nur verzögert und sukzessiv aus der Matrix herauslösen lassen.In a further embodiment of the invention it is provided that soluble particles of at least two substances are used, each one of the substances by a solvent is removable, against which the other substance (s) is or are stable. This opens up the possibility first remove only part of the soluble components and then after installing the web and one one group or several times during certain operating times soluble particles and thus the initial To restore permeability of the material web when the Permeability in operation decreased due to contamination etc. Has. This idea is basically that EP-A-0 303 798 and EP-A-0 320 559 in which the use of soluble fibers within a felt is suggested has been. It is understood that these soluble particles compared to the conditions of use for which the material web is intended is, must be constant, d. H. in case of use as Paper machine belt compared to those coming from the paper web Liquids or vapors. Alternatively, can be provided be that the soluble particles are only delayed and successive let out of the matrix.

Nach der Erfindung ist ferner vorgesehen, daß auf der anderen Seite des Trägers eine zweite Kunststoffschicht mit Durchgangskanälen auf die gleiche Weise wie auf der einen Seite erzeugt wird. Dabei sollte die Anzahl und/oder Größe der löslichen Teilchen in der zweiten Kunststoffschicht vom Träger weggerichtet zunehmen, und es sollte die Anzahl und/oder Größe der löslichen Teilchen in den dem Träger benachbarten Bereichen beider Kunststoffschicht gleich groß sein. Es versteht sich, daß auch andere Verteilungen möglich sind, wenn dies für den vorgesehenen Einsatz zweckmäßiger ist. Selbstverständlich kann die Außenseite der zweiten Kunststoffschicht gleichfalls in der schon oben beschriebenen Weise mit Einprägungen versehen sein, die durch Eindrücken von löslichen Partikeln erzeugt werden.According to the invention it is further provided that on the other Side of the carrier a second plastic layer with through channels created in the same way as on one side becomes. The number and / or size of the soluble particles should be considered facing away from the carrier in the second plastic layer increase, and it should be the number and / or size of soluble Particles in the areas of both plastic layers adjacent to the carrier be the same size. It is understood that others too Distributions are possible if this is for the intended Use is more appropriate. Of course, the outside the second plastic layer also in the already be described above with impressions that be generated by pressing in soluble particles.

Der Träger der erfindungsgemäßen Materialbahn hat die Aufgabe, der Materialbahn im wesentlichen allein Form- und Strukturfestigkeit zu geben und ggf. Längs- und Querkräfte aufzunehmen. Außerdem sollte der flüssigkeitsdurchlässig sein. Hierzu eignen sich insbesondere aus Fäden gebildete Textilträger, wie beispielsweise Fadengelege, Gestricke, Gewirke, Gewebe oder Kombinationen solcher Textilträger. Je nach Einsatzgebiet und Ansprüchen an die Festigkeit kann der Träger ein- oder mehrlagig aufgebaut sein. Im Fall eines Trägergewebes kommen alle Gewebearten in Frage, insbesondere solche, die aus dem Bereich der Papiermaschinenbänder bekannt sind. Für die Fäden sind sowohl Monofilamente als auch Multifilamente aus vorzugsweise thermoplastischen Kunststoffmaterialien einsetzbar. Der Träger kann alternativ oder in Kombination dazu ein Spinnfaservlies und/oder eine gestanzte oder extrudierte Netzstruktur aufweisen. Er kann darüberhinaus mit einem Faservlies versehen sein, so daß er Filzcharakter hat. The carrier of the material web according to the invention has the task the material web essentially only has dimensional and structural strength to give and if necessary absorb longitudinal and transverse forces. In addition, the should be permeable to liquids. Suitable for this textile supports formed in particular from threads, such as, for example Threads, knitted fabrics, knitted fabrics, fabrics or combinations such textile carrier. Depending on the area of application and requirements the carrier can have one or more layers of strength be constructed. In the case of a base fabric, all types of fabric come in question, especially those from the field of Paper machine tapes are known. For the threads are both Monofilaments as well as multifilaments made of preferably thermoplastic Plastic materials can be used. The carrier can alternatively or in combination, a spunbonded nonwoven and / or have a punched or extruded network structure. It can also be provided with a fleece, so that it has a felt character.

Als Materialien für den Träger eignen sich Kunststoffe, wie sie insbesondere aus dem Bereich der Papiermaschinenbänder bekannt und in den oben erwähnten Dokumenten genannt sind. Die Auswahl des Kunststoffs kann an den jeweiligen Einsatzzweck und die dort vorherrschenden Bedingungen angepaßt werden. Insbesondere sollten solche Kunststoffe ausgewählt werden, die bei der Erzeugung der Kunststoffschicht und der damit verbundenen Hitzeeinwirkung keine Beeinträchtigungen erleiden.Plastics such as these are suitable as materials for the carrier especially known from the field of paper machine tapes and are mentioned in the documents mentioned above. The selection The plastic can be used for the respective purpose and prevailing conditions there are adapted. In particular such plastics should be selected that are used in the production the plastic layer and the associated heat do not suffer any impairments.

Für die Kunststoffschicht eignen sich Polyamide, wie Polyamid 4.6, 6, 6.6, 6.10, 6.12, 11 und 12 sowie thermoplastische aromatische Polyamide. Darüberhinaus können auch Polyester, Polyphenylensulfid, Polyetheretherketon, Polyurethan, Polysylfone, Polyphthalamide und Polypropylene zum Einsatz kommen. Es kommen jedoch auch andere polymere und elastomere Kunststoffe in Frage, wie sie sich beispielsweise der EP-B-0 196 045 und EP-B-0 273 613 entnehmen lassen. Es können auch Mischungen von verschiedenen Kunststoffen verwendet werden, beispielsweise mit unterschiedlichem elastischen Vermögen, wobei die Kunststoffschicht auch aus Schichten bestehen kann, die aus Kunststoffen mit unterschiedlichem elastischem Vermögen bestehen. Insoweit kann die Auswahl der Kunststoffe und deren elastischen Eigenschaften an den jeweiligen Einsatzzweck ebenfalls angepaßt werden.Polyamides, such as polyamide, are suitable for the plastic layer 4.6, 6, 6.6, 6.10, 6.12, 11 and 12 as well as thermoplastic aromatic Polyamides. In addition, polyester, polyphenylene sulfide, Polyether ether ketone, polyurethane, polysyl phones, Polyphthalamides and polypropylenes are used. Coming however also other polymeric and elastomeric plastics in Question how they are, for example, EP-B-0 196 045 and Have EP-B-0 273 613 removed. Mixtures of various plastics are used, for example with different elastic assets, the plastic layer can also consist of layers made of plastics with different elastic assets. So far can the selection of plastics and their elastic properties can also be adapted to the respective application.

In der Zeichnung ist die Erfindung anhand eines stark vergrößert dargestellten Ausführungsbeispiels näher veranschaulicht. Sie zeigt im Querschnitt einen Ausschnitt aus einer Materialbahn 1. Die Materialbahn 1 hat einen Träger 2, der mit Längsfaden 3 und Querfaden 4 als Gewebe ausgebildet ist. Auf der Ober- und Unterseite des Trägers 2 befindet sich jeweils eine Kunststoffschicht 5, 6.In the drawing, the invention is greatly enlarged on the basis of a illustrated embodiment illustrated in more detail. It shows a section of a section of a material web 1. The material web 1 has a carrier 2, the longitudinal thread 3 and cross thread 4 is formed as a fabric. On the upper and the underside of the carrier 2 is each a plastic layer 5, 6.

Die erste Kunststoffschicht 5 ist entsprechend dem erfindungsgemäßen Verfahren dadurch hergestellt worden, daß eine Mischung aus einem Kunststoffpulver und löslichen Teilchen auf den Träger 2 aufgestreut und beides zusammen einer Wärme- und Druckbehandlung unterzogen worden ist. Hierdurch ist eine homogene Kunststoffschicht 5 mit darin im wesentlichen gleichmäßig verteilten löslichen Teilchen erzeugt worden, wobei sich aufgrund der Druckbehandlung eine ebene Außenfläche ergeben hat. Auf die noch erhitzte und deshalb plastisch gut verformbare Außenseite 7 der Kunststoffschicht 5 sind dann weitere lösliche Partikel aufgestreut und anschließend mittels Druckwalzen oder dergleichen in die Kunststoffschicht 5 eingedrückt worden. In entsprechender Weise ist mit der unteren Kunststoffschicht 6 verfahren worden, insbesondere in Bezug auf die Behandlung von deren Außenseite 8.The first plastic layer 5 is in accordance with the invention Process prepared by using a mixture from a plastic powder and soluble particles on the carrier 2 sprinkled and both together a heat and pressure treatment has undergone. This is a homogeneous Plastic layer 5 with substantially evenly distributed therein soluble particles have been generated, due to the pressure treatment has resulted in a flat outer surface. On the still heated and therefore plastically easily deformable outside 7 of the plastic layer 5 are then further soluble particles sprinkled and then by means of pressure rollers or the like has been pressed into the plastic layer 5. In corresponding The procedure is with the lower plastic layer 6 , especially with regard to the treatment of their Outside 8.

Danach ist die Materialbahn 1 einer Behandlung mit einem Lösungsmittel für die löslichen Partikel und Teilchen unterzogen worden. Bei dieser Behandlung haben sich zunächst die in die Außenseiten 7, 8 der Kunststoffschichten 5, 6 eingedrückten löslichen Partikel aufgelöst und dabei Einprägungen - beispielhaft mit 9 bezeichnet - hinterlassen. Diese Einprägungen 9 haben zumindest teilweise nicht nur untereinander, sondern auch Verbindung zu den den Außenseiten 7, 8 naheliegenden löslichen Teilchen der Kunststoffschichten 5, 6 geschaffen, so daß das Lösungsmittel auch diese Teilchen erreicht und auflöst. Die Auflösung hat zur Folge, daß in den Kunststoffschichten 5, 6 Porenhohlräume - beispielhaft mit 10 bezeichnet - entstehen, welche die Formgebung des jeweils herausgelösten Teilchen haben und untereinander in Verbindung stehen. Dabei ist eine Verbindung nicht nur in vertikaler Richtung gegeben, sondern aufgrund der gleichmäßigen Verteilung der löslichen Teilchen auch in horizontaler Richtung. Damit ist eine Porenstruktur vorhanden, die einem offenporigen Kunststoffschaum ähnelt, wobei sich die Porenhohlräume 10 zu Durchgangskanälen ergänzen.Thereafter, the material web 1 is a treatment with a solvent subjected to the soluble particles and particles been. With this treatment, those in the Outside 7, 8 of the plastic layers 5, 6 indented soluble Particles dissolved and impressions - exemplary designated 9 - leave. These impressions 9 have at least sometimes not only with each other, but also connection to the soluble particles close to the outer sides 7, 8 the plastic layers 5, 6 created so that the solvent these particles are also reached and dissolved. The resolution has the consequence that 5, 6 pore cavities in the plastic layers - exemplified with 10 - arise, which have the shape of the particle detached and communicate with each other. There is a connection not only given in the vertical direction, but due to the even distribution of the soluble particles also in horizontal Direction. This creates a pore structure that resembles an open-pore plastic foam, with the Complement pore cavities 10 to form through channels.

Die Porenhohlräume 10 der obenseitigen Kunststoffschicht 5 sind zum Träger 2 hin größer als im Bereich der Außenseite 7. Dies läßt sich dadurch herstellen, daß zunächst eine Mischung aus Kunststoffpulver und relativ großen löslichen Teilchen und danach eine weitere Mischung aus Kunststoffpulver und demgegenüber kleineren löslichen Teilchen aufgetragen wird. Bei der untenseitigen Kunststoffschicht 6 ist ein Kunststoffpulver mit noch größeren löslichen Teilchen verwendet worden, so daß die Porenhohlräume 10 größer sind als die der obenseitigen Kunststoffschicht 3.The pore cavities 10 of the top plastic layer 5 are towards the carrier 2 larger than in the area of the outside 7. This can be prepared by first mixing Plastic powder and relatively large soluble particles and after another mixture of plastic powder and in contrast smaller soluble particles is applied. With the underside Plastic layer 6 is a plastic powder with even larger soluble particles have been used so that the Pore cavities 10 are larger than that of the plastic layer on the top 3rd

Claims (31)

  1. Process for the production of a web of material (1), wherein on at least one side of a backing (2) a plastics layer (5, 6) consisting of a mixture of plastics material and particulate soluble particles is produced and joined to the backing, the soluble particles being able to be dissolved out by a solvent against which the plastics material is resistant, and thereafter at least a proportion of the soluble particles are dissolved out from the plastics layer (5, 6) to form through-channels,
    characterised in that as the plastics material a polymer powder is prepared, which is blended with the soluble particles and applied to the backing (2), and that through heat and pressure treatment a plastics layer (5, 6) with the soluble particles present therein is produced from the mixture of polymer powder and soluble particles, before at least a proportion of the soluble particles are dissolved out of the plastics layer (5, 6).
  2. Process according to claim 1,
    characterised in that the polymer powder and the soluble particles are blended before being applied to the backing (2).
  3. Process according to claim 1 or 2,
    characterised in that the soluble particles have a mean diameter of 30 to 500 µm.
  4. Process according to either of claims 2 and 3,
    characterised in that the mean particle size of the polymer powder is smaller than that of the soluble particles.
  5. Process according to claim 4,
    characterised in that the mean particle size of the polymer powder is no greater than 100 µm.
  6. Process according to any of claims 1 to 5,
    characterised in that the polymer powder and the soluble particles are blended in a volumetric ratio of between 1/4:3/4 and 1/2:1/2.
  7. Process according to any of claims 1 to 6,
    characterised in that the polymer powder and the soluble particles are applied in a plurality of layers.
  8. Process according to any of claims 1 to 7,
    characterised in that the soluble particles become larger from layer to layer towards the backing (2).
  9. Process according to any of claims 1 to 8,
    characterised in that the number of soluble particles increases from layer to layer towards the backing (2).
  10. Process according to any of claims 1 to 9,
    characterised in that during or after the production of the plastics layer (5, 6), soluble particles are applied to the exterior (7, 8) of the plastics layer (5, 6) and then impressed into the plastics layer (5, 6), the soluble particles being able to be dissolved out by a solvent against which the plastics material (1) is resistant, and that thereafter these soluble particles are dissolved out.
  11. Process according to claim 10,
    characterised in that the soluble particles are applied to the plastics layer (5, 6) in a density such that at least some of the impressions (9) which remain after the dissolving-out operation communicate with one another and with the through-channels.
  12. Process according to claim 10 or 11,
    characterised in that the soluble particles are impressed into the plastics layer (5, 6) at a temperature of the latter at which the plastics layer (5, 6) has softened in relation to its state at room temperature.
  13. Process according to claim 12,
    characterised in that following the production of the plastics layer (5, 6), the soluble particles are applied and impressed at a still higher temperature.
  14. Process according to any of claims 10 to 13,
    characterised in that the soluble particles have a mean diameter of 5 to 100 µm.
  15. Process according to any of claims 10 to 14,
    characterised in that the soluble particles consist of the same material.
  16. Process according to any of claims 1 to 15,
    characterised in that inorganic substances are used for the soluble particles.
  17. Process according to claim 16,
    characterised in that salts such as NaCl, KCl and/or CaCo3 are used as the inorganic substances.
  18. Process according to any of claims 1 to 17,
    characterised in that organic substances or salts of organic acids are used for the soluble components and particles.
  19. Process according to any of claims 1 to 18,
    characterised in that antioxidants are added to the polymer powder.
  20. Process according to any of claims 1 to 19,
    characterised in that soluble particles composed of at least two substances are used, a respective one of the substances being able to be dissolved out by a solvent against which the respective other substance(s) is/are resistant.
  21. Process according to claims 1 to 20,
    characterised in that on the other side of the backing (2) a second plastics layer (6) with through-channels is produced in the same way as on the first side.
  22. Process according to claim 21,
    characterised in that the number of soluble particles in the second plastics layer (6) increases in the direction away from the backing.
  23. Process according to claim 21 or 22,
    characterised in that the size of the soluble particles in the second plastics layer (6) increases in the direction away from the backing (2).
  24. Process according to any of claims 21 to 23,
    characterised in that the number and/or size of the soluble particles in the regions of the two plastics layers (5, 6) that adjoin the backing (2) is identical.
  25. Process according to any of claims 21 to 24,
    characterised in that a textile backing constituted by threads is used at least in part as the backing (2).
  26. Process according to claim 25,
    characterised in that a collection of threads, a knitted and/or a woven fabric and/or a combination of such textile backings is used as the textile backing.
  27. Process according to any of claims 1 to 26,
    characterised in that a spun-bonded tissue and/or a punched or extruded network structure is used at least in part as the backing.
  28. Process according to any of claims 1 to 27,
    characterised in that the backing is provided with a non-woven tissue.
  29. Process according to any of claims 1 to 28,
    characterised in that polyamide, polyester, polypropylene sulphite, polyether ether ketone, polyurethane, polysylphonene, polyphthalamide and/or polypropylene is used for the plastics layer (5, 6).
  30. Process according to any of claims 1 to 29,
    characterised in that a mixture of plastics materials of varying elastic capacity is used for the plastics layer (5, 6).
  31. Process according to any of claims 1 to 30,
    characterised in that the plastics layer (5, 6) is produced from layers with plastics materials of varying elastic capacity.
EP96101070A 1996-01-25 1996-01-25 Process for making a web of material Expired - Lifetime EP0786551B1 (en)

Priority Applications (24)

Application Number Priority Date Filing Date Title
PT96101070T PT786551E (en) 1996-01-25 1996-01-25 PROCESS FOR OBTAINING A BAND OF FLAT MATERIAL
ES96101070T ES2144163T3 (en) 1996-01-25 1996-01-25 PROCEDURE TO MANUFACTURE A BAND OF MATERIAL.
AT96101070T ATE189017T1 (en) 1996-01-25 1996-01-25 METHOD FOR PRODUCING A MATERIAL WEB
DE59604228T DE59604228D1 (en) 1996-01-25 1996-01-25 Process for the production of a material web
DK96101070T DK0786551T3 (en) 1996-01-25 1996-01-25 Method of manufacturing material web
EP96101070A EP0786551B1 (en) 1996-01-25 1996-01-25 Process for making a web of material
PL97322379A PL182279B1 (en) 1996-01-25 1997-01-17 Method of producing a web of material
PCT/EP1997/000214 WO1997027361A1 (en) 1996-01-25 1997-01-17 Process for the production of a web of material
EP97901544A EP0817887B1 (en) 1996-01-25 1997-01-17 Process for the production of a web of material
SK1299-97A SK279862B6 (en) 1996-01-25 1997-01-17 Process for the production of a web of material
CZ19972998A CZ287859B6 (en) 1996-01-25 1997-01-17 Process for the production of a web of material
AU15422/97A AU702029B2 (en) 1996-01-25 1997-01-17 Process for the manufacture of a strip material
TR97/01031T TR199701031T1 (en) 1996-01-25 1997-01-17 A process for the production of strip material.
CA002214003A CA2214003C (en) 1996-01-25 1997-01-17 Process for the manufacture of a strip material
SI9730088T SI0817887T1 (en) 1996-01-25 1997-01-17 Process for the production of a web of material
US08/913,809 US6017583A (en) 1996-01-25 1997-01-17 Process for the production of a web of material
KR1019970706657A KR100257804B1 (en) 1996-01-25 1997-01-17 Process for making a web of material
BR9704640A BR9704640A (en) 1996-01-25 1997-01-17 Process for producing a material strip
TW086100622A TW339383B (en) 1996-01-25 1997-01-21 Process for the manufacture of a strip material
MYPI97000234A MY119139A (en) 1996-01-25 1997-01-22 Process for the production of a web of material
ZA9700597A ZA97597B (en) 1996-01-25 1997-01-24 Process for the manufacture of a strip material.
MX9707251A MX9707251A (en) 1996-01-25 1997-09-23 Process for the production of a web of material.
NO19974422A NO311809B1 (en) 1996-01-25 1997-09-24 Method of manufacturing a web of materials
GR20010400003T GR3035184T3 (en) 1996-01-25 2001-01-02 Process for the production of a web of material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP96101070A EP0786551B1 (en) 1996-01-25 1996-01-25 Process for making a web of material

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EP0786551A1 EP0786551A1 (en) 1997-07-30
EP0786551B1 true EP0786551B1 (en) 2000-01-19

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EP97901544A Expired - Lifetime EP0817887B1 (en) 1996-01-25 1997-01-17 Process for the production of a web of material

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US (1) US6017583A (en)
EP (2) EP0786551B1 (en)
KR (1) KR100257804B1 (en)
AT (1) ATE189017T1 (en)
AU (1) AU702029B2 (en)
BR (1) BR9704640A (en)
CA (1) CA2214003C (en)
CZ (1) CZ287859B6 (en)
DE (1) DE59604228D1 (en)
DK (1) DK0786551T3 (en)
ES (1) ES2144163T3 (en)
GR (1) GR3035184T3 (en)
MX (1) MX9707251A (en)
MY (1) MY119139A (en)
NO (1) NO311809B1 (en)
PL (1) PL182279B1 (en)
PT (1) PT786551E (en)
SI (1) SI0817887T1 (en)
SK (1) SK279862B6 (en)
TR (1) TR199701031T1 (en)
TW (1) TW339383B (en)
WO (1) WO1997027361A1 (en)
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US6017583A (en) 2000-01-25
KR100257804B1 (en) 2000-06-01
CZ287859B6 (en) 2001-02-14
DE59604228D1 (en) 2000-02-24
EP0817887A1 (en) 1998-01-14
MX9707251A (en) 1998-08-30
GR3035184T3 (en) 2001-04-30
NO974422D0 (en) 1997-09-24
EP0817887B1 (en) 2000-11-02
AU702029B2 (en) 1999-02-11
SK279862B6 (en) 1999-04-13
PL322379A1 (en) 1998-01-19
DK0786551T3 (en) 2000-06-26
SI0817887T1 (en) 2001-02-28
NO974422L (en) 1997-09-24
TW339383B (en) 1998-09-01
PT786551E (en) 2000-06-30
ATE189017T1 (en) 2000-02-15
CA2214003C (en) 2000-11-21
MY119139A (en) 2005-04-30
TR199701031T1 (en) 1997-12-21
EP0786551A1 (en) 1997-07-30
WO1997027361A1 (en) 1997-07-31
SK129997A3 (en) 1998-06-03
CA2214003A1 (en) 1997-07-31
CZ299897A3 (en) 1997-12-17
ES2144163T3 (en) 2000-06-01
ZA97597B (en) 1997-08-04
KR19980703253A (en) 1998-10-15
NO311809B1 (en) 2002-01-28
PL182279B1 (en) 2001-12-31
AU1542297A (en) 1997-08-20
BR9704640A (en) 1998-06-09

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