EP2765007B1 - Matériel d'enregistrement sensible à la chaleur - Google Patents

Matériel d'enregistrement sensible à la chaleur Download PDF

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Publication number
EP2765007B1
EP2765007B1 EP13154683.0A EP13154683A EP2765007B1 EP 2765007 B1 EP2765007 B1 EP 2765007B1 EP 13154683 A EP13154683 A EP 13154683A EP 2765007 B1 EP2765007 B1 EP 2765007B1
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EP
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Prior art keywords
heat
sensitive recording
recording material
group
methyl
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EP13154683.0A
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German (de)
English (en)
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EP2765007A1 (fr
Inventor
Svenja Eisernitz
Annette Schreiber
Gerhard Stork
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Mitsubishi HiTec Paper Europe GmbH
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Mitsubishi HiTec Paper Europe GmbH
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
    • B41M5/333—Colour developing components therefor, e.g. acidic compounds
    • B41M5/3333—Non-macromolecular compounds
    • B41M5/3335—Compounds containing phenolic or carboxylic acid groups or metal salts thereof
    • 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

Definitions

  • the present invention relates to a thermosensitive recording material comprising a substrate, and to a thermosensitive recording layer comprising one or more dye precursors and one or more color developers.
  • thermosensitive recording materials of the type described above with, for example, a sheet of paper, a synthetic paper sheet or a plastic film as substrate are known since the early years of chemically reactive recording materials and enjoy a constantly growing distribution, which is due, inter alia, that their use in particular as a ticket for the Ticket issuing is associated with great benefits.
  • the color-forming components are located in the thermosensitive recording material itself, the production of a thermally-induced recording (heat-induced printing image, hereinafter also referred to as thermal expression) on such thermosensitive recording material is carried out by toner and ink cartridge-free and hence low-maintenance and inexpensive printer. This is particularly advantageous for applications where large amounts of thermal prints are required to be generated quickly.
  • this technology has prevailed in particular in public transport, buses and trains as well as air traffic, stadium and museum funds, ticket sales for major events and parking ticket issuers.
  • thermo-print heat-induced recording
  • US Pat DE 10 2004 044 204 A1 a heat-sensitive recording material whose heat-sensitive recording layer has conventional dye precursors and the combination of a phenolic color developer and a urea-urethane-based color developer.
  • thermosensitive recording material containing at least the components of two color-forming systems to form an irreversible printed image, one being a chelate-type system and the other being a conventional leuco-dye system.
  • a disadvantage of the recording materials corresponding to the publications discussed above is, in particular in the first case, too low plasticizer resistance, associated with very low whiteness of the recording material, and the much too expensive production processes.
  • thermosensitive recording material may be used in its typical uses as a ticket, ticket, ticket, parking ticket, and the like. can come in contact with a variety of different substances that can affect the durability of the thermal expression. In addition to water and substances acting as solvents, these also include fats and oils. The latter often act much like plasticizers. Therefore, there is a continuing need to improve the resistance of the thermal term to various environmental conditions.
  • the object of the present invention is thus to provide a heat-sensitive recording material which, when printed, has a high resistance of the thermal expression to one or more substances selected from the group consisting of water, solvents, fats, oils and mixtures thereof, preferably both to water and solvents as well as fats and oils.
  • Color developers are substances which color-form with the dye precursor or dye precursors under the action of heat.
  • additional color developers can be used; Frequently, however, no further color developers are provided in addition to the substances mentioned.
  • the present invention also relates to the use of a condensation product of the formula (I) as defined above for improving the durability of the heat-sensitive recording material whose heat-sensitive recording layer contains the color developer N- (p-toluenesulphonyl) -N'-3- (p-toluenesulphonyl -Oxyphenyl) urea, available thermal terms to substances selected from the group consisting of water, alcohols, fats, oils and mixtures thereof.
  • R 1 is an alkoxy group having 1 to 5 carbon atoms, it is preferably selected from the group consisting of methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy and t-butoxy ,
  • R 1 is an aryl group, this is preferably selected from the group consisting of phenyl, toluyl and naphthyl group, and is preferably a phenyl group.
  • R 1 is an aralkyl group, it is preferably selected from the group consisting of cumyl and o-methylbenzyl groups.
  • the structural elements R 1 are preferably attached to one or both meta positions and / or to the para position to the hydroxyl group of the phenol ring, more preferably the or at least one of the structural elements R 1 is attached to the para position to the hydroxyl group of the phenol group.
  • R 2 is an alkyl group having 1 to 5 carbon atoms, it is preferably selected from the group consisting of methyl, ethyl, n-propyl, i-propyl, n-butyl and t-butyl.
  • R 2 is an aryl group, it is preferably selected from the group consisting of phenyl, tolyl and naphthyl, and is preferably a phenyl group.
  • condensation products of the formula (I) with two phenol rings preference is given to condensation products of the formula (I) with two phenol rings, where phenol rings which may be present in the structural elements R 1 and R 2 are not to be included.
  • the proportion of the condensation products of the formula (I) with two phenol rings is preferably 40 to 99%, more preferably 45 to 98%, particularly preferably 50 to 80%. , based on area in the analysis by high performance liquid chromatography.
  • a condensation product of formula (I) is obtainable by reacting one or more optionally substituted phenols with a ketone compound or an aldehyde compound in the presence of an acid catalyst (eg, hydrochloric acid, p-toluenesulfonic acid and the like).
  • an acid catalyst eg, hydrochloric acid, p-toluenesulfonic acid and the like.
  • the reaction is usually carried out in a suitable inert solvent in which the starting materials and the condensation product are soluble, such as water, methanol, ethanol, n-propyl alcohol, isopropyl alcohol, acetonitrile, toluene, chloroform, diethyl ether, N, N-dimethylacetamide, benzene, chlorobenzene , Dichlorobenzene, diethyl ketone, ethyl methyl ketone, acetone, tetrahydrofuran and the like, at a reaction temperature of 0 to 150 ° C for several hours to several dozen hours performed.
  • a suitable inert solvent in which the starting materials and the condensation product are soluble, such as water, methanol, ethanol, n-propyl alcohol, isopropyl alcohol, acetonitrile, toluene, chloroform, diethyl ether, N, N-dimethylacetamide, benzene, chloro
  • the phenols for preparing a condensation product of the formula (I) are preferably selected from the group consisting of phenol, p-chlorophenol, m-chlorophenol, o-chlorophenol, catechol, resorcinol, hydroquinone, p-cresol, m-cresol, o-cresol , p-ethylphenol, m-ethylphenol, o-ethylphenol, p-propylphenol, o-propylphenol, p-isopropylphenol, m-isopropylphenol, o-isopropylphenol, pt-butylphenol, mt-butylphenol, ot-butylphenol, pt-amylphenol, p Methoxyphenol, m-methoxyphenol, o-methoxyphenol, p-phenylphenol, m-phenylphenol, o-phenylphenol, p-cumylphenol, p
  • Para-substituted phenols having at least one unsubstituted ortho position are preferred, and of these, p-cresol, p-ethylphenol and p-t-butylphenol are particularly preferred, and p-cresol and p-t-butylphenol are most preferred.
  • the ketone and aldehyde compounds for preparing a condensation product of the formula (I) are preferably selected from the group consisting of dimethyl ketone, diethyl ketone, ethyl methyl ketone, methyl isobutyl ketone, formaldehyde and benzaldehyde.
  • Condensation products of the formula (I) are structurally novolaks.
  • thermosensitive recording materials The use of specific novolak-type phenol condensation products as color developers for thermosensitive recording materials is basically known, but their use has the disadvantage of low stability to plasticizers.
  • alkylphenol-formalin condensation product wherein R 1 is a tert-butyl group.
  • the dye precursor (s) contained in the thermosensitive recording layer of the thermosensitive recording material of the present invention are preferably selected from the group consisting of 3-dibutylamino-6-methyl-7-anilinofluoran, 3-diethylamino-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 and 3- (N-ethyl-N-tolyl) amino-6-methyl-7-anilinofluoran.
  • the recording material according to the invention contains, in addition to one or more dye precursors, one or more near infrared absorbing compounds selected from the group consisting of 3,6-bis (dimethylamino) fluorene-9-spiro-3 '- ( 6'-dimethylaminophthalide), 3-diethylamino-6-dimethylaminofluorene-9-spiro-3 '- (6'-dimethylaminophthalide), 3,6-bis (diethylamino) -fluorene-9-spiro-3' - (6'- dimethylaminophthalide), 3-dibutylamino-6-dimethylaminofluorene-9-spiro-3 '- (6'-dimethylaminophthalide), 3-dibutylamino-6-diethylaminofluorene-9-spiro-3' - (6'-dimethylaminophthalide), 3.6 Bis (dimethylamino) fluorene-9-spir
  • the heat-sensitive recording layer of the heat-sensitive recording material according to the invention contains one or more sensitizers having a melting point of 60 ° C to 180 ° C, more preferably having a melting point of 80 ° C to 140 ° C.
  • Such sensitizers are preferably selected from A group consisting of benzyl p-benzyloxybenzoate, stearamide, N-methylol stearamide, p-benzylbiphenyl, 1,2-di (phenoxy) ethane, 1,2-di (m-methylphenoxy) ethane, m-terphenyl, dibenzyl oxalate, Benzyl naphthyl ether and diphenyl sulfone, with benzyl naphthyl ether, diphenyl sulfone, 1,2-di (m-methylphenoxy) ethane and 1,2-di (phenoxy) ethane being particularly preferred.
  • the addition of one or more sensitizers increases the thermal responsiveness of the thermosensitive recording material.
  • the atro weight ratio of the total amount of the condensation product (s) of formula (I) to N- (p-toluenesulphonyl) -N'-3- (p-toluenesulphonyl-oxyphenyl) urea is preferably in the range of 1: 2.5 to 1:14, more preferably from 1: 3.2 to 1: 12.8, more preferably in the range of 1: 5 to 1: 8.
  • Suitable binders for the heat-sensitive recording layer are, for example, water-soluble binders such as starch, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, gelatin, casein, polyvinyl alcohols, modified polyvinyl alcohols, sodium polyacrylates, acrylamide-acrylate copolymers, Acrylamide-acrylate-methacrylate terpolymers, alkali metal salts of styrene-maleic anhydride copolymers or ethylene-maleic anhydride copolymers, which binders may be used alone or in combination with one another; Also, water-insoluble latex binders such as styrene-butadiene copolymers, acrylonitrile-butadiene copolymers and methyl acrylate-butadiene copolymers are suitable binders for the heat-sensitive recording layer.
  • water-soluble binders such as starch, hydroxyethyl cellulose, methyl cellulose, carboxy
  • the thermosensitive recording layer of the thermosensitive recording material of the present invention contains a crosslinked or uncrosslinked binder, which preferably contains a polyvinyl alcohol and an acrylate copolymer.
  • the total weight content of polyvinyl alcohol and acrylate copolymer is in a range of 12 to 21 wt .-%, based on the total weight of the heat-sensitive recording layer.
  • the coating composition for forming the heat-sensitive recording layer of the heat-sensitive recording material of the present invention contains, in addition to the binder, one or more crosslinking agents for the binder.
  • the crosslinking agent (s) is selected from the group consisting of zirconium carbonate, polyamine epichlorohydrin resins, boric acid, glyoxal and glyoxal derivatives.
  • a heat-sensitive recording material of the present invention whose heat-sensitive recording layer is formed from such a coating composition containing a binder and one or more crosslinking agents for the binder contains, in the heat-sensitive recording layer, a binder crosslinked by reaction with one or more crosslinking agents, wherein the crosslinking agent (s) are selected the group consisting of zirconium carbonate, polyamine-epichlorohydrin resins, boric acid, glyoxal and glyoxal derivatives.
  • crosslinked binder is meant the reaction product formed by reaction of a binder with one or more crosslinking agents.
  • Suitable glyoxal derivatives are, for example, adducts of glyoxal with S, O and / or N nucleophiles.
  • S-nucleophiles are sodium bisulfite and potassium bisulfite
  • O-nucleophiles are adducts with aliphatic (C1 to C20)
  • Monoalcohols or polyhydric alcohols
  • suitable N-nucleophiles are aliphatic monoamines, amides, urea and / or cyclic ureas.
  • the heat-sensitive recording layer may contain lubricants and release agents such as metal salts of higher fatty acids, for example, zinc stearate and / or calcium stearate, and waxes such as paraffin, oxidized paraffin, polyethylene, polyethylene oxide , Stearamide and castor wax.
  • Further constituents of the heat-sensitive recording layer are, for example, pigments, preferably inorganic pigments such as, for example, aluminum (hydr) oxide, silica and calcium carbonate.
  • inorganic pigment preferably inorganic pigments such as, for example, aluminum (hydr) oxide, silica and calcium carbonate.
  • calcium carbonate is used, which is preferably contained in an amount of from 10 to 18% by weight, based on the total weight of the heat-sensitive recording layer, in the heat-sensitive recording layer.
  • the heat-sensitive recording layer preferably has a whiteness in a range of 79 to 85% when using light having no UV portion and whitening in a range of 87 to 93% when using light with UV Each measured according to ISO 2469 / ISO 2470, but D65 light is used at a viewing angle of 8 °.
  • the coating composition used to form the heat-sensitive 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 in the final heat-sensitive recording material of the present invention is preferably in the range of 2 to 6 g / m 2, and more preferably 2.3 to 5.8 g / m 2 .
  • the present invention is not limited to paper as the substrate, paper, and especially a non-surface treated base paper, is preferred a basis weight in the range of 45 to 130 g / m 2, a substrate which has prevailed in the market and is preferred for use in a heat-sensitive recording material according to the invention. This is especially true because of the good recyclability of such papers.
  • a non-surface treated base paper is to be understood as meaning a base paper which has not been treated in a size press or in a coater.
  • a non-surface-treated, sized in the coating base paper with an inorganic pigment, in particular calcium carbonate, in the mass is particularly suitable for use in a heat-sensitive recording material according to the invention.
  • films for example of polyolefin
  • coated with polyolefin papers are suitable as a substrate.
  • thermosensitive recording layer and the substrate of the thermosensitive recording material of the present invention differ in structure from both the substrate and the thermosensitive recording layer preferably one or more pigments.
  • structure here includes the microscopic and macroscopic structure, the chemical composition and other aspects of the nature of the layers concerned.
  • the intermediate layer is applied with leveling coating devices, such as roller coater, doctor blade or doctor blade coaters.
  • the intermediate layer contributes to the leveling of the substrate surface, whereby the amount of coating material to be applied necessarily for forming the heat-sensitive recording layer is regularly reduced.
  • the basis weight of the intermediate layer is preferably in the range of 5 to 20 g / m 2 and more preferably 7 to 11 g / m 2 .
  • inorganic oil-absorbing pigments are incorporated into the intermediate layer disposed between the heat-sensitive recording layer and the substrate, these pigments can absorb the wax constituents of the heat-sensitive recording layer liquefied by heat of the thermal head during the printing image formation and thus promote an even safer and faster functioning of the heat-induced recording, which is why such an embodiment is considered preferable.
  • the pigments of the intermediate layer has an oil absorption of at least 80 cm3 / 100 g, and more preferably 100 cm3 / 100 g, determined according to the Japanese standard JIS K 5101, is having.
  • Calcined kaolin has proven particularly useful due to its large absorption reservoir in the cavities.
  • the following inorganic pigments are also very well suited as constituents of the intermediate layer: silicon dioxide, bentonite, calcium carbonate and aluminum (hydr) oxide and here in particular boehmite. Also mixtures of several different types of inorganic pigments are conceivable.
  • organic pigments in the intermediate layer can also be very advantageous, which may be due to the fact that such organic pigments are to a particular extent conducive to a high heat reflectivity of the intermediate layer.
  • Organic, so-called hollow body pigments arranged in an intermediate layer of a heat-sensitive recording material according to the invention are preferred; they have in their interior air, which is a good heat insulator.
  • An interlayer thus formed as a heat reflection layer increases the response of the heat-sensitive recording layer to heat. This significantly increases the resolving power of the thermosensitive recording material and further increases the printing speed in the thermal printer.
  • the amount ratio between organic and inorganic pigment By adjusting the amount ratio between organic and inorganic pigment, a compromise of the effects caused by the two types of pigments is achieved; it is preferred if the pigment mixture to 5 to 30 wt .-% or better to 8 to 20 wt .-% of organic and 95 to 70 wt .-% or better to 92 to 80 wt .-% of inorganic Pigment exists.
  • Pigment mixtures comprising different organic pigments are also suitable.
  • the intermediate layer contains at least one binder, preferably a binder comprising a synthetic polymer, wherein, for example, styrene-butadiene latex as binder agent gives particularly good results.
  • a synthetic binder with admixture of at least one natural polymer, as particularly preferred Starch, represents a particularly preferred embodiment.
  • the synthetic polymer blended with the natural polymer is referred to in this context as a cobinder.
  • the heat-sensitive recording layer is completely or partially covered with a protective layer.
  • the heat-sensitive recording material according to the invention has a protective layer, although the presence of one or more condensation products of the formula (I) as defined above in the heat-sensitive recording layer of the heat-sensitive recording material according to the invention, the stability of a on a inventive heat-sensitive recording material available thermal expression compared to substances selected from the group consisting of water, alcohols, fats, oils and mixtures thereof, even without a protective layer for certain applications is already sufficient.
  • the protective layer of the heat-sensitive recording material according to the invention preferably comprises one or more crosslinked or uncrosslinked binders selected from the group consisting of carboxyl-modified polyvinyl alcohols, silanol-modified polyvinyl alcohols, diacetone-modified polyvinyl alcohols, partially and fully hydrolyzed polyvinyl alcohols and film-forming acrylic copolymers.
  • the coating composition for forming the protective layer of the heat-sensitive recording material according to the invention contains, in addition to one or more binders, one or more crosslinking agents for the one or more binders Binder.
  • the crosslinking agent is preferably selected from the group consisting of boric acid, polyamines, epoxy resins, dialdehydes, formaldehyde oligomers, epichlorohydrin resins, adipic dihydrazide melamine formaldehyde, urea, methylol urea, ammonium zirconium carbonate and polyamide-epichlorohydrin resins.
  • a heat-sensitive recording material according to the invention contains in the protective layer one or more binders crosslinked by reaction with one or more crosslinking agents, wherein the one or more Crosslinking agents are selected from the group consisting of boric acid, polyamines, epoxy resins, dialdehydes, formaldehyde oligomers, epichlorohydrin resins, adipic dihydrazide melamine formaldehyde, urea, methylol urea, ammonium zirconium carbonate and polyamide epichlorohydrin resins.
  • crosslinked binder is meant the reaction product formed by reaction of a binder with one or more crosslinking agents.
  • the protective layer completely or partially covering the heat-sensitive recording layer is obtainable from a coating composition comprising one or more polyvinyl alcohols and one or more crosslinking agents. It is preferred that the polyvinyl alcohol of the protective layer is modified with carboxyl or in particular silanol groups. It is also possible to use mixtures of different carboxyl-group- or silanol-modified polyvinyl alcohols.
  • a protective layer has a high affinity with respect to the preferably UV-crosslinking printing ink used in the offset printing process. This helps significantly to meet the demand for excellent printability within the offset printing.
  • the one or more crosslinking agents for the protective layer according to this embodiment are preferably selected from the group consisting of boric acid, polyamines, epoxy resins, dialdehydes, formaldehyde oligomers, polyamine-epichlorohydrin resin, adipic dihydrazide and melamine-formaldehyde. It is also possible to use mixtures of different crosslinking agents.
  • the weight ratio of the modified polyvinyl alcohol to the crosslinking agent in a range of 20: 1 to 5: 1, and more preferably in a range of 12: 1 to 7: 1.
  • a ratio of the modified polyvinyl alcohol to the crosslinking agent in the range of 100 parts by weight to 8 to 11 parts by weight.
  • the protective layer according to this embodiment additionally contains an inorganic pigment.
  • the inorganic pigment is preferably selected from the group consisting of silicon dioxide bentonite, aluminum hydroxide, calcium carbonate, kaolin and mixtures of said inorganic pigments.
  • the protective layer according to this embodiment with a basis weight in a range from 1.0 g / m 2 to 6 g / m 2 and more preferably from 1.2 g / m 2 to 3.8 g / m 2 , In this case, the protective layer is preferably formed in one layer.
  • a self-crosslinking acrylic polymer within the protective layer according to the second embodiment described herein is preferably selected from the group consisting of styrene-acrylic acid ester copolymers, acrylamide-containing copolymers of styrene and acrylic acid esters and copolymers based on acrylonitrile, methacrylamide and acrylic esters. The latter are preferred.
  • a pigment alkaline bentonite natural or precipitated calcium carbonate, kaolin, silica or aluminum hydroxide may be incorporated into the protective layer.
  • Preferred crosslinking agents are selected from the group consisting of cyclic urea, methylol urea, ammonium zirconium carbonate and polyamide-epichlorohydrin resins.
  • the protective layer itself may be applied by means of conventional brushing, for which, inter alia, a coating color is usable, preferably with a surface-related mass in a range of 1.0 to 4.5 g / m 2 .
  • the protective layer is printed. Processing technology and in terms of their technological properties are particularly suitable such protective layers which are curable by means of actinic radiation.
  • actinic radiation UV or ionizing radiation, such as electron beams to understand.
  • the appearance of the protective layer is significantly determined by the type of smoothing and the friction in the calender and calender influencing roll surfaces and their materials.
  • a roughness (Parker Print Surf roughness) of the protective layer is less than 1.5 microns (determined in accordance with ISO standard 8791, Part 4) considered preferred.
  • the use of calenders using NipcoFlex TM or zone controlled Nipco-P TM rolls has proven particularly useful; however, the invention is not limited thereto.
  • a protective layer can be dispensed with, because the presence of one or more condensation products of the formula (I) as defined above in the heat-sensitive recording layer of the heat-sensitive recording material of the present invention, the durability of a thermal printable on a heat-sensitive recording material according to the invention is selected from materials Group consisting of water, alcohols, fats, oils and their mixtures sufficient for certain applications. This is advantageous in that a protective layer is cost-intensive both in terms of the necessary raw materials as well as in terms of the necessary for their production machines and process energies.
  • thermosensitive recording material of the present invention i. a printed thermosensitive recording material.
  • the thermosensitive recording layer contains dyes formed on printing by a heat-induced reaction of the dye precursor (s) with the color developer (s).
  • a heat-sensitive recording layer having a face-related one is applied to the intermediate layer in this order and within a coater passage by means of a doctor blade coater Mass of 5.4 g / m 2 and applied by means of air brush, a protective layer with a basis weight of 2.0 g / m 2 and dried conventionally after each order.
  • a formulation which comprises as binder a mixture comprising polyvinyl alcohol and an acrylate copolymer and as the pigment calcium carbonate.
  • Further constituents of the heat-sensitive recording layers of the individual exemplary embodiments are given in Table 1 below: Table 1 component Comparative example Example 1 (according to the invention) Example 1 (according to the invention) Data in atro-parts by weight N- (p-toluensulphonyl) -N'-3- (p-toluensulphonyl-oxyphenyl) -urea 100.00 100.00 100.00 100.00 dye precursor 47.92 47.92 47.97 Condensation product as defined above - 31.25 15.63
  • a coating composition comprising a diacetone-modified polyvinyl alcohol (100 parts by weight), kaolin (40 parts by weight), zinc stearate (26.5 parts by weight) and adipic dihydrazide as a crosslinking agent (10 parts by weight) is used.
  • thermosensitive recording material to be tested For metrological detection of margarine and lanolin resistance, a sample of the thermosensitive recording material to be tested was satisfactorily coated with the above-described thermoprob expression and then allowed to stand for 24 hours at 23 ° C and 50% humidity. Thereafter, the margarine or lanolin was wiped off by the thermoprobe print.
  • thermosensitive recording material of Comparative Example whose heat-sensitive recording layer contains no condensation product of the formula (I) as defined above have significantly lower resistance to all substances tested (water, ethanol-water mixture, Milk, margarine and lanolin) compared to the Thermoprobeausdrucken on the heat-sensitive recording materials according to the invention of Examples 1 and 2.
  • the thermosensitive recording material of Example 2 represents a particularly preferred embodiment of the present invention, because compared to all substances tested, the dynamic print density remains at a value of more than 1 ODU. It is an example of a heat-sensitive recording material of the invention having an atro-weight ratio of the condensation product of the formula (I) in the range of 1: 5 to 1: 8.

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

Claims (12)

  1. Matériau d'enregistrement thermosensible comprenant un substrat
    et
    une couche d'enregistrement thermosensible, comprenant
    - un ou plusieurs précurseurs de colorant ;
    - de la N-(p-toluènesulfonyl)-N'-3-(p-toluènesulfonyl-oxyphényl)-urée,
    - et un ou plusieurs produits de condensation de formule (I)
    Figure imgb0004
     où, dans la formule (I),
    - chaque élément structural R1 est choisi dans le groupe consistant en les atomes d'halogène, le groupe hydroxy, les groupes alkyle ayant 1 à 5 atomes de carbone, les groupes alcoxy ayant 1 à 5 atomes de carbone, le groupe cyano, le groupe nitro, les groupes aryle et les groupes alkaryle, et les éléments structuraux individuels R1 sont identiques ou différents,
    - chaque élément structural R2 est choisi dans le groupe consistant en l'atome d'hydrogène, les groupes alkyle ayant 1 à 5 atomes de carbone et les groupes aryle, et les éléments structuraux individuels R2 sont identiques ou différents,
    - m est un nombre entier de 0 à 3,
    - n est un nombre entier de 0 à 3.
  2. Matériau d'enregistrement thermosensible selon la revendication 1, dans lequel
    (a) dans la formule (I) :
    - m est un nombre entier de 1 à 3,
    - chaque élément structural R1 est choisi dans le groupe consistant en les groupes alkyle ayant 1 à 5 atomes de carbone, et les éléments structuraux individuels R1 sont identiques ou différents,
    - tous les éléments structuraux R2 sont des atomes d'hydrogène,
    - n a la signification telle que donnée dans la revendication 1 et/ou
    (b) le ou les produits de condensation de formule (I) peuvent être obtenus par condensation d'un phénol à substitution alkyle avec du formaldéhyde en présence d'un catalyseur acide.
  3. Matériau d'enregistrement thermosensible selon la revendication 1 ou 2, dans lequel le ou les précurseurs de colorant de la couche d'enregistrement thermosensible sont choisis dans le groupe consistant en le 3-diéthylamino-6-méthyl-7-anilinofluoranne, le 3-dibutylamino-6-méthyl-7-anilinofluoranne, le 3-(N-méthyl-N-propyl)amino-6-méthyl-7-anilinofluoranne, le 3-(N-éthyl-N-isoamyl)amino-6-méthyl-7-anilinofluoranne, le 3-(N-méthyl-N-cyclohexyl)amino-6-méthyl-7-anilinofluoranne et le 3-(N-éthyl-N-tolyl)amino-6-méthyl-7-anilinofluoranne.
  4. Matériau d'enregistrement thermosensible selon l'une des revendications 1 à 3, dans lequel le rapport en poids, à l'état sec absolu, entre la quantité totale du ou des produits de condensation de formule (I) et la N-(p-toluènesulfonyl)-N'-3-(p-toluènesulfonyl-oxyphényl)-urée est compris dans la plage de 1:2,5 à 1:14, de préférence de 1:3,2 à 1:12,8, d'une manière particulièrement préférée dans la plage de 1:5 à 1:8.
  5. Matériau d'enregistrement thermosensible selon l'une des revendications 1 à 4, dans lequel la couche d'enregistrement thermosensible contient un liant réticulé ou non réticulé, qui de préférence contient un poly(alcool vinylique) et un copolymère d'acrylate.
  6. Matériau d'enregistrement thermosensible selon l'une des revendications 1 à 5, contenant dans la couche d'enregistrement thermosensible un liant réticulé par réaction avec un ou plusieurs agents de réticulation, le ou les agents de réticulation étant choisis dans le groupe consistant en le carbonate de zirconium, les résines de polyaminépichlorhydrine, l'acide borique et le glyoxal.
  7. Matériau d'enregistrement thermosensible selon l'une des revendications 1 à 6, le matériau d'enregistrement thermosensible comprenant une ou plusieurs couches intermédiaires disposées entre le substrat et la couche d'enregistrement thermosensible, les couches intermédiaires se distinguant, par leur structure, du substrat et de la couche d'enregistrement thermosensible.
  8. Matériau d'enregistrement thermosensible selon l'une des revendications 1 à 7, dans lequel la couche d'enregistrement thermosensible est en totalité ou en partie recouverte d'une couche de protection.
  9. Matériau d'enregistrement thermosensible selon la revendication 8, dans lequel la couche de protection contient un ou plusieurs liants réticulés ou non réticulés, choisis dans le groupe consistant en les poly(alcools vinyliques) modifiés par des groupes carboxyle, les poly(alcools vinyliques) modifiés par des groupes silanol, les poly(alcools vinyliques) modifiés par de la diacétone, et les poly(alcools vinyliques) saponifiés en totalité ou en partie et les copolymères acryliques filmogènes.
  10. Matériau d'enregistrement thermosensible selon l'une des revendications 8 et 9, contenant dans la couche de protection un ou plusieurs liants réticulés par réaction avec un ou plusieurs agents de réticulation, le ou les agents de réticulation étant choisis dans le groupe consistant en l'acide borique, les polyamines, les résines époxy, les dialdéhydes, les oligomères du formaldéhyde, les résines d'épichlorhydrine, la diméthylurée, le mélamineformaldéhyde, l'hydrazide de l'acide adipique, l'urée, la méthylolurée, le carbonate d'ammonium et de zirconium, et les résines de polyamidépichlorhydrine.
  11. Utilisation d'un produit de condensation de formule (I) tel que défini dans les revendications 1 et 2 pour améliorer la résistance de l'impression thermique pouvant être obtenue sur un matériau d'enregistrement thermosensible dont la couche thermosensible contient le révélateur de couleur N-(p-toluènesulfonyl)-N'-3-(p-toluènesulfonyl-oxyphényl)-urée, vis-à-vis de substances choisies dans le groupe consistant en l'eau, les alcools, les graisses, les huiles et leurs mélanges.
  12. Matériau d'enregistrement thermosensible imprimé, comprenant un substrat
    et
    une couche d'enregistrement thermosensible comprenant
    - un ou plusieurs précurseurs de colorant,
    - de la N-(p-toluènesulfonyl)-N'-3-(p-toluènesulfonyl-oxyphényl)-urée,
    - et un ou plusieurs produits de condensation de formule (I), tels que définis dans les revendications 1 et 2,
    ainsi que
    - un ou plusieurs colorants formés par réaction du ou des précurseurs de colorant avec de la N-(p-toluènesulfonyl)-N'-3-(p-toluènesulfonyl-oxyphényl)-urée.
EP13154683.0A 2013-02-08 2013-02-08 Matériel d'enregistrement sensible à la chaleur Not-in-force EP2765007B1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111655501A (zh) * 2018-01-31 2020-09-11 三菱高新技术纸业欧洲有限公司 热敏记录材料

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102019103679A1 (de) * 2019-02-13 2020-08-13 Mitsubishi Hitec Paper Europe Gmbh Wärmeempfindliches Aufzeichnungsmaterial mit Farbentwicklern aus nachwachsenden Rohstoffen

Family Cites Families (9)

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Publication number Priority date Publication date Assignee Title
EP1393923B1 (fr) 2001-06-01 2009-08-12 API Corporation Revelateurs destines a des materiaux de thermogravure et materiaux de thermogravure
EP1437231B1 (fr) 2001-09-27 2008-01-09 API Corporation Revelateur pour support de gravure thermique et materiaux de gravure thermiques
FI110677B (fi) 2001-10-12 2003-03-14 Jujo Thermal Oy Lämpöherkkä tallennusmateriaali
WO2005087503A1 (fr) 2004-03-11 2005-09-22 Api Corporation Melange revelateur pour materiaux d’enregistrement thermique et materiaux d’enregistrement thermique
DE102004044204A1 (de) 2004-09-06 2005-11-17 Siemens Ag Vorrichtung zur Betätigung von Türen
EP2072274B1 (fr) 2006-09-29 2011-12-28 Nippon Paper Industries Co., Ltd. Matériau d'impression sensible à la chaleur
US8492308B2 (en) 2007-08-21 2013-07-23 Nippon Paper Industries Co., Ltd. Thermosensitive recording medium
ES2366451T3 (es) 2007-09-04 2011-10-20 Mitsubishi Hitec Paper Europe Gmbh Material de registro termosensible.
CN101984753A (zh) 2008-03-27 2011-03-09 日本制纸株式会社 热敏记录体

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111655501A (zh) * 2018-01-31 2020-09-11 三菱高新技术纸业欧洲有限公司 热敏记录材料

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