EP3274184B1 - Matières de reproduction thermosensible - Google Patents

Matières de reproduction thermosensible Download PDF

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Publication number
EP3274184B1
EP3274184B1 EP16717087.7A EP16717087A EP3274184B1 EP 3274184 B1 EP3274184 B1 EP 3274184B1 EP 16717087 A EP16717087 A EP 16717087A EP 3274184 B1 EP3274184 B1 EP 3274184B1
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Prior art keywords
heat
recording material
sensitive recording
approximately
material according
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German (de)
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EP3274184A1 (fr
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Michael Horn
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Papierfabrik August Koehler SE
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Papierfabrik August Koehler SE
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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
    • 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
    • B41M5/3375—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
    • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
    • B41M5/337—Additives; Binders
    • B41M5/3377—Inorganic compounds, e.g. metal salts of organic acids

Definitions

  • the invention relates to a heat-sensitive recording material comprising a carrier substrate and a heat-sensitive color-forming layer containing at least one color former and at least one phenol-free color developer, a process for its production and the use of the phenol-free color developer contained in the heat-sensitive recording material.
  • Heat-sensitive recording materials for direct thermal printing which have a heat-sensitive color-forming layer (thermal reaction layer) applied to a carrier substrate, have been known for a long time.
  • a color former and a color developer are usually present, which react with one another under the action of heat and thus lead to color development.
  • heat-sensitive recording materials which contain a non-phenolic color developer in the heat-sensitive color-forming layer. These were developed to improve the durability of the typeface, especially when the printed, heat-sensitive recording material is stored for a long period of time or comes into contact with hydrophobic substances such as plasticizer-containing materials or oils.
  • the EP 0 620 122 B1 discloses non-phenolic color developers from the class of the aromatic sulfonyl ureas. With these, heat-sensitive recording materials can be obtained which are distinguished by high image stability. Furthermore, the thermosensitive recording materials based on these color developers have a useful thermal sensitivity with good surface whiteness, so that with an appropriate design of the formulation of the thermosensitive color-forming layer it is comparatively easy to produce high print densities using commercially available thermal printers. In practice, N, N '- [methylenebis (4,1-phenyleneiminocarbonyl)] bis [4-methyl-benzenesulfonamide] (B-TUM) have prevailed.
  • a non-phenolic developer from this class widely used in practice 4-methyl-N - [[[3 - [[(4-methylphenyl) sulfonyl] oxy] phenyl] amino] carbonyl] benzene sulfonamide (trade name Pergafast 201®, BASF ) is distinguished by the balance of the application properties of the heat-sensitive recording materials produced with this developer. In particular, these have good dynamic responsiveness and high resistance of the printout to hydrophobic substances.
  • JP2001071647A discloses heat-sensitive recording materials with phenol-free color developers which are sulfonylureas substituted with an NH-heterocyclic group.
  • the JP2006068961 A and the JP2000355172A disclose thermal printing processes using azo coupling.
  • the coupling components used for the diazonium salt are compounds which come under formula (I).
  • All non-phenolic developer substances of the prior art have in common a higher structural complexity of the molecules compared to the (bis) phenolic developer substances. This usually requires a multi-stage synthesis for the Manufacturing and the need to use a large number of often expensive raw materials. All of these factors negatively affect the manufacturing cost and price of such fabrics and prevent the widespread use of such materials.
  • the requirements mentioned under a) relate to the resistance or constancy of the composition of the heat-sensitive color-forming layer, in particular the chemical resistance of the color-forming components, even with long-term storage and under severe climatic conditions
  • the requirements mentioned under b) are aimed at the stability of the color complex that forms in the heat-sensitive color-forming layer during the printing process.
  • the above-mentioned heat-sensitive recording materials with color developers based on sulfonyl ureas meet the requirements specified under b), but show weaknesses with regard to the requirements specified under a).
  • the sulfonyl ureas are chemically unstable, especially in the presence of water. This tendency of sulfonyl ureas to decompose over a wide pH range is known and well documented ( AK Sarmah, J. Sabadie, J. Agric. Food Chem., 50, 6253 (2002 )).
  • the object of the present invention is therefore to eliminate the disadvantages of the prior art described above.
  • the object of the present invention is to provide a heat-sensitive recording material which uses non-phenolic color developers inexpensively from readily available raw materials and in some cases produced by one-step syntheses.
  • the heat-sensitive recording material should have a balanced profile of application properties and at least achieve the performance of the heat-sensitive recording materials based on known non-phenolic color developers, in particular sulfonyl ureas.
  • the requirements mentioned under a) above, i.e. the functional properties required for application, such as thermal Responsiveness and surface whiteness should also be met, even when stored over long periods of time and under severe climatic conditions.
  • This last sub-task accordingly relates to the profile of properties of an unprinted heat-sensitive recording material.
  • the object of the present invention is therefore to provide a heat-sensitive recording material based on inexpensive color developers that can be easily synthesized, while at the same time providing a balanced performance ratio with regard to various properties, such as in particular background white, optical density, static starting point, artificial aging and Should have durability of the printed image.
  • a heat-sensitive recording material according to claim 1, according to which it comprises a carrier substrate and a heat-sensitive color-forming layer containing at least one color former and at least one phenol-free color developer, and is characterized in that the at least one color developer is a compound of the formula (I) is, where Ar is an aryl radical or a benzyl radical and Y is an aryl radical, a benzyl radical, an aryloxy radical, a benzyloxy radical, an arylamino radical, or a benzylamino radical and where the at least a color former is a triphenylmethane type, fluorane type, azaphthalide type and / or fluorene type dye.
  • Ar is an aryl radical or a benzyl radical
  • Y is an aryl radical, a benzyl radical, an aryloxy radical, a benzyloxy radical, an arylamino radical, or a benzylamino radical
  • An aryl radical is understood to mean a monovalent atomic group which is derived from aromatic hydrocarbons by removing a hydrogen atom bonded to the ring.
  • a benzyl radical is understood to mean a —CH 2 —C 6 H 5 group.
  • An aryloxy radical (Ar-O-) is understood to mean a monovalent atomic group in which an aryl radical is bonded to a molecule via an oxygen atom.
  • a benzyloxy group is understood to mean an —OCH 2 —C 6 H 5 - group.
  • An arylamino radical (Ar-NH-) is understood to mean a monovalent atomic group in which an aryl radical is bonded to a molecule via an NH group via the nitrogen.
  • a benzylamino group is understood to mean an —NHCH 2 —C 6 H 5 - group.
  • Ar can be unsubstituted or substituted.
  • the substitution can be single or multiple.
  • the substituents can be the same or different.
  • Particularly preferred substituents of Ar and / or Y are selected from the group consisting of C 1 -C 5 -alkyl, preferably methyl and ethyl, C 2 -C 5 -alkenyl, C 2 -C 5 -alkynyl, , Alkoxy (RO), halide, carboxyl (ROCO-), cyanide, Ar 1 -O 2 SO-, nitro and / or -NH-CO-NH-Ar 1 radicals, where R is a C 1 -C 5 -alkyl, preferably a methyl and / or ethyl radical, a C 2 -C 5 -alkenyl, a C 2 -C 5 -alkynyl or a phenyl radical, and where Ar 1 is an aromatic radical A radical, preferably a phenyl radical, which is optionally substituted with one or more C 1 -C 5 -alkyl, preferably methyl and / or ethyl
  • Ar is an aryl radical, in particular a phenyl, a 1- or a 2-naphthyl radical.
  • Y is an aryl radical, in particular a phenyl, a 1- or a 2-naphthyl radical, or an arylamino radical, especially a phenylamino or a naphthylamino radical.
  • Ar is a phenyl radical and Y is a phenyl or a phenylamino radical.
  • Ar is a 4-methoxycarbonylphenyl radical and Y is a phenyl or a phenylamino radical.
  • the color developer of the heat-sensitive recording material according to the invention is selected from the group consisting of N-phenyl-N '[(phenylamino) sulfonyl] urea, N- (4-methylphenyl) -N' [(4-methylphenylamino) sulfonyl] -urea, N- (4-ethoxycarbonylphenyl) -N '[(4-ethoxycarbonylphenylamino) sulfonyl] urea, N- (1-naphthyl) -N' [(1-naphthylamino) sulfonyl] urea, N - [(phenylamino ) sulfonyl] benzamide, N - [(4-methoxycarbonylphenyl) aminosulfonyl] benzamide, N - ( ⁇ 2 - [(phenylcarbamoyl
  • the compounds of the formula I can be prepared by known processes.
  • the compound of the formula (I) is preferably present in an amount of about 3 to about 35% by weight, particularly preferably in an amount of about 10 to about 25% by weight, based on the total solids content of the heat-sensitive layer.
  • the carrier substrate is not critical. However, it is preferred to use paper, synthetic paper and / or a plastic film as the carrier substrate. If necessary, there is at least one further intermediate layer between the carrier substrate and the heat-sensitive layer. At least one protective layer and / or at least one layer which promotes printability can also be present in the heat-sensitive recording material according to the invention, these layers being applied to the front or back of the substrate.
  • the color former is a triphenylmethane type, fluorane type, azaphthalide type and / or fluorene type dye.
  • a very particularly preferred color former is a dye of the fluoran type, since, thanks to its availability and the balanced application-related properties, it enables the provision of a recording material with an attractive price-performance ratio.
  • the color formers can be used individually or as mixtures of two or more color formers, provided the desirable performance properties of the recording materials do not suffer.
  • At least two compounds falling under the formula I are present as color developers.
  • one or more further (bis) phenolic or non-phenolic color developers can be present in the heat-sensitive color-forming layer in addition to the compound (s) of the formula I.
  • the one or more other non-phenolic color developers are preferably 4-methyl-N - [[[3 - [[(4-methylphenyl) sulfonyl] oxy] phenyl] amino] carbonyl] benzenesulfonamide or N- [2 - [[(phenylamino) carbonyl] amino] phenyl] benzenesulfonamide.
  • one or more sensitizers also called thermal solvents
  • one or more sensitizers can be present in the heat-sensitive color-forming layer, which has the advantage that the control of the thermal pressure sensitivity is easier to implement.
  • substances with a melting point between about 90 and about 150 ° C. that dissolve the color-forming components (color former and color developer) in the molten state without interfering with the formation of the color complex are advantageous as sensitizers.
  • the sensitizer is a fatty acid amide, such as stearamide, beheneamide or palmitamide, an ethylene-bis-fatty acid amide, such as N, N'-ethylene-bis-stearic acid amide or N, N'-ethylene-bis-oleic acid amide, a wax such as polyethylene wax or Montan wax, a carboxylic acid ester such as dimethyl terephthalate, dibenzyl terephthalate, benzyl p-benzyloxybenzoate, di- (p-methylbenzyl) oxalate, di- (p-chlorobenzyl) oxalate or di- (p-benzyl) oxalate, an aromatic ether such as 1, 2-diphenoxyethane, 1,2-di- (3-methylphenoxy) ethane, 2-benzyloxynaphthalene or 1,4-diethoxynaphthalene, an aromatic sulfone, such as diphenyl sulf
  • At least one stabilizer is present in the heat-sensitive color-forming layer.
  • the stabilizer is preferably sterically hindered phenols, particularly preferably 1,1,3-tris- (2-methyl-4-hydroxy-5-cyclohexyl-phenyl) -butane, 1,1,3-tris- ( 2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,1-bis (2-methyl-4-hydroxy-5-tert-butylphenyl) butane.
  • urea-urethane compounds of the general formula (II) are particularly preferred.
  • the stabilizer is preferably present in an amount of 0.2 to 0.5 part by weight, based on the at least one phenol-free color developer of the compound of the formula (I).
  • At least one binder is present in the heat-sensitive color-forming layer.
  • These are preferably water-soluble starches, starch derivatives, starch-based biolatices of the EcoSphere® type, methyl cellulose, hydroxyethyl cellulose, carboxymethyl celluloses, partially or completely saponified polyvinyl alcohols, chemically modified polyvinyl alcohols or styrene-maleic anhydride copolymers, styrene-butadiene copolymers, styrene-butadiene copolymers acrylate copolymers, acrylamide-acrylate-methacrylate terpolymers, polyacrylates, poly (meth) acrylic acid esters, acrylate-butadiene copolymers, polyvinyl acetates and / or acrylonitrile-butadiene copolymers.
  • At least one release agent (anti-stick agent) or lubricant is present in the heat-sensitive color-forming layer.
  • agents are preferably fatty acid metal salts such as zinc stearate or calcium stearate, or also behenate salts, synthetic waxes, for example in the form of fatty acid amides such as stearic acid amide and behenic acid amide, fatty acid alkanolamides such as stearic acid methylolamide, paraffin waxes with different melting points, ester waxes different molecular weights, ethylene waxes, propylene waxes of different hardnesses and / or natural waxes, such as carnauba wax or montan wax.
  • fatty acid metal salts such as zinc stearate or calcium stearate, or also behenate salts
  • synthetic waxes for example in the form of fatty acid amides such as stearic acid amide and behenic acid amide, fatty acid alkanolamides such as
  • the heat-sensitive color-forming layer contains pigments.
  • pigments have the advantage, among other things, that they can fix the chemical melt created in the thermal printing process on their surface.
  • the surface whiteness and opacity of the heat-sensitive color-forming layer and its printability with conventional printing inks can also be controlled via pigments.
  • pigments have an "extender function", for example for the relatively expensive functional coloring chemicals.
  • Particularly suitable pigments are inorganic pigments, both of synthetic and natural origin, preferably clays, precipitated or natural calcium carbonates, aluminum oxides, aluminum hydroxides, silicas, precipitated and pyrogenic silicas (e.g. Aerodisp® types), diatomaceous earths, magnesium carbonates, talc, but also organic pigments, such as hollow pigments with a styrene / acrylate copolymer wall or urea / formaldehyde condensation polymers. These can be used alone or in any mixtures.
  • optical brighteners can be incorporated into the heat-sensitive color-forming layer. These are preferably stilbenes.
  • rheological aids such as. B. thickeners and / or surfactants to add.
  • the application weight per unit area of the (dry) heat-sensitive layer is preferably about 1 to about 10 g / m 2 , more preferably about 3 to about 6 g / m 2 .
  • the heat-sensitive recording material is one according to claim 2, a dye of the fluorane type being used as the color former and, in addition, a sensitizing agent selected from the group consisting of fatty acid amides, aromatic sulfones and / or aromatic ethers , is present.
  • a sensitizing agent selected from the group consisting of fatty acid amides, aromatic sulfones and / or aromatic ethers .
  • the heat-sensitive recording material according to the invention can be obtained by known production methods.
  • the recording material according to the invention with a process in which an aqueous suspension containing the starting materials of the heat-sensitive color-forming layer is applied to a carrier substrate and dried, the aqueous application suspension having a solids content of about 20 to about 75% by weight. , preferably from about 30 to about 50% by weight, and is applied and dried using the curtain coating method at an operating speed of the coating system of at least about 400 m / min.
  • the heat-sensitive recording material according to the invention by means of a method in which the aqueous application suspension is applied using the curtain coating method at an operating speed of the coating system of at least about 400 m / min.
  • the so-called curtain coating process is known to the person skilled in the art and is characterized by the following criteria:
  • the coating dispersion which is in the form of a thin film (curtain), is "poured" onto a substrate by free fall in order to apply the coating dispersion to the substrate.
  • the DE 10196052 T1 discloses the use of the curtain coating method in the production of information recording materials, including heat-sensitive recording materials, with multilayer recording layers being made by applying the curtain consisting of several coating dispersion films to substrates (max. 200 m / min).
  • the operating speed of the coating system has both economic and technical advantages.
  • the operating speed is particularly preferably at least about 750 m / min, very particularly preferably at least about 1000 m / min and very particularly preferably at least about 1500 m / min. It was particularly surprising that even at the last-mentioned speed, the heat-sensitive recording material obtained is in no way impaired and that the operation is carried out optimally even at this high speed.
  • the aqueous, deaerated application suspension has a viscosity of about 150 to about 800 mPas (Brookfield, 100 rpm, 20 ° C.). If the value falls below about 150 mPas or the value of about 800 mPas is exceeded, then this leads to inadequate runnability of the coating slip on the coating unit.
  • the viscosity of the aqueous, deaerated application suspension is particularly preferably about 200 to about 500 mPas.
  • the surface tension of the aqueous application suspension can be adjusted to about 25 to about 60 mN / m, preferably to about 35 to about 50 mN / m (measured according to the static ring method according to Du Noüy, DIN 53914).
  • the heat-sensitive color-forming layer can be formed on-line or off-line in a separate coating process. This also applies to any subsequently applied layers or intermediate layers.
  • the dried heat-sensitive color-forming layer is subjected to a smoothing measure.
  • the surface of the recording material is preferably smoothed with a shoe smoothing device according to FIG DE 10 2004 029 261 B4 . It is advantageous here to set the Bekk smoothness, measured in accordance with ISO 5627, to about 100 to about 1000 seconds, preferably to about 250 to about 600 seconds.
  • the surface roughness (PPS) according to ISO 8791-4 is preferably in the range from approximately 0.50 to approximately 2.50 ⁇ m, particularly preferably between 1.00 and 2.00 ⁇ m.
  • the present invention also relates to a heat-sensitive recording material which can be obtained by the method described above.
  • the method described above is advantageous from an economic point of view and allows the coating system to be carried out at a high level, even at a speed of more than 1500 m / min, without adversely affecting the process product, i.e. the heat-sensitive recording material according to the invention.
  • the process can be carried out on-line and off-line, which results in a desirable flexibility.
  • the heat-sensitive recording material according to the invention is phenol-free and well suited for POS (point-of-sale) and / or label applications. It is also suitable for the production of parking tickets, tickets, entry tickets, lottery and betting tickets, etc., which can be printed in direct thermal processes and the images recorded on it are highly durable under long-term storage, even under harsh climatic conditions with regard to temperature and ambient humidity, and the Bringing the typeface into contact with hydrophobic substances, such as plasticizers, greasy or oily substances, etc., is guaranteed.
  • the application of an aqueous application suspension for the formation of the heat-sensitive color-forming layer of a heat-sensitive recording paper was carried out on a laboratory scale by means of a bar doctor blade on one side of a synthetic base paper (Yupo® FP680) of 63 g / m 2 (coating formulations R1, R2) or of a paper with an undercoat 45 g / m 2 (coating formulations R3 to R11), the precoat being formulated with organic hollow sphere pigments (of the Ropaque TM type). After drying, a thermal recording sheet was obtained.
  • the application amount of the heat-sensitive color-forming layer was between 4.0-4.5 g / m 2 .
  • the aqueous application suspension was applied to a paper web with a basis weight of 43 g / m 2 by means of the curtain coating method.
  • the viscosity of the aqueous application suspension was 450 mPas (according to Brookfield, 100 rpm, 20 ° C.) (in the deaerated state). Their surface tension was 46 mN / m (statistical ring method).
  • the string unit was arranged in-line.
  • the curtain coating process was operated at a speed of 1550 m / min.
  • the coated paper carrier was dried in the usual way.
  • the basis weight application of the dry heat-sensitive layer was 4.0-4.5 g / m 2 .
  • a heat-sensitive recording material or thermal paper was produced, the following formulations of aqueous application suspensions being used to form a composite structure on a carrier substrate and then the other layers, in particular a protective layer, being formed in the usual way, which is not discussed separately here shall be.
  • the aqueous dispersion A1 (color former dispersion) is prepared by grinding 20 parts by weight of 3-Nn-dibutylamine-6-methyl-7-anilinofluoran (ODB-2) with 33 parts by weight a 15% aqueous solution of Ghosenex TM L-3266 (sulfonated polyvinyl alcohol, Nippon Ghosei) in a pearl mill.
  • the aqueous dispersion A2 (2-component color-forming agent dispersion) is a mixture of two color-forming agents, which is obtained by mixing a first dispersion obtained by grinding 12 parts by weight of 3-Nn-dibutylamine-6-methyl-7-anilinofluorane (ODB- 2) with 20 parts by weight of a 15% aqueous solution of Ghosenex TM L-3266 in a pearl mill, and a second dispersion made by grinding 8 parts by weight of 3- (N-ethyl-N- isopentylamino) -6-methyl-7-anilinofluoran (S-205) with 14 parts by weight of a 15% aqueous solution of Ghosenex TM L-3266 in a bead mill.
  • the aqueous dispersion B1 (color developer dispersion) is prepared by grinding 40 parts by weight of the color developer together with 66 parts by weight of a 15% strength aqueous solution of Ghosenex TM L-3266 in the pearl mill.
  • the aqueous dispersion B2 (2-component color developer dispersion made from FE I and FE II) was prepared by mixing a first dispersion obtained by grinding 20 parts of FE I with 33 parts by weight of a 15% aqueous solution of Ghosenex TM L-3266 in a Bead Mill and a second color developer dispersion made by grinding 20 parts by weight of FE II with 33 parts by weight of a 15% aqueous solution of Ghosenex TM L-3266 in a bead mill (for definitions of FEI and FEII, reference is made to Tables 3 and 4).
  • the aqueous dispersion B3 (2-component color developer dispersion from FE I and FE II) was prepared by mixing a first dispersion, which is obtained by grinding 28 parts of FE I with 46 parts by weight of a 15% aqueous solution of Ghosenex TM L-3266 in a Bead Mill and a second color developer dispersion made by grinding 12 parts by weight of FE II with 20 parts by weight of a 15% aqueous solution of Ghosenex TM L-3266 in a bead mill.
  • Aqueous Dispersion C (Sensitizer Dispersion) was prepared by grinding 40 parts by weight of sensitizer with 33 parts by weight of a 15% aqueous solution of Ghosenex TM L-3266 in a bead mill.
  • Aqueous dispersion D antioxidant or stabilizer dispersion
  • UU urea-urethane
  • Ghosenex TM L-3266 aqueous solution of Ghosenex TM L-3266 in a pearl mill .
  • All dispersions produced by grinding have an average particle size D (4.3) of 0.80-1.20 ⁇ m.
  • the binder consists of a 10% aqueous polyvinyl alcohol solution (Mowiol 28-99, Kuraray Europe)
  • the application suspension is prepared by mixing the dispersions with stirring in accordance with the quantities given in Table 1, taking into account the order of entry B, E, C, D, P, A, binder and brought to a solids content of approx. 25% with water.
  • the particle size distribution of the application dispersions was measured by laser diffraction using a Coulter LS230 device from Beckman Coulter.
  • Table 2 summarizes the developers used in the example formulations.
  • Sample preparation 2 circular areas are punched out of the paper sample with a punch and weighed.
  • the paper samples are extracted with 3 ml of acetonitrile (HPLC quality) in an ultrasonic bath for 30 minutes and the extract is filtered off through a PTFE syringe filter (0.45 ⁇ m).
  • HPLC separation of the ingredients the above extract was applied to the separation column (Zorbax Eclipse XDB-C18) by means of an autosampler and eluted with the eluent acetonitrile: THF: H 2 O (450: 89: 200 parts by weight) with an acetonitrile gradient. Quantitative evaluation of the chromatograms is carried out by comparing the area of the sample peaks assigned via tr times with a calibration line determined via the reference sample. The measurement error in the HPLC quantification is ⁇ 2%.
  • Table 3 summarizes the evaluation of the recording materials produced with synthetic paper (Yupo® FP680) as the carrier, Table 4 the evaluation of the recording materials produced with a prepainted carrier paper.
  • Table 5 shows the maximum image densities achieved (OD max.) Of the fresh papers with the corresponding values after thermal printing of the (unprinted) stored papers for 4 weeks at 60 ° C and 50% relative humidity, as well as the change in paper whiteness after storage shown for selected patterns.
  • FEI is FE1
  • FEII is FE10
  • No. 28 FEI is FE5
  • FEII is FE10
  • No. 29 FEI is FE1
  • FEII is FE10
  • No. 30 FEI is FE5
  • FEII is FE10 ** Comparison Evaluation of selected samples from Table 3 after storage * in the unprinted state Test parameters Sample (no.) 5 6th 7th 9 10 (comparison) 11 (comparison) Surface whiteness (%) fresh 88.5 89.9 87.9 88.2 88.2 88.5 4 weeks storage 75.3 83.4 70.0 69.6 69.7 76.0 % Change - 14.9 -7.6 - 20.3 15.5 -20.9 -14.1 o.

Claims (15)

  1. Matériau d'enregistrement thermosensible comprenant un substrat de support et une couche chromogène thermosensible contenant au moins un agent chromogène et au moins un révélateur chromogène exempt de phénol, ledit au moins un agent chromogène étant un colorant du type triphénylméthane, du type fluorane, du type azaphthalide et/ou du type fluorène,
    caractérisé en ce que ledit au moins un révélateur chromogène est un composé de la formule (I)
    Figure imgb0010
     dans laquelle Ar est un radical aryle ou un radical benzyle, et Y est un radical aryle, radical benzyle, un radical aryloxy, un radical benzyloxy, un radical arylamino, un radical benzylamino.
  2. Matériau d'enregistrement thermosensible selon la revendication 1, caractérisé en ce que Ar et/ou Y contient au moins un substituant.
  3. Matériau d'enregistrement thermosensible selon la revendication 2, caractérisé en ce que ledit au moins un substituant est choisi parmi le groupe comprenant les radicaux alkyle en C1-C5, alcényle en C2-C5, alcynyle en C2-C5, alcoxy (RO-), halogénure, carboxyle (ROCO-), cyanure, Ar1-O2SO-, nitro, -NH-CO-NH-Ar1,
    R étant un radical alkyle en C1-C5, alcényle en C2-C5, alcynyle en C2-C5 ou phényle, et Ar1 étant un radical aromatique, de préférence un radical phényle, qui est éventuellement substitué par un ou plusieurs radicaux alkyle en C1-C5, alcényle en C2-C5 et/ou alcynyle en C2-C5.
  4. Matériau d'enregistrement thermosensible selon l'une des revendications précédentes,
    caractérisé en ce que Ar est un radical phényle et Y est un radical arylamino.
  5. Matériau d'enregistrement thermosensible selon l'une des revendications précédentes,
    caractérisé en ce que Ar est un radical phényle et Y est un radical 4-méthoxycarbonylphényle.
  6. Matériel d'enregistrement thermosensible selon l'une des revendications précédentes,
    caractérisé en ce que le révélateur chromogène exempt de phénol est choisi parmi le groupe constitué par N-phényl-N'[(phénylamino)sulfonyl]urée,N-(4-méthylphényl)-N'[(4-méthylphénylamino)sulfonyl]urée, N-(4-éthoxycarbonylphényl)-N'[(4-éthoxycarbonylphénylamino)sulfonyl]urée, N-(1-naphtyl)-N'[(1-naphtylamino)sulfonyl]-urée, N-[(phénylamino)sulfonyl]-benzamide, N- [(4-méthoxycarbonylphényl)aminosulfonyl]-benzamide, N-({2-[(phénylcarbamoyl)amino]phényl}sulfamoyl)benzamide, N-[(4-nitrophényl)aminosulfonyl]benzamide et/ou N-[2-[[(phénylamino)carbonyl]amino]phényl]benzénesulfonamide.
  7. Matériau d'enregistrement thermosensible selon l'une au moins des revendications précédentes,
    caractérisé en ce que ledit au moins un agent chromogène est un colorant du type fluorane.
  8. Matériau d'enregistrement thermosensible selon l'une au moins des revendications précédentes,
    caractérisé en ce que, outre le composé de la formule (I), un ou plusieurs autres révélateurs chromogènes non phénoliques, en particulier de préférence le 4-méthyl-N-[[[3-[[(4-méthylphényl) sulfonyl]oxyjphényl]amino]carbonyl]benzènesulfonamide et/ou le N-[2-[[(phénylamino)carbonyl]amino]phényl]benzènesulfonamide sont présents.
  9. Matériau d'enregistrement thermosensible selon l'une au moins des revendications précédentes,
    caractérisé en ce qu'au moins deux composés de la formule (I) sont présents comme révélateurs.
  10. Matériau d'enregistrement thermosensible selon l'une au moins des revendications précédentes,
    caractérisé en ce qu'environ 0,5 à environ 10 parties en poids, de préférence environ 1,5 à environ 4 parties en poids, du composé de la formule (I), par rapport à l'agent chromogène, sont présentes.
  11. Matériau d'enregistrement thermosensible selon l'une au moins des revendications précédentes,
    caractérisé en ce que le composé de la formule (I) est présent en une quantité d'environ 3 à environ 35 % en poids, de préférence d'environ 10 à environ 25 % en poids, par rapport à la teneur totale en matières solides de la couche thermosensible.
  12. Matériau d'enregistrement thermosensible selon l'une au moins des revendications précédentes,
    caractérisé en ce que la couche chromogène thermosensible contient des agents sensibilisateurs, des stabilisateurs, des liants, des agents séparateurs, des pigments et/ou des agents azurants.
  13. Matériau d'enregistrement thermosensible selon l'une au moins des revendications précédentes,
    caractérisé en ce que la couche chromogène thermosensible contient un composé urée-uréthane de la formule générale (II)
    Figure imgb0011
  14. Procédé de fabrication d'un matériau d'enregistrement thermosensible selon l'une au moins des revendications précédentes,
    caractérisé en ce qu'une suspension aqueuse contenant les matières de départ de la couche chromogène thermosensible est appliquée sur un substrat de support et est séchée,
    dans lequel la suspension aqueuse d'application présente une teneur en matières solides d'environ 20 à environ 75 % en poids, de préférence d'environ 30 à environ 50 % en poids, et est appliquée par le procédé d'enduction au rideau à une vitesse de fonctionnement de la coucheuse d'au moins 400 m/min, de préférence d'au moins 1000 m/min, de manière tout particulièrement préférée d'au moins 1500 m/min, et est séchée.
  15. Matériau d'enregistrement thermosensible pouvant être obtenu par le procédé selon la revendication 14.
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Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SG11201806745RA (en) 2016-02-16 2018-09-27 Univ Queensland Sulfonylureas and related compounds and use of same
EP3305538A1 (fr) * 2016-10-07 2018-04-11 Mitsubishi HiTec Paper Europe GmbH Matériel d'enregistrement sensible à la chaleur
WO2018065330A1 (fr) 2016-10-07 2018-04-12 Mitsubishi Hitec Paper Europe Gmbh Matériau d'enregistrement thermosensible
DE102017102702B4 (de) * 2017-02-10 2019-09-12 Papierfabrik August Koehler Se Wärmeempfindliches Aufzeichnungsmaterial
DE102018102177A1 (de) 2018-01-31 2019-08-01 Mitsubishi Hitec Paper Europe Gmbh Beschichtungszusammensetzung, wärmeempfindliche Aufzeichnungsschicht, wärmeempfindliches Aufzeichnungsmaterial sowie entsprechende Verwendungen und Verfahren
DE102018102180A1 (de) 2018-01-31 2019-08-01 Mitsubishi Hitec Paper Europe Gmbh Wärmeempfindliches Aufzeichnungsmaterial
DE102018133168B4 (de) * 2018-12-20 2021-02-18 Papierfabrik August Koehler Se Wärmeempfindliches Aufzeichnungsmaterial
KR102004118B1 (ko) * 2019-01-16 2019-07-25 최영규 감열지 제조방법 및 이로부터 제조된 감열지
DE102019126220A1 (de) 2019-09-27 2021-04-01 Mitsubishi Hitec Paper Europe Gmbh Wärmeempfindliches Aufzeichnungsmaterial, umfassend phenolfreie organische Farbentwickler
EP3957488A1 (fr) 2020-08-19 2022-02-23 Mitsubishi HiTec Paper Europe GmbH Matériau d'enregistrement thermosensible ainsi que couche d'enregistrement thermosensible et sa composition de revêtement de fabrication, utilisations correspondantes et procédé
DE102023104323A1 (de) 2022-02-22 2023-08-24 Mitsubishi Hitec Paper Europe Gmbh Beschichtung für ein umweltfreundliches wärmeempfindliches Aufzeichnungsmaterial

Family Cites Families (34)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE931225C (de) 1952-06-29 1955-08-04 Hoechst Ag Verfahren zur Herstellung von Stickstoff, Schwefel und Chlor enthaltenden Kondensationsprodukten
DE940292C (de) 1952-07-01 1956-03-15 Hoechst Ag Verfahren zur Herstellung von Stickstoff und Schwefel enthaltenden Kondensationsprodukten
DE940529C (de) 1952-07-01 1956-03-22 Hoechst Ag Verfahren zur Herstellung von acylierten Sulfamiden
US4531139A (en) * 1983-10-02 1985-07-23 The Standard Register Company Color developers for pressure-sensitive or heat-sensitive recording papers
JP3193075B2 (ja) * 1991-07-05 2001-07-30 三菱製紙株式会社 塗被紙の製造方法
JPH06297860A (ja) 1993-04-14 1994-10-25 New Oji Paper Co Ltd 感熱記録体
DE4337847A1 (de) * 1993-11-05 1995-05-11 Bayer Ag Substituierte Phenylaminosulfonylharnstoffe
JP3514901B2 (ja) * 1996-03-25 2004-04-05 新日鐵化学株式会社 感熱記録材料
JP3050126B2 (ja) * 1996-06-11 2000-06-12 日本製紙株式会社 感熱記録体
JPH11216957A (ja) * 1998-02-04 1999-08-10 Nippon Paper Industries Co Ltd 感熱記録体
JP3843586B2 (ja) * 1998-03-23 2006-11-08 日本製紙株式会社 感熱記録体
JP2000229970A (ja) 1999-02-12 2000-08-22 Fuji Photo Film Co Ltd ピロロ［１，２−ａ］ピリミジン化合物、その製造方法および感熱記録材料
US6329116B1 (en) 1998-11-20 2001-12-11 Fuji Photo Film Co., Ltd. Pyrrolo[1,2-a]pyrimidine compound and heat-sensitive recording material using the same
GB9827569D0 (en) 1998-12-16 1999-02-10 Ciba Geigy Ag Heat sensitive recording material
JP2000355172A (ja) * 1999-06-14 2000-12-26 Fuji Photo Film Co Ltd 感熱記録材料
JP4112127B2 (ja) * 1999-08-31 2008-07-02 株式会社リコー 感熱記録材料
US6746718B2 (en) 2000-04-11 2004-06-08 Mitsubishi Paper Mills Ltd. Process of curtain for producing an information recording material
WO2001076884A1 (fr) 2000-04-11 2001-10-18 Mitsubishi Paper Mills Ltd. Procede de production de materiau d'enregistrement d'information et liquide de revetement a utiliser dans ledit procede
US6372421B1 (en) * 2000-06-13 2002-04-16 Eastman Kodak Company Photothermographic imaging element having improved contrast and methods of image formation
JP2003054138A (ja) * 2001-08-14 2003-02-26 Oji Paper Co Ltd 感熱記録体
WO2003059639A1 (fr) * 2001-12-20 2003-07-24 Fuji Photo Film Co., Ltd. Materiau d'impression sensible a la chaleur
JP2003182231A (ja) * 2001-12-20 2003-07-03 Fuji Photo Film Co Ltd 感熱記録材料
JP3733081B2 (ja) 2002-04-04 2006-01-11 昭和高分子株式会社 フェノール樹脂系顕色剤
CN100379580C (zh) * 2003-02-18 2008-04-09 三光株式会社 1,2-双(3-甲基苯氧基)乙烷组合物和通过使用该组合物制备的热记录介质
JP2005238539A (ja) * 2004-02-25 2005-09-08 Nippon Paper Industries Co Ltd 情報用記録材料の製造方法及び情報記録材料
JPWO2005087504A1 (ja) * 2004-03-11 2008-01-24 株式会社エーピーアイ コーポレーション 感熱記録材料用顕色剤混合物及び感熱記録材料
DE102004029261B4 (de) 2004-06-17 2006-05-18 Papierfabrik August Koehler Ag Verfahren zur Herstellung eines wärmeempfindlichen Aufzeichnungsmaterials sowie ein durch das Verfahren hergestelltes Aufzeichnungsmaterial
JP2006068961A (ja) * 2004-08-31 2006-03-16 Fuji Photo Film Co Ltd 感光感熱記録材料
KR20070100255A (ko) * 2005-01-28 2007-10-10 오지 세이시 가부시키가이샤 감열 기록체
JP5485608B2 (ja) * 2008-07-30 2014-05-07 日本製紙株式会社 フェノールスルホン酸エステル、顕色剤及び感熱記録材料
JP5485749B2 (ja) * 2010-03-04 2014-05-07 三菱製紙株式会社 感熱記録材料
CN103072396B (zh) * 2012-11-12 2015-01-07 中国乐凯集团有限公司 一种4-羟基-4’异丙氧基二苯砜热敏显色剂分散液及透明热敏记录材料
US9518011B2 (en) 2012-11-21 2016-12-13 Nippon Soda Co., Ltd. Recording material produced using non-phenol compound
JP2014172195A (ja) * 2013-03-06 2014-09-22 Oji Holdings Corp 感熱記録体

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JP6709227B2 (ja) 2020-06-10
CN107454874A (zh) 2017-12-08
EP3274184A1 (fr) 2018-01-31
US10265985B2 (en) 2019-04-23
US20180079243A1 (en) 2018-03-22
ES2883073T3 (es) 2021-12-03
KR20170129257A (ko) 2017-11-24
DE102015104306A1 (de) 2016-09-29
CN107454874B (zh) 2019-06-14
JP2018513794A (ja) 2018-05-31
BR112017020441B1 (pt) 2022-07-26

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