EP2809843B1 - Roll cover with improved dynamic properties and high resilience behavior - Google Patents

Roll cover with improved dynamic properties and high resilience behavior Download PDF

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Publication number
EP2809843B1
EP2809843B1 EP13702601.9A EP13702601A EP2809843B1 EP 2809843 B1 EP2809843 B1 EP 2809843B1 EP 13702601 A EP13702601 A EP 13702601A EP 2809843 B1 EP2809843 B1 EP 2809843B1
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EP
European Patent Office
Prior art keywords
weight
parts
crosslinked
roll
rubber
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EP13702601.9A
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German (de)
French (fr)
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EP2809843A1 (en
Inventor
Peter PUTSCHÖGL
Stephan Ully
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Voith Patent GmbH
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Voith Patent GmbH
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    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21F—PAPER-MAKING MACHINES; METHODS OF PRODUCING PAPER THEREON
    • D21F3/00—Press section of machines for making continuous webs of paper
    • D21F3/02—Wet presses
    • D21F3/08—Pressure rolls
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21F—PAPER-MAKING MACHINES; METHODS OF PRODUCING PAPER THEREON
    • D21F5/00—Dryer section of machines for making continuous webs of paper
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21G—CALENDERS; ACCESSORIES FOR PAPER-MAKING MACHINES
    • D21G1/00—Calenders; Smoothing apparatus
    • D21G1/02—Rolls; Their bearings
    • D21G1/0233—Soft rolls
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21G—CALENDERS; ACCESSORIES FOR PAPER-MAKING MACHINES
    • D21G1/00—Calenders; Smoothing apparatus
    • D21G1/02—Rolls; Their bearings
    • D21G1/0246—Hard rolls
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
    • D21H23/02—Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
    • D21H23/22—Addition to the formed paper
    • D21H23/52—Addition to the formed paper by contacting paper with a device carrying the material
    • D21H23/56—Rolls
    • D21H23/58—Details thereof, e.g. surface characteristics, peripheral speed

Definitions

  • the present invention relates to a roll, in particular for a roll for treating a paper, board or other fibrous web in a machine for producing and / or finishing the same suitable roll cover, a roll comprising this roll cover and the use of such a roll.
  • rolls and in particular rubber rolls having an elastic surface are used in a plurality of process steps, such as sheet formation in the wire section of the paper machine, dewatering in the press section of the paper machine, and painting, drying and smoothing in the final section of the paper machine paper machine.
  • a large number of the rolls used in papermaking are each pressed against a mating roll during operation, wherein a pulp or paper web is carried out in the nip formed between the roll and the mating roll.
  • a film press for example, which is used for the surface treatment of paper webs, a film of, for example, glue or coating color is produced on rapidly rotating applicator rollers, for example by means of roller blades, which is transferred in the nip to the guided through the nip paper web.
  • rollers are subjected to enormous loads during their use and therefore have to meet a variety of both mechanical and dynamic properties.
  • such rollers in addition to good mechanical Properties such as high tensile strength, abrasion resistance, tear resistance, tear propagation resistance, compressive strength and impact strength, also have excellent dynamic properties, such as low hysteresis and low tan ⁇ , among other things, the heat build-up during roll operation is sufficiently low.
  • such rollers must have a good and fast recovery behavior.
  • rolls are usually provided on their surface with a roll cover arranged on a roll core, the material of which is formulated with regard to the required application properties.
  • roll covers are composed of materials containing a matrix of a rubber or a mixture of two or more rubbers in which one or more fillers are embedded.
  • This solution is based on the surprising discovery that it is possible to obtain a roll cover made of a rubber composition having not only excellent mechanical properties, but at the same time excellent dynamic properties, namely a low tan ⁇ value and a low hysteresis, and in particular with an excellent recovery behavior by mixing a (meth) acrylate compound having a very high degree of dispersion or finely divided with a rubber component comprising at least one crosslinked hydrogenated nitrile rubber and optionally other conventional filler (s) and additive (s).
  • the rubber forms the rubber component which forms the matrix of the at least one layer of the roll cover, in which the at least one (meth) acrylate compound and optionally other fillers and additives are embedded.
  • the roll cover according to the invention is particularly suitable for use in a roll which is used in a fast-running glue or coating unit of a paper or board machine and is exposed in their use enormous centrifugal forces and deformation forces ,
  • rubber means any vulcanized rubber, irrespective of whether this is a vulcanized natural rubber or a vulcanized synthetic rubber.
  • rubber component denotes the sum of all crosslinked and uncrosslinked rubbers contained in the rubber composition, that is to say the matrix of the at least one layer of the roll cover
  • Rubber composition denotes the sum of all compounds contained in the at least one layer of the roll cover, ie the sum of the crosslinked and uncrosslinked rubbers embedded therein at least one (meth) acrylate compound and the optional other fillers and additives.
  • (meth) acrylate compound means all compounds which have at least one acrylate group and / or at least one methacrylate group, ie in particular all at least one acrylate group and / or at least one methacrylate group-containing molecular compounds, ionic compounds or salts and complex connections.
  • the at least one layer of the roll cover according to the invention has a return speed of at least 12 mm / sec. which, as stated above, can be achieved by mixing the at least one (meth) acrylate compound having a sufficiently high degree of dispersion or finely divided with the rubber component comprising at least one crosslinked hydrogenated nitrile rubber.
  • the at least one layer of the roll cover has a return speed of at least 14 mm / sec, preferably a return speed of at least 16 mm / sec and particularly preferably a return speed of at least 18 mm / sec. having.
  • FIG. 1 Fig. 3 is an example of a diagram showing a plurality of displacement and force signals for each one cycle at a force of 100 N (curve A) and one cycle at a force of 200 N (curve B). Performing the cycles, each with a hold period of 900 milliseconds and a force pulse phase for a duration of 100 milliseconds, simulates the passage of the roll cover through the nip and the subsequent clearance of the roll cover outside the nip.
  • the at least one layer of the roll cover according to the invention has a maximum plastic deformation degree of 0.9%.
  • the at least one (meth) acrylate compound having a sufficiently high degree of dispersion or finely divided with the rubber component comprising at least one crosslinked hydrogenated nitrile rubber.
  • Specific manufacturing methods will be described below. Particularly good results are obtained in this embodiment, if the at least one layer has a plastic deformation of not more than 0.7%, preferably of at most 0.5% and more preferably of at most 0.3%.
  • the degree of deformation is determined to be ((H a -H n ) / H a) x 100, where H a denotes the initial height of the sample body and H n denotes the height of the sample body after performing the force cycles. From the thus determined five degrees of deformation then the arithmetic mean is calculated. This value corresponds to the degree of deformation specified above.
  • the at least one layer of the roll cover according to the invention both has a return speed of at least 12 mm / sec, preferably of at least 14 mm / sec, more preferably of at least 16 mm / sec. and most preferably at least 18 mm / sec, as well as a plastic deformation degree of maximum 0.9%, preferably of at most 0.7%, more preferably of at most 0.5% and most preferably of at most 0.3%.
  • the at least one layer of the roll cover according to the invention also has a tan ⁇ value of not more than 0.16 determined according to DIN 53513 at 60 ° C., tension, 10 Hz, 15% static elongation and 1% dynamic elongation.
  • the tan ⁇ value is a measure of the heat buildup of the rubber composition, which in turn correlates with the hysteresis of the rubber composition, with a low tan ⁇ value correlating with low hysteresis and low heat build-up property.
  • this low tan ⁇ value can be achieved by mixing the at least one (meth) acrylate compound with a sufficiently high degree of dispersion or finely divided with the rubber component comprising at least one crosslinked hydrogenated nitrile rubber. Particularly good results are achieved if the at least one layer has a tan ⁇ value of not more than 0.14, preferably of not more than 0.12 and particularly preferably not more than 0.10.
  • the at least one layer of the roll cover according to the invention has a tear propagation resistance of more than 14 N / mm, preferably more than 15 N / mm N / mm and more preferably more than 16 N / mm N / mm.
  • the tear resistance is determined according to DIN ISO 34-1, Method B, Method B.
  • the at least one layer of the roll cover according to the invention comprises at least one crosslinked one hydrogenated nitrile rubber in which the at least one (meth) acrylate compound is embedded in finely divided form.
  • Hydrogenated nitrile rubber in this context means both completely hydrogenated and partially hydrogenated nitrile rubber.
  • the crosslinked hydrogenated nitrile rubber is crosslinked partially hydrogenated nitrile rubber, wherein the degree of hydrogenation is preferably 85 to less than 100%, and more preferably 90 to less than 100%.
  • the rubber composition of the at least one layer of the roll cover comprises a crosslinked hydrogenated nitrile rubber having an acrylonitrile content between 20 and 50% by weight, preferably between 30 and 40% by weight. % and more preferably between 33 and 37 wt .-% and accordingly with a butadiene content between 50 and 80 wt .-%, preferably between 60 and 70 wt .-% and particularly preferably between 67 and 63 wt .-%.
  • the at least one crosslinked hydrogenated nitrile rubber has a Mooney viscosity determined according to DIN 53253-3 between 20 and 80 and preferably between 30 and 70.
  • the rubber component of the rubber composition may be wholly composed of a crosslinked hydrogenated nitrile rubber or of two or more different crosslinked hydrogenated nitrile rubbers, that is, the rubber component and thus also the rubber composition contain no other rubber except a crosslinked hydrogenated nitrile rubber or more crosslinked hydrogenated nitrile rubbers.
  • the rubber composition may be prepared by mixing the at least one (meth) acrylate compound in the uncrosslinked hydrogenated nitrile rubber and finely dispersing with a high degree of dispersion before the mixture thus prepared is vulcanized ,
  • the rubber composition may be prepared by first mixing the at least one (meth) acrylate compound into a first uncrosslinked hydrogenated nitrile rubber and finely dispersing it with a high degree of dispersion before entering the first a second and optionally one or more further uncrosslinked hydrogenated nitrile rubber (s) is / are blended and the mixture thus produced is finally vulcanized.
  • the at least one (meth) acrylate compound is first mixed into a first crosslinked hydrogenated nitrile rubber and finely divided with a high degree of dispersion before mixing this mixture with a second crosslinked hydrogenated nitrile rubber ,
  • the rubber component of the rubber composition contains, in addition to the at least one crosslinked hydrogenated nitrile rubber, at least one other rubber other than crosslinked hydrogenated nitrile rubber which is preferably selected from the group consisting of crosslinked nitrile rubbers and crosslinked carboxylated ones Nitrile rubbers, crosslinked styrene-butadiene rubbers and any copolymers and / or mixtures of two or more of the aforementioned crosslinked rubbers.
  • the preparation of the rubber composition can be carried out analogously to the variants described above in relation to the embodiment in which the rubber component consists exclusively of hydrogenated / hydrogenated nitrile rubber (s).
  • the rubber composition can be prepared by first mixing the at least one (meth) acrylate compound into an uncrosslinked hydrogenated nitrile rubber and finely dispersing it with a high degree of dispersion before a second and optionally one or more further uncrosslinked ( r) of hydrogenated nitrile rubber different rubber is / are mixed and the mixture thus prepared is finally vulcanized.
  • the at least one To mix (meth) acrylate compound in an uncrosslinked hydrogenated nitrile rubber and finely dispersed with a high degree of dispersion before this mixture is vulcanized and then mixed with a second and optionally one or more other rubber other than hydrogenated nitrile rubber.
  • the rubber component contains 1 to 60 wt .-%, particularly preferably 5 to 50 wt .-% and most preferably 15 to 40 wt .-% of one or more different crosslinked hydrogenated nitrile rubber (s) and preferably 40 bis 99 wt .-%, particularly preferably 50 to 95 wt .-% and most preferably 60 to 85 wt .-% of one or more rubbers selected from the group consisting of crosslinked nitrile rubbers, crosslinked carboxylated nitrile rubbers, crosslinked styrene-butadiene rubbers and any copolymers and / or mixtures of two or more of the aforementioned crosslinked rubbers.
  • the at least one (meth) acrylate compound contained in the at least one layer of the roll cover of the present invention may be any molecular compound, ionic compound or complex compound having at least one acrylate group and / or at least one methacrylate group.
  • the at least one (meth) acrylate compound is selected from the group consisting of zinc monoacrylates, zinc diacrylates, zinc monomethacrylates, zinc dimethacrylates, Lithium acrylates, lithium methacrylates, sodium acrylates, sodium methacrylates, potassium acrylates, potassium methacrylates, magnesium acrylates, magnesium methacrylates, calcium acrylates, calcium methacrylates, aluminum acrylates, aluminum methacrylates, copper acrylates, copper methacrylates, ammonium acrylates, ammonium methacrylates, quaternary ammonium acrylates, quaternary ammonium methacrylates, alkyl diol monoacrylates, alkyl diol diacrylates, alkyl diol monomethacrylates, alkyl diol dimethacrylates, trimethylol propane trimethacrylates, and any mixtures consists of two or more of the aforementioned compounds.
  • the at least one (meth) acrylate compound is particularly preferably selected from the group consisting of zinc monoacrylates, zinc diacrylates, zinc monomethacrylates, zinc dimethacrylates, butanediol dimethacrylates, trimethylolpropane trimethacrylates and any desired mixtures of two or more of the abovementioned compounds.
  • the zinc monoacrylates and zinc monomethacrylates have a monovalent (meth) acrylate anion and a divalent zinc ion, and may have as the second negative group for generating the charge neutrality any monovalent anion, such as preferably a hydroxide ion, a chloride ion, a bromide ion or an iodide ion.
  • the rubber composition based on 100 parts by weight of the rubber component, 1 to 20 parts by weight, preferably 5 to 15 parts by weight and particularly preferably 7.5 to 12.5 parts by weight, such as 10 parts by weight, containing at least one (meth) acrylate compound.
  • the rubber composition of the at least one layer of the roll cover according to the invention may optionally contain further fillers and / or additives.
  • the reinforcing filler can be, for example, carbon black and / or silica, but also an inorganic compound such as calcium carbonate, or a mineral such as mica.
  • the at least one layer of the roll cover according to the invention based on 100 parts by weight of the rubber component, 1 to 150 parts by weight, preferably 10 to 100 parts by weight, more preferably 20 to 70 parts by weight and most preferably 40 to 50 parts by weight of carbon black, such as 45 parts by weight of carbon black.
  • carbon black it is possible to use all types of carbon black known to the person skilled in the art, and preferably carbon black having a specific BET surface area of from 5 to 120 m 2 / g.
  • the at least one layer of the invention based on 100 parts by weight of the rubber component, 1 to 100 parts by weight, preferably 5 to 40 parts by weight and particularly preferably 10 to 20 parts by weight of silica, such as 15 parts by weight of silica.
  • silica All the types of silica known to those skilled in the art can be used as the silica, and preferably silica having a BET specific surface area between 5 and 210 m 2 / g.
  • the at least one layer of the roll cover of the present invention contains silica
  • silicone coupling agent there may be used any of those known in the art such as sulfide type silane coupling agents such as bis (3-triethoxysilylpropyl) tetrasulfide, bis (2-triethoxysilylethyl) tetrasulfide, bis (3-trimethoxysilylpropyl) tetrasulfide, bis (2-trimethoxysilylethyl) tetrasulfide , Bis (3-triethoxysilylpropyl) trisulfide, bis (3-trimethoxysilylpropyl) trisulfide and the like, mercapto-type silane coupling agents such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane and the like, vinyl type silane coupling agents such as 3-
  • the rubber composition may contain, as an alternative or in addition to carbon black and / or silica, at least one filler and / or additive, which is preferably selected from the group consisting of plasticizers, antioxidants, resins, polymer fillers, pigments and any mixtures of two or more of the aforementioned compounds exists.
  • the rubber composition of the at least one layer of the roll cover according to the invention may be added to all plasticizers and / or antioxidants known to those skilled in the art, the plasticizer preferably being present in an amount between 0 and 30 parts by weight, preferably between 0 and 15 parts by weight and Antioxidants are preferably present in an amount between 0 and 5 parts by weight and preferably between 1 and 4 parts by weight, based in each case on 100 parts by weight of the gum component.
  • the at least one resin is a phenolic resin and / or an acrylate resin.
  • the amount of the at least one resin in this embodiment is preferably more than 0 to 80 parts by weight, more preferably 2 to 40 parts by weight, and most preferably 5 to 30 parts by weight based on 100 parts by weight of the rubber component.
  • the rubber composition based on 100 parts by weight of the rubber component, between more than 0 and 80 parts by weight, preferably between 2 and 40 parts by weight and more preferably between 5 and 30 parts by weight of at least one polymer filler.
  • the at least one polymer filler is preferably selected from the group consisting of polyolefins, polyamides, Polyurethanes, polyesters, gums and any mixtures of two or more of the aforementioned compounds.
  • suitable rubbers for the polymer filler are crosslinked natural rubbers, crosslinked styrene-butadiene rubbers, crosslinked chloroprene rubbers, crosslinked nitrile rubbers, crosslinked hydrogenated nitrile rubbers, crosslinked carboxylated nitrile rubbers and any desired copolymers and / or mixtures of two or more of the aforementioned crosslinked rubbers.
  • the polymer filler is particularly preferably composed of polyethylene or of polypropylene and very particularly preferably of a high-density polyethylene.
  • the average particle diameter (d 50 ) of the polymer filler is preferably between 1 ⁇ m and 500 ⁇ m and preferably between 10 ⁇ m and 150 ⁇ m.
  • the mean particle diameter d 50 of the polymer filler is understood to be the value of the particle diameter which is less than 50% of the particles present in the polymer filler, ie 50% of all particles of the polymer filler have a smaller particle diameter than the d 50 Value on.
  • the roll cover comprises at least one layer consisting of the previously described rubber composition. Since this layer has very good mechanical properties as well as excellent dynamic properties, in particular a low tan ⁇ value, and in particular an excellent recovery behavior, this at least one layer preferably forms the cover layer of the roll cover. Good results are achieved in this embodiment in particular when the at least one layer has a thickness between 5 and 25 mm.
  • the roll cover consists of the at least one layer, wherein it is particularly preferred in this embodiment that the roll cover has a thickness between 5 and 25 mm.
  • the roll cover according to the invention can be produced in particular by a process in which the at least one (meth) acrylate compound having a high degree of dispersion is mixed in uncrosslinked hydrogenated nitrile rubber and finely divided therein, before the mixture thus prepared optionally further uncrosslinked hydrogenated nitrile rubber or another uncrosslinked rubber is added and the mixture thus prepared is vulcanized.
  • steps a) and b) can also be carried out simultaneously.
  • the uncrosslinked hydrogenated nitrile rubber added in step c) may be identical to the uncrosslinked hydrogenated nitrile rubber provided in step a) or may differ therefrom, for example with regard to the molecular weight or the acrylonitrile content. Further, steps b) and c) may be performed simultaneously or sequentially.
  • steps a) and b) can be performed simultaneously.
  • the crosslinked hydrogenated nitrile rubber added in the step d) may be the same as or different from the crosslinked hydrogenated nitrile rubber produced by vulcanization in the step c), for example, in terms of molecular weight or acrylonitrile content.
  • the mixing in of the at least one crosslinking agent may be simultaneous or separate, i. before or after mixing in the at least one (meth) acrylate compound.
  • any compound known to the person skilled in the art for this purpose may be used as the vulcanizing agent, in particular sulfur, one or more vulcanizing agents based on polysulfides, one or more vulcanizing agents based on thiourea compounds, one or more vulcanizing agents based on triazine derivatives and / or one or more vulcanizing agents based on peroxide compounds, vulcanizing agents based on peroxide compounds being particularly preferred.
  • one or more vulcanization accelerators may be added in addition to the vulcanizing agent.
  • all compounds which are known to the person skilled in the art for this purpose can be used as the vulcanization accelerator.
  • sulfenamide compounds such as N-cyclohexyl-2-benzothiazylsulfenamid
  • thiazole compounds such as 2-mercaptobenzothiazole
  • thiuram compounds such as tetramethylthiuram monosulfide and tetramethylthiuram disulfide mentioned.
  • the vulcanization can be carried out under the customary pressure and temperature conditions known to the person skilled in the art for example, in an autoclave at a temperature between 40 and 170 ° C and preferably between 90 and 160 ° C and at a pressure between 2 and 10 bar and preferably between 3 and 5 bar.
  • the present invention relates to a roll cover obtainable by any of the methods described above.
  • the roll cover according to the invention is characterized in that the at least one (meth) acrylate compound is finely dispersed in the rubber component, whereby the above-described excellent mechanical and dynamic properties and in particular the excellent recovery behavior described above is obtained.
  • Another object of the present invention is a roll having a roll core and an elastic roll cover formed on the roll core, which is composed as described above.
  • the present invention relates to the use of the roller described above in a paper or board machine and preferably in a film press, in a size press, in a coater or in a coater.

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  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Description

Die vorliegende Erfindung betrifft einen insbesondere für eine Walze zur Behandlung einer Papier-, Karton- oder einer anderen Faserstoffbahn in einer Maschine zur Herstellung und/oder Veredlung derselben geeigneten Walzenbezug, eine diesen Walzenbezug umfassende Walze und die Verwendung einer solchen Walze.The present invention relates to a roll, in particular for a roll for treating a paper, board or other fibrous web in a machine for producing and / or finishing the same suitable roll cover, a roll comprising this roll cover and the use of such a roll.

Bei der Papierherstellung werden bei einer Vielzahl von Verfahrensschritten Walzen und insbesondere Gummiwalzen mit einer elastischen Oberfläche eingesetzt, wie beispielsweise bei der Blattbildung in der Siebpartie der Papiermaschine, bei dem Entwässern in der Presspartie der Papiermaschine und bei dem Streichen, Trocknen sowie Glätten in der Endpartie der Papiermaschine. Eine Vielzahl der bei der Papierherstellung eingesetzten Walzen wird bei deren Betrieb jeweils gegen eine Gegenwalze gepresst, wobei in dem zwischen der Walze und der Gegenwalze ausgebildeten Walzenspalt eine Faserstoff- bzw. Papierbahn durchgeführt wird. In einer Filmpresse beispielsweise, welche zur Oberflächenbehandlung von Papierbahnen eingesetzt wird, wird auf schnell rotierende Auftragswalzen zum Beispiel mittels Rollrakeln jeweils ein Film aus beispielsweise Leim oder Streichfarbe erzeugt, welcher in dem Walzenspalt auf die durch den Walzenspalt geführte Papierbahn übertragen wird. Derartige Walzen sind bei ihrer Verwendung enormen Belastungen ausgesetzt und müssen daher eine Vielzahl von sowohl mechanischen als auch dynamischen Eigenschaften erfüllen. Insbesondere müssen solche Walzen neben guten mechanischen Eigenschaften, wie einer hohen Zugfestigkeit, Abrasionsbeständigkeit, Reißfestigkeit, Weiterreißfestigkeit, Druckfestigkeit und Schlagfestigkeit, auch exzellente dynamische Eigenschaften aufweisen, wie insbesondere eine geringe Hysterese sowie einen niedrigen tanδ, unter anderem damit der Wärmeaufbau während des Walzenbetriebs ausreichend niedrig ist. Zudem müssen solche Walzen ein gutes und schnelles Rückstellverhalten aufweisen. Diese guten dynamischen Eigenschaften uns insbesondere das gute und schnelle Rückstellverhalten sind auch deshalb erforderlich, damit der in dem Walzenspalt durch den Druck der Gegenwalze deformierte Oberflächenbereich der Walze nach dem Verlassen des Walzenspalts möglichst schnell und möglichst vollständig zu seiner ursprünglichen Form und Dimension zurückkehrt, und zwar auch nach sehr langer Betriebsdauer der Walze. Um den Oberflächen von Walzen die für ihre Verwendung erforderlichen anwendungstechnischen Eigenschaften zu verleihen, werden Walzen an ihrer Oberfläche üblicherweise mit einem auf einem Walzenkern angeordneten Walzenbezug versehen, dessen Material im Hinblick auf die erforderlichen anwendungstechnischen Eigenschaften formuliert wird. Üblicherweise sind derartige Walzenbezüge aus Materialien zusammengesetzt, welche eine Matrix aus einem Gummi oder aus einer Mischung aus zwei oder mehr Gummis enthalten, in welche ein oder mehrere Füllstoffe eingebettet sind.In papermaking, rolls and in particular rubber rolls having an elastic surface are used in a plurality of process steps, such as sheet formation in the wire section of the paper machine, dewatering in the press section of the paper machine, and painting, drying and smoothing in the final section of the paper machine paper machine. A large number of the rolls used in papermaking are each pressed against a mating roll during operation, wherein a pulp or paper web is carried out in the nip formed between the roll and the mating roll. In a film press, for example, which is used for the surface treatment of paper webs, a film of, for example, glue or coating color is produced on rapidly rotating applicator rollers, for example by means of roller blades, which is transferred in the nip to the guided through the nip paper web. Such rollers are subjected to enormous loads during their use and therefore have to meet a variety of both mechanical and dynamic properties. In particular, such rollers in addition to good mechanical Properties such as high tensile strength, abrasion resistance, tear resistance, tear propagation resistance, compressive strength and impact strength, also have excellent dynamic properties, such as low hysteresis and low tanδ, among other things, the heat build-up during roll operation is sufficiently low. In addition, such rollers must have a good and fast recovery behavior. These good dynamic properties and in particular the good and quick restoring behavior are also necessary so that the surface area of the roller deformed in the nip by the pressure of the counter roller returns to its original shape and dimension as quickly and completely as possible after leaving the nip, namely even after a very long service life of the roller. In order to give the surfaces of rolls the performance properties required for their use, rolls are usually provided on their surface with a roll cover arranged on a roll core, the material of which is formulated with regard to the required application properties. Typically, such roll covers are composed of materials containing a matrix of a rubber or a mixture of two or more rubbers in which one or more fillers are embedded.

Allerdings handelt es sich bei den mechanischen und dynamischen Eigenschaften von Gummiwalzen um gegenläufige Eigenschaften, weil eine Verbesserung der mechanischen Eigenschaften einer Gummiwalze üblicherweise eine Verschlechterung der dynamischen Eigenschaften der Walze mit sich bringt und andererseits eine Verbesserung der dynamischen Eigenschaften einer Gummiwalze üblicherweise eine Verschlechterung der mechanischen Eigenschaften der Walze bedingt.However, the mechanical and dynamic properties of rubber rolls are contradictory properties because improvement of the mechanical properties of a rubber roll usually entails deterioration of the dynamic properties of the roll and, on the other hand, improvement of the dynamic properties of a rubber roll usually results in deterioration of mechanical properties the roller conditionally.

Aus der DE 199 42 743 A1 beispielsweise ist ein Walzenbezug aus einer Gummizusammensetzung bekannt, welche einen vernetzten Nitrilkautschuk, wie vernetzten hydrierten Nitrilkautschuk, ein Metallacrylatsalz, wie Zinkdiacrylat, eine flüssige Acrylatverbindung und einen Füllstoff enthält. Allerdings sind sowohl die mechanischen Eigenschaften als auch die dynamischen Eigenschaften dieser Gummizusammensetzung verbesserungsbedürftig.From the DE 199 42 743 A1 For example, a roll cover of a rubber composition containing a crosslinked nitrile rubber such as crosslinked hydrogenated nitrile rubber, a metal acrylate salt such as zinc diacrylate, a liquid acrylate compound and a filler is known. However, both the mechanical properties and the dynamic properties of this rubber composition are in need of improvement.

DE 199 42 743 A1 beschreibt einen Walzenbezug mit den Merkmalen des Oberbegriffs des Anspruchs 1. Weitere Walzenbezüge sind aus WO 00/43593 A1 bekannt geworden. DE 199 42 743 A1 describes a roll cover with the features of the preamble of claim 1. Further roll covers are made WO 00/43593 A1 known.

Aufgabe der vorliegenden Erfindung ist es daher, einen Walzenbezug bereitzustellen, welcher sowohl hervorragende mechanischen Eigenschaften aufweist als sich auch durch exzellente dynamische Eigenschaften auszeichnet und aufgrund dessen hervorragend zur Verwendung in einer Walze geeignet ist, welche in einem schnell laufenden Leim- oder Streichaggregat einer Papier- oder Kartonmaschine eingesetzt wird. Erfindungsgemäß wird diese Aufgabe gelöst durch einen Walzenbezug, insbesondere für eine Walze zur Behandlung einer Papier-, Karton- oder einer anderen Faserstoffbahn in einer Maschine zur Herstellung und/oder Veredlung derselben, welcher wenigstens eine Schicht umfasst, wobei die wenigstens eine Schicht eine Gummizusammensetzung enthält, welche eine wenigstens einen vernetzten hydrierten Nitrilkautschuk umfassende Gummikomponente sowie wenigstens eine (Meth)acrylatverbindung enthält, und, wobei die wenigstens eine Schicht

  1. a) eine Rückstellgeschwindigkeit von wenigstens 12 mm/Sek. und/oder einen plastischen Verformungsgrad von maximal 0,9% sowie
  2. b) einen gemäß der DIN 53513 bei 60°C, Zug, 10 Hz, 15% statischer Dehnung und 1% dynamischer Dehnung bestimmten tan δ-Wert von maximal 0,16
aufweist.It is therefore an object of the present invention to provide a roll cover which has both excellent mechanical properties and excellent dynamic properties and is therefore outstandingly suitable for use in a roll which is used in a high-speed glue or coating unit of a paper mill. or board machine is used. According to the invention, this object is achieved by a roll cover, in particular for a roll for treating a paper, cardboard or other fibrous web in a machine for producing and / or finishing the same, which comprises at least one layer, wherein the at least one layer contains a rubber composition compound containing a rubber component comprising at least one crosslinked hydrogenated nitrile rubber and at least one (meth) acrylate compound, and wherein the at least one layer
  1. a) a return speed of at least 12 mm / sec. and / or a plastic deformation of not more than 0.9% and
  2. b) a tan δ value of not more than 0.16 determined according to DIN 53513 at 60 ° C., tension, 10 Hz, 15% static elongation and 1% dynamic elongation
having.

Diese Lösung basiert auf der überraschenden Erkenntnis, dass es möglich ist, einen Walzenbezug aus einer Gummizusammensetzung mit nicht nur hervorragenden mechanischen Eigenschaften, sondern mit gleichzeitig auch exzellenten dynamischen Eigenschaften, nämlich einem niedrigen tanδ-Wert und einer geringen Hysterese, und insbesondere mit einem hervorragenden Rückstellverhalten zu erhalten, indem eine (Meth)acrylatverbindung mit einem sehr hohen Dispersionsgrad bzw. feinstverteilt mit einer wenigstens einen vernetzten hydrierten Nitrilkautschuk umfassenden Gummikomponente und optional anderen herkömmlichen Füllstoff(en) und Additiv(en) vermischt wird. Dabei bildet der Gummi bzw. bilden die Gummis die Gummikomponente aus, welche die Matrix der wenigstens einen Schicht des Walzenbezugs ausbildet, in welcher die wenigstens eine (Meth)acrylatverbindung und optional sonstigen Füllstoffe und Additive eingebettet sind. Aufgrund der hervorragenden mechanischen und dynamischen Eigenschaften und insbesondere dem hervorragenden Rückstellverhalten eignet sich der erfindungsgemäße Walzenbezug insbesondere zur Verwendung in einer Walze, welche in einem schnell laufenden Leim- oder Streichaggregat einer Papier- oder Kartonmaschine eingesetzt wird und bei ihrer Verwendung enormen Zentrifugalkräften und Deformationskräften ausgesetzt ist.This solution is based on the surprising discovery that it is possible to obtain a roll cover made of a rubber composition having not only excellent mechanical properties, but at the same time excellent dynamic properties, namely a low tanδ value and a low hysteresis, and in particular with an excellent recovery behavior by mixing a (meth) acrylate compound having a very high degree of dispersion or finely divided with a rubber component comprising at least one crosslinked hydrogenated nitrile rubber and optionally other conventional filler (s) and additive (s). In this case, the rubber forms the rubber component which forms the matrix of the at least one layer of the roll cover, in which the at least one (meth) acrylate compound and optionally other fillers and additives are embedded. Due to the excellent mechanical and dynamic properties and in particular the excellent recovery behavior, the roll cover according to the invention is particularly suitable for use in a roll which is used in a fast-running glue or coating unit of a paper or board machine and is exposed in their use enormous centrifugal forces and deformation forces ,

Unter Gummi wird im Sinne der vorliegenden Erfindung jeder vulkanisierte Kautschuk verstanden, und zwar unabhängig davon, ob dies ein vulkanisierter Naturkautschuk oder ein vulkanisierter synthetischer Kautschuk ist.For the purposes of the present invention, rubber means any vulcanized rubber, irrespective of whether this is a vulcanized natural rubber or a vulcanized synthetic rubber.

Ferner bezeichnet der Begriff Gummikomponente im Rahmen der vorliegenden Erfindung die Summe aller in der Gummizusammensetzung enthaltenen vernetzten sowie unvernetzten Kautschuke, also die Matrix der wenigstens einen Schicht des Walzenbezugs, wohingegen der Begriff Gummizusammensetzung die Summe aller in der wenigstens einen Schicht des Walzenbezugs enthaltenen Verbindungen, also die Summe der vernetzten sowie unvernetzten Kautschuke, der darin eingebetteten wenigstens einen (Meth)acrylatverbindung und der optionalen sonstigen Füllstoffe und Additive bezeichnet.Furthermore, in the context of the present invention, the term rubber component denotes the sum of all crosslinked and uncrosslinked rubbers contained in the rubber composition, that is to say the matrix of the at least one layer of the roll cover, whereas the term Rubber composition denotes the sum of all compounds contained in the at least one layer of the roll cover, ie the sum of the crosslinked and uncrosslinked rubbers embedded therein at least one (meth) acrylate compound and the optional other fillers and additives.

Zudem werden im Rahmen der vorliegenden Erfindung unter (Meth)acrylatverbindung alle Verbindungen verstanden, welche wenigstens eine Acrylatgruppe und/oder wenigstens eine Methacrylatgruppe aufweisen, also insbesondere alle wenigstens eine Acrylatgruppe und/oder wenigstens eine Methacrylatgruppe aufweisenden molekularen Verbindungen, ionischen Verbindungen bzw. Salze und komplexen Verbindungen.In addition, in the context of the present invention (meth) acrylate compound means all compounds which have at least one acrylate group and / or at least one methacrylate group, ie in particular all at least one acrylate group and / or at least one methacrylate group-containing molecular compounds, ionic compounds or salts and complex connections.

Gemäß einer ersten besonders bevorzugten Ausführungsform der vorliegenden Erfindung weist die wenigstens eine Schicht des erfindungsgemäßen Walzenbezugs eine Rückstellgeschwindigkeit von wenigstens 12 mm/Sek. auf, welche, wie vorstehend dargelegt, dadurch erreicht werden kann, dass die wenigstens eine (Meth)acrylatverbindung mit einem ausreichend hohen Dispersionsgrad bzw. feinstverteilt mit der wenigstens einen vernetzten hydrierten Nitrilkautschuk umfassenden Gummikomponente vermischt wird. Entsprechende konkrete Herstellungsverfahren werden weiter unten beschrieben. Besonders gute Ergebnisse werden bei dieser Ausführungsform erhalten, wenn die wenigstens eine Schicht des Walzenbezugs eine Rückstellgeschwindigkeit von wenigstens 14 mm/Sek., bevorzugt eine Rückstellgeschwindigkeit von wenigstens 16 mm/ Sek. und besonders bevorzugt eine Rückstellgeschwindigkeit von wenigstens 18 mm/Sek. aufweist.According to a first particularly preferred embodiment of the present invention, the at least one layer of the roll cover according to the invention has a return speed of at least 12 mm / sec. which, as stated above, can be achieved by mixing the at least one (meth) acrylate compound having a sufficiently high degree of dispersion or finely divided with the rubber component comprising at least one crosslinked hydrogenated nitrile rubber. Corresponding concrete production methods are described below. Particularly good results are obtained in this embodiment when the at least one layer of the roll cover has a return speed of at least 14 mm / sec, preferably a return speed of at least 16 mm / sec and particularly preferably a return speed of at least 18 mm / sec. having.

Dabei wird die Rückstellgeschwindigkeit gemäß der vorliegenden Erfindung wie folgt bestimmt: Zunächst werden aus der wenigstens einen Schicht des Walzenbezugs fünf zylindrische Prüfkörper mit einem Durchmesser von jeweils 13 mm und mit einer Höhe von jeweils 6 mm herausgearbeitet. Anschließend wird für jeden Prüfkörper dessen exakte Höhe mit einem Messschieber bestimmt. Danach werden die Prüfkörper nacheinander in einem dynamischen Prüfgerät, z.B. einem dynamischen Prüfgerät MTS-831 der Firma MTS, bei 30°C ± 2°C jeweils mit dem nachfolgenden Kraft-Zeit-Verlauf auf Druck belastet, wobei bei jedem Zyklus zunächst ein rechteckiger Kraftimpuls für eine Dauer von 100 Millisekunden angelegt wird und dann eine Haltephase für eine Dauer von 900 Millisekunden bei einer Kraft von 5 N, um ein Abheben des Hydraulikstempels der Prüfmaschine von dem Prüfkörper zu vermeiden, durchgeführt wird und während des Zyklus die Weg- und Kraftsignale aufgenommen werden:

  1. 1. 300 Zyklen mit jeweils einem Kraftimpuls von 100 N, wobei bei jedem Zyklus die Weg- und Kraftsignale mit einer Auflösung von 20 Hz aufgenommen werden, dann
  2. 2. 5 Zyklen mit jeweils einem Kraftimpuls von 100 N, wobei bei jedem Zyklus die Weg- und Kraftsignale mit einer Auflösung von 200 Hz aufgenommen werden, dann
  3. 3. 300 Zyklen mit jeweils einem Kraftimpuls von 200 N, wobei bei jedem Zyklus die Weg- und Kraftsignale mit einer Auflösung von 20 Hz aufgenommen werden, dann
  4. 4. 5 Zyklen mit jeweils einem Kraftimpuls von 200 N, wobei bei jedem Zyklus die Weg- und Kraftsignale mit einer Auflösung von 200 Hz aufgenommen werden, dann
  5. 5. 300 Zyklen mit jeweils einem Kraftimpuls von 300 N, wobei bei jedem Zyklus die Weg- und Kraftsignale mit einer Auflösung von 20 Hz aufgenommen werden, dann
  6. 6. 5 Zyklen mit jeweils einem Kraftimpuls von 300 N, wobei bei jedem Zyklus die Weg- und Kraftsignale mit einer Auflösung von 200 Hz aufgenommen werden, und dann
  7. 7. 10 Minuten Haltezeit bei 5 N.
The recovery speed according to the present invention is determined as follows: First, five cylindrical test specimens each having a diameter of 13 mm and a height of 6 mm each are machined out of the at least one layer of the roll cover. Then the exact height of each specimen is determined with a vernier caliper. Thereafter, the test specimens successively in a dynamic tester, such as a dynamic tester MTS-831 MTS, at 30 ° C ± 2 ° C each loaded with the subsequent force-time curve to pressure, with each cycle first a rectangular force pulse is applied for a duration of 100 milliseconds and then a holding phase for a duration of 900 milliseconds at a force of 5 N to prevent lifting of the hydraulic stamp of the testing machine from the test specimen is performed and recorded during the cycle, the travel and force signals become:
  1. 1. 300 cycles, each with a force pulse of 100 N, the path and force signals are recorded with a resolution of 20 Hz in each cycle, then
  2. 2. 5 cycles, each with a force pulse of 100 N, with the path and force signals are recorded with a resolution of 200 Hz in each cycle, then
  3. 3. 300 cycles, each with a force pulse of 200 N, with the path and force signals are recorded with a resolution of 20 Hz, then at each cycle
  4. 4. 5 cycles, each with a force pulse of 200 N, the path and force signals are recorded with a resolution of 200 Hz, then at each cycle
  5. 5. 300 cycles, each with a force impulse of 300 N, whereby the path and force signals are recorded with a resolution of 20 Hz for each cycle, then
  6. 6. 5 cycles, each with a force pulse of 300 N, the path and force signals are recorded with a resolution of 200 Hz for each cycle, and then
  7. 7. 10 minutes hold time at 5 N.

Unter Weg- und Kraftsignalen werden hierbei die Wertepaare für die Höhe des Prüfkörpers bei der angelegten Kraft zu einer gegebenen Zeit verstanden. In der Fig. 1 ist ein Beispiel für ein Diagramm gezeigt, in dem eine Vielzahl für Weg- und Kraftsignale für jeweils einen Zyklus bei einer Kraft von 100 N (Kurve A) und einen Zyklus bei einer Kraft von 200 N (Kurve B) dargestellt ist. Die Durchführung der Zyklen mit jeweils einer Haltephase für eine Dauer von 900 Millisekunden und einer Kraftimpulsphase für eine Dauer von 100 Millisekunden simuliert den Durchgang des Walzenbezugs durch den Walzenspalt und den anschließenden Freigang des Walzenbezugs außerhalb des Walzenspaltes.Under path and force signals are here understood the value pairs for the height of the specimen in the applied force at a given time. In the Fig. 1 Fig. 3 is an example of a diagram showing a plurality of displacement and force signals for each one cycle at a force of 100 N (curve A) and one cycle at a force of 200 N (curve B). Performing the cycles, each with a hold period of 900 milliseconds and a force pulse phase for a duration of 100 milliseconds, simulates the passage of the roll cover through the nip and the subsequent clearance of the roll cover outside the nip.

Aus den erhaltenen Daten wird berechnet, welche Zeit erforderlich war, bis sich jeder einzelne Prüfkörper nach jedem der 5 Zyklen mit jeweils einem Kraftimpuls von 300 N, bei denen die Weg- und Kraftsignale mit einer Auflösung von 200 Hz aufgenommen wurden, auf 80% seiner ursprünglichen Höhe zurückverformte. Für jeden der fünf Prüfkörper wird aus den so bestimmten fünf Einzelwerten der arithmetische Mittelwert berechnet, um so für jeden Prüfkörper die Rückstellgeschwindigkeit zu bestimmen. Danach wird aus den fünf Rückstellgeschwindigkeiten der arithmetische Mittelwert berechnet. Dieser Wert entspricht der vorstehend spezifizierten Rückstellgeschwindigkeit.From the data obtained, it is calculated what time was required for each individual specimen after each of the 5 cycles, each with a force of 300 N, in which the travel and force signals were recorded with a resolution of 200 Hz, to 80% of its original height deformed. For each of the five test specimens, the arithmetic mean is calculated from the five individual values thus determined so as to determine the resetting speed for each test specimen. Then the arithmetic mean is calculated from the five reset speeds. This value corresponds to the reset speed specified above.

Gemäß einer zweiten besonders bevorzugten Ausführungsform der vorliegenden Erfindung weist die wenigstens eine Schicht des erfindungsgemäßen Walzenbezugs einen plastischen Verformungsgrad von maximal 0,9% auf, welcher, wie vorstehend dargelegt, dadurch erreicht werden kann, dass die wenigstens eine (Meth)acrylatverbindung mit einem ausreichend hohen Dispersionsgrad bzw. feinstverteilt mit der wenigstens einen vernetzten hydrierten Nitrilkautschuk umfassenden Gummikomponente vermischt wird. Konkrete Herstellungsverfahren werden weiter unten beschrieben. Besonders gute Ergebnisse werden bei dieser Ausführungsform erhalten, wenn die wenigstens eine Schicht einen plastischen Verformungsgrad von maximal 0,7%, bevorzugt von maximal 0,5% und besonders bevorzugt von maximal 0,3% aufweist.According to a second particularly preferred embodiment of the present invention, the at least one layer of the roll cover according to the invention has a maximum plastic deformation degree of 0.9%. which, as stated above, can be achieved by mixing the at least one (meth) acrylate compound having a sufficiently high degree of dispersion or finely divided with the rubber component comprising at least one crosslinked hydrogenated nitrile rubber. Specific manufacturing methods will be described below. Particularly good results are obtained in this embodiment, if the at least one layer has a plastic deformation of not more than 0.7%, preferably of at most 0.5% and more preferably of at most 0.3%.

Zur Bestimmung des Verformungsgrades wird wie vorstehend bezüglich der Bestimmung der Rückstellgeschwindigkeit vorgegangen, wobei jeweils nach der abschließenden 10 minütigen Haltezeit bei 5 N gemäß 7. die Höhe der einzelnen Prüfkörper gemessen wird und daraus der Quotient aus der Differenz der anfänglichen Höhe und der Höhe nach der Haltezeit geteilt durch die anfängliche Höhe in Prozent bestimmt wird. Mit anderen Worten wird der Verformungsgrad als ((Ha-Hn)/Ha)·100 bestimmt, wobei Ha die anfängliche Höhe des Probenkörpers bezeichnet und Hn die Höhe des Probenkörpers nach der Durchführung der Kraftzyklen bezeichnet. Aus den so bestimmten fünf Verformungsgraden wird dann der arithmetische Mittelwert berechnet. Dieser Wert entspricht dem vorstehend spezifizierten Verformungsgrad.To determine the degree of deformation is proceeded as above with respect to the determination of the recovery speed, in each case after the final 10 minute hold time at 5 N according to 7, the height of the individual specimens is measured and from the quotient of the difference of the initial height and the height of the Holding time divided by the initial height in percent. In other words, the degree of deformation is determined to be ((H a -H n ) / H a) x 100, where H a denotes the initial height of the sample body and H n denotes the height of the sample body after performing the force cycles. From the thus determined five degrees of deformation then the arithmetic mean is calculated. This value corresponds to the degree of deformation specified above.

Gemäß einer dritten besonders bevorzugten Ausführungsform der vorliegenden Erfindung weist die wenigstens eine Schicht des erfindungsgemäßen Walzenbezugs sowohl eine Rückstellgeschwindigkeit von wenigstens 12 mm/Sek., bevorzugt von wenigstens 14 mm/Sek., besonders bevorzugt von wenigstens 16 mm/Sek. und ganz besonders bevorzugt von wenigstens 18 mm/Sek., als auch einen plastischen Verformungsgrad von maximal 0,9%, bevorzugt von maximal 0,7%, besonders bevorzugt von maximal 0,5% und ganz besonders bevorzugt von maximal 0,3% auf.According to a third particularly preferred embodiment of the present invention, the at least one layer of the roll cover according to the invention both has a return speed of at least 12 mm / sec, preferably of at least 14 mm / sec, more preferably of at least 16 mm / sec. and most preferably at least 18 mm / sec, as well as a plastic deformation degree of maximum 0.9%, preferably of at most 0.7%, more preferably of at most 0.5% and most preferably of at most 0.3%.

Wie vorstehend dargelegt, weist die wenigstens eine Schicht des erfindungsgemäßen Walzenbezugs erfindungsgemäß zudem einen gemäß der DIN 53513 bei 60°C, Zug, 10 Hz, 15% statischer Dehnung und 1% dynamischer Dehnung bestimmten tan δ-Wert von maximal 0,16 auf. Der tan δ-Wert ist ein Maß für den Wärmeaufbau der Gummizusammensetzung, welcher wiederum mit der Hysterese der Gummizusammensetzung korreliert, wobei ein niedriger tan δ-Wert mit einer niedrigen Hysterese und einer niedrigen Wärmeaufbaueigenschaft korreliert. Wie die zuvor spezifizierte Rückstellgeschwindigkeit sowie der zuvor spezifizierte plastische Verformungsgrad kann dieser niedrige tan δ-Wert dadurch erreicht werden, dass die wenigstens eine (Meth)acrylatverbindung mit einem ausreichend hohen Dispersionsgrad bzw. feinstverteilt mit der wenigstens einen vernetzten hydrierten Nitrilkautschuk umfassenden Gummikomponente vermischt wird. Besonders gute Ergebnisse werden erreicht, wenn die wenigstens eine Schicht einen tan δ-Wert von maximal 0,14, bevorzugt von maximal 0,12 und besonders bevorzugt von maximal 0,10 aufweist.As explained above, the at least one layer of the roll cover according to the invention also has a tan δ value of not more than 0.16 determined according to DIN 53513 at 60 ° C., tension, 10 Hz, 15% static elongation and 1% dynamic elongation. The tan δ value is a measure of the heat buildup of the rubber composition, which in turn correlates with the hysteresis of the rubber composition, with a low tan δ value correlating with low hysteresis and low heat build-up property. Like the previously specified recovery rate and the previously specified degree of plastic deformation, this low tan δ value can be achieved by mixing the at least one (meth) acrylate compound with a sufficiently high degree of dispersion or finely divided with the rubber component comprising at least one crosslinked hydrogenated nitrile rubber. Particularly good results are achieved if the at least one layer has a tan δ value of not more than 0.14, preferably of not more than 0.12 and particularly preferably not more than 0.10.

Um eine gute Verschleißbeständigkeit zu erreichen, wird es in Weiterbildung des Erfindungsgedankens vorgeschlagen, dass die wenigstens eine Schicht des erfindungsgemäßen Walzenbezugs eine Weiterreißfestigkeit von mehr als 14 N/mm, bevorzugt von mehr als 15 N/mm N/mm und besonders bevorzugt von mehr als 16 N/mm N/mm aufweist. Im Rahmen der vorliegenden Erfindung wird die Weiterreißfestigkeit gemäß der DIN ISO 34-1, Methode B, Verfahren B bestimmt.In order to achieve good wear resistance, it is proposed in a further development of the invention that the at least one layer of the roll cover according to the invention has a tear propagation resistance of more than 14 N / mm, preferably more than 15 N / mm N / mm and more preferably more than 16 N / mm N / mm. In the context of the present invention, the tear resistance is determined according to DIN ISO 34-1, Method B, Method B.

Wie vorstehend dargelegt, ist es erfindungswesentlich, dass die wenigstens eine Schicht des erfindungsgemäßen Walzenbezugs wenigstens einen vernetzten hydrierten Nitrilkautschuk enthält, in dem die wenigstens eine (Meth)acrylatverbindung feinstverteilt eingebettet ist. Unter hydriertem Nitrilkautschuk wird in diesem Zusammenhang sowohl vollständig hydrierter als auch partiell hydrierter Nitrilkautschuk verstanden. Vorzugsweise handelt es sich bei dem vernetzten hydrierten Nitrilkautschuk um vernetzten partiell hydrierten Nitrilkautschuk, wobei der Hydrierungsgrad bevorzugt 85 bis weniger als 100% und besonders bevorzugt 90 bis weniger als 100% beträgt.As stated above, it is essential to the invention that the at least one layer of the roll cover according to the invention comprises at least one crosslinked one hydrogenated nitrile rubber in which the at least one (meth) acrylate compound is embedded in finely divided form. Hydrogenated nitrile rubber in this context means both completely hydrogenated and partially hydrogenated nitrile rubber. Preferably, the crosslinked hydrogenated nitrile rubber is crosslinked partially hydrogenated nitrile rubber, wherein the degree of hydrogenation is preferably 85 to less than 100%, and more preferably 90 to less than 100%.

Im Hinblick auf die mechanischen und dynamischen Eigenschaften des Walzenbezugs hat es sich zudem als vorteilhaft erwiesen, der Gummizusammensetzung der wenigstens einen Schicht des Walzenbezugs einen vernetzten hydrierten Nitrilkautschuk mit einem Acrylnitrilgehalt zwischen 20 und 50 Gew.-%, bevorzugt zwischen 30 und 40 Gew.-% und besonders bevorzugt zwischen 33 und 37 Gew.-% und dementsprechend mit einem Butadiengehalt zwischen 50 und 80 Gew.-%, bevorzugt zwischen 60 und 70 Gew.-% und besonders bevorzugt zwischen 67 und 63 Gew.-% zuzusetzen.In view of the mechanical and dynamic properties of the roll cover, it has also proven to be advantageous for the rubber composition of the at least one layer of the roll cover to comprise a crosslinked hydrogenated nitrile rubber having an acrylonitrile content between 20 and 50% by weight, preferably between 30 and 40% by weight. % and more preferably between 33 and 37 wt .-% and accordingly with a butadiene content between 50 and 80 wt .-%, preferably between 60 and 70 wt .-% and particularly preferably between 67 and 63 wt .-%.

Aus den gleichen Gründen wird es in Weiterbildung des Erfindungsgedankens vorgeschlagen, dass der wenigstens eine vernetzte hydrierte Nitrilkautschuk eine gemäß der DIN 53253-3 bestimmte Mooney-Viskosität zwischen 20 und 80 und bevorzugt zwischen 30 und 70 aufweist.For the same reasons, it is proposed in a further development of the inventive concept that the at least one crosslinked hydrogenated nitrile rubber has a Mooney viscosity determined according to DIN 53253-3 between 20 and 80 and preferably between 30 and 70.

Grundsätzlich kann die Gummikomponente der Gummizusammensetzung vollständig aus einem vernetzten hydrierten Nitrilkautschuk oder aus zwei oder mehr verschiedenen vernetzten hydrierten Nitrilkautschuken zusammengesetzt sein, d.h. die Gummikomponente und damit auch die Gummizusammensetzung enthalten keinen anderen Kautschuk außer einem vernetzten hydrierten Nitrilkautschuk bzw. mehreren vernetzten hydrierten Nitrilkautschuken.Basically, the rubber component of the rubber composition may be wholly composed of a crosslinked hydrogenated nitrile rubber or of two or more different crosslinked hydrogenated nitrile rubbers, that is, the rubber component and thus also the rubber composition contain no other rubber except a crosslinked hydrogenated nitrile rubber or more crosslinked hydrogenated nitrile rubbers.

Sofern bei der vorstehenden Ausführungsform nur eine Art von hydriertem Nitrilkautschuk eingesetzt wird, kann die Gummizusammensetzung so hergestellt werden, dass die wenigstens eine (Meth)acrylatverbindung in den unvernetzten hydrierten Nitrilkautschuk eingemischt und mit einem hohen Dispergiergrad feinstverteilt wird, bevor die so hergestellte Mischung vulkanisiert wird. Allerdings ist es bevorzugt, die wenigstens eine (Meth)acrylatverbindung zunächst nur in eine Teilmenge des unvernetzten hydrierten Nitrilkautschuks einzumischen und mit einem hohen Dispergiergrad feinst zu verteilen, bevor dann diese Mischung mit der Restmenge des hydrierten Nitrilkautschuks vermischt und vulkanisiert wird. Prinzipiell ist es auch möglich, die Gummizusammensetzung so herzustellen, dass die wenigstens eine (Meth)acrylatverbindung in den vernetzten hydrierten Nitrilkautschuk eingemischt und mit einem hohen Dispergiergrad feinstverteilt wird; allerdings ist diese Alternative weniger bevorzugt.In the above embodiment, if only one kind of hydrogenated nitrile rubber is used, the rubber composition may be prepared by mixing the at least one (meth) acrylate compound in the uncrosslinked hydrogenated nitrile rubber and finely dispersing with a high degree of dispersion before the mixture thus prepared is vulcanized , However, it is preferred to mix the at least one (meth) acrylate compound initially only in a subset of the uncrosslinked hydrogenated nitrile rubber and to finely disperse with a high degree of dispersion before this mixture is then mixed with the remaining amount of the hydrogenated nitrile rubber and vulcanized. In principle, it is also possible to prepare the rubber composition so that the at least one (meth) acrylate compound is mixed in the crosslinked hydrogenated nitrile rubber and finely divided with a high degree of dispersion; however, this alternative is less preferred.

Sofern bei der vorstehenden Ausführungsform zwei oder mehr Arten von hydriertem Nitrilkautschuk eingesetzt werden, kann die Gummizusammensetzung so hergestellt werden, dass die wenigstens eine (Meth)acrylatverbindung zunächst in einen ersten, unvernetzten hydrierten Nitrilkautschuk eingemischt und mit einem hohen Dispergiergrad feinstverteilt wird, bevor in die so hergestellte Mischung ein zweiter und ggf. ein oder mehrere weitere unvernetzte(r) hydrierte(r) Nitrilkautschuk(e) eingemischt wird/werden und die so hergestellte Mischung schließlich vulkanisiert wird. Alternativ dazu ist es auch möglich, wenn auch weniger bevorzugt, zunächst die wenigstens eine (Meth)acrylatverbindung in einen ersten, unvernetzten hydrierten Nitrilkautschuk einzumischen und mit einem hohen Dispergiergrad feinst zu verteilen, bevor diese Mischung vulkanisiert wird und danach mit einem zweiten und ggf. ein oder mehreren weiteren vernetzten hydrierten Nitrilkautschuk(en) vermischt wird. Schließlich ist es auch möglich, auch wenn dies noch weniger bevorzugt ist, dass zunächst die wenigstens eine (Meth)acrylatverbindung in einen ersten, vernetzten hydrierten Nitrilkautschuk eingemischt und mit einem hohen Dispergiergrad feinstverteilt wird, bevor diese Mischung mit einem zweiten vernetzten hydrierten Nitrilkautschuk vermischt wird.In the above embodiment, if two or more kinds of hydrogenated nitrile rubber are used, the rubber composition may be prepared by first mixing the at least one (meth) acrylate compound into a first uncrosslinked hydrogenated nitrile rubber and finely dispersing it with a high degree of dispersion before entering the first a second and optionally one or more further uncrosslinked hydrogenated nitrile rubber (s) is / are blended and the mixture thus produced is finally vulcanized. Alternatively, it is also possible, although less preferred, first to mix the at least one (meth) acrylate compound into a first uncrosslinked hydrogenated nitrile rubber and finely disperse with a high degree of dispersion before mixing is vulcanized and then mixed with a second and optionally one or more further crosslinked hydrogenated nitrile rubber (s). Finally, although still less preferred, it is also possible that the at least one (meth) acrylate compound is first mixed into a first crosslinked hydrogenated nitrile rubber and finely divided with a high degree of dispersion before mixing this mixture with a second crosslinked hydrogenated nitrile rubber ,

Gemäß einer zu der vorstehenden Ausführungsform alternativen Ausführungsform der vorliegenden Erfindung enthält die Gummikomponente der Gummizusammensetzung zusätzlich zu dem wenigstens einen vernetzten hydrierten Nitrilkautschuk wenigstens einen weiteren, von vernetztem hydriertem Nitrilkautschuk verschiedenen Kautschuk, welcher vorzugsweise aus der Gruppe ausgewählt ist, welche aus vernetzten Nitrilkautschuken, vernetzten carboxylierten Nitrilkautschuken, vernetzten Styrol-Butadien-Kautschuken und beliebigen Copolymeren und/oder Mischungen aus zwei oder mehr der vorgenannten vernetzten Kautschuke besteht.According to an alternative embodiment of the present invention to the above embodiment, the rubber component of the rubber composition contains, in addition to the at least one crosslinked hydrogenated nitrile rubber, at least one other rubber other than crosslinked hydrogenated nitrile rubber which is preferably selected from the group consisting of crosslinked nitrile rubbers and crosslinked carboxylated ones Nitrile rubbers, crosslinked styrene-butadiene rubbers and any copolymers and / or mixtures of two or more of the aforementioned crosslinked rubbers.

Die Herstellung der Gummizusammensetzung kann analog zu den vorstehend in Bezug auf die Ausführungsform, bei der die Gummikomponente ausschließlich aus hydriertem/hydrierten Nitrilkautschuk(en) besteht, beschriebenen Varianten erfolgen. Mit anderen Worten kann die Gummizusammensetzung so hergestellt werden, dass die wenigstens eine (Meth)acrylatverbindung zunächst in einen unvernetzten hydrierten Nitrilkautschuk eingemischt und mit einem hohen Dispergiergrad feinstverteilt wird, bevor in die so hergestellte Mischung ein zweiter und ggf. ein oder mehrere weitere unvernetzte(r) von hydriertem Nitrilkautschuk verschiedener Kautschuk eingemischt wird/werden und die so hergestellte Mischung schließlich vulkanisiert wird. Alternativ dazu ist es auch möglich, wenn auch weniger bevorzugt, zunächst die wenigstens eine (Meth)acrylatverbindung in einen unvernetzten hydrierten Nitrilkautschuk einzumischen und mit einem hohen Dispergiergrad feinst zu verteilen, bevor diese Mischung vulkanisiert wird und danach mit einem zweiten und ggf. ein oder mehreren weiteren von hydriertem Nitrilkautschuk verschiedenen Kautschuk vermischt wird. Schließlich ist es auch möglich, auch wenn dies noch weniger bevorzugt ist, dass zunächst die wenigstens eine (Meth)acrylatverbindung in einen vernetzten hydrierten Nitrilkautschuk eingemischt und mit einem hohen Dispergiergrad feinstverteilt wird, bevor diese Mischung mit einem zweiten von vernetztem hydrierten Nitrilkautschuk verschiedenen Kautschuk vermischt wird.The preparation of the rubber composition can be carried out analogously to the variants described above in relation to the embodiment in which the rubber component consists exclusively of hydrogenated / hydrogenated nitrile rubber (s). In other words, the rubber composition can be prepared by first mixing the at least one (meth) acrylate compound into an uncrosslinked hydrogenated nitrile rubber and finely dispersing it with a high degree of dispersion before a second and optionally one or more further uncrosslinked ( r) of hydrogenated nitrile rubber different rubber is / are mixed and the mixture thus prepared is finally vulcanized. Alternatively, it is also possible, albeit less preferred, first the at least one To mix (meth) acrylate compound in an uncrosslinked hydrogenated nitrile rubber and finely dispersed with a high degree of dispersion before this mixture is vulcanized and then mixed with a second and optionally one or more other rubber other than hydrogenated nitrile rubber. Finally, although still less preferred, it is also possible to first mix the at least one (meth) acrylate compound into a crosslinked hydrogenated nitrile rubber and finely disperse with a high degree of dispersion before mixing this mixture with a second rubber other than crosslinked hydrogenated nitrile rubber becomes.

Vorzugsweise enthält bei dieser Ausführungsform die Gummikomponente 1 bis 60 Gew.-%, besonders bevorzugt 5 bis 50 Gew.-% und ganz besonders bevorzugt 15 bis 40 Gew.-% von einem oder mehreren verschiedenen vernetzten hydrierten Nitrilkautschuk(en) sowie bevorzugt 40 bis 99 Gew.-%, besonders bevorzugt 50 bis 95 Gew.-% und ganz besonders bevorzugt 60 bis 85 Gew.-% von einem oder mehreren Kautschuken ausgewählt aus der Gruppe bestehend aus vernetzten Nitrilkautschuken, vernetzten carboxylierten Nitrilkautschuken, vernetzten Styrol-Butadien-Kautschuken und beliebigen Copolymeren und/oder Mischungen aus zwei oder mehr der vorgenannten vernetzten Kautschuke.Preferably, in this embodiment, the rubber component contains 1 to 60 wt .-%, particularly preferably 5 to 50 wt .-% and most preferably 15 to 40 wt .-% of one or more different crosslinked hydrogenated nitrile rubber (s) and preferably 40 bis 99 wt .-%, particularly preferably 50 to 95 wt .-% and most preferably 60 to 85 wt .-% of one or more rubbers selected from the group consisting of crosslinked nitrile rubbers, crosslinked carboxylated nitrile rubbers, crosslinked styrene-butadiene rubbers and any copolymers and / or mixtures of two or more of the aforementioned crosslinked rubbers.

Wie vorstehend dargelegt, kann die wenigstens eine in der wenigstens einen Schicht des erfindungsgemäßen Walzenbezugs enthaltene (Meth)acrylatverbindung eine beliebige, wenigstens eine Acrylatgruppe und/oder wenigstens eine Methacrylatgruppe aufweisende molekulare Verbindung, ionische Verbindung oder komplexe Verbindung sein. Gute Ergebnisse werden jedoch insbesondere erhalten, wenn die wenigstens eine (Meth)acrylatverbindung aus der Gruppe ausgewählt ist, welche aus Zinkmonoacrylaten, Zinkdiacrylaten, Zinkmonomethacrylaten, Zinkdimethacrylaten, Lithiumacrylaten, Lithiummethacrylaten, Natriumacrylaten, Natriummethacrylaten, Kaliumacrylaten, Kaliummethacrylaten, Magnesiumacrylaten, Magnesiummethacrylaten, Calciumacrylaten, Calciummethacrylaten, Aluminiumacrylaten, Aluminiummethacrylaten, Kupferacrylaten, Kupfermethacrylaten, Ammoniumacrylaten, Ammoniummethacrylaten, quaternären Ammoniumacrylaten, quaternären Ammoniummethacrylaten, Alkyldiolmonoacrylaten, Alkyldioldiacrylaten, Alkyldiolmonomethacrylaten, Alkyldioldimethacrylaten, Trimethylolpropantrimethacrylaten und beliebigen Mischungen aus zwei oder mehr der vorgenannten Verbindungen besteht.As set forth above, the at least one (meth) acrylate compound contained in the at least one layer of the roll cover of the present invention may be any molecular compound, ionic compound or complex compound having at least one acrylate group and / or at least one methacrylate group. However, good results are obtained especially when the at least one (meth) acrylate compound is selected from the group consisting of zinc monoacrylates, zinc diacrylates, zinc monomethacrylates, zinc dimethacrylates, Lithium acrylates, lithium methacrylates, sodium acrylates, sodium methacrylates, potassium acrylates, potassium methacrylates, magnesium acrylates, magnesium methacrylates, calcium acrylates, calcium methacrylates, aluminum acrylates, aluminum methacrylates, copper acrylates, copper methacrylates, ammonium acrylates, ammonium methacrylates, quaternary ammonium acrylates, quaternary ammonium methacrylates, alkyl diol monoacrylates, alkyl diol diacrylates, alkyl diol monomethacrylates, alkyl diol dimethacrylates, trimethylol propane trimethacrylates, and any mixtures consists of two or more of the aforementioned compounds.

Besonders bevorzugt ist die wenigstens eine (Meth)acrylatverbindung aus der Gruppe ausgewählt, welche aus Zinkmonoacrylaten, Zinkdiacrylaten, Zinkmonomethacrylaten, Zinkdimethacrylaten, Butandioldimethacrylaten, Trimethylolpropantrimethacrylaten und beliebigen Mischungen aus zwei oder mehr der vorgenannten Verbindungen besteht. Die Zinkmonoacrylate und Zinkmonomethacrylate weisen ein einwertiges (Meth)acrylatanion und ein zweiwertiges Zinkion auf und können als zweite negative Gruppe zur Herstellung der Ladungsneutralität jedes beliebige einwertige Anion aufweisen, wie vorzugsweise ein Hydroxidion, ein Chloridion, ein Bromidion oder ein Iodidion.The at least one (meth) acrylate compound is particularly preferably selected from the group consisting of zinc monoacrylates, zinc diacrylates, zinc monomethacrylates, zinc dimethacrylates, butanediol dimethacrylates, trimethylolpropane trimethacrylates and any desired mixtures of two or more of the abovementioned compounds. The zinc monoacrylates and zinc monomethacrylates have a monovalent (meth) acrylate anion and a divalent zinc ion, and may have as the second negative group for generating the charge neutrality any monovalent anion, such as preferably a hydroxide ion, a chloride ion, a bromide ion or an iodide ion.

Um die gewünschte Verbesserung sowohl der dynamischen als auch des Rückstellvermögens zu erreichen, wird es in Weiterbildung des Erfindungsgedankens vorgeschlagen, dass die Gummizusammensetzung, bezogen auf 100 Gewichtsteile der Gummikomponente, 1 bis 20 Gewichtsteile, bevorzugt 5 bis 15 Gewichtsteile und besonders bevorzugt 7,5 bis 12,5 Gewichtsteile, wie etwa 10 Gewichtsteile, der wenigstens einen (Meth)acrylatverbindung enthält.In order to achieve the desired improvement of both the dynamic and the recovery, it is proposed in development of the invention that the rubber composition, based on 100 parts by weight of the rubber component, 1 to 20 parts by weight, preferably 5 to 15 parts by weight and particularly preferably 7.5 to 12.5 parts by weight, such as 10 parts by weight, containing at least one (meth) acrylate compound.

Neben dem wenigstens einen vernetzten hydrierten Nitrilkautschuk sowie der wenigstens einen (Meth)acrylatverbindung kann die Gummizusammensetzung der wenigstens einen Schicht des erfindungsgemäßen Walzenbezugs optional weitere Füllstoffe und/oder Additive enthalten.In addition to the at least one crosslinked hydrogenated nitrile rubber and the at least one (meth) acrylate compound, the rubber composition of the at least one layer of the roll cover according to the invention may optionally contain further fillers and / or additives.

Um die Matrix zu verstärken und die Eigenschaften des Walzenbezugs im Hinblick auf die geplante Verwendung der den Walzenbezug umfassenden Walze maßzuschneiden, kann es vorteilhaft sein, der wenigstens einen Schicht des erfindungsgemäßen Walzenbezugs einen verstärkenden Füllstoff zuzusetzen. Bei dem verstärkenden Füllstoff kann es sich beispielsweise um Ruß und/oder Silica, aber auch um eine anorganische Verbindung, wie Calciumcarbonat, oder um ein Mineral, wie Glimmer, handeln.In order to reinforce the matrix and tailor the properties of the roll cover in view of the intended use of the roll cover comprising the roll cover, it may be advantageous to add a reinforcing filler to the at least one layer of the roll cover according to the invention. The reinforcing filler can be, for example, carbon black and / or silica, but also an inorganic compound such as calcium carbonate, or a mineral such as mica.

Vorzugsweise enthält die wenigstens eine Schicht des erfindungsgemäßen Walzenbezugs , bezogen auf 100 Gewichtsteile der Gummikomponente, 1 bis 150 Gewichtsteile, bevorzugt 10 bis 100 Gewichtsteile, besonders bevorzugt 20 bis 70 Gewichtsteile und ganz besonders bevorzugt 40 bis 50 Gewichtsteile Ruß, wie beispielsweise 45 Gewichtsteile Ruß. Als Ruß können dabei alle dem Fachmann bekannten Rußsorten eingesetzt werden und vorzugsweise Ruß mit einer spezifischen BET-Oberfläche zwischen 5 und 120 m2/g.Preferably, the at least one layer of the roll cover according to the invention, based on 100 parts by weight of the rubber component, 1 to 150 parts by weight, preferably 10 to 100 parts by weight, more preferably 20 to 70 parts by weight and most preferably 40 to 50 parts by weight of carbon black, such as 45 parts by weight of carbon black. As carbon black, it is possible to use all types of carbon black known to the person skilled in the art, and preferably carbon black having a specific BET surface area of from 5 to 120 m 2 / g.

Zusätzlich zu der vorgenannten Ausführungsform oder alternativ dazu kann die wenigstens eine Schicht des erfindungsgemäßen, bezogen auf 100 Gewichtsteile der Gummikomponente, 1 bis 100 Gewichtsteile, bevorzugt 5 bis 40 Gewichtsteile und besonders bevorzugt 10 bis 20 Gewichtsteile Silica enthalten, wie beispielsweise 15 Gewichtsteile Silica. Als Silica können dabei alle dem Fachmann bekannten Silicaarten eingesetzt werden und vorzugsweise Silica mit einer spezifischer BET-Oberfläche zwischen 5 und 210 m2/g.In addition to the aforementioned embodiment, or alternatively, the at least one layer of the invention, based on 100 parts by weight of the rubber component, 1 to 100 parts by weight, preferably 5 to 40 parts by weight and particularly preferably 10 to 20 parts by weight of silica, such as 15 parts by weight of silica. All the types of silica known to those skilled in the art can be used as the silica, and preferably silica having a BET specific surface area between 5 and 210 m 2 / g.

Wenn die wenigstens eine Schicht des erfindungsgemäßen Walzenbezugs Silica enthält, ist es ferner bevorzugt, dieses in Kombination mit einem Siliankupplungsmittel einzusetzen, um die Kompatibilität der Gummimatrix mit dem Silica zu erhöhen und so die Dispersion des Silicas in der Matrix zu verbessern. Als Siliankupplungsmittel können alle dem Fachmann bekannten Verbindungen eingesetzt werden, wie beispielsweise Silankupplungsmittel vom Sulfidtyp, wie Bis(3-triethoxysilylpropyl)-tetrasulfid, Bis(2-triethoxysilylethyl)tetrasulfid, Bis(3-trimethoxysilylpropyl)tetrasulfid, Bis(2-trimethoxysilylethyl)tetrasulfid, Bis(3-triethoxysilylpropyl)trisulfid, Bis(3-trimethoxysilylpropyl)trisulfid und dergleichen, Silankupplungsmittel vom Mercaptotyp, wie 3-Mercaptopropyltrimethoxysilan, 3-Mercaptopropyltriethoxysilan, 2-Mercaptoethyltrimethoxysilan, 2-Mercaptoethyltriethoxysilan und dergleichen, Silankupplungsmittel vom Vinyltyp, wie Vinyltriethoxysilan, Vinyltrimethoxysilan und dergleichen, Silankupplungsmittel vom Aminotyp, wie 3-Aminopropyltriethoxysilan, 3-Aminopropyltrimethoxysilane und dergleichen, Silankupplungsmittel vom Glycidoxytyp, wie γ-Glycidoxypropyltriethoxysilan, γ-Glycidoxypropyltrimethoxysilan und dergleichen, Silankupplungsmittel vom Nitrotyp, wie 3-Nitropropyltrimethoxysilan, 3-Nitropropyltriethoxysilan und dergleichen, sowie Silankupplungsmittel vom Chlortyp, wie 3-Chlorpropyltrimethoxysilan, 3-Chlorpropyltriethoxysilan und dergleichen.Further, when the at least one layer of the roll cover of the present invention contains silica, it is preferable to use it in combination with a silicone coupling agent to increase the compatibility of the rubber matrix with the silica to improve dispersion of the silica in the matrix. As the silicone coupling agent, there may be used any of those known in the art such as sulfide type silane coupling agents such as bis (3-triethoxysilylpropyl) tetrasulfide, bis (2-triethoxysilylethyl) tetrasulfide, bis (3-trimethoxysilylpropyl) tetrasulfide, bis (2-trimethoxysilylethyl) tetrasulfide , Bis (3-triethoxysilylpropyl) trisulfide, bis (3-trimethoxysilylpropyl) trisulfide and the like, mercapto-type silane coupling agents such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane and the like, vinyl type silane coupling agents such as vinyltriethoxysilane, vinyltrimethoxysilane and the like, amino type silane coupling agents such as 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilanes and the like, glycidoxy type silane coupling agents such as γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane and the like, nitrone-type silane coupling agents such as 3-nitropropyltrimethoxysilane n, 3-nitropropyltriethoxysilane and the like, and chlorine-type silane coupling agents such as 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane and the like.

Ferner kann die Gummizusammensetzung - alternativ oder zusätzlich zu Ruß und/oder Silica - wenigstens einen Füllstoff und/oder Additiv enthalten, welcher bzw. welches bevorzugt aus der Gruppe ausgewählt ist, welche aus Weichmachern, Antioxidationsmitteln, Harzen, Polymerfüllstoffen, Pigmenten und beliebigen Mischungen aus zwei oder mehr der vorgenannten Verbindungen besteht.Further, the rubber composition may contain, as an alternative or in addition to carbon black and / or silica, at least one filler and / or additive, which is preferably selected from the group consisting of plasticizers, antioxidants, resins, polymer fillers, pigments and any mixtures of two or more of the aforementioned compounds exists.

Als Weichmacher bzw. Antioxidationsmittel können der Gummizusammensetzung der wenigstens einen Schicht des erfindungsgemäßen Walzenbezugs alle dem Fachmann zu diesem Zweck bekannten Weichmacherund/oder Antioxidationsmittel zugesetzt sein, wobei der Weichmacher vorzugsweise in einer Menge zwischen 0 und 30 Gewichtsteilen und bevorzugt zwischen 0 und 15 Gewichtsteilen und das Antioxidationsmittel vorzugsweise in einer Menge zwischen 0 und 5 Gewichtsteilen und bevorzugt zwischen 1 und 4 Gewichtsteilen, jeweils bezogen auf 100 Gewichtsteile der Gummikomponente, enthalten sind.As softening agents or antioxidants, the rubber composition of the at least one layer of the roll cover according to the invention may be added to all plasticizers and / or antioxidants known to those skilled in the art, the plasticizer preferably being present in an amount between 0 and 30 parts by weight, preferably between 0 and 15 parts by weight and Antioxidants are preferably present in an amount between 0 and 5 parts by weight and preferably between 1 and 4 parts by weight, based in each case on 100 parts by weight of the gum component.

Um die Härte der wenigstens einen Schicht des erfindungsgemäßen Walzenbezugs auf einen gewünschten Wert einzustellen, kann es beispielsweise bevorzugt sein, der Gummizusammensetzung der wenigstens einen Schicht wenigstens ein Harz zuzusetzen. Gute Ergebnisse werden dabei insbesondere erhalten, wenn das wenigstens eine Harz ein Phenolharz und/oder ein Acrylatharz ist. Die Menge des wenigstens ein Harzes beträgt bei dieser Ausführungsform vorzugsweise zwischen mehr als 0 und 80 Gewichtsteilen, besonders bevorzugt zwischen 2 und 40 Gewichtsteilen und ganz besonders bevorzugt zwischen 5 und 30 Gewichtsteilen bezogen auf 100 Gewichtsteile der Gummikomponente.In order to set the hardness of the at least one layer of the roll cover according to the invention to a desired value, it may be preferable, for example, to add at least one resin to the rubber composition of the at least one layer. Good results are obtained in particular when the at least one resin is a phenolic resin and / or an acrylate resin. The amount of the at least one resin in this embodiment is preferably more than 0 to 80 parts by weight, more preferably 2 to 40 parts by weight, and most preferably 5 to 30 parts by weight based on 100 parts by weight of the rubber component.

Um die Abrasionsbeständigkeit der wenigstens einen Schicht des erfindungsgemäßen Walzenbezugs zu erhöhen und auf einen gewünschten Wert einzustellen, wird es in Weiterbildung des Erfindungsgedankens vorgeschlagen, dass die Gummizusammensetzung, bezogen auf 100 Gewichtsteile der Gummikomponente, zwischen mehr als 0 und 80 Gewichtsteilen, bevorzugt zwischen 2 und 40 Gewichtsteilen und besonders bevorzugt zwischen 5 und 30 Gewichtsteilen wenigstens eines Polymerfüllstoffs enthält. Dabei ist der wenigstens eine Polymerfüllstoff vorzugsweise aus der Gruppe ausgewählt, welche aus Polyolefinen, Polyamiden, Polyurethanen, Polyestern, Gummis und beliebigen Mischungen aus zwei oder mehr der vorgenannten Verbindungen besteht. Als geeignete Gummis für den Polymerfüllstoff seien beispielsweise vernetzte Naturkautschuke, vernetzte Styrol-Butadien-Kautschuke, vernetzte Chloroprenkautschuke, vernetzte Nitrilkautschuke, vernetzte hydrierte Nitrilkautschuke, vernetzte carboxylierte Nitrilkautschuke und beliebige Copolymere und/oder Mischungen aus zwei oder mehr der vorgenannten vernetzten Kautschuke genannt. Besonders bevorzugt ist der Polymerfüllstoff aus Polyethylen oder aus Polypropylen und ganz besonders bevorzugt aus einem hochdichten Polyethylen zusammengesetzt.In order to increase the abrasion resistance of at least one layer of the roll cover according to the invention and set to a desired value, it is proposed in a development of the invention that the rubber composition, based on 100 parts by weight of the rubber component, between more than 0 and 80 parts by weight, preferably between 2 and 40 parts by weight and more preferably between 5 and 30 parts by weight of at least one polymer filler. In this case, the at least one polymer filler is preferably selected from the group consisting of polyolefins, polyamides, Polyurethanes, polyesters, gums and any mixtures of two or more of the aforementioned compounds. Examples of suitable rubbers for the polymer filler are crosslinked natural rubbers, crosslinked styrene-butadiene rubbers, crosslinked chloroprene rubbers, crosslinked nitrile rubbers, crosslinked hydrogenated nitrile rubbers, crosslinked carboxylated nitrile rubbers and any desired copolymers and / or mixtures of two or more of the aforementioned crosslinked rubbers. The polymer filler is particularly preferably composed of polyethylene or of polypropylene and very particularly preferably of a high-density polyethylene.

Vorzugsweise beträgt der mittlere Partikeldurchmessers (d50) des Polymerfüllstoffs zwischen 1 µm und 500 µm und bevorzugt von zwischen 10 µm und 150 µm. Im Einklang mit der üblichen Definition dieses Parameters wird unter dem mittleren Partikeldurchmesser d50 des Polymerfüllstoffs der Wert des Partikeldurchmessers verstanden, den 50% der vorliegenden Partikel aus dem Polymerfüllstoff unterschreiten, d.h. 50% aller Partikel aus dem Polymerfüllstoff weisen einen kleineren Partikeldurchmesser als den d50-Wert auf.The average particle diameter (d 50 ) of the polymer filler is preferably between 1 μm and 500 μm and preferably between 10 μm and 150 μm. In accordance with the usual definition of this parameter, the mean particle diameter d 50 of the polymer filler is understood to be the value of the particle diameter which is less than 50% of the particles present in the polymer filler, ie 50% of all particles of the polymer filler have a smaller particle diameter than the d 50 Value on.

Erfindungsgemäß umfasst der Walzenbezug wenigstens eine aus der zuvor beschriebenen Gummizusammensetzung bestehende Schicht. Da diese Schicht sehr gute mechanische Eigenschaften als auch exzellente dynamische Eigenschaften, wie insbesondere einen niedrigen tanδ-Wert, und insbesondere ein hervorragendes Rückstellverhalten aufweist, bildet diese wenigstens eine Schicht vorzugsweise die Deckschicht des Walzenbezugs aus. Gute Ergebnisse werden bei dieser Ausführungsform insbesondere erreicht, wenn die wenigstens eine Schicht eine Dicke zwischen 5 und 25 mm aufweist.According to the invention, the roll cover comprises at least one layer consisting of the previously described rubber composition. Since this layer has very good mechanical properties as well as excellent dynamic properties, in particular a low tanδ value, and in particular an excellent recovery behavior, this at least one layer preferably forms the cover layer of the roll cover. Good results are achieved in this embodiment in particular when the at least one layer has a thickness between 5 and 25 mm.

Gemäß einer dazu alternativen und besonders bevorzugten Ausführungsform der vorliegenden Erfindung besteht der Walzenbezug aus der wenigstens einen Schicht, wobei es bei dieser Ausführungsform besonders bevorzugt ist, dass der Walzenbezug eine Dicke zwischen 5 und 25 mm aufweist.According to an alternative and particularly preferred embodiment of the present invention, the roll cover consists of the at least one layer, wherein it is particularly preferred in this embodiment that the roll cover has a thickness between 5 and 25 mm.

Wie vorstehend dargelegt kann der erfindungsgemäße Walzenbezug insbesondere durch ein Verfahren hergestellt werden, bei dem die wenigstens eine (Meth)acrylatverbindung mit einem hohen Dispergiergrad in unvernetzten hydrierten Nitrilkautschuk eingemischt und darin feinstverteilt wird, bevor der so hergestellten Mischung optional weiterer unvernetzter hydrierter Nitrilkautschuk oder ein anderer unvernetzter Kautschuk zugesetzt wird und die so hergestellte Mischung vulkanisiert wird.As set forth above, the roll cover according to the invention can be produced in particular by a process in which the at least one (meth) acrylate compound having a high degree of dispersion is mixed in uncrosslinked hydrogenated nitrile rubber and finely divided therein, before the mixture thus prepared optionally further uncrosslinked hydrogenated nitrile rubber or another uncrosslinked rubber is added and the mixture thus prepared is vulcanized.

Ein Verfahren zum Herstellen des vorstehend beschriebenen erfindungsgemäßen Walzenbezugs umfasst die nachfolgenden Schritte :

  1. a) Bereitstellen eines unvernetzten hydrierten Nitrilkautschuks,
  2. b) Einmischen und Dispergieren wenigstens einer (Meth)acrylatverbindung in den in dem Schritt a) bereitgestellten unvernetzten hydrierten Nitrilkautschuk,
  3. c) Einmischen von wenigstens einem Vernetzungsmittel sowie optional eines weiteren Kautschuks, welcher vorzugsweise aus der Gruppe ausgewählt ist, welche aus unvernetzten hydrierten Nitrilkautschuken, unvernetzten Nitrilkautschuken, unvernetzten carboxylierten Nitrilkautschuken, unvernetzten Styrol-Butadien-Kautschuken und beliebigen Copolymeren und/oder Mischungen aus zwei oder mehr der vorgenannten vernetzten Kautschuke besteht, und
  4. d) Vulkanisieren der in dem Schritt c) hergestellten Mischung.
A method for producing the roll cover according to the invention described above comprises the following steps:
  1. a) providing an uncrosslinked hydrogenated nitrile rubber,
  2. b) incorporating and dispersing at least one (meth) acrylate compound in the uncrosslinked hydrogenated nitrile rubber provided in step a),
  3. c) incorporating at least one crosslinking agent and optionally another rubber, which is preferably selected from the group consisting of uncrosslinked hydrogenated nitrile rubbers, uncrosslinked nitrile rubbers, uncrosslinked carboxylated nitrile rubbers, uncrosslinked styrene-butadiene rubbers and any copolymers and / or mixtures of two or more more of the aforementioned crosslinked rubbers, and
  4. d) vulcanizing the mixture prepared in step c).

Dabei können die Schritte a) und b) auch gleichzeitig durchgeführt werden.The steps a) and b) can also be carried out simultaneously.

Dabei kann der in dem Schritt c) zugegebene unvernetzte hydrierte Nitrilkautschuk mit dem in dem Schritt a) bereitgestellten unvernetzten hydrierten Nitrilkautschuk identisch sein oder sich von diesem beispielsweise im Hinblick auf das Molekulargewicht oder den Acrylnitrilgehalt unterscheiden. Ferner können die Schritte b) und c) gleichzeitig oder nacheinander durchgeführt werden.In this case, the uncrosslinked hydrogenated nitrile rubber added in step c) may be identical to the uncrosslinked hydrogenated nitrile rubber provided in step a) or may differ therefrom, for example with regard to the molecular weight or the acrylonitrile content. Further, steps b) and c) may be performed simultaneously or sequentially.

Gemäß einer dazu alternative Ausführungsform umfasst ein Verfahren zum Herstellen des vorstehend beschriebenen erfindungsgemäßen Walzenbezugs die nachfolgenden Schritte:

  1. a) Bereitstellen eines unvernetzten hydrierten Nitrilkautschuks,
  2. b) Einmischen und Dispergieren wenigstens einer (Meth)acrylatverbindung in den in dem Schritt a) bereitgestellten unvernetzten hydrierten Nitrilkautschuk sowie Einmischen wenigstens eines Vernetzungsmittels,
  3. c) Vulkanisieren der in dem Schritt b) hergestellten Mischung und
  4. d) Vermischen der in dem Schritt c) erhaltenen Mischung mit einem Kautschuk, welcher vorzugsweise aus der Gruppe ausgewählt ist, welche aus vernetzten hydrierten Nitrilkautschuken, vernetzten Nitrilkautschuken, vernetzten carboxylierten Nitrilkautschuken, vernetzten Styrol-Butadien-Kautschuken und beliebigen Copolymeren und/oder Mischungen aus zwei oder mehr der vorgenannten vernetzten Kautschuke besteht.
According to an alternative embodiment, a method for producing the roll cover according to the invention described above comprises the following steps:
  1. a) providing an uncrosslinked hydrogenated nitrile rubber,
  2. b) incorporating and dispersing at least one (meth) acrylate compound in the uncrosslinked hydrogenated nitrile rubber provided in step a) and mixing in at least one crosslinking agent,
  3. c) vulcanizing the mixture prepared in step b) and
  4. d) mixing the mixture obtained in step c) with a rubber which is preferably selected from the group consisting of crosslinked hydrogenated nitrile rubbers, crosslinked nitrile rubbers, crosslinked carboxylated nitrile rubbers, crosslinked styrene-butadiene rubbers and any copolymers and / or mixtures two or more of the aforementioned crosslinked rubbers.

Auch bei dieser Ausführungsform können die Schritte a) und b) gleichzeitig durchgeführt werden.Also in this embodiment, steps a) and b) can be performed simultaneously.

Auch bei dieser Ausführungsform kann der in dem Schritt d) zugegebene vernetzte hydrierte Nitrilkautschuk mit dem in dem Schritt c) durch Vulkanisation erzeugten vernetzten hydrierten Nitrilkautschuk identisch sein oder sich von diesem beispielsweise im Hinblick auf das Molekulargewicht oder den Acrylnitrilgehalt unterscheiden. In dem Schritt b) kann das Einmischen des wenigstens einen Vernetzungsmittels gleichzeitig oder getrennt, d.h. vor oder nach, dem Einmischen der wenigstens einen (Meth)acrylatverbindung erfolgen.Also in this embodiment, the crosslinked hydrogenated nitrile rubber added in the step d) may be the same as or different from the crosslinked hydrogenated nitrile rubber produced by vulcanization in the step c), for example, in terms of molecular weight or acrylonitrile content. In step b), the mixing in of the at least one crosslinking agent may be simultaneous or separate, i. before or after mixing in the at least one (meth) acrylate compound.

Bei den beiden vorstehenden Verfahrensvarianten kann als Vulkanisationsmittel jede dem Fachmann zu diesem Zweck bekannte Verbindung eingesetzt werden, und zwar insbesondere Schwefel, ein oder mehrere Vulkanisationsmittel auf Basis von Polysulfiden, ein oder mehrere Vulkanisationsmittel auf Basis von Thioharnstoffverbindungen, ein oder mehrere Vulkanisationsmittel auf Basis von Triazinderivaten und/oder ein oder mehrere Vulkanisationsmittel auf Basis von Peroxidverbindungen, wobei Vulkanisationsmittel auf Basis von Peroxidverbindungen besonders bevorzugt sind.In the case of the two preceding process variants, any compound known to the person skilled in the art for this purpose may be used as the vulcanizing agent, in particular sulfur, one or more vulcanizing agents based on polysulfides, one or more vulcanizing agents based on thiourea compounds, one or more vulcanizing agents based on triazine derivatives and / or one or more vulcanizing agents based on peroxide compounds, vulcanizing agents based on peroxide compounds being particularly preferred.

Ferner können in den entsprechenden Verfahrensschritten zusätzlich zu dem Vulkanisationsmittel ein oder mehrere Vulkanisationsbeschleuniger zugegeben werden. Dabei können als Vulkanisationsbeschleuniger all diejenigen Verbindungen eingesetzt werden, welche dem Fachmann zu diesem Zweck bekannt sind. Lediglich beispielsweise seien Sulfenamidverbindungen, wie N-Cyclohexyl-2-benzothiazylsulfenamid, Thiazolverbindungen, wie 2-Mercaptobenzothiazol, sowie Thiuramverbindungen, wie Tetramethylthiurammonosulfid und Tetramethylthiuramdisulfid, genannt.Further, in the respective process steps, one or more vulcanization accelerators may be added in addition to the vulcanizing agent. In this case, all compounds which are known to the person skilled in the art for this purpose can be used as the vulcanization accelerator. Only examples are sulfenamide compounds, such as N-cyclohexyl-2-benzothiazylsulfenamid, thiazole compounds, such as 2-mercaptobenzothiazole, and thiuram compounds, such as tetramethylthiuram monosulfide and tetramethylthiuram disulfide mentioned.

Die Vulkanisation kann unter den üblichen, dem Fachmann bekannten Druck- und Temperaturbedingungen durchgeführt werden, und zwar beispielsweise in einem Autoklaven bei einer Temperatur zwischen 40 und 170°C und bevorzugt zwischen 90 und 160°C sowie bei einem Druck zwischen 2 und 10 bar und bevorzugt zwischen 3 und 5 bar.The vulcanization can be carried out under the customary pressure and temperature conditions known to the person skilled in the art for example, in an autoclave at a temperature between 40 and 170 ° C and preferably between 90 and 160 ° C and at a pressure between 2 and 10 bar and preferably between 3 and 5 bar.

Zudem betrifft die vorliegende Erfindung einen Walzenbezug, der mit einem der vorstehend beschriebenen Verfahren erhältlich ist. Der erfindungsgemäße Walzenbezug zeichnet sich dadurch aus, dass die wenigstens eine (Meth)acrylatverbindung in der Gummikomponente feinstverteilt dispergiert vorliegt, wodurch die vorstehend beschriebenen hervorragenden mechanischen und dynamischen Eigenschaften und insbesondere das zuvor beschriebene exzellente Rückstellverhalten erhalten wird.In addition, the present invention relates to a roll cover obtainable by any of the methods described above. The roll cover according to the invention is characterized in that the at least one (meth) acrylate compound is finely dispersed in the rubber component, whereby the above-described excellent mechanical and dynamic properties and in particular the excellent recovery behavior described above is obtained.

Ein weiterer Gegenstand der vorliegenden Erfindung ist eine Walze mit einem Walzenkern und einem auf dem Walzenkern ausgebildeten elastischen Walzenbezug, welcher wie zuvor beschrieben zusammengesetzt ist.Another object of the present invention is a roll having a roll core and an elastic roll cover formed on the roll core, which is composed as described above.

Ferner betrifft die vorliegende Erfindung die Verwendung der zuvor beschriebenen Walze in einer Papier- oder Kartonmaschine und bevorzugt in einer Filmpresse, in einer Leimpresse, in einem Streichaggregat oder in einem Coater.Furthermore, the present invention relates to the use of the roller described above in a paper or board machine and preferably in a film press, in a size press, in a coater or in a coater.

Claims (22)

  1. Roll covering, in particular for a roll for the treatment of a paper web, paperboard web, or any other web of fibrous material in a machine for the production and/or finishing of same, where said roll covering encompasses at least one layer, and the at least one layer comprises a rubber composition which comprises at least one (meth)acrylate compound and a rubber component encompassing at least one crosslinked hydrogenated nitrile rubber, characterized in that the at least one layer has
    a) a recovery rate of at least 12 mm/sec. and/or a maximal degree of plastic deformation of 0.9%, and
    b) a maximal tan δ value of 0.16 determined in accordance with DIN 53513 at 60°C in tension at 10 Hz, 15% static elongation, and 1% dynamic elongation.
  2. Roll covering according to Claim 1,
    characterized in that
    the at least one layer has a recovery rate of at least 14 mm/sec., preferably of at least 16 mm/sec., and particularly preferably of at least 18 mm/sec.
  3. Roll covering according to Claim 1 or 2,
    characterized in that
    the at least one layer has a maximal degree of plastic deformation of 0.7%, preferably of 0.5%, and particularly preferably of 0.3%.
  4. Roll covering according to at least one of the preceding claims,
    characterized in that
    the at least one layer has has a maximal tan δ value of 0.14, preferably of 0.12, and particularly preferably of 0.10.
  5. Roll covering according to at least one of the preceding claims,
    characterized in that
    the at least one layer has a tear strength of more than 14 N/mm, preferably of more than 15 N/mm, and particularly preferably of more than 16 N/mm.
  6. Roll covering according to at least one of the preceding claims,
    characterized in that
    the at least one crosslinked hydrogenated nitrile rubber has an acrylonitrile content of from 20 to 50% by weight, preferably from 30 to 40% by weight, and particularly preferably from 33 to 37% by weight.
  7. Roll covering according to at least one of the preceding claims,
    characterized in that
    the rubber component of the rubber composition is composed entirely of one crosslinked hydrogenated nitrile rubber or of two or more different crosslinked hydrogenated nitrile rubbers.
  8. Roll covering according to at least one of Claims 1 to 6,
    characterized in that
    the rubber component of the rubber composition comprises, in addition to the at least one crosslinked hydrogenated nitrile rubber, at least one other rubber which differs from crosslinked hydrogenated nitrile rubber and which is preferably selected from the group consisting of crosslinked nitrile rubbers, crosslinked carboxylated nitrile rubbers, crosslinked styrenebutadiene rubbers, and any desired copolymers and/or mixtures of two or more of the abovementioned crosslinked rubbers.
  9. Roll covering according to Claim 8,
    characterized in that
    the rubber component comprises from 1 to 60% by weight, preferably from 5 to 50% by weight, and particularly preferably from 15 to 40% by weight, of one, or a plurality of different, crosslinked hydrogenated nitrile rubber(s), and from 40 to 99% by weight, preferably from 50 to 95% by weight, and particularly preferably from 60 to 85% by weight of one or more rubbers selected from the group consisting of crosslinked nitrile rubbers, crosslinked carboxylated nitrile rubbers, crosslinked styrene-butadiene rubbers, and any desired copolymers and/or mixtures of two or more of the abovementioned crosslinked rubbers.
  10. Roll covering according to at least one of the preceding claims,
    characterized in that
    the at least one (meth)acrylate compound is selected from the group consisting of zinc monoacrylates, zinc diacrylates, zinc monomethacrylates, zinc dimethacrylates, lithium acrylates, lithium methacrylates, sodium acrylates, sodium methacrylates, potassium acrylates, potassium methacrylates, magnesium acrylates, magnesium methacrylates, calcium acrylates, calcium methacrylates, aluminum acrylates, aluminum methacrylates, copper acrylates, copper methacrylates, ammonium acrylates, ammonium methacrylates, quaternary ammonium acrylates, quaternary ammonium methacrylates, alkyldiol monoacrylates, alkyldiol diacrylates, alkyldiol monomethacrylates, alkyldiol dimethacrylates, trimethylolpropane trimethacrylates, and any desired mixtures of two of more of the abovementioned compounds.
  11. Roll covering according to Claim 10,
    characterized in that
    the at least one (meth)acrylate compound is selected from the group consisting of zinc monoacrylates, zinc diacrylates, zinc monomethacrylates, zinc dimethacrylates, butanediol dimethacrylates, trimethylolpropane trimethacrylates, and any desired mixtures of two of more of the abovementioned compounds.
  12. Roll covering according to at least one of the preceding claims,
    characterized in that
    the rubber composition comprises, based on 100 parts by weight of the rubber component, from 1 to 20 parts by weight, preferably from 5 to 15 parts by weight, and particularly preferably from 7.5 to 12.5 parts by weight, of the at least one (meth)acrylate compound.
  13. Roll covering according to at least one of the preceding claims,
    characterized in that
    the rubber composition also comprises, based on 100 parts by weight of the rubber component, from 1 to 150 parts by weight, preferably from 10 to 100 parts by weight, particularly preferably from 20 to 70 parts by weight, and very particularly preferably from 40 to 50 parts by weight, of carbon black.
  14. Roll covering according to Claim 13,
    characterized in that
    the carbon black has a specific BET surface area of from 5 to 120 m2/g.
  15. Roll covering according to at least one of the preceding claims,
    characterized in that
    the rubber composition also comprises, based on 100 parts by weight of the rubber component, from 1 to 100 parts by weight, preferably from 5 to 40 parts by weight, and particularly preferably from 10 to 20 parts by weight, of silica.
  16. Roll covering according to Claim 15,
    characterized in that
    the silica has a specific BET surface area of from 5 to 210 m2/g.
  17. Roll covering according to at least one of the preceding claims,
    characterized in that
    the rubber composition also comprises at least one filler and/or one additive selected from the group consisting of plasticizers, antioxidants, resins, polymer fillers, pigments and any desired mixtures of two of more of the abovementioned compounds.
  18. Roll covering according to Claim 17,
    characterized in that
    the rubber composition comprises, based on 100 parts by weight of the rubber component, from more than 0 to 80 parts by weight, preferably from 2 to 40 parts by weight, and particularly preferably from 5 to 30 parts by weight, of at least one resin, preferably a phenolic resin and/or an acrylate resin.
  19. Roll covering according to Claim 17 or 18,
    characterized in that
    the rubber composition comprises, based on 100 parts by weight of the rubber component, from more than 0 to 80 parts by weight, preferably from 2 to 40 parts by weight, and particularly preferably from 5 to 30 parts by weight, of at least one polymer filler, where the at least one polymer filler is preferably selected from the group consisting of polyolefins, polyamides, polyurethanes, polyesters, rubbers, and any desired mixtures of two or more of the abovementioned compounds.
  20. Roll covering according to at least one of the preceding claims,
    characterized in that
    the at least one layer forms the outer layer of the roll covering and has a thickness of from 5 to 25 mm.
  21. Roll with a roll core and with a resilient roll covering according to at least one of Claims 1 to 20, formed on the roll core.
  22. Use of a roll according to Claim 21 in a papermaking machine or paperboard machine, and preferably in a film press, in a size press, in a coating assembly, or in a coater.
EP13702601.9A 2012-01-31 2013-01-24 Roll cover with improved dynamic properties and high resilience behavior Active EP2809843B1 (en)

Applications Claiming Priority (2)

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DE102012201310A DE102012201310A1 (en) 2012-01-31 2012-01-31 Roll cover with improved dynamic properties and high resilience
PCT/EP2013/051313 WO2013113608A1 (en) 2012-01-31 2013-01-24 Roll cover with improved dynamic properties and high resilience behavior

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DE102012205206A1 (en) * 2012-03-30 2013-10-02 Voith Patent Gmbh roll cover
DE102016114013A1 (en) * 2016-07-29 2018-02-01 Voith Patent Gmbh Roll cover and roller and their use
CN111058327A (en) * 2019-11-06 2020-04-24 福建省青山纸业股份有限公司 Method for improving roller coating

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JP2657823B2 (en) * 1988-06-09 1997-09-30 日本ゼオン株式会社 Vulcanizable rubber composition
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US9290887B2 (en) 2016-03-22

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