EP2487044B1 - Procédé de fabrication d'un matériel d'enregistrement sensible à la chaleur - Google Patents

Procédé de fabrication d'un matériel d'enregistrement sensible à la chaleur Download PDF

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Publication number
EP2487044B1
EP2487044B1 EP20110157084 EP11157084A EP2487044B1 EP 2487044 B1 EP2487044 B1 EP 2487044B1 EP 20110157084 EP20110157084 EP 20110157084 EP 11157084 A EP11157084 A EP 11157084A EP 2487044 B1 EP2487044 B1 EP 2487044B1
Authority
EP
European Patent Office
Prior art keywords
coating composition
heat
sensitive recording
coating
substrate
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.)
Not-in-force
Application number
EP20110157084
Other languages
German (de)
English (en)
Other versions
EP2487044A1 (fr
Inventor
Gerhard Dr. Stork
Matthias Marx
Falk Jahns
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.)
Filing date
Publication date
Application filed by Mitsubishi HiTec Paper Europe GmbH filed Critical Mitsubishi HiTec Paper Europe GmbH
Priority to EP20110157084 priority Critical patent/EP2487044B1/fr
Priority to PCT/EP2012/052154 priority patent/WO2012107507A1/fr
Publication of EP2487044A1 publication Critical patent/EP2487044A1/fr
Application granted granted Critical
Publication of EP2487044B1 publication Critical patent/EP2487044B1/fr
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

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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
    • B41M5/30—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
    • 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
    • B41M5/323—Organic colour formers, e.g. leuco dyes
    • B41M5/327—Organic colour formers, e.g. leuco dyes with a lactone or lactam ring
    • B41M5/3275—Fluoran 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
    • B41M5/337—Additives; Binders
    • B41M5/3372—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
    • B41M5/337—Additives; Binders
    • B41M5/3375—Non-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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
    • B41M2205/34—Both sides of a layer or material are treated, e.g. coated
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
    • B41M2205/36—Backcoats; Back layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
    • B41M2205/38—Intermediate layers; Layers between substrate and imaging layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
    • B41M2205/40—Cover layers; Layers separated from substrate by imaging layer; Protective layers; Layers applied before imaging
    • 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

Definitions

  • Such a method is for example from the EP 1 684 989 B1 which is characterized in particular by the heat-sensitive recording layer being applied during a machine pass and the at least one protective layer covering this heat-sensitive recording layer being printed.
  • the combination of printing and coating processes for producing a heat-sensitive recording material is decisive for the named document.
  • no further suggestions for the formation of the heat-sensitive recording layer and for the formation of the protective layer covering this heat-sensitive recording layer can be taken from the cited document.
  • Heat-sensitive recording materials have been known in their general form for many years and are enjoying ever-increasing popularity, which, among other things, is due to the fact that their use, in particular as ticket 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. But even with the so important application of parking tickets, there are still many problems that, to this day, in their entirety and with regard to various individual problems could not be solved convincingly, which concerns in particular the interplay of economically convincing production and satisfactory product features.
  • Another serious and serious problem is the risk of blockage of ticket rolls after water contact: If, for example, in rainy weather or heavy fog rolls or even zigzag stacks with the still issued Parktickets heat-sensitive recording material in the ticket machine filled, it may happen that these roles or Zig-zag stacks get wet through mist or raindrops and then this moisture enters the ticket rolls or zigzag stacks. Due to a possible dissolution of the constituents, in particular in the outer layers of the parking tickets, gluing of the individual layers within a roll or within the zigzag stacks can then occur with the parking tickets still to be issued, which leads to complete failure of the affected parking ticket machine. Dust generation is another problem in the processing of thermosensitive recording material into zig-zag stacks. In particular, heat-sensitive recording materials with protective layers which have a high water resistance are often very brittle and thus it may happen that the protective layers chip off at the cut and folded edges. Dust and production disruption are the result.
  • the document EP-A1-2 112 000 describes a heat-sensitive recording material.
  • This recording material contains (a) a UV-crosslinked acrylate protective layer, (b) a heat-sensitive recording layer containing an isocyanate component, an imino component, and a dye precursor-color acceptor leuco dye system, (c) a support, and (d) a backing layer.
  • the proposed method initially provides for the preparation of a first coating composition, with the use of container scales for the precise feeding and metering of bulk components and liquid components to a particular extent.
  • the first coating composition provided for forming the heat-sensitive recording layer comprises at least 80% by weight, based on the total content of color acceptors in the first coating composition, of 4,4'-dihydroxydiphenylsulfone as a color acceptor.
  • 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 formula C12H10O4S and can be represented as the following formula (1):
  • 4,4'-Dihydroxydiphenylsulfon as a color acceptor is for example from the EP 2 279 877 A1 which also discloses the combination of 4,4'-dihydroxydiphenyl sulfone with a sensitizer such as methylol stearamide, stearic acid amide and dimethyl terephthalate.
  • a sensitizer such as methylol stearamide, stearic acid amide and dimethyl terephthalate.
  • the above color acceptors individually or also combined with each other, to a maximum of 5.5 wt .-%, most preferably to a maximum of 4.25 wt .-% - based on the total amount of Farbakzeptoren in the first coating composition - in involved in this first coating composition, the remainder forms 4,4'-Dihydroxydiphenylsulfon.
  • 4,4'-dihydroxydiphenylsulfone is the sole color acceptor in the first coating composition is preferred as to a very particular extent.
  • the first coating composition has more than one color former, each selected from the color formers listed in the above paragraph.
  • the method according to the invention for the preparation of a heat-sensitive recording material may contain one or more of the following compounds which absorb in the near infrared range within the first coating composition, in addition to or as an alternative to the substances mentioned in the previous paragraph as color formers:
  • the first coating composition contains at least one sensitiser selected from the list comprising stearic acid amide, dimethylsulfone, 2- (2H-benzotriazol-2-yl) -p-cresol and dimethyl terephthalate, which means according to a first preferred embodiment alone, for increasing the thermal responsiveness , not in combination with the other three sensitisers listed above.
  • at least two sensitisers selected from the list comprising stearic acid amide, dimethylsulfone, 2- (2H-benzotriazol-2-yl) -p-cresol and dimethyl terephthalate, are incorporated in the first coating composition.
  • dimethylsulfone on the one hand and dimethyl terephthalate on the other hand are considered to be very particularly preferred.
  • the above-mentioned sensitizers may be used in the first coating composition each optionally in combination with the following products: methylol stearamide, benzyl p-benzyloxy benzoate, p-benzyl biphenyl, 1,2-di (phenoxy) ethane, 1,2-di (m-methylphenoxy) ethane, m-terphenyl, dibenzyl oxalate, benzyl naphthyl ether and diphenyl sulfone.
  • Total color acceptor total sensitizer and in particular 4,4'-Dihydroxydiphenylsulfone: total sensitizer and especially 4,4'-dihydroxydiphenylsulfone: Sensitizer selected from the list comprising: stearic acid amide, dimethylsulfone, 2- (2H-benzotriazol-2-yl) -p-cresol and dimethyl terephthalate preferably in one Range from 1: 0.5 to 1: 2, and most preferably in a range of 1: 0.8 to 1: 1.4.
  • Suitable binders for incorporation into the first coating composition 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 may 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 first coating composition.
  • water-soluble binders such as starch, hydroxyethyl
  • polyvinyl alcohol, ethylene-vinyl alcohol copolymers or polyvinyl alcohol in combination with ethylene-vinyl alcohol copolymers are particularly preferred binders which together in a range from 10 to 20% by weight, based on the total weight of the first coating composition. incorporated into the first coating composition.
  • the first coating composition for forming the thermosensitive recording layer 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 paraffin, oxidized paraffin , Polyethylene, polyethylene oxide, stearamides and castor wax.
  • slip 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 first coating composition 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, which should preferably be incorporated in an amount of 0 to 28% by weight in the first coating composition , as preferred.
  • the proposed method according to the invention further provides for the preparation of a second coating composition.
  • Such a coating composition is for example from EP 1 663 662 B1 known. Unfortunately, this document, however, no suggestions to remove a method, as it is the subject of the present document.
  • the formulation of the second coating composition is adopted, so that the method manages the preparation and application of the first, second, optionally fourth and optionally fifth coating composition.
  • the second coating composition is then used both for forming the protective layer covering the heat-sensitive recording layer and for forming the at least one coating arranged on the back of the substrate.
  • the second and third coating compositions differ only in the presence of the wax in the second coating composition as opposed to its absence in the third coating composition.
  • the proposed method provides for the preparation of a fourth coating composition, wherein the fourth coating composition for the preferably desired formation of a pigmented intermediate layer arranged between the front side of the substrate and the heat-sensitive recording layer particularly preferably comprises organic pigments and inorganic pigments which comprise the inorganic pigments individually or in solution Combined among themselves selected from the list comprising: calcined kaolin, silica, bentonite, calcium carbonate and alumina, and here especially boehmite.
  • 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 .-% consists of inorganic pigment.
  • Pigment mixtures of different organic pigments are conceivable.
  • the fourth coating composition 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 addition of at least one natural polymer, particularly preferably starch, is a particularly suitable embodiment.
  • a binder-pigment ratio within the fourth coating composition between 3: 7 and 1: 9, in each case based on wt .-%, a particularly suitable embodiment is present.
  • the proposed method provides for the preparation of a fifth coating composition, wherein the fifth coating composition primarily for forming a rear-side intermediate coating positioned between the rear side of the substrate and the at least one coating disposed on the rear side of the substrate comprises a plurality of binders and most preferably is prepared on an aqueous basis.
  • the fifth coating composition primarily for forming a rear-side intermediate coating positioned between the rear side of the substrate and the at least one coating disposed on the rear side of the substrate comprises a plurality of binders and most preferably is prepared on an aqueous basis.
  • polyvinyl alcohol and modified polyvinyl alcohols are particularly suitable as binders. Shares of 0 to 10 wt .-% pigment, based on the entire fifth coating composition, can bring about positive effects, in which case, in particular, calcium carbonate is preferred.
  • At least two machines can be used to process the above process steps (i) to (xiv), wherein process steps (i) to (iv) and optionally additionally process steps (vii) to ( viii) plus a downstream reeling of the substrate by a machine designed as a paper machine, while the process steps (v) to (xiv), optionally without the process steps (vii) to (viii), plus an upstream unrolling of the substrate with optionally applied fourth and / or fifth coating composition by a second machine designed as a coating machine with integrated printing and cross-linking units and packaging devices.
  • a second machine designed as a coating machine with integrated printing and cross-linking units and packaging devices.
  • Another particularly preferred embodiment provides for carrying out the method steps (x) to (xiv) plus an upstream unwinding of the substrate with applied coating compositions by a packaging machine with integrated printing and cross-linking units, wherein the packaging machine in the sense of the present invention is to be understood as a machine selected from the list comprising: rewinder, slitter, cross cutter, guillotine, without any of these typical representatives of paper processing and finishing machines Way to be limited.
  • the remaining process steps (i) to (xiv) at least in addition to a subsequent rolling up of the substrate with applied coating compositions are then carried out either by a paper machine or by two machines designed as paper and / or coating machines.
  • the method steps (i) to (iv) plus a downstream reeling of the substrate are carried out by the first machine designed as a paper machine, while the method steps (v) to (xiv) plus an upstream unwinding the substrate by a second machine or alternatively by a second machine for the process steps (v) to (ix) and by a third machine for the process steps (x) to (xiv), in each case plus the necessary additional roll-up and unrolling process steps, be executed.
  • the implementation of further process steps is conceivable.
  • the formation of the web-like substrate is done for example and in a preferred embodiment on a paper machine, in which at least one upstream Mischbütte a paper pulp of different pulps, optionally groundwood, fillers and water is applied and where preferred to this paper pulp before being fed to the paper machine more Components such as resin size for engine sizing and other conventional additives, such as pigments, Nuancierfarbstoffe and / or optical brightener are added.
  • a paper machine in which at least one upstream Mischbütte a paper pulp of different pulps, optionally groundwood, fillers and water is applied and where preferred to this paper pulp before being fed to the paper machine more Components such as resin size for engine sizing and other conventional additives, such as pigments, Nuancierfarbstoffe and / or optical brightener are added.
  • the second and / or the third coating composition for forming the protective layer covering the heat-sensitive recording layer or for forming the at least one coating arranged on the back side of the substrate are each preferably provided with an application layer and with a mass per unit area in a range from 0.5 to 4.5 g / m 2 applied.
  • the basis weight of the total protective layer and / or the back coating is preferably in a range of 1.2 to 6 g / m 2 and especially between 1.5 and 4 g / m 2 .
  • the second and / or the third coating composition for forming the protective layer covering the heat-sensitive recording layer or for forming the coating arranged on the back side of the substrate UV and electron radiation are particularly suitable as high-energy radiation, UV radiation being very particularly preferred applies.
  • the second contains and / or the third coating composition photoinitiators in a range of 2 to 20 wt .-%.
  • the first coating composition for forming the thermosensitive recording layer within the process step (v) is applied by means of a coating process selected from the list comprising: a roller blade coater, knife coater, curtain coater or air brush.
  • the first coating composition used to form the recording layer is preferably aqueous.
  • the subsequent drying of the coating material within the process step (vi) 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 fourth coating composition for forming the pigmented intermediate layer is applied to the front side of the substrate within the optional process step (ii) by a leveling spread process selected from the list comprising: roller coater, doctor blade or doctor blade coater.
  • the intermediate layer can positively contribute to leveling of the substrate surface, thus reducing the amount of the applied mass of the first coating composition for forming the heat-sensitive recording layer.
  • the subsequent drying of the coating material within the optional process step (iii) 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.
  • a preferred range between 5 and 20 g / m 2 and even better between 7 and 12 g / m 2 has proven.
  • the fifth coating composition for forming a backside intermediate coating positioned between the back of the substrate and the at least one coating disposed on the backside of the substrate is applied within the optional process step (vii) by means of a coating process selected from the list comprising: roller blade coater, knife coater , Curtain coater or airbrush.
  • the fifth coating composition used to form the backside intermediate coating is preferably aqueous.
  • the subsequent drying of the coating composition within the process step (viii) is usually done by a method in which heat is supplied, as done by hot-air floatation dryer or contact dryer. Proven is also a combination of the listed dry processes.
  • the basis weight of the backside intermediate coating is preferably between 2.0 and 5.5 g / m 2 and more preferably between 2.2 and 4.0 g / m 2 .
  • the proposed method for producing a heat-sensitive recording material comprises smoothing the substrate with the applied and dried fourth coating composition and within the optional method step (ix) Smoothing the substrate with the optionally applied and dried fourth and / or fifth coating composition and the applied and dried first coating composition.
  • the aim of such smoothing steps which can be done in both cases by a calender or a calender, is to create a flattened, possibly glossy surface, which appear on the printed protective layer and / or on the printed back coating applied color images vivid and vibrant. Further, a smoother surface of the thermosensitive recording layer by improved contact with the thermal head promotes heat transfer and thus the sensitivity of this thermosensitive recording layer.
  • a non-surface treated base paper is to be understood as meaning a base paper which has not been treated in a size press or in a coating device.
  • films of, for example, polyolefin and polyolefin-coated papers as a substrate are possible to the same extent, without such an embodiment having an exclusive character.
  • the present invention in addition to the disclosed methods - in all its various and mutually complementary embodiments and variants - for producing a heat-sensitive recording material, also claims the use of a heat-sensitive recording material produced by one of these methods as a parking ticket and / or a punitive ticket.
  • Numerous tests and series of heat-sensitive recording materials made by one of the methods disclosed herein have been able to demonstrate their superior effect in their use as a parking and / or toll ticket.
  • the above-described problems of a strong background graying due to direct sunlight as well as blocking and sticking due to the action of moisture could be regarded as convincingly solved by the recording materials, which were prepared by one of the methods disclosed herein.
  • the method in all its various and mutually complementary embodiments and variants, ensures economically justifiable production costs, including, in particular, the flexibly applicable combination of coating ink applications and two-sided printing jobs together contribute with the perfectly matched components within the first, second, third, and optionally fourth and fifth coating compositions.
  • the surface mass,% by weight (% by weight) and parts by weight (parts by weight) given in the specification and claims refer to the "atro" weight, respectively. absolutely dry parts by weight.
  • the relevant figures are calculated from the "lutro" weight, i. air-dry parts by weight, minus the proportion by weight of water around and inside the pigments in their form of delivery.
  • a paper pulp of eucalyptus pulp and other pulp fibers with fillers and water is applied in a mixing chest.
  • Other constituents of the pulp to be added are resin size for engine sizing with an amount of 0.6% by weight (atro), based on the total weight of the pulp, and other customary additives, such as, for example, pigments and / or optical brighteners.
  • the paper web is still dried within the paper machine by means of radiant heaters and in contact with hot rollers - process step (iii), in a Mehrwalzenglätttechnik smoothed - process step (iv) - and then rolled up as a semi-finished paper drum.
  • the heat-sensitive recording layer is dried as process step (vi) by means of a hot-air floating dryer and in contact with hot rolls.
  • This is followed by the order of the prepared fifth coating composition comprising mainly unmodified polyvinyl alcohol and aqueous-based calcium carbonate to form a backside intermediate coating - process step (vii), drying this application process step (viii) - and, in a multi-roll calender, smoothing the paper web with the respective applied and dried pigmented intermediate layer, the heat-sensitive recording layer and the backside intermediate coating - process step (ix). It follows the re-roll on a spool.
  • the spool thus produced is fed to a slitter with integrated printing units and UV lamps, where on the continuously rewound paper web by means of a multi-color flexographic printing unit within the used slitter first as process step (x) the prepared second coating composition for forming the heat-sensitive recording layer the covering protective layer and, immediately following process step (xii), the prepared third coating composition for forming the at least one coating arranged on the back side of the substrate, each with a surface-related coating Mass of 2.0 g / m 2 is printed.
  • the second coating composition used was prepared as follows:
  • the third coating composition is identical to the second coating composition except for the absence of the PTFE-modified polyethylene wax.
  • the two previously printed coatings are crosslinked on the one hand to form the heat-sensitive recording layer covering protective layer and on the other to form the at least one arranged on the back of the substrate coating by means of UV radiation.
  • the thus finished heat-sensitive recording material is cut into smaller rolls and further assembled according to customer requirements - process step (xiv) - and is then ready for its use as a parking and / or penalty ticket.

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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)

Claims (16)

  1. Procédé de fabrication d'un matériau d'enregistrement thermosensible comprenant :
    un substrat sous forme de feuille continue, présentant un recto et un verso opposé au recto,
    une couche d'enregistrement thermosensible, disposée sur le recto du substrat, contenant des chromogènes et des accepteurs de couleur,
    une couche de protection recouvrant cette couche d'enregistrement thermosensible,
    au moins un revêtement disposé sur le verso du substrat, le procédé comprenant au moins les étapes suivantes :
    préparation d'une première composition de revêtement, cette première composition de revêtement comprenant au moins :
    - en tant qu'accepteur de couleur, au moins 80 % en poids, par rapport à la quantité totale des accepteurs de couleur dans la première composition de revêtement, de 4,4'-dihydroxy-diphénylsulfone,
    - au moins un sensibilisateur, choisi parmi la liste comprenant le stéaramide, la diméthylsulfone, le 2-(2H-benzotriazol-2-yl)-p-crésol et le téréphtalate de diméthyle,
    préparation d'une deuxième composition de revêtement, cette deuxième composition de revêtement comprenant au moins :
    - de 65 à 95 % en poids d'un ou plusieurs (méth)acrylates,
    - de 0 à 20 % en poids de photoamorceurs, et
    - de 0,5 à 20 % en poids de cire,
    les indications de pourcentage en poids, allant de 65,5 à 100 % en poids s'ajoutent à la deuxième composition de revêtement,
    préparation d'une troisième composition de revêtement,
    cette troisième composition de revêtement comprenant au moins:
    - de 65 à 95 % en poids d'un ou plusieurs (méth)acrylates,
    - de 0 à 20 % en poids de photoamorceurs, et
    les indications de pourcentage en poids, allant de 65 à 100 % en poids s'ajoutent à la deuxième composition de revêtement,
    formation d'un substrat sous forme de feuille continue, présentant un recto et un verso opposé au recto,
    application de la première composition de revêtement préparée pour former la couche de revêtement thermosensible disposée sur le recto du substrat,
    séchage de la première composition de revêtement,
    application de la deuxième composition de revêtement préparée pour former la couche de protection recouvrant la couche d'enregistrement thermosensible,
    réticulation, au moyen d'un rayonnement de haute énergie, de la couche de protection recouvrant la couche d'enregistrement thermosensible,
    application de la troisième composition de revêtement préparée pour former l'au moins un revêtement disposé au verso du substrat,
    réticulation, au moyen d'un rayonnement de haute énergie, de l'au moins un revêtement disposé au verso du substrat, confection du matériau d'enregistrement thermosensible, comprenant au moins :
    - le substrat sous forme de feuille continue,
    - la couche d'enregistrement thermosensible disposée sur le recto du substrat, formée à partir de la première composition de revêtement,
    - la couche de protection recouvrant la couche d'enregistrement thermosensible, formée à partir de la deuxième composition de revêtement,
    - l'au moins un revêtement côté verso, disposé au verso du substrat, formé à partir de la troisième composition de revêtement.
  2. Procédé de fabrication d'un matériau d'enregistrement thermosensible selon la revendication 1, caractérisé en ce que la 4,4'-dihydroxydiphénylsulfone est l'accepteur de couleur unique se trouvant dans la première composition de revêtement.
  3. Procédé de fabrication d'un matériau d'enregistrement thermosensible selon l'une quelconque des revendications 1 et 2, caractérisé en ce que les chromogènes de la première composition de revêtement sont choisis parmi la liste comprenant : le 3-diéthylamino-6-méthyl-7-anilinofluoranne, le 3-dibutylamino-6-méthyl-7-anilinofluoranne, le 3-(N-méthyl-N-propyl)amino-6-méthyl-7-anilinofluoranne, le 3-(N-éthyl-N-isoamyl)amino-6-méthyl-7-anilinofluoranne, le 3-(N-méthyl-N-cyclohexyl)-amino-6-méthyl-7-anilinofluoranne, le 3-(N-éthyl-N-tolyl)amino-6-méthyl-7-anilinofluoranne et le 3-(N-éthyl-N-tétrahydrofuryl)amino-6-méthyl-7-anilinofluoranne.
  4. Procédé de fabrication d'un matériau d'enregistrement thermosensible selon l'une quelconque des revendications 1 à 3, caractérisé en ce que le rapport 4,4'-dihydroxydiphénylsulfone/sensibilisateur, rapporté au pourcentage en poids à l'intérieur de la première composition de revêtement, se situe dans une plage allant de 1/0,5 à 1/2.
  5. Procédé de fabrication d'un matériau d'enregistrement thermosensible selon l'une quelconque des revendications 1 à 4, caractérisé en ce que le procédé comprend au moins trois étapes supplémentaires :
    préparation d'une quatrième composition de revêtement, la quatrième composition de revêtement comprenant des pigments organiques et des pigments inorganiques, les pigments inorganiques étant choisis parmi la liste comprenant : le kaolin calciné, l'oxyde de silicium, la bentonite, le carbonate de calcium, ainsi que l'oxyde d'aluminium et ici, en particulier, la boehmite,
    application de la quatrième composition de revêtement préparée pour former une couche intermédiaire pigmentée disposée entre le recto du substrat et la couche d'enregistrement thermosensible,
    séchage de la quatrième composition de revêtement,
    ces au moins trois étapes supplémentaires devant être insérées avant l'étape "application de la première composition de revêtement préparée pour former la couche d'enregistrement thermosensible disposée au recto du substrat.
  6. Procédé de fabrication d'un matériau d'enregistrement thermosensible selon l'une quelconque des revendications 1 à 5, caractérisé en ce que la deuxième composition de revêtement est appliquée par impression analogique pour former la couche de protection recouvrant la couche d'enregistrement thermosensible.
  7. Procédé de fabrication d'un matériau d'enregistrement thermosensible selon l'une quelconque des revendications 1 à 6, caractérisé en ce que la troisième composition de revêtement est appliquée par impression analogique pour former l'au moins un revêtement disposé au verso du substrat.
  8. Procédé de fabrication d'un matériau d'enregistrement thermosensible selon l'une quelconque des revendications 1 à 7, caractérisé en ce que
    (a.) l'application de la deuxième composition de revêtement pour former la couche de protection recouvrant la couche d'enregistrement thermosensible, et
    (b.) l'application de la troisième composition de revêtement pour former l'au moins un revêtement disposé au verso du substrat,
    sont réalisées exactement dans le cadre d'un passage en machine.
  9. Procédé de fabrication d'un matériau d'enregistrement thermosensible selon l'une quelconque des revendications 1 à 8, caractérisé en ce que le rayonnement de haute énergie, pour la réticulation
    (a.) de la deuxième composition de revêtement pour former la couche de protection recouvrant la couche d'enregistrement thermosensible, et/ou
    (b.) de la troisième composition de revêtement pour former l'au moins un revêtement disposé au verso du substrat,
    est un rayonnement UV.
  10. Procédé de fabrication d'un matériau d'enregistrement thermosensible selon l'une quelconque des revendications 1 à 9, caractérisé en ce que
    (a.) la deuxième composition de revêtement pour former la couche de protection recouvrant la couche d'enregistrement thermosensible, et/ou
    (b.) la troisième composition de revêtement pour former l'au moins un revêtement disposé au verso du substrat,
    sont appliquées, respectivement, en au moins deux couches disposées l'une au-dessus de l'autre.
  11. Procédé de fabrication d'un matériau d'enregistrement thermosensible selon l'une quelconque des revendications 1 à 10, caractérisé en ce que la première composition de revêtement pour former la couche d'enregistrement thermosensible est appliquée au moyen d'un procédé d'enduction choisi parmi la liste comprenant : une enduiseuse à racle tournante, une enduiseuse à lame, une enduiseuse à rideau ou une lame d'air.
  12. Procédé de fabrication d'un matériau d'enregistrement thermosensible selon l'une quelconque des revendications 5 à 11, caractérisé en ce que la quatrième composition de revêtement pour former la couche intermédiaire pigmentaire est appliquée au recto du substrat au moyen d'un procédé d'enduction choisi parmi la liste comprenant : une enduiseuse au rouleau, une enduiseuse à lame ou une enduiseuse à racle (tournante).
  13. Procédé de fabrication d'un matériau d'enregistrement thermosensible selon l'une quelconque des revendications 1 à 12, caractérisé en ce que le séchage
    (a.) de la première composition de revêtement pour former la couche d'enregistrement thermosensible et/ou
    (b.) de la quatrième composition de revêtement pour former la couche intermédiaire pigmentée
    est réalisé par amenée de chaleur.
  14. Procédé de fabrication d'un matériau d'enregistrement thermosensible selon l'une quelconque des revendications 1 à 13, caractérisé en ce que le procédé comprend au moins les trois étapes supplémentaires suivantes :
    préparation d'une cinquième composition de revêtement, la cinquième composition de revêtement comprenant en premier lieu des liants,
    application de la cinquième composition de revêtement préparée pour former un revêtement intermédiaire côté verso, positionné entre le verso du substrat et l'au moins un revêtement disposé au verso du substrat,
    séchage ou réticulation de la cinquième composition de revêtement.
  15. Procédé de fabrication d'un matériau d'enregistrement thermosensible selon l'une quelconque des revendications 1 à 14, caractérisé en ce que le substrat est un papier.
  16. Utilisation d'un matériau d'enregistrement thermosensible fabriqué selon un procédé tel que revendiqué dans l'une quelconque des revendications 1 à 15 en tant que ticket de stationnement ou avis de procès-verbal.
EP20110157084 2011-02-11 2011-03-04 Procédé de fabrication d'un matériel d'enregistrement sensible à la chaleur Not-in-force EP2487044B1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP20110157084 EP2487044B1 (fr) 2011-02-11 2011-03-04 Procédé de fabrication d'un matériel d'enregistrement sensible à la chaleur
PCT/EP2012/052154 WO2012107507A1 (fr) 2011-02-11 2012-02-08 Procédé pour produire un matériau d'enregistrement thermosensible

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP20110154121 EP2487043B1 (fr) 2011-02-11 2011-02-11 Procédé de fabrication d'un matériel d'enregistrement sensible à la chaleur
EP20110157084 EP2487044B1 (fr) 2011-02-11 2011-03-04 Procédé de fabrication d'un matériel d'enregistrement sensible à la chaleur

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EP2487044A1 EP2487044A1 (fr) 2012-08-15
EP2487044B1 true EP2487044B1 (fr) 2013-10-23

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EP20110157084 Not-in-force EP2487044B1 (fr) 2011-02-11 2011-03-04 Procédé de fabrication d'un matériel d'enregistrement sensible à la chaleur

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US (1) US9079444B2 (fr)
EP (2) EP2487043B1 (fr)
DK (1) DK2487044T3 (fr)
ES (1) ES2443162T3 (fr)
WO (2) WO2012107504A1 (fr)

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JP6649618B2 (ja) * 2016-03-28 2020-02-19 王子ホールディングス株式会社 感熱記録ライナーレスラベル及びその製造方法

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US4485123A (en) 1982-02-12 1984-11-27 Union Carbide Corporation Process for producing textured coatings
DE3526016A1 (de) 1985-07-20 1987-01-22 Huels Chemische Werke Ag Lagerstabile, strahlenhaertbare, nco-freie, waessrige emulsionen
US5801288A (en) * 1994-06-06 1998-09-01 Nippon Soda Co., Ltd. Diphenyl sulfone derivative and recording material prepared therefrom
DE10341168A1 (de) 2003-09-06 2005-04-07 Mitsubishi Hitec Paper Flensburg Gmbh Wärmeempfindliches Aufzeichnungsmaterial und seine Verwendung
EP1684989B1 (fr) 2003-11-12 2008-10-29 Mitsubishi Hitec Paper Flensburg GmbH Procede de fabrication d'un materiau d'enregistrement thermosensible comportant une couche de protection et machine de couchage destinee a la fabrication dudit materiau
US7501381B2 (en) * 2004-09-14 2009-03-10 Ricoh Company, Ltd. Reversible thermosensitive recording medium, image processing method, and image processing apparatus
US8143191B2 (en) * 2008-03-18 2012-03-27 Ricoh Company, Ltd. Thermosensitive recording material
EP2112000B8 (fr) * 2008-03-27 2011-03-30 Mitsubishi HiTec Paper Europe GmbH Matériel d'enregistrement sensible à la chaleur
ES2385179T3 (es) 2009-07-28 2012-07-19 Mitsubishi Hitec Paper Europe Gmbh Material de registro termosensible

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US20140057783A1 (en) 2014-02-27
EP2487043A1 (fr) 2012-08-15
ES2443162T3 (es) 2014-02-18
WO2012107507A1 (fr) 2012-08-16
EP2487044A1 (fr) 2012-08-15
US9079444B2 (en) 2015-07-14
WO2012107504A1 (fr) 2012-08-16
DK2487044T3 (da) 2014-01-13
EP2487043B1 (fr) 2013-10-09

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