EP2329959B1 - Matériel d'enregistrement sensible à la chaleur doté d'un revêtement de barrière - Google Patents

Matériel d'enregistrement sensible à la chaleur doté d'un revêtement de barrière Download PDF

Info

Publication number
EP2329959B1
EP2329959B1 EP20090177678 EP09177678A EP2329959B1 EP 2329959 B1 EP2329959 B1 EP 2329959B1 EP 20090177678 EP20090177678 EP 20090177678 EP 09177678 A EP09177678 A EP 09177678A EP 2329959 B1 EP2329959 B1 EP 2329959B1
Authority
EP
European Patent Office
Prior art keywords
heat
sensitive recording
recording material
recording layer
material according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Not-in-force
Application number
EP20090177678
Other languages
German (de)
English (en)
Other versions
EP2329959A1 (fr
Inventor
Ulf Behrens
Gerhard Dr. Stork
Svenja Eisernitz
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 EP20090177678 priority Critical patent/EP2329959B1/fr
Priority to ES09177678T priority patent/ES2394407T3/es
Priority to PCT/EP2010/063412 priority patent/WO2011067004A1/fr
Priority to US13/512,979 priority patent/US9050844B2/en
Publication of EP2329959A1 publication Critical patent/EP2329959A1/fr
Application granted granted Critical
Publication of EP2329959B1 publication Critical patent/EP2329959B1/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
    • B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
    • B41M5/42—Intermediate, backcoat, or covering layers
    • B41M5/44—Intermediate, backcoat, or covering layers characterised by the macromolecular compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
    • B41M5/323—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
    • B41M5/40—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
    • B41M5/41—Base layers supports or substrates
    • 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
    • B41M2205/38—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
    • B41M3/00—Printing processes to produce particular kinds of printed work, e.g. patterns
    • B41M3/10—Watermarks
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M3/00—Printing processes to produce particular kinds of printed work, e.g. patterns
    • B41M3/14—Security printing
    • 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
    • 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
    • B41M5/337—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
    • B41M5/42—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

Definitions

  • the invention relates to a heat-sensitive recording material having a substrate which carries on the front side at least one heat-sensitive recording layer, which in turn has at least one dye precursor and at least one color acceptor, which react color-forming with one another under the action of heat. Further, the heat-sensitive recording material has a barrier coating containing an ethylene-vinyl alcohol copolymer (EVOH) disposed between the substrate and the heat-sensitive recording layer, which is capable of preventing the thermosensitive recording layer from backward penetration of chemicals causing uncontrolled desensitization and color reactions the heat-sensitive recording layer can cause to protect.
  • EVOH ethylene-vinyl alcohol copolymer
  • thermosensitive recording material is the same EP 2 033 802 A1 according to which the recording material comprises a substrate, on the front side coated with a protective layer heat-sensitive recording layer is applied and the back has a backside coating, the backside coating comprises in addition to pigments and binders acting as a crosslinking component polyurethane-based.
  • thermosensitive recording materials have proven themselves on the market quite well and solve the problem of a plasticizers, oils and fats protective backing coating quite outstanding.
  • both documents give no indication as to how the heat-sensitive recording layer is to be protected against chemicals that can either cause an unwanted color-forming reaction in the recording layer or a weakening or erasure of a trained in the recording layer or typeface and the - even in larger Amounts - contained in the substrate and / or applied to the back of the substrate.
  • the achievement of this task was preceded by the time-consuming analysis of numerous defective productions, which made it necessary to put the formulation of the task also the usual basic process for the production of heat-sensitive recording materials to the test.
  • the heat-sensitive recording layer is to the substrate through the barrier layer containing ethylene-vinyl alcohol copolymer (EVOH) shielded, which represents a perfect and - very much - permanent protection against organic solvents. Even a long-term exposure of organic solvents from the direction of the substrate is able to keep the barrier coating containing ethylene-vinyl alcohol copolymer (EVOH) from the heat-sensitive recording layer.
  • EVOH ethylene-vinyl alcohol copolymer
  • the heat-sensitive recording material of the present invention is produced by the roll and then stored, the front and back sides of the recording material in the roll come into contact, respectively.
  • a protective layer covering the heat-sensitive recording layer, the heat-sensitive recording layer is also shielded to the outside of the next layer within a roll by the protective layer, which is also to be formed to provide good organic solvent protection.
  • the barrier coating of the heat-sensitive recording material according to the invention preferably comprises at least 90% by weight, most preferably at least 98% by weight, based in each case on the total weight of the barrier coating, of the ethylene-vinyl alcohol copolymer.
  • Further constituents of this barrier coating are, for example, defoamers and / or agents for stabilizing the color curtain in the case of a possible application of the coating composition for the barrier coating by means of curtain or slide coaters.
  • the coating weight for the barrier coating is preferably in a range from 0.9 to 5.0 g / m 2 , very particularly preferably in a range from 1.5 to 3.5 g / m 2 .
  • Particularly suitable coating compositions for the application of this barrier coating are, in particular, contactless application devices such as air brushes and curtain coater or slide coater, without being limited to these in any way.
  • thermosensitive recording layer is of integral importance to the present invention.
  • a protective layer based on very good results, which has at least 60 wt .-%, particularly preferably at least 85 wt .-% diacetone-modified polyvinyl alcohol as a binder, wherein the two values to the weight. % refer to the total amount of binder in the protective layer.
  • a protective layer constructed in this way is considered to be preferred in the context of the present invention.
  • the thus preferred protective layer of the heat-sensitive recording material according to the invention in addition to the diacetone-modified polyvinyl alcohol in a first possible embodiment, further binders, in particular mixtures of different carboxyl or silanol-modified polyvinyl alcohols have. These then make up a maximum of 40 wt .-%, more preferably only a maximum of 15 wt .-%, again, based on the total amount of binder in the protective layer.
  • the protective layer of the heat-sensitive recording material according to the invention has as binders exclusively diacetone-modified polyvinyl alcohol.
  • the binder content in the protective layer be in the range of 35 to 65% by weight based on the total weight of the protective layer.
  • Suitable crosslinking aids in the protective layer are, in particular, those selected from the group comprising: boric acid, polyamine, epoxy resin, dialdehyde, formaldehyde oligomers, epiochlorohydrin resin, adipic dihydrazide, dimethylurea, melamine-formaldehyde. It is also possible to use mixtures of different crosslinking aids.
  • the ratio of the weight% of the binder, especially the diacetone-modified polyvinyl alcohol, to the crosslinking aid is in a range of 20: 1 to 5: 1, and more preferably in a range of 12: 1 to 7 : 1 is.
  • the protective layer additionally contains an inorganic pigment.
  • the inorganic pigment is selected from the group comprising silica, aluminum hydroxide, bentonite, calcium carbonate, kaolin or a mixture of said inorganic pigments.
  • roller coater, knife coater, curtain coater or air brush are particularly suitable as coating devices for applying the protective layer covering the heat-sensitive recording layer.
  • the basis weight of the protective layer is preferably between 1.0 and 3.0 g / m 2 and more preferably between 1.6 and 2.3 g / m 2 .
  • the configuration of the heat-sensitive recording layer is less limited.
  • the recording layer may initially include all known dye precursors in principle, and combinations of several dye precursors are possible.
  • the heat-sensitive recording layer as color acceptor comprises at least 33% by weight, based on the total amount of color acceptors in the heat-sensitive recording layer, of N- (p-toluenesulphonyl ) -N'-3- (p-toluenesulphonyl-oxy-phenyl) -urea according to the following formula (1), wherein the two CH 3 end- molecules are also frequently omitted in the literature.
  • N- (p-toluensulphonyl) -N'-3- (p-toluensulphonyl-oxy-phenyl) -urea is known as Pergafast ® 201 from Ciba Specialty Chemicals Inc.
  • N- (p-toluenesulphonyl) -N'-3- (p-toluenesulphonyl-oxy-phenyl) urea is the sole color acceptor. Based on the total weight of the recording layer, the color acceptor then makes up to 32% by weight, but preferably in the range of 18 to 30% by weight and more preferably 20 to 28.5% by weight of the heat-sensitive recording layer ,
  • the recording layer of the heat-sensitive recording material of the present invention within this first embodiment may preferably also contain sensitizers to increase the thermal responsiveness.
  • sensitizers are on the one hand the substances listed in paragraph [0036];
  • 2- (2H-benzotriazol-2-yl) -p-cresol according to the following formula (2) is particularly preferred, although here too the CH 3 end molecule is frequently omitted from the literature:
  • 2- (2H-benzotriazol-2-yl) -p-cresol of formula (2) available as Tinuvin® from CIBA Specialty Chemicals Inc., may be used as the sole sensitizer or in combination with the sensitizers mentioned in paragraph [0036] in the recording layer of the recording material according to the invention are used.
  • the heat-sensitive recording layer as color acceptor is at least 66 2/3% by weight, based on the total amount of color acceptors in the heat-sensitive Recording Layer - 4,4'-Dihydroxydiphenylsulfone.
  • 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 C12H1004S and can be represented as the following formula (3):
  • the above color acceptors are preferably incorporated into this heat-sensitive recording layer to a maximum of 10% by weight, based on the total amount of color acceptors in the heat-sensitive recording layer, the remainder being 4,4'-dihydroxydiphenylsulfone.
  • 4,4'-dihydroxydiphenylsulfone is the sole color acceptor in the thermosensitive recording layer is considered to be most preferred.
  • thermosensitive recording material preferably has as the dye precursor in the thermosensitive recording layer at least one substance selected from the list comprising: 3-diethylamino-6-methyl-7-anilinofluoran, 3-dibutylamino-6-methyl-7-anilinofluoran, 3- (N -methyl-N-propyl) amino-6-methyl-7-anilinofluoran, 3- (N-ethyl-N-isoamyl) amino-6-methyl- 7-anilinofluoran, 3- (N -methyl-N-cyclohexyl) amino-6-methyl-7-anilinofluoran, 3- (N-ethyl) -N-tolyl) amino-6-methyl-7-anilinofluoran and 3- N-ethyl-N-tetrahydrofuryl) amino-6-methyl-7-anilinofluoran.
  • ODB 3-dibutylamino-6-methyl-7-anilinofluoran
  • thermosensitive recording layer has more than one dye precursor each selected from the dye precursors listed in the above paragraph.
  • the recording material according to the invention may, in addition to these substances given as dye precursors, also contain one or more of the following compounds absorbing in the near infrared range:
  • the recording layer of the heat-sensitive recording material of the present invention may also preferably contain sensitisers having a melting point of preferably from 60 ° C to 180 ° C, more preferably having a melting point of from 80 ° C to 140 ° C, to increase the thermal responsiveness.
  • Such sensitizers are, for example: benzyl p-benzyloxybenzoate, methylolstearamide, stearic acid amide, p-benzylbiphenyl, 1,2-di (phenoxy) ethane, 1,2-di (m-methylphenoxy) ethane, m-terphenyl, dibenzyl oxalate, Benzylnaphthylether, dimethyl terephthalate and diphenylsulfone, with methylolstearamide, and in particular stearic acid amide and dimethyl terephthalate are considered to be very preferred.
  • Suitable binders for incorporation into the heat-sensitive recording layer are, for example, water-soluble binders such as starch, hydroxyethylcellulose, methylcellulose, carboxymethylcellulose, gelatin, casein, polyvinyl alcohols, modified polyvinyl alcohols, ethylene-vinyl alcohol copolymers, sodium polyacrylates, acrylamide-acrylate copolymers, acrylamide-acrylate-methacrylate Terpolymers and alkali salts of styrene-maleic anhydride copolymer or ethylene-maleic anhydride copolymer, which binders can be used alone or in combination with one another; Water-insoluble latex binders such as styrene-butadiene copolymers, acrylonitrile-butadiene copolymers and methyl acrylate-butadiene copolymers are also suitable as binders for incorporation into the heat-sensitive recording layer.
  • water-soluble binders such as starch, hydroxye
  • polyvinyl alcohol ethylene-vinyl alcohol copolymers or polyvinyl alcohol in conjunction with ethylene-vinyl alcohol copolymers as particularly preferred binders which together, based on the total weight of the recording layer, in a range of 10 to 20 wt .-% in the heat-sensitive recording layer is incorporated.
  • the coating composition for forming the heat-sensitive recording layer may further contain lubricants and release agents such as metal salts higher fatty acids, for example, zinc stearate, calcium stearate, and waxes, such as paraffin, oxidized paraffin, polyethylene, polyethylene oxide, stearamides, and castor wax.
  • lubricants and release agents such as metal salts higher fatty acids, for example, zinc stearate, calcium stearate, and waxes, such as paraffin, oxidized paraffin, polyethylene, polyethylene oxide, stearamides, and castor wax.
  • pigments preferably inorganic pigments such as, for example, aluminum (hydr) oxide, silica and calcium carbonate, in which case in particular Calcium carbonate, which is preferably incorporated in the recording layer in an amount of 0 to 28% by weight, based on the total weight of the recording layer, is preferred.
  • inorganic pigments such as, for example, aluminum (hydr) oxide, silica and calcium carbonate, in which case in particular Calcium carbonate, which is preferably incorporated in the recording layer in an amount of 0 to 28% by weight, based on the total weight of the recording layer, is preferred.
  • the heat-sensitive recording layer - offer in particular roller blade coater, knife coater, curtain coater or air brush.
  • the coating composition used to form the recording layer is aqueous.
  • the subsequent drying of the coating composition is usually done by a method in which heat is supplied, as is done by hot-air floating dryer or contact dryer. Proven is also a combination of the listed dry processes.
  • the basis weight of the heat-sensitive recording layer is preferably from 2 to 6 g / m 2, and more preferably from 2.2 to 4.8 g / m 2 .
  • the heat-sensitive recording material according to the invention comprises a pigment-containing intermediate layer, which is arranged between the barrier coating and the heat-sensitive recording layer.
  • Suitable pigments of the intermediate layer are both organic void pigments and inorganic pigments, the latter preferably selected from the group comprising natural and calcined kaolin, silica and in particular bentonite, calcium carbonate and aluminum hydroxide and here especially boehmite.
  • organic void pigments and inorganic pigments the latter preferably selected from the group comprising natural and calcined kaolin, silica and in particular bentonite, calcium carbonate and aluminum hydroxide and here especially boehmite.
  • such an intermediate layer can make a positive contribution to the leveling of the surface to be coated, which reduces the amount of coating color necessarily to be applied for the heat-sensitive recording layer. For this reason, offer to coat the pigment-containing intermediate layer leveling coating, such as Walzenstreichwerke, doctor blade and (roll) doctor blade coating.
  • the pigments of this intermediate layer can absorb the liquefied by heat wax components of the heat-sensitive recording layer in the typeface training and thus favor a safe and rapid operation of the heat-induced on drawing.
  • the basis weight of the pigment-containing intermediate layer is preferably between 5 and 20 g / m 2 and more preferably between 7 and 11 g / m 2 .
  • paper is the substrate that has prevailed on the market with regard to the good environmental compatibility because of good recyclability and is preferred in the context of the invention.
  • the barrier coating between the substrate and heat-sensitive recording layer it is also possible to use those substrates which, due to their ingredients and their negative influence on the heat-sensitive recording layer, would rather be forbidden, for example films or films coated with films in which the respective films contain larger amounts of plasticizers, or even papers from recycled fibers of the lowest quality.
  • the proposed heat-sensitive recording material has a coating of a tincture applied to the substrate in the form of at least one character or in the form of a pattern, the tincture comprising at least one organic solvent. It is also possible that the tincture comprises a mixture of several organic solvents. In a preferred embodiment, the tincture also contains other constituents, such as, for example, fluorescent fibers and / or pigments.
  • Applying the tincture with at least one organic solvent to the substrate formed to form the paper authentication feature causes the opacity of the substrate to change at the sites wetted with the tincture relative to the non-wetted areas of the substrate. If one keeps the thus treated, here proposed heat-sensitive recording material against a light source, makes the change in transparency in the review sharp-edged as easily recognizable image or pattern.
  • analog printing methods such as, for example, the flexographic and gravure printing methods
  • the tincture is applied by means of digital printing methods. If the order of tincture digital printing technology, which is considered preferable and what is given, inter alia, in the inkjet printing process, the formation of an individual authentication feature per single section of the heat-sensitive recording material proposed here. If the heat-sensitive recording material proposed here is used as a ticket and / or in particular as an admission ticket, each individual ticket can be provided with an individual authentication feature.
  • the heat-sensitive recording material proposed here as a ticket, very particularly preferably as an admission ticket.
  • a paper web of bleached and ground deciduous and softwood pulps with a basis weight of 130 g / m 2 with the addition of conventional additives in conventional amounts is first prepared on a fourdrinier paper machine as a substrate. From the paper web 3 sample rolls are cut for further treatment.
  • the coating material used for the heat-sensitive recording layer essentially contains the following components: Dye precursors: 3-dibutylamino-6-methyl-7 anilinofluoran, that is ODB-2; color acceptor: N- (p-toluenesulphonyl) -N'-3- (p-toluenesulphonyl-oxy-phenyl) urea, that is Pergafast® 201; sensitizer: Benzylnaphthyl ether, that is BNE; Binder: polyvinyl alcohol; co-binders: Acrylate copolymer; Pigment: Calcium carbonate.
  • a protective layer of 2.0 g / m 2 is applied to the heat-sensitive recording layer by means of air brushing in each case for all 3 pattern rolls.
  • a coating composition which essentially contains the following components: Binder: Diacetone-modified polyvinyl alcohol; 61.3% by weight (atro) crosslinkers: adipic; 6.0% by weight (atro) Pigment: Kaolin; 16.6% by weight (atro) Lubricant: Hidorin Z-7-30; 8.1% by weight (atro) aids: pH regulator, optical brightener; 8.0% by weight (atro)
  • the desired barrier effect of the barrier layer against organic solvents should then be investigated.
  • 0.5 ml of ethanol is applied to the respective reverse side of test strips from the 3 sample rolls corresponding to Example 1 according to the invention and the two comparative examples 2 and 3 using a pipette. After a respective exposure time of 10 minutes, the ethanol is completely absorbed. The effect of the solvent application on the heat-sensitive recording layer is visually evaluated.
  • the heat-sensitive recording layer of Inventive Example 1 shows no thermal reactions at all, the present invention is excellently confirmed in terms of quality.
  • Comparative Example 2 shows an intense thermoreactions, this barrier coating is not at all suitable to develop a far-reaching protective effect against organic solvents from the direction of the substrate over a longer exposure time.
  • Comparative Example 3 there are scattered color reaction points on the heat-sensitive recording layer: below these colored dots, the barrier coating of the coating composition BS3 has cracks and voids due to the too high viscosity of the silanized polyvinyl alcohol. Again, the barrier effect against organic solvents is not convincing, because not without flaws.
  • thermosensitive recording material finally expected by the inventors.

Landscapes

  • 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 (15)

  1. Matériau d'enregistrement thermosensible, comportant au moins :
    - un substrat,
    - une couche d'enregistrement thermosensible agencée sur la face avant du substrat avec au moins un précurseur de colorant et au moins un accepteur de couleur, dans lequel le précurseur de colorant et l'accepteur de couleur réagissent l'un avec l'autre sous l'effet de la chaleur pour former une couleur,
    - un revêtement de barrière agencé entre le substrat et la couche d'enregistrement thermosensible et contenant un copolymère éthylène-alcool vinylique (EVOH), approprié pour la protection de la couche d'enregistrement thermosensible contre une pénétration de produits chimiques provoquant des réactions de désensibilisation et de coloration non contrôlées dans la couche d'enregistrement thermosensible,
    - ainsi qu'une couche intermédiaire contenant un pigment, qui est agencée entre le revêtement de barrière et la couche d'enregistrement thermosensible,
    caractérisé en ce que
    - la couche d'enregistrement thermosensible est recouverte d'une couche de protection, qui présente, comme liant, au moins 60 % en poids, par rapport à la proportion totale de liant dans la couche de protection, d'un poly(alcool de vinyle) modifié à la diacétone.
  2. Matériau d'enregistrement thermosensible selon la revendication 1, caractérisé en ce que le revêtement de barrière contient au moins 90 % en poids, par rapport au poids total du revêtement de barrière, du copolymère éthylène-alcool vinylique (EVOH).
  3. Matériau d'enregistrement thermosensible selon la revendication 1, caractérisé en ce que le revêtement de barrière contient au moins 98 % en poids, par
    rapport au poids total du revêtement de barrière, du copolymère éthylène-alcool vinylique (EVOH).
  4. Matériau d'enregistrement thermosensible selon l'une quelconque des revendications 1 à 3, caractérisé en ce que la couche de protection présente, comme liant, exclusivement un poly(alcool de vinyle) modifié à la diacétone.
  5. Matériau d'enregistrement thermosensible selon l'une quelconque des revendications 1 à 4, caractérisé en ce que la couche de protection contient un adjuvant de réticulation, choisi dans le groupe comprenant l'acide borique, une polyamine, une résine époxy, un dialdéhyde, des oligomères de formaldéhyde, une résine épichlorohydrine, un dihydrazide d'acide adipique, la diméthylurée et un mélamineformaldéhyde.
  6. Matériau d'enregistrement thermosensible selon la revendication 5, caractérisé en ce que le rapport exprimé en % en poids du poly(alcool de vinyle) modifié à la diacétone sur l'adjuvant de réticulation se situe dans une plage de 20:1 à 5:1 et particulièrement de préférence dans une plage de 12:1 à 7:1.
  7. Matériau d'enregistrement thermosensible selon l'une quelconque des revendications 1 à 6, caractérisé en ce que la couche de protection contient un pigment inorganique, de préférence choisi dans la liste comprenant le dioxyde de silicium, l'hydroxyde d'aluminium, la bentonite, le carbonate de calcium, le kaolin ou un mélange des pigments inorganiques cités.
  8. Matériau d'enregistrement thermosensible selon l'une quelconque des revendications 1 à 7, caractérisé en ce que la couche d'enregistrement thermosensible contient, comme accepteur de couleur, au moins une substance choisie dans la liste comprenant :
    - le 2,2 bis-(4-hydroxyphényl)-propane,
    - le 4-[(4-(1-méthyléthoxy)phényl)sulfonyl]phénol,
    - la 4,4'-dihydroxydiphénylsulfone,
    - la N-(p-toluènesulfonyl)-N'-(3-p-toluènesulfonyl-oxy-phényl)-urée,
    - la 2,4'-dihydroxy-diphénylsulfone,
    - le N-(2-hydroxyphényl)-2-[(4-hydroxyphényl)thio]acétamide.
  9. Matériau d'enregistrement thermosensible selon l'une quelconque des revendications 1 à 7, caractérisé en ce que la couche d'enregistrement thermosensible comporte de la 4,4'-dihydroxydiphénylsulfone comme seul accepteur de couleur.
  10. Matériau d'enregistrement thermosensible selon l'une quelconque des revendications 1 à 7, caractérisé en ce que la couche d'enregistrement thermosensible comporte la N-(p-toluènesulfonyl)-N'-3-(p-toluènesulfonyl-oxy-phényl)-urée comme seul accepteur de couleur.
  11. Matériau d'enregistrement thermosensible selon l'une quelconque des revendications 1 à 10, caractérisé en ce que la couche d'enregistrement thermosensible présente, comme précurseur de colorant, au moins une substance qui est choisie dans la liste comprenant le 3-diéthylamino-6-méthyl-7-anilinofluorane,
    le 3-dibutylamino-6-méthyl-7-anilinofluorane,
    le 3-(N-méthyl-N-propyl)amino-6-méthyl-7-anilinofluorane,
    le 3-(N-éthyl-N-isoamyl)amino-6-méthyl-7-anilinofluorane,
    le 3-(N-méthyl-N-cyclohéxyl)amino-6-méthyl-7-anilinofluorane,
    le 3-(N-éthyl-N-tolyl)amino-6-méthyl-7-anilinofluorane et le 3-(N-éthyl-N-tétrahydrofuryl)amino-6-méthyl-7-anilinofluorane.
  12. Matériau d'enregistrement thermosensible selon l'une quelconque des revendications 1 à 11, caractérisé en ce que la couche d'enregistrement thermosensible présente au moins un sensibilisateur choisi dans la liste comprenant le méthylolstéaramide, l'amide d'acide stéarique et le téréphtalate de diméthyle.
  13. Matériau d'enregistrement thermosensible selon la revendication 9, caractérisé en ce qu'un rapport 4,4'-dihydroxydiphénylsulfone: sensibilisateur à l'intérieur de la couche d'enregistrement, exprimé en % en poids, se situe dans une plage de 1:0,5 à 1:2, le sensibilisateur étant choisi dans la liste comprenant le méthylolstéaramide, l'amide d'acide stéarique et le téréphtalate de diméthyle.
  14. Matériau d'enregistrement thermosensible selon l'une quelconque des revendications 1 à 13, caractérisé en ce que la couche d'enregistrement thermosensible contient, comme liant, une substance choisie dans la liste comprenant le poly(alcool de vinyle), un copolymère éthylène-alcool vinylique ou une combinaison de poly(alcool de vinyle) et d'un copolymère éthylène-alcool vinylique.
  15. Matériau d'enregistrement thermosensible selon l'une quelconque des revendications 1 à 14, caractérisé en ce que le matériau d'enregistrement présente une caractéristique d'authentification, dans lequel la caractéristique d'authentification se présente sous la forme d'une application sur la face arrière du substrat d'une teinture comprenant au moins un solvant organique.
EP20090177678 2009-12-01 2009-12-01 Matériel d'enregistrement sensible à la chaleur doté d'un revêtement de barrière Not-in-force EP2329959B1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP20090177678 EP2329959B1 (fr) 2009-12-01 2009-12-01 Matériel d'enregistrement sensible à la chaleur doté d'un revêtement de barrière
ES09177678T ES2394407T3 (es) 2009-12-01 2009-12-01 Material de registro termosensible con revestimiento de barrera
PCT/EP2010/063412 WO2011067004A1 (fr) 2009-12-01 2010-09-13 Matière d'enregistrement thermosensible comprenant un revêtement barrière
US13/512,979 US9050844B2 (en) 2009-12-01 2010-09-13 Heat-sensitive recording material with barrier coating

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP20090177678 EP2329959B1 (fr) 2009-12-01 2009-12-01 Matériel d'enregistrement sensible à la chaleur doté d'un revêtement de barrière

Publications (2)

Publication Number Publication Date
EP2329959A1 EP2329959A1 (fr) 2011-06-08
EP2329959B1 true EP2329959B1 (fr) 2012-08-29

Family

ID=42173647

Family Applications (1)

Application Number Title Priority Date Filing Date
EP20090177678 Not-in-force EP2329959B1 (fr) 2009-12-01 2009-12-01 Matériel d'enregistrement sensible à la chaleur doté d'un revêtement de barrière

Country Status (4)

Country Link
US (1) US9050844B2 (fr)
EP (1) EP2329959B1 (fr)
ES (1) ES2394407T3 (fr)
WO (1) WO2011067004A1 (fr)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102015014036A1 (de) * 2015-10-30 2017-05-04 Giesecke & Devrient Gmbh Sicherheitselement
US10653135B2 (en) * 2016-07-11 2020-05-19 Covestro Llc Methods for treating seeds with an aqueous composition and seeds treated therewith
US10653136B2 (en) * 2016-07-11 2020-05-19 Covestro Llc Aqueous compositions for treating seeds, seeds treated therewith, and methods for treating seeds
EP3625058A2 (fr) * 2017-05-19 2020-03-25 Mitsubishi HiTec Paper Europe GmbH Composition de revêtement pour fabriquer un composite stratifié
JP6865656B2 (ja) * 2017-08-31 2021-04-28 三光株式会社 感熱記録材料
DE102018101109A1 (de) * 2018-01-18 2019-07-18 Mitsubishi Hitec Paper Europe Gmbh Wärmeempfindliches Aufzeichnungsmaterial umfassend eine Mehrzahl von Submikrometerpartikeln mit monomodaler Partikelgrößenverteilung
CN111778773A (zh) * 2020-05-26 2020-10-16 湖南天琪智慧印刷有限公司 具有高保留率和防乙醇性能的热敏纸及其制作方法

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3501430B2 (ja) 1994-09-29 2004-03-02 株式会社リコー 可逆的熱発色性組成物及びそれを用いた記録媒体
JPH1024657A (ja) 1996-05-10 1998-01-27 Mitsubishi Paper Mills Ltd 感熱記録材料およびその製造方法
EP0844097B1 (fr) 1996-11-21 2001-07-18 Ncr International Inc. Papier thermique avec des caractéristiques de sécurité et encre de sécurité à cet effet
ATE197574T1 (de) 1997-09-12 2000-12-15 Mitsubishi Hitec Paper Flensbu Wärmeempfindlicher aufzeichnungsbogen mit einer rückseitenbeschichtung die stärke, ein acrylatcopolymer und einen alkalischen katalysator enthält
EP0933228B1 (fr) * 1998-02-02 2003-06-25 Ncr International Inc. Matériau d'enregistrement thermosensible
JPH11286174A (ja) 1998-04-02 1999-10-19 Fuji Photo Film Co Ltd 感熱記録材料
DE19842866A1 (de) * 1998-09-19 2000-03-30 Stora Spezialpapiere Gmbh Wärmeempfindliches Aufzeichnungsmaterial mit Sicherheitsmerkmal
FR2828897B1 (fr) * 2001-08-21 2004-01-23 Danel Article d'imprimerie filigrane, en particulier pour imprimante thermique
ES2265300B1 (es) 2006-07-17 2008-02-01 Antonio Oliva Gurgui "derivados de poliuretanos y usos correspondientes y procedimientos de fabricacion de marcas al agua".
ES2294965B1 (es) 2007-05-07 2009-04-16 Antonio Oliva Gurgui "derivados de uretanos y oligouretanos y usos correspondientes y procedimientos de fabricacion de marcas al agua mediante la tecnica de impresion offset".
PL2033802T3 (pl) 2007-09-10 2010-08-31 Mitsubishi Hitec Paper Europe Gmbh Wrażliwy na ciepło materiał do zapisu wyposażony w powłokę od tylnej strony

Also Published As

Publication number Publication date
US20140274681A1 (en) 2014-09-18
WO2011067004A1 (fr) 2011-06-09
ES2394407T3 (es) 2013-01-31
EP2329959A1 (fr) 2011-06-08
US9050844B2 (en) 2015-06-09

Similar Documents

Publication Publication Date Title
EP2329959B1 (fr) Matériel d'enregistrement sensible à la chaleur doté d'un revêtement de barrière
EP2033799B1 (fr) Matériel d'enregistrement sensible à la chaleur
EP2574645B1 (fr) Accepteur de couleur réagissant en formant des couleurs avec un précurseur de colorant et matériau d'enregistrement sensible à la chaleur doté d'un tel accepteur de couleur
EP3305538A1 (fr) Matériel d'enregistrement sensible à la chaleur
EP2910384B1 (fr) Matériel d'enregistrement thermosensible doté d'une combinaison d'absorbeurs de couleur d'un nouveau type
EP2279877B1 (fr) Matériau pour l'enregistrement par la chaleur
EP2979888B1 (fr) Matériel d'enregistrement sensible à la chaleur ayant un dérivé d'acide salicylique comme développeur (de couleur) pouvant réagir à un précurseur de colorant
EP2953797B1 (fr) Matériau d'enregistrement thermosensible
DE60032686T2 (de) Wärmeempfindliches aufzeichnungsmaterial
EP2329955B1 (fr) Matériel d'enregistrement sensible à la chaleur doté d'une marque d'authenticité
EP2112000B1 (fr) Matériel d'enregistrement sensible à la chaleur
EP2033802B1 (fr) Matériel d'enregistrement sensible à la chaleur doté d'un revêtement de face arrière
DE202020005616U1 (de) Wärmeempfindliches Aufzeichnungsmaterial, umfassend phenolfreie organische Farbentwickler
EP2329958B1 (fr) Matériel d'enregistrement sensible à la chaleur doté d'un revêtement de face arrière
DE102005050418A1 (de) Wärmeempfindliches Aufzeichnungsmaterial
EP2070714B1 (fr) Procédé de fabrication d'un matériel d'enregistrement sensible à la chaleur
EP2765007A1 (fr) Matériel d'enregistrement sensible à la chaleur
DE102006050420B3 (de) Wärmeempfindliches Aufzeichnungsmaterial
EP2758249B1 (fr) Matériau d'enregistrement destiné à une impression offset
EP2033800B1 (fr) Matériel d'enregistrement sensible à la chaleur
EP2480415B1 (fr) Matériau d'enregistrement thermosensible pourvu d'un revêtement au verso
EP2414173B1 (fr) Matériau d'enregistrement thermosensible
EP2505374A1 (fr) Matériel d'enregistrement sensible à la chaleur, son utilisation et son procédé de fabrication
DE102006056003A1 (de) Wärmeempfindliches Aufzeichnungsmaterial mit Authentifikationsmerkmal
EP1813436A2 (fr) Matériau thermosensible pour l'enregistrement comprenant un dispositif d'authentification

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

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO SE SI SK SM TR

AX Request for extension of the european patent

Extension state: AL BA RS

17P Request for examination filed

Effective date: 20111208

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: MITSUBISHI HITEC PAPER EUROPE GMBH

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 HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO SE SI SK SM 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: AT

Ref legal event code: REF

Ref document number: 572850

Country of ref document: AT

Kind code of ref document: T

Effective date: 20120915

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: GERMAN

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 502009004526

Country of ref document: DE

Effective date: 20121025

REG Reference to a national code

Ref country code: NL

Ref legal event code: T3

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

Effective date: 20120829

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

Ref country code: HR

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: 20120829

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: 20120829

Ref country code: NO

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: 20121129

Ref country code: LT

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: 20120829

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: 20121229

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2394407

Country of ref document: ES

Kind code of ref document: T3

Effective date: 20130131

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

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: 20121231

Ref country code: LV

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: 20120829

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: 20120829

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: 20121130

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: 20120829

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

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: 20120829

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: 20120829

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: 20120829

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: 20120829

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: 20120829

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: 20120829

BERE Be: lapsed

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

Effective date: 20121231

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: 20121129

Ref country code: MC

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

Effective date: 20121231

26N No opposition filed

Effective date: 20130530

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 502009004526

Country of ref document: DE

Effective date: 20130530

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

Ref country code: BE

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

Effective date: 20121231

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

Ref country code: IE

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

Effective date: 20121201

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

Ref country code: MT

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: 20120829

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: 20120829

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: 20120829

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: 20121201

Ref country code: SM

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: 20120829

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: 20091201

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: 20131231

Ref country code: CH

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

Effective date: 20131231

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

Ref country code: MK

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: 20120829

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 7

REG Reference to a national code

Ref country code: AT

Ref legal event code: MM01

Ref document number: 572850

Country of ref document: AT

Kind code of ref document: T

Effective date: 20141201

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: 20141201

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 8

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 9

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

Ref country code: GB

Payment date: 20201227

Year of fee payment: 12

Ref country code: FR

Payment date: 20201228

Year of fee payment: 12

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

Ref country code: NL

Payment date: 20201223

Year of fee payment: 12

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

Ref country code: IT

Payment date: 20201231

Year of fee payment: 12

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

Ref country code: DE

Payment date: 20201224

Year of fee payment: 12

Ref country code: ES

Payment date: 20210108

Year of fee payment: 12

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 502009004526

Country of ref document: DE

REG Reference to a national code

Ref country code: NL

Ref legal event code: MM

Effective date: 20220101

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

Effective date: 20211201

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

Ref country code: NL

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

Effective date: 20220101

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: 20211201

Ref country code: DE

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

Effective date: 20220701

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: 20211231

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: 20211201

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20230302

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: 20211202