EP2546066B2 - Matériel d'enregistrement sensible à la pression et procédé pour sa fabrication - Google Patents

Matériel d'enregistrement sensible à la pression et procédé pour sa fabrication Download PDF

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Publication number
EP2546066B2
EP2546066B2 EP11173923.1A EP11173923A EP2546066B2 EP 2546066 B2 EP2546066 B2 EP 2546066B2 EP 11173923 A EP11173923 A EP 11173923A EP 2546066 B2 EP2546066 B2 EP 2546066B2
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EP
European Patent Office
Prior art keywords
coating
substrate
recording material
zinc salicylate
material according
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.)
Active
Application number
EP11173923.1A
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German (de)
English (en)
Other versions
EP2546066B1 (fr
EP2546066A1 (fr
Inventor
Dr. Horst Heyer
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.)
Mitsubishi HiTec Paper Europe GmbH
Original Assignee
Mitsubishi HiTec Paper Europe GmbH
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.)
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Application filed by Mitsubishi HiTec Paper Europe GmbH filed Critical Mitsubishi HiTec Paper Europe GmbH
Priority to ES11173923.1T priority Critical patent/ES2525570T5/es
Priority to PL11173923T priority patent/PL2546066T5/pl
Priority to EP11173923.1A priority patent/EP2546066B2/fr
Priority to ES12155798.7T priority patent/ES2477553T3/es
Priority to EP12155798.7A priority patent/EP2546067B1/fr
Priority to EP12175324.8A priority patent/EP2546068B1/fr
Publication of EP2546066A1 publication Critical patent/EP2546066A1/fr
Publication of EP2546066B1 publication Critical patent/EP2546066B1/fr
Publication of EP2546066B2 publication Critical patent/EP2546066B2/fr
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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
    • B41M5/124Duplicating or marking methods; Sheet materials for use therein using pressure to make a masked colour visible, e.g. to make a coloured support visible, to create an opaque or transparent pattern, or to form colour by uniting colour-forming components
    • B41M5/132Chemical colour-forming components; Additives or binders therefor
    • B41M5/155Colour-developing components, e.g. acidic compounds; Additives or binders therefor; Layers containing such colour-developing components, additives or binders
    • 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
    • B41M5/124Duplicating or marking methods; Sheet materials for use therein using pressure to make a masked colour visible, e.g. to make a coloured support visible, to create an opaque or transparent pattern, or to form colour by uniting colour-forming components

Definitions

  • the invention also relates to a method for producing a recording material for the pressure-induced formation of a typeface to the same extent.
  • zinc benzoates are generally known as color acceptors in color-reactive recording materials.
  • the non-generic EP 1 375 182 A1 the zinc 4-nitrobenzoate, which is not identical to zinc salicylate, as a developer component in heat-sensitive recording materials.
  • zinc benzoates, and also those color developers, which include the zinc salicylate proposed here are generally disclosed as components of color-reactive recording materials, without being concerned with possible concentrations in the color reaction layers.
  • Subject of the US 4,257,935 A is a color-developing coating composition which, according to introductory passages, is to be used preferably for pressure-sensitive recording systems.
  • a coating composition contains, in addition to zinc salicylate as the color acceptor and starch and latex as binder, a clay pigment whose possible inclusion in the description of the coating composition proposed there is not mentioned.
  • a SC (selfcontained) coating composition for forming a carbonless paper are disclosed for the zinc-salicylate as a color acceptor, a variety of possible components such as starch and polyvinyl alcohol as a binder and optionally also various pigments as possible fillers.
  • the recording material proposed here is formed from a web-shaped substrate, on the front side of which a first coating composition is applied for forming a so-called CF layer as a possibility of a color reaction layer .
  • CF layers are understood as meaning layers having color developers (colorants or color acceptors) which can be formed as color developer pigment or, as in the case according to the invention, as oil-soluble acidic organic substances and which are admixed with suitable dye precursors, preferably leuco dyes a color reaction, in which a color complex is formed.
  • organic color acceptors well known in the art include phenolic substances such as phenol, resorcinol, naphthols and salicylic acid, which may also be alkyl substituted and may be present as monomers, oligomers or polymers (resins).
  • the recording material proposed here is formed from a web-shaped substrate, on the front side of which a coating composition is applied for forming a so-called SC layer as a further possibility of a color reaction layer .
  • SC layers are understood as meaning layers which contain a zinc salicylate as well as at least one color acceptor as well as encapsulated dye precursors for the purposes of the present invention.
  • Silica, kaolin, aluminum (hydr) oxide and, in particular, natural calcium carbonate are suitable as inorganic pigment within this backside coating, and it is also conceivable to mix these inorganic pigments with one another or with other inorganic pigments. If, in addition to the previously disclosed pigments, other pigments are also to be used within the backcoat coating, it is preferred if these other inorganic pigments have a mixing ratio, relative to wt.%, Of silica, aluminum (hydr) oxide or, in particular, natural calcium carbonate 1: 4 and 1:25 are incorporated within the second coating composition.
  • Styrene-acrylate latex, starch, polyvinyl alcohol and very particularly preferably styrene-butadiene latex are suitable as binders within this backside coating.
  • Wax and / or AKD glue are used in particular as a means of hydrophobing the pigmented coating.
  • the proposed here Recording material formed from a web-shaped substrate, on the front side as a first coating composition the composition for forming the coating with zinc salicylate as at least one color acceptor is applied to form a CF layer, while on the back of the substrate, a so-called CB layer (coated back) is formed.
  • recording materials which have on the front side a CF layer with color acceptors or color acceptors and on the backside a CB layer are referred to as so-called CFB materials, sheets or sheets.
  • the CB layer contains microcapsules containing dye precursors in a suitable solvent.
  • the application of a localized pressure to the CB coating causes the microcapsules to break up, resulting in a release of the previously encapsulated dye precursors. Then come dye precursors from the microcapsules of the CB or SC layer in contact with the zinc salicylate as at least one color acceptor within the CF or SC layer, it leads to the formation of a color reaction, which takes place exactly where previously by the Pressure exerted the microcapsules are broken: usually this happens along a script line, which is formed by inscription using a pen or typewriter.
  • the CF coatings and / or the CB coatings are underlaminated with barrier-forming intermediate coatings, which means that the barrier-forming intermediate coatings between substrate and CF coating and / or are formed between the substrate and the CB coating.
  • the dye precursors are encapsulated in microcapsules having the size and leuco dyes preferably used therein are largely not restricted.
  • those microcapsules which have a wall material of melamine-formaldehyde resin with a preferred average capsule size in a range in particular of 4 to 6 ⁇ m are particularly well-proven.
  • Diisopropylnaphthalene oil (KMC oil from Rütgers Novares GmbH, Duisburg, Germany) is preferably used as the capsule content, containing as dye precursor leuco dyes in a range from 4 to 7.5% by weight.
  • the coating with the zinc salicylate preferably contains at least one binder selected from the list, comprising: styrene-butadiene latex, styrene-acrylate latex, starch, polyvinyl alcohol.
  • binder selected from the list, comprising: styrene-butadiene latex, styrene-acrylate latex, starch, polyvinyl alcohol.
  • the preference of the inventors is styrene-butadiene latex, which is used in particular together with starch.
  • the invention also relates, to the same extent, to a method for producing a recording material for the pressure-induced formation of a typeface in all the embodiments and variants already proposed here.
  • such a method comprises the method steps defined in claim 12.
  • the formation of the web-like substrate is done for example on a paper machine, in which at least one upstream Mischbütte a paper pulp of different pulp, optionally groundwood, fillers and water is applied and where to this paper pulp before being fed to the paper machine preferably further ingredients such as resin glue for engine sizing and other customary additives, such as pigments, shading dyes and / or optical brighteners are added.
  • a paper machine in which at least one upstream Mischbütte a paper pulp of different pulp, optionally groundwood, fillers and water is applied and where to this paper pulp before being fed to the paper machine preferably further ingredients such as resin glue for engine sizing and other customary additives, such as pigments, shading dyes and / or optical brighteners are added.
  • the first coating composition is preferably applied to the front of the substrate using a coater, the coater preferably selected from the list comprising: roller coater, roller blade coater, knife coater, air brush and all particularly preferred curtain coater.
  • the first coating composition used to form a color reaction layer is preferably aqueous.
  • the subsequent drying of the first coating composition is usually carried out by a method in which heat is supplied, as is done by hot-air floatation dryer or contact dryer. Proven is also a combination of the listed dry processes.
  • the color reaction layer thus formed is preferably at least slightly frosted.
  • the basis weight of the color reaction layer of the first coating composition is preferably from 3.2 to 7.2 g / m 2, and more preferably from 3.4 to 4.8 g / m 2 .
  • the application of the second coating composition to form a pigmented and preferably hydrophobic coating on the back side of the substrate is preferably accomplished by means of a coater selected from the list comprising: roller coater, curtain coater, doctor blade and doctor roll coater.
  • the second coating composition used to form this pigmented backside coating is also preferably aqueous.
  • the subsequent drying after application of the second Again, coating composition is usually done by a process of adding heat, such as by hot-air floatation dryers or contact dryers. Proven is also a combination of the listed dry processes.
  • the basis weight of the pigmented backcoat of the second coating composition is preferably between 2.5 and 4.2 g / m 2, and more preferably between 2.7 and 3.7 g / m 2 .
  • the application of the third coating composition to form a CB layer on the back surface of the substrate is preferably accomplished by means of a coater selected from the list comprising: roller coater, curtain coater, doctor blade and doctor blade coater.
  • a coater selected from the list comprising: roller coater, curtain coater, doctor blade and doctor blade coater.
  • a curtain coater both in its design as Schlitzg teller with downwardly open color head from which immediately forms the color curtain, as well as in its design as Gleit vombe harsher, in which the paint head is the coating mass on an inclined flow sheet, from where forming the color curtain, excellent product and especially machine running properties could be observed within the coating process, eventually leading to a particularly homogeneous appearance of the CB coating from the third coating composition.
  • the third coating composition used to form the CB layer is preferably aqueous.
  • the subsequent drying of the second coating composition after the application is again usually carried out by a method in which heat is supplied, as is done by hot-air floatation dryer or contact dryer. Proven is also a combination of the listed dry processes.
  • the basis weight of a CB layer of the third coating composition is preferably between 2.2 and 6.2 g / m 2, and more preferably between 2.4 and 3.8 g / m 2 .
  • a paper web of bleached and ground deciduous and softwood pulps having a basis weight of 67 g / m 2 with conventional additives and in particular with the addition of resin size for engine sizing is produced as a web-shaped substrate and at the end of the paper machine as a semi-finished product rolled up on a spool.
  • a color reaction layer is applied on the front side using a curtain coater in its slitter coater design, and a second coater composition for forming a pigmented and hydrophobic coater is applied using a further curtain coater as slot coater ,
  • the second coating composition contains as main constituents natural calcium carbonate as pigment, styrene-acrylate latex and starch as binder mixture and AKD glue as a means for hydrophobizing the pigmented backcoat. While the back coating is applied at a basis weight of 3.0 g / m 2 , the basis weight for the color reaction layer is 4.0 g / m 2 .
  • the color reaction layer is alternatively formed from seven different first coating compositions, these coating compositions differing as shown in Table 2 below.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Paper (AREA)
  • Color Printing (AREA)

Claims (13)

  1. Matériau d'enregistrement pour la formation d'un caractère sous l'effet d'une pression, comprenant au moins :
    ■ un substrat en forme de bande,
    présentant une face avant, comme étant la première des deux faces du substrat, et une face arrière, comme étant la seconde des deux faces du substrat,
    ■ un revêtement réalisé sur au moins l'une des deux faces du substrat, présentant :
    - un salicylate de zinc, comme au moins un accepteur de couleur,
    - un pigment inorganique,
    doté des caractéristiques selon lesquelles
    ■ le salicylate de zinc est incorporé dans ce revêtement selon une proportion comprise dans la plage de 4 à 14 % en poids - par rapport au poids total du revêtement et du salicylate de zinc - comme accepteur de couleur,
    ■ en tant que pigment inorganique, un mélange de pigments, constitué de deux pigments inorganiques matériellement différents, est incorporé dans ce revêtement,
    caractérisé en ce que
    a) le revêtement comprenant le salicylate de zinc contient en tant que pigment inorganique un mélange de pigments constitué de kaolin naturel et de carbonate de calcium précipité, et le rapport de mélange, en % en poids, du kaolin naturel et du carbonate de calcium précipité, est compris dans la plage de 2:1 à 1:2,
    ou
    b) le revêtement comprenant le salicylate de zinc contient en tant que pigment inorganique un mélange de pigments constitué de kaolin calciné et d'hydroxyde d'aluminium,
    ou
    c) le revêtement comprenant le salicylate de zinc contient en tant que pigment inorganique un mélange de pigments constitué de kaolin calciné et de talc.
  2. Matériau d'enregistrement selon la revendication 1, caractérisé en ce que le matériau d'enregistrement comprend au moins :
    ■ un substrat en forme de bande,
    ■ un revêtement comprenant le salicylate de zinc, sur la face avant du substrat,
    ■ un revêtement pigmenté, sur la face arrière du substrat.
  3. Matériau d'enregistrement selon l'une des revendications 1 et 2, caractérisé en ce que le revêtement comprenant le salicylate de zinc contient en outre des précurseurs de colorant encapsulés.
  4. Matériau d'enregistrement selon la revendication 1, caractérisé en ce que le matériau d'enregistrement comprend au moins :
    ■ un substrat en forme de bande,
    ■ un revêtement comprenant le salicylate de zinc, sur la face avant du substrat,
    ■ un revêtement comprenant des précurseurs de colorant encapsulés, sur la face arrière du substrat.
  5. Matériau d'enregistrement selon l'une des revendications 1 à 4, caractérisé en ce que le salicylate de zinc est incorporé dans ce revêtement selon une proportion comprise dans la plage de 5,5 à 11,0 % en poids, par rapport au poids total du revêtement comprenant le salicylate de zinc.
  6. Matériau d'enregistrement selon l'une des revendications 1 à 5, caractérisé en ce que la proportion, en % en poids, à l'intérieur du revêtement comprenant le salicylate de zinc,
    salicylate de zinctotal : pigment inorganiquetotal,
    est comprise dans la plage de 1:6,5 à 1:14,0.
  7. Matériau d'enregistrement selon l'une des revendications 1 à 6, caractérisé en ce que le rapport de mélange, en % en poids, du kaolin calciné et de l'hydroxyde d'aluminium, est compris dans la plage de 1:1,8 à 1:2,8.
  8. Matériau d'enregistrement selon l'une des revendications 1 à 6, caractérisé en ce que le rapport de mélange, en % en poids, du kaolin calciné et du talc, est compris dans la plage de 1:3,5 à 1:6,5.
  9. Matériau d'enregistrement selon l'une des revendications 1 à 8, caractérisé en ce que le revêtement comprenant le salicylate de zinc contient en outre au moins un liant choisi dans la liste comprenant le latex styrène-butadiène, le latex styrène-acrylate, l'amidon, le poly(alcool vinylique).
  10. Matériau d'enregistrement en forme de bande selon l'une des revendications 1 à 9, caractérisé en ce que le revêtement comprenant le salicylate de zinc n'est que partiellement appliqué.
  11. Matériau d'enregistrement en forme de bande selon l'une des revendications 2, 3 et 5 à 10, caractérisé en ce que le revêtement pigmenté, sur la face arrière du substrat, comprend au moins :
    ■ un pigment inorganique,
    ■ un liant,
    ■ des agents pour l'hydrophobisation de ce revêtement pigmenté, sur la face arrière du substrat.
  12. Procédé de fabrication d'un matériau d'enregistrement pour la formation d'un caractère sous l'effet d'une pression, le procédé comprenant au moins les étapes suivantes :
    - formation d'un substrat en forme de bande, présentant une face avant comme étant la première des deux faces du substrat, et une face arrière comme étant la deuxième des deux faces du substrat ;
    - préparation d'une première composition de revêtement, cette première composition de revêtement comprenant au moins :
    - un mélange de pigments, constitué de kaolin naturel et de carbonate de calcium précipité, en tant que pigment inorganique, le rapport de mélange, en % en poids, du kaolin naturel et du carbonate de calcium précipité étant compris dans la plage de 2:1 à 1:2,
    - un liant,
    - du salicylate de zinc, le salicylate de zinc étant présent en une quantité comprise dans la plage de 4 à 14 % en poids par rapport au poids total du revêtement,
    - application, sur la face avant du substrat, pour la formation d'une couche de réaction colorée, de la première composition de revêtement préparée ;
    - séchage de la première composition de revêtement ;
    - enroulement du substrat en forme de bande comprenant la couche de réaction colorée.
  13. Procédé de fabrication d'un matériau d'enregistrement selon la revendication 12, caractérisé en ce que la première composition de revêtement est appliquée à l'aide d'un équipement d'enduction, choisi dans la liste comprenant une enduiseuse à rouleaux, une enduiseuse à la racle tournante, une enduiseuse à lame, une enduiseuse à rideau ou une lame d'air.
EP11173923.1A 2011-07-14 2011-07-14 Matériel d'enregistrement sensible à la pression et procédé pour sa fabrication Active EP2546066B2 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
ES11173923.1T ES2525570T5 (es) 2011-07-14 2011-07-14 Material de impresión piezosensible y procedimiento para su producción
PL11173923T PL2546066T5 (pl) 2011-07-14 2011-07-14 Materiał rejestrujący wrażliwy na ciśnienie i jego sposób otrzymywania
EP11173923.1A EP2546066B2 (fr) 2011-07-14 2011-07-14 Matériel d'enregistrement sensible à la pression et procédé pour sa fabrication
EP12155798.7A EP2546067B1 (fr) 2011-07-14 2012-02-16 Méthode pour la fabrication d'un matériau pour l'enregistrement sensible à la pression
ES12155798.7T ES2477553T3 (es) 2011-07-14 2012-02-16 Procedimiento para la preparación de un material de registro sensible a la presión
EP12175324.8A EP2546068B1 (fr) 2011-07-14 2012-07-06 Matériel d'enregistrement pour formation induite par pression d'un sigle et procédé de fabrication d'un tel matériel d'enregistrement

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP11173923.1A EP2546066B2 (fr) 2011-07-14 2011-07-14 Matériel d'enregistrement sensible à la pression et procédé pour sa fabrication

Publications (3)

Publication Number Publication Date
EP2546066A1 EP2546066A1 (fr) 2013-01-16
EP2546066B1 EP2546066B1 (fr) 2014-09-10
EP2546066B2 true EP2546066B2 (fr) 2018-06-27

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Application Number Title Priority Date Filing Date
EP11173923.1A Active EP2546066B2 (fr) 2011-07-14 2011-07-14 Matériel d'enregistrement sensible à la pression et procédé pour sa fabrication
EP12155798.7A Active EP2546067B1 (fr) 2011-07-14 2012-02-16 Méthode pour la fabrication d'un matériau pour l'enregistrement sensible à la pression
EP12175324.8A Active EP2546068B1 (fr) 2011-07-14 2012-07-06 Matériel d'enregistrement pour formation induite par pression d'un sigle et procédé de fabrication d'un tel matériel d'enregistrement

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Application Number Title Priority Date Filing Date
EP12155798.7A Active EP2546067B1 (fr) 2011-07-14 2012-02-16 Méthode pour la fabrication d'un matériau pour l'enregistrement sensible à la pression
EP12175324.8A Active EP2546068B1 (fr) 2011-07-14 2012-07-06 Matériel d'enregistrement pour formation induite par pression d'un sigle et procédé de fabrication d'un tel matériel d'enregistrement

Country Status (3)

Country Link
EP (3) EP2546066B2 (fr)
ES (2) ES2525570T5 (fr)
PL (1) PL2546066T5 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102014108341A1 (de) 2014-06-13 2015-12-17 Papierfabrik August Koehler Se CF-Papier
ES2623811T3 (es) 2014-07-29 2017-07-12 Mitsubishi Hitec Paper Europe Gmbh Material de registro termosensible con un derivado del ácido salicílico como revelador (del color) capaz de reaccionar con un precursor de colorante

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US4360548A (en) 1980-10-24 1982-11-23 The Standard Register Company Self-contained covert image
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EP0657300A1 (fr) 1993-12-10 1995-06-14 ZANDERS Feinpapiere AG Couche acceptrice pour feuilles d'enregistrement sensible à la pression
EP0428994B1 (fr) 1989-11-22 1999-03-10 Sanko Kaihatsu Kagaku Kenkyusho Méthode pour préparer une dispersion aqueuse de développateur et un papier d'enregistrement sensible à la pression
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DE3923586A1 (de) 1988-07-18 1990-02-01 Kanzaki Paper Mfg Co Ltd Akzeptor-beschichtetes blatt fuer ein druckempfindliches kopiersystem
EP0428994B1 (fr) 1989-11-22 1999-03-10 Sanko Kaihatsu Kagaku Kenkyusho Méthode pour préparer une dispersion aqueuse de développateur et un papier d'enregistrement sensible à la pression
DE4224719A1 (de) 1992-07-27 1994-02-03 Feldmuehle Ag Stora Verfahren zur Herstellung einer eine CF-Schicht aufweisenden Papierbahn für druckempfindliches Durchschreibepapier
EP0657300A1 (fr) 1993-12-10 1995-06-14 ZANDERS Feinpapiere AG Couche acceptrice pour feuilles d'enregistrement sensible à la pression
JP2002347339A (ja) 2001-05-30 2002-12-04 Oji Paper Co Ltd 感圧記録紙およびその製造方法
JP2005111695A (ja) 2003-10-03 2005-04-28 Nippon Paper Industries Co Ltd 感圧複写用顕色シート
CN101373183A (zh) 2008-08-01 2009-02-25 东莞市天盛特种纸制品有限公司 用基准纸检测无碳复写纸cb面和cf面显色方法

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Also Published As

Publication number Publication date
EP2546068B1 (fr) 2014-09-10
EP2546067A1 (fr) 2013-01-16
EP2546066B1 (fr) 2014-09-10
ES2477553T3 (es) 2014-07-17
PL2546066T3 (pl) 2015-02-27
EP2546067B1 (fr) 2014-04-09
ES2525570T5 (es) 2018-11-07
EP2546066A1 (fr) 2013-01-16
EP2546068A1 (fr) 2013-01-16
ES2525570T3 (es) 2014-12-26
PL2546066T5 (pl) 2018-10-31

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