EP2279877B1 - Wärmeempfindliches Aufzeichnungsmaterial - Google Patents

Wärmeempfindliches Aufzeichnungsmaterial Download PDF

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Publication number
EP2279877B1
EP2279877B1 EP09166559A EP09166559A EP2279877B1 EP 2279877 B1 EP2279877 B1 EP 2279877B1 EP 09166559 A EP09166559 A EP 09166559A EP 09166559 A EP09166559 A EP 09166559A EP 2279877 B1 EP2279877 B1 EP 2279877B1
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EP
European Patent Office
Prior art keywords
heat
sensitive recording
recording material
recording layer
material according
Prior art date
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EP09166559A
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German (de)
English (en)
French (fr)
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EP2279877A1 (de
Inventor
Diana Valentina Becerra Siabato
Annette Schreiber
Gerhard Dr. Stork
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Mitsubishi HiTec Paper Europe GmbH
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Mitsubishi HiTec Paper Europe GmbH
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Priority to EP09166559A priority Critical patent/EP2279877B1/de
Priority to AT09166559T priority patent/ATE551201T1/de
Priority to ES09166559T priority patent/ES2385179T3/es
Priority to US12/621,553 priority patent/US8603943B2/en
Publication of EP2279877A1 publication Critical patent/EP2279877A1/de
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Publication of EP2279877B1 publication Critical patent/EP2279877B1/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
    • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
    • B41M5/333—Colour developing components therefor, e.g. acidic compounds
    • B41M5/3333—Non-macromolecular compounds
    • B41M5/3335—Compounds containing phenolic or carboxylic acid groups or metal salts thereof
    • B41M5/3336—Sulfur compounds, e.g. sulfones, sulfides, sulfonamides

Definitions

  • the present invention relates to a thermosensitive recording material having a substrate to which a thermosensitive recording layer containing a color former and color acceptors, and a protective layer covering this thermosensitive recording layer are applied.
  • the present invention also relates to the use of such a proposed heat-sensitive recording material as a ticket and in particular as a parking ticket.
  • Heat-sensitive recording materials have been known for many years and are enjoying ever increasing popularity, which is due in part to the fact that their use, in particular as tickets for the ticket issuer, has great advantages. Because the color-forming components are stuck in the recording material itself in the heat-sensitive recording method, the toner and color-cartridge-free thermal printers, which are no longer required to be regularly controlled by anyone, can be set in large numbers. Thus, this innovative technology has prevailed in particular in public passenger transport, buses and trains as well as in air traffic, stadium and museum funds and parking ticket machines nationwide. However, there are still numerous problems in the very important field of application of parking tickets, which up to the present day could not be solved convincingly in their entirety.
  • thermosensitive recording material having protective layers which have high water resistance is often very brittle and so it may happen that the protective layers chip off at the cut and folded edges. Dust and production disruption are the result.
  • 4,4'-Dihydroxydiphenylsulfone is also commonly referred to as 4,4'-sulfonyldiphenol and is also known under the tradename 4,4 Bisphenol S.
  • 4,4'-Dihydroxydiphenylsulfone has the chemical empirical formula C 12 H 10 O 4 S and can be represented as the following formula (1):
  • 4,4'-dihydroxydiphenylsulfone is known as one of 20 named color acceptors, among other group designations for alternative color acceptors for use in the heat-sensitive recording layer of the prepublished specification
  • a combination of diacetone-modified polyvinyl alcohol as binder in the protective layer and 4,4 'Dihydroxydiphenylsulfon as a color acceptor in the heat-sensitive recording layer are excluded altogether, especially since the problems to be solved, such as an improvement in heat, folding and buckling resistance found in the prepublished document as little as a use of dimethyl terephthalate as a sensitizer in the heat-sensitive recording layer, in order to solve the problem of a too strong background graying of the tickets up to a full-scale blackening lasting.
  • thermosensitive recording material is also from the European patent application EP-A-1 900 541
  • disclosure content does not exceed the disclosure content of the previously discussed EP-B-0 899 126 with the only exception that dimethyl terephthalate acts as a sensitizer in the heat-sensitive recording layer is mentioned as one of all presently known in this respect acting substances.
  • thermosensitive recording material in which the recording layer contains 4,4'-dihydroxydiphenylsulfone, but all other features are not mentioned in the present invention.
  • the above color acceptors are incorporated in this heat-sensitive recording layer to a maximum of 10% by weight, based on the total amount of color acceptors in the heat-sensitive recording layer, the remainder being 4,4'-dihydroxydiphenylsulfone.
  • 4,4'-dihydroxydiphenylsulfone is the sole color acceptor in the thermosensitive recording layer is considered to be most preferred.
  • thermosensitive recording material preferably has, as a color former in the thermosensitive recording layer, those selected from the list comprising: 3-diethylamino-6-methyl-7-anilinofluoran, 3-dibutylamino-6-methyl-7-anilinofluoran, 3- ( N-methyl-N-propyl) amino-6-methyl-7-anilinofluoran, 3- (N-ethyl-N-isoamyl) amino-6-methyl-7-anilinofluoran, 3- (N-methyl-N-cyclohexyl) amino-6-methyl-7-anilinofluoran, 3- (N-ethyl-N-tolyl) amino-6-methyl-7-anilinofluoran and 3- (N-ethyl-N-tetrahydrofuryl) amino-6-methyl-7- anilinofluoran.
  • 3-dibutylamino-6-methyl-7-anilinofluoran also known as ODB-2.
  • thermosensitive recording layer has more than one color former each selected from the color formers listed in the above paragraph.
  • the recording material according to the invention may be used in addition to these Colorants also contain one or more of the following near infrared absorbing compounds:
  • the recording layer may also contain other sensitizers having a melting point, ideally from 60 ° C to 180 ° C, more preferably having a melting point of from 80 ° C to 140 ° C.
  • sensitizers are, for example: benzyl p-benzyloxybenzoate, methylolstearamide, stearic acid amide, p-benzylbiphenyl, 1,2-di (phenoxy) ethane, 1,2-di (m-methylphenoxy) ethane, m-terphenyl, dibenzyl oxalate, Benzylnaphthylether and diphenylsulfone, wherein Methylolstearamid, and in particular stearic acid amide are considered to be very preferred.
  • 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, ethylene-vinyl alcohol copolymers, sodium polyacrylates, acrylamide-acrylate copolymers, Acrylamide-acrylate-methacrylate terpolymers and alkali metal salts of styrene-maleic anhydride copolymers or ethylene-maleic anhydride copolymers, which binders 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.
  • water-soluble binders such as starch,
  • polyvinyl alcohol ethylene-vinyl alcohol copolymers or polyvinyl alcohol in conjunction with ethylene-vinyl alcohol copolymers as particularly preferred binders which together, based on the total weight of the recording layer, in a range of 10 to 20 wt .-% in the heat-sensitive recording layer is incorporated.
  • the coating composition for forming the heat-sensitive recording layer may further contain lubricants and release agents such as metal salts of higher fatty acids, for example, zinc stearate, calcium stearate, and waxes such as paraffin, oxidized paraffin, Polyethylene, polyethylene oxide, stearamides and castor wax.
  • Further constituents of the recording layer are, if appropriate, 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 0 to 28% by weight, based on the total weight of the recording layer the recording layer is to be included as being preferred.
  • roller coater, knife coater, curtain coater or air brush are particularly suitable as coating apparatus for applying the heat-sensitive recording layer.
  • the coating composition used to form the recording layer is aqueous.
  • the subsequent drying of the coating composition is usually done by a method in which heat is supplied, as is done by hot-air floating dryer or contact dryer. Proven is also a combination of the listed dry processes.
  • the basis weight of the heat-sensitive recording layer is preferably from 2 to 6 g / m 2, and more preferably from 2.2 to 4.8 g / m 2 .
  • the protective layer of the heat-sensitive recording material according to the invention comprises, in addition to the diacetone-modified polyvinyl alcohol, in a first possible embodiment, further binders, in particular mixtures of different carboxyl groups. or silanol-modified polyvinyl alcohols. These make up according to the invention a maximum of 40 wt .-%, preferably at most 15 wt .-%, - based on the total amount of binder in the protective layer - from.
  • the protective layer of the heat-sensitive recording material according to the invention has as binders exclusively diacetone-modified polyvinyl alcohol.
  • the binder content in the protective layer is in a range of from 35 to 65% by weight based on the total weight of the protective layer.
  • Suitable crosslinking aids in the protective layer are, in particular, those selected from the group comprising: boric acid, polyamine, epoxy resin, dialdehyde, formaldehyde oligomers, epiochlorohydrin resin, adipic dihydrazide, dimethylurea, melamine-formaldehyde. It is also possible to use mixtures of different crosslinking aids.
  • the ratio of the weight% of the binder, especially the diacetone-modified polyvinyl alcohol, to the crosslinking aid is in a range of 20: 1 to 5: 1, and more preferably in a range of 12: 1 to 7 : 1 is.
  • the protective layer additionally contains an inorganic pigment.
  • the inorganic pigment is selected from the group comprising silica, aluminum hydroxide, bentonite, calcium carbonate, kaolin or a mixture of said inorganic pigments.
  • roller coater, knife coater, curtain coater or air brush are particularly suitable as coating devices for applying the protective layer covering the heat-sensitive recording layer.
  • the basis weight of the protective layer is preferably between 1.0 and 3.0 g / m 2 and more preferably between 1.6 and 2.3 g / m 2 .
  • films and paper As a substrate for the heat-sensitive recording material proposed here are films and paper and very particularly preferably a base paper with Masseleimung suitable, but without being limited in any way.
  • the substrate is a paper web with a proportion of recycled fibers of at least 70 wt .-%, based on the total pulp content in the paper web.
  • the recording material according to the invention of this very particularly preferred embodiment can, in addition to the proportion of recycled fibers of at least 70% by weight, also comprise fresh pulp, preferably eucalyptus pulp.
  • the paper web even has a proportion of recycled fibers of at least 85% by weight and further even from 98% by weight up to 100% by weight, based on the total pulp content in the paper web.
  • the proportion of recycled fibers may be composed of one or several types of waste paper in accordance with the European Standard EN 643 of December 2001. Particularly suitable are those types of waste paper belonging to class IV, higher grades, according to CEPI definition. These include in particular: 2.03 / 2.04 - White chips, light or heavy printed, mainly of wood pulp, 2.05 - Office papers, 2.07 - Pulp books, 2.09 Carbon copy paper, 2.10 / 2.11 PE coated cardboard, 3.01 / 3.02 / 3.04 - Schnitzel of Printing and writing papers, partly wood-free, as well as pulp-containing chips from demolitions, 3.05 / 3.06 - white writing and business papers, 3.14 - white newspapers, 5.06 / 5.07 wet-strength papers made of cellulose, printed and unprinted.
  • the invention It.
  • This very particularly preferred embodiment is not limited to the aforementioned types of waste paper. It is also possible to use such waste paper grades for the recycled fibers of the paper web belonging to Class 1, mixed grades, and Class III, newspapers and magazines, according to CEPI definition. In this case, the formation of a pigmented intermediate layer positioned between the paper web and the heat-sensitive recording layer becomes more important for optical reasons, without such an intermediate layer being technically compelling.
  • the recycling fibers used in the context of the present invention It.
  • This most preferred embodiment variant are fundamentally different depending on whether the collection of waste paper before or after use by the end user, as household collection or higher quality waste paper grades. Accordingly, higher-quality waste paper types are those types of waste paper that did not come into the hands of end users, but for example directly from publishers and / or printers The collection of recovered paper is done while household collection is one of those waste paper that has come into the hands of end users at least once.
  • Particularly preferred for the present invention are those recycled fiber webs in which the recycled fibers provide as high a percentage as possible of recycled fibers from higher quality recovered paper grades - in numbers: a recycled fiber content of higher grade recovered paper grades of at least 70% by weight, better of at least 90% by weight and most preferably of 100% by weight, wherein the abovementioned percentages (atro) refer to the pulp fraction of recycled fibers in the paper web as the substrate.
  • a particularly high proportion of higher quality waste paper grades can be ensured virtually constant quality and composition of recycled fibers, which is for printing and durability guarantees, which are increasingly required in the market of thermosensitive recording materials, is of great importance.
  • the paper web of this particularly preferred embodiment has filler, in which case a ratio by weight of fiber fraction: filler in a range from 15: 1 to 2: 1, more preferably from 10: 1 to 3: 1 and most preferably from 5: 1 to 3: 1 is considered particularly suitable.
  • Filler in which case a ratio by weight of fiber fraction: filler in a range from 15: 1 to 2: 1, more preferably from 10: 1 to 3: 1 and most preferably from 5: 1 to 3: 1 is considered particularly suitable.
  • Calcium carbonate, talc and kaolin are particularly preferred as fillers, other fillers such as alumina and especially boehmite are conceivable without being limited to the fillers mentioned.
  • the paper web of the heat-sensitive recording material of the present invention preferably has a Cobb 60 value X of 15 g / m 2 ⁇ X ⁇ 40 g / m 2 , more preferably a Cobb 60 value of 15 g on the side facing the heat-sensitive recording layer / m 2 ⁇ X ⁇ 35 g / m 2 .
  • the Cobb 60 value is limited primarily by economic considerations and handling limitations with respect to such paper webs.
  • too strong penetration of the applied coatings into the paper web is observed, which is detrimental to the external appearance of the proposed recording material and in particular means losses in the dynamic and static print density of printed images to be formed.
  • the Cobb 60 values specified within the scope of the present invention within this description were determined using the method specified in DIN / EN 20535 or in ISO 535 with distilled water at 20 ° C.
  • a pigmented intermediate layer is expediently arranged between the heat-sensitive recording layer and the substrate of the heat-sensitive recording material according to the invention.
  • this pigmented intermediate layer is considered to be preferred, regardless of whether the substrate is a film, a base paper or a paper web with a proportion of recycled fibers of at least 70 wt .-% It.
  • the intermediate layer can also make a positive contribution to equalization of the substrate surface, thus increasing the amount of coating material necessarily to be applied to the substrate heat-sensitive recording layer reduced.
  • leveling coating devices such as, for example, roller coater, doctor blade or doctor blade coaters
  • the intermediate layer can also make a positive contribution to equalization of the substrate surface, thus increasing the amount of coating material necessarily to be applied to the substrate heat-sensitive recording layer reduced.
  • a preferred range between 5 and 20 g / m 2 and even better between 7 and 12 g / m 2 has proven.
  • inorganic oil-absorbing pigments When inorganic oil-absorbing pigments are incorporated into the intermediate layer sandwiched between the recording layer and the substrate, these pigments can absorb the thermoset liquefied wax components of the thermosensitive recording layer in the typeface formation, thereby promoting still safer and faster operation of the thermally-induced recording, and thus such an embodiment is considered preferred.
  • the pigments of the intermediate layer has an oil absorption of at least 80 cm3 / 100 g, and more preferably 100 cm3 / 100 g, determined according to the Japanese standard JIS K 5101, is having.
  • Calcined kaolin has proven particularly useful due to its large absorption reservoir in the cavities.
  • the following inorganic pigments are also very well suited as constituents of the intermediate layer: silicon oxide, bentonite, calcium carbonate and aluminum oxide and, in particular, boehmite here. Also mixtures of several different types of inorganic pigments are conceivable.
  • the ratio between organic and inorganic pigment is a compromise of the effects caused by the two types of pigments, which is particularly advantageously solved when the pigment mixture to 5 to 30 wt .-% or better to 8 to 20 wt .-% of organic and 95 to 70 wt .-% or better to 92 to 80 wt.% Of inorganic pigment.
  • Pigment mixtures of different organic pigments are conceivable.
  • the pigmented intermediate layer contains at least one binder, preferably based on a synthetic polymer, wherein, for example, styrene-butadiene latex gives particularly good results.
  • a synthetic binder with the admixture of at least one natural polymer, more preferably starch, is a particularly suitable embodiment.
  • the heat-sensitive recording material proposed here in all its preferred embodiments and variants, is particularly intended for use as a parking ticket, since the fulfillment of the requirements imposed on the new recording material according to the statements in paragraphs [0003] and [0005] has a particularly positive effect here ,
  • a paper pulp of fibers with fillers and water is prepared in a mixing vessel, wherein the fibers are made of 100% higher class class IV recovered paper grades according to the CEPI definition, in particular here the waste paper grades 2.03 / 2.04 - White chips, light or heavy printed, mainly of wood pulp, 2.05 - Office papers, 2.07 - Pulpwood books, 2.09 Carbonless copy paper, 3.01 / 3.02 / 3.04 - Schnitzel of printing and writing papers, partly woodfree, as well as pulp-containing chips from demolitions, 3.05 / 3.06 - white writing and business papers.
  • the printing inks in the pulp are separated by a deinking process via the flotation process. Subsequently, the pulp is bleached reductively by means of formamidine sulfinic acid (FAS). Further constituents of the pulp are finally resin size for engine sizing with an amount of 0.6% by weight (atro), based on the total weight of the pulp, and optionally further conventional additives, such as additional pigments and / or optical brighteners. After completion of the pulp this is then fed to a fourdrinier paper machine, where it is processed into a paper web with a basis weight of 69 g / m 2 .
  • FAS formamidine sulfinic acid
  • the front Cobb 60 value is determined to be 18.6 g / m 2 , the ratio total fiber content : pigment in this paper web (A) is 4.98: 1.
  • a paper web of bleached and ground hardwood and softwood pulps with a basis weight of 58 g / m 2 is prepared on a four-wire paper machine with the addition of conventional additives in conventional amounts .
  • the filler used for the paper web (B) is ground calcium carbonate and talc with a wt.% Content of 8%, based on the total weight fraction of the paper web (B).
  • the heat-sensitive recording layer After drying the heat-sensitive recording layer is applied by means of air brush coater as a second coating unit of the coating machine used in the same coating machine passage in which previously the recording layer has been applied, covering this heat-sensitive recording layer protective layer having a basis weight of 1.9 g / m 2 .
  • aqueous coating compositions are used according to the formulations according to Table 2 below: ⁇ u> Table 2: ⁇ / u> Recipe 1 Recipe 2 (Invention) (Comparison) component % By weight (atro) component % By weight (atro) Diacetone-modified polyvinyl alcohol 61.3
  • Acrylate copolymer 66 Pigment: kaolin 16.6 Pigment: aluminum hydroxide 12 Hidorin Z-7-30 8.1 Hidorin Z-7-30 8th adipic 6.0
  • the samples and the comparative samples respectively give black / white checkered thermographic printouts with a device of the Atlantek type 400 of the company Viex (USA), whereby a thermal head with resolution of 300 dpi and an energy per unit area of 16 mJ / mm 2 is used.
  • the print density of the black-colored areas is first measured in three printouts using the Gretag MacBeth TYPE D19C NB / U densitometer (Gretag MacBeth, 8105 Regensdorf, Switzerland). Subsequently, the respective TREATMENT of the thermal sample is carried out.
  • this TREATMENT provides for immersion of the thermal sample in an oil bath (corn oil from Mazola, Unilever GmbH, 20457 Hamburg) at 23 ° C oil temperature over 20 minutes. The printout is then gently blotted with blotter paper and then allowed to rest for 4 hours at 23 ° C and 50% humidity.
  • TREATMENT envisages full application of the pig liver lime thermal print (Laru, Bottrop). The coated thermal print is then allowed to rest for 24 hours at 23 ° C and 50% humidity.
  • the print density is again determined at three points on the black-colored areas using the densitometer Gretag MacBeth TYPE D19C NB / U.
  • the respective mean values of the measurements before / after the TREATMENT, that is before / after the oil bath or before / after the fat treatment, are formed and the mean value after the bath as a percentage of the mean value before the bath.
  • thermal test expression is about 10 cm long piece of TESA ® graphic film 57331 glued. Subsequently, the print density of the black-colored areas is measured immediately at three points using the densitometer Gretag MacBeth TYPE D19C NB / U. The print is then allowed to rest for 24 hours at 23 ° C and 50% humidity. After resting, the print density is again determined at three points on the black-colored areas using the densitometer Gretag MacBeth TYPE D19C NB / U. The respective mean values of the measurements before / after resting are formed and the mean value after resting is allowed to rest relative to the mean value.
  • the measured values initially show a superiority of the inventive patterns 1 and 3 in comparison to the comparative samples 5 and 6 with respect to the resistances of thermographic printouts of oil, grease and plasticizer, while the comparative samples 2 and 4 which have a heat-sensitive recording layer of coating slip 2 still show more pronounced resistances than the inventive patterns 1 and 3, which have a heat-sensitive recording layer of coating 1.
  • the print density of the black-colored areas are measured using the densitometer Gretag MacBeth TYPE D19C NB / U (Gretag MacBeth, 8105 Regensdorf, Switzerland), whereby the print densities are measured at three locations for each measured value and the arithmetic mean is formed from the three individual values.
  • Gretag MacBeth TYPE D19C NB / U (Gretag MacBeth, 8105 Regensdorf, Switzerland)
  • FIG. 1 shows a clear superiority of the inventive pattern 3 in direct comparison to the comparison patterns 4 and 6 with respect to the static pressure density, in which case in this case an increase in the curves is possible beyond temperatures above 100 ° C is desired.
  • Outstanding is solely the result of the inventive pattern 3, which has a heat-sensitive recording layer of coating 1, since a significant thermal reaction of the recording material according to the invention is observed only beyond 100 ° C.
  • Completely rejected in the market is the result of the comparison pattern 4, which has a heat-sensitive recording layer of coating 2, since there is already an obvious background graying at 95 ° C is given.
  • Catastrophic is the comparison pattern 6, since there is no background graying, but a background blackening from 95 ° C is given.
  • thermo print samples from the sample webs 1, 2, 3, 4, 5 and 6 are created with a device of the Atlantek 400 type from Viex (USA) Thermal head with resolution of 300 dpi and an energy per unit area of 16 mJ / mm 2 is used.
  • the thermal printouts are folded in half lengthwise so that the left and the right half of a thermographic printout are superimposed on each other. Under the same constant and constant contact pressure, the thermal sample printout along the folding line is run with a laboratory roller until the thermal sample printout is folded together continuously and with sharp edges.
  • the thermal printout is then unfolded again and a strip of TESA® Graphic Film 57331 is adhered to the inner fold line of the thermal printout, removed immediately and glued onto a white sheet of paper.
  • the chipped brittle material then shows up as a more or less strong black stripe on the white sheet of paper.
  • thermo print samples from the sample webs 1, 2, 3, 4, 5 and 6 are made with a device of the Atlantek 400 type from Viex (USA) Thermal head with resolution of 300 dpi and an energy per unit area of 16 mJ / mm 2 is used.
  • the thermal printouts are immersed in 23 ° C water for 10 seconds, then placed on a glass plate so that the protective layer comes into contact with the glass sheet. Subsequently, the thermal print samples are allowed to dry for one day at 23 ° C and 50% humidity. Subsequently, the thermal printouts are subtracted from the glass.

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  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)
EP09166559A 2009-07-28 2009-07-28 Wärmeempfindliches Aufzeichnungsmaterial Active EP2279877B1 (de)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP09166559A EP2279877B1 (de) 2009-07-28 2009-07-28 Wärmeempfindliches Aufzeichnungsmaterial
AT09166559T ATE551201T1 (de) 2009-07-28 2009-07-28 Wärmeempfindliches aufzeichnungsmaterial
ES09166559T ES2385179T3 (es) 2009-07-28 2009-07-28 Material de registro termosensible
US12/621,553 US8603943B2 (en) 2009-07-28 2009-11-19 Thermosensitive recording material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP09166559A EP2279877B1 (de) 2009-07-28 2009-07-28 Wärmeempfindliches Aufzeichnungsmaterial

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EP2279877A1 EP2279877A1 (de) 2011-02-02
EP2279877B1 true EP2279877B1 (de) 2012-03-28

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EP (1) EP2279877B1 (es)
AT (1) ATE551201T1 (es)
ES (1) ES2385179T3 (es)

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EP2487043B1 (de) 2011-02-11 2013-10-09 Mitsubishi HiTec Paper Europe GmbH Verfahren zur Herstellung eines wärmeempfindlichen Aufzeichnungsmaterials
US9034790B2 (en) * 2013-03-14 2015-05-19 Appvion, Inc. Thermally-responsive record material
ES2621232T3 (es) * 2013-03-27 2017-07-03 Mitsubishi Hitec Paper Europe Gmbh Composición para la configuración de un color reconocible visualmente y material de registro termosensible correspondiente
US20160196248A1 (en) * 2015-01-05 2016-07-07 Musaed Ruzeg N. ALRAHAILI System, apparatus, method and computer program product to set up a request for, generate, receive and send official communications
EP3263666B1 (de) 2016-06-27 2018-06-27 Evonik Degussa GmbH Permeationsinhibierende trennbeschichtung
EP4309907A1 (en) * 2021-03-19 2024-01-24 Nippon Paper Industries Co., Ltd. Heat-sensitive recording material

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Publication number Priority date Publication date Assignee Title
DE69810217T2 (de) * 1997-08-25 2003-11-06 Oji Paper Co Wärmeempfindliches Aufzeichnungsmaterial
DE60127079T2 (de) * 2000-12-04 2007-07-05 Fujifilm Corp. Thermisches Aufzeichnungsmaterial
JP2008030275A (ja) 2006-07-27 2008-02-14 Ricoh Co Ltd 感熱記録材料
US7906458B2 (en) 2006-09-15 2011-03-15 Ricoh Company, Ltd. Heat-sensitive recording material and production method thereof

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US20110028317A1 (en) 2011-02-03
ATE551201T1 (de) 2012-04-15
ES2385179T3 (es) 2012-07-19
EP2279877A1 (de) 2011-02-02
US8603943B2 (en) 2013-12-10

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