EP2329955B1 - Matériel d'enregistrement sensible à la chaleur doté d'une marque d'authenticité - Google Patents

Matériel d'enregistrement sensible à la chaleur doté d'une marque d'authenticité Download PDF

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Publication number
EP2329955B1
EP2329955B1 EP20090177679 EP09177679A EP2329955B1 EP 2329955 B1 EP2329955 B1 EP 2329955B1 EP 20090177679 EP20090177679 EP 20090177679 EP 09177679 A EP09177679 A EP 09177679A EP 2329955 B1 EP2329955 B1 EP 2329955B1
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EP
European Patent Office
Prior art keywords
heat
sensitive recording
recording material
material according
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.)
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Application number
EP20090177679
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German (de)
English (en)
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EP2329955A1 (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 EP20090177679 priority Critical patent/EP2329955B1/fr
Priority to ES09177679T priority patent/ES2391928T3/es
Priority to US13/512,985 priority patent/US8859460B2/en
Priority to PCT/EP2010/068494 priority patent/WO2011067239A1/fr
Publication of EP2329955A1 publication Critical patent/EP2329955A1/fr
Application granted granted Critical
Publication of EP2329955B1 publication Critical patent/EP2329955B1/fr
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Classifications

    • 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
    • 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
    • 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
    • B41M5/333—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
    • B41M5/3372—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
    • B41M5/42—Intermediate, backcoat, or covering layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • 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 invention relates to a heat-sensitive recording material with a paper substrate which carries at least one heat-sensitive recording layer on the front, which in turn has at least one dye precursor and at least one color acceptor which react with each other in a color-forming manner under the action of heat.
  • the proposed thermosensitive recording material carries an authenticity-proofing security feature by means of which the authenticity of a present recording material can be detected.
  • Recording materials determine daily life in society and in professional life. For the use of recording materials, the authorized use of which is generally to be demonstrated by a specific marking of the material approved for this purpose, various solutions of authenticity-proofing security features have already been proposed in the past.
  • a watermark is generally understood to mean a drawing in the paper, which is caused by different paper thickness.
  • a distinction is made between genuine watermarks which are produced by displacement (so-called light watermarks) or by enrichment (so-called shadow watermarks) of the fiber mass, for example using a dandy cutter in the wire section of a paper machine Embossing of the still wet paper in the press section of a paper machine are generated, and finally spurious watermarks, the latter being created either by printing the finished paper outside the paper machine with a colorless paint or by embossing the finished paper outside the paper machine.
  • a synthetic print carrier with pseudo watermark comprises a plastic substrate, at least one, preferably by means of gravure applied, the opacity of the print carrier changing authentication or security mark and at least one character covering printable pigment coating.
  • the monochrome or polychrome character should hardly be visible in reflected light, but should be clearly visible in transmitted light.
  • the fundamental drawback that the printed pseudo watermark can be forged relatively easily, which can not be prevented even by applying it to simple pigment coatings.
  • heat-sensitive recording materials having authenticity-proofing security features in the form of watermarks are also known. So revealed the EP 0 844 097 A 1 for a heat-sensitive recording material as a first security feature in the form of a spurious watermark, a latent image printed on the back of the recording material, which is prepared by means of a security ink containing a fluorescent reagent. To form a second security feature in the form of a watertight image on the backside of the thermosensitive recording material, the security ink contains a water-repellent agent. The fluorescent ink containing the fluorescent reagent and the water repellent-containing security ink is contained or dispersed in an aqueous vehicle which may contain a binder other than these components.
  • the application of the tincture with the at least one organic solvent to the substrate for forming the authentication feature of paper causes a change in the opacity or the transparency of the paper substrate at the places wetted with the tincture in comparison 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. It is also possible that the tincture comprises a mixture of several organic solvents. In a likewise claimed embodiment, the tincture contains, in addition to the at least one organic solvent, further constituents, such as, for example, fluorescent fibers and / or pigments.
  • analogue printing methods such as, for example, the flexo printing and gravure printing methods
  • the tincture is applied by digital printing techniques.
  • the order of the tincture is digital printing technology, among other things, the inkjet printing method is particularly effective, which is also very particularly preferred, because the formation of an individual authentication feature per single sheet or single section of the proposed here heat-sensitive recording material is made possible.
  • 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.
  • a ticket for a soccer game organizer, venue, event time, soccer teams opposing each other, place of sale and time of sale of the ticket and perhaps a continuous check digit may be formed as an individual authentication feature on the heat-sensitive recording material proposed herein.
  • the falsification of such an authentication feature is difficult and absolutely hopeless with appropriate control at the venue.
  • the authenticity-proofing security feature of which is a mark on the substrate made of a tincture having at least one organic solvent formed individually per single section, a ticket material is made available to the public which serves as an entry ticket can no longer be falsified successfully: the proof of the forgery attempt is immediately possible by the particularly simple identification of the individual security feature.
  • the barrier coating as binder has at least 60% by weight, more preferably at least 85% by weight % Diacetone-modified polyvinyl alcohol, the values being in terms of weight percent based on the total binder content in the barrier coating.
  • the barrier coating may comprise further binders, in particular mixtures of various fully or partially hydrolyzed polyvinyl alcohols, carboxyl group- or silanol-modified polyvinyl alcohols, and film-forming acrylic copolymers. 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 barrier coating.
  • the barrier coating of the heat-sensitive recording material according to the invention has as binders exclusively diacetone-modified polyvinyl alcohol.
  • Suitable crosslinking aids in the barrier coating according to the first embodiment 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 percent 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 barrier coating contains ethylene-vinyl alcohol copolymer (EVOH).
  • EVOH ethylene-vinyl alcohol copolymer
  • the barrier coating preferably comprises at least 90% by weight, very particularly 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 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.
  • the configuration of the heat-sensitive recording layer is little 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 material as the dye precursor in the heat-sensitive recording layer preferably has at least one A 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.
  • a substance selected from the list comprising: 3-diethylamino-6-methyl-7-anilinofluoran
  • the recording material of the present invention may further contain, in addition to these substances as the dye precursor, one or more of the following near infrared absorbing compounds:
  • the heat-sensitive recording layer as color acceptor comprises at least 331/3 wt%, based on the total amount of color acceptors in the heat-sensitive recording layer, N- (p toluene-sulphonyl) -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 [0034];
  • 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 [0034] 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 C12H10O4S 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.
  • 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; also water-insoluble latex binders such as styrene-butadiene copolymers, Acrylonitrile-butadiene copolymers and methyl acrylate-butadiene copolymers are useful 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 combination with ethylene-vinyl alcohol copolymers are particularly preferred binders which together in a range from 10 to 20% by weight, based on the total weight of the recording layer the heat-sensitive recording layer is incorporated.
  • the coating composition for forming the heat-sensitive recording layer may further contain slip 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.
  • slip 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, silicic acid and calcium carbonate, in which case in particular calcium carbonate, preferably in an amount of from 0 to 28% by weight, based on the total weight of the recording layer, should be included in the recording layer, as is preferred.
  • inorganic pigments such as, for example, aluminum (hydr) oxide, silicic acid and calcium carbonate, in which case in particular calcium carbonate, preferably in an amount of from 0 to 28% by weight, based on the total weight of the recording layer, should be included in the recording layer, as 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 heat-liquefied wax constituents of the thermosensitive recording layer in the typeface formation and thus promote a safe and rapid operation of the heat-induced recording.
  • the basis weight of the pigment-containing intermediate layer is preferably between 5 and 20 g / m 2 and more preferably between 7 and 11 g / m 2 .
  • the heat-sensitive recording layer is shielded toward the substrate through the barrier coating which is to provide perfect and durable protection against organic solvents ,
  • thermosensitive recording material When the tincture having the at least one organic solvent for forming a mark as an authenticity-proofing security feature is applied to the back surface of the substrate early in the production of the proposed thermosensitive recording material, it is to be noted that in production and subsequent storage in roll form, respectively front and back sides of the substrate Recording material in the role come into contact.
  • a protective layer covering the heat-sensitive recording layer By arranging a protective layer covering the heat-sensitive recording layer, the heat-sensitive recording layer can also be exposed to the outside Substrate of the next layer within a role are shielded by such a protective layer. For this reason, the formation of a protective layer covering the heat-sensitive recording layer is preferred, which is to be formed to provide good protection against organic solvents.
  • a protective layer which is the same as the barrier coating based on ethylene-vinyl alcohol copolymer (EVOH) is prepared and then preferably at least 90 wt .-%, most preferably at least 98 wt .-% - in each case based
  • modified polyvinyl alcohol wherein the two values relate to the wt .-% on the total content 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 protective layer of the heat-sensitive recording material according to the invention may comprise, in addition to the diacetone-modified polyvinyl alcohol in a first possible embodiment, further binders, in particular mixtures of different carboxyl-group- or silanol-modified polyvinyl alcohols. 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 is in a 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.
  • 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 .
  • 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.
  • Example 1 to 3 the three coating compositions are now applied on the front side to the respective substrate of the 3 pattern rolls having a respective basis weight of 2.8 g / m 2 (for Examples 1 and 2 ) and 2.0 g / m 2 ( for example 3) .
  • 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-toluensulphonyl) -N'-3- (p-toluensulphonyl-oxy-phenyl) -urea, this 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)
  • a tincture with ethanol is then applied by means of a stamp with ethanol as a main component to form a mark as an authenticity-proofing security feature.
  • the effect of the tincture 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, and an ethylene-vinyl alcohol copolymer (EVOH) -based barrier coating is excellently confirmed in terms of quality.
  • EVOH ethylene-vinyl alcohol copolymer
  • this barrier coating is still suitable to develop a sufficient protective effect against organic solvents from the direction of the substrate, as long as the amount and time of exposure of the solvent are deliberately kept very low.
  • the smaller amount of coating applied is sufficient with the silanized polyvinyl alcohol in order to develop a sufficient protective action against organic solvents from the direction of the substrate. Again, the amount and time of exposure of the solvent should not be too large.
  • thermosensitive recording material finally expected by the inventors.

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

Claims (18)

  1. Matériau d'enregistrement thermosensible, présentant au moins :
    ° un substrat de papier,
    ° 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, formant ainsi une couleur,
    ° une caractéristique de sécurité prouvant l'authenticité,
    caractérisé en ce que
    ■ la caractéristique de sécurité justifiant l'authenticité est un marquage appliqué sur la face arrière du substrat de papier et constitué d'une teinture avec au moins un solvant organique,
    ■ et en ce qu'un revêtement de barrière est agencé entre le substrat de papier et la couche d'enregistrement thermosensible, et convient à la protection de la couche d'enregistrement thermosensible contre une pénétration par la face arrière de la teinture dans la couche d'enregistrement thermosensible.
  2. Matériau d'enregistrement thermosensible selon la revendication 1, caractérisé en ce que la caractéristique de sécurité justifiant l'authenticité est appliquée individuellement par feuille unitaire.
  3. Matériau d'enregistrement thermosensible selon la revendication 2, caractérisé en ce que la teinture est appliquée au moyen d'un procédé d'impression à jet d'encre.
  4. Matériau d'enregistrement thermosensible selon l'une quelconque des revendications 1 à 3, caractérisé en ce que le revêtement de barrière présente, en tant que liant, au moins 60 % en poids - par rapport au poids total du revêtement de barrière - d'alcool polyvinylique modifié par la diacétone.
  5. Matériau d'enregistrement thermosensible selon la revendication 4, caractérisé en ce que le revêtement de barrière présente 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 épichlorhydrine, un dihydrazide d'acide adipique, la diméthylurée et le formaldéhyde de mélamine.
  6. Matériau d'enregistrement thermosensible selon l'une quelconque des revendications 1 à 3, caractérisé en ce que le revêtement de barrière contient au moins 90 % en poids - par rapport au poids total du revêtement de barrière - d'un copolymère d'éthylène-alcool vinylique (EVOH).
  7. Matériau d'enregistrement thermosensible selon l'une quelconque des revendications 1 à 3, caractérisé en ce que le revêtement de barrière contient au moins 98 % en poids - par rapport au poids total du revêtement de barrière - d'un copolymère d'éthylène-alcool vinylique (EVOH).
  8. Matériau d'enregistrement thermosensible selon l'une quelconque des revendications 1 à 7, caractérisé en ce que la couche d'enregistrement thermosensible contient, en tant qu'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 la revendication 8, caractérisé en ce que la 4,4'-dihydroxydiphénylsulfone est le seul accepteur de couleur dans la couche d'enregistrement thermosensible.
  10. Matériau d'enregistrement thermosensible selon la revendication 8, caractérisé en ce que la N-(p-toluènesulfonyl)-N'-3-(p-toluènesulfonyl-oxy-phényl)-urée est le seul accepteur de couleur dans la couche d'enregistrement thermosensible.
  11. Matériau d'enregistrement thermosensible selon l'une quelconque des revendications 1 et 10, caractérisé en ce que la couche d'enregistrement thermosensible présente, en tant que 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-cyclohexyle)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 la revendication 9, caractérisé en ce qu'un rapport exprimé en % en poids à l'intérieur de la couche d'enregistrement de 4,4'-dihydroxydiphénylsulfone:sensibilisateur, choisi dans la liste comprenant le méthylolstéaramide, l'amide d'acide stéarique et le téréphtalate de diméthyle, se situe dans une plage de 1:0,5 à 1:2.
  13. Matériau d'enregistrement thermosensible selon l'une quelconque des revendications 1 à 12, caractérisé en ce que la couche d'enregistrement thermosensible contient, en tant que liant, une substance choisie dans la liste comprenant l'alcool polyvinylique, un copolymère d'éthylène-alcool vinylique ou une combinaison d'alcool polyvinylique et d'un copolymère d'éthylène-alcool vinylique.
  14. Matériau d'enregistrement thermosensible selon l'une quelconque des revendications 1 à 13, caractérisé en ce que le matériau d'enregistrement présente en outre une couche intermédiaire contenant un pigment, qui est agencée entre le revêtement de barrière et la couche d'enregistrement thermosensible.
  15. Matériau d'enregistrement thermosensible selon l'une quelconque des revendications 1 à 14, caractérisé en ce que le matériau d'enregistrement présente en outre une couche de protection.
  16. Matériau d'enregistrement thermosensible selon la revendication 15, caractérisé en ce que la couche de protection présente, en tant que liant, au moins 60 % en poids - par rapport à la proportion totale de liant dans la couche de protection - d'un d'alcool polyvinylique modifié par la diacétone.
  17. Matériau d'enregistrement thermosensible selon l'une quelconque des revendications 15 à 16, 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 épichlorhydrine, un dihydrazide d'acide adipique, la diméthylurée et le formaldéhyde de mélamine.
  18. Matériau d'enregistrement thermosensible selon la revendication 17, caractérisé en ce que le rapport, exprimé en % en poids, de l'alcool polyvinylique modifié par la diacétone à l'adjuvant de réticulation se situe dans une plage de 20:1 à 5:1 et, mieux encore, dans une plage de 12:1 à 7:1.
EP20090177679 2009-12-01 2009-12-01 Matériel d'enregistrement sensible à la chaleur doté d'une marque d'authenticité Active EP2329955B1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP20090177679 EP2329955B1 (fr) 2009-12-01 2009-12-01 Matériel d'enregistrement sensible à la chaleur doté d'une marque d'authenticité
ES09177679T ES2391928T3 (es) 2009-12-01 2009-12-01 Material de registro termosensible con una característica de autenticidad
US13/512,985 US8859460B2 (en) 2009-12-01 2010-11-30 Heat-sensitive recording material having authenticity feature
PCT/EP2010/068494 WO2011067239A1 (fr) 2009-12-01 2010-11-30 Matière d'enregistrement thermosensible comprenant une marque d'authenticité

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP20090177679 EP2329955B1 (fr) 2009-12-01 2009-12-01 Matériel d'enregistrement sensible à la chaleur doté d'une marque d'authenticité

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EP2329955A1 EP2329955A1 (fr) 2011-06-08
EP2329955B1 true EP2329955B1 (fr) 2012-07-25

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JP6649620B2 (ja) * 2016-04-20 2020-02-19 王子ホールディングス株式会社 感熱記録体
JP6717055B2 (ja) * 2016-05-27 2020-07-01 王子ホールディングス株式会社 感熱記録体
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EP0203499B1 (fr) * 1985-05-28 1991-10-09 Belmarque Systems S.A. Procédé et appareil pour appliquer des marques sur le papier et papier utilisé dans cette méthode
DE3920378C1 (en) 1989-06-22 1991-01-24 Heinr. Aug. Schoeller Soehne Gmbh & Co Kg, 5160 Dueren, De Artificial watermark paper prodn. - by printing paper with engraved plate with watermark in high pressure process with crosslinked polyether and isocyanate
FR2654386B1 (fr) 1989-11-14 1992-01-17 Arjomari Prioux Support plastique filigrane.
FR2742380B1 (fr) * 1995-12-15 1999-01-29 Ricoh Kk Support d'enregistrement thermosensible a couche protectrice
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
ES2181470T3 (es) * 1998-09-19 2003-02-16 Mitsubishi Hitec Paper Flensbu Materiales de registro sensibles al calor y procedimiento para la prueba de autenticidad.
DE10116058B4 (de) 2001-03-30 2006-05-11 Tesa Scribos Gmbh Verfahren zum Herstellen digitaler Hologramme in einem Speichermedium und Lithograph zum Herstellen digitaler Hologramme in einem Speichermedium
JP2008504988A (ja) * 2004-06-29 2008-02-21 カンザキ スペシャルテー ペーパーズ インコーポレテッド 多機能の直接熱記録体

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US20130123101A1 (en) 2013-05-16
US8859460B2 (en) 2014-10-14
WO2011067239A1 (fr) 2011-06-09
ES2391928T3 (es) 2012-12-03
EP2329955A1 (fr) 2011-06-08

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