WO2024078971A1 - Matériau d'enregistrement thermosensible - Google Patents

Matériau d'enregistrement thermosensible Download PDF

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Publication number
WO2024078971A1
WO2024078971A1 PCT/EP2023/077632 EP2023077632W WO2024078971A1 WO 2024078971 A1 WO2024078971 A1 WO 2024078971A1 EP 2023077632 W EP2023077632 W EP 2023077632W WO 2024078971 A1 WO2024078971 A1 WO 2024078971A1
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WO
WIPO (PCT)
Prior art keywords
heat
alkyl
color
group
recording material
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Application number
PCT/EP2023/077632
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German (de)
English (en)
Inventor
Timo DR. STALLING
Ansgar DR. SEHLINGER
Uwe DR. BRASCH
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Koehler Innovation & Technology Gmbh
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Publication of WO2024078971A1 publication Critical patent/WO2024078971A1/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
    • 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
    • B41M5/337—Additives; Binders
    • B41M5/3375—Non-macromolecular compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
    • B41M5/42—Intermediate, backcoat, or covering layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
    • B41M5/42—Intermediate, backcoat, or covering layers
    • B41M5/44—Intermediate, backcoat, or covering layers characterised by the macromolecular compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
    • B41M2205/04—Direct thermal recording [DTR]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
    • B41M2205/36—Backcoats; Back layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • 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

Definitions

  • the present invention relates to a heat-sensitive recording material comprising a carrier substrate which has a first side and a second side facing away from the first side, a heat-sensitive color-forming layer which is arranged on the first side of the carrier substrate and comprises at least one color former, at least one color developer, and at least one stabilizer, and an adhesive layer which is arranged on the second side of the carrier substrate and comprises at least one adhesive.
  • the weight ratio of stabilizer to color developer in the heat-sensitive color-forming layer is selected such that migration of components from the adhesive layer into the heat-sensitive color-forming layer according to the stability test defined in the description leads to a remaining image stability of the heat-sensitive color-forming layer of at least 35% after a period of two weeks.
  • the present invention relates to a method for producing a heat-sensitive recording material, comprising the following method steps: providing a carrier substrate which has a first side and a second side facing away from the first side, applying an application suspension to the first side of the carrier substrate, wherein the application suspension comprises at least one color former, at least one color developer, and at least one stabilizer, drying the application suspension in order to obtain a heat-sensitive color-forming layer arranged on the first side of the carrier substrate, and applying an adhesive layer to the second side of the carrier substrate.
  • the present invention relates to a heat-sensitive recording material producible by a method according to the second aspect.
  • the present invention relates to a use of at least one stabilizer and at least one color developer in a heat-sensitive recording material
  • a heat-sensitive recording material comprising a carrier substrate which has a first side and a second side facing away from the first side, a heat-sensitive color-forming layer which is arranged on the first side of the carrier substrate and comprises at least one color former, at least one color developer, and at least one stabilizer, and an adhesive layer which is arranged on the second side of the carrier substrate, wherein the adhesive layer comprises at least one adhesive.
  • Heat-sensitive recording materials also known as thermal papers, are used in a variety of applications, such as sales receipts in retail stores.
  • Back preparations are used in conjunction with heat-sensitive recording materials to obtain adhesive labels or thermal labels or to improve various application properties.
  • the back preparation can be a self-adhesive layer and/or a coating (“back coat”) consisting essentially of polymeric binders and pigments.
  • Thermal labels Heat-sensitive recording materials with a self-adhesive layer on the back, so-called thermal labels, are known from the state of the art for direct thermal printing.
  • JPS 59 162 087 A, US 4 370 370 A and US 4 388 362 A describe thermal labels with a release paper.
  • DE 19 757 589 B4 describes a release paper-free (“linerless”) thermal label with a protective layer over the heat-sensitive layer.
  • DE19 806 433 B4 discloses a linerless thermal label with a protective layer free of silicone compounds, which has been cured by means of actinic radiation.
  • EP 0600622 A1 and DE 19 724647 C1 describe a linerless thermal label with a protective layer which has been coated on the back with hotmelts.
  • EP 1 085 069 B1 and EP 2 474 963 B1 disclose thermal label materials in linerless design with a heat-activated adhesive, whereby thermal labels are described both with and without a protective layer.
  • EP 3 219 507 A1 claims a linerless thermal label without an actual protective layer, in which the surface of the heat-sensitive layer is designed to be dehesive towards adhesives.
  • Heat-sensitive recording materials equipped with so-called “back-coat” coatings to improve the printability of the back side with conventional printing processes or to minimize the curling of a carrier substrate under unfavorable humidity conditions are also known from the prior art.
  • JP 2018 167483 discloses ways to improve the durability of the thermally generated typeface in heat-sensitive recording materials, which have been coated on the back with oil-based printing inks or inks by applying coatings to the back.
  • the formulations of these back coatings often contain aqueous emulsion polymers, such as styrene-butadiene or acrylate latices, as an essential component.
  • JP 2003 175 671 claims back-coatings for heat-sensitive recording materials produced with aqueous latices, which form soft polymer films (glass transition temperature >-30°C).
  • JPH 0 720 735 B2 and JP 2000 204 123 disclose back-coat formulations with acrylate emulsion polymers for heat-sensitive recording materials.
  • the publications EP 3 957 488 A1 and WO 2022/038242 A1 describe a heat-sensitive recording layer comprising phenol group-free organic color developers, a coating composition for producing the heat-sensitive recording layer and a heat-sensitive recording material, in particular thermal paper, comprising the heat-sensitive recording layer.
  • the use of the heat-sensitive recording layer for producing the heat-sensitive recording material, a process for producing the heat-sensitive recording material and the use of the heat-sensitive recording material in thermal paper applications are also described. Due to its composition, the heat-sensitive recording material has particularly good recyclability and high environmental compatibility.
  • Heat-sensitive recording materials are also described in the publications US 2021/0060994, CA 3 149 562 A1 and WO 2021/041600 A2.
  • the colour-forming layer of heat-sensitive recording materials usually contains a colour former and a colour developer, which, under the influence of heat, react with each other and thus lead to color development.
  • Inexpensive color developers containing phenol groups bisphenol A, bisphenol S, etc. are widely used. These can be used to produce thermal labels that have an acceptable performance profile for certain applications.
  • Thermal labels that contain a phenol group-free color developer in the heat-sensitive color-forming layer are also known from the state of the art. These were developed to improve the durability of the typeface, especially when the printed heat-sensitive recording material comes into contact with hydrophobic substances, such as plasticizer-containing substances or materials or oils. In addition to the technical advantages, public discussions about the toxic potential of (bis)phenolic chemicals have greatly stimulated interest in phenol group-free color developers.
  • thermally printed self-adhesive thermal labels or heat-sensitive recording materials with back-coatings can result in impairments in the application properties.
  • heat-sensitive recording materials with such back-coatings may no longer achieve the specified values for the degree of blackness of the print (e.g. the barcode or the typeface) or the surface whiteness after storage.
  • the cause of this phenomenon is said to be the adhesive layer on the back, from which substances migrate through the carrier substrate into the chemically reactive heat-sensitive recording layer over the course of storage and interact with it in a way that is harmful to the color complex.
  • Substances with a relatively low molecular weight ( ⁇ 10 kDa) contribute to the migration problem. Impairment of performance after storage can also occur when a heat-activated adhesive, ie one that is solid at room temperature, is used.
  • colour developers with more complex chemical structures than structurally relatively simple (bis)phenols which have a large number of reactive sites in the molecule, as is often the case with colour developers free of phenol groups, can be affected by the problem of undesirable interaction with substances that can be released from heat-sensitive recording materials provided with a backside preparation.
  • typical pressure-sensitive adhesive formulations use a base polymer as well as non-polymeric tacky resins (e.g. natural or carbon resins) and/or plasticizers, tackifiers and possibly other small-molecular additives such as crosslinkers, stabilizers, etc. If one takes into account that the base polymers contain residual monomers or oligomers from the synthesis process and can form further monomers due to the hydrolytic degradation promoted by high ambient humidity and temperatures, the migration potential of small-molecular substances inherent in an adhesive layer can easily be recognized.
  • non-polymeric tacky resins e.g. natural or carbon resins
  • plasticizers e.g., plasticizers, tackifiers and possibly other small-molecular additives such as crosslinkers, stabilizers, etc.
  • the object of the present invention is to optimize the property profile of a thermally printed heat-sensitive recording material which has an adhesive layer on the back, in particular to achieve the greatest possible limitation of the loss of image stability after storage of the heat-sensitive recording material, in particular when the heat-sensitive recording material is stored over a longer period of time.
  • the image stability is characterized by the image durability after storage of the heat-sensitive recording material, whereby the image stability can also be characterized in particular by the print contrast.
  • the present invention aims to improve the minimum shelf life of a heat-sensitive recording material, while at the same time maintaining the usual high requirements for such a heat-sensitive recording material, such as dynamic sensitivity, contrast, etc.
  • this combination consisting of the corresponding at least one color developer and stabilizer in the heat-sensitive layer of the heat-sensitive recording material leads to a limitation of the loss of image stability after storage under demanding environmental conditions of heat-sensitive recording materials provided with backside preparations, so that the use of both components in the heat-sensitive layer leads to a synergistic effect.
  • a heat-sensitive recording material comprising a carrier substrate which has a first side and a second side facing away from the first side; a heat-sensitive color-forming layer which is arranged on the first side of the carrier substrate, wherein the heat-sensitive color-forming layer comprises at least one color former, at least one color developer, and at least one stabilizer; and an adhesive layer which is arranged on the second side of the carrier substrate, wherein the adhesive layer comprises at least one adhesive; wherein the weight ratio of stabilizer to color developer in the heat-sensitive color-forming layer is selected such that migration of components from the adhesive layer into the heat-sensitive color-forming layer according to the stability test defined in the description after a period of two weeks leads to a remaining image stability of the heat-sensitive color-forming layer of at least 35%.
  • the at least one colour developer comprises a compound of formula (Nl): wherein R1, R2, and R3 are independently selected from the group comprising hydrogen, halogen, nitro, C1-C4-alkyl, C1-C4-alkoxyl, C2-C4-alkenyl, C1-C4-fluoroalkyl, N(R4)2, NHCORs, optionally substituted phenyl, and optionally substituted benzyl, wherein R4 is selected from the group comprising hydrogen, phenyl, benzyl, and C1-C4-alkyl, wherein R5 is selected as C1-C4-alkyl, wherein n1 and n3 are independently selected from an integer from 1 to 5, and wherein n2 is an integer from 1 to 4; and/or the at least one color developer comprises a compound of formula (1): where Ri is selected from the group comprising unsubstituted or substituted phenyl, naphthyl and Ci-C
  • the combination of the stabilizer and the color developer in the heat-sensitive color-forming layer advantageously leads to the limitation of the loss of image stability and in particular also of the relative print contrast, whereby the image stability and/or the relative print contrast of the heat-sensitive recording material stored according to the stability test (as defined below) is always greater than is the value obtained using the same heat-sensitive recording material without the use of the stabilizer. This effect is particularly evident in the commercially available, critical medium current range of 9.00 mJ/mm 2 .
  • the stabilizer due to the color complex-stabilizing interactions resulting from its functional groups, such as hydrogen bonds, TT-TT interactions and/or ionic interactions, contributes to the preservation of the color complex, in interaction with the color developer and color former, and of the typeface under the influence of destabilizing influences such as water, chemicals and critical climatic conditions.
  • the at least one stabilizer comprises a compound of formula (I) which does not comprise a hydroxy-substituted phenyl radical and can thus also be referred to in particular as a phenol group-free compound.
  • the at least one color developer comprises a compound of the formula (N-I) or (1) which does not comprise a hydroxy-substituted phenyl radical and can thus also be referred to in particular as a phenol group-free compound.
  • the heat-sensitive recording material is well suited for applications in which the heat-sensitive recording material is provided with an adhesive layer on the back, which is printed using the direct thermal process and must ensure a long storage life even under critical environmental conditions, with regard to the specified image stability and print contrast values.
  • the present invention is not subject to any significant restrictions with regard to the choice of adhesive applied to the back.
  • the application technology of the adhesive to the back of the heat-sensitive recording material does not restrict the scope of the invention in any way.
  • Aqueous dispersions of the adhesive or adhesives dissolved or suspended in organic media, as well as adhesives applied in a molten state, so-called hotmelt adhesives, can be used.
  • the heat-sensitive recording material according to the invention relates to the application-relevant case of a self-adhesive heat-sensitive recording material, i.e. a heat-sensitive recording material which has an adhesive layer on the side of the carrier substrate facing away from the heat-sensitive color-forming layer
  • the stability test defined below comprises storing the heat-sensitive recording material for a period of two weeks between two glass plates at 60°C, at a pressure of 1350 N/m 2 , at a relative humidity of 50% and under exclusion of light.
  • the image stability of the heat-sensitive recording material is determined based on the optical density once before the heat-sensitive recording material is stored and after the heat-sensitive recording material has been stored for two weeks.
  • the two determined values of the optical density are related to one another as illustrated by the following formula A, with the scatter of the calculated % values being ⁇ 2 percentage points:
  • Image stability in % (optical density after storage / optical density before storage) x 100 (Formula A)
  • the optical density was measured using a SpectroEye densitometer from X-Rite, with the measurement uncertainty of the measured value being estimated at ⁇ 2%.
  • the image stability of a heat-sensitive recording material according to the present invention tested according to the stability test preferably at an energization energy of 9.00 mJ/mm 2 , is at least 35% after the storage period of two weeks.
  • a DIN A4 heat-sensitive recording material with an adhesive layer on the side of the carrier substrate facing away from the heat-sensitive color-forming layer is divided lengthwise into at least two 6 cm wide strips.
  • a strip of this is printed and measured to determine the optical density before storage.
  • the unprinted strip is placed on the printed strip (simulating a thermal roll) and then the stack is stored for two weeks (or, according to some embodiments, for four weeks) between two glass plates at 60°C, at a pressure of 1350 N/m 2 , at a relative humidity of 50% and in the absence of light.
  • the optical density is determined, averaged and related to the initial optical density values determined before storage to determine the image permanence according to Formula A above.
  • the relative print contrast can also be taken into account as a further criterion for the image stability of the heat-sensitive recording material.
  • the relative print contrast (DK in %) is calculated based on the value of the optical density of a thermally printed area, i.e. an optical density of a print pattern (oDs) and the optical density of a non-printed area (oDw) according to the following formula B, whereby the scatter of the calculated % values is ⁇ 2 percentage points:
  • the relative print contrast of a heat-sensitive recording material examined according to the stability test preferably at an energization energy of 9.00 mJ/mm 2 , is at least 50% after the storage period of two weeks.
  • the stabilizer comprises a compound of formula (I): wherein R and R are independently selected from the group comprising hydrogen, Ci-Cis-alkyl, Ci-Cs-alkoxy-Ci-Cs-alkyl, and (Rg ⁇ N-Ci-Cs-AI- kyl, wherein Rg is selected from the group comprising Ci-Cs-alkyl, Cs-Ce-cycloalkyl; or a compound of formula (II)
  • the hydrocarbon group having three or four carbon atoms formed by R2 and R3 and Rs and Rs together includes trimethylene, tetramethylene, propenylene, 2-butenylene or 1,3-butadienylene.
  • Rs is selected as a halogen, with Rs more preferably selected as chlorine.
  • Q is selected from -CH2-, -CH2-CH2-, -CH2-O-, -CH2-CH2-O-, -CH2-CH2- CH 2 -, -CH2-CH2-CH2-, -C(Me)H-, -C(Et)H-, -C(n-Pr)H-, -C(i-Pr)H-, -C(n-Bu)H-, -C(i-Bu)H-, -C(sec-Bu)H-, -C(tert-Bu)H-, -C(Me)HCH2-, -CMe2CH2-, where Q is more preferably selected from -CH2-, -CH2-CH2-, -CH2-CH2-O- or -C(Me)H-.
  • the selection “Ci-Ci8-alkyl” includes methyl, ethyl, propyl, isopropyl, N-butyl, isobutyl, sec-butyl, tert-butyl, amyl, tert-amyl (1,1-dimethylpropyl), 1,1,3,3-tetramethylbutyl, N-hexyl, 2-methylpentyl, neopentyl, N-heptyl, 2-ethylhexyl or N-octyl, N-nonyl, N-decyl, N-undecyl, N-dodecyl, N-tridecyl, N-tetradecyl, N-pentadecyl, N-hexadecyl, N-heptadecyl, or N-octadecyl.
  • the selection “Ci-Cs-alkyl” comprises methyl, ethyl, propyl, isopropyl, N-butyl, isobutyl, sec-butyl, tert-butyl, amyl, tert-amyl (1,1-dimethylpropyl), 1,1,3,3-tetramethylbutyl, N-hexyl, 2-methylpentyl, neopentyl, N-heptyl, 2-ethylhexyl or N-octyl, or tridecyl, more preferably methyl, ethyl, N-propyl, isopropyl, N-butyl, isobutyl, sec-butyl, tert-butyl, 2-ethylhexyl or tridecyl.
  • the selection “Ci-Cs-alkoxy” includes methoxy, ethoxy, N-propoxy, isopropoxy, N-butyloxy, N-pentyloxy, N-hexyloxy, N-heptyloxy, or N-octyloxy. More preferably, the selection “Ci-Cs-alkoxy” includes the selection “Ci-Cs-alkoxy”, even more preferably methoxy, ethoxy, N-propoxy, isopropoxy, N-butyloxy, or N-hexyloxy.
  • the selection “Ci-Cs-alkoxy-Ci-Cs-alkyl” comprises methoxymethyl, ethoxymethyl, N-propoxymethyl, isopropoxymethyl, N-butyloxymethyl, N-pentyloxymethyl, N-hexyloxymethyl, N-heptyloxymethyl, N-octyloxymethyl, methoxyethyl, ethoxyethyl, N-propoxyethyl, isopropoxyethyl, N-butyloxyethyl, N-pentyloxyethyl, N-hexyloxyethyl, N-heptyloxyethyl, N-octyloxyethyl, methoxymethyl, 1-methoxyethyl, 2-methoxyethyl, 3-methoxy-n-propyl, 1-methoxy-2-propyl, 4-methoxy-n-butyl, 5-methoxy-n-pent
  • Cs-Cs-cycloalkyl comprises cyclopentyl or cyclohexyl, more preferably cyclohexyl.
  • the selection “(R ⁇ N-Ci-Cs-alkyl” comprises 2-(dimethylamino)methyl, 2-(dimethylamino)ethyl, 2-(diethylamino)ethyl, 2-(diisopropylamino)ethyl, 2-(n-propylamino)ethyl, 3-(dimethylamino)propyl, or 3-(cyclohexylamino)propyl.
  • the selection “R2 and R3 together” comprises tetramethylene if R2 and R3, or R4 and R5 or both, or if R3 and R4, or R5 and Re or both, or if (R2 and R3) and (R5 and Re) together form a hydrocarbon group having three or four carbon atoms, such as in particular trimethylene, tetramethylene, propenylene, 2-butenylene, or 1,3-butadienylene.
  • the compound of formula (II) is phenyl, benzyl, 3-methylphenyl, 2,6-diethylphenyl, o-isopropylphenyl, p-acetamidophenyl, 1-phenylethyl, 2-phenylethyl, 2-phenoxyethyl, 1-tetralino, or 2-tetralino.
  • the stabilizer comprises a compound of formula (la): or the stabilizer comprises a compound of formula (Ib):
  • the compound of formula (Ia) comprises at least one of the following compounds, 5-(N-benzyl-sulfonylamido)-(N',N"-dibenzyl)-isophthalic acid diamide, 5-(N-3-methylphenyl-sulfonylamido)-(N',N"-bis-(3-methylphenyl)-isophthalic acid diamide, 5-(N- 2,6-diethylphenyl-sulfonylamido)-(N',N"-bis-(2,6-diethylphenyl)-isophthalic acid diamide, 5-(N-phenyl-sulfonylamido)-(N',N"-bisphenyl)-isophthalic acid diamide, 5-(No-isopropyl- phenyl-sulfonylamido)-(N',N"-bis-(o-isopropylphenyl)-isophthalic acid diamide
  • the heat-sensitive marking material comprises a bisamide of the formula (Ic):
  • the stabilizer is selected as a compound of formula (Ia) and the heat-sensitive recording material comprises a bisamide of formula (Ic), more preferably the amount of bisamide (Ic) is from 0.01 mol% to 10 mol% with respect to the compound of formula (Ia).
  • the stabilizer comprises 5-(N-3-methylphenyl-sulfonylamido)-(N',N"-bis- ⁇ 3-methylphenyl)-isophthalic acid diamide.
  • the compound 5-(N-3-methylphenylsulfonylamido)-(N',N"-bis- ⁇ 3-methylphenyl)isophthalic acid diamide comprises in particular three different polymorphic forms, comprising an ⁇ -polymorphic form with a melting point determined by DSC of 211.2 °C, a ⁇ -polymorphic form with a melting point determined by DSC of 192.2 °C and a ⁇ -polymorphic form with a melting point determined by DSC of 215.6 °C.
  • the at least one colour developer comprises a compound of formula (Nl): wherein R1, R2, and R3 are independently selected from the group comprising hydrogen, halogen, nitro, C1-C10 alkyl, C1-C10 alkoxyl, C2-C10 alkenyl, C1-C10 fluoroalkyl, N(R4)2, NHCORs, optionally substituted phenyl, and optionally substituted benzyl, wherein R4 is selected from the group comprising hydrogen, phenyl, benzyl, and C1-C10 alkyl, wherein R5 is selected as C1-C10 alkyl, wherein n1 and n3 are independently selected from an integer from 1 to 5, and wherein n2 is an integer from 1 to 4.
  • R1, R2, and R3 are independently selected from the group comprising hydrogen, halogen, nitro, C1-C10 alkyl, C1-C10 alkoxyl, C2-C10 alkenyl, C1-C10 fluor
  • the compound of formula (Nl) is a compound of formula (IV) or a compound of formula (V), wherein Ri and R3 are as defined for the compound of formula (Nl): (IV)
  • the compound of formula (N-1) is a benzenesulfonamide compound.
  • R1, R2 and/or R3 is selected from hydrogen, halogen, more preferably fluorine, chlorine, bromine or iodine, nitro, a straight, branched or cyclic Ci-Ce-alkyl group, more preferably methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, t-butyl, pentyl, isopentyl, neopentyl, hexyl, isohexyl, cyclopropyl, cyclobutyl, 2-methylcyclopropyl, cyclopropylmethyl, cyclopentyl, or cyclohexyl, a straight, branched or cyclic Ci-Ce-alkoxy group, more preferably methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, t-butoxy, pentyloxy, isopen
  • Ci-Ce-alkyl group selected according to R4 or R5 are the same as for the Ci-Ce-alkyl group selected according to R1.
  • the optional substituents of the optionally substituted groups are selected from hydroxy, halogen, most preferably fluorine, chlorine, bromine or iodine, Ci-Ce-alkyl, most preferably methyl, ethyl, N-propyl, isopropyl, N-butyl, sec-butyl, T-butyl, N-pentyl, isopentyl, neopentyl, T-pentyl, N-hexyl, isohexyl, 1-methyl-pentyl, or 2-methyl-pentyl, and Ci-Ce-alkoxy, most preferably methoxy, ethoxy, N-propoxy, isopropoxy, N-butoxy, sec-butoxy, or T-butoxy.
  • the compound of formula (N-1) is selected from 4-methyl-N-(2-(3-phenylureido)phenyl)benzenesulfonamide and N-(2-(3-phenylureido)phenyl)benzenesulfonamide, more preferably N-(2-(3-phenylureido)phenyl)benzenesulfonamide.
  • the at least one color developer comprises a compound of formula (N-1), wherein R1, R2, and R3 are selected as hydrogen.
  • the at least one color developer comprises N-(2-(3-phenylureido)phenyl)benzenesulfonamide, preferably the ⁇ -polymorph and/or the ⁇ -polymorph of N-(2-(3-phenylureido)phenyl)benzenesulfonamide.
  • the a-polymorph is characterized by an X-ray diffraction pattern with Bragg angles (20/CuKa) of 5.8, 9.3, 13.2, 15.7, 17.3, 18.3, 18.7, 19.5, 20.3, 21.1, 21.9, 22.8, 23.3, 23.6, 24.4, 24.9, 25.6, 26.7, 27.8, 28.1, 29.3, 29.6, 30.2, 31.6, 32.3, 32.8 and/or a melting point of 158°C to 159°C (onset) determined by DSC.
  • the ß-polymorph is characterized by an X-ray diffraction pattern with Bragg angles (26/CuKa) of 10.0, 11.0, 12.3, 12.7, 13.8, 14.9, 15.6, 16.8, 17.7, 18.5, 20.1, 20.9, 21.6, 22.0, 22.8, 23.0, 23.6, 24.3, 25.5, 26.7, 27.8, 28.4, 29.0, 29.8, 30.5, 31.1, 31.3 and/or a melting point of 173°C to 174°C (onset) determined by DSC.
  • the corresponding X-ray diffraction pattern was obtained by X-ray diffraction (XRD) measurement with a Bruker D2 Phaser, a Cu electrode, a voltage of 30 kV and a Lynxeye detector.
  • XRD X-ray diffraction
  • the corresponding melting point determined by DSC was measured by differential scanning calorimetry using a Netzsch DSC 200 F3 Maia® instrument, an Al crucible with a cold-welded, perforated lid, a heating rate of 10 K/min and a temperature range of 25°C to 200°C under ⁇ atmosphere.
  • N-(2-(3-phenylureido)phenyl)benzenesulfonamide is also sold under the name NKK-1304.
  • Ri is selected as phenyl or naphthyl, which may be unsubstituted or substituted by, for example, Ci-Cs-alkyl, Ci-Cs-alkoxy or halogen.
  • the substituents are selected from Ci-C4-alkyl, most preferably methyl or ethyl, Ci-C4-alkoxy, more preferably methoxy or ethoxy, or halogen, more preferably chlorine.
  • Ri is selected as unsubstituted naphthyl.
  • Ri is selected as substituted phenyl, most preferably the substituents are selected as one of the above-mentioned alkyl substituents.
  • Ri is selected as unsubstituted or substituted Ci-C2o-alkyl, more preferably Ci-C8-alkoxy or halogen, even more preferably Ci-C4-alkoxy, most preferably methoxy or ethoxy, or halogen, most preferably chlorine.
  • Ri is selected as unsubstituted Ci-C2o-alkyl.
  • R is unsubstituted phenyl or phenyl which is substituted by Ci-Cs-alkyl, Ci-Cs-alkoxy or halogen, with substituted phenyl being even more preferred. Most preferred is phenyl which is substituted by Ci-C4-alkyl, even more preferably methyl.
  • A is an unsubstituted phenylene or an unsubstituted naphthylene group, or a phenylene or a naphthylene group, which is further preferably substituted by Ci-Cs-alkyl, halogen-substituted Ci-Cs-alkyl, Ci-Cs-alkoxy-substituted Ci-Cs-alkyl, Ci-Cs-alkoxy, halogen-substituted Ci-Cs-alkoxy, Ci-Cs-alkylsulphonyl, halogen, phenyl, phenoxy or phenoxycarbonyl.
  • alkyl and alkoxy substituents which comprise 1 to 4 carbon atoms, with Ci-Cs-alkyl, halogen-substituted Ci-Cs-alkyl, Ci-Cs-alkyl-sulphonyl or halogen being most preferred.
  • A is an unsubstituted naphthylene group.
  • A is a heterocyclic group, which more preferably comprises unsubstituted pyrimidylene or pyrimidylene which is substituted by Ci-Cs-alkyl, even more preferably Ci-C4-alkyl.
  • A is a Ci-Ci2-alkylene group, more preferably Ci-Cs-alkylene, even more preferably Ci-C4-alkylene.
  • A is unsubstituted phenylene or phenylene which is substituted by Ci-Cs-alkyl, halogen-substituted Ci-Cs-alkyl, Ci-Cs-alkoxy-substituted Ci-Cs-alkyl, Ci-Cs-alkoxy, halogen-substituted Ci-Cs-alkoxy, Ci-Cs-alkylsulphonyl, halogen, phenyl, phenoxy or phenoxycarbonyl, even more preferably Ci-Cs-alkyl, halogen-substituted Ci-Cs-alkyl, Ci-Cs-alkylsulphonyl or halogen.
  • A is unsubstituted phenylene or phenylene substituted by Ci-C4 alkyl or halogen, even more preferably unsubstituted phenylene.
  • B is selected from — O — SO2 — , — SO2 — O — , — SO2 — NH — , — S — SO2 — , — O — , — O — CO — and — O — CO — NH — , more preferably from — O — SO2 — , — SO2 — O — and — SO2 — NH — , and most preferably from — O — SO2 — and — O— .
  • R2 is aryl, more preferably phenyl or naphthyl, which is unsubstituted or substituted, even more preferably by Ci-Cs-alkyl, halogen-substituted Ci-Cs-alkyl, Ci-Cs-alkoxy-substituted Ci-Cs-alkyl, Ci-Cs-alkoxy, halogen-substituted C1-Cs-alkoxy or halogen, most preferably alkyl and alkoxy substituents comprising 1 to 4 carbon atoms, with Ci-C4-alkyl and halogen being the even more preferred substituents.
  • R2 is naphthyl, which is more preferably unsubstituted.
  • R2 is benzyl which is substituted by the substituents already mentioned for the selection of R2 as phenyl or naphthyl, with unsubstituted benzyl being further preferred.
  • R2 is Ci-C2o-alkyl, more preferably Ci-Cs-alkyl, even more preferably Ci-Cs-alkyl, which is unsubstituted or substituted by, for example, Ci-Cs-alkoxy, halogen, phenyl or naphthyl, most preferably unsubstituted alkyl groups, even more preferably Ci-C4-alkyl.
  • R2 is Ci-Cs-alkyl, halogen-substituted Ci-Cs-alkyl, phenyl-substituted Ci-Cs-alkyl, naphthyl-substituted Ci-Cs-alkyl, unsubstituted phenyl, or phenyl which is substituted by Ci-Cs-alkyl, halogen-substituted Ci-Cs-alkyl, Ci-Cs-alkoxy-substituted Ci-Cs-alkyl, Ci-Cs-alkoxy, halogen-substituted Ci-Cs-alkoxy or halogen, naphthyl and benzyl which is substituted by Ci-C4-alkyl or halogen.
  • R2 is C1-C4-alkyl, halogen-substituted C1-C4-alkyl, phenyl which is unsubstituted or substituted by C1-C4-alkyl or halogen, naphthyl and benzyl which is unsubstituted or substituted by C1-C4-alkyl or halogen, most preferably phenyl which is unsubstituted or substituted by C1-C4-alkyl or halogen.
  • Ri is phenyl which is substituted by Ci-C4-alkyl, more preferably methyl
  • A is phenylene which is unsubstituted or substituted by Ci-Cs-alkyl or halogen, with unsubstituted phenylene being further preferred, such as 1,3-phenylene
  • B is a group of the formula — O — SO2 — or — O —
  • R2 is phenyl, naphthyl or benzyl which is unsubstituted or substituted by C1-C4-alkyl or halogen, with phenyl which is substituted by Ci-C4-alkyl being further preferred.
  • the at least one color developer of the formula (1) comprises 4-methyl-N-(((3-(((4-methylphenyl)sulfonyl)oxy)phenyl)amino)carbonyl)benzenesulfonamide, preferably the ⁇ -polymorph and/or the ⁇ -polymorph of 4-methyl-N-(((3-(((4-methylphenyl)sulfonyl)oxy)phenyl)amino)carbonyl)benzenesulfonamide.
  • the a-polymorph is characterized by an X-ray diffraction pattern with Bragg angles (26/CuKa) of 8.5, 9.5, 11.8, 12.1, 12.2, 13.7, 14.1, 16.6, 17.1, 18.3, 18.6, 19.1, 19.3, 20.1, 20.4, 20.9, 21.3, 23.1, 24.2, 24.6, 25.0, 27.9, 28.6 and/or a melting point determined by DSC of 161 °C to 162 °C.
  • the ß-polymorph is characterized by an X-ray diffraction pattern with Bragg angles (26/CuKa) of 10.3, 11.0, 12.9, 13.2, 15.4, 17.1, 18.0, 18.2, 19.4, 20.0, 20.7, 21.2, 23.0, 24.9, 25.3, 26.5, 26.8, 27.5, 30.7, 32.7 and/or a melting point determined by DSC of 166°C to 167°C.
  • the corresponding X-ray diffraction pattern was obtained by X-ray diffraction (XRD) measurement with a Bruker D2 Phaser, a Cu electrode, a voltage of 30 kV and a Lynxeye detector.
  • XRD X-ray diffraction
  • the corresponding melting point determined by DSC was measured by differential scanning calorimetry using a Netzsch DSC 200 F3 Maia® instrument, an Al crucible with a cold-welded, perforated lid, a heating rate of 10 K/min and a temperature range of 25°C to 200°C under ⁇ atmosphere.
  • the weight ratio of stabilizer to color developer in the heat-sensitive color-forming layer is from 1 to 11 to 1 to 1, preferably from 1 to 8 to 1 to 4, more preferably from 1 to 7 to 1 to 5, and most preferably 1 to 6.
  • the stability test defined in the description shows a particularly high image stability of the heat-sensitive marking material after a period of two weeks, and in particular also a high remaining print contrast.
  • the stabilizer is selected as 5-(N-3-methylphenylsulfonylamido)-(N',N"-bis- ⁇ 3-methylphenyl)isophthalic acid diamide (trade name PF425) and the at least one color developer is selected as N-(2-(3-phenylureido)phenyl)benzenesulfonamide (trade name NKK-1304), and/or 4-methyl-N-(((3-(((4-methylphenyl)sulfonyl)oxy)phenyl)amino)carbonyl)benzenesulfonamide (trade name PF-201), wherein the weight ratio of stabilizer to color developer in the heat-sensitive color-forming layer is from 1 to 11 to 1 to 1, preferably from 1 to 8 to 1 to 4, more preferably from 1 to 7 to 1 to 5, and most preferably 1 to 6.
  • the stabilizer has a weight proportion of 1 wt.% to 10 wt.% based on the total solids content of the heat-sensitive color-forming layer, wherein the weight proportion is preferably from 2 wt.% to 8 wt.%, more preferably from 3 wt.% to 6 wt.%, and most preferably 4 wt.%.
  • the stability test defined in the description shows a particularly high remaining image stability of the heat-sensitive color-forming layer after a period of two weeks, and in particular also a high remaining print contrast.
  • the stabilizer is selected as 5-(N-3-methylphenyl-sulfonylamido)-(N',N"-bis- ⁇ 3-methylphenyl)-isophthalic acid diamide (trade name PF425) and has the Stabilizer has a weight proportion of 1 wt.% to 10 wt.% based on the total solids content of the heat-sensitive color-forming layer, wherein the weight proportion is preferably from 2 wt.% to 8 wt.%, more preferably from 3 wt.% to 6 wt.%, and most preferably 4 wt.%.
  • the at least one color developer has a weight proportion of 6 wt.% to 35 wt.% based on the total solids content of the heat-sensitive color-forming layer, wherein the weight proportion is preferably from 10 wt.% to 30 wt.%, more preferably from 20 wt.% to 30 wt.%, and most preferably 24 wt.%.
  • the at least one color developer is selected from N-(2-(3-phenylureido)phenyl)benzenesulfonamide (trade name NKK-1304), and/or 4-methyl-N-(((3-(((4-methylphenyl)sulfonyl)oxy)phenyl)amino)carbonyl)benzenesulfonamide (trade name PF-201), wherein the at least one color developer has a weight proportion of 6 wt.% to 35 wt.% based on the total solids content of the heat-sensitive color-forming layer, wherein the weight proportion is preferably from 10 wt.% to 30 wt.%, more preferably from 20 wt.% to 30 wt.%, and most preferably 24 wt.%.
  • the image stability of the heat-sensitive color-forming layer remaining after a period of two weeks is at least 40%, preferably at least 45%, more preferably at least 50%, even more preferably at least 55%, even more preferably at least 60%, even more preferably at least 65%, even more preferably at least 70%, even more preferably at least 75% and most preferably at least 80%.
  • a correspondingly high image fastness of the heat-sensitive color-forming layer remaining after a period of two weeks ensures a high image stability of the heat-sensitive recording material.
  • the adhesive comprises a pressure-sensitive adhesive and/or a heat-activatable adhesive, wherein the adhesive is preferably a permanently adhesive hot-melt adhesive based on styrene-isoprene and PVC copolymers, and/or wherein the adhesive is preferably a removable adhesive based on acrylate, and/or wherein the adhesive is preferably a permanently adhesive hot-melt adhesive based on synthetic rubber.
  • a permanently adhesive hot melt adhesive based on styrene-isoprene and PVC copolymers is the S2200 adhesive from Avery Dennison.
  • an acrylic-based removable adhesive is Avery Dennison's R5000N adhesive.
  • a permanently adhesive hot melt adhesive based on synthetic rubber is the adhesive Technomelt PS 8746 from Henkel.
  • the adhesive comprises a permanently adhesive hot melt adhesive based on styrene-isoprene and PVC copolymers, wherein the weight ratio of stabilizer to color developer in the heat-sensitive color-forming layer is from 1 to 11 to 1 to 1, preferably from 1 to 8 to 1 to 4, more preferably from 1 to 7 to 1 to 5, and most preferably 1 to 6.
  • the color developer comprises the ⁇ -polymorphic form of N- ⁇ 2-[(phenylcarbamoyl)amino]phenyl ⁇ benzenesulfonamide, and/or the color developer comprises the ⁇ -polymorphic form of 4-methyl-N-(((3-(((4-methylphenyl)sulfonyl)oxy)phenyl)amino)carbonyl)benzenesulfonamide.
  • the image stability of the heat-sensitive color-forming layer remaining after a period of two weeks is at least 40%, preferably at least 45%, more preferably at least 50%, even more preferably at least 55%, even more preferably at least 60%, even more preferably at least 65%, even more preferably at least 70%, even more preferably at least 75% and most preferably at least 80%.
  • the adhesive comprises a removable acrylic-based adhesive, wherein the weight ratio of stabilizer to color developer in the heat-sensitive color-forming layer is from 1 to 11 to 1 to 1, preferably from 1 to 8 to 1 to 4, more preferably from 1 to 7 to 1 to 5, and most preferably 1 to 6.
  • the color developer comprises the ⁇ -polymorphic form of N- ⁇ 2-[(phenylcarbamoyl)amino]phenyl ⁇ benzenesulfonamide.
  • the image stability of the heat-sensitive color-forming layer remaining after a period of two weeks is at least 40%, preferably at least 45%, more preferably at least 50%, even more preferably at least 55%, even more preferably at least 60%, even more preferably at least 65%, even more preferably at least 70%, even more preferably at least 75% and most preferably at least 80%.
  • the adhesive comprises a permanently adhesive hot-melt adhesive based on synthetic rubber, wherein the weight ratio of stabilizer to color developer in the heat-sensitive color-forming layer is from 1 to 11 to 1 to 1, preferably from 1 to 8 to 1 to 4, more preferably from 1 to 7 to 1 to 5, and most preferably 1 to 6.
  • the color developer comprises the ⁇ -polymorphic form of N- ⁇ 2-[(phenylcarbamoyl)amino]phenyl ⁇ benzenesulfonamide, and/or the color developer comprises the ⁇ -polymorphic form of 4-methyl-N-(((3-(((4-methylphenyl)sulfonyl)oxy)phenyl)amino)carbonyl)benzenesulfonamide.
  • the image stability of the heat-sensitive color-forming layer remaining after a period of two weeks is at least 40%, preferably at least 45%, more preferably at least 50%, even more preferably at least 55%, even more preferably at least 60%, even more preferably at least 65%, more preferably at least 70%, even more preferably at least 75% and most preferably at least 80%.
  • the image stability is determined by thermally printing the heat-sensitive recording material with a print pattern using a printer at an energy level of 9.00 mJ/mm 2 and a printing speed of about 100 mm/s, then measuring the optical density of the print pattern with a densitometer before storing the heat-sensitive recording material and measuring the optical density of the print pattern with the densitometer after a storage period of two weeks of the heat-sensitive recording material, wherein the image stability corresponds in particular to the quotient of the optical density of the print pattern after the storage period and the optical density of the print pattern before storage in %.
  • a temperature of 60°C and a humidity of 50% are maintained during the storage period of two weeks.
  • the weight ratio of stabilizer to color developer in the heat-sensitive color-forming layer is selected such that the image stability of the heat-sensitive color-forming layer remaining after a period of two weeks is at least 35%, and that the print contrast of the heat-sensitive color-forming layer remaining after a period of two weeks is at least 50%, preferably at least 60%, and more preferably at least 70%, and most preferably at least 80%.
  • the at least one color former is a dye of the triphenylmethane type, the fluoran type, the azaphthalide type and/or the fluorene type, preferably a dye of the fluoran type.
  • the use of the particularly preferred fluoran-type dye as at least one color former enables the provision of a heat-sensitive recording material with an advantageous price-performance ratio due to its availability and balanced application-related properties.
  • a fluoran-type dye is selected from the group comprising 3-diethylamino-6-methyl-7-anilinofluoran, 3-(N-ethyl-N-4-toludin-amino)-6-methyl-7-anilinofluoran, 3-(N-ethyl-N-isoamylamino)-6-methyl-7-anilinofluoran, 3-diethylamino-6-methyl-7-(2, 4-dimethylanilino)fluoran, 3-pyrrolidino-6-methyl-7-anilinofluoran, 3-(cyclohexyl-N-methylamino)-6-methyl-7-anilinofluoran, 3-diethylamino-7-(3-trifluoromethylanilino)fluoran, 3-Nn-dibutylamino-6-methyl-7-anilinofluoran, 3-diethylamino-6-methyl-7-(3-methylanilino)fluoran
  • the at least one color former has a weight proportion of 3 wt.% to 30 wt.% based on the total solids content of the heat-sensitive color-forming layer, wherein the weight proportion is preferably from 5 wt.% to 20 wt.% and particularly preferably from 8 wt.% to 15 wt.%.
  • the carrier substrate comprises paper, synthetic paper, and/or a plastic film.
  • the carrier substrate is not limited here.
  • the carrier material preferably has a basis weight of 30 g/m 2 to 100 g/m 2 , in particular of 40 g/m 2 to 80 g/m 2 .
  • the carrier substrate comprises a paper substrate made of hardwood and/or softwood pulp.
  • the heat-sensitive recording material has at least one intermediate layer which is arranged between the carrier substrate and the heat-sensitive color-forming layer, wherein the intermediate layer preferably comprises at least one pigment, and more preferably organic hollow sphere pigments and/or calcined kaolins.
  • the organic hollow sphere pigments preferably comprise a styrene-acrylate copolymer.
  • the organic hollow sphere pigments preferably have a glass transition temperature of 40 °C to 80 °C and/or an average particle size of 0.1 .m to 2.5 .m.
  • the average particle size comprises the average particle size (D50).
  • the intermediate layer serves as a heat barrier between the carrier substrate and the heat-sensitive color-forming layer, and also makes it possible to improve the surface smoothness of the carrier substrate for the heat-sensitive color-forming layer.
  • the heat-sensitive recording material has at least one protective layer and/or pressure support layer, which is arranged on the heat-sensitive color-forming layer on a side facing away from the adhesive layer, wherein the protective layer preferably comprises a binder and at least one pigment, and more preferably a binder and an inorganic pigment.
  • the protective layer and/or print support layer arranged on the outside of the heat-sensitive color-forming layer ensures effective protection or advantageous printability of the heat-sensitive color-forming layer.
  • the binder is selected from the group comprising water-soluble starches, starch derivatives, starch-based biolatices of the EcoSphere type, methylcellulose, hydroxyethylcellulose, carboxymethylcellulose, partially or fully saponified polyvinyl alcohols, chemically modified polyvinyl alcohols, such as acetoacetyl, diacetone, carboxy, silanol-modified polyvinyl alcohols, ethylene-vinyl alcohol copolymer (EVOH) or styrene-maleic anhydride copolymers, styrene-butadiene copolymers, acrylamide-(meth)acrylate copolymers, acrylamide-acrylate-methacrylate terpolymers, polyacrylates, poly(meth)acrylic acid esters, acrylate-butadiene copolymers, polyvinyl acetates, acrylonitrile-butadiene copolymers and mixtures thereof, with particular use being made of (me
  • the binder has a weight proportion of 30% to 90% by weight based on the total solids content of the protective layer, wherein the weight proportion is preferably from 40% to 80% by weight.
  • the binder is designed as a crosslinked binder, wherein the crosslinked binder is preferably designed as a self-crosslinking binder, or wherein the protective layer comprises a crosslinker which is designed to react with the binder to obtain the crosslinked binder.
  • the binder is preferably present in cross-linked form in the protective layer, with the optimum degree of cross-linking of the binder being established during a drying step of the coating process, in particular in the presence of a cross-linking agent.
  • the self-crosslinking binder comprises modified polyvinyl alcohols and/or modified acrylates.
  • Self-crosslinking binders such as specially modified polyvinyl alcohols and/or modified acrylates, enable crosslinking without the addition of a crosslinker due to the reactive groups which are already part of the polymer of the self-crosslinking binder.
  • the crosslinker is selected from the group comprising polyhydric aldehydes, preferably glyoxal, dialdehyde starch, and/or glutaraldehyde, in particular alone or in admixture with boron salts, salts or esters of glyoxylic acid, ammonium zirconium carbonate, polyamidoamine epichlorohydrin resins, adipic acid dihydrazide, boric acid or salts thereof, polyamines, epoxy resins, formaldehyde oligomers, cyclic ureas, methylol urea, and melamine formaldehyde oligomers and mixtures thereof, wherein the crosslinker is further preferably selected from the group comprising ammonium zirconium carbonate and polyamidoamine epichlorohydrin resins.
  • the crosslinker has a weight fraction of 0.01 wt.% to 25.0 wt.% based on the total solids content of the protective layer, wherein the weight fraction is preferably from 0.05 wt.% to 15 wt.%.
  • the pigment comprises an inorganic pigment which is selected from the group comprising calcium carbonates, preferably synthetic, natural or precipitated calcium carbonates, aluminum oxides, aluminum hydroxides, silicas, precipitated and pyrogenic silicas, diatomaceous earths, magnesium carbonates, talc, kaolin, titanium oxide, bentonite and mixtures thereof, or wherein the pigment an organic pigment selected from the group comprising hollow pigments with a styrene/acrylate copolymer wall, urea/formaldehyde condensation polymers, and mixtures thereof.
  • the pigment has a weight fraction of 5% to 50% by weight based on the total solids content of the protective layer, wherein the weight fraction is preferably from 10% to 45% by weight.
  • the protective layer has at least one lubricant, wherein the lubricant is preferably selected from the group comprising fatty acid metal salts, preferably zinc stearate or calcium stearate, behenate salts or synthetic waxes, preferably in the form of fatty acid amides, more preferably stearic acid amide and behenic acid amide, fatty acid alkanolamides, preferably stearic acid methylolamide, paraffin waxes of various melting points, ester waxes of different molecular weights, polyethylene waxes, polypropylene waxes of different hardnesses, natural waxes, preferably carnauba wax or montan wax, and mixtures thereof.
  • the lubricant is preferably selected from the group comprising fatty acid metal salts, preferably zinc stearate or calcium stearate, behenate salts or synthetic waxes, preferably in the form of fatty acid amides, more preferably stearic acid amide and behenic
  • the lubricant has a weight proportion of 1 wt.% to 30 wt.% based on the total solids content of the protective layer, wherein the weight proportion is preferably from 2 wt.% to 20 wt.%.
  • the protective layer comprises at least one brightener, wherein the brightener is preferably selected as a stilbene.
  • the brightener can be used to advantageously adjust the surface whiteness of the heat-sensitive color-forming layer.
  • the protective layer has a basis weight of 0.3 g/m 2 to 5.0 g/m 2 , preferably from 1.0 g/m 2 to 3.0 g/m 2 .
  • the protective layer has a thickness of 0.3 .m to 6.0 .m, preferably from 0.5 .m to 2.0 .m. According to one embodiment, the protective layer has a Bekk smoothness of 100 see to 3000 see, preferably 500 see to 2000 see, measured according to ISO 5267:1995-03.
  • a corresponding advantageous Bekk smoothness can be achieved by a smoothing process.
  • the protective layer has a surface roughness measured according to the standard ISO 8791-4:2008-05 of 0.5 .m to 2.50 .m, preferably of 1.00
  • the heat-sensitive color-forming layer can further comprise at least one sensitizer, which has the advantage that the control of the thermal pressure sensitivity is easier to realize.
  • sensitizing agents can be present alone or as mixtures.
  • the at least one sensitizer is preferably selected from the group comprising a fatty acid amide, in particular stearic acid amide, beheneamide or palmitamide, an ethylene-bis-fatty acid amide, in particular /V,/V'-ethylene-bis-stearic acid amide or /V,/V'-ethylene-bis-oleic acid amide, a fatty acid alkanolamide, in particular N-(hydroxymethyl)stearic acid amide, /V-hydroxymethylpalmitamide or hydroxyethylstearic acid amide, a wax, in particular polyethylene wax or montan wax, a carboxylic acid ester, in particular dimethyl terephthalate, dibenzyl terephthalate, benzyl 4-benzyloxybenzoate, di-(4-methylbenzyl)oxalate, di-(4-chlorobenzyl)oxalate or di-(4-benzyl)oxalate, an aromatic ether, in particular 1,2-
  • the sensitizing agent has a weight proportion of 5 wt.% to 40 wt.% based on the total solids content of the heat-sensitive color-forming layer, wherein the weight proportion is preferably from 10 wt.% to 25 wt.%.
  • the heat-sensitive color-forming layer can, according to one embodiment, further comprise at least one further stabilizer.
  • the additional stabilizing agent serves as an anti-aging agent for the color complex in the heat-sensitive color-forming layer.
  • the further stabilizing agent is selected from the group comprising sterically hindered phenols, more preferably 1,1,3-tris-(2-methyl-4-hydroxy-5-cyclohexylphenyl)butane, 1,1,3-tris-(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, and/or 1,1-bis-(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, urea-urethane compounds, ethers derived from 4,4'-dihydroxydiphenylsulfone, more preferably 4-benzyloxy-4'-(2-methylglycidyloxy)-diphenylsulfone, oligomeric ethers and mixtures thereof.
  • sterically hindered phenols more preferably 1,1,3-tris-(2-methyl-4-hydroxy-5-cyclohexylphenyl)butane, 1,1,3-tris-(2-methyl-4-hydroxy-5-tert-butylphenyl
  • the further stabilizing agent preferably has a weight proportion of 0.2 wt.% to 1.0 wt.% based on the total proportion of the color developer in the heat-sensitive color-forming layer.
  • the heat-sensitive color-forming layer comprises at least one further binder, which is preferably selected from the group comprising water-soluble starches, starch derivatives, starch-based biolatices of the EcoSphere® type, methylcelluloses, hydroxyethylcelluloses, carboxymethylcellulose, partially or fully saponified polyvinyl alcohols, chemically modified polyvinyl alcohols, ethylene-vinyl alcohol copolymer (EVOH) or styrene-maleic anhydride copolymers, styrene-butadiene copolymers, acrylamide-(meth)acrylate copolymers, acrylamide-acrylate-methacrylate terpolymers, polyacrylates, poly(meth)acrylic acid esters, acrylate-butadiene copolymers, polyvinyl acetates, acrylonitrile-butadiene copolymers, and mixtures thereof, with particular use being made of (meth)acrylamide-acrylic acid ester-
  • the binder is preferably present in cross-linked form in the heat-sensitive layer, the optimum degree of cross-linking of the binder being established in the drying step of the coating process in the presence of a cross-linking agent.
  • the binder is formed as a cross-linked further binder, wherein the cross-linked further binder is preferably formed as a self-cross-linking further binder, or wherein the heat-sensitive color-forming layer comprises a further cross-linker which is formed to react with the further binder in order to obtain the cross-linked further binder.
  • the self-crosslinking additional binder comprises modified polyvinyl alcohols and/or modified acrylates.
  • the further crosslinker is selected from the group comprising polyhydric aldehydes, preferably glyoxal, dialdehyde starch, and/or glutaraldehyde, in particular alone or in admixture with boron salts, salts or esters of glyoxylic acid, ammonium zirconium carbonate, polyamidoamine epichlorohydrin resins, adipic acid dihydrazide, boric acid or salts thereof, and mixtures thereof. More preferably, the further crosslinker has a weight proportion of 2.5 wt. % to 20 wt. % based on the total proportion of the crosslinkable further binder in the heat-sensitive color-forming layer, wherein the weight proportion is preferably from 5 wt. % to 15 wt. %.
  • the carrier substrate, the heat-sensitive color-forming layer, and/or the adhesive layer are formed in one layer or in multiple layers.
  • the heat-sensitive color-forming layer has a release agent which is preferably selected from the group comprising fatty acid metal salts, more preferably zinc stearate or calcium stearate, behenate salts, synthetic waxes, in particular in the form of fatty acid amides, more preferably stearic acid amide and behenic acid amide, fatty acid alkanolamides, more preferably stearic acid methylolamide, paraffin waxes of various melting points, ester waxes of different molecular weights, polyethylene waxes, propylene waxes of different hardnesses, natural waxes, more preferably carnauba wax or montan wax and mixtures thereof.
  • fatty acid metal salts more preferably zinc stearate or calcium stearate
  • behenate salts synthetic waxes, in particular in the form of fatty acid amides, more preferably stearic acid amide and behenic acid amide, fatty acid alkanolamides, more preferably
  • the release agent has a weight proportion of 1 wt. % to 10 wt. % based on the total solids content in the heat-sensitive color-forming layer, wherein the weight proportion is preferably from 3 wt. % to 6 wt. %.
  • the heat-sensitive color-forming layer has a further pigment, which has the advantage that these further pigments can fix the chemical melt created in the thermal printing process on their surface, and that the surface whiteness and opacity of the heat-sensitive color-forming layer and its printability with conventional printing inks can be controlled via the further pigments.
  • the corresponding further pigments have an "extender function", for example for the relatively expensive color-imparting functional chemicals.
  • the further pigment is preferably selected from the group comprising inorganic pigments, both synthetic and natural origin, precipitated or natural calcium carbonates, clays, aluminum oxides, aluminum hydroxides, silicas, precipitated and pyrogenic silicas, diatomaceous earths, magnesium carbonates, talc, but also organic pigments, more preferably hollow pigments with a styrene/acrylate copolymer wall, urea/formaldehyde condensation polymers and mixtures thereof.
  • inorganic pigments both synthetic and natural origin, precipitated or natural calcium carbonates, clays, aluminum oxides, aluminum hydroxides, silicas, precipitated and pyrogenic silicas, diatomaceous earths, magnesium carbonates, talc, but also organic pigments, more preferably hollow pigments with a styrene/acrylate copolymer wall, urea/formaldehyde condensation polymers and mixtures thereof.
  • the additional pigment preferably has a weight proportion of 15 wt.% to 50 wt.% based on the total solids content in the heat-sensitive color-forming layer, wherein the weight proportion is preferably from 20 wt.% to 35 wt.%.
  • the heat-sensitive color-forming layer comprises at least one further brightener, wherein the further brightener is preferably selected as a stilbene.
  • the additional brightener can be used to control the surface whiteness of the heat-sensitive recording material.
  • the heat-sensitive color-forming layer comprises a rheology aid, preferably a thickener and/or a surfactant.
  • the application weight of the heat-sensitive color-forming layer is from 1 g/m 2 to 10 g/m 2 , preferably from 3 g/m 2 to 5 g/m 2 .
  • the heat-sensitive color-forming layer has a Bekk smoothness of 100 see to 1500 see, preferably 200 see to 750 see, measured according to ISO 5267:1995-03.
  • the surface application weight of the adhesive layer is from 10 g/m 2 to 150 g/m 2 , preferably from 15 g/m 2 to 30 g/m 2 .
  • the application suspension comprises at least one color former, at least one color developer, and at least one stabilizer;
  • the weight ratio of stabilizer to color developer in the application suspension is selected such that migration of components of the adhesive layer of the heat-sensitive recording material into the heat-sensitive color-forming layer of the heat-sensitive recording material according to the stability test defined in the description after a period of two weeks leads to a remaining image stability of the heat-sensitive color-forming layer of at least 35%, wherein the stabilizer comprises a compound of formula (I):
  • applying the adhesive layer to the second side of the carrier substrate may comprise applying, in particular laminating, an adhesive film to the second side of the carrier substrate.
  • applying the adhesive layer to the second side of the carrier substrate may comprise applying an adhesive dispersion to the second side of the carrier substrate and subsequently drying the adhesive dispersion to obtain the adhesive layer arranged on the second side of the carrier substrate.
  • the drying of the adhesive layer is carried out at a temperature of 60 °C to 80 °C, preferably at 70 °C.
  • the method comprises the further method step, which is carried out after the application of the adhesive layer:
  • release paper is preferably designed as a siliconized release paper.
  • the application of the adhesive layer comprises applying an adhesive dispersion and subsequently drying the adhesive dispersion, the method comprising the further method step which is carried out before the application of the adhesive dispersion:
  • the application and drying of the application dispersion on the first side of the carrier substrate is carried out before the application of the adhesive layer on the second side of the carrier substrate, or the application of the adhesive layer to the second side of the carrier substrate is carried out before the application and drying of the application dispersion to the first side of the carrier substrate, wherein preferably the application and drying of the application dispersion to the first side of the carrier substrate is carried out before the application of the adhesive layer to the second side of the carrier substrate.
  • the application of the application dispersion to the first side of the carrier substrate is carried out by means of curtain coating or by means of a bar doctor on the coating side of a carrier substrate pre-coated with a pigment coating
  • the pigmented pre-coat preferably comprises calcined kaolin and a binder based on styrene-butadiene and/or polyvinyl alcohol (PVA) and/or starch, or organic pigments in a mixture with inorganic pigments, wherein the application amount of the pigmented pre-coat is more preferably from 2 g/m 2 to 12 g/m 2 .
  • the application amount of the application dispersion is between 3 g/m 2 and 5 g/m 2 , preferably between 3.6 g/m 2 and 4.8 g/m 2 , and/or the application amount of the adhesive dispersion is between 10 g/m 2 and 30 g/m 2 , preferably 20 g/m 2 .
  • the application suspension is produced in particular by grinding and preferably has an average grain size D ⁇ 4.3) of 0.5 pm to 5.0 pm, particularly preferably of 0.50 pm to 1.50 pm and very particularly preferably of 1.5 pm to 2.50 pm.
  • the embodiments given for the heat-sensitive recording material according to the first aspect are also embodiments for the method for producing a heat-sensitive recording material according to the second aspect and vice versa.
  • the above object is achieved according to the third aspect by a heat-sensitive recording material producible by a method according to the second aspect.
  • the embodiments given for the heat-sensitive recording material according to the first aspect and the method for producing a heat-sensitive recording material according to the second aspect are also embodiments for the heat-sensitive recording material producible by a method according to the third aspect.
  • the above-mentioned object is achieved according to the fourth aspect by using at least one stabilizer and at least one color developer in a heat-sensitive recording material, comprising a carrier substrate which has a first side and a second side facing away from the first side, a heat-sensitive color-forming layer which is arranged on the first side of the carrier substrate, wherein the heat-sensitive color-forming layer comprises at least one color former, the at least one color developer, and the at least one stabilizer, and an adhesive layer which is arranged on the second side of the carrier substrate, wherein the adhesive layer comprises at least one adhesive, wherein the weight ratio of stabilizer to color developer in the heat-sensitive color-forming layer is selected such that migration of components of the adhesive layer of the heat-sensitive recording material into the heat-sensitive color-forming layer of the heat-sensitive recording material according to the stability test defined in the description after a period of two weeks leads to a remaining image stability of the heat-sensitive color-forming layer of at least 35%, wherein the stabilizer comprises a compound of formula (I):
  • the embodiments given for the heat-sensitive recording material according to the first aspect and those given for the method for producing a heat-sensitive recording material according to the second aspect are also embodiments for the use of at least one stabilizer and at least one color developer in a heat-sensitive recording material according to the fourth aspect.
  • a large number of heat-sensitive recording materials or thermal papers were produced by applying aqueous application suspensions and adhesive dispersions to form a composite structure on a carrier substrate.
  • the adhesive dispersion is applied with a doctor blade to the second side of a carrier substrate, in particular A4 paper, which bears the color-forming heat-sensitive layer on the first side, which is the front side, and dried with a hot air dryer at a maximum of 70°C in order to obtain the adhesive layer.
  • a siliconized release paper is laminated onto the adhesive layer, avoiding air pockets and wrinkles.
  • the sticky side of the adhesive layer is laminated to the second side, which forms the back of the carrier substrate, while avoiding air pockets and wrinkles. It is irrelevant whether, during the production of the heat-sensitive recording material, the adhesive layer is first applied to the second side of the carrier substrate and then the heat-sensitive recording layer is applied to the opposite first side of the carrier substrate bearing the adhesive layer, or vice versa.
  • an aqueous application suspension for forming the heat-sensitive color-forming layer of a heat-sensitive recording material is carried out, in particular on a laboratory scale, by means of a doctor blade on the coating side of a paper pre-coated with a pigment coating and having a basis weight of 65 g/m 2 and 72 g/m 2 .
  • the composition of the pigmented primer is not critical.
  • this coating consists of calcined kaolin and a binder based on styrene-butadiene and/or starch.
  • primers with organic (hollow sphere) pigments, possibly mixed with inorganic pigments, are also possible.
  • the application quantity of this pigmented layer is between about 2 and 10 g/m 2 .
  • the heat-sensitive color-forming layer After drying the aqueous application suspension of the heat-sensitive coating material, the heat-sensitive color-forming layer is obtained.
  • the application quantity of the heat-sensitive color-forming layer is between 3.8 g/m 2 and 4.3 g/m 2 .
  • a composite material suitable for use as a thermal label is obtained.
  • the amount of adhesive applied is approximately 20 g/m 2 .
  • Color former dispersion A was prepared by grinding 20 parts by weight of 3-/Vn-dibutylamine-6-methyl-7-anilinofluorane (ODB-2) with 33 parts by weight of a 12% aqueous solution of GohsenxTM L-3266 (sulfonated polyvinyl alcohol, Nippon Gohsei) in a bead mill.
  • ODB-2 3-/Vn-dibutylamine-6-methyl-7-anilinofluorane
  • Stabilizer dispersion B was prepared by grinding 40 parts by weight of (N-3-methylphenylsulfonylamido)-(N',N"-bis- ⁇ 3-methylphenyl)-isophthalic acid diamide (GAS# 2375645-78-4, referred to as Compound I in the table below) together with 66 parts by weight of a 12% aqueous solution of GohsenxTM L-3266 (sulfonated polyvinyl alcohol, Nippon Gohsei) in a bead mill.
  • GohsenxTM L-3266 sulfonated polyvinyl alcohol, Nippon Gohsei
  • the aqueous color developer dispersions C were prepared by grinding 40 parts by weight of the respective color developer 4-methyl-N-(((3-(((4-methylphenyl)sulfonyl)oxy)phenyl)amino)carbonyl)benzenesulfonamide (GAS# 232938-43-1, a-polymorph, referred to as compound II in the table below), 4-methyl-N-(((3-(((4-methylphenyl)sulfonyl)oxy)phenyl)amino)carbonyl)benzenesulfonamide (GAS# 232938-43-1, ß-polymorph, referred to as compound III in the table below), N-(2-(3-phenylureido)phenyl)benzenesulfonamide (GAS# 215917-77-4, a-polymorph, referred to as compound IV in the table below), or N-(2-(3-phenylureido)pheny
  • Sensitizing dispersion D was prepared by grinding 40 parts by weight of 1,2-diphenoxyethane with 66 parts by weight of a 12% aqueous solution of GohsenxTM L-3266 (sulfonated polyvinyl alcohol, Nippon Gohsei) in a bead mill. All dispersions A, B, C and D produced by grinding have an average grain size D(4.3) of 0.7 .m to 1.3 .m. The grain size distribution of the dispersions was measured by laser diffraction with a Coulter LS13320 device from Beckman Coulter.
  • the lubricant dispersion E is a 20% zinc stearate dispersion comprising 9 parts by weight of zinc stearate, 1 part by weight of GohsenxTM L-3266 (sulfonated polyvinyl alcohol, Nippon Gohsei) and 40 parts by weight of water.
  • Pigment P is a 72% coating kaolin suspension (Lustra® S, BASF).
  • the binder solution consists of a 10% aqueous polyvinyl alcohol solution (Poval 28-99, Kuraray Europe).
  • the heat-sensitive application suspension was prepared by mixing, while stirring, 1 part by weight of the color former dispersion A, 1 part by weight of the stabilizer dispersion B, 1.5 parts by weight of the respective color developer dispersion C, 2.5 parts by weight of the sensitizing dispersion D, 1 part by weight of the lubricant dispersion E, 2.1 parts by weight of the pigment P and 2.5 parts by weight of the binder solution, taking into account the order of addition C, D, B, E, P, A, and brought to a solids content of about 25% with water.
  • the application suspension was presented as an example for the color developer-stabilizer ratio of 1.5:1.
  • the heat-sensitive application suspensions thus obtained were used to produce composite structures consisting of a paper carrier and a heat-sensitive color-forming layer.
  • Adhesives In order to produce self-adhesive thermal labels, the following commercially available adhesives were used on the side of the paper carrier facing away from the heat-sensitive color-forming layer, or the second side of the carrier substrate:
  • R5000N (Avery Dennison) is a removable acrylic-based adhesive.
  • the relative print contrast was determined using the value of the optical density of a thermally printed area (oDs) and the optical density of a non-printed area (oDw) is calculated according to the following formula B, where s stands for a black area and w for a white area:
  • a strip of the heat-sensitive recording material was measured according to the measurement described above and the optical density (oD) before storage was determined.
  • the heat-sensitive recording material was then stored for two or four weeks between two glass plates at 60 °C, a pressure of 1350 N/m 2 , a relative humidity of 50% and under exclusion of light.
  • the optical densities of the printed (oDs, at an energization energy of 9.00 mJ/mm 2 ) and non-printed (oDw) areas were measured, averaged and used to determine the relative print contrast according to formula B.
  • Image stability in % (optical density after storage / optical density before storage) x 100
  • the table below describes the results of the described image stability and print contrast measurements for a variety of different heat-sensitive recording materials, which were tested on a a heat-sensitive color-forming layer on the first side of the carrier substrate and an adhesive layer on the side of the carrier substrate facing away from the first side.
  • results obtained in the table are based on the analysis of the image stability and the print contrast of the respective heat-sensitive recording material as a function of a migration of components of the adhesive layer into the heat-sensitive color-forming layer, after the corresponding period of two weeks or four weeks.
  • the adhesives tested for the adhesive layer were the previously mentioned adhesives R5000N from Avery Dennison, S2200 from Avery Dennison, and Technomelt PS 8746 from Henkel.
  • the compound 5-(N-3-methylphenylsulfonylamido)-(N',N"-bis- ⁇ 3-methylphenyl)isophthalic acid diamide (PF425) was investigated as a stabilizer of the heat-sensitive color-forming layer, which is designated as compound I in the table.
  • the compound 4-methyl-N-(((3-(((4-methylphenyl)sulfonyl)oxy)phenyl)amino)carbonyl)benzenesulfonamide (PF-201) which comprises the ⁇ -polymorph as compound II and ⁇ -polymorph as compound III shown in the table was investigated as the color developer of the heat-sensitive color-forming layer.
  • the compound N-(2-(3-phenylureido)phenyl)benzenesulfonamide (NKK-1304) which comprises the ⁇ -polymorph as compound IV and ⁇ -polymorph as compound V shown in the table was investigated as the color developer of the heat-sensitive color-forming layer.
  • the heat-sensitive recording material according to the present invention exhibits the following advantageous properties.
  • the print contrast remaining after the two-week test period is also optimized by optimizing the weight ratio between the respective color developer and the stabilizer.

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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)

Abstract

L'invention concerne un matériau d'enregistrement thermosensible comprenant un substrat de support qui présente une première face et une seconde face opposée à la première face ; une couche de formation de couleur thermosensible qui est disposée sur la première face du substrat de support, la couche de formation de couleur thermosensible comprenant au moins un agent de formation de couleur, au moins un révélateur de couleur et au moins un stabilisateur ; et une couche adhésive qui est disposée sur la seconde face du substrat de support, ladite couche adhésive comprenant au moins un adhésif. Le rapport en poids du stabilisateur par rapport au révélateur de couleur dans la couche de formation de couleur thermosensible est sélectionné de telle sorte que la migration de composants de la couche adhésive dans la couche de formation de couleur thermosensible donne lieu à une permanence d'image restante de la couche de formation de couleur thermosensible d'au moins 35 % après un laps de temps de deux semaines selon le test de stabilité défini dans la description.
PCT/EP2023/077632 2022-10-11 2023-10-05 Matériau d'enregistrement thermosensible WO2024078971A1 (fr)

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JPS59162087A (ja) 1983-03-07 1984-09-12 Ricoh Co Ltd 感熱記録型剥離紙
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JPH0720735B2 (ja) 1988-09-02 1995-03-08 新王子製紙株式会社 感熱記録材料
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EP3533619A1 (fr) * 2018-03-02 2019-09-04 Basf Se Matériel d'enregistrement sensible à la chaleur et révélateur de couleur
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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

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US4370370A (en) 1981-06-08 1983-01-25 Ricoh Company, Ltd. Thermosensitive recording adhesive label
JPS59162087A (ja) 1983-03-07 1984-09-12 Ricoh Co Ltd 感熱記録型剥離紙
JPH0720735B2 (ja) 1988-09-02 1995-03-08 新王子製紙株式会社 感熱記録材料
EP0600622A1 (fr) 1992-11-30 1994-06-08 Moore Business Forms, Inc. Label pour bagage, dépourvu de revêtement de détachement, imprimé par impression thermique
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DE19724647C1 (de) 1997-06-11 1999-04-15 Zweckform Buero Prod Gmbh Selbstklebendes Flächengebilde für Thermodruckverfahren und Verfahren zu dessen Herstellung
DE19806433B4 (de) 1998-02-17 2004-11-11 Mitsubishi Hitec Paper Flensburg Gmbh Verwendung eines wärmeempfindlichen Aufzeichnungsmaterials als Etikett
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EP2474963B1 (fr) 2009-09-03 2013-11-13 Nippon Paper Industries Co., Ltd. Etiquette d'enregistrement thermosensible
EP3219507A1 (fr) 2016-03-14 2017-09-20 Papierfabrik August Koehler SE Matériel d'enregistrement autocollant sensible à la chaleur
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EP3533619A1 (fr) * 2018-03-02 2019-09-04 Basf Se Matériel d'enregistrement sensible à la chaleur et révélateur de couleur
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DE202020005616U1 (de) 2019-09-27 2021-10-25 Mitsubishi Hitec Paper Europe Gmbh Wärmeempfindliches Aufzeichnungsmaterial, umfassend phenolfreie organische Farbentwickler
KR20220070021A (ko) 2019-09-27 2022-05-27 미츠비시 하이텍 페이퍼 유럽 게엠베하 무페놀 유기 색상 현상제를 포함하는 감열 기록 재료
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
WO2022038242A1 (fr) 2020-08-19 2022-02-24 Mitsubishi Hitec Paper Europe Gmbh Matière d'impression thermosensible et couche d'impression thermosensible et composition de revêtement pour la réaliser, utilisations correspondantes et procédé

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