EP2594691B1 - Method for producing a paper machine fabric and paper machine fabric - Google Patents

Method for producing a paper machine fabric and paper machine fabric Download PDF

Info

Publication number
EP2594691B1
EP2594691B1 EP20110189294 EP11189294A EP2594691B1 EP 2594691 B1 EP2594691 B1 EP 2594691B1 EP 20110189294 EP20110189294 EP 20110189294 EP 11189294 A EP11189294 A EP 11189294A EP 2594691 B1 EP2594691 B1 EP 2594691B1
Authority
EP
European Patent Office
Prior art keywords
layer
polymer
paper machine
fabric
carrier layer
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.)
Not-in-force
Application number
EP20110189294
Other languages
German (de)
French (fr)
Other versions
EP2594691A1 (en
Inventor
Walter Dr. Best
Kai Dr. Klopp
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.)
Heimbach GmbH and Co KG
Original Assignee
Heimbach GmbH and Co KG
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
Application filed by Heimbach GmbH and Co KG filed Critical Heimbach GmbH and Co KG
Priority to EP20110189294 priority Critical patent/EP2594691B1/en
Priority to CN2012104649604A priority patent/CN103112205A/en
Publication of EP2594691A1 publication Critical patent/EP2594691A1/en
Application granted granted Critical
Publication of EP2594691B1 publication Critical patent/EP2594691B1/en
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21F—PAPER-MAKING MACHINES; METHODS OF PRODUCING PAPER THEREON
    • D21F1/00—Wet end of machines for making continuous webs of paper
    • D21F1/0027—Screen-cloths
    • D21F1/0054—Seams thereof
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21F—PAPER-MAKING MACHINES; METHODS OF PRODUCING PAPER THEREON
    • D21F7/00—Other details of machines for making continuous webs of paper
    • D21F7/08—Felts
    • D21F7/083—Multi-layer felts

Definitions

  • the present invention relates to a method for producing a covering for a paper machine, in particular in the form of a Formiersiebes or a fabric for the press section of the paper machine, with a single- or multi-layer support layer and at least one side applied thereto porous polymer layer, and a papermachine fabric according to produced by such a method.
  • Paper machine clothing serves to form the paper webs on a paper machine, then to dewater mechanically and to further ensure the heat transfer to the drying cylinder.
  • the fabric must support the still fragile paper web when passing through the paper webs through the paper machine and ensure the most possible draft-free run.
  • the stock is sprayed through the headbox onto a sieve or between two sieves.
  • the aggregates of the Formier Anlagens withdraw water from the pulp continuously and increase the solids content to about 20%.
  • the one or even both paper surfaces come into close contact with the forming fabric, so that the fabric surface structure of the forming fabric on the adjacent surface of the paper webs can print, resulting in undesirable marking patterns on the paper surface.
  • paper machine clothing with the finest possible and structurally poor surfaces are desirable in order to minimize the above-described marking effects or to bring them to a level that they do not interfere at least during printing.
  • fillers are added to the pulp to recover whiteness and to adjust the specification, which tend to be flushed out as the water is removed.
  • the sieve meshes of conventional forming fabrics are comparatively coarse in relation to the diameters of the aforementioned filler particles, so that they can be washed away by the adjacent fabric, unless a fiber cake has built up by the mechanical retention of the forming fabric, which can retain these fillers. But even for the production of a good fiber cake fine Siebmaschen to form the initial fiber layer as the starting layer for the fiber cake are required.
  • press felts consist of a plastic carrier, which is occupied on one or both sides with at least one synthetic fiber fleece layer of the same or different fiber fineness.
  • the fibers are supplied in a Benadelungsrea as a nonwoven fabric needle machine and needled with needled needles in the structure of the plastic carrier.
  • the quality and structure of the needled nonwoven in particular its uniformity, also has an effect on the quality of the dewatering and the quality of the paper obtained.
  • scarcity of the needled press felt surface deteriorates the surface of the paper webs.
  • the loss of fibers due to wear and breakage can lead to problems, since these fibers can later find themselves in the paper web.
  • a method for coating a carrier web with a polymer layer is described.
  • a particulate polymeric resin material, a binder and a solvent are homogenized and knife-coated onto the carrier web.
  • the polymeric resin particles are made of polyethylene, polyurethane, especially polyether and polyester polyurethanes.
  • the binders are polyamides or polyamide resins, water being used as the solvent. After application of the above mixture, the water is evaporated again in a subsequent process step, whereby a provided with a polymer foam paper machine clothing is obtained.
  • the press felt has a single-layer or multi-layer base layer which is provided with a plastic, fiber-reinforced resin matrix layer.
  • This matrix layer comprises a polymer resin and uniformly distributed textile fibers and air channels as well as cavities.
  • the resin matrix consists for example of polyurethane polymers or polyvinyl chloride polymers and has thermoplastic properties.
  • the synthetic polymer layer contains, inter alia, polyolefins, polyurethanes, in particular polyether and polyester polyurethanes, and a polyamide- or polyimide-based binder resin.
  • polyolefins polyurethanes, in particular polyether and polyester polyurethanes
  • polyamide- or polyimide-based binder resin a polyamide- or polyimide-based binder resin.
  • the aforementioned paper machine clothing does not meet the requirements in all respects.
  • the applied polymer layers for some applications have too small a pore volume, which adversely affects the water absorbency.
  • the proportion of open pores is not always available at the desired height, but only such pores can absorb moisture from outside and drain the water through the structure.
  • the object of the present invention was therefore to provide an improved manufacturing process, with which papermachine clothing with a larger available pore volume, a higher proportion of open pores and an increased permeability are available.
  • the paper machine clothing should also meet the high mechanical requirements in terms of flexibility and elasticity, especially in terms of elastic recovery after compression and wear resistance.
  • the object is achieved by a method for producing a covering for a paper machine, in particular in the form of a forming fabric or a clothing for the press section of the paper machine, with a single or multilayer carrier layer and a porous polymer layer applied thereto at least on one side, whereby the method is characterized characterized in that a solution of the polymer in an ionic liquid on the carrier layer applied as far as possible over the entire surface and then the polymer is brought to coagulation, wherein the porous polymer layer is formed on the carrier layer.
  • a paper machine clothing in particular in the form of a forming fabric or a press fabric, can be produced, with which paper of high quality can be produced. Because of the irregularly configured surface of the papermachine fabric which can be produced according to the invention, it is not possible, for example in the forming section, to impress regularly recurring patterns as in the case of woven forming fabric surfaces.
  • the highly pronounced porosity of the polymer layer of the papermachine fabric can be produced according to the invention allows a high water absorption, so that when passing the wet paper webs with a press fabric according to the invention through the press nip a significant increase in the solids content of the paper web is possible. Even in the construction of the press pressure, the pores are hardly closed, so that a high degree of permeability is ensured even under these conditions. This is attributed to the formation of statistically distributed dewatering channels in the micrometer range in the polymer layer applied according to the invention, which distinguishes them from the hitherto known polymer layers, which were produced, for example, by sintering processes.
  • Another advantage of this invention covering is that they usually lose no fibers during wear, which can be stored in the paper web.
  • the paper machine clothing according to the invention exhibits pronounced elasticity. This has an advantageous effect, in particular when used as a press fabric, since such paper machine clothing is constantly subjected to high compressive stress when passing through the press nip, and insofar a good resilience for a constant press output is desirable.
  • the polymers used for the process according to the invention or the papermachine clothing according to the invention preferably have thermoplastic properties. They may in particular be selected from the group comprising polyamides, such as polyamide 6, polyamide 6.6, polyamide 6.10, polyethylene terephthalate, polybutylene terephthalate, polyurethanes, especially polyester-polyurethanes or Polyether polyurethanes, polyvinyl chloride or combinations or copolymers thereof.
  • polyamides such as polyamide 6, polyamide 6.6, polyamide 6.10, polyethylene terephthalate, polybutylene terephthalate, polyurethanes, especially polyester-polyurethanes or Polyether polyurethanes, polyvinyl chloride or combinations or copolymers thereof.
  • polyamides such as polyamide 6, polyamide 6.6, polyamide 6.10, polyethylene terephthalate, polybutylene terephthalate, polyurethanes, especially polyester-polyurethanes or Polyether polyurethanes,
  • the polymer concentration in the polymer solution used can also be varied over wide ranges. In this way, for example, the desired application viscosity of the solution can be adjusted, which in turn is closely related to the molecular weight of the polymers used as well as the temperature of the polymer solution.
  • the polymer concentration may be, for example, 5 to 95% by weight, based on the weight of the total solution, in particular 50 to 80% by weight.
  • the concentration of the polymer solution can be adjusted to the desired result with a few experiments.
  • the application viscosity that is to say the viscosity of the polymer solution at the respective application temperature, is advantageously in the range from 100 to 100,000 mPas, in particular from 1000 to 50,000 mPas.
  • Ionic liquids are a group of solvents which, unlike traditional organic or aqueous solvents, are composed of anions and cations.
  • ionic liquids are typically composed of an organic cation, which is often obtained by alkylation of a compound.
  • These may be selected from imidazoles, pyrazoles, thiazoles, isothiazoles, azathiazoles, oxothiazoles, oxazines, oxazolines, oxazaboroles, dithiozoles, triazoles, selenozoles, oxaphospholes, pyrroles, borols, furans, thiophenes, phospholes, pentazoles, indoles, indolines, oxazoles, isoxazoles , Isotriazoles, tetrazoles, benzofurans, dibenzofurans, benzothiophenes, dibenzothiophenes, thiadiazoles, pyridines, pyrimidines, pyrazines, pyridazines, piperazines, piperidines, morpholones, pyrans, anolines, phthalazines, quinazolines, quinoxalines, and combinations thereof.
  • the anionic portion of the ionic liquid may be composed of inorganic or organic anions. Typical examples of these are halides, BX 4 - , PF 6 - , AsF 6 - , SbF 6 - , NO 2 - , NO 3 - , SO 4 2- , BR 4 - , substituted or unsubstituted carboranes, substituted or unsubstituted metallocarboranes, phosphates , Phosphites, polyoxometalates, substituted or unsubstituted carboxylates such as acetate, triflates and non-coordinating anions.
  • halides BX 4 - , PF 6 - , AsF 6 - , SbF 6 - , NO 2 - , NO 3 - , SO 4 2- , BR 4 - , substituted or unsubstituted carboranes, substituted or unsubstituted metallocarboranes, phosphate
  • X independently of one another can stand for fluoride, chloride, bromide or iodide and R independently of one another Hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy-aryloxy, acyl, silyl, boryl, phosphino, amino, thio or seleno.
  • the polymer solution used for the process according to the invention can be prepared, for example, by introducing the polymer as polymer granulate into the ionic liquid at a suitable temperature with stirring.
  • the polymer can be converted by heating into a polymer melt, in which then subsequently the ionic liquid is introduced.
  • the polymer solution may contain a filler and / or pore former which is in particular selected from the group comprising micro- and nanoparticles or fibers, preferably plastic or glass (hollow) balls, ceramic (hollow) balls, plastic Glass, carbon, metal or ceramic fibers, phyllosilicates or combinations thereof.
  • Suitable pore formers are, for example, salts, in particular salts free of water of crystallization, such as sodium chloride.
  • the pore formers can be dissolved out after the production of the fabric.
  • the pore formers are expediently so on the coagulant agreed that they dissolve in it.
  • a sodium chloride pore-forming agent is in particular water as a coagulant in question.
  • fillers it is possible, for example, to modify the mechanical properties of the porous polymer layer, such as their tensile strength and elasticity.
  • the wear resistance of the fabric can be increased by the use of fillers.
  • the specific weight can be reduced, for example, by using lightweight fillers. Light fillers are understood as meaning those fillers whose specific weight is less than one gram per cm 3 .
  • the carrier layer used in the context of the method according to the invention or the papermachine fabric according to the invention can, in principle, have any shape and structure known for papermachine clothing.
  • the carrier layer may be a woven, knitted fabric, scrim or consolidated nonwoven, in particular fibers, threads or threads, or a netting.
  • the carrier layer can be constructed in one or more layers.
  • an intermediate layer can be provided on at least one side of the carrier layer, to which the polymer solution is applied, wherein the intermediate layer is in particular selected from an anchored nonwoven fabric, a layer of layered and sintered polymer powder or polymer microspheres, a foam layer, a comparison with Carrier layer finer or coarser structured layer of woven, knitted fabric, scrim or bonded nonwoven, in particular of fibers, threads or threads, or of netting or a combination of these.
  • the mechanical properties and the water absorption behavior of the papermachine clothing can be modified.
  • the carrier layer and / or the intermediate layer may comprise or consist of a polymer material which is in particular selected from the group comprising polyamides, in particular aramid, polyesters, polyolefins, polyurethanes, copolymers, mixtures and combinations thereof , wherein the carrier layer and the intermediate layer may each consist of different materials.
  • the polymer solution is heated to a temperature of 10 to 300 ° C prior to application of the polymer solution, in particular to a temperature of 80 to 200 ° C, preferably from 90 to 150 ° C.
  • a temperature of 10 to 300 ° C prior to application of the polymer solution, in particular to a temperature of 80 to 200 ° C, preferably from 90 to 150 ° C.
  • This is particularly advantageous since in this way polymer solutions with comparatively high polymer concentration can be applied uniformly.
  • To apply temperature jumps To avoid it is also advantageous to heat the support layer to the aforementioned temperatures, in particular to at least the same temperature as the polymer solution.
  • the application of the polymer solution can in principle be carried out in any suitable manner, for example by doctoring, brushing, brushing, dipping, spraying, sprinkling, casting, spraying, roller coating, printing, for example by rotary screen printing or inkjet, impregnation or calendering is applied , Also combinations of these are possible.
  • the order may be full-surface or sectionally limited, regular or irregular, in defined or random patterns, punctiform or linear, or in any other pattern.
  • machine components in the form of doctor blades or rollers can be used on one or both sides of the substrate optionally with an existing intermediate layer.
  • the coagulation can be carried out in a single step or in several stages.
  • the applied polymer solution layer may first be lightly sprayed or sprinkled with a coagulant to produce a thin skin on the surface that is less porous. In other words, this makes it possible to produce a particularly smooth surface.
  • the thus pretreated web can be dipped into the coagulant to complete the precipitation process. This preserves the polymer layer inside its highly porous structure.
  • the applied layer thickness of the polymer solution can be varied within wide ranges.
  • the polymer solution can be applied in a layer thickness of 100 to 3000 .mu.m, in particular from 200 to 2500 .mu.m, preferably from 500 to 1500 .mu.m.
  • the applied layer thickness is typically related to the desired layer thickness of the porous polymer layer.
  • the polymer solution at least partially penetrates into the carrier layer and / or the intermediate layer and, in particular, at least partially completely penetrates the latter.
  • the anchoring of the polymer layer on the carrier layer can be improved.
  • the machine side of the papermachine fabric can be provided with a polymer layer in this way, if this completely penetrates the carrier layer.
  • this also the resilience and water absorption capacity can be further increased.
  • the carrier layer can be coated on both sides with a polymer solution of the type mentioned above. This can either take place in one step or else a polymer layer is first produced by application and coagulation and then subsequently the opposite side coated accordingly. Regardless of the type the generation of the two layers is opened by this process variant, the possibility to produce a different polymer coating on both sides, but this is not mandatory.
  • a particularly firm mechanical cohesion of the polymer layers applied on both sides can be generated with one another. In this way, for example, a particularly wear-resistant surface can be produced for the later machine side of the paper machine clothing, whereas the paper side of the clothing can be interpreted as having a particularly high water absorption capacity.
  • the coagulation of the polymer from the polymer solution can be effected, for example, by contacting it with a coagulant selected from protic solvents, in particular with water, a C 1 to C 4 alcohol or mixtures thereof.
  • the job can be done, for example, by brushing, brushing, dipping, spraying, sprinkling, pouring, spraying, printing, impregnating or combinations thereof.
  • the clothing After coagulation of the polymer, it is expedient to dry the clothing. This can be done for example via a freeze-drying. Alternatively, a drying at a temperature of 20 ° C to the boiling point of the coagulant such as 40 to 100 ° C is possible, possibly also under reduced pressure.
  • the layer thickness of the dried porous polymer layer which is outside the support layer or the intermediate layer, 100 to 2000 .mu.m, in particular 200 to 1700 .mu.m, preferably 500 to 1500 .mu.m.
  • these layer thicknesses are particularly advantageous, since such papermachine clothing has good mechanical properties, such as a high mechanical resilience and at the same time have a large water absorption capacity.
  • the porous polymer layer also extends into the carrier layer, the total layer thickness of the porous polymer layer may also be above the above-mentioned values.
  • the paper machine clothing according to the invention can be subjected to a subsequent surface treatment.
  • the porous polymer layer can be mechanically processed, for example after drying, in particular via a grinding process. In this way, particularly smooth surfaces can be produced, so that the risk of the formation of marking patterns is further reduced.
  • by such a surface treatment and the water absorption behavior can be changed later.
  • a skin formation on the porous polymer layer can occur, which can reduce the pore accessibility. This may be desirable in individual cases.
  • the porosity of the porous polymer layer is to be increased, this can be done by the abovementioned mechanical removal.
  • the porous polymer layers which can be produced by means of the process according to the invention have, for example, an average pore size of from 0.1 to 300 ⁇ m, in particular from 0.5 to 200 ⁇ m. Particularly preferably, the average pore size is about 0.5 to 20 microns.
  • the pore volume may be, for example, 30 to 70%, i. H. 30 to 70% of a sample volume is formed by pores.
  • the pore volume is 40 to 60%.
  • the pore volume, the pore size and their distribution can be determined by methods known per se, such as mercury porosimetry or BET measurements.
  • the present invention also relates to a clothing for a paper machine, in particular in the form of a forming fabric or a clothing for the press section of the paper machine, which is produced by the inventive method.
  • the porous polymer layer expediently forms the paper side of the fabric.
  • the porous polymer layer may additionally form the machine side of the fabric.
  • the present invention is further directed to a paper machine equipped with a fabric according to the invention.
  • the present invention relates to the use of a solution of a polymer in an ionic liquid for producing a paper machine clothing, in particular in the form of a forming fabric or a covering for the press section of the paper machine.
  • a two-layer carrier layer in the form of a forming fabric is used.
  • This carrier layer has a paper-side and a machine-side fabric layer, which are interconnected by intrinsic weft threads.
  • the paper-side fabric layer is formed of plain weave interwoven threads, whereas the machine side fabric layer threads are woven in satin weave.
  • the threads of the paper-side fabric layer have a smaller diameter than those of the machine-side fabric layer.
  • the ionic liquid used was 1-ethyl-3-methylimidazolium diethyl phosphate (ENIM DEP from BASF).
  • ENIM DEP 1-ethyl-3-methylimidazolium diethyl phosphate
  • PA6 polymer polyamide 6
  • the ionic liquid was heated to about 80 ° C. The suitable temperature depends on the mixture composition. In the present case, the weight fraction was 40% ENIM DEP to 60% PA6.
  • the solution of the polymer in the ionic liquid was applied to the two-layer support layer by means of a doctor blade with only slight cooling.
  • the viscosity was 700 mPas.
  • a coagulant de-contaminated and deionized water was used, which was previously heated to about 80 ° C.
  • the heating of the coagulant is advantageous so that the mixture of polymer and ionic liquid does not cool. Furthermore, the viscosity of the coagulant decreases and the exchange of coagulant and ionic liquid is accelerated.
  • the coated carrier layer is passed through a bath of the coagulant while the polymer coagulates from the solution to form the porous polymer layer.
  • the residence time of the covering in the bath is chosen as a function of the layer thickness so that the polymer coagulates quantitatively.
  • the fabric is dried at a temperature of 80 ° C.
  • FIGS. 1 to 5 A paper machine clothing produced in this way is in the SEM images according to the FIGS. 1 to 5 shown.
  • Fig. 1 is shown in side sectional view in the form of a scanning electron micrograph.
  • the spongy pore structure with comparatively thin webs and the resulting high porosity of the polymer layer is in FIGS. 2 and 3 clearly visible.
  • FIG. 2 a partial cross section through the polymer layer with coarse drainage channels (white) and thick-walled polymer webs (black).
  • Fig. 3 is another cross-sectional view to see. Thereafter, on one side of the polymer layer, the in Fig. 2 shown coarse drainage channels and thick-walled polymer webs to see, whereas the opposite side has comparatively finer drainage channels (white) and thin-walled polymer webs (black).
  • FIGS. 4 and 5 the paper side of the fabric is shown in plan view.
  • the polymeric material is black and the open areas are white.
  • Fig. 5 shows the inverse representation. This results in an open area of 42% with pore sizes of 1-7 microns.

Landscapes

  • Laminated Bodies (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Description

Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung einer Bespannung für eine Papiermaschine, insbesondere in Form eines Formiersiebes oder einer Bespannung für die Pressensektion der Papiermaschine, mit einer ein-oder mehrlagigen Trägerschicht und einer wenigstens einseitig darauf aufgebrachten porösen Polymerschicht, sowie eine Papiermaschinenbespannung, die nach einem solchen Verfahren hergestellt ist.The present invention relates to a method for producing a covering for a paper machine, in particular in the form of a Formiersiebes or a fabric for the press section of the paper machine, with a single- or multi-layer support layer and at least one side applied thereto porous polymer layer, and a papermachine fabric according to produced by such a method.

Papiermaschinenbespannungen dienen dazu, auf einer Papiermaschine die Papierbahnen zu formieren, anschließend mechanisch zu entwässern und im Weiteren dem Wärmeübergang am Trockenzylinder zu gewährleisten. Zusätzlich muss die Bespannung beim Durchlaufen der Papierbahnen durch die Papiermaschine die noch bruchempfindliche Papierbahn unterstützen und für einen möglichst zugfreien Lauf sorgen.Paper machine clothing serves to form the paper webs on a paper machine, then to dewater mechanically and to further ensure the heat transfer to the drying cylinder. In addition, the fabric must support the still fragile paper web when passing through the paper webs through the paper machine and ensure the most possible draft-free run.

Im Formierbereich wird der Papierstoff durch den Stoffauflauf auf ein Sieb oder zwischen zwei Siebe gespritzt. Die Aggregate des Formierbereichs entziehen dem Papierstoff kontinuierlich Wasser und steigern den Feststoffgehalt auf ca. 20%. Bei diesem Vorgang kommt die eine oder auch beide Papieroberflächen mit dem Formiersieb in engen Kontakt, so dass sich die Gewebeoberflächenstruktur des Formiersiebes auf der anliegenden Oberfläche der Papierbahnen abdrücken kann, was zu unerwünschten Markierungsmustern auf der Papieroberfläche führt. Aus diesem Grunde sind Papiermaschinenbespannungen mit möglichst feinen und strukturarmen Oberflächen erwünscht, um die zuvor erläuterten Markierungseffekte möglichst gering zu halten bzw. auf ein Niveau zu bringen, dass diese sich zumindest beim Bedrucken nicht störend auswirken.In the forming area, the stock is sprayed through the headbox onto a sieve or between two sieves. The aggregates of the Formierbereichs withdraw water from the pulp continuously and increase the solids content to about 20%. In this process, the one or even both paper surfaces come into close contact with the forming fabric, so that the fabric surface structure of the forming fabric on the adjacent surface of the paper webs can print, resulting in undesirable marking patterns on the paper surface. For this reason, paper machine clothing with the finest possible and structurally poor surfaces are desirable in order to minimize the above-described marking effects or to bring them to a level that they do not interfere at least during printing.

Zudem werden aufgrund des zunehmend verstärkten Einsatzes von Papierfasern aus Altpapier ständig steigende Ansprüche an die mechanische Faserrückhaltung (mechanische Retention) der Formiersiebe gestellt. Die auf der Papierseite zurückzuhaltenden Fasern werden immer kürzer, weshalb auch die papierseitigen Siebmaschen immer kleiner ausfallen müssen.In addition, due to the increasing use of paper fibers from waste paper, ever increasing demands are placed on the mechanical fiber retention (mechanical retention) of the forming fabrics. The fibers to be retained on the paper side become shorter and shorter, which is why the paper-side wire meshes also have to be smaller and smaller.

Gleichzeitig werden zur Gewinnung von Weisse und zur Einstellung der Spezifikation dem Papierstoff Füllstoffe hinzugefügt, die dazu neigen, bei der Entfernung des Wassers ausgeschwemmt zu werden. Die Siebmaschen üblicher Formiersiebe sind selbst bei feingewebten Sieben vergleichsweise grob in Relation zu den Durchmessern der vorgenannten Füllstoffteilchen so dass diese durch das anliegende Gewebe weggeschwemmt werden können, sofern sich nicht durch die mechanische Retention des Formiersiebes ein Faserkuchen aufgebaut hat, welcher diese Füllstoffe zurückhalten kann. Doch auch für die Erzeugung eines guten Faserkuchens sind feine Siebmaschen zur Ausbildung der initialen Faserlage als Ausgangsschicht für den Faserkuchen erforderlich. Bei ungleichmäßiger Ausschwemmung der Füllstoffe auf der Ober- und Unterseite der Papierbahnen entsteht eine Zweiseitigkeit, die zu qualitativ unterschiedlichen Druckbildern auf der Ober- und Unterseite der Papierbahnen bzw. des Papierblatts führen kann. Zudem kann sich dieser Umstand negativ auf die Opazität des Papierblattes auswirken.At the same time fillers are added to the pulp to recover whiteness and to adjust the specification, which tend to be flushed out as the water is removed. Even with finely woven sieves, the sieve meshes of conventional forming fabrics are comparatively coarse in relation to the diameters of the aforementioned filler particles, so that they can be washed away by the adjacent fabric, unless a fiber cake has built up by the mechanical retention of the forming fabric, which can retain these fillers. But even for the production of a good fiber cake fine Siebmaschen to form the initial fiber layer as the starting layer for the fiber cake are required. In case of uneven washing out of the fillers on the top and bottom of the paper webs creates a two-sidedness, which can lead to qualitatively different print images on the top and bottom of the paper webs or the paper sheet. In addition, this circumstance may adversely affect the opacity of the paper sheet.

Aufgrund der Erfahrung, dass regelmäßige bzw. regelmäßig wiederkehrende Strukturen vom menschlichen Auge leichter wiedererkannt werden können als eine unregelmäßige Struktur, bemühen sich die Hersteller von Formiersieben, Gewebebindungen zu entwickeln, die möglichst unregelmäßige Bindungsbilder an der Sieboberfläche erzeugen. Dies gelingt jedoch zumeist nur unzureichend, da der Webprozess per sé eine gewisse Regelmäßigkeit, nämlich einen Bindungsrapport, voraussetzt.Based on the experience that regular or regularly recurring structures can be recognized more easily by the human eye than an irregular structure, the manufacturers of forming fabrics are endeavoring to develop weaves that produce the most irregular weave patterns on the surface of the sieve. However, this usually succeeds only inadequately, since the weaving process presupposes a certain regularity, namely a weave repeat, per se.

Was nun den Pressenbereich der Papiermaschine betrifft, wird darin der Papierbahn durch mechanischen Druck Wasser entzogen. Hierzu wird die nasse Papierbahn mit mindestens einem Pressenfilz gemeinsam durch einen Pressenspalt geführt, in welchem im Wesentlichen der Pressenfilz die Entwässerung übernimmt. Der Feststoffgehalt der Papierbahn wird in der Pressenpartie von ca. 20% auf etwa 50% erhöht. Üblicherweise bestehen Pressenfilze aus einem Kunststoffträger, welcher ein- oder auch beidseitig mit mindestens einer synthetischen Faservliesschicht gleicher oder verschiedener Faserfeinheit besetzt ist. Bei der Herstellung des Pressenfilzes werden die Fasern in einem Benadelungsprozess als Faservlies der Nadelmaschine zugeführt und mit Feltingnadeln in die Struktur des Kunststoffträgers eingenadelt.As far as the press area of the paper machine is concerned, water is removed from the paper web by mechanical pressure. For this purpose, the wet paper web is guided together with at least one press felt through a press nip, in which substantially the press felt takes over the drainage. The solids content of the paper web is increased in the press section from about 20% to about 50%. Usually press felts consist of a plastic carrier, which is occupied on one or both sides with at least one synthetic fiber fleece layer of the same or different fiber fineness. In the production of the press felt, the fibers are supplied in a Benadelungsprozess as a nonwoven fabric needle machine and needled with needled needles in the structure of the plastic carrier.

Wie in der Formiersektion kommt auch in der Pressensektion eine oder auch beide Papieroberflächen mit je einem Pressenfilz in Kontakt. Dabei wirkt sich auch in diesem Fertigungsschritt die Qualität und Struktur des aufgenadelten Vlieses insbesondere dessen Gleichmäßigkeit auf die Güte der Entwässerung und die erhaltene Papierqualität aus. So verschlechtert beispielsweise Narbigkeit der vernadelten Pressenfilzoberfläche die Oberfläche der Papierbahnen. Insbesondere der Verlust von Fasern durch Verschleiß und Abbrechen kann zu Problemen führen, da sich diese Fasern später in der Papierbahn wiederfinden können.As in the forming section, one or even both paper surfaces come into contact, in each case with one press felt, in the press section. In this production step, the quality and structure of the needled nonwoven, in particular its uniformity, also has an effect on the quality of the dewatering and the quality of the paper obtained. For example, scarcity of the needled press felt surface deteriorates the surface of the paper webs. In particular, the loss of fibers due to wear and breakage can lead to problems, since these fibers can later find themselves in the paper web.

Aus diesen Gründen sind aus dem Stand der Technik Formiersiebe und Bespannungen für die Pressensektion bekannt, die zumindest auf ihrer papierseitigen Oberfläche mit einer Polymerbeschichtung versehen sind, so dass sich die Gewebestruktur der Bespannung nicht mehr auf der Papierbahn abdrücken kann. Die Polymerbeschichtung muss hierbei gleichzeitig hinreichend porös sein, damit die erforderliche Entwässerung im Formier- und Pressenbereich der Papiermaschine gewährleistet ist.For these reasons, from the prior art forming fabrics and fabrics for the press section are known, which are provided at least on their paper-side surface with a polymer coating, so that the fabric structure of the fabric can no longer be pressed on the paper web. At the same time, the polymer coating must be sufficiently porous to ensure the required dewatering in the forming and pressing area of the paper machine.

In EP 0 342 171 ist ein Verfahren zur Beschichtung einer Trägerbahn mit einer Polymerschicht beschrieben. Darin wird ein partikuläres polymeres Harzmaterial, ein Binder sowie ein Lösungsmittel homogenisiert und auf die Trägerbahn aufgerakelt. Die polymeren Harzpartikel bestehen aus Polyethylen, Polyurethan, insbesondere aus Polyether- und Polyesterpolyurethanen. Als Bindemittel werden Polyamide bzw. Polyamidharze vorgeschlagen, wobei als Lösungsmittel Wasser verwendet wird. Nach dem Auftragen der vorgenannten Mischung wird das Wasser in einem folgenden Verfahrensschritt wieder verdampft wodurch eine mit einem Polymerschaum versehene Papiermaschinenbespannung erhalten wird.In EP 0 342 171 a method for coating a carrier web with a polymer layer is described. Therein, a particulate polymeric resin material, a binder and a solvent are homogenized and knife-coated onto the carrier web. The polymeric resin particles are made of polyethylene, polyurethane, especially polyether and polyester polyurethanes. The binders are polyamides or polyamide resins, water being used as the solvent. After application of the above mixture, the water is evaporated again in a subsequent process step, whereby a provided with a polymer foam paper machine clothing is obtained.

Weiterhin ist aus EP 0 273 613 ein Pressfilz mit einer harzbasierenden Matrixoberfläche bekannt. Der Pressfilz weist eine ein- oder mehrlagige Basisschicht auf, welche mit einer plastischen, faserverstärkten Harzmatrixschicht versehen ist. Diese Matrixschicht umfasst ein Polymerharz sowie darin gleichmäßig verteilte Textilfasern und Luftkanäle sowie Hohlräume. Die Harzmatrix besteht beispielsweise aus Polyurethan-Polymeren oder Polyvinylchlorid-Polymeren und besitzt thermoplastische Eigenschaften.Furthermore, it is off EP 0 273 613 a press felt with a resin-based matrix surface known. The press felt has a single-layer or multi-layer base layer which is provided with a plastic, fiber-reinforced resin matrix layer. This matrix layer comprises a polymer resin and uniformly distributed textile fibers and air channels as well as cavities. The resin matrix consists for example of polyurethane polymers or polyvinyl chloride polymers and has thermoplastic properties.

Schließlich ist aus EP 0 187 967 ein Nasspressenfilz für eine Papiermaschine mit einer Trägerstruktur und einer darauf aufgebrachten synthetischen Polymerschicht bekannt. Die synthetische Polymerschicht enthält u. a. Polyolefine, Polyurethane, insbesondere Polyether- und Polyesterpolyurethane, sowie ein Bindeharz auf Polyamid-oder Polyimidbasis. Zur Herstellung der Oberflächenschicht aus dem Polymer-Kunstharz wird dieses zunächst in Form loser Partikel auf der Oberfläche des Grundgewebes verteilt und die Partikel anschließend über Ihren Erweichungspunkt erhitzt, wobei diese miteinander und mit dem Grundgewebe verschmelzen. Hierbei kommt es zur Ausbildung von Hohlräumen innerhalb der Polymerschicht die gleichzeitig an dem Grundgewebe verankert wird.Finally is off EP 0 187 967 a wet press felt for a paper machine having a support structure and a synthetic polymer layer applied thereon. The synthetic polymer layer contains, inter alia, polyolefins, polyurethanes, in particular polyether and polyester polyurethanes, and a polyamide- or polyimide-based binder resin. To produce the surface layer of the polymer resin, this is first distributed in the form of loose particles on the surface of the base fabric and the particles are then heated above their softening point, wherein these melt together and with the base fabric. This leads to the formation of cavities within the polymer layer which is simultaneously anchored to the base fabric.

Die vorgenannten Papiermaschinenbespannungen erfüllen die gestellten Anforderungen jedoch nicht in jeder Hinsicht. So wird es als nachteilig empfunden, dass die aufgebrachten Polymerschichten für manche Anwendungszwecke ein zu geringes Porenvolumen besitzen, was sich nachteilig auf die Wasseraufnahmefähigkeit auswirkt. Zudem ist auch der Anteil an offenen Poren nicht immer in der gewünschten Höhe verfügbar, jedoch können nur derartige Poren von au-ßen Feuchtigkeit aufnehmen und das Wasser durch die Struktur ableiten.However, the aforementioned paper machine clothing does not meet the requirements in all respects. Thus, it is considered disadvantageous that the applied polymer layers for some applications have too small a pore volume, which adversely affects the water absorbency. In addition, the proportion of open pores is not always available at the desired height, but only such pores can absorb moisture from outside and drain the water through the structure.

Die Aufgabe der vorliegenden Erfindung bestand somit darin, ein verbessertes Herstellungsverfahren anzugeben, mit welchem Papiermaschinenbespannungen mit einem größeren verfügbaren Porenvolumen, einem höheren Anteil an offenen Poren und einer gesteigerten Permeabilität erhältlich sind. Die Papiermaschinenbespannung soll zudem den hohen mechanischen Anforderungen in Bezug auf Flexibilität und Elastizität gerecht werden, insbesondere, was das elastische Rückstellvermögen nach einer Kompression sowie die Verschleißfestigkeit angeht.The object of the present invention was therefore to provide an improved manufacturing process, with which papermachine clothing with a larger available pore volume, a higher proportion of open pores and an increased permeability are available. The paper machine clothing should also meet the high mechanical requirements in terms of flexibility and elasticity, especially in terms of elastic recovery after compression and wear resistance.

Die Aufgabe wird gelöst durch ein Verfahren zur Herstellung einer Bespannung für eine Papiermaschine, insbesondere in Form eines Formiersiebes oder einer Bespannung für die Pressensektion der Papiermaschine, mit einer ein-oder mehrlagigen Trägerschicht und einer wenigstens einseitig darauf aufgebrachten porösen Polymerschicht, wobei sich das Verfahren dadurch auszeichnet, dass eine Lösung des Polymers in einer ionischen Flüssigkeit auf die Trägerschicht weitestgehend vollflächig aufgebracht und anschließend das Polymer zur Koagulation gebracht wird, wobei auf der Trägerschicht die poröse Polymerschicht entsteht.The object is achieved by a method for producing a covering for a paper machine, in particular in the form of a forming fabric or a clothing for the press section of the paper machine, with a single or multilayer carrier layer and a porous polymer layer applied thereto at least on one side, whereby the method is characterized characterized in that a solution of the polymer in an ionic liquid on the carrier layer applied as far as possible over the entire surface and then the polymer is brought to coagulation, wherein the porous polymer layer is formed on the carrier layer.

Überraschenderweise hat sich herausgestellt, dass mithilfe des erfindungsgemäßen Herstellungsverfahrens eine Papiermaschinenbespannung insbesondere in Form eines Formiersiebes oder einer Pressenbespannung erzeugt werden kann, mit der Papier von hoher Qualität herstellbar ist. Aufgrund der unregelmäßig ausgestalteten Oberfläche der erfindungsgemäß herstellbaren Papiermaschinenbespannung kommt es beispielsweise in der Formiersektion nicht zum Eindrücken regelmäßig wiederkehrender Muster wie bei gewobenen Formiersieboberflächen.Surprisingly, it has been found that by means of the production method according to the invention, a paper machine clothing, in particular in the form of a forming fabric or a press fabric, can be produced, with which paper of high quality can be produced. Because of the irregularly configured surface of the papermachine fabric which can be produced according to the invention, it is not possible, for example in the forming section, to impress regularly recurring patterns as in the case of woven forming fabric surfaces.

Zudem ermöglicht die stark ausgeprägte Porosität der Polymerschicht der erfindungsgemäß herstellbaren Papiermaschinenbespannung ein hohes Wasseraufnahmevermögen, so dass beim Durchführen der nassen Papierbahnen mit einer erfindungsgemäßen Pressenbespannung durch den Pressenspalt eine deutliche Erhöhung des Feststoffgehaltes der Papierbahn möglich ist. Dabei werden selbst beim Aufbau des Pressendrucks die Poren kaum verschlossen, sodass auch unter diesen Bedingungen ein hohes Maß an Permeabilität sichergestellt ist. Dies wird auf die Ausbildung von statistisch verteilten Entwässerungskanälen im Mikrometerbereich in der erfindungsgemäß aufgebrachten Polymerschicht zurückgeführt, wodurch sich diese von den bislang bekannten Polymerschichten unterscheidet, die beispielsweise über Sinterprozesse erzeugt wurden.In addition, the highly pronounced porosity of the polymer layer of the papermachine fabric can be produced according to the invention allows a high water absorption, so that when passing the wet paper webs with a press fabric according to the invention through the press nip a significant increase in the solids content of the paper web is possible. Even in the construction of the press pressure, the pores are hardly closed, so that a high degree of permeability is ensured even under these conditions. This is attributed to the formation of statistically distributed dewatering channels in the micrometer range in the polymer layer applied according to the invention, which distinguishes them from the hitherto known polymer layers, which were produced, for example, by sintering processes.

Da sich die erfindungsgemäß hergestellten Papiermaschinenbespannungen in ihren Eigenschaften von den bislang bekannten unterscheiden besteht ein weiterer Gegenstand der vorliegenden Erfindung in einer Bespannung für eine Papiermaschine, insbesondere in Form eines Formiersiebes oder einer Bespannung für die Pressensektion der Papiermaschine, wobei die Bespannung nach dem erfindungsgemäßen Verfahren hergestellt ist.Since the paper machine clothing produced according to the invention differ in their properties from the hitherto known, a further subject of the present invention in a fabric for a paper machine, in particular in the form of a forming fabric or a fabric for the press section of the paper machine, wherein the fabric produced by the process according to the invention is.

Ein weiterer Vorteil dieser erfindungsgemäßen Bespannung besteht darin, dass diese beim Verschleiß in der Regel keine Fasern verlieren, die sich in der Papierbahn einlagern können.Another advantage of this invention covering is that they usually lose no fibers during wear, which can be stored in the paper web.

Zudem zeigt die erfindungsgemäße Papiermaschinenbespannung eine ausgeprägte Elastizität. Dies wirkt sich insbesondere bei der Verwendung als Pressenbespannung in vorteilhafter Weise aus, da solche Papiermaschinenbespannungen beim Durchführen durch den Pressenspalt ständig starker Druckbeanspruchung ausgesetzt werden und insofern ein gutes Rückstellvermögen für eine gleichbleibende Pressenleistung wünschenswert ist.In addition, the paper machine clothing according to the invention exhibits pronounced elasticity. This has an advantageous effect, in particular when used as a press fabric, since such paper machine clothing is constantly subjected to high compressive stress when passing through the press nip, and insofar a good resilience for a constant press output is desirable.

Die für das erfindungsgemäße Verfahren bzw. die erfindungsgemäße Papiermaschinenbespannung eingesetzten Polymere haben vorzugsweise thermoplastische Eigenschaften. Sie können insbesondere ausgewählt sein aus der Gruppe umfassend Polyamide, wie Polyamid 6, Polyamid 6.6, Polyamid 6.10, Polyethylenterephthalat, Polybutylenterephthalat, Polyurethane, speziell Polyester-Polyurethane oder Polyether-Polyurethane, Polyvinylchlorid oder Kombinationen oder Copolymere hiervon. Allerdings ist die vorgenannte Aufstellung lediglich beispielhaft und nicht beschränkend für die vorliegende Erfindung anzusehen. Was die Molmassen der verwendeten Polymere betrifft, so können diese auch über weite Bereiche variiert werden.The polymers used for the process according to the invention or the papermachine clothing according to the invention preferably have thermoplastic properties. They may in particular be selected from the group comprising polyamides, such as polyamide 6, polyamide 6.6, polyamide 6.10, polyethylene terephthalate, polybutylene terephthalate, polyurethanes, especially polyester-polyurethanes or Polyether polyurethanes, polyvinyl chloride or combinations or copolymers thereof. However, the above list is merely illustrative and not restrictive to the present invention. As far as the molar masses of the polymers used are concerned, they can also be varied over a wide range.

Die Polymerkonzentration in der verwendeten Polymerlösung kann ebenfalls über breite Bereiche variiert werden. Auf diese Weise kann beispielsweise die gewünschte Auftragsviskosität der Lösung eingestellt werden, wobei diese wiederum im engen Zusammenhang mit der Molmasse der verwendeten Polymere sowie auch der Temperatur der Polymerlösung zusammenhängt. Die Polymerkonzentration kann beispielsweise 5 bis 95 Gew.-% bezogen auf das Gewicht der Gesamtlösung betragen, insbesondere 50 bis 80 Gew.-%.The polymer concentration in the polymer solution used can also be varied over wide ranges. In this way, for example, the desired application viscosity of the solution can be adjusted, which in turn is closely related to the molecular weight of the polymers used as well as the temperature of the polymer solution. The polymer concentration may be, for example, 5 to 95% by weight, based on the weight of the total solution, in particular 50 to 80% by weight.

Letztlich kann die Konzentration der Polymerlösung mit wenigen Versuchen an das gewünschte Ergebnis angepasst werden. In vorteilhafter Weise liegt die Auftragsviskosität, das heißt die Viskosität der Polymerlösung bei der jeweiligen Auftragstemperatur im Bereich von 100 bis 100.000 mPas, insbesondere von 1000 bis 50.000 mPas.Ultimately, the concentration of the polymer solution can be adjusted to the desired result with a few experiments. The application viscosity, that is to say the viscosity of the polymer solution at the respective application temperature, is advantageously in the range from 100 to 100,000 mPas, in particular from 1000 to 50,000 mPas.

Bei der Einstellung der Konzentration beziehungsweise der Temperatur spielt auch eine möglicherweise gewünschte Penetration der Trägerschicht mit der Polymerlösung eine Rolle. So können niedriger konzentrierte beziehungsweise höher temperierte und damit niedriger viskose Polymerlösungen leichter in die Trägerschicht eindringen oder vollständig bis auf die Gegenseite penetrieren.When setting the concentration or the temperature, a possibly desired penetration of the carrier layer with the polymer solution also plays a role. Thus, lower-concentrated or higher-tempered and thus lower-viscosity polymer solutions can more easily penetrate into the carrier layer or penetrate completely to the opposite side.

Für das erfindungsgemäße Verfahren können eine Vielzahl an sich bekannter ionischer Flüssigkeiten verwendet werden. Bei ionischen Flüssigkeiten handelt es sich um eine Gruppe von Lösungsmitteln, welche im Gegensatz zu traditionellen organischen oder wässrigen Lösungsmitteln aus Anionen und Kationen aufgebaut sind. Hierbei sind ionische Flüssigkeiten typischerweise aus einem organischen Kation aufgebaut, welches häufig durch Alkylierung einer Verbindung erhalten wird. Diese können ausgewählt sein aus Imidazolen, Pyrazolen, Thiazolen, Isothiazolen, Azathiazolen, Oxothiazolen, Oxazinen, Oxazolinen, Oxazaborolen, Dithiozolen, Triazolen, Selenozolen, Oxaphospholen, Pyrrolen, Borolen, Furanen, Thiophenen, Phospholen, Pentazolen, Indolen, Indolinen, Oxazolen, Isoxazolen, Isotriazolen, Tetrazolen, Benzofuranen, Dibenzofuranen, Benzothiopherien, Dibenzothiophenen, Thiadiazolen, Pyridinen, Pyrimidinen, Pyrazinen, Pyridazinen, Piperazinen, Piperidinen, Morpholonen, Pyranen, Anolinen, Phthalazinen, Quinazolinen, Quinoxalinen und Kombinationen davon.A multiplicity of ionic liquids known per se can be used for the process according to the invention. Ionic liquids are a group of solvents which, unlike traditional organic or aqueous solvents, are composed of anions and cations. Here, ionic liquids are typically composed of an organic cation, which is often obtained by alkylation of a compound. These may be selected from imidazoles, pyrazoles, thiazoles, isothiazoles, azathiazoles, oxothiazoles, oxazines, oxazolines, oxazaboroles, dithiozoles, triazoles, selenozoles, oxaphospholes, pyrroles, borols, furans, thiophenes, phospholes, pentazoles, indoles, indolines, oxazoles, isoxazoles , Isotriazoles, tetrazoles, benzofurans, dibenzofurans, benzothiophenes, dibenzothiophenes, thiadiazoles, pyridines, pyrimidines, pyrazines, pyridazines, piperazines, piperidines, morpholones, pyrans, anolines, phthalazines, quinazolines, quinoxalines, and combinations thereof.

Der anionische Teil der ionischen Flüssigkeit kann aus anorganischen oder organischen Anionen aufgebaut sein. Typische Beispiele hierfür sind Halogenide, BX4 -, PF6 -, AsF6 -, SbF6 -, NO2 -, NO3 -, SO4 2-,BR4 -, substituierte oder unsubstituierte Carborane, substituierte oder unsubstituierte Metallocarborane, Phosphate, Phosphite, Polyoxometalate, substituierte oder unsubstituierte Carboxylate wie Acetat, Triflate und nicht koordinierende Anionen. Dabei kann X unabhängig voneinander für Fluorid, Chlorid, Bromid oder Iodid stehen und R unabhängig voneinander Wasserstoff, Alkyl, substituiertes Alkyl, Cycloalkyl, substituiertes Cycloalkyl, Heteroalkyl, Heterocycloalkyl, substituiertes Heterocycloalkyl, Aryl, substituiertes Aryl, Heteroaryl, substituiertes Heteroaryl, Alkoxy- Aryloxy, Acyl, Silyl, Boryl, Phosphino, Amino, Thio oder Seleno umfassen. Durch Veränderung der Kombinationen von Kationen und Anionen ist es möglich, die ionische Flüssigkeit mit den gewünschten Lösungseigenschaften für ein spezifisches thermoplastisches Polymer einzustellen.The anionic portion of the ionic liquid may be composed of inorganic or organic anions. Typical examples of these are halides, BX 4 - , PF 6 - , AsF 6 - , SbF 6 - , NO 2 - , NO 3 - , SO 4 2- , BR 4 - , substituted or unsubstituted carboranes, substituted or unsubstituted metallocarboranes, phosphates , Phosphites, polyoxometalates, substituted or unsubstituted carboxylates such as acetate, triflates and non-coordinating anions. In this case, X independently of one another can stand for fluoride, chloride, bromide or iodide and R independently of one another Hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy-aryloxy, acyl, silyl, boryl, phosphino, amino, thio or seleno. By changing the combinations of cations and anions, it is possible to adjust the ionic liquid having the desired solution properties for a specific thermoplastic polymer.

Die für das erfindungsgemäße Verfahren eingesetzte Polymerlösung kann beispielsweise dadurch hergestellt werden, dass das Polymer als Polymergranulat in die ionische Flüssigkeit bei einer geeigneten Temperatur unter Rühren eingebracht wird. Alternativ hierzu kann das Polymer durch Erhitzen in eine Polymerschmelze überführt werden, in welche dann anschließend die ionische Flüssigkeit eingebracht wird.The polymer solution used for the process according to the invention can be prepared, for example, by introducing the polymer as polymer granulate into the ionic liquid at a suitable temperature with stirring. Alternatively, the polymer can be converted by heating into a polymer melt, in which then subsequently the ionic liquid is introduced.

In weiterer Ausgestaltung des erfindungsgemäßen Verfahrens kann die Polymerlösung einen Füllstoff und/ oder Porenbildner enthalten der insbesondere aus der Gruppe ausgewählt ist umfassend Mikro- und Nanopartikel oder - Fasern, vorzugsweise Kunststoff- oder Glas(hohl)kugeln, keramische (Hohl)kugeln, Kunststoff-, Glas-, Kohlenstoff-, Metall- oder Keramikfasern, Schichtsilikate oder Kombinationen hiervon. Als Porenbildner kommen beispielsweise Salze, insbesondere kristallwasserfreie Salze wie Natriumchlorid in Betracht. Die Porenbildner können nach der Herstellung der Bespannung herausgelöst werden. Hierzu werden die Porenbildner zweckmäßigerweise so auf das Koagulationsmittel abgestimmt, dass sie sich darin lösen. Als Beispiel für einen Natriumchlorid-Porenbildner kommt insbesondere Wasser als Koagulationsmittel in Frage.In a further embodiment of the method according to the invention, the polymer solution may contain a filler and / or pore former which is in particular selected from the group comprising micro- and nanoparticles or fibers, preferably plastic or glass (hollow) balls, ceramic (hollow) balls, plastic Glass, carbon, metal or ceramic fibers, phyllosilicates or combinations thereof. Suitable pore formers are, for example, salts, in particular salts free of water of crystallization, such as sodium chloride. The pore formers can be dissolved out after the production of the fabric. For this purpose, the pore formers are expediently so on the coagulant agreed that they dissolve in it. As an example of a sodium chloride pore-forming agent is in particular water as a coagulant in question.

Mithilfe der vorgenannten Füllstoffe lassen sich beispielsweise die mechanischen Eigenschaften der porösen Polymerschicht modifizieren, wie deren Reißfestigkeit und Elastizität. Zudem kann die Verschleißfestigkeit der Bespannung durch den Einsatz von Füllstoffen gesteigert werden. Das spezifische Gewicht lässt sich beispielsweise durch den Einsatz von Leichtfüllstoffen reduzieren. Unter Leichtfüllstoffen werden solche Füllstoffe verstanden, deren spezifisches Gewicht bei unter einem Gramm pro cm3 liegt.With the aid of the abovementioned fillers, it is possible, for example, to modify the mechanical properties of the porous polymer layer, such as their tensile strength and elasticity. In addition, the wear resistance of the fabric can be increased by the use of fillers. The specific weight can be reduced, for example, by using lightweight fillers. Light fillers are understood as meaning those fillers whose specific weight is less than one gram per cm 3 .

Die im Rahmen des erfindungsgemäßen Verfahrens bzw. der erfindungsgemäßen Papiermaschinenbespannung eingesetzte Trägerschicht kann im Prinzip jede für Papiermaschinenbespannungen bekannte Form und Struktur aufweisen. Es kann sich bei der Trägerschicht um ein Gewebe, Gewirke, Gelege oder verfestigtes Vlies, insbesondere aus Fasern, Fäden oder Zwirnen, oder um ein Netting handeln. Die Trägerschicht kann einlagig oder auch mehrlagig aufgebaut sein.The carrier layer used in the context of the method according to the invention or the papermachine fabric according to the invention can, in principle, have any shape and structure known for papermachine clothing. The carrier layer may be a woven, knitted fabric, scrim or consolidated nonwoven, in particular fibers, threads or threads, or a netting. The carrier layer can be constructed in one or more layers.

Weiterhin kann auf wenigstens einer Seite der Trägerschicht eine Zwischenschicht vorgesehen sein, auf welche die Polymerlösung aufgebracht wird, wobei die Zwischenschicht insbesondere ausgewählt ist aus einem verankerten Faservlies, einer Schicht aus geschichtetem und gesintertem Polymerpulver oder Polymer-Mikrokugeln, einer Schaumstoffschicht, einer im Vergleich zur Trägerschicht feiner oder gröber strukturierten Schicht aus Gewebe, Gewirke, Gelege oder verfestigtes Vlies, insbesondere aus Fasern, Fäden oder Zwirnen, oder aus Netting oder einer Kombination von diesen. Mithilfe einer solchen Zwischenschicht oder auch mehreren Zwischenschichten auf einer oder beiden Seiten der Trägerschicht können beispielsweise die mechanischen Eigenschaften und das Wasseraufnahmeverhalten der Papiermaschinenbespannung modifiziert werden. So ist es hierdurch unter anderem möglich, bei einer für die Pressenpartie einer Papiermaschine vorgesehen Bespannung durch Einsatz einer Vlies-Zwischenschicht das Wasseraufnahmevermögen der Bespannung zu erhöhen.Furthermore, an intermediate layer can be provided on at least one side of the carrier layer, to which the polymer solution is applied, wherein the intermediate layer is in particular selected from an anchored nonwoven fabric, a layer of layered and sintered polymer powder or polymer microspheres, a foam layer, a comparison with Carrier layer finer or coarser structured layer of woven, knitted fabric, scrim or bonded nonwoven, in particular of fibers, threads or threads, or of netting or a combination of these. By means of such an intermediate layer or even several intermediate layers on one or both sides of the carrier layer, for example, the mechanical properties and the water absorption behavior of the papermachine clothing can be modified. Thus, it is thereby possible, inter alia, to increase the water absorption capacity of the fabric in a covering provided for the press section of a paper machine by using a nonwoven intermediate layer.

Nach einer Weiterbildung des erfindungsgemäßen Verfahrens und der erfindungsgemäßen Bespannung kann die Trägerschicht und/oder die Zwischenschicht ein Polymermaterial umfassen oder hieraus bestehen, welches insbesondere ausgewählt ist aus der Gruppe umfassend Polyamide, insbesondere Aramid, Polyester, Polyolefine, Polyurethane, Copolymere, Mischungen sowie Kombinationen hiervon, wobei die Trägerschicht und die Zwischenschicht aus jeweils unterschiedlichen Materialien bestehen können.According to a development of the method according to the invention and the covering according to the invention, the carrier layer and / or the intermediate layer may comprise or consist of a polymer material which is in particular selected from the group comprising polyamides, in particular aramid, polyesters, polyolefins, polyurethanes, copolymers, mixtures and combinations thereof , wherein the carrier layer and the intermediate layer may each consist of different materials.

Nach einer bevorzugten Ausführungsform des erfindungsgemäßen Verfahrens wird die Polymerlösung vor dem Aufbringen der Polymerlösung auf eine Temperatur von 10 bis 300 °C erwärmt wird, insbesondere auf eine Temperatur von 80 bis 200 °C, bevorzugt von 90 bis 150 °C. Dies ist besonders vorteilhaft, da auf diese Weise Polymerlösungen mit vergleichsweise hoher Polymerkonzentration gleichmäßig aufgetragen werden können. Um beim Auftragen Temperatursprünge zu vermeiden ist es weiterhin von Vorteil auch die Trägerschicht auf die vorgenannten Temperaturen zu erwärmen, insbesondere auf wenigstens dieselbe Temperatur wie die Polymerlösung.According to a preferred embodiment of the method according to the invention, the polymer solution is heated to a temperature of 10 to 300 ° C prior to application of the polymer solution, in particular to a temperature of 80 to 200 ° C, preferably from 90 to 150 ° C. This is particularly advantageous since in this way polymer solutions with comparatively high polymer concentration can be applied uniformly. To apply temperature jumps To avoid it is also advantageous to heat the support layer to the aforementioned temperatures, in particular to at least the same temperature as the polymer solution.

Der Auftrag der Polymerlösung kann im Prinzip auf jede geeignete Weise erfolgen, beispielsweise durch Rakeln, Bepinseln, Bestreichen, Tauchen, Sprühen, Berieseln, Gie-βen, Spritzen, Walzenauftrag, Drucken, beispielsweise über Rotationssiebdruck oder Inkjet-Verfahren, Imprägnieren oder Kalandrieren aufgetragen wird. Auch Kombinationen hiervon sind möglich. Der Auftrag kann vollflächig oder sektional begrenzt, regelmäßig oder unregelmäßig, in definierten oder zufälligen Mustern, punktförmig oder linienförmig oder nach einem anderen Raster erfolgen. Zur Verbesserung des Auftragsergebnisses können maschinelle Komponenten in Form von Rakeln oder Walzen einseitig oder beidseitig vom Substrat gegebenenfalls mit vorhandener Zwischenschicht eingesetzt werden.The application of the polymer solution can in principle be carried out in any suitable manner, for example by doctoring, brushing, brushing, dipping, spraying, sprinkling, casting, spraying, roller coating, printing, for example by rotary screen printing or inkjet, impregnation or calendering is applied , Also combinations of these are possible. The order may be full-surface or sectionally limited, regular or irregular, in defined or random patterns, punctiform or linear, or in any other pattern. To improve the order result, machine components in the form of doctor blades or rollers can be used on one or both sides of the substrate optionally with an existing intermediate layer.

Die Koagulation kann in einem einzigen Schritt oder auch in mehreren Stufen durchgeführt werden. So kann in einem ersten Schritt die aufgetragene Polymerlösungsschicht zunächst leicht mit einem Koagulationsmittel besprüht oder berieselt werden, um eine dünne Haut auf der Oberfläche zu erzeugen, die weniger stark porös ist. Hierdurch lässt sich mit anderen Worten eine besonders glatte Oberfläche erzeugen. In einem zweiten Schritt kann die so vorbehandelte Bahn in das Koagulationsmittel getaucht werden um den Ausfällungsprozess abzuschließen. Hierdurch erhält die Polymerschicht im Inneren seine stark poröse Struktur.The coagulation can be carried out in a single step or in several stages. Thus, in a first step, the applied polymer solution layer may first be lightly sprayed or sprinkled with a coagulant to produce a thin skin on the surface that is less porous. In other words, this makes it possible to produce a particularly smooth surface. In a second step, the thus pretreated web can be dipped into the coagulant to complete the precipitation process. This preserves the polymer layer inside its highly porous structure.

Die aufgetragene Schichtdicke der Polymerlösung kann in weiten Bereichen variiert werden. So kann die Polymerlösung in einer Schichtdicke von 100 bis 3000 µm aufgetragen werden, insbesondere von 200 bis 2500 µm, bevorzugt von 500 bis 1500 µm. Dabei hängt die aufgetragene Schichtdicke typischerweise mit der gewünschten Schichtdicke der porösen Polymerschicht zusammen.The applied layer thickness of the polymer solution can be varied within wide ranges. Thus, the polymer solution can be applied in a layer thickness of 100 to 3000 .mu.m, in particular from 200 to 2500 .mu.m, preferably from 500 to 1500 .mu.m. The applied layer thickness is typically related to the desired layer thickness of the porous polymer layer.

Im Rahmen des erfindungsgemäßen Verfahrens kann weiterhin vorgesehen sein, dass die Polymerlösung zumindest teilweise in die Trägerschicht und/ oder die Zwischenschicht eindringt und diese insbesondere wenigstens zum Teil vollständig durchsetzt. Auf diese Weise kann zum einen die Verankerung der Polymerschicht auf der Trägerschicht verbessert werden. Zum anderen kann auf diese Weise auch die Maschinenseite der Papiermaschinenbespannung mit einer Polymerschicht versehen sein, wenn diese die Trägerschicht vollständig durchsetzt. Zudem können hierdurch auch das Rückstellvermögen und das Wasseraufnahmevermögen weiter gesteigert werden.In the context of the method according to the invention, it can further be provided that the polymer solution at least partially penetrates into the carrier layer and / or the intermediate layer and, in particular, at least partially completely penetrates the latter. In this way, on the one hand, the anchoring of the polymer layer on the carrier layer can be improved. On the other hand, the machine side of the papermachine fabric can be provided with a polymer layer in this way, if this completely penetrates the carrier layer. In addition, this also the resilience and water absorption capacity can be further increased.

Hierbei liegt es ebenfalls im Rahmen der vorliegenden Erfindung, dass die Trägerschicht beidseitig mit einer Polymerlösung der eingangs genannten Art beschichtet werden kann. Dies kann entweder in einem Schritt erfolgen oder aber es wird zunächst eine Polymerschicht durch Auftragen und Koagulation erzeugt und dann anschließend die Gegenseite entsprechend beschichtet. Unabhängig von der Art der Erzeugung der zwei Schichten wird durch diese Verfahrensvariante die Möglichkeit eröffnet, auf beiden Seiten eine unterschiedliche Polymerbeschichtung zu erzeugen, was jedoch nicht zwingend ist. Dabei kann durch das teilweise Eindringen der Polymerlösungen in die Trägerschicht ein besonders fester mechanischer Zusammenhalt der auf beiden Seiten aufgebrachten Polymerschichten untereinander erzeugt werden. Auf diese Weise kann für die spätere Maschinenseite der Papiermaschinenbespannung beispielsweise eine besonders verschleißfeste Oberfläche erzeugt werden wohingegen die Papierseite der Bespannung auf ein besonders hohes Wasseraufnahmevermögen auslegbar ist.It is also within the scope of the present invention that the carrier layer can be coated on both sides with a polymer solution of the type mentioned above. This can either take place in one step or else a polymer layer is first produced by application and coagulation and then subsequently the opposite side coated accordingly. Regardless of the type the generation of the two layers is opened by this process variant, the possibility to produce a different polymer coating on both sides, but this is not mandatory. In this case, by the partial penetration of the polymer solutions into the carrier layer, a particularly firm mechanical cohesion of the polymer layers applied on both sides can be generated with one another. In this way, for example, a particularly wear-resistant surface can be produced for the later machine side of the paper machine clothing, whereas the paper side of the clothing can be interpreted as having a particularly high water absorption capacity.

Die Koagulation des Polymers aus der Polymerlösung kann beispielsweise durch in Kontakt bringen mit einem einem Koagulationsmittel ausgewählt aus protischen Lösungsmitteln erfolgen, insbesondere mit Wasser, einem C1 bis C4 Alkohol oder Mischungen hiervon. Der Auftrag kann beispielsweise durch Bepinseln, Bestreichen, Tauchen, Sprühen, Berieseln, Gießen, Spritzen, Drucken, Imprägnieren oder Kombinationen hiervon erfolgen.The coagulation of the polymer from the polymer solution can be effected, for example, by contacting it with a coagulant selected from protic solvents, in particular with water, a C 1 to C 4 alcohol or mixtures thereof. The job can be done, for example, by brushing, brushing, dipping, spraying, sprinkling, pouring, spraying, printing, impregnating or combinations thereof.

Nach der Koagulation des Polymers ist es zweckmäßig, die Bespannung zu trocknen. Dies kann beispielsweise über eine Gefriertrocknung erfolgen. Alternativ ist auch eine Trocknung bei einer Temperatur von 20°C bis zum Siedepunkt des Koagulationsmittels wie etwa 40 bis 100°C möglich, ggf. auch unter vermindertem Druck.After coagulation of the polymer, it is expedient to dry the clothing. This can be done for example via a freeze-drying. Alternatively, a drying at a temperature of 20 ° C to the boiling point of the coagulant such as 40 to 100 ° C is possible, possibly also under reduced pressure.

Nach einer weiteren Ausführungsform des erfindungsgemäßen Verfahrens und der erfindungsgemäßen Bespannung beträgt die Schichtdicke der getrockneten porösen Polymerschicht, die außerhalb der Trägerschicht beziehungsweise der Zwischenschicht liegt, 100 bis 2000 µm, insbesondere 200 bis 1700 µm, bevorzugt 500 bis 1500 µm. Diese Schichtdicken sind besonders vorteilhaft, da solche Papiermaschinenbespannungen gute mechanische Eigenschaften aufweisen, wie ein hohes mechanisches Rückstellvermögen und dabei gleichzeitig eine große Wasseraufnahmekapazität besitzen. Wenn sich die poröse Polymerschicht auch in die Trägerschicht erstreckt, kann die Gesamtschichtdicke der porösen Polymerschicht auch über den oben genannten Werten liegen.According to a further embodiment of the method according to the invention and the covering according to the invention the layer thickness of the dried porous polymer layer, which is outside the support layer or the intermediate layer, 100 to 2000 .mu.m, in particular 200 to 1700 .mu.m, preferably 500 to 1500 .mu.m. These layer thicknesses are particularly advantageous, since such papermachine clothing has good mechanical properties, such as a high mechanical resilience and at the same time have a large water absorption capacity. If the porous polymer layer also extends into the carrier layer, the total layer thickness of the porous polymer layer may also be above the above-mentioned values.

Die erfindungsgemäße Papiermaschinenbespannung kann gewünschtenfalls einer nachträglichen Oberflächenbehandlung unterzogen werden. So kann die poröse Polymerschicht beispielsweise nach erfolgter Trocknung mechanisch bearbeitet werden, insbesondere über einen Schleifprozess. Auf diese Weise lassen sich besonders glatte Oberflächen herstellen, so dass die Gefahr der Ausbildung von Markierungsmustern weiter reduziert wird. Außerdem kann durch eine solche Oberflächenbehandlung auch das Wasserabsorptionsverhalten nachträglich verändert werden. So kann je nach Führung des Koagulationsprozesses eine Hautbildung auf der porösen Polymerschicht auftreten welche die Porenzugänglichkeit reduzieren kann. Dies kann im Einzelfall erwünscht sein. Wenn die Offenporigkeit der porösen Polymerschicht jedoch erhöht werden soll, kann dies durch den vorgenannten mechanischen Abtrag erfolgen.If desired, the paper machine clothing according to the invention can be subjected to a subsequent surface treatment. Thus, the porous polymer layer can be mechanically processed, for example after drying, in particular via a grinding process. In this way, particularly smooth surfaces can be produced, so that the risk of the formation of marking patterns is further reduced. In addition, by such a surface treatment and the water absorption behavior can be changed later. Thus, depending on the guidance of the coagulation process, a skin formation on the porous polymer layer can occur, which can reduce the pore accessibility. This may be desirable in individual cases. However, if the porosity of the porous polymer layer is to be increased, this can be done by the abovementioned mechanical removal.

Die mithilfe des erfindungsgemäßen Verfahrens erzeugbaren porösen Polymerschichten besitzen beispielsweise eine mittlere Porengröße von 0,1 bis 300 µm, insbesondere von 0,5 bis 200 µm. Besonders bevorzugt liegt die mittlere Porengröße bei etwa 0,5 bis 20 µm.The porous polymer layers which can be produced by means of the process according to the invention have, for example, an average pore size of from 0.1 to 300 μm, in particular from 0.5 to 200 μm. Particularly preferably, the average pore size is about 0.5 to 20 microns.

Das Porenvolumen kann beispielsweise bei 30 bis 70% liegen, d. h. 30 bis 70% eines Probenvolumens wird durch Poren gebildet. Insbesondere liegt das Porenvolumen bei 40 bis 60%. Das Porenvolumen, die Porengröße und deren Verteilung kann über an sich bekannte Methoden wie Quecksilberporosimetrie oder BET-Messungen ermittelt werden.The pore volume may be, for example, 30 to 70%, i. H. 30 to 70% of a sample volume is formed by pores. In particular, the pore volume is 40 to 60%. The pore volume, the pore size and their distribution can be determined by methods known per se, such as mercury porosimetry or BET measurements.

Wie vorstehend ausgeführt wurde, betrifft die vorliegende Erfindung auch eine Bespannung für eine Papiermaschine, insbesondere in Form eines Formiersiebes oder einer Bespannung für die Pressensektion der Papiermaschine, welche durch das erfindungsgemäße Verfahren hergestellt ist. Dabei bildet zweckmäßigerweise die poröse Polymerschicht die Papierseite der Bespannung. Weiterhin kann die poröse Polymerschicht zusätzlich auch die Maschinenseite der Bespannung bilden.As stated above, the present invention also relates to a clothing for a paper machine, in particular in the form of a forming fabric or a clothing for the press section of the paper machine, which is produced by the inventive method. The porous polymer layer expediently forms the paper side of the fabric. Furthermore, the porous polymer layer may additionally form the machine side of the fabric.

Die vorliegende Erfindung ist ferner auf eine Papiermaschine gerichtet, die mit einer erfindungsgemäßen Bespannung ausgerüstet ist.The present invention is further directed to a paper machine equipped with a fabric according to the invention.

Schließlich betrifft die vorliegende Erfindung die Verwendung einer Lösung eines Polymers in einer ionischen Flüssigkeit zur Herstellung einer Papiermaschinenbespannung, insbesondere in Form eines Formiersiebes oder einer Bespannung für die Pressensektion der Papiermaschine.Finally, the present invention relates to the use of a solution of a polymer in an ionic liquid for producing a paper machine clothing, in particular in the form of a forming fabric or a covering for the press section of the paper machine.

Die vorliegende Erfindung wird im Folgenden anhand eines Ausführungsbeispiels näher erörtert:The present invention will be discussed in more detail below with reference to an exemplary embodiment:

Zur Herstellung einer erfindungsgemäßen Bespannung eine zweilagige Trägerschicht in Form eines Formiersiebes verwendet. Diese Trägerschicht weist eine papierseitige und eine maschinenseitige Gewebelage auf, die durch intrinsische Schussfäden miteinander verbunden sind. Die papierseitige Gewebelage ist aus in Leinwandbindung miteinander verwobenen Fäden gebildet, wohingegen die Fäden der maschinenseitigen Gewebelage in Atlas-Bindung verwoben sind. Die Fäden der papierseitigen Gewebelage besitzen einen geringeren Durchmesser als diejenigen der maschinenseitigen Gewebelage.To produce a fabric according to the invention, a two-layer carrier layer in the form of a forming fabric is used. This carrier layer has a paper-side and a machine-side fabric layer, which are interconnected by intrinsic weft threads. The paper-side fabric layer is formed of plain weave interwoven threads, whereas the machine side fabric layer threads are woven in satin weave. The threads of the paper-side fabric layer have a smaller diameter than those of the machine-side fabric layer.

Als ionische Flüssigkeit wurde 1-Ethyl-3-methyl-Imidazoliumdiethylphosphat (ENIM DEP der Firma BASF) verwendet. Zum Mischen mit dem Polymer Polyamid 6 (PA6) wurde die ionische Flüssigkeit auf ca. 80 °C erwärmt. Die geeignete Temperatur ist abhängig von der Mischungszusammensetzung. Vorliegend betrug der Gewichtsanteil 40 % ENIM DEP zu 60 % PA6.The ionic liquid used was 1-ethyl-3-methylimidazolium diethyl phosphate (ENIM DEP from BASF). For mixing with the polymer polyamide 6 (PA6), the ionic liquid was heated to about 80 ° C. The suitable temperature depends on the mixture composition. In the present case, the weight fraction was 40% ENIM DEP to 60% PA6.

Die Lösung des Polymers in der ionischen Flüssigkeit wurde bei nur geringer Abkühlung per Rakel auf die zweilagige Trägerschicht aufgetragen. Die Viskosität lag hierbei bei 700 mPas.The solution of the polymer in the ionic liquid was applied to the two-layer support layer by means of a doctor blade with only slight cooling. The viscosity was 700 mPas.

Als Koagulationsmittel kam von Verunreinigungen befreites und entionisiertes Wasser zum Einsatz, welches zuvor auf etwa 80°C erwärmt wurde. Hierbei ist die Erwärmung des Koagulationsmittels von Vorteil, damit sich die Mischung aus Polymer und ionischer Flüssigkeit nicht abkühlt. Weiterhin sinkt die Viskosität des Koagulationsmittels und der Austausch von Koagulationsmittel und ionischer Flüssigkeit wird beschleunigt.As a coagulant de-contaminated and deionized water was used, which was previously heated to about 80 ° C. Here, the heating of the coagulant is advantageous so that the mixture of polymer and ionic liquid does not cool. Furthermore, the viscosity of the coagulant decreases and the exchange of coagulant and ionic liquid is accelerated.

Die beschichtete Trägerschicht wird im Durchlauf durch ein Bad des Koagulationsmittels geführt, wobei das Polymer aus der Lösung unter Ausbildung der porösen Polymerschicht koaguliert. Die Verweilzeit der Bespannung im Bad wird in Abhängigkeit der Schichtdicke so gewählt, dass das Polymer quantitativ koaguliert. Anschließend wird die Bespannung bei einer Temperatur von 80 °C getrocknet.The coated carrier layer is passed through a bath of the coagulant while the polymer coagulates from the solution to form the porous polymer layer. The residence time of the covering in the bath is chosen as a function of the layer thickness so that the polymer coagulates quantitatively. Subsequently, the fabric is dried at a temperature of 80 ° C.

Eine auf diese Weise hergestellte Papiermaschinenbespannung ist in den REM-Aufnahmen gemäß den Fign. 1 bis 5 gezeigt. In der Fig. 1 ist in seitlicher Schnittdarstellung in Form einer Rasterelektronenmikroskop-Aufnahme dargestellt. Die schwammartige Porenstruktur mit vergleichsweise dünnen Stegen und der hieraus resultierenden hohen Porosität der Polymerschicht ist in Fign. 2 und 3 gut zu erkennen.A paper machine clothing produced in this way is in the SEM images according to the FIGS. 1 to 5 shown. In the Fig. 1 is shown in side sectional view in the form of a scanning electron micrograph. The spongy pore structure with comparatively thin webs and the resulting high porosity of the polymer layer is in FIGS. 2 and 3 clearly visible.

Dabei zeigt die Figur 2 einen ausschnittsweisen Querschnitt durch die Polymerschicht mit groben Entwässerungskanälen (weiß) und dickwandigen Polymerstegen (schwarz).It shows the FIG. 2 a partial cross section through the polymer layer with coarse drainage channels (white) and thick-walled polymer webs (black).

In Fig. 3 ist eine weitere Querschnittsaufnahme zu sehen. Danach sind auf einer Seite der Polymerschicht die in Fig. 2 dargestellten groben Entwässerungskanäle und dickwandigen Polymerstege zu sehen, wohingegen die gegenüberliegende Seite vergleichsweise feinere Entwässerungskanäle (weiß) und dünnwandigere Polymerstege (schwarz) aufweist.In Fig. 3 is another cross-sectional view to see. Thereafter, on one side of the polymer layer, the in Fig. 2 shown coarse drainage channels and thick-walled polymer webs to see, whereas the opposite side has comparatively finer drainage channels (white) and thin-walled polymer webs (black).

In Fign. 4 und 5 ist die Papierseite der Bespannung in der Draufsicht abgebildet. In der Draufsicht nach Fig. 4 ist zur Bestimmung der anteiligen papierkontaktierenden offenen Fläche das Polymermaterial schwarz und die offenen Flächen weiß dargestellt. Fig. 5 zeigt die hierzu inverse Darstellung. Hieraus ergibt sich eine offene Fläche von 42 % mit Porengrößen von 1-7 µm.In FIGS. 4 and 5 the paper side of the fabric is shown in plan view. In the plan view Fig. 4 For example, to determine the proportionate paper-contacting open area, the polymeric material is black and the open areas are white. Fig. 5 shows the inverse representation. This results in an open area of 42% with pore sizes of 1-7 microns.

Claims (15)

  1. A method for producing a cover for a paper machine, in particular in the form of a forming fabric or a cover for the pressing section of the paper machine, comprising a single- or multi-layered carrier layer and a porous polymer layer applied to at least one side of the latter, characterised in that a solution of the polymer in an ionic liquid is applied as far as possible to the whole surface of the carrier layer and the polymer is then brought to coagulation, the porous polymer layer being produced on the carrier layer.
  2. The method according to claim 1, characterised in that the polymer is a thermoplastic polymer and in particular is selected from the group comprising polyamides such as polyamide 6, polyamide 6.6, polyamide 6.10, polyethylene terephthalate, polybutylene terephthalate, polyurethane, polyester polyurethane, polyether polyurethane, polyvinyl chloride or combinations or copolymers of the latter.
  3. The method according to claim 1 or 2, characterised in that the polymer concentration in the polymer solution is 5 to 95 % by weight in relation to the weight of the overall solution, in particular 50 to 80 % by weight.
  4. The method according to any of the preceding claims, characterised in that the polymer solution contains a filler and/or pore forming material which is selected in particular from the group comprising micro- and nanoparticles or fibres, preferably plastic or glass balls, plastic or glass hollow balls, ceramic balls or hollow balls, plastic, glass, carbon, metal or ceramic fibres, layer silicates, salts or combinations of the latter.
  5. The method according to any of the preceding claims, characterised in that the carrier layer is in the form of a woven or knitted fabric, a scrim or reinforced fleece, in particular made of fibres, threads or yarns, or in the form of netting.
  6. The method according to any of the preceding claims, characterised in that there is provided on at least one side of the carrier layer an intermediate layer to which the polymer solution is applied, the intermediate layer being selected in particular from an anchored fibrous web, a layer of layered and sintered polymer powder or polymer microspheres, a foam layer, a layer of woven or knitted fabric, a non-woven layer or reinforced fleece, in particular made of fibres, threads or yarns or of netting or a combination of the latter, which has a finer or coarser structure in comparison to the carrier layer.
  7. The method according to any of the preceding claims, characterised in that the polymer solution and if so desired also the carrier layer is heated to a temperature of 10 to 300°C, in particular to a temperature of 80 to 200°C, preferably of 90 to 150°C before applying the polymer solution, and/or that the polymer solution is applied in a layer thickness of 100 to 200 µm, in particular of 200 to 2500 µm, preferably of 500 to 1500 µm.
  8. The method according to any of the preceding claims, characterised in that the polymer solution penetrates at least partially into the carrier layer and/or the intermediate layer and in particular completely passes through the latter, at least in part.
  9. The method according to any of the preceding claims, characterised in that the coagulation of the polymer takes places by bringing the applied polymer solution into contact with a coagulation agent selected from protic solvents such as water or a C1 to C4 alcohol, in particular by brushing on, coating, immersing, spraying, sprinkling, pouring, injecting, printing, impregnating or combinations of the latter, and/or that a drying step follows the coagulation step, the drying taking place in particular by means of freeze-drying or at a temperature of from 20°C to the boiling point of the coagulation medium, in particular at 40 to 100°C, optionally at reduced pressure.
  10. The method according to any of the preceding claims, characterised in that the layer thickness of the dried porous polymer layer, which lies outside of the carrier layer and the intermediate layer, is 100 to 2000 µm, in particular 200 to 1700 µm, preferably 500 to 1500 µm.
  11. The method according to any of the preceding claims, characterised in that the porous polymer layer is mechanically processed, preferably ground, after drying has taken place.
  12. The method according to any of the preceding claims, characterised in that the average pore size in the porous polymer layer is 0.1 to 300 µm, in particular 0.5 to 200 µm, preferably 0.5 to 20 µm and/or that the pore volume in the porous polymer layer is 30 to 70 %, in particular 40 to 60 %.
  13. A cover for a paper machine, in particular in the form of a forming fabric or a cover for the pressing section of the paper machine, produced by a method according to any of claims 1 to 18.
  14. The cover according to claim 13, characterised in that the porous polymer layer forms the paper side and/or the machine side of the cover.
  15. The paper machine, equipped with a cover according to either of claims 13 or 14.
EP20110189294 2011-11-16 2011-11-16 Method for producing a paper machine fabric and paper machine fabric Not-in-force EP2594691B1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP20110189294 EP2594691B1 (en) 2011-11-16 2011-11-16 Method for producing a paper machine fabric and paper machine fabric
CN2012104649604A CN103112205A (en) 2011-11-16 2012-11-16 Method for producing a paper machine fabric and paper machine fabric

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP20110189294 EP2594691B1 (en) 2011-11-16 2011-11-16 Method for producing a paper machine fabric and paper machine fabric

Publications (2)

Publication Number Publication Date
EP2594691A1 EP2594691A1 (en) 2013-05-22
EP2594691B1 true EP2594691B1 (en) 2014-01-08

Family

ID=45002712

Family Applications (1)

Application Number Title Priority Date Filing Date
EP20110189294 Not-in-force EP2594691B1 (en) 2011-11-16 2011-11-16 Method for producing a paper machine fabric and paper machine fabric

Country Status (2)

Country Link
EP (1) EP2594691B1 (en)
CN (1) CN103112205A (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE202013103055U1 (en) * 2013-07-10 2014-10-13 Heimbach Gmbh & Co. Kg The paper machine belt
CN106460332A (en) * 2016-03-23 2017-02-22 许长云 A warp self-binding forming network
CN106283818B (en) * 2016-08-24 2018-03-23 四川环龙技术织物有限公司 A kind of paper machine clothing and the technique for producing the paper machine clothing
CN106245403B (en) * 2016-08-24 2018-02-16 四川环龙技术织物有限公司 A kind of composite fibre polyester multilayer wire structure

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4571359A (en) 1984-12-18 1986-02-18 Albany International Corp. Papermakers wet-press felt and method of manufacture
US4795480A (en) 1986-12-10 1989-01-03 Albany International Corp. Papermakers felt with a resin matrix surface
US4847116A (en) * 1988-05-09 1989-07-11 Albany International Corp. Method for depositing particles and a binder system on a base fabric
GB9803172D0 (en) * 1998-02-14 1998-04-08 Scapa Group Plc Porous belts
TW538175B (en) * 1999-07-08 2003-06-21 Heimbach Gmbh Thomas Josef Transfer belt for a paper making machine
US7156956B2 (en) * 2003-08-11 2007-01-02 Albany International Corp. Paper industry process belt with a surface structure composed of a porous membrane
JP2006176904A (en) * 2004-12-21 2006-07-06 Ichikawa Co Ltd Conveyor felt for papermaking, and press device of paper machine having the conveyor felt for papermaking

Also Published As

Publication number Publication date
EP2594691A1 (en) 2013-05-22
CN103112205A (en) 2013-05-22

Similar Documents

Publication Publication Date Title
DE69616413T2 (en) Press cloth for papermaking
DE3419708C2 (en) Process for producing a wet press felt cloth for paper machines and wet press felt cloth produced therewith
DE68925345T2 (en) Pressed fabric with foam coating to control the empty volume
DE3685975T2 (en) PAPER MAKING FELT FOR WET PRESS AND METHOD FOR THE PRODUCTION THEREOF.
DE60103999T2 (en) METHOD FOR PRODUCING A WET LUBRICANT
DE60107223T2 (en) MANUFACTURE OF FIBER MATS FROM CHOPPED STRANDS
DE69909085T2 (en) MATERIAL FOR PHASE SEPARATION
EP2594691B1 (en) Method for producing a paper machine fabric and paper machine fabric
EP4110983B1 (en) Process and apparatus for producing a composite nonwoven
DE3614949C2 (en)
EP0786551A1 (en) Process for making a web of material
DE2900771C2 (en) Decorative laminate
DE69914413T2 (en) Improvements to paper machine fabrics
DE60008658T2 (en) Transfer belt for a wet web
DE102004054804A1 (en) Paper machine clothing
EP0817886B1 (en) Web of fabric and process for its production
WO2012113466A1 (en) Press section of a machine for producing a fibrous web and method for producing a fibrous web
DE2655136B2 (en) Process for the production of a nonwoven fabric containing binding fibers
DE102017126210A1 (en) HIGH-DENSITY ART LEATHER, WHICH HAS AN EXCELLENT SURFACE PATTERN, AND A METHOD FOR MANUFACTURING THE SAME
DE1807329A1 (en) Forming medium for the forming section of a paper machine
DE68920411T2 (en) Paper machine fabric with controlled release properties.
DE102010039364A1 (en) Wire for machine for manufacturing tissue web from fibrous material suspension, has laser source extending at region in transverse direction to machine direction, where extending regions are welded with one another
DE69118054T2 (en) Fabric and felt for heating press made of PEEK fibers
DE2713311C2 (en) Process for the production of paper, cardboard or paperboard
DE2406126A1 (en) POROESE FILM MATERIAL

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20120306

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

RIC1 Information provided on ipc code assigned before grant

Ipc: D21F 7/08 20060101ALI20130611BHEP

Ipc: D21F 1/00 20060101AFI20130611BHEP

INTG Intention to grant announced

Effective date: 20130717

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: GERMAN

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 648849

Country of ref document: AT

Kind code of ref document: T

Effective date: 20140215

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 502011001981

Country of ref document: DE

Effective date: 20140220

REG Reference to a national code

Ref country code: SE

Ref legal event code: TRGR

REG Reference to a national code

Ref country code: NL

Ref legal event code: VDEP

Effective date: 20140108

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140508

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140108

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140408

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140108

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140108

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140508

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140108

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140108

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140108

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140108

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 502011001981

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140108

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140108

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140108

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140108

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140108

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140108

26N No opposition filed

Effective date: 20141009

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 502011001981

Country of ref document: DE

Effective date: 20141009

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140108

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20141116

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140108

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20141130

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20141130

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20141130

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20150731

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20141116

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20141201

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140108

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140108

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140409

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20111116

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140108

Ref country code: MT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140108

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140108

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140108

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20211014

Year of fee payment: 11

Ref country code: FI

Payment date: 20211117

Year of fee payment: 11

Ref country code: SE

Payment date: 20211123

Year of fee payment: 11

Ref country code: AT

Payment date: 20211022

Year of fee payment: 11

Ref country code: DE

Payment date: 20211014

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20211130

Year of fee payment: 11

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 502011001981

Country of ref document: DE

REG Reference to a national code

Ref country code: SE

Ref legal event code: EUG

REG Reference to a national code

Ref country code: AT

Ref legal event code: MM01

Ref document number: 648849

Country of ref document: AT

Kind code of ref document: T

Effective date: 20221116

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20221116

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20221116

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20221117

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20221116

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20221116

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20230601

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20221116