EP1543984B1 - Matériau d'enregistrement sensible à la chaleur pour l'impression recto-verso - Google Patents

Matériau d'enregistrement sensible à la chaleur pour l'impression recto-verso Download PDF

Info

Publication number
EP1543984B1
EP1543984B1 EP04027595A EP04027595A EP1543984B1 EP 1543984 B1 EP1543984 B1 EP 1543984B1 EP 04027595 A EP04027595 A EP 04027595A EP 04027595 A EP04027595 A EP 04027595A EP 1543984 B1 EP1543984 B1 EP 1543984B1
Authority
EP
European Patent Office
Prior art keywords
heat
sensitive recording
recording material
weight
recording layer
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
EP04027595A
Other languages
German (de)
English (en)
Other versions
EP1543984A3 (fr
EP1543984A2 (fr
Inventor
Karsten Lerius
Annette Schreiber
Volker Hiller
Gerhard Dr. Stork
Takao Masuda
Matthias Neukirch
Wolfgang Dr. Wagner
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
Original Assignee
Mitsubishi HiTech Paper Flensburg 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 HiTech Paper Flensburg GmbH filed Critical Mitsubishi HiTech Paper Flensburg GmbH
Publication of EP1543984A2 publication Critical patent/EP1543984A2/fr
Publication of EP1543984A3 publication Critical patent/EP1543984A3/fr
Application granted granted Critical
Publication of EP1543984B1 publication Critical patent/EP1543984B1/fr
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • 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
    • B41M5/3377—Inorganic compounds, e.g. metal salts of organic acids
    • 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
    • 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
    • B41M2205/04—Direct thermal recording [DTR]
    • 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
    • B41M5/423—Intermediate, backcoat, or covering layers characterised by non-macromolecular compounds, e.g. waxes
    • 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
    • B41M5/426—Intermediate, backcoat, or covering layers characterised by inorganic compounds, e.g. metals, metal salts, metal complexes
    • 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

  • the present invention relates to heat-sensitive recording materials having a sheet-like substrate, on the first side of which a heat-sensitive recording layer and a protective layer covering the heat-sensitive recording layer are applied.
  • the recording layer contains at least one dye precursor and at least one color acceptor as components which react color-forming with one another under the action of heat.
  • the sheet-shaped substrate On the side of the substrate opposite to the side of the substrate having the recording layer, the sheet-shaped substrate carries a backside coating.
  • the invention relates to the use of the proposed thermosensitive recording material for printing with an analog printing method.
  • thermosensitive recording material having a substrate and a recording layer applied to the substrate on the front side, which is optionally covered by a protective layer, is known.
  • the substrate On the reverse side, the substrate carries a coating of water-soluble high polymers, such as starch, gelatin, styrene-maleic anhydride copolymer hydrolysates or polyvinyl alcohol, and of water-insoluble polymers, such as latices.
  • 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 recording layer of the known heat-sensitive recording material contains a very high proportion of calcium carbonate as pigment and a content of binders of polyvinyl alcohol and methyl cellulose which precipitates very small in relation to the pigment content.
  • the barrier layer comprises substantially water-soluble Polymeric materials such as polyvinyl alcohol, various cellulose ethers, starch, gelatin, casein, and polyvinylpyrolidone; and 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 result in the fading and / or discoloring of the images developed in the recording layer.
  • Subject of the US 2003/0073576 A1 is a medically transparent light-sensitive recording material whose recording layer is coated with a protective layer.
  • This protective layer is intended to improve the resistance of the known recording material to chemicals, water and light, and preferably consists entirely of a resin for which there are scarcely any limits in the list of names; inter alia, diisocyanate is enumerated as a possible material.
  • pigments are included in the resin of the protective layer, for which all known inorganic pigments appear suitable. If the known recording material to be provided with a backside coating, the components of the protective layer are also considered to be suitable for the backside coating, without which there are exemplary embodiments thereof.
  • this document discloses a color developer based on salicylic acid.
  • the binder content in the recording layer is not limited; up to 65% by weight are considered suitable. No information is given on the proportion of pigments in the recording layer. Surface properties or other uses of the thus proposed recording material are not disclosed.
  • thermosensitive recording paper capable of generating high color density recordings suitable as templates for diazotype copying processes.
  • a substrate is provided on one or both sides with a resin coating, on the front side, a heat-sensitive recording layer optionally covered with a protective layer is applied to the resin-coated substrate.
  • the recording paper thus known has the disadvantage of being neither suitable for printing in the offset and flexographic printing processes on the reverse side, nor for being designed to be at the front.
  • a non-generic recording material which has a heat-sensitive recording layer on the front side and a pigment coating suitable for ink-jet recording on the back side.
  • the recording material which is quite trend-setting in this way mentions isocyanate compounds, which, however, find use as a color-developing substance in the heat-sensitive recording layer.
  • isocyanate compounds which, however, find use as a color-developing substance in the heat-sensitive recording layer.
  • EP 1 040 933 A1 a recording material of the same type which has a heat-sensitive recording layer on the front side and a pigment coating suitable for ink-jet recording on the reverse side.
  • the document can be found neither the use of diisocyanate compounds in the back coating nor a particular suitability of the thus-known recording material for printing in high-speed offset and flexographic printing machines.
  • 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 99/14055 A1 after a backside coating, which has a good barrier effect compared to the substances used in offset and flexographic printing, in particular organic solvents, as well as to plasticizers, oils and fats.
  • 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.
  • heat-sensitive recording materials are known to be printed by various printing techniques.
  • a disadvantage of the known recording materials is that they often do not have the necessary nip strength in order to withstand the high adhesion forces occurring in the case of abrupt removal of the blanket from the surface to be printed, especially in fast-running, modern printing presses.
  • Due to ever new applications there is also a growing demand for heat-sensitive recording materials which can be printed on both the front side and the back side, for example by means of offset printing, without problems and at high press speeds.
  • more economical to produce because faster printed tickets allows the front side next to the heat-induced printed images with individual entry parameters also contain printed general entry information, while printed on the back general information such as advertising.
  • the laying invention thus provides a first object to provide a recording material with front-applied thermosensitive recording layer on the front side with a high resistance to offset and flexographic printing substances and in particular to organic solvents, plasticizers, optionally photoinitiators in the printing UV-curing printing inks, oils and greases, and at the same time easy to print in offset and flexo printing processes without problems and at high speeds.
  • a second object of the present invention is to provide a recording material having a thermosensitive recording layer provided on the front side which, in addition to the above-described front properties, simultaneously has a high barrier to offset and flexographic printing substances, and especially organic solvents, plasticizers, oils and fats and the back as well as the front side in the offset and flexo printing process is easy to print without problems and at high speeds.
  • the novel recording material has, in addition to the other features of claim 1, in particular a particularly high proportion of the color-forming components dye precursor and dye acceptor in the heat-sensitive Recording layer on.
  • the pigment content in the recording layer is intentionally kept low.
  • the novel recording material has a backcoat with at least one substance acting as a crosslinker, which contains diisocyanate as an effective component. It is particularly preferred if such a crosslinker is provided on the basis of hexamethylene diisocyanate as an effective component.
  • the recording material according to the invention has, with diisocyanate or hexamethylene diisocyanate as crosslinking agent acting substances on a backside coating of a coating color, which is storage stable for 3 days with moderate stirring before their order and also does not begin to cure.
  • a preferred embodiment of the proposed recording material provides a proportion of heat-sensitive color-reacting components in the heat-sensitive recording layer in a range from 36.5 to 48% by weight (atro) and in particular from 37.5 to 42% by weight. (atro) ago.
  • the statements made above on the wt .-% of the color-forming mutually reactive components in the heat-sensitive recording layer again refer to the total solids content (atro) of the heat-sensitive recording layer.
  • the ratio of pigment in wt% (atro) to binder in wt% (atro) in the heat-sensitive recording layer is in a range of 0.65: 1 to 1.45: 1.
  • the statements made on the ratio of pigment in wt .-% (atro) to binder in wt .-% (atro) each relate to the total solids content (atro) of the heat-sensitive recording layer.
  • a ratio of the color-forming components in% by weight (atro) applies to binder in% by weight (atro) in the heat-sensitive recording layer in a range of 1.5: 1 to 12: 1, and particularly preferably between 1.85: 1 and 4: 1.
  • Suitable pigments in the heat-sensitive recording layer are those which are a good compromise of whiteness, oil absorption behavior and economy.
  • preferred examples of particular inorganic oil-absorbing pigments are listed: natural and calcined kaolin, silicon (di) oxide, bentonite, calcium carbonate, aluminum oxide and aluminum hydroxide and especially boehmite, the pigments can be used individually as well as in combination.
  • a particularly preferred pigment with the most balanced properties in the context of this invention is calcium carbonate.
  • starch as the binder in the heat-sensitive recording layer, starch, cellulose derivatives such as CMC and acrylate, butadiene-styrene, polyvinyl acetate-based plastic dispersions, and more preferably polyvinyl alcohol alone or in admixture with each other in the recording layer can be used.
  • polyvinyl alcohols partly or better completely saponified polyvinyl alcohols and ethylene-vinyl alcohol copolymers are considered suitable.
  • the training for the heat-sensitive recording layer used coating color aqueous can be done by means of infrared radiation.
  • hot-air floating dryers and contact dryers such as drying cylinders.
  • the different drying options can be combined in any kind and order.
  • the limits will be up due to too low sensitivity and down given by otherwise too strong inclination of the heat-sensitive recording material for graying.
  • the invention relates to an irreversible thermosensitive recording material which can form a permanent color or typeface in the recording layer under the action of heat.
  • the recording material according to the invention has a protective layer covering the heat-sensitive recording layer, which preferably completely covers it covers.
  • the protective layer performs a task, as it must also be partially fulfilled by the backside coating, namely on the one hand, the protection of the arranged under her recording layer from environmental influences such as oils, fats, water and plasticizers and on the other the improvement of printability, especially in the offset and flexographic printing.
  • it preferably contains the ink-receptive pigments and is designed particularly gap-resistant.
  • the protective layer itself can be applied by means of conventional brushing or, alternatively, printed, with a surface-related mass in a range from 0.5 to 4.5 g / m 2 being preferred. Processing technology and in terms of their technological properties are particularly suitable such protective layers that are crosslinkable and crosslinked by high-energy radiation.
  • high-energy radiation means heat, IR, UV or ionizing radiation, such as electron beams.
  • an intermediate layer is expediently arranged, which contains in addition to binder inorganic oil-absorbing and optionally also organic (hollow body) pigments.
  • inorganic oil-absorbing pigments include natural and calcined kaolin, silicon (di) oxide, bentonite, calcium carbonate, aluminum oxide and aluminum hydroxide, in particular boehmite, where the pigments can be used individually as well as in combination with one another.
  • an intermediate layer acts as a heat reflector which reflects the heat emitted by the thermal head, the recording layer and previously which penetrates covering protective and printing layers, focused on the heat-sensitive recording layer.
  • the intermediate layer can furthermore make a positive contribution to the leveling of the substrate surface, with the result that the amount of coating color necessarily to be applied for the heat-sensitive recording layer can be further reduced if necessary. For this reason, offer to coat the intermediate layer leveling strokes, such as Walzenstreichwerke, doctor blade or (roll) doctor blade coating.
  • the pigments of this intermediate layer can absorb the heat-liquefied wax components of the heat-sensitive recording layer in the typeface formation and thus promote a Safe and fast functioning of the heat-induced recording.
  • the preferred intermediate layer also comprises at least one oil or wax-absorbing pigment.
  • the basis weight of the pigmented intermediate layer is preferably between 5 and 20 g / m 2 and more preferably between 7 and 10 g / m 2 (atro).
  • the quantitative ratio between the two types of pigments represents a compromise between the effects produced by the two types of pigments, which is achieved particularly advantageously if the pigment mixture contains 15 to 50% by weight. more preferably from 18 to 25% by weight of organic and from 85 to 50% by weight and more preferably from 82 to 75% by weight of inorganic pigment.
  • the particle size of the organic pigments present in the intermediate layer is in a range from 0.75 ⁇ m to less than 1.5 ⁇ m, preferably in a range from 0.8 ⁇ m to 1.1 ⁇ m. Particle sizes below 0.75 microns prohibit due to rheological processing difficulties. Particle sizes above 1.5 microns show too coarse-grained behavior and prevent a preferred leveling effect of the intermediate layer.
  • the particle size is ideally less than 2 ⁇ m, determined as the D 50 value. Pigments which have a particle size distribution of from 34 to 40% by weight of less than 1 ⁇ m and from 57 to 63% by weight of less than 2 ⁇ m have proved to be advantageous.
  • the backcoat comprises binders and in particular starch, styrene-butadiene latex and carboxymethylcellulose.
  • binders and in particular starch, styrene-butadiene latex and carboxymethylcellulose.
  • the mixture of different binders in sometimes highly divergent mixing ratios is possible and preferred.
  • optical brighteners and antifoams are customary additives according to the respective requirements.
  • the backcoat preferably contains 1 to 7% by weight (atro) starch, more preferably cationic cornstarch and 4 to 15% by weight (atro) styrene butadiene latex, while carboxy-methyl cellulose only in areas below 0.5 wt .-% (atro) entrance into the binder mixture.
  • Particularly positive results can be achieved with a coating weight for the backcoat in a range of 2 to 15 g / m 2 , preferably in a range of 8 to 12 g / m 2 .
  • a coating weight for the backcoat in a range of 2 to 15 g / m 2 , preferably in a range of 8 to 12 g / m 2 .
  • 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 backside coating is formed in two layers, of which the first layer oriented towards the substrate can be formed as a pure binder pigment coating, while the second external layer contains the substance acting as a crosslinker with diisocyanate or even better with hexamethylene diisocyanate as an effective component.
  • the airbrush and curtain coater is available for the second layer as an applicator device.
  • a paper web is particularly suitable, although the invention is not limited to paper as a substrate.
  • mass-sized paper is preferred to a particular extent.
  • the paper on the side, which is optional with the pigmented intermediate layer and with the recording layer is to be provided with a polyolefin coating for sealing.
  • the present invention also encompasses the use of the heat-sensitive recording material according to the invention in all its proposed embodiments and variants in the form of its printing with an analog printing process selected from the group comprising offset printing, gravure printing, screen printing and flexographic printing.
  • the printing on the front side and / or on the back can be done for example for the production of advertising information tickets, receipts or purchase receipts, guarantee certificates, tickets for public transport such as buses, trains, ships, aircraft, as well as for ski lifts.
  • a paper web of bleached and ground hardwood and softwood pulps with a mass per unit area of 67 g / m 2 is prepared as substrate with the addition of customary admixture substances in conventional amounts.
  • customary admixture substances in conventional amounts.
  • a mixture of different tree resins is used in an amount of 0.5% by weight (atro) based on the total solids content (atro) of the paper web.
  • An intermediate layer of 9 g / m 2 is applied to the substrate on the front side by means of a doctor blade applicator within the paper machine.
  • the intermediate layer comprises a pigment mixture of 20% by weight (atro) organic pigment having a particle size (D50) of 1 ⁇ m and 80% by weight (atro) calcined kaolin having a particle size (D50) of 0.9 ⁇ m and an oil absorption of 110 cm 3 / 100g.
  • the intermediate layer further comprises a binder mixture of 75% by weight of styrene-butadiene latex and 25% by weight of starch, respectively (atro).
  • thermosensitive recording layer containing a colorant and color acceptors having a basis weight of 3.0 g / m 2 and a protective layer of 1.9 g / m 2 are applied to the intermediate layer in this order .
  • the formulation for the protective layer in all three cases provides as pigment a highly purified, alkaline-treated bentonite with platelet structure, whose intrinsic adhesion enables its fixation with low binder requirement and whose specific surface area in the non-dispersed state is given as 85 m 2 / g in one area Edge ratio, which in the powdered bentonite ranges from 20 to 50.
  • a binder / pigment ratio of 6: 1 and a crosslinker / binder ratio of 1: 5 are set.
  • the crosslinking agent polyamide-picornylarine resin, as the binder, is used the aqueous dispersion of a self-crosslinking copolymer of acrylonitrile, methacrylamide and acrylic ester.
  • the coating composition for the preparation of the protective layer contains as further components a defoamer, as a lubricant stearic acid and various dispersants on the one hand for the pigment and on the other hand for the lubricant.
  • a proportion of 40.39 wt .-% or 38.64 wt .-% (atro) is determined in the heat-sensitive recording layer, color-reactive with each other under heat, in Comparative Example 3 is this Proportion only at 30.50 wt .-% (atro).
  • the ratio of pigment in wt .-% (atro) to binder in wt .-% (atro) formed in the heat-sensitive recording layer in the inventive examples 1 and 2 at 1.33: 1 and 0.71: 1, respectively Comparative Example 3, this value is 2.03: 1.
  • the splitting strength the high adhesion forces occurring in the offset printing process are to be simulated.
  • each of the patterns of the recording material to be examined is placed on a glass plate with the back side.
  • Each approximately 25 cm long adhesive film strip (Scotch 810 Magic Tape, Item No. 11257) is adhered to the protective layer of the recording material by means of a Finat standard pressure roller with a mass of 2 ⁇ 0.05 kg, after gluing the adhesive film strip is still 3 times the pressure roller over the adhesive film strip.
  • the orientation of the adhesive film strip must be in the machine direction of the recording material. When machine direction is considered in the production of a recording paper, the direction of the paper web in the paper or coating machine. Furthermore, the adhesive film strip must not protrude beyond the edges of the pattern.
  • the adhesive film strip should be evenly drawn from the pattern at an angle of 45 ° beginning with the last end glued on.
  • the detached adhesive film strip is glued onto a black cardboard sheet.
  • the break-off point on the respective sample is coated with a solvent tincture. If residues of the pattern (individual particles, smaller or larger protective layer and / or recording layer fragments) have been torn out of the black cardboard sheet, discoloration reactions in the region of the tear-off point appear in reaction to the applied solvent tincture, the nip strength of the respective recording material pattern is low and the test results are considered poor. Without a splitting of the recording material pattern only a few or even no particles or layer fragments are torn out and the layer structure of the recording material is retained. There are little or no discoloration reactions in the area of the breakpoint in response to the applied solvent tincture and the test results are considered to be good.
  • Example 2 of the invention Starting from a heat-sensitive recording material according to Example 2 of the invention, the following coating compositions are prepared for the respective formation of a backcoat according to the following Tabeiie 2 to be taken recipes and by means of a doctor blade with a basis weight of 10 in the context of a 30 further individual experiments comprehensive second series of experiments 1 g / m 2 applied to the back of the substrate.
  • Too high viscosity can not be used 8 * 2 7.5 250 after a day Bad 9 * 1 7.5 640 after 3 hours Well 10 * 2 6.9 1800 after 3 hours Not enough * 3 11 * 2 8.3 430 after 3 hours Not enough * 3 11 * 2 7.1 590 after 3 hours Not enough * 3 13 * 2 7.4 470 after 3 hours Bad 14 * 1 7.3 40 after 2 days Well 15 * 2 6.8 150 after 2 days Bad Low fraction formation in coating color 16 * 2 7.5 Firmly Bad Solid sediment 17 * 2 7.2 25 after 2 days Moderate Strong fractionation with solid sediment 18 * 2 7.4 80 after 2 days Bad Strong faction formation in coating color 19 * 1 7.1 20 after a day Well 20 * 2 5.6 210 after a day Bad 21 * 2 8.8 20 after a day Bad 22 * 2 6.4 20 after a day Moderate 23 * 2 6.7 20 after a day Bad 24 * 1 5.7 290 after 3 hours Still good 25 * 2 5.5 10000 after 3 hours Bad Wg.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)

Claims (16)

  1. Matériau d'enregistrement sensible à la chaleur avec un substrat en forme de bande,
    - dans lequel le substrat en forme de bande porte, sur sa première face, une couche d'enregistrement sensible à la chaleur, comprenant
    (i) au moins un précurseur de colorant et au moins un accepteur de couleur comme composants réagissant l'un avec l'autre de manière chromogène sous l'action de la chaleur,
    (ii) au moins un pigment et
    (iii) au moins un liant,
    - ainsi qu'une couche protectrice recouvrant la couche d'enregistrement sensible à la chaleur,
    - dans lequel la part de composants réagissant l'un avec l'autre de manière chromogène sous l'action de la chaleur dans la couche d'enregistrement sensible à la chaleur se situe dans une plage de 35 à 58 % en poids (atro) et
    - dans lequel le rapport du pigment en % en poids (atro) au liant en % en poids (atro) dans la couche d'enregistrement sensible à la chaleur se situe dans une plage de 0,5:1 à 1,5:1,
    caractérisé en ce que
    - le substrat en forme de bande porte, sur sa seconde face opposée à la première face, un revêtement de verso contenant des pigments, convenant à l'impression en mode d'impression offset et en mode d'impression flexographique et
    - le revêtement de verso contient au moins une substance agissant comme agent de réticulation avec un composant actif choisi dans la liste comprenant un diisocyanate et le diisocyanate d'hexaméthylène.
  2. Matériau d'enregistrement sensible à la chaleur selon la revendication 1, caractérisé en ce que la part de composants réagissant l'un avec l'autre de manière chromogène sous l'action de la chaleur dans la couche d'enregistrement sensible à la chaleur se situe dans une plage de 37,5 % à 42 % en poids (atro).
  3. Matériau d'enregistrement sensible à la chaleur selon l'une quelconque des revendications 1 et 2, caractérisé en ce que le rapport du pigment en % en poids (atro) au liant en % en poids (atro) dans la couche d'enregistrement sensible à la chaleur se situe dans une plage de 0,65:1 à 1,45:1.
  4. Matériau d'enregistrement sensible à la chaleur selon l'une quelconque des revendications 1 à 3, caractérisé en ce que la couche d'enregistrement sensible à la chaleur contient du carbonate de calcium comme pigment.
  5. Matériau d'enregistrement sensible à la chaleur selon l'une quelconque des revendications 1 à 4, caractérisé en ce que le liant de la couche d'enregistrement est de l'alcool polyvinylique entièrement saponifié.
  6. Matériau d'enregistrement sensible à la chaleur selon l'une quelconque des revendications 1 à 5, caractérisé en ce que le liant de la couche d'enregistrement est un copolymère d'éthylène/alcool vinylique.
  7. Matériau d'enregistrement sensible à la chaleur selon l'une quelconque des revendications 1 à 6, caractérisé en ce que la couche d'enregistrement est recouverte d'une couche protectrice réticulable imprimée et réticulée sous l'action de rayons fortement énergétiques.
  8. Matériau d'enregistrement sensible à la chaleur selon l'une quelconque des revendications 1 à 7, caractérisé en ce que la couche d'enregistrement est complètement recouverte de la couche protectrice.
  9. Matériau d'enregistrement sensible à la chaleur selon l'une quelconque des revendications 1 à 8, caractérisé en ce qu'une couche intermédiaire pigmentée est agencée entre le substrat et la couche d'enregistrement sensible à la chaleur.
  10. Matériau d'enregistrement sensible à la chaleur selon l'une quelconque des revendications 1 à 9, caractérisé en ce que le revêtement de verso contient au moins une substance agissant comme agent de réticulation avec du diisocyanate d'hexaméthylène comme composant actif.
  11. Matériau d'enregistrement sensible à la chaleur selon l'une quelconque des revendications 1 à 10, caractérisé en ce que le revêtement de verso contient du carbonate de calcium comme pigment.
  12. Matériau d'enregistrement sensible à la chaleur selon l'une quelconque des revendications 1 à 11, caractérisé en ce que le revêtement de verso contient un ou plusieurs liants parmi les liants énumérés suivants : amidon, latex de styrène/butadiène, carboxyméthylcellulose.
  13. Matériau d'enregistrement sensible à la chaleur selon l'une quelconque des revendications 1 à 12, caractérisé en ce que le revêtement de verso contient dans une plage de 0,5 à 8 % en poids (atro) une substance agissant comme agent de réticulation avec du diisocyanate et/ou du diisocyanate d'hexaméthylène comme composant actif.
  14. Matériau d'enregistrement sensible à la chaleur selon l'une quelconque des revendications 1 à 13, caractérisé en ce que la part de pigment dans le revêtement de verso se situe dans une plage de 75 à 90 % en poids (atro).
  15. Matériau d'enregistrement sensible à la chaleur selon l'une quelconque des revendications 1 à 14, caractérisé en ce que
    - le rapport du pigment en % en poids (atro) au liant en % en poids (atro) dans le revêtement de verso se situe dans une plage de 18:1 à 3,4:1 et
    - le rapport du liant en % en poids (atro) à l'agent de réticulation en % en poids (atro) dans le revêtement de verso se situe dans une plage de 20:1 à 1:1.
  16. Utilisation d'un matériau d'enregistrement sensible à la chaleur selon l'une quelconque des revendications 1 à 15 pour l'impression avec un procédé d'impression analogue choisi dans le groupe comprenant l'impression offset, l'impression en taille douce, la sérigraphie et l'impression flexographique.
EP04027595A 2003-12-18 2004-11-19 Matériau d'enregistrement sensible à la chaleur pour l'impression recto-verso Not-in-force EP1543984B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10359978 2003-12-18
DE10359978 2003-12-18

Publications (3)

Publication Number Publication Date
EP1543984A2 EP1543984A2 (fr) 2005-06-22
EP1543984A3 EP1543984A3 (fr) 2006-02-08
EP1543984B1 true EP1543984B1 (fr) 2009-02-25

Family

ID=34485524

Family Applications (1)

Application Number Title Priority Date Filing Date
EP04027595A Not-in-force EP1543984B1 (fr) 2003-12-18 2004-11-19 Matériau d'enregistrement sensible à la chaleur pour l'impression recto-verso

Country Status (4)

Country Link
EP (1) EP1543984B1 (fr)
AT (1) ATE423682T1 (fr)
DE (1) DE502004009042D1 (fr)
ES (1) ES2321399T3 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102008057270A1 (de) * 2008-11-13 2010-05-20 Kanzan Spezialpapiere Gmbh Aufzeichnungsmaterial
WO2010074018A1 (fr) * 2008-12-26 2010-07-01 三菱製紙株式会社 Matériau d'impression sensible à la chaleur et son procédé de fabrication
DE102018113022A1 (de) * 2018-05-30 2019-12-05 Mitsubishi Hitec Paper Europe Gmbh Wärmeempfindliches Aufzeichnungsmaterial mit glänzender und bedruckbarer Rückseite und Verfahren zur Herstellung eines wärmeempfindlichen Aufzeichnungsmaterials

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5543382A (en) * 1993-12-27 1996-08-06 New Oji Paper Co., Ltd. Heat-sensitive recording paper
JP2000318319A (ja) * 1998-12-02 2000-11-21 Mitsubishi Paper Mills Ltd 情報記録材料
JP4038929B2 (ja) * 1999-03-29 2008-01-30 王子製紙株式会社 両面記録媒体

Also Published As

Publication number Publication date
EP1543984A3 (fr) 2006-02-08
ES2321399T3 (es) 2009-06-05
EP1543984A2 (fr) 2005-06-22
ATE423682T1 (de) 2009-03-15
DE502004009042D1 (de) 2009-04-09

Similar Documents

Publication Publication Date Title
EP3109059B1 (fr) Materiel d'enregistrement sensible a la chaleur
WO2011067004A1 (fr) Matière d'enregistrement thermosensible comprenant un revêtement barrière
DE60222210T2 (de) Wärmeempfindliches Aufzeichnungsmaterial
EP2033801B1 (fr) Matériau d'enregistrement sensible à la chaleur
EP2953797B1 (fr) Matériau d'enregistrement thermosensible
DE60032686T2 (de) Wärmeempfindliches aufzeichnungsmaterial
EP1543984B1 (fr) Matériau d'enregistrement sensible à la chaleur pour l'impression recto-verso
EP2033802B1 (fr) Matériel d'enregistrement sensible à la chaleur doté d'un revêtement de face arrière
EP2329955B1 (fr) Matériel d'enregistrement sensible à la chaleur doté d'une marque d'authenticité
EP2112000B1 (fr) Matériel d'enregistrement sensible à la chaleur
DE102021115909A1 (de) Wärmeempfindliche Aufzeichnungsmaterialien
WO2021058661A1 (fr) Matériau d'enregistrement thermosensible comprenant des révélateurs chromatiques organiques exempts de phénol
WO2015189231A1 (fr) Papier cf
EP2487043B1 (fr) Procédé de fabrication d'un matériel d'enregistrement sensible à la chaleur
EP2505374B1 (fr) Matériel d'enregistrement sensible à la chaleur, son utilisation et son procédé de fabrication
DE4022537C2 (fr)
DE10392446T5 (de) Thermisches Aufzeichnungsmaterial für den Offset-Druck
EP1527900B1 (fr) Matériau pour l'enregistrement par la chaleur, son utilisation et méthode pour sa fabrication
DE102021133333A1 (de) Bahnförmiges wärmeempfindliches Aufzeichnungsmaterial
EP2758249B1 (fr) Matériau d'enregistrement destiné à une impression offset
EP2636533B1 (fr) Procédé de fabrication d'un matériel d'enregistrement doté d'une marque d'authentification
EP1925459A2 (fr) Matériel d'enregistrement sensible à la chaleur doté d'une marque d'authentification
EP2033800A1 (fr) Matériel d'enregistrement sensible à la chaleur
EP2480415A1 (fr) Matériau d'enregistrement thermosensible pourvu d'un revêtement au verso

Legal Events

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

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20041119

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LU MC NL PL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL HR LT LV MK YU

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LU MC NL PL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL HR LT LV MK YU

AKX Designation fees paid

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LU MC NL PL PT RO SE SI SK TR

17Q First examination report despatched

Effective date: 20071018

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LU MC NL PL PT RO SE SI SK TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: GERMAN

REF Corresponds to:

Ref document number: 502004009042

Country of ref document: DE

Date of ref document: 20090409

Kind code of ref document: P

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2321399

Country of ref document: ES

Kind code of ref document: T3

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

Ref country code: SI

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

Effective date: 20090225

Ref country code: FI

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

Effective date: 20090225

Ref country code: NL

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

Effective date: 20090225

NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

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

Effective date: 20090525

Ref country code: PL

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

Effective date: 20090225

Ref country code: IS

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

Effective date: 20090625

REG Reference to a national code

Ref country code: IE

Ref legal event code: FD4D

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

Ref country code: CZ

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

Effective date: 20090225

Ref country code: IE

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

Effective date: 20090225

Ref country code: PT

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

Effective date: 20090812

Ref country code: EE

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

Effective date: 20090225

Ref country code: DK

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

Effective date: 20090225

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

Ref country code: SK

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

Effective date: 20090225

Ref country code: RO

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

Effective date: 20090225

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

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

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

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

Ref country code: BG

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

Effective date: 20090525

26N No opposition filed

Effective date: 20091126

BERE Be: lapsed

Owner name: MITSUBISHI HITEC PAPER FLENSBURG G.M.B.H.

Effective date: 20091130

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

Ref country code: MC

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

Effective date: 20091130

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

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

Ref country code: LI

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

Effective date: 20091130

Ref country code: CH

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

Effective date: 20091130

Ref country code: BE

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

Effective date: 20091130

Ref country code: GR

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

Effective date: 20090526

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

Ref country code: AT

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

Effective date: 20091119

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

Ref country code: FR

Payment date: 20101209

Year of fee payment: 7

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

Ref country code: DE

Payment date: 20101201

Year of fee payment: 7

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

Ref country code: IT

Payment date: 20101120

Year of fee payment: 7

Ref country code: GB

Payment date: 20101213

Year of fee payment: 7

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

Ref country code: LU

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

Effective date: 20091119

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

Ref country code: HU

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

Effective date: 20090826

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

Ref country code: ES

Payment date: 20101125

Year of fee payment: 7

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

Ref country code: TR

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

Effective date: 20090225

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

Ref country code: CY

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

Effective date: 20090225

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

Effective date: 20111119

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20120731

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

Ref country code: IT

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

Effective date: 20111119

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 502004009042

Country of ref document: DE

Effective date: 20120601

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

Ref country code: GB

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

Effective date: 20111119

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

Ref country code: FR

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

Effective date: 20111130

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20130603

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

Ref country code: DE

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

Effective date: 20120601

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

Ref country code: ES

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

Effective date: 20111120