EP2033802B1 - Wärmeempfindliches Aufzeichnungsmaterial mit Rückseitenbeschichtung - Google Patents

Wärmeempfindliches Aufzeichnungsmaterial mit Rückseitenbeschichtung Download PDF

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Publication number
EP2033802B1
EP2033802B1 EP07017657A EP07017657A EP2033802B1 EP 2033802 B1 EP2033802 B1 EP 2033802B1 EP 07017657 A EP07017657 A EP 07017657A EP 07017657 A EP07017657 A EP 07017657A EP 2033802 B1 EP2033802 B1 EP 2033802B1
Authority
EP
European Patent Office
Prior art keywords
heat
sensitive recording
recording material
recording layer
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
EP07017657A
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German (de)
English (en)
French (fr)
Other versions
EP2033802A1 (de
Inventor
Gerhard Dr. Stork
Karsten Lerius
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 HiTech Paper Flensburg GmbH
Stora Spezialpapiere GmbH
Original Assignee
Mitsubishi HiTech Paper Flensburg GmbH
Stora Spezialpapiere 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.)
Filing date
Publication date
Priority to PL07017657T priority Critical patent/PL2033802T3/pl
Priority to DE502007002946T priority patent/DE502007002946D1/de
Priority to ES07017657T priority patent/ES2339168T3/es
Priority to EP07017657A priority patent/EP2033802B1/de
Priority to AT07017657T priority patent/ATE458623T1/de
Application filed by Mitsubishi HiTech Paper Flensburg GmbH, Stora Spezialpapiere GmbH filed Critical Mitsubishi HiTech Paper Flensburg GmbH
Priority to US12/677,119 priority patent/US8470732B2/en
Priority to PCT/EP2008/007151 priority patent/WO2009033590A1/de
Publication of EP2033802A1 publication Critical patent/EP2033802A1/de
Application granted granted Critical
Publication of EP2033802B1 publication Critical patent/EP2033802B1/de
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
    • B41M5/42—Intermediate, backcoat, or covering layers
    • B41M5/44—Intermediate, backcoat, or covering layers characterised by the macromolecular compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
    • B41M5/405—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography characterised by layers cured by radiation

Definitions

  • the invention relates to a heat-sensitive recording material having a substrate which carries on its first side at least one heat-sensitive recording layer and on its second side a backside coating.
  • the heat-sensitive recording layer has at least one dye precursor and at least one color acceptor, which react color-forming with one another under the action of heat.
  • a heat-sensitive recording material of the type specified above is known from DE-C-38 36 660 known.
  • the backside coating can here be formed from water-soluble high polymers, such as starch, gelatin, styrene-maleic anhydride copolymer hydrolysates or polyvinyl alcohol, and from water-insoluble polymers, such as latexes. The polymers are used alone or as a mixture.
  • the known backside coating is to prevent that when using the known recording material as a label, in particular plasticizers which are present on a provided with the label sheet can penetrate from the back of the recording layer and thus a weakening or deletion of a possible Effect typeface.
  • the barrier layer comprises substantially water-soluble polymer materials such as polyvinyl alcohol, various cellulose ethers, starch, gelatin, casein, and polyvinylpyrrolidone, as well as water-dispersed resins such as polystyrene emulsions.
  • the function of the barrier layer is to protect against materials such as oils and plasticizers, which are known to cause the image and / or decolorization of the images developed in the recording layer.
  • the desired back-printing of a heat-sensitive recording material in the offset and flexographic printing process is the reason for the stated problem in the WO 99/14056 A1 after a backside coating, which is opposite to the Offset and flexographic printing substances used, in particular organic solvents, as well as plasticizers, oils and fats has a good sponging effect.
  • the backside coating of the known recording material comprises a mixture containing starch, a non-styrene or vinyl acetate acrylate copolymer having a film-forming temperature of less than 5 ° C and preferably less than 2 ° C and an alkaline catalyst such as calcium carbonate.
  • a heat-sensitive recording material to be considered in addition to the back printability on the front also good Bestkov stresses and Enhnrert zucchini has to be considered that the front and back coatings of a centrally positioned substrate mutually influence each other to take.
  • the focus of the invention is not only on the back of the new recording material but also on its front side, that is, on its heat-sensitive recording layer and / or its protective layer covering the heat-sensitive recording layer.
  • a recording material is also conceivable which, if appropriate, works with a likewise simply designed protective layer on a completely new recording layer.
  • the recording material according to the invention has a backcoat of a coating color which is stable to storage with moderate stirring before its application for 51 ⁇ 2 days and also does not begin to cure.
  • crosslinking component component acting as a crosslinking component component, it was also important to the inventors that the component has no major impact on the pH of the coating color, since such a change in the pH always, possibly not desired or unpredictable effects the surface properties of the stroke has.
  • crosslinking components it is an important aspect of the proposed here as crosslinking components that they are not classified as hazardous substances, which makes their handling within the manufacturing process of the recording materials of the invention is not critical and with which of these components at most a negligible hazard to humans and the environment emanates.
  • the backcoat comprises binders and in particular starch, styrene-butadiene latex and optionally carboxy- methyl-cellulose.
  • binders in sometimes highly divergent mixing ratios is possible and preferred.
  • optical brighteners, defoamers and components for viscosity control according to the respective requirements are common additives.
  • a coating weight for the backside coating in a range of 2 to 16 g / m 2 .
  • a range for the coating weight of the back coating of 2.5 to 4.5 g / m 2
  • a range of 8.5 to 12 g / m 2 is very particularly preferred.
  • particularly suitable brushing particularly equalizing application devices such as doctor blade and (roll) doctor blade coater and Walzenstreichwerke into consideration, without being limited in any way.
  • the heat-sensitive recording layer of the heat-sensitive recording material according to the invention may likewise include in principle all color acceptors suitable for the possible, in particular the preferred, dye precursors, in particular organic color acceptors.
  • the heat-sensitive recording layer has at least one color acceptor selected from the list comprising: 2,2 bis (4-hydroxyphenyl) propane, 4 - [(4- (1-methylethoxy) phenyl) sulfonyl] phenol, 4-hydroxy 4'-isopropoxydiphylsulfone, 4,4'-dihydroxydiphenylsulfone, 2,4'-dihydroxy-diphenylsulfone, N- (2-hydroxyphenyl) -2 - [(4-hydroxyphenyl) thio] -acetamide, N- (p-) toluenesulphonyl) -N'-3- (p-toluenesulphonyl-oxy-phenyl) -urea according to the following formula (1): and
  • this recording layer has a combination of two special color acceptors which are: N (p-toluenesulphonyl) -N'-3- (p-toluenesulphonyl-oxy-phenyl) -urea according to the formula (1) as well as urea-urethane compounds according to formula (2).
  • Other color acceptors are not present in the recording layer.
  • thermosensitive recording layer In order to obtain as high a whiteness as possible of the thermosensitive recording layer, it is necessary to supply the urea-urethane compounds of the formula (2) to 60 ° C before blending with the other color acceptor and / or other components of the thermosensitive recording layer heat and continue this heat treatment 24 hours continuously.
  • the two color acceptors of Formal (1) and Formal (2) can be up to 60% by weight, but preferably in the range of 25 to 35% by weight of the heat-sensitive recording layer.
  • the effect of the mixture of the two color acceptors in their entirety is a combination resulting from the peculiarities of the two individual dye acceptors: while N- (p-toluenesulphonyl) -N'-3- (p-toluenesulphonyl -Oxyphenyl) -urea according to formula (1) has been recognized as a color acceptor after numerous single and cross experiments, which is expected to high sensitivity of the thermosensitive recording layer to energy action, urea-urethane compounds according to the formula (2) may be used as such color acceptors be described, in which the energy-induced print image has a high stability, especially against environmental influences.
  • thermosensitive recording material which has a tendency of little background graying, has a heat-induced printed image resistant to environmental influences, and ensures good stampability and desmeability.
  • the recording layer of the heat-sensitive recording material of the present invention for increasing the thermal responsiveness may also preferably have sensitizers having a melting point of preferably from 60 ° C to 180 ° C, more preferably having a melting point from 80 ° C to 140 ° C.
  • Such sensitizers are, for example: benzyl p-benzyloxybenzoate, stearamide, N-methylol stearamide, p-benzylbiphenyl, 1,2-di (phenoxy) ethane, 1,2-di (m-methylphenoxy) ethane, m-terphenyl, Dibenzyl oxalate, benzylnaphthyl ether, diphenylsulfone and 2- (2H-benzotriazol-2-yl) -p-cresol, wherein benzylnaphthyl ether, diphenylsulfone, 1,2-di (m-methylphenoxy) ethane and 1,2-di (phenoxy) - ethane are considered preferred.
  • the recording layer has as a sole sensitizer 2- (2H-benzotriazol-2-yl) -p-cresol represented by the following formula (3):
  • the recording layer It of the second preferred embodiment for the heat-sensitive recording layer has, as a color acceptor, N- (p-toluenesulphonyl) -N'-3- (p-toluenesulphonyl-oxy-phenyl) -urea according to formula (1).
  • This color acceptor may be incorporated into the thermosensitive recording layer either in combination with other color acceptors, but preferably as the sole color acceptor.
  • the ratio by weight of (%) (atro) of the sensitizer of the formula (3) to the color acceptor of the formula (1) a range of from 5:10 to 9:10 is particularly preferable, and this ratio is independent of the fact that the Color acceptor according to formula (3) is used alone or in combination, is set.
  • the heat-sensitive recording layer has not only good printing but also excellent resistance to light.
  • 3-dibutylamino-6-methyl-7-anilinofluoran is considered to be the most suitable dye precursor within the second most preferred embodiment, but is not limited to it in any way.
  • the dye precursors mentioned by way of example in paragraph [0017] can also be used individually or in combination with one another the heat-sensitive recording layer is incorporated with the second embodiment related to the heat-sensitive recording layer and discussed herein.
  • Suitable binders for incorporation into the heat-sensitive recording layer are, for example, water-soluble binders such as starch, hydroxyethylcellulose, methylcellulose, carboxymethylcellulose, gelatin, casein, polyvinyl alcohols, modified polyvinyl alcohols, sodium polyacrylates, acrylamide-acrylate copolymers, acrylamide-acrylate copolymers.
  • water-soluble binders such as starch, hydroxyethylcellulose, methylcellulose, carboxymethylcellulose, gelatin, casein, polyvinyl alcohols, modified polyvinyl alcohols, sodium polyacrylates, acrylamide-acrylate copolymers, acrylamide-acrylate copolymers.
  • Methacrylate terpolymers alkali metal salts of styrene-maleic anhydride copolymers or ethylene-maleic anhydride copolymers, which can be used alone or in combination with one another;
  • Water-insoluble latex binders such as styrene-butadiene copolymers, acrylonitrile-butadiene copolymers and methyl acrylate-butadiene copolymers are also suitable as binders for incorporation into the heat-sensitive recording layer.
  • polyvinyl alcohol in combination with acrylate copolymer are considered to be particularly preferred binders which are incorporated together in the heat-sensitive recording layer in a range from 12 to 21% by weight, based on the total weight of the recording layer.
  • the coating composition for forming the heat-sensitive recording layer of any embodiments and variants may further contain slip and release agents such as metal salts of higher fatty acids, for example, zinc stearate, calcium stearate and waxes such as For example, paraffin, oxidized paraffin, polyethylene, polyethylene oxide, stearamides and castor wax.
  • Further constituents of the recording layer are, for example, pigments, preferably inorganic pigments such as, for example, aluminum (hydr) oxide, silica and calcium carbonate, in which case in particular calcium carbonate, preferably in an amount of from 10 to 18% by weight, based on the total weight of the recording layer the recording layer is to be included as being preferred.
  • a permanent color or typeface image can be formed in the recording layer under the action of heat.
  • the basis weight of the heat-sensitive recording layer is preferably between 2.5 and 12 g / m 2 and more preferably between 3 and 6.5 g / m 2 .
  • a brush for applying the heat-sensitive recording layer in particular, offer a doctor blade and (roll) doctor blade coater, curtain coater and air brush.
  • the coating color used to form the recording layer is aqueous.
  • the subsequent drying of the coating color can be done by means of microwave irradiation. Usually and proven it is just as much to supply heat, as happens by hot-air floatation dryer or contact dryer. Also conceivable is a combination of the listed dry processes.
  • a pigment-containing intermediate layer between the substrate layer and the recording layer is the same regardless of which embodiments and variants related to the recording layer.
  • pigments of the intermediate layer both organic void pigments and inorganic pigments have proven useful, the latter preferably selected from the group comprising natural and calcined kaolin, silica and in particular bentonite, calcium carbonate and aluminum hydroxide, in particular boehmite here.
  • such an intermediate layer can make a positive contribution to the leveling of the base layer surface, which reduces the amount of coating color necessarily required for the heat-sensitive recording layer. For this reason, offer to coat the intermediate layer leveling strokes, such as roller coater, doctor blade and (roll) doctor blade coating.
  • the pigments of this intermediate layer can absorb the heat-liquefied wax constituents of the thermosensitive recording layer in the typeface formation and thus promote a safe and rapid operation of the heat-induced recording.
  • the basis weight of the pigmented intermediate layer is preferably between 5 and 20 g / m 2 and more preferably between 7 and 11 g / m 2 .
  • the recording material according to the invention may have a protective layer which is applied to the heat-sensitive recording layer, regardless of which embodiments and variants, and covers this in whole or in part.
  • the Protective layer takes on a task, as it must also be partially fulfilled by the backside coating, namely on the one hand the protection of the recording layer arranged under it from environmental influences such as oils, fats, water and plasticizers and on the other hand the improvement of the printability especially in offset and flexographic printing.
  • the protective layer itself can be applied by means of conventional brushing, for which, inter alia, a coating color is usable, as described above and for which a surface-related mass in a range of 1.5 to 4.5 g / m 2 is preferred, or the protective layer may alternatively be printed. Processing technology and in terms of their technological properties are particularly suitable such protective layers which are curable by means of actinic radiation.
  • actinic radiation UV or ionizing radiation, such as electron beams to understand.
  • a variant of the protective layer which completely or partially covers the heat-sensitive recording layer as an alternative to the above-described embodiment provides as binder a polyvinyl alcohol, zinc stearate, as pigment aluminum hydroxide or alternatively also silicon dioxide and one or more crosslinkers, particularly preferred amounts for such a protective layer in Table 1 below: ⁇ u> Table 1: ⁇ / u> product % By weight [otro] Alumininhydroxid 10 - 25 polyvinyl alcohol 5 - 70 zinc stearate 7 - 9 crosslinkers 6 - 7
  • thermosensitive recording material of the present invention Since the proposed backcoat of the thermosensitive recording material of the present invention is very easy to dry, both the back coat and the thermosensitive recording layer including the protective layer completely covering it can be applied and dried in a single operation, for example, within a coating machine.
  • such a coating machine (a) a rolling device, (b) a first coating, for example, a curtain coater, an air brush or a Roltrakel coating machine for application of the heat-sensitive recording layer, (c) a first non-contact Schwebetrocknerkanal, (d) a curtain coater or an airbrush for applying the protective layer, (e) optionally and depending on the type, a contactless web guiding system, (f) a film applicator for application of the backside coating, (g) a second non-contact floating dryer channel, (h) an after-dryer section with several drying cylinders, ( i) a remoistening system or a coating installation such as a film applicator for optimizing the flatness or for reducing the roll tendency, (j) an IR drying system, (k) one or more calendering units each having one or more press nips, in particular using zone-controllable and / or shoe press rolls or belt calenders and (I) an A Provide rolling
  • a further coating unit (b ') for example a doctor blade applicator with associated drying apparatus (b "), which can be a floating dryer channel and / or a drying cylinder, is provided is.
  • paper is the substrate that has prevailed on the market with regard to the good environmental compatibility because of good recyclability and is preferred in the context of the invention.
  • a paper web of bleached and ground deciduous and softwood pulps with a basis weight of 67 g / m 2 is prepared on a fourdrinier paper machine as the substrate layer with the addition of conventional additives in conventional amounts.
  • a mainly calcined kaolin pigment, Styrolbutadienlatex as a binder and starch as Cobinder having intermediate layer of 8 g / m 2 is applied online within the coater with a roller blade coating.
  • a heat-sensitive recording layer containing a colorant and color acceptors having a basis weight of 5.4 g / m 2 is applied to the intermediate layer in this order by means of a doctor blade coater Air brush a protective layer of 2.0 g / m 2 , applied by roller coater with a downstream roller blade a backcoat of 3 g / m 2 .
  • the viscosity of the mixed coating colors is determined according to Brookfield (spindle 3/100 rpm / 23 ° C.), the latter after a stirring time of one hour (h), of one day (d) and of two days
  • Brookfield spindle 3/100 rpm / 23 ° C.
  • the risk of greatly increased viscosity up to solidification can be observed as in the present case.
  • the use of an oxalic aldehyde crosslinking agent may entail the risk of agglomerate and fractionation.
  • crosslinkers based on epichlorohydrin resin or oxalic aldehyde that they are both hazardous substances and therefore already for reasons of environmental and human dangers alone are critical.
  • Another possible crosslinker, that is ammonium zirconium carbonate was not considered in the experimental series on which this invention is based, because of its extremely strong odor nuisance for ammonia.
  • the crosslinking agent according to the invention based on polyurethane can completely convince in terms of low viscosity increase and delayed unfolding of the crosslinking effect in all examples.
  • the effectiveness of the crosslinkers used in the examples is examined by 3 days after preparation of the recording material samples are wetted on their back with a few drops of water on a measuring surface and rubbed with a finger under moderate pressure in a circular motion on the moistened measuring surface. It should be considered good if the measuring surface remains smooth on the surface and no particles are released. Bad are samples in which particles are released from the surface or even the entire surface dissolves. Again, only the tried crosslinker based on polyurethane convince. The other crosslinkers have hardly any result-increasing effect in some examples.

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  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)
EP07017657A 2007-09-10 2007-09-10 Wärmeempfindliches Aufzeichnungsmaterial mit Rückseitenbeschichtung Active EP2033802B1 (de)

Priority Applications (7)

Application Number Priority Date Filing Date Title
DE502007002946T DE502007002946D1 (de) 2007-09-10 2007-09-10 Wärmeempfindliches Aufzeichnungsmaterial mit Rückseitenbeschichtung
ES07017657T ES2339168T3 (es) 2007-09-10 2007-09-10 Material de registro sensible al calor con recubrimiento de la cara del reverso.
EP07017657A EP2033802B1 (de) 2007-09-10 2007-09-10 Wärmeempfindliches Aufzeichnungsmaterial mit Rückseitenbeschichtung
AT07017657T ATE458623T1 (de) 2007-09-10 2007-09-10 Wärmeempfindliches aufzeichnungsmaterial mit rückseitenbeschichtung
PL07017657T PL2033802T3 (pl) 2007-09-10 2007-09-10 Wrażliwy na ciepło materiał do zapisu wyposażony w powłokę od tylnej strony
US12/677,119 US8470732B2 (en) 2007-09-10 2008-09-02 Thermosensitive recording material comprising a back coating
PCT/EP2008/007151 WO2009033590A1 (de) 2007-09-10 2008-09-02 Wärmeempfindliches aufzeichnungsmaterial mit rückseitenbeschichtung

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP07017657A EP2033802B1 (de) 2007-09-10 2007-09-10 Wärmeempfindliches Aufzeichnungsmaterial mit Rückseitenbeschichtung

Publications (2)

Publication Number Publication Date
EP2033802A1 EP2033802A1 (de) 2009-03-11
EP2033802B1 true EP2033802B1 (de) 2010-02-24

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EP07017657A Active EP2033802B1 (de) 2007-09-10 2007-09-10 Wärmeempfindliches Aufzeichnungsmaterial mit Rückseitenbeschichtung

Country Status (7)

Country Link
US (1) US8470732B2 (es)
EP (1) EP2033802B1 (es)
AT (1) ATE458623T1 (es)
DE (1) DE502007002946D1 (es)
ES (1) ES2339168T3 (es)
PL (1) PL2033802T3 (es)
WO (1) WO2009033590A1 (es)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102009016108A1 (de) * 2009-04-03 2010-10-07 Mitsubishi Hitec Paper Flensburg Gmbh Wärmeempfindliches Aufzeichnugnsmaterial
ES2394407T3 (es) 2009-12-01 2013-01-31 Mitsubishi Hitec Paper Europe Gmbh Material de registro termosensible con revestimiento de barrera
PL2574645T3 (pl) * 2011-09-30 2015-03-31 Mitsubishi Hitec Paper Europe Gmbh Akceptor barwy reagujący z prekursorem barwnika w sposób tworzący barwę i wrażliwy na ciepło materiał zapisujący z takim akceptorem barwy

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6147292A (ja) * 1984-08-15 1986-03-07 Jujo Paper Co Ltd 感熱記録紙
SE500916C2 (sv) * 1986-06-16 1994-10-03 Ricoh Kk Termokänsligt registreringsmaterial med registreringsskikt innehållande fluorescensfärgämneskomposition
ES2153707T3 (es) * 1997-09-12 2001-03-01 Mitsubishi Hitec Paper Flensbu Hoja de grabacion termosensible con un recubrimiento de la cara dorsal que contiene almidon, un copolimero de acrilato y un catalizador alcalino.

Also Published As

Publication number Publication date
PL2033802T3 (pl) 2010-08-31
ATE458623T1 (de) 2010-03-15
DE502007002946D1 (de) 2010-04-08
US20100197493A1 (en) 2010-08-05
EP2033802A1 (de) 2009-03-11
ES2339168T3 (es) 2010-05-17
WO2009033590A1 (de) 2009-03-19
US8470732B2 (en) 2013-06-25

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