EP2861429A1 - Couche de réception pour procédés d'impression numériques comprenant de la cellulose nanofibrillée - Google Patents

Couche de réception pour procédés d'impression numériques comprenant de la cellulose nanofibrillée

Info

Publication number
EP2861429A1
EP2861429A1 EP13730200.6A EP13730200A EP2861429A1 EP 2861429 A1 EP2861429 A1 EP 2861429A1 EP 13730200 A EP13730200 A EP 13730200A EP 2861429 A1 EP2861429 A1 EP 2861429A1
Authority
EP
European Patent Office
Prior art keywords
receiving layer
layer
dye
weight
pigment
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP13730200.6A
Other languages
German (de)
English (en)
Other versions
EP2861429B1 (fr
Inventor
Wolfgang Schmidt
Gerd Papier
Michael SCHLENSTEDT
Ralf Gericke
Andreas FEHLKER
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Schoeller Technocell GmbH and Co KG
Original Assignee
Schoeller Technocell GmbH and Co KG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Schoeller Technocell GmbH and Co KG filed Critical Schoeller Technocell GmbH and Co KG
Publication of EP2861429A1 publication Critical patent/EP2861429A1/fr
Application granted granted Critical
Publication of EP2861429B1 publication Critical patent/EP2861429B1/fr
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41MPRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52Macromolecular coatings
    • B41M5/5236Macromolecular coatings characterised by the use of natural gums, of proteins, e.g. gelatins, or of macromolecular carbohydrates, e.g. cellulose
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41MPRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52Macromolecular coatings
    • B41M5/5254Macromolecular coatings characterised by the use of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H11/00Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
    • D21H11/16Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only modified by a particular after-treatment
    • D21H11/18Highly hydrated, swollen or fibrillatable fibres
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00Coated paper; Coating material
    • D21H19/10Coatings without pigments
    • D21H19/14Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • D21H19/34Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising cellulose or derivatives thereof
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00Coated paper; Coating material
    • D21H19/36Coatings with pigments
    • D21H19/44Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/52Cellulose; Derivatives thereof
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H21/00Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/50Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by form
    • D21H21/52Additives of definite length or shape
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41MPRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/502Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording characterised by structural details, e.g. multilayer materials
    • B41M5/506Intermediate layers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41MPRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52Macromolecular coatings
    • B41M5/5218Macromolecular coatings characterised by inorganic additives, e.g. pigments, clays

Definitions

  • the invention relates to a recording material for digital printing processes comprising a support and a color receiving layer disposed on the support.
  • the work that led to the invention was supported by the Seventh Framework Program of the European Union [FP7 / 2007-2013] under grant agreement n ° 22802.
  • Digital printing processes include the inkjet printing process. This printing process is also used for high-quality printing of photos.
  • high demands are placed on the recording materials for the inkjet printing process.
  • the applied inks must dry quickly, which requires a high absorbency for the ink fluid.
  • the ink ⁇ materials are to be fixed by the ink receiving layer, that is, they should be held so that they no longer migrate under the influence of moisture or may become detached from the ink receiving layer.
  • a high color density is he ⁇ wishes.
  • the paper must have a high light resistance, ie a high resistance to discoloration under the action of light.
  • the dimensional stability of the image carrier should be high and the material must have good throughput. Shafts have in the printer. Finally, a smooth and possibly shiny surface is desired.
  • Another quality feature is that crack formation in the image layer is avoided as far as possible.
  • the cracking depends strongly on the drying course after the application of the receiving layer, after printing with ink liquid or rewetting the dye-receiving layer on the support.
  • an increase in layer thickness appears to correlate with increased cracking.
  • US Pat. No. 6,372,329 B1 describes an ink-jet recording material for dye and pigmented ink imaging in which a first and a second ink-receiving layer are applied to a substrate and in which the second ink-receiving layer is a mixture of one with Maleic acid or itaconic acid-modified polyvinyl alcohol and a plasticizer.
  • the second layer is applied to the first layer.
  • Plasticizers are phosphates, substituted phthalic anhydrides, glycerols and glycols.
  • the pH of the second coating composition should preferably not be greater than 4.0.
  • US 2002/0064633 A1 describes a receiving material for the ink-jet printing process for aqueous, oily and solid inks.
  • the receiving layer contains a polymer and a crosslinking agent ⁇ .
  • the polymer comprises a quaternary ammonium in the molecule.
  • a certain ratio of organic An ⁇ part to inorganic content in this polymer is required.
  • the invention has for its object to provide a further On ⁇ recording material for digital imaging process, in particular ⁇ sondere for the ink jet printing process, in addition to the usual requirements such as high color density, dimensional stability and photo-like feel special Festig ⁇ ness to cracking in the receiving layer has.
  • a recording material for digital printing processes comprising a support and at least one dye-receiving layer on the support with a binder, the dye-receiving layer containing a nanofibrillated cellulose (NFC).
  • NFC nanofibrillated cellulose
  • Nanofibrillated celluloses according to the invention include celluloses called microfibrillated cellulose (MFC), nanocrystalline cellulose and bacterial nanocellulose (BNC).
  • MFC microfibrillated cellulose
  • BNC bacterial nanocellulose
  • the fibers of such nanofibrillated celluloses have a diameter in the nanometer range (nm).
  • the length of the fibers can be up to a few micrometers ( ⁇ m).
  • the use of the invention enables nano- fibrillated cellulose in the ink receiving layer to increase the coating speed at the same Schichtdi ⁇ blocks of the printing receiving layer as compared to conventional to ⁇ sammen applicanten of receiving layers for digital printing process.
  • the nanofibrillated cellulose celluloses used according to the invention can be obtained by known wood pulping processes, for example with a mixture of sodium hydroxide and sodium sulphide (kraft pulp) or salts of sulphurous acid (sulphite pulp), subsequent delamination of the pulp by chemical treatment, such as introduction of charged groups into the pulp fibers and a subsequent homogenizing treatment of the pulp.
  • kraft pulp sodium hydroxide and sodium sulphide
  • sulphurous acid sulphurous acid
  • the pulp obtained after defibration 2, 6 can be oxidatively by treatmen ⁇ lung with 2, 6-tetramethylpiperidine-l-oxyl (TEMPO) are decomposed and then homogenised mechanically.
  • TEMPO 2, 6-tetramethylpiperidine-l-oxyl
  • This oxidative treatment facilitates the defibrillation of the cellulose-containing material during the subsequent mechanical homogenization.
  • the mechanical homogenization ultimately gives the nanofibrillated cellulose.
  • the defibrillation can be done by different methods.
  • microfluidizers high-performance grinders, combinations of beating, rubbing and homogenizing, high-shear refiner and cryo-shredder were described.
  • delamination with ball mills and sonication nanocelluloses can be produced.
  • the fiber diameter of the fibers used according to the invention can be 3 to 100 nm, in particular 5 to 60 nm or 10 to 30 nm.
  • the fiber length of the fibers used in the invention Fa ⁇ may be 100 nm or 200 nm to 800 nm, 1 micron or a few microns. The fiber length may vary depending on the pulp used and the manufacturing process used.
  • the cellulose is nanofibrillATOR loading in ⁇ coating compound for the receiving layer in a concentra ⁇ on from 0.01 to 1%, particularly preferably from 0.02 to 0.5% and most preferably 0.04 to 0, 08 wt .-%, based on the dry weight of the coating material is ⁇ sets.
  • the nanofibrillated cellulose is used fresh. Freshly a two week period means ⁇ inner half after the preparation of nanofibrill convinced cellulose.
  • the receiving layer contains a water-soluble and / or water-dispersible binder.
  • Suitable binders are in ⁇ play, polyvinyl alcohol, completely or partially ver soaped ⁇ , cationically modified polyvinyl alcohol, silyl group-having polyvinyl alcohol, acetal groups exhibiting polyvinyl alcohol, gelatin, polyvinylpyrrolidone, starch, carboxymethyl cellulose, polyethylene glycol, styrene / butadiene latex, Acrylatcopo- mers such as styrene / acrylate latex, vinyl acetate homo- and copolymers and ethylene vinyl acetate copolymers. Fully or partially saponified polyvinyl alcohols are particularly preferred.
  • the amount of binding by means of 60 to 5 wt -.%, Preferably 50 to 10 wt. ⁇ 6, but in particular 35 to 8 wt .-%, based on the weight of the dried ⁇ dried layer amount.
  • the receiving layer (image recording layer) according to the invention may further comprise one or more pigments and at least one binding agent . Since with the use of carrier materials with a resin layer, the resin layer has a barrier action for the ink and the base paper can not absorb the ink liquid applied thereto recording must layer / s have a high absorption capacity, which as example ⁇ harnessabsorptiver by the use of inorganic particles can be achieved. Such microporous layers provide high ink receptivity.
  • Suitable pigments are for example alumina, aluminum ⁇ hydroxide, aluminum oxide hydroxide, aluminum oxide hydrate, silicon dioxide, magnesium hydroxide, kaolin, titanium dioxide, zinc oxide, zinc ⁇ hydroxide, calcium silicate, magnesium silicate, calcium carbonate, MAG nesiumcarbonat and barium sulfate.
  • the amount of the pigment in the receiving layer may be 40 to 95% by weight, preferably 60 to 90% by weight, based on the weight of the dried layer.
  • the particle size distribution of the pigment of the receiving layer may preferably be less than 1000 nm, but in particular 50 to 150 nm.
  • the average particle size of the primary particles is preferably less than 100 nm, in particular less than 50 nm. Such particle sizes of the pigment are suitable for glossy surfaces.
  • pigments with a particle size of 1 .mu.m to 10 .mu.m can be used in the receiving layer
  • the receiving layer may comprise conventional additives and auxiliaries ammonium compounds contained ⁇ th such as crosslinking agents, ionic and / or nonionic upper ⁇ surface-active substances, dye-fixing agents such as polyammonium, UV absorbers, antioxidants and other Lichtstabltician- and gas resistance-improving agents and other auxiliaries.
  • the application weight of the ink receiving layer may be 5 to 60 g / m 2 , preferably 10 to 50 g / m 2 , particularly preferably 20 to 40 g / m 2 .
  • the receiving layer may be single-layered or multi-layered.
  • the receiving layer can be constructed from an ink-absorbing lower layer and a dye-fixing upper layer.
  • suitable pigments of the ink unte ⁇ ren layer are then, for example, alumina, aluminum ⁇ hydroxide, aluminum oxide hydroxide, aluminum oxide hydrate, Siliciumdi- oxide, silica, barium sulphate and titanium dioxide.
  • a pigment based on alumina and / or alumina hydroxide is particularly preferred.
  • Such a pigment may be cationically modified.
  • the concentration of the pigment in the ink-absorbing layer is 40 to 95% by weight, preferably about 60 to 90% by weight, based on the weight of the dried layer.
  • the grain size distribution of the pigment of the ink-absorbing layer may preferably be in the range of 70 to 1000 nm preferential ⁇ , 80 to 200 nm, particularly preferably from 90 to 150 nm lie ⁇ gene.
  • the average particle size of the pigment of tintenabsorbie ⁇ Governing layer may be 50 to 350 nm , preferably 80 to 120 nm. According to the invention suitable pigments of the dye-fixing
  • the concentration of the pigment in the dye-fixing layer can be 70 to 95 wt .-%, preferably 80 to 90 wt .-%, carry be ⁇ .
  • the grain size distribution of the pigment of the dye-fixing layer may preferably be in the range of 50 to 200 nm, preferably, 70 to 120 nm ⁇ lie.
  • the average particle size of the pig ment ⁇ the dye-fixing layer may be preferably 70 to 120 nm, in particular around 100 nm.
  • the pigments may have a particle size of 1 .mu.m to 10 .mu.m aufwei ⁇ sen.
  • Suitable binders include polyvinyl alcohol, completely or partially saponified, cationic mo ⁇ d byer polyvinyl alcohol, silyl groups exhibiting polyvinyl alcohol, acetal groups exhibiting polyvinyl alcohol, acetate group-having polyvinyl alcohol, gelatin, polyvinylpyrrolidone, starch, carboxymethyl cellulose, polyethylene glycol, styrene polymers rol / Butadiene latex and styrene / acrylate latex.
  • the amount of binding agent in the dye-fixing and the ink-absorbing layer is in each case from 5 to 45% by weight, preferably from 10 to 35% by weight, based on the weight of the dried layer.
  • Both layers may contain conventional additives and auxiliaries such as surfactants, crosslinking agents and dye fixing agents.
  • the coating weights of the ink and the dye-fixing layer can ⁇ are each 10 to 60 g / m 2, preferably 15 to 30 g / m 2.
  • the receiving layer can be applied to the support in ⁇ example, by a doctor blade method, blade method, film press, air brush, the so-called slot die method or a Tur- tain coating method.
  • further layers such as protective layers or layers improving the gloss can be applied to the receiving layer.
  • the application weight is preferably less than 1 g / m 2 .
  • a carrier for the inventive receiving layer a base paper, a resin-coated paper or a plastic film- ⁇ material can be used.
  • Base paper an uncoated or surface Pa ⁇ pier.
  • a base paper besides cellulose fibers, sizing agents such as Alkylkentendimere, fatty acids and / or fatty acid salts, epoxidised fatty acid amides, alkenyl or Alkylbernsteinkla- anhydride, starch, resin, wet strength agents such as polyamine-polyamide epichlorohydrin, dry strength agent such as anionic, ka ⁇ tionische or amphoteric polyamides, optical may contain brighteners, Pig ⁇ ments, dyes, defoamers and other known in the industry Textilin ⁇ aids.
  • the base paper can be surface-sized. Examples of suitable sizing agents are polyvinyl alcohol or oxidized starch.
  • Raw paper can be produced on a Fourdrinier or a Yankee paper machine (cylinder paper machine).
  • the basis weight of the base paper may be 50 to 250 g / m 2 , in particular especially 80 to 180 g / m 2 , amount.
  • the raw paper can be used in un-compacted or compacted form (smoothed).
  • Particularly suitable are base papers having a density of 0.8 to 1.05 g / cm 3 , in particular 0.95 to 1.02 g / cm 3 .
  • the pulp for the Pa ⁇ pierher ein is preferably a eucalyptus pulp with a fiber content of less than 200 ym after refining of 10 to 35 wt .-% and an average fiber length of 0.5 to 0.75 mm. It has been found that the use of a pulp with a limited fraction of fibers less than 200 ym reduces the loss of stiffness occurring when using filler. Hardwood pulps (NBHK - Northern Blazed Hardwood Kraft Pulp) and softwood pulps may also be used.
  • Suitable fillers for sheet production for example, kaolins, calcium carbonate can be used in its natural form, such as limestone, marble or dolomite, precipitated calcium carbonate, calcium sulfate, barium sulfate, titanium dioxide, talc, silica, alumina and mixtures thereof in the base paper ⁇ the.
  • Particularly suitable is calcium carbonate having a Korngrö ⁇ size distribution wherein at least 60% of the particles are less than 2 .mu.m and at most 40% are smaller than 1 micron.
  • calcite is used with a particle size distribution in which about 25% of the particles have a particle size of less than 1 micron and about 85% of the particles have a particle size of less than 2 ym aufwei ⁇ sen.
  • a calcium carbonate with a particle size distribution can be used in which at least 70%, preferably at least 80%, the particles are smaller than 2 microns and at most 70% of the particles are smaller than 1 micron.
  • the carrier may be a resin-coated paper.
  • a resin-coated paper contains a arranged at least on ei ⁇ ner side of the base paper a synthetic resin layer.
  • the synthetic resin layer may preferably contain a thermoplastic polymer .
  • Particularly suitable for this purpose are polyolefins, particularly low density polyethylene (LDPE), high density polyethylene (HDPE), ethylene / a-olefin copolymers (LLDPE), Po ⁇ lypropylen, polyisobutylene, polymethylpentene, and mixtures thereof. But also other thermoplastic polymers like
  • (Meth) acrylate homopolymers (meth) acrylic acid ester copolymers, vinyl polymers such as polyvinyl butyral, polyamides, Po ⁇ lyester, polyacetals, polylactic acids (PLA) and / or polycarbonates can be used.
  • vinyl polymers such as polyvinyl butyral, polyamides, Po ⁇ lyester, polyacetals, polylactic acids (PLA) and / or polycarbonates
  • the resin layer may contain white pigments such as titanium dioxide and calcium carbonate as well as other adjuvants such as optical brightening ⁇ ler, dyes and dispersing.
  • ⁇ weight of the resin layer on the front side may be 5 to 50 g / m 2, especially 10 to 30 g / m 2 or in accordance with another preferred embodiment, 10 to 20 g / m 2.
  • the resin layer may be a single layer extruded or coextruded Distanceschich ⁇ tig. The extrusion coating can be carried out at machine speeds up to 600 m / min.
  • the back of the base paper can be coated with a clear, ie pigment-free synthetic resin, in particular polyethylene.
  • the coating weight of the synthetic resin layer on the back can be 5 to 50 g / m 2 , in particular 10 to 40 g / m 2 or according to a further preferred embodiment 10 to 20 g / m 2 .
  • the synthetic resin layer on the back of the base paper but can also be pigmented.
  • the back of the substrate may also include other functional layers such as antistatic or ⁇ comprise anticurl layers.
  • hydro ⁇ hydrophilic binder-containing layer may be disposed between base paper and a synthetic resin layer.
  • Hydrophilic binders are, for example, hydroxypropylated starch and / or thermally modified starches.
  • This layer may preferably contain other polymers such as polyamide copolymers and / or polyvinylamine copolymers.
  • the base paper can also have a size press order with egg ⁇ nem binder, wherein the order amount is 0.3 to 5 g / m 2 .
  • Suitable binders are conventional surface sizing agents and polyacrylates. This order may contain pigments.
  • a layer may be applied with pigment.
  • the layer containing the hydrophilic binder may be disposed directly on the front side of the base paper or on the back side of the base paper. It can be applied as a single layer or as a multilayer to the base paper.
  • the coating composition can be applied in-line or off-line with all customary in papermaking application units, the amount is chosen so that after drying the coating weight per layer at most 20 g / m 2 , insbesonde ⁇ re 8 to 17 g / m 2 , or in a particularly preferred embodiment is 2 to 6 g / m 2 .
  • the layer may preferably contain a pigment.
  • the Pig ⁇ ment can be selected from a group of metal oxides, silicates, carbonates te, sulfides and sulfates.
  • pigments such as kaolins, talc, calcium carbonate and / or barium sulfate.
  • a pigment having a narrow particle size distribution wherein at least 70% of the pigment particles have a size of less than 1 ym.
  • the proportion of the pigment with the narrow particle size distribution of the total amount of pigment should be at least 5% by weight, in particular from 10 to 90% by weight. Particularly good results can be achieved with a proportion of 30 to 80 wt .-% of the total pigment.
  • At least 70 wt .-% of the pigment particle has in which a size of less than 1 .mu.m and at 40 to 80 wt .-% of these pigment particles, the difference between the pigment having the largest grain size (diameter) and the pigment of the smallest grain size is smaller than about 0.4 ⁇ m.
  • Particularly advantageous is a calcium carbonate with egg ⁇ nem proved d 50% value of about 0.7 microns.
  • a pigment mixture which consists of the above-mentioned calcium carbonate and kaolin.
  • the amount ratio of calcium carbonate ⁇ / kaolin is preferably from 30:70 to 70:30. It has surprisingly been found that despite the high proportion of prone to yellowing kaolin only an insignificant nega ⁇ tive effect was observed on the whiteness of the coated material.
  • the amount ratio of binder / pigment in the layer can be from 0.1 to 2.5, preferably from 0.2 to 1.5, but in particular from 0.9 to 1.3.
  • the solids content of the coating composition of the invention may be from 15 to 35% by weight, based on the weight of the coating composition.
  • a plastic film can be used as the carrier.
  • suitable plastic films are those of polyolefin (s), polycarbonates, acrylic resin (s), polyvinyl chloride and polyethylene terephthalate.
  • the ink receiving layer may contain an electrically conductive ⁇ compo nent.
  • Suitable electrically conductive components are, for example, an electrically conductive polymer or finely divided electrically conductive pigments.
  • the amount of the electroconductive component in the dye-receiving layer may be 0 to 50% by weight, especially 0.1 to 4.0% by weight, based on the mass of the dried layer.
  • the pulp was first disintegrated in water for 15 minutes. It was added from a pre-made ⁇ mixture and then added to the Natriumhy ⁇ pochlorid and the mixture left for two hours in the tank at a pH around 10 TEMPO and sodium bromide. The pH was adjusted with 1 M NaOH. The reaction was stopped ge ⁇ by the addition of ethanol, which reacts with the remaining sodium hypobromite. After the reaction, the functionalized cell ⁇ material four times was washed and centrifuged.
  • the TEMPO fibers were used to produce nanofibrillated cellulose.
  • the material to be homogenized was treated at a consistency of 4% in a GEA Ariete homogenizer in two passes at 150 MPa (1500 bar).
  • a eucalyptus pulp was used.
  • the pulp was ground to a freeness of 36 ° SR using about 5% aqueous suspension (thick stock) using a refiner.
  • the mean fiber length was 0.64 mm.
  • the concentration of pulp fibers in the thin was 1 wt .-%, based on the mass of the pulp suspension.
  • the thin stock additives were added as a neutral sizing medium ⁇ alkyl ketene dimer (AKD) in an amount of 0.48 wt .-%, wet strength agents polyamine-polyamide-epichlorohydrin resin (Kymene ®) in an amount of 0.36 wt .-% and natural CaCO 3 in an amount of 10% by weight.
  • the quantities are based on the pulp mass.
  • the thinstock whose pH was adjusted to about 7.5, was transferred from the head box to the wire of the paper machine, followed by sheet formation by dewatering the web in the wire section of the paper machine.
  • the further dewatering of the paper web to a water content of 60 wt .-%, based on the web weight. Further drying took place in the dryer section of the paper machine with heated drying cylinders.
  • the result was a base paper with a basis weight of 160 g / m 2 and a humidity of about 7%.
  • the base paper is coated on both sides with a coating of a styrene-acrylate binder, starch and a pigment mixture of calcium carbonate and kaolin with a coating weight of 15 g / m 2 on both sides, dried and then smoothed with a calender.
  • a coating of a styrene-acrylate binder, starch and a pigment mixture of calcium carbonate and kaolin with a coating weight of 15 g / m 2 on both sides, dried and then smoothed with a calender.
  • the thickness of the layer was 17 ⁇ m.
  • the front side of the base paper was coated with a synthetic resin mixture of 71% by weight of a low-density polyethylene (LDPE, 0.923 g / cm 3 ), 16% by weight of a TiO 2 masterbatch (50% by weight LDPE and 50% by weight). % TiO 2 ) and 13 wt .-% of other additives such as optical brightener, calcium stearate and blue pigment with aquestge ⁇ weight of about 17 g / m 2 coated in the laminator at a speed of about 250 m / min. The thickness of the front art ⁇ resin layer was 17 microns. A receiving layer for the inkjet printing process was then applied to the vorderseiti ⁇ ge resin layer.
  • LDPE low-density polyethylene
  • the dilutions of nanofibrillated cellulose were used in the pilot coater test planned formulations under standard conditions for aluminum oxide based coating formulations.
  • the following table shows an overview of the used Re ⁇ zepturen and the test values after production in the laboratory.
  • NFC nanofibrillated cellulose.
  • TE stands for the treatment according to the TEMPO procedure.
  • Drying profile gradually increased and the Crackingmati ⁇ each tested in comparison to the standard.
  • the potential for speed ⁇ increase can be estimated at a constant drying profile.
  • the formulations with nanofibrillated cellulose showed no abnormalities during the test run during the application to the carrier by means of curtain coating. There were no differences between the individual formulations with regard to curette stability or running behavior in the casting process.

Landscapes

  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Ink Jet Recording Methods And Recording Media Thereof (AREA)
  • Paper (AREA)
  • Ink Jet (AREA)
  • Laminated Bodies (AREA)

Abstract

Un matériau d'enregistrement pour le procédé d'impression à jet d'encre comprenant un support et au moins une couche de réception de couleur disposée sur le support contient dans la couche de réception de couleur une cellulose nanofibrillée et présente un comportement de fendillement amélioré dans la couche d'image.
EP13730200.6A 2012-06-15 2013-06-14 Couche de réception pour procédés d'impression numériques comprenant de la cellulose nanofibrillée Not-in-force EP2861429B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102012011774 2012-06-15
PCT/EP2013/062392 WO2013186367A1 (fr) 2012-06-15 2013-06-14 Couche de réception pour procédés d'impression numériques comprenant de la cellulose nanofibrillée

Publications (2)

Publication Number Publication Date
EP2861429A1 true EP2861429A1 (fr) 2015-04-22
EP2861429B1 EP2861429B1 (fr) 2016-06-08

Family

ID=48669927

Family Applications (1)

Application Number Title Priority Date Filing Date
EP13730200.6A Not-in-force EP2861429B1 (fr) 2012-06-15 2013-06-14 Couche de réception pour procédés d'impression numériques comprenant de la cellulose nanofibrillée

Country Status (5)

Country Link
US (1) US20150140237A1 (fr)
EP (1) EP2861429B1 (fr)
JP (1) JP2015527217A (fr)
CN (1) CN104379358A (fr)
WO (1) WO2013186367A1 (fr)

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2941100C (fr) 2014-03-14 2022-07-19 Stora Enso Oyj Procede de fabrication de materiau d'emballage, et materiau d'emballage fabrique par le procede
CN106457865B (zh) * 2014-05-09 2019-04-12 Fp创新研究中心 用于印刷的纤维素纳米晶体涂层介质
CN106573487B (zh) * 2014-07-31 2019-11-22 惠普发展公司,有限责任合伙企业 印刷基底
EP3353347B1 (fr) * 2015-09-23 2021-05-05 Stora Enso Oyj Papier d'impression sans encre
ES2857512T3 (es) 2016-04-05 2021-09-29 Fiberlean Tech Ltd Productos de papel y cartón
US11846072B2 (en) 2016-04-05 2023-12-19 Fiberlean Technologies Limited Process of making paper and paperboard products
WO2018052400A1 (fr) 2016-09-13 2018-03-22 Hewlett-Packard Development Company, L.P. Compositions de réception d'image
CN110431022A (zh) * 2017-03-13 2019-11-08 富士胶片株式会社 转印薄膜及图像形成方法
JP7139202B2 (ja) * 2018-09-11 2022-09-20 大王製紙株式会社 加飾フィルム及びその製造方法
CN109706792B (zh) * 2019-01-04 2021-05-14 衢州五洲特种纸业股份有限公司 一种透明防粘纸及其制备方法
JP6645604B1 (ja) * 2019-03-27 2020-02-14 王子ホールディングス株式会社 シートおよびシートの製造方法
CN115125767A (zh) * 2022-07-25 2022-09-30 广东伽立实业投资有限公司 一种表面涂布纳米纤维素的热升华转印纸及其制备方法

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07156536A (ja) * 1993-12-07 1995-06-20 Dainippon Printing Co Ltd 受像シート及びその記録方法
DE19618607C2 (de) * 1996-05-09 1999-07-08 Schoeller Felix Jun Foto Aufzeichnungsmaterial für Tintenstrahl-Druckverfahren
DE10009247C1 (de) * 2000-02-28 2001-10-18 Schoeller Felix Jun Foto Schichtträger
WO2001070510A1 (fr) * 2000-03-17 2001-09-27 Hitachi Maxell, Ltd. Support d'enregistrement à jet d'encre et procédé de production
US20030152720A1 (en) * 2002-02-08 2003-08-14 Michael Lubar Ink jet recording sheet, method for the preparation of same, and ink jet recording method using same
US7829160B2 (en) * 2006-02-28 2010-11-09 Eastman Kodak Company Glossy inkjet recording element on absorbent paper
CN100393533C (zh) * 2006-06-20 2008-06-11 南开大学 防水喷墨打印介质及其制备方法
US20080311384A1 (en) * 2007-06-15 2008-12-18 Christopher Arend Toles Coating composition
WO2011001706A1 (fr) * 2009-06-29 2011-01-06 日本製紙株式会社 Papier pour enregistrement d'informations et papier traité
JP2013256546A (ja) * 2010-09-28 2013-12-26 Nippon Paper Industries Co Ltd セルロースナノファイバー

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2013186367A1 *

Also Published As

Publication number Publication date
JP2015527217A (ja) 2015-09-17
WO2013186367A1 (fr) 2013-12-19
EP2861429B1 (fr) 2016-06-08
CN104379358A (zh) 2015-02-25
US20150140237A1 (en) 2015-05-21

Similar Documents

Publication Publication Date Title
EP2861429B1 (fr) Couche de réception pour procédés d'impression numériques comprenant de la cellulose nanofibrillée
DE4312463C1 (de) CaCO¶3¶ -Talkum-Streichpigmentslurry, Verfahren zu seiner Herstellung und seine Verwendung
DE69202766T2 (de) Aufzeichnungsblatt für Tintenstrahlschreiber.
DE60314608T2 (de) Zusammensetzung zur oberflächenbehandlung von papier
DE69305603T2 (de) Aufzeichnungsblatt für den Tintenstrahldruck
DE69826121T3 (de) Tiefdruckpapiere beschichtet mit ausgefälltem aragonit kalciumkarbonatpigment
DE19955081C1 (de) Basispapier für ein Aufzeichnungsmaterial für das Tintenstrahl-Druckverfahren
DE60316583T2 (de) Beschichtetes druckblatt und sein herstellungsverfahren
EP1126081B1 (fr) Support pour couches d'enregistrement
DE69011991T2 (de) Registriermittel und Verfahren zum Registrieren damit.
EP2010712B1 (fr) Support de couche pour matériaux d'enregistrement
EP3323624B1 (fr) Matériau de transfert adhésif microporeux
EP1379729A1 (fr) Papier support pour l'impregnation avec resines synthetiques
DE60107725T3 (de) Für eine pigmenthaltige Tinte geeignetes Tintenstrahlaufzeichnungsmaterial
EP3098085A1 (fr) Matériau de transfert pour l'impression par sublimation
EP0387893B1 (fr) Papier d'enregistrement par jet d'encre
EP2076398B1 (fr) Materiau d'impression a jet d'encre dote d'une couche arriere perforee en resine synthetique
EP2326992B1 (fr) Matériau d'enregistrement pour un procédé d'impression laser
DE602004007492T2 (de) Tintenstrahlaufzeichnungsblatt
EP3028866B1 (fr) Matériau d'enregistrement pour un procédé d'impression thermique
DE69127432T2 (de) Schichtträger für photographische Abzüge
DE102012204893A1 (de) Gestrichenes Druckpapier und dessen Herstellungsverfahren
WO2022184768A1 (fr) Matériau de transfert pour impression par sublimation à base de papier en tant que support ayant une fonction de barrière aux encres
DE1945104B (de) Verfahren zur Herstellung von Papier mit verbesserten Eigenschaften
EP2428840A1 (fr) Matériau de support pour papier photographique à l'halogénure d'argent revêtu des deux côtés

Legal Events

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

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20141106

AK Designated contracting states

Kind code of ref document: A1

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

AX Request for extension of the european patent

Extension state: BA ME

RIN1 Information on inventor provided before grant (corrected)

Inventor name: PAPIER, GERD

Inventor name: SCHMIDT, WOLFGANG

Inventor name: FEHLKER, ANDREAS

Inventor name: SCHLENSTEDT, MICHAEL

Inventor name: GERICKE, RALF

DAX Request for extension of the european patent (deleted)
GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

INTG Intention to grant announced

Effective date: 20160111

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

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

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 4

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: GERMAN

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 804927

Country of ref document: AT

Kind code of ref document: T

Effective date: 20160715

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 502013003353

Country of ref document: DE

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20160608

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

Ref country code: FI

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

Effective date: 20160608

Ref country code: LT

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

Effective date: 20160608

Ref country code: NO

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

Effective date: 20160908

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

Ref country code: NL

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

Effective date: 20160608

Ref country code: GR

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

Effective date: 20160909

Ref country code: SE

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

Effective date: 20160608

Ref country code: ES

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

Effective date: 20160608

Ref country code: LV

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

Effective date: 20160608

Ref country code: RS

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

Effective date: 20160608

Ref country code: HR

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

Effective date: 20160608

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

Ref country code: BE

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

Effective date: 20160630

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

Ref country code: RO

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

Effective date: 20160608

Ref country code: IS

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

Effective date: 20161008

Ref country code: IT

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

Effective date: 20160608

Ref country code: EE

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

Effective date: 20160608

Ref country code: SK

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

Effective date: 20160608

Ref country code: CZ

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

Effective date: 20160608

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

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

Ref country code: SM

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

Effective date: 20160608

Ref country code: PL

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

Effective date: 20160608

Ref country code: PT

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

Effective date: 20161010

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 502013003353

Country of ref document: DE

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

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

Ref country code: MC

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

Effective date: 20160608

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

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

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

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

Ref country code: LI

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

Effective date: 20160630

Ref country code: CH

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

Effective date: 20160630

26N No opposition filed

Effective date: 20170309

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

Ref country code: IE

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

Effective date: 20160614

Ref country code: SI

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

Effective date: 20160608

Ref country code: DK

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

Effective date: 20160608

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 5

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

Ref country code: HU

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

Effective date: 20130614

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 6

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

Ref country code: MK

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

Effective date: 20160608

Ref country code: CY

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

Effective date: 20160608

Ref country code: MT

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

Effective date: 20160608

Ref country code: LU

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

Effective date: 20160614

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

Ref country code: BG

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

Effective date: 20160608

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

Ref country code: AL

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

Effective date: 20160608

Ref country code: TR

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

Effective date: 20160608

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

Ref country code: DE

Payment date: 20190619

Year of fee payment: 7

REG Reference to a national code

Ref country code: AT

Ref legal event code: MM01

Ref document number: 804927

Country of ref document: AT

Kind code of ref document: T

Effective date: 20180614

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

Ref country code: FR

Payment date: 20190619

Year of fee payment: 7

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

Ref country code: GB

Payment date: 20190619

Year of fee payment: 7

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

Ref country code: AT

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

Effective date: 20180614

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 502013003353

Country of ref document: DE

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

Effective date: 20200614

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

Ref country code: FR

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

Effective date: 20200630

Ref country code: GB

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

Effective date: 20200614

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

Ref country code: DE

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

Effective date: 20210101